Organic-inorganic composite waterproof material, preparation method and application

Abstract

The application relates to the technical field of waterproof materials, in particular to an organic-inorganic composite waterproof material, a preparation method and application, which comprises the following steps: weighing raw materials according to weight parts; first, weighing A-component raw materials: water glass 5-10 parts, calcium oxide 4-7 parts, modified superfine fly ash 6-10 parts, sodium-based bentonite 5-8 parts, silicate cement 35-40 parts and water 25-30 parts; the organic-inorganic composite waterproof material of the application is mixed and optimized by A-component raw materials and B-component raw materials, and the A-component raw materials are mixed and optimized by the water glass, the calcium oxide, the sodium-based bentonite and the silicate cement, and the modified superfine fly ash is further mixed and optimized; the product has excellent balance and coordination of coagulation rate, mechanical strength and waterproof and anti-permeability, and the product has remarkable acid and alkali stability.

Description

Technical Field

[0001] This invention relates to the field of waterproof materials technology, specifically to an organic-inorganic composite waterproof material, its preparation method, and its application. Background Technology

[0002] Waterproofing materials are suitable for sealing water inrushes in tunnels, mines, underground engineering projects, and other similar scenarios. The typical construction process involves the following steps: first, pumping out water and clearing silt; then, locating the water inrush cracks; sealing the cracks with a sealant; allowing it to solidify for one hour; then, drilling holes at 0.5-meter intervals along the rock fissures at the water inrush site; inserting injection needles; and simultaneously leaving observation tubes; using a pump to inject the prepared waterproofing material into the rock fissures until waterproofing material overflows from the observation tubes; the seal is achieved within 3-10 minutes. However, existing waterproofing materials, in order to increase the setting rate during construction, often reduce the product's mechanical strength and waterproofing / seepage-resistant properties, resulting in poor performance balance and coordination. This is a pain point and challenge of this invention. Furthermore, the product of this invention has poor stability against varying degrees of acid and alkali, limiting its application efficiency. Summary of the Invention

[0003] In view of the deficiencies of the prior art, the purpose of this invention is to provide an organic-inorganic composite waterproof material, its preparation method, and its application, 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:

[0005] This invention provides a method for preparing an organic-inorganic composite waterproof material, comprising the following steps:

[0006] Step 1: Weigh the raw materials according to their weight proportions:

[0007] First, weigh out component A of the raw material:

[0008] 5-10 parts water glass, 4-7 parts calcium oxide, 6-10 parts modified ultrafine fly ash, 5-8 parts sodium-based bentonite, 35-40 parts silicate cement, and 25-30 parts water.

[0009] Weigh out the raw materials for component B:

[0010] 5-9 parts modified silica sol, 25-30 parts acrylate polymer emulsion, and 4-6 parts silane coupling agent KH560;

[0011] Step 2: Mix component A raw materials evenly to form improved component A, mix component B raw materials evenly to form improved component B, and mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material.

[0012] The method for preparing the modified ultrafine fly ash is as follows:

[0013] S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2 with stirring at a temperature of 58-62℃ for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the boron nitride pretreatment agent.

[0014] S2: Preparation of sodium alginate-titanium oxide complex:

[0015] S2a: Sodium alginate and a tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5 are mixed evenly at a weight ratio of (2-3):5 to obtain sodium alginate solution;

[0016] S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:(8-9) to obtain sodium alginate-titanium oxide complex.

[0017] 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). After the modification is completed, the modified body based on joint regulation is obtained.

[0018] S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to two-stage modification treatment at a weight ratio of (7-11):5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash.

[0019] The modified silica sol is prepared by:

[0020] S11: Mix 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 evenly to obtain the additive.

[0021] S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea at 5-8 times the total amount of nano-silica sol to obtain a nano-silica sol solution;

[0022] Add 30-40% of the additive to the nano silica sol solution and stir evenly to obtain nano silica sol. Then, continue ball milling the nano silica sol and the modifier at a weight ratio of 7:(3-5) for 2 hours at a speed of 1000-1200 r / min. After ball milling, filter and dry to obtain modified silica sol.

[0023] The modifier is prepared by uniformly mixing nanocellulose, basalt fiber and kaolin in a weight ratio of (2-3):(4-5):(11-13).

[0024] Preferably, the acrylate polymer emulsion is prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic Polymer Emulsion and Its Preparation Method".

[0025] Preferably, the ball milling speed for the first-stage modification treatment is 1000-1500 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 500-700 r / min, and the ball milling time is 5 h.

[0026] Preferably, the specific surface area of ​​the ultrafine fly ash is 2000~2400 m². 2 / kg, water requirement ratio less than 85%, 28-day strength activity index greater than 75%.

[0027] Preferably, the basalt fibers have a diameter of 12-15 μm and a length of 0.5-1 mm.

[0028] This invention also provides a method for preparing an organic-inorganic composite waterproof material.

[0029] This invention also provides a method for preparing organic-inorganic composite waterproof materials and its application in tunnel, mine, and underground engineering construction.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] This invention relates to an organic-inorganic composite waterproof material, which uses component A and component B to blend and optimize the materials. Component A, consisting of water glass and calcium oxide, is blended with sodium bentonite and silicate cement, with modified ultrafine fly ash added for further optimization. Component B, consisting of modified silica sol, is blended with acrylate polymer emulsion and silane coupling agent KH560. Using the acrylate polymer emulsion as the matrix in component B, combined with silicate cement and other materials, a three-dimensional network structure is formed, enhancing the structural stability. The addition of silane coupling agent KH560 further strengthens the interfacial properties between the materials, and the addition of modified silica sol improves the blending of the modified ultrafine fly ash. The synergistic effect of the materials further optimizes the connection stability between the structural components. The product exhibits excellent balance and coordination in setting rate, mechanical strength, and waterproof and impermeable performance. Furthermore, this invention demonstrates significant resistance to varying degrees of acid and alkali stability.

[0032] The modified ultrafine fly ash is produced by secondary modification and optimization of ultrafine fly ash through a modifier based on joint regulation. The modifier based on joint regulation is prepared by modifying boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane to produce aminated boron nitride. At the same time, titanium dioxide, cerium oxide and silicon carbide are improved and optimized by sintering, and then blended with sodium alginate and tris(hydroxymethyl)aminomethane buffer solution with pH 8.5. Through further coordination of titanium dioxide body and sodium alginate solution, and further optimization by aminated boron nitride, the modified ultrafine fly ash based on joint regulation is produced by coordinating the combination of raw materials. This results in better distribution of ultrafine fly ash in the system, enhances the functional effect of modified ultrafine fly ash in the system, and optimizes the performance coordination and performance stability of the product.

[0033] The modified silica sol uses nano-silica sol, which is mixed and dispersed in urea solution, then improved and optimized by stirring with additives, and further improved by ball milling of the modifier. The additives, including β-cyclodextrin, tetrabutyl titanate, acetone solvent, and alkylamide betaine, are blended and optimized. Through the coordination of the raw materials, the interfacial connectivity of the modified silica sol in the system is enhanced. At the same time, the modifier is made of nano-cellulose, basalt fiber, and kaolin. The combination of nano-cellulose, basalt fiber, and kaolin, through the needle-like structure of basalt fiber combined with the layered kaolin and nano-cellulose dispersed in the system, further enhances the performance of the modified silica sol in the system and further optimizes the performance coordination and stability of the system. Detailed Implementation

[0034] 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.

[0035] This embodiment describes a method for preparing an organic-inorganic composite waterproof material, comprising the following steps:

[0036] Step 1: Weigh the raw materials according to their weight proportions:

[0037] First, weigh out the raw materials of component A: 5-10 parts water glass, 4-7 parts calcium oxide, 6-10 parts modified ultrafine fly ash, 5-8 parts sodium bentonite, 35-40 parts silicate cement, and 25-30 parts water.

[0038] Weigh out the raw materials for component B:

[0039] 5-9 parts modified silica sol, 25-30 parts acrylate polymer emulsion, and 4-6 parts silane coupling agent KH560;

[0040] Step 2: Mix component A raw materials evenly to form improved component A, and mix component B raw materials evenly to form improved component B. Mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material.

[0041] The acrylate polymer emulsion in this embodiment is prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic Polymer Emulsion and Its Preparation Method".

[0042] The method for preparing the modified ultrafine fly ash in this embodiment is as follows:

[0043] S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2 with stirring at a temperature of 58-62℃ for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the boron nitride pretreatment agent.

[0044] S2: Preparation of sodium alginate-titanium oxide complex:

[0045] S2a: Sodium alginate and a tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5 are mixed evenly at a weight ratio of (2-3):5 to obtain sodium alginate solution;

[0046] S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:(8-9) to obtain sodium alginate-titanium oxide complex;

[0047] S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex were subjected to primary modification treatment at a weight ratio of 9:(4-5). After the modification was completed, the modified body based on joint regulation was obtained.

[0048] S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to secondary modification at a weight ratio of (7-11):5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash.

[0049] In this embodiment, the ball milling speed for the first-stage modification treatment is 1000-1500 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 500-700 r / min, and the ball milling time is 5 h.

[0050] The ultrafine fly ash in this embodiment has a specific surface area of ​​2000~2400m² / kg, a water requirement ratio of less than 85%, and a 28-day strength activity index of greater than 75%.

[0051] The preparation method of the modified silica sol in this embodiment is as follows:

[0052] S11: Mix 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 evenly to obtain the additive.

[0053] S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea at 5-8 times the total amount of nano-silica sol to obtain a nano-silica sol solution;

[0054] Add 30-40% of the additive to the nano silica sol solution and stir evenly to obtain nano silica sol. Then, continue ball milling the nano silica sol and the modifier at a weight ratio of 7:(3-5) for 2 hours at a speed of 1000-1200 r / min. After ball milling, filter and dry to obtain modified silica sol.

[0055] The modifier in this embodiment is prepared by uniformly mixing nanocellulose, basalt fiber and kaolin in a weight ratio of (2-3):(4-5):(11-13).

[0056] The basalt fibers in this embodiment have a diameter of 12-15 μm and a length of 0.5-1 mm.

[0057] This embodiment describes a method for preparing an organic-inorganic composite waterproof material.

[0058] This embodiment describes the application of a method for preparing an organic-inorganic composite waterproof material in tunnel, mine, and underground engineering construction.

[0059] Example 1:

[0060] This embodiment describes a method for preparing an organic-inorganic composite waterproof material, comprising the following steps:

[0061] Step 1: Weigh the raw materials according to their weight proportions:

[0062] First, weigh out component A of the raw material:

[0063] 5 parts water glass, 4 parts calcium oxide, 6 parts modified ultrafine fly ash, 5 parts sodium bentonite, 35 parts silicate cement, and 25 parts water;

[0064] Weigh out the raw materials for component B:

[0065] 5 parts modified silica sol, 25 parts acrylate polymer emulsion, and 4 parts silane coupling agent KH560;

[0066] Step 2: Mix component A raw materials evenly to form improved component A, and mix component B raw materials evenly to form improved component B. Mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material.

[0067] The acrylate polymer emulsion in this embodiment is prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic Polymer Emulsion and Its Preparation Method".

[0068] The method for preparing the modified ultrafine fly ash in this embodiment is as follows:

[0069] S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2. The reaction was carried out at 58°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the boron nitride pretreatment agent.

[0070] S2: Preparation of sodium alginate-titanium oxide complex:

[0071] S2a: Sodium alginate and a tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5 are mixed evenly at a weight ratio of 2:5 to obtain sodium alginate solution;

[0072] S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:8 to obtain sodium alginate-titanium dioxide complex;

[0073] S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex were subjected to primary modification treatment at a weight ratio of 9:4. After the modification was completed, the modified body based on joint regulation was obtained.

[0074] S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to two-stage modification at a weight ratio of 7:5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash.

[0075] In this embodiment, the ball milling speed for the first-stage modification treatment is 1000 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 500 r / min, and the ball milling time is 5 h.

[0076] The ultrafine fly ash in this embodiment has a specific surface area of ​​2000 m² / kg, a water requirement of less than 85%, and a 28-day strength activity index of greater than 75%.

[0077] The preparation method of the modified silica sol in this embodiment is as follows:

[0078] S11: Mix 3 parts of β-cyclodextrin, 2 parts of tetrabutyl titanate, 5 parts of acetone solvent, and 1 part of alkylamide betaine evenly to obtain the additive;

[0079] S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea at 5 times the total amount of nano-silica sol to obtain a nano-silica sol solution;

[0080] Add 30% of the additive to the nano silica sol solution and stir until homogeneous to obtain nano silica sol. Then, continue ball milling the nano silica sol and modifier at a weight ratio of 7:3 at a speed of 1000 r / min for 2 hours. After ball milling, filter and dry to obtain modified silica sol.

[0081] The modifier in this embodiment is prepared by uniformly mixing nanocellulose, basalt fiber and kaolin in a weight ratio of 2:4:11.

[0082] The basalt fiber in this embodiment has a diameter of 12μm and a length of 0.5mm.

[0083] This embodiment describes a method for preparing an organic-inorganic composite waterproof material.

[0084] This embodiment describes the application of a method for preparing an organic-inorganic composite waterproof material in tunnel, mine, and underground engineering construction.

[0085] Example 2:

[0086] This embodiment describes a method for preparing an organic-inorganic composite waterproof material, comprising the following steps:

[0087] Step 1: Weigh the raw materials according to their weight proportions:

[0088] First, weigh out component A of the raw material:

[0089] 10 parts water glass, 7 parts calcium oxide, 10 parts modified ultrafine fly ash, 8 parts sodium bentonite, 40 parts silicate cement, and 30 parts water;

[0090] Weigh out the raw materials for component B:

[0091] 9 parts modified silica sol, 30 parts acrylate polymer emulsion, and 6 parts silane coupling agent KH560;

[0092] Step 2: Mix component A raw materials evenly to form improved component A, and mix component B raw materials evenly to form improved component B. Mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material.

[0093] The acrylate polymer emulsion in this embodiment is prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic Polymer Emulsion and Its Preparation Method".

[0094] The method for preparing the modified ultrafine fly ash in this embodiment is as follows:

[0095] S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2 with stirring at 62°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the boron nitride pretreatment agent.

[0096] S2: Preparation of sodium alginate-titanium oxide complex:

[0097] S2a: Sodium alginate and a tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5 are mixed evenly at a weight ratio of 3:5 to obtain sodium alginate solution;

[0098] S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:9 to obtain sodium alginate-titanium dioxide complex;

[0099] S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex are subjected to primary modification treatment at a weight ratio of 9:5. After the modification is completed, the modified body based on joint regulation is obtained.

[0100] S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to two-stage modification at a weight ratio of 11:5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash.

[0101] In this embodiment, the ball milling speed for the first-stage modification treatment is 1500 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 700 r / min, and the ball milling time is 5 h.

[0102] The ultrafine fly ash in this embodiment has a specific surface area of ​​2400 m² / kg, a water requirement of less than 85%, and a 28-day strength activity index of greater than 75%.

[0103] The preparation method of the modified silica sol in this embodiment is as follows:

[0104] S11: Mix 5 parts of β-cyclodextrin, 3 parts of tetrabutyl titanate, 8 parts of acetone solvent, and 2 parts of alkylamide betaine evenly to obtain the additive;

[0105] S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea (8 times the total amount of nano-silica sol) to obtain a nano-silica sol solution.

[0106] Add 40% of the additive to the nano silica sol solution and stir until homogeneous to obtain nano silica sol. Then, continue ball milling the nano silica sol and modifier at a weight ratio of 7:5 at a speed of 1200 r / min for 2 hours. After ball milling, filter and dry to obtain modified silica sol.

[0107] The modifier in this embodiment is prepared by uniformly mixing nanocellulose, basalt fiber and kaolin in a weight ratio of 3:5:13.

[0108] The basalt fiber in this embodiment has a diameter of 15 μm and a length of 1 mm.

[0109] This embodiment describes a method for preparing an organic-inorganic composite waterproof material.

[0110] This embodiment describes the application of a method for preparing an organic-inorganic composite waterproof material in tunnel, mine, and underground engineering construction.

[0111] Example 3:

[0112] This embodiment describes a method for preparing an organic-inorganic composite waterproof material, comprising the following steps:

[0113] Step 1: Weigh the raw materials according to their weight proportions:

[0114] First, weigh out component A of the raw material:

[0115] 7.5 parts water glass, 5.5 parts calcium oxide, 8 parts modified ultrafine fly ash, 6.5 parts sodium bentonite, 37.5 parts silicate cement, and 27.5 parts water;

[0116] Weigh out the raw materials for component B:

[0117] 7 parts modified silica sol, 27.5 parts acrylate polymer emulsion, and 5 parts silane coupling agent KH560;

[0118] Step 2: Mix component A raw materials evenly to form improved component A, and mix component B raw materials evenly to form improved component B. Mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material.

[0119] The acrylate polymer emulsion in this embodiment is prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic Polymer Emulsion and Its Preparation Method".

[0120] The method for preparing the modified ultrafine fly ash in this embodiment is as follows:

[0121] S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2. The reaction was carried out at 60°C for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the boron nitride pretreatment agent.

[0122] S2: Preparation of sodium alginate-titanium oxide complex:

[0123] S2a: Sodium alginate and a tris(hydroxymethyl)aminomethane buffer solution with a pH of 8.5 are mixed evenly at a weight ratio of 2.5:5 to obtain sodium alginate solution;

[0124] S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:8.5 to obtain sodium alginate-titanium dioxide complex;

[0125] S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex were subjected to primary modification treatment at a weight ratio of 9:4.5. After the modification was completed, the modified body based on joint regulation was obtained.

[0126] S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to two-stage modification at a weight ratio of 9:5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash.

[0127] In this embodiment, the ball milling speed for the first-stage modification treatment is 1250 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 600 r / min, and the ball milling time is 5 h.

[0128] The ultrafine fly ash in this embodiment has a specific surface area of ​​22,400 m² / kg, a water requirement of less than 85%, and a 28-day strength activity index of greater than 75%.

[0129] The preparation method of the modified silica sol in this embodiment is as follows:

[0130] S11: Mix 4 parts β-cyclodextrin, 2.5 parts tetrabutyl titanate, 6.5 parts acetone solvent, and 1.5 parts alkylamide betaine evenly to obtain the additive;

[0131] S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea at 6.5 times the total amount of nano-silica sol to obtain a nano-silica sol solution;

[0132] Add 35% of the additive to the nano silica sol solution and stir until homogeneous to obtain nano silica sol. Then, continue ball milling the nano silica sol and modifier at a weight ratio of 7:4 at a speed of 1100 r / min for 2 hours. After ball milling, filter and dry to obtain modified silica sol.

[0133] The modifier in this embodiment is prepared by uniformly mixing nanocellulose, basalt fiber and kaolin in a weight ratio of 2.5:4.5:12.

[0134] The basalt fiber in this embodiment has a diameter of 13.5 μm and a length of 0.75 mm.

[0135] This embodiment describes a method for preparing an organic-inorganic composite waterproof material.

[0136] This embodiment describes the application of a method for preparing an organic-inorganic composite waterproof material in tunnel, mine, and underground engineering construction.

[0137] Comparative Example 1:

[0138] Unlike Example 3, no modified ultrafine fly ash was added.

[0139] Comparative Example 2:

[0140] Unlike Example 3, no modifier based on joint regulation was added in the preparation of the modified ultrafine fly ash.

[0141] Comparative Example 3:

[0142] Unlike Example 3, no boron nitride pretreatment agent was added in the preparation of the modified body based on joint regulation.

[0143] Comparative Example 4:

[0144] Unlike Example 3, boron nitride was used instead of boron nitride as the pretreatment agent.

[0145] Comparative Example 5:

[0146] Unlike Example 3, the sodium alginate-titanium oxide complex was not added in the preparation of the modified body based on joint regulation.

[0147] Comparative Example 6:

[0148] Unlike Example 3, no titanium dioxide was added in the preparation of the sodium alginate-titanium oxide conjugate.

[0149] Comparative Example 7:

[0150] Unlike Example 3, cerium oxide and silicon carbide were not added during the preparation of the titanium oxide body.

[0151] Comparative Example 8:

[0152] Unlike Example 3, no modified silica sol was added.

[0153] Comparative Example 9:

[0154] Unlike Example 3, no additives were added during the preparation of the modified silica sol.

[0155] Comparative Example 10:

[0156] Unlike Example 3, β-cyclodextrin and tetrabutyl titanate were not added to the additives.

[0157] Comparative Example 11:

[0158] Unlike Example 3, no modifier was added during the preparation of the modified silica sol.

[0159] Comparative Example 12:

[0160] Unlike Example 3, basalt fiber and kaolin were not added during the preparation of the modifier.

[0161] Comparative Example 13:

[0162] Unlike Example 3, nanocellulose was not added during the preparation of the modifier.

[0163] Routine testing was conducted on the products of Examples 1-3 and Comparative Examples 1-13, with a 28-day compressive strength test. The setting time and impermeability of the products were also tested. The performance test results are as follows.

[0164]

[0165] As can be seen from Comparative Examples 1-13 and Examples 1-3;

[0166] The product in Example 3 has excellent compressive strength (MPa), as well as excellent setting time and impermeability. The product's strength, impermeability and gelation efficiency can be improved in a coordinated manner.

[0167] As can be seen from Comparative Examples 1-3 and Example 3, the performance of the product was significantly reduced when neither modified ultrafine fly ash nor modified silica sol was added. The performance of the product was significantly improved when both were used in combination.

[0168] In the preparation of modified ultrafine fly ash, no modifier based on joint regulation was added; in the preparation of the modifier based on joint regulation, no boron nitride pretreatment agent was added; boron nitride was used instead of boron nitride pretreatment agent; no sodium alginate-titanium oxide complex was added in the preparation of the modifier based on joint regulation; no titanium oxide was added in the preparation of the sodium alginate-titanium oxide complex; and no cerium oxide and silicon carbide were added in the preparation of the titanium oxide. The performance of the products all showed a certain degree of deterioration. The modifier based on joint regulation, prepared by combining the sodium alginate-titanium oxide complex obtained by the specific method of this invention with the boron nitride pretreatment agent, showed the most significant performance improvement in the modified ultrafine fly ash obtained by improving ultrafine fly ash with the modifier based on joint regulation. Other methods were not as effective as those of this invention.

[0169] In the preparation of modified silica sol, no additives were added, and neither β-cyclodextrin nor tetrabutyl titanate were added among the additives. Furthermore, no modifiers were added during the preparation of the modified silica sol, and neither basalt fiber nor kaolin were added during the preparation of the modifiers. Additionally, no nanocellulose was added. The performance of all these products tended to deteriorate. Only the modified silica sol prepared using the method of this invention exhibited the most significant performance improvement. Other methods were not as effective as those of this invention, and the modifier obtained using the specific method of this invention also showed the most significant performance improvement.

[0170] Test the acid and alkali stability of the products to different degrees (pour the products of Examples 1-3 and Comparative Examples 1-13 into a 70mm×70mm×70mm mold to solidify and form a specimen. Immerse the specimen in an 8% sulfuric acid solution for 24 hours. Remove the specimen and wipe it clean. Then immerse the specimen in a 10% sodium hydroxide solution for 24 hours. Remove the specimen and wipe it clean. Measure the weight of the specimen before and after immersion. (The weight of the specimen after the test - the weight of the specimen before the test) / the weight of the specimen before the test × 100%;

[0171] The mass fractions of sulfuric acid solution and sodium hydroxide solution were adjusted to a mass fraction of 12% for sulfuric acid solution and 15% for sodium hydroxide solution. The acid and alkali resistance of the product was then tested, and the test results are as follows.

[0172]

[0173] As can be seen from Comparative Examples 1-13 and Example 3, the product has significant stability against different levels of acid and alkali. Under conditions of high mass fraction of acid and alkali, the product still has excellent performance stability.

[0174] Meanwhile, the performance of modified ultrafine fly ash prepared by different methods and without the addition of modified silica sol all tend to deteriorate. Only the product prepared using the raw material formula and process of this invention has the most significant performance effect.

[0175] 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.

[0176] 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. A method for preparing an organic-inorganic composite waterproof material, characterized in that, Includes the following steps: Step 1: Weigh the raw materials according to their weight proportions: First, weigh out component A of the raw materials: 5-10 parts water glass, 4-7 parts calcium oxide, 6-10 parts modified ultrafine fly ash, 5-8 parts sodium-based bentonite, 35-40 parts silicate cement, and 25-30 parts water. Weigh out the raw materials for component B: 5-9 parts modified silica sol, 25-30 parts acrylate polymer emulsion, and 4-6 parts silane coupling agent KH560; Step 2: Mix component A raw materials evenly to form improved component A, mix component B raw materials evenly to form improved component B, and mix improved component A and improved component B in a weight ratio of 1:1 to obtain organic-inorganic composite waterproof material. The method for preparing the modified ultrafine fly ash is as follows: S1: Boron nitride, anhydrous ethanol, water and 3-aminopropyltriethoxysilane were reacted in a weight ratio of 3:5:7:2 with stirring at a temperature of 58-62℃ for 5 hours. After stirring, the mixture was filtered, washed and dried to obtain the 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 of 8.5 are mixed evenly at a weight ratio of (2-3):5 to obtain sodium alginate solution; S2b: Titanium dioxide, cerium oxide and silicon carbide are sintered in a weight ratio of 4:3:2 to obtain titanium dioxide body; titanium dioxide body and sodium alginate solution are mixed and stirred evenly in a weight ratio of 5:(8-9) to obtain sodium alginate-titanium oxide complex; S3: Boron nitride pretreatment agent and sodium alginate-titanium oxide complex were subjected to primary modification treatment at a weight ratio of 9:(4-5). After the modification was completed, the modified body based on joint regulation was obtained. S4: The ultrafine fly ash and the modified body based on joint regulation are subjected to secondary modification at a weight ratio of (7-11):

5. After the modification is completed, the mixture is filtered and dried to obtain the modified ultrafine fly ash. The modified silica sol is prepared by: S11: Mix 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 evenly to obtain the additive. S12: Mix the nano-silica sol thoroughly with a urea solution containing 8% urea at 5-8 times the total amount of nano-silica sol to obtain a nano-silica sol solution; Add 30-40% of the additive to the nano silica sol solution and stir evenly to obtain nano silica sol. Then, continue ball milling the nano silica sol and the modifier at a weight ratio of 7:(3-5) for 2 hours at a speed of 1000-1200 r / min. After ball milling, filter and dry to obtain the modified silica sol. The modifier is prepared by uniformly mixing 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 was prepared using the prior art described in Example 3 of CN104151481B, "An Acrylic 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 for the first-stage modification treatment is 1000-1500 r / min, and the ball milling time is 2 h; the ball milling speed for the second-stage modification treatment is 500-700 r / min, and the ball milling time is 5 h.

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

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

6. The organic-inorganic composite waterproof material prepared by the method for preparing an organic-inorganic composite waterproof material as described in any one of claims 1 to 5.

7. The application of the organic-inorganic composite waterproof material prepared by the method of preparing the organic-inorganic composite waterproof material according to any one of claims 1 to 5 in the construction of tunnels, mines, and underground space engineering projects.

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