Organic-inorganic composite waterproof material, preparation method and application

Abstract

The invention relates to the technical field of waterproof materials, in particular to an organic-inorganic composite waterproof material, a preparation method and application, and the preparation method comprises the following steps: weighing raw materials in parts by weight: firstly weighing a component A raw material: 5-10 parts of water glass, 4-7 parts of calcium oxide, 6-10 parts of modified superfine fly ash, 5-8 parts of sodium bentonite, 35-40 parts of Portland cement and 25-30 parts of water; according to the organic-inorganic composite waterproof material, the component A raw material and the component B raw material are blended, optimized and co-matched, the water glass and the calcium oxide in the component A raw material are blended with the sodium bentonite and the Portland cement, and meanwhile, the modified superfine fly ash is added for further synergistic optimization and improvement. The product is excellent in condensation rate, mechanical strength and waterproof impermeability balance coordination, and meanwhile, the product has a remarkable effect of resisting different degrees of acid-base stability.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof materials, and in particular to an organic-inorganic composite waterproof material, a preparation method and applications thereof. Background Art

[0002] Waterproof materials are suitable for blocking water gushing in scenes such as tunnels, mines, and underground projects. The following steps are usually used for construction: first, pump out water and clear silt, then find the gushing cracks, and use a leak-proof sealer to block the cracks. After solidifying for one hour, drill holes at intervals of 0.5 meters along the rock cracks at the gushing point, insert grouting needles, and leave an observation tube. Use a pump to drive the prepared waterproof material into the rock cracks until the waterproof material overflows from the observation tube. The cracks can be blocked in 3-10 minutes. However, in order to increase the coagulation rate during construction, the existing waterproof materials are prone to reduce the mechanical strength and waterproof and anti-seepage properties of the product, resulting in poor performance balance and coordination of the product, which is the pain point and difficulty of the present invention. At the same time, the product of the present invention has poor acid and alkali stability to different degrees, which limits the efficiency of the product. Summary of the Invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide an organic-inorganic composite waterproof material, a preparation method and an application thereof, so as to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solutions: The present invention provides a method for preparing an organic-inorganic composite waterproof material, comprising the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 5-10 parts of water glass, 4-7 parts of calcium oxide, 6-10 parts of modified ultrafine fly ash, 5-8 parts of sodium bentonite, 35-40 parts of Portland cement, and 25-30 parts of water; Weigh the raw materials of component B: 5-9 parts of modified silica sol, 25-30 parts of acrylic polymer emulsion, 4-6 parts of silane coupling agent KH560; Step 2: uniformly blending the raw materials of component A to form an improved body A, uniformly mixing the raw materials of component B to form an improved body B, and uniformly mixing the improved body A and the improved body B in a weight ratio of 1:1 to obtain an organic-inorganic composite waterproof material; The preparation method of the modified ultrafine fly ash is: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were stirred and reacted in a weight ratio of 3:5:7:2 at a stirring temperature of 58-62°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain a boron nitride pretreatment agent; S2: Preparation of sodium alginate-titanium oxide complex: S2a: Sodium alginate and tris(hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of (2-3):5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:(8-9) to obtain a sodium alginate-titanium oxide complex; S3: a boron nitride pretreatment agent and a sodium alginate-titanium oxide complex are subjected to a primary modification treatment in a weight ratio of 9:(4-5), and the modification is completed to obtain a modified product based on the combined adjustment; S4: subjecting the ultrafine fly ash and the modified product based on the combined adjustment to a secondary modification treatment in a weight ratio of (7-11):5, filtering and drying after the modification is completed to obtain modified ultrafine fly ash; The preparation method of the modified silica sol is as follows: S11: uniformly blending 3-5 parts of β-cyclodextrin, 2-3 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, and 1-2 parts of alkylamide betaine to obtain an additive; S12: fully mixing the nano-silica sol with an 8% urea solution having a mass fraction of 5-8 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Adding an additive in an amount of 30-40% of the total amount of the nano-silica sol solution to the nano-silica sol solution and stirring the mixture uniformly to obtain a nano-silica sol; further ball-milling the nano-silica sol and the modifier at a weight ratio of 7:(3-5) at a ball-milling speed of 1000-1200 r / min for 2 hours; after the ball-milling is completed, filtering and drying the mixture to obtain a modified silica sol; The modifier is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of (2-3): (4-5): (11-13).

[0005] Preferably, the acrylic ester polymer emulsion is prepared using the prior art of Example 3 of CN104151481B, an acrylic ester polymer emulsion and its preparation method.

[0006] Preferably, the ball milling speed for the primary modification treatment is 1000-1500 r / min, and the ball milling is performed for 2 hours; the ball milling speed for the secondary modification treatment is 500-700 r / min, and the ball milling is performed for 5 hours.

[0007] Preferably, the specific surface area of ​​the ultrafine fly ash is 2000~2400m 2 / kg, water requirement ratio is less than 85%, and 28d intensity activity index is greater than 75%.

[0008] Preferably, the basalt fiber has a diameter of 12-15 μm and a length of 0.5-1 mm.

[0009] The present invention also provides an organic-inorganic composite waterproof material prepared by a method for preparing the organic-inorganic composite waterproof material.

[0010] The present invention also provides an application of a preparation method of an organic-inorganic composite waterproof material in the construction of tunnels, mines and underground projects.

[0011] Compared with the prior art, the present invention has the following beneficial effects: The organic-inorganic composite waterproof material of the present invention adopts A component raw material and B component raw material to be blended and optimized, and coordinated together. The water glass and calcium oxide in the A component raw material are coordinated with sodium bentonite and silicate cement, and modified ultrafine fly ash is added to further coordinate and optimize the improvement. The modified silica sol in the B component raw material is blended with acrylic polymer emulsion and silane coupling agent KH560. The acrylic polymer emulsion is used as the matrix in the B component, and the silicate cement and other raw materials of the system are combined to form a three-dimensional network structure, thereby enhancing the stability of the system structure. The addition of the silane coupling agent KH560 further enhances the interface between the raw materials, and the addition of the modified silica sol better coordinates the modified ultrafine fly ash. The raw materials work together to further optimize the connection stability between the system structures. The product has excellent balance and coordination in setting rate, mechanical strength and waterproof and anti-seepage performance. At the same time, the product of the present invention has significant acid and alkali stability effect to different degrees. The modified ultrafine fly ash is prepared by subjecting ultrafine fly ash to secondary modification optimization through a modified body based on combined regulation, and the modified body based on combined regulation is modified and optimized with boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane to prepare amino boron nitride. Meanwhile, titanium dioxide, cerium oxide and silicon carbide are sintered, improved and optimized, and blended with sodium alginate and tris(hydroxymethyl)aminomethane buffer solution with a pH value of 8.5. The titanium oxide body and sodium alginate solution are further coordinated and further optimized through amino boron nitride. Through the coordination between the raw materials, the modified body based on combined regulation is prepared to coordinate and optimize the ultrafine fly ash, thereby better distributing the ultrafine fly ash into the system, enhancing the functional effect of the modified ultrafine fly ash in the system, and optimizing the performance coordination and performance stability of the product. The modified silica sol agent is prepared by mixing and dispersing nano silica sol with a urea solution, stirring and improving and optimizing the additive, and ball milling and improving the modifier. The β-cyclodextrin, tetrabutyl titanate, and acetone solvent in the additive and alkyl amide betaine are mixed and optimized. The raw materials are matched and coordinated to enhance the interface connectivity of the modified silica sol agent in the system. The modifier is mixed with nano cellulose, basalt fiber, and kaolin to further enhance the performance of the modified silica sol agent in the system, and further optimize the performance coordination and stability of the system. DETAILED DESCRIPTION

[0012] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0013] The preparation method of the organic-inorganic composite waterproof material in the embodiment comprises the following steps: Step one, the raw materials are weighed according to the weight parts: First, the A component raw materials are weighed: water glass 5-10 parts, calcium oxide 4-7 parts, modified ultra-fine fly ash 6-10 parts, sodium-based bentonite 5-8 parts, silicate cement 35-40 parts, and water 25-30 parts; The B component raw materials are weighed: Modified silica sol agent 5-9 parts, acrylate polymer emulsion 25-30 parts, and silane coupling agent KH560 4-6 parts; Step two, the A component raw materials are uniformly blended to form an A improvement body, and the B component raw materials are uniformly mixed to form a B improvement body. The A improvement body and the B improvement body are mixed and uniformly obtained according to the weight ratio of 1:1 to obtain the organic-inorganic composite waterproof material.

[0014] The acrylate polymer emulsion in the embodiment is prepared by the prior art in Example 3 of CN104151481B One kind of acrylate polymer emulsion and its preparation method.

[0015] The preparation method of the modified ultra-fine fly ash in the embodiment is as follows: S1: Boron nitride, anhydrous ethanol, water, and 3-aminopropyl triethoxysilane are stirred and reacted according to the weight ratio of 3:5:7:2. The stirring temperature is 58-62℃, and the stirring time is 5h. After stirring, filtration, washing, and drying, a boron nitride pretreatment agent is obtained. S2: Preparation of sodium alginate-titanium oxide combination: S2a: Sodium alginate and tris(hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of (2-3):5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:(8-9) to obtain a sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment in a weight ratio of 9:(4-5), and the modification is completed to obtain a modified product based on combined regulation; S4: subjecting the ultrafine fly ash and the modified product based on the combined adjustment to a secondary modification treatment in a weight ratio of (7-11):5. After the modification is completed, the modified product is filtered and dried to obtain the modified ultrafine fly ash.

[0016] In this embodiment, the ball milling speed for the primary modification treatment is 1000-1500 r / min, and the ball milling is performed for 2 h; the ball milling speed for the secondary modification treatment is 500-700 r / min, and the ball milling is performed for 5 h.

[0017] The specific surface area of ​​the ultrafine fly ash of this embodiment is 2000-2400 m² / kg, the water requirement ratio is less than 85%, and the 28d strength activity index is greater than 75%.

[0018] The preparation method of the modified silica sol agent of this embodiment is: S11: uniformly blending 3-5 parts of β-cyclodextrin, 2-3 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, and 1-2 parts of alkylamide betaine to obtain an additive; S12: fully mixing the nano-silica sol with an 8% urea solution having a mass fraction of 5-8 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Adding an additive accounting for 30-40% of the total amount of the nano-silica sol liquid to the nano-silica sol liquid, stirring evenly to obtain a nano-silica sol; continuing to ball-mill the nano-silica sol and the modifier in a weight ratio of 7: (3-5), at a ball-milling speed of 1000-1200 r / min, for 2 hours, after the ball-milling is completed, filtering, and drying to obtain a modified silica sol.

[0019] The modifier of this embodiment is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of (2-3): (4-5): (11-13).

[0020] The basalt fiber of this embodiment has a diameter of 12-15 μm and a length of 0.5-1 mm.

[0021] The organic-inorganic composite waterproof material is prepared by a method for preparing an organic-inorganic composite waterproof material in this embodiment.

[0022] The present embodiment provides a method for preparing an organic-inorganic composite waterproof material for use in tunnel, mine, and underground engineering construction.

[0023] Example 1:

[0024] The method for preparing an organic-inorganic composite waterproof material of this embodiment includes the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 5 parts of water glass, 4 parts of calcium oxide, 6 parts of modified ultrafine fly ash, 5 parts of sodium bentonite, 35 parts of Portland cement, and 25 parts of water; Weigh the raw materials of component B: 5 parts of modified silica sol, 25 parts of acrylic polymer emulsion, 4 parts of silane coupling agent KH560; Step 2: evenly blend the raw materials of component A to form an improved body A, evenly mix the raw materials of component B to form an improved body B, and evenly mix the improved body A and the improved body B in a weight ratio of 1:1 to obtain an organic-inorganic composite waterproof material.

[0025] The acrylate polymer emulsion of this embodiment is prepared using the prior art of Example 3 of CN104151481B, an acrylate polymer emulsion and its preparation method.

[0026] The preparation method of the modified ultrafine fly ash of this embodiment is: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were stirred and reacted in a weight ratio of 3:5:7:2 at a stirring temperature of 58°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain a boron nitride pretreatment agent; S2: Preparation of sodium alginate-titanium oxide complex: S2a: Sodium alginate and a tris (hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of 2:5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:8 and stirring them uniformly to obtain a sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment in a weight ratio of 9:4, and the modification is completed to obtain a modified product based on combined regulation; S4: subjecting the ultrafine fly ash and the modified product based on the combined regulation to a secondary modification treatment in a weight ratio of 7:5. After the modification is completed, the modified ultrafine fly ash is filtered and dried to obtain the modified ultrafine fly ash.

[0027] In this embodiment, the ball milling speed for the primary modification treatment is 1000 r / min, and the ball milling is performed for 2 h; the ball milling speed for the secondary modification treatment is 500 r / min, and the ball milling is performed for 5 h.

[0028] The specific surface area of ​​the ultrafine fly ash of this embodiment is 2000 m² / kg, the water requirement ratio is less than 85%, and the 28d strength activity index is greater than 75%.

[0029] The preparation method of the modified silica sol agent of this embodiment is: S11: 3 parts of β-cyclodextrin, 2 parts of tetrabutyl titanate, 5 parts of acetone solvent, and 1 part of alkylamide betaine are uniformly mixed to obtain an additive; S12: fully mixing the nano-silica sol with an 8% urea solution having a mass fraction of 5 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Add 30% of the total amount of the nano-silica sol to the nano-silica sol, stir evenly, and obtain a nano-silica sol; continue to ball-mill the nano-silica sol and the modifier according to a weight ratio of 7:3, the ball-milling speed is 1000 r / min, the ball-milling is carried out for 2 hours, and after the ball-milling is completed, the mixture is filtered and dried to obtain a modified silica sol.

[0030] The modifier of this embodiment is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of 2:4:11.

[0031] The basalt fiber of this embodiment has a diameter of 12 μm and a length of 0.5 mm.

[0032] The organic-inorganic composite waterproof material is prepared by a method for preparing an organic-inorganic composite waterproof material in this embodiment.

[0033] The present embodiment provides a method for preparing an organic-inorganic composite waterproof material for use in tunnel, mine, and underground engineering construction.

[0034] Example 2: The method for preparing an organic-inorganic composite waterproof material of this embodiment includes the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 10 parts of water glass, 7 parts of calcium oxide, 10 parts of modified ultrafine fly ash, 8 parts of sodium bentonite, 40 parts of Portland cement, and 30 parts of water; Weigh the raw materials of component B: 9 parts of modified silica sol, 30 parts of acrylic polymer emulsion, 6 parts of silane coupling agent KH560; Step 2: evenly blend the raw materials of component A to form an improved body A, evenly mix the raw materials of component B to form an improved body B, and evenly mix the improved body A and the improved body B in a weight ratio of 1:1 to obtain an organic-inorganic composite waterproof material.

[0035] The acrylate polymer emulsion of this embodiment is prepared using the prior art of Example 3 of CN104151481B, an acrylate polymer emulsion and its preparation method.

[0036] The preparation method of the modified ultrafine fly ash of this embodiment is: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were stirred and reacted in a weight ratio of 3:5:7:2 at a stirring temperature of 62°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain a boron nitride pretreatment agent; S2: Preparation of sodium alginate-titanium oxide complex: S2a: Sodium alginate and a tris (hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of 3:5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:9 and stirring them uniformly to obtain a sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment in a weight ratio of 9:5, and the modification is completed to obtain a modified product based on joint regulation; S4: subjecting the ultrafine fly ash and the modified product based on the combined adjustment to a secondary modification treatment in a weight ratio of 11:5. After the modification is completed, the modified product is filtered and dried to obtain the modified ultrafine fly ash.

[0037] In this embodiment, the ball milling speed for the primary modification treatment is 1500 r / min, and the ball milling is performed for 2 h; the ball milling speed for the secondary modification treatment is 700 r / min, and the ball milling is performed for 5 h.

[0038] The specific surface area of ​​the ultrafine fly ash of this embodiment is 2400 m² / kg, the water requirement ratio is less than 85%, and the 28d strength activity index is greater than 75%.

[0039] The preparation method of the modified silica sol agent of this embodiment is: S11: 5 parts of β-cyclodextrin, 3 parts of tetrabutyl titanate, 8 parts of acetone solvent, and 2 parts of alkylamide betaine are uniformly blended to obtain an additive; S12: fully mixing the nano-silica sol with an 8% urea solution having a mass fraction of 8 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Add 40% of the total amount of the nano-silica sol to the nano-silica sol, stir evenly, and obtain a nano-silica sol; continue to ball-mill the nano-silica sol and the modifier according to a weight ratio of 7:5, the ball-milling speed is 1200 r / min, the ball-milling is carried out for 2 hours, and after the ball-milling is completed, the mixture is filtered and dried to obtain a modified silica sol.

[0040] The modifier of this embodiment is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of 3:5:13.

[0041] The basalt fiber of this embodiment has a diameter of 15 μm and a length of 1 mm.

[0042] The organic-inorganic composite waterproof material is prepared by a method for preparing an organic-inorganic composite waterproof material in this embodiment.

[0043] The present embodiment provides a method for preparing an organic-inorganic composite waterproof material for use in tunnel, mine, and underground engineering construction.

[0044] Example 3: The method for preparing an organic-inorganic composite waterproof material of this embodiment includes the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 7.5 parts of water glass, 5.5 parts of calcium oxide, 8 parts of modified ultrafine fly ash, 6.5 parts of sodium bentonite, 37.5 parts of Portland cement, and 27.5 parts of water; Weigh the raw materials of component B: 7 parts of modified silica sol, 27.5 parts of acrylic polymer emulsion, 5 parts of silane coupling agent KH560; Step 2: evenly blend the raw materials of component A to form an improved body A, evenly mix the raw materials of component B to form an improved body B, and evenly mix the improved body A and the improved body B in a weight ratio of 1:1 to obtain an organic-inorganic composite waterproof material.

[0045] The acrylate polymer emulsion of this embodiment is prepared using the prior art of Example 3 of CN104151481B, an acrylate polymer emulsion and its preparation method.

[0046] The preparation method of the modified ultrafine fly ash of this embodiment is: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were stirred and reacted in a weight ratio of 3:5:7:2 at 60°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain a boron nitride pretreatment agent; S2: Preparation of sodium alginate-titanium oxide complex: S2a: Sodium alginate and a tris (hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of 2.5:5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:8.5 and stirring them uniformly to obtain a sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment at a weight ratio of 9:4.5, and the modification is completed to obtain a modified product based on combined regulation; S4: subjecting the ultrafine fly ash and the modified product based on the combined regulation to a secondary modification treatment in a weight ratio of 9:5. After the modification is completed, the modified product is filtered and dried to obtain the modified ultrafine fly ash.

[0047] In this embodiment, the ball milling speed for the primary modification treatment is 1250 r / min, and the ball milling is performed for 2 h; the ball milling speed for the secondary modification treatment is 600 r / min, and the ball milling is performed for 5 h.

[0048] The specific surface area of ​​the ultrafine fly ash of this embodiment is 22400 m² / kg, the water requirement ratio is less than 85%, and the 28d strength activity index is greater than 75%.

[0049] The preparation method of the modified silica sol agent of this embodiment is: S11: 4 parts of β-cyclodextrin, 2.5 parts of tetrabutyl titanate, 6.5 parts of acetone solvent, and 1.5 parts of alkylamide betaine are uniformly blended to obtain an additive; S12: fully mixing the nano-silica sol with a urea solution having a mass fraction of 8% and a volume fraction that is 6.5 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Add 35% of the total amount of the nano-silica sol to the nano-silica sol, stir evenly, and obtain a nano-silica sol; continue to ball-mill the nano-silica sol and the modifier according to a weight ratio of 7:4, the ball-milling speed is 1100 r / min, the ball-milling is carried out for 2 hours, and after the ball-milling is completed, the mixture is filtered and dried to obtain a modified silica sol.

[0050] The modifier of this embodiment is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of 2.5:4.5:12.

[0051] The basalt fiber of this embodiment has a diameter of 13.5 μm and a length of 0.75 mm.

[0052] The organic-inorganic composite waterproof material is prepared by a method for preparing an organic-inorganic composite waterproof material in this embodiment.

[0053] The present embodiment provides a method for preparing an organic-inorganic composite waterproof material for use in tunnel, mine, and underground engineering construction.

[0054] Comparative Example 1: The difference from Example 3 is that no modified ultrafine fly ash is added.

[0055] Comparative Example 2: The difference from Example 3 is that no modifier based on combined regulation is added in the preparation of the modified ultrafine fly ash.

[0056] Comparative Example 3: The difference from Example 3 is that no boron nitride pretreatment agent is added in the preparation of the modified body based on combined regulation.

[0057] Comparative Example 4: The difference from Example 3 is that the boron nitride pretreatment agent is replaced by boron nitride.

[0058] Comparative Example 5: The difference from Example 3 is that no sodium alginate-titanium oxide complex is added in the preparation of the modified product based on the combined regulation.

[0059] Comparative Example 6: The difference from Example 3 is that no titanium oxide was added in the preparation of the sodium alginate-titanium oxide complex.

[0060] Comparative Example 7: The difference from Example 3 is that cerium oxide and silicon carbide are not added during the preparation of the titanium oxide body.

[0061] Comparative Example 8: The difference from Example 3 is that no modified silica sol agent is added.

[0062] Comparative Example 9: The difference from Example 3 is that no additives are added in the preparation of the modified silica sol.

[0063] Comparative Example 10: The difference from Example 3 is that β-cyclodextrin and tetrabutyl titanate are not added to the additives.

[0064] Comparative Example 11: The difference from Example 3 is that no modifier is added in the preparation of the modified silica sol.

[0065] Comparative Example 12: The difference from Example 3 is that basalt fiber and kaolin were not added in the preparation of the modifier.

[0066] Comparative Example 13: The difference from Example 3 is that no nanocellulose is added in the preparation of the modifier.

[0067] Conventional tests were conducted on the products of Examples 1 to 3 and Comparative Examples 1 to 13 for 28d compressive strength performance test, and the setting time and anti-permeability performance of the products were also tested. The performance test results are as follows:

[0068] It can be seen from Comparative Examples 1 to 13 and Examples 1 to 3 that; The product of Example 3 has excellent compressive strength (MPa), and at the same time, the product has excellent setting time and anti-seepage performance. The strength, anti-seepage and gel efficiency of the product can achieve coordinated improvements; From Comparative Examples 1 to 3 and Example 3, it can be seen that when either the modified ultrafine fly ash or the modified silica sol is not added, the performance of the product is significantly attenuated. When the two are coordinated, the performance of the product is significantly improved. No modifier based on combined regulation was added in the preparation of the modified ultrafine fly ash, no boron nitride pretreatment agent was added in the preparation of the modifier based on combined regulation, the boron nitride pretreatment agent was replaced by boron nitride, no sodium alginate-titanium oxide complex was added in the preparation of the sodium alginate-titanium oxide complex, no titanium oxide was added in the preparation of the titanium oxide complex, and no cerium oxide and silicon carbide were added in the preparation of the titanium oxide. The performance of the products showed a trend of deterioration to varying degrees. The modified ultrafine fly ash obtained by improving the ultrafine fly ash with the modifier based on combined regulation had the most significant performance effect, and the effects of other methods were not as obvious as those of the present invention. No additives were added in the preparation of the modified silica sol, no β-cyclodextrin and tetrabutyl titanate were added to the additives, no modifier was added in the preparation of the modified silica sol, no basalt fiber and kaolin were added in the preparation of the modifier, and no nanocellulose was added in the preparation of the modifier. The performance of the products all tended to deteriorate. Only the modified silica sol prepared by the method of the present invention had the most significant product performance effect. The effects of other methods were not as obvious as those of the present invention. The modifier obtained by the specific method of the present invention had the most significant product performance effect.

[0069] The products were tested for different degrees of acid and alkali stability (the products of Examples 1 to 3 and Comparative Examples 1 to 13 were poured into a 70 mm × 70 mm × 70 mm test mold and cured to form test pieces. The test pieces were immersed in an 8% by mass sulfuric acid solution for 24 hours, removed, and scrubbed until the surface was clean. The test pieces were then immersed in a 10% by mass sodium hydroxide solution for 24 hours, removed, and scrubbed until the surface was clean). The weight of the test pieces before and after immersion was measured (post-test weight - pre-test weight) / pre-test weight × 100%). The mass fractions of the sulfuric acid solution and the sodium hydroxide solution were changed to 12% and 15% respectively. The acid and alkali stability of the product was tested. The test results are as follows:

[0070] From Comparative Examples 1 to 13 and Example 3, it can be seen that the product has significant acid and alkali stability at different levels. Under high mass fraction acid and alkali conditions, the product still has excellent performance stability. At the same time, the performance of the modified ultrafine fly ash prepared by different methods and without the addition of modified silica sol all tends to deteriorate. Only the raw material formula and process of the present invention can produce the most significant product performance effect.

[0071] 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 embodied 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 illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0072] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing an organic-inorganic composite waterproof material, characterized in that: The following steps are involved: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 5-10 parts of water glass, 4-7 parts of calcium oxide, 6-10 parts of modified ultrafine fly ash, 5-8 parts of sodium bentonite, 35-40 parts of Portland cement, and 25-30 parts of water; Weigh the raw materials of component B: 5-9 parts of modified silica sol, 25-30 parts of acrylic polymer emulsion, 4-6 parts of silane coupling agent KH560; Step 2: uniformly blending the raw materials of component A to form an improved body A, uniformly mixing the raw materials of component B to form an improved body B, and uniformly mixing the improved body A and the improved body B in a weight ratio of 1:1 to obtain an organic-inorganic composite waterproof material; The preparation method of the modified ultrafine fly ash is: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were stirred and reacted in a weight ratio of 3:5:7:2 at a stirring temperature of 58-62°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain a boron nitride pretreatment agent; S2: Preparation of sodium alginate-titanium oxide complex: S2a: Sodium alginate and tris(hydroxymethyl)aminomethane) buffer solution with a pH value of 8.5 are uniformly mixed in a weight ratio of (2-3):5 to obtain a sodium alginate solution; S2b: Sintering titanium dioxide, cerium oxide, and silicon carbide in a weight ratio of 4:3:2 to obtain a titanium oxide body; blending the titanium oxide body and sodium alginate solution in a weight ratio of 5:(8-9) to obtain a sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment in a weight ratio of 9:(4-5), and the modification is completed to obtain a modified product based on combined regulation; S4: subjecting the ultrafine fly ash and the modified product based on the combined adjustment to a secondary modification treatment in a weight ratio of (7-11):5, filtering and drying after the modification is completed to obtain modified ultrafine fly ash; The preparation method of the modified silica sol is: S11: uniformly blending 3-5 parts of β-cyclodextrin, 2-3 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, and 1-2 parts of alkylamide betaine to obtain an additive; S12: fully mixing the nano-silica sol with an 8% urea solution having a mass fraction of 5-8 times the total amount of the nano-silica sol to obtain a nano-silica sol solution; Adding an additive in an amount of 30-40% of the total amount of the nano-silica sol solution to the nano-silica sol solution and stirring the mixture uniformly to obtain a nano-silica sol; further ball-milling the nano-silica sol and the modifier at a weight ratio of 7:(3-5) at a ball-milling speed of 1000-1200 r / min for 2 hours; after the ball-milling is completed, filtering and drying the mixture to obtain a modified silica sol; The modifier is prepared by uniformly blending nanocellulose, basalt fiber and kaolin in a weight ratio of (2-3): (4-5): (11-13).

2. The method for preparing an organic-inorganic composite waterproof material according to claim 1, characterized in that: The acrylate polymer emulsion is prepared by using the prior art of Example 3 of CN104151481B, an acrylate polymer emulsion and its preparation method.

3. The method for preparing an organic-inorganic composite waterproof material according to claim 2, characterized in that: The ball milling speed of the first-level modification treatment is 1000-1500 r / min, and the ball milling is 2 hours; the ball milling speed of the second-level modification treatment is 500-700 r / min, and the ball milling is 5 hours.

4. The method for preparing an organic-inorganic composite waterproof material according to claim 3, characterized in that: The specific surface area of ​​the ultrafine fly ash is 2000-2400 m² / kg, the water requirement ratio is less than 85%, and the 28d strength activity index is greater than 75%.

5. The method for preparing an organic-inorganic composite waterproof material according to claim 4, characterized in that: The basalt fiber has a diameter of 12-15 μm and a length of 0.5-1 mm.

6. An organic-inorganic composite waterproof material prepared by the method for preparing an organic-inorganic composite waterproof material according to any one of claims 1 to 5.

7. Use of the preparation method of the organic-inorganic composite waterproof material according to any one of claims 1 to 5 in the construction of tunnels, mines, and underground space projects.

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