Acid response dynamic bonding high-strength earth and rockfill dam plugging material and preparation method thereof

Abstract

The invention discloses a preparation method of an acid response dynamic bonding high-strength earth and rockfill dam leaking stoppage material. The preparation method specifically comprises the following steps: preparing an acid response adhesive MPDA from 3-(methacrylamido phenyl) boric acid, MAPBA and dopamine; preparing a solid phase of the plugging material by utilizing MPDA, PMMA and benzoyl peroxide; preparing a liquid phase of the leakage material by using DHPT, BHT and MMA; and mixing and stirring the solid phase and the liquid phase. According to the high-strength earth and rockfill dam leaking stoppage material, PMMA serves as a base body, MPDA serves as an acid response adhesive, cracks are effectively plugged, dynamic improvement of the bonding performance is achieved in the environment with gradually-enhanced acidity, and excellent mechanical performance is provided. Meanwhile, by combining the synergistic enhancement of excellent compressive strength and water absorption expansion stress of PMMA, a firm support is formed for a surrounding earth and rockfill dam, the dynamic bonding strength and the interface stability in an acid environment are enhanced, and high-strength leaking stoppage in the acid environment is realized.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of earth-rock dam seepage plugging and repairing materials, and particularly relates to a preparation method of high-strength earth-rock dam plugging material with acid-responsive dynamic adhesion, and also relates to the high-strength earth-rock dam plugging material. BACKGROUND

[0002] At present, the plugging materials commonly used in the field of earth-rock dam seepage repair mainly include two systems: organic and inorganic. The organic plugging materials include polyurethane, epoxy resin and acrylate resin, etc., and the inorganic plugging materials mainly include silicate cement-based materials and aluminate cement-based materials. In the inorganic plugging materials, the silicate cement-based plugging material has a compressive strength of 40-60 MPa after solidification, and can provide stable mechanical support, but it has the disadvantages of slow hardening and setting (>6 h), long solidification time and low adhesion strength on a wet base surface (<0.5 MPa). The aluminate cement-based plugging material can be solidified and formed in a short time (initial setting <15 min), and has a wet base surface bonding strength of 1.5-2.0 MPa, which is suitable for emergency rescue, but its late strength declines by 30%-50%. The above inorganic plugging materials have poor compatibility with earth and rock, and are easy to cause adhesion interface failure and falling off due to hydration and washing when encountering water, cannot adapt to dam deformation, are easy to form new seepage channels, have insufficient long-term plugging effect, and have safety hazards. In the organic plugging materials, polyurethane can react with water to foam and quickly stop water in a few minutes, and can also adapt to small deformation of cracks, but has poor aging resistance and is easy to degrade in ultraviolet light, high temperature or chemical medium, resulting in a decrease in mechanical properties and a decrease in sealing performance. The adhesion strength of epoxy resin to various substrates such as earth and rock can reach 5-8 MPa, but has poor durability, a service life of only 5-10 years and is easy to hydrolyze, and has low compressive strength (30-50 MPa). Acrylate has a fast solidification speed, and can form a tough adhesive film at room temperature in 10-20 minutes, and has a tensile strength of 30-70 MPa, but is easy to have performance decline in use and difficult to maintain high strength and good swelling properties for a long time. In the existing modification research on organic plugging materials, the structure of polyurethane molecules is adjusted to enhance the tensile strength and thermal stability and reduce the negative influence of hydrophilic groups. Liquid rubber is used to toughen epoxy resin, and dynamic covalent chemistry is designed to significantly improve the brittleness and give repairability. The polymerization process of acrylate is optimized to enhance the toughness of adhesive film and alleviate the strength decline. Although the existing research improves the basic properties of organic plugging materials through mechanical enhancement and toughening modification, the plugging materials still have problems of easy hydrolysis and swelling in actual application environment, which further leads to interface bonding failure, frequent material falling off and difficulty in achieving long-term plugging.

[0003] A Chinese patent (application number: 202211117020.8, filing date: September 14, 2022, publication number: CN115340342A) discloses a dual-liquid reactive grouting and plugging material, consisting of liquid A and liquid B, for grouting concrete cracks. Liquid A is a silica-modified active polymer, and liquid B is a super-fast-setting resin adhesive. However, the silicon-oxygen bonds of the silica-modified polymer are easily broken, resulting in poor structural stability. Relying solely on physical filling and rapid-setting reactions can lead to interface cracking, weak chemical bonding, and insufficient durability.

[0004] A Chinese patent application (Application Number: 202310062021.5, Application Date: January 17, 2023, Publication Number: CN116285311A) discloses a novel polyurethane water-plugging grouting material and its preparation method. The material, composed of isocyanate, polymer polyol, epoxy resin, modifier, graphene oxide, catalyst, curing agent, and foam stabilizer, features adjustable reaction rate, low viscosity, high solid body strength, and low cost. However, the polyurethane's urethane groups are susceptible to hydrolysis, leading to degradation of mechanical properties. The material also suffers from poor dispersibility and poor penetration in complex media, reduced adhesion to substrates, and insufficient structural longevity, preventing it from forming a long-lasting, stable plugging structure. A Chinese patent application (application number: 202510120341.0, filing date: January 25, 2025, publication number: CN119822745A) discloses a cement-based leak-proof material for tunnel maintenance and its preparation method. The material comprises the following raw materials: cement, fine aggregate, admixtures, expansive agent, accelerator, water reducer, and viscosity enhancer; the accelerator comprises a nucleating agent and aluminum sulfate. This cement-based leak-proof material has a short setting time, high bond strength, and excellent micro-expansion and resistance to dynamic water pressure. However, its cement hydration products react with the medium, causing structural disintegration. The material relies on physical filling, resulting in weak interfacial chemical bonds that are prone to detachment. It also lacks environmental response regulation, uncontrollable setting time, and low leak-proofing efficiency, making it ineffective in ensuring the structural safety of earth-rockfill dams.

[0005] A Chinese patent application (Application Number: 202010172881.0, Application Date: March 12, 2020, Publication Number: CN111620615A) discloses an environmentally friendly acrylic ester leak-proof reinforcement grouting material, its preparation method, and application. The grouting material comprises a liquid material A containing water, acrylic ester, a crosslinker, and an accelerator, and a powder material B containing an initiator, silica powder, cement, a water reducer, and a hydrophobic agent. The grouting material exhibits high strength and durability, and its low viscosity allows it to penetrate fine cracks and repair and reinforce loose layers and porous honeycomb structures. However, the acrylic ester group is susceptible to hydrolysis, which degrades its bonding and mechanical properties. Under water, it primarily relies on physical adsorption, resulting in weak chemical bonding. It is easily detached due to erosion or deformation, making it ineffective for long-term waterproofing.

[0006] The plugging material in the above technology solves the plugging problem of earth-rock dams in normal water environment, but has the disadvantages of poor long-term stability and mechanical property decay in acidic environment, and more importantly, the bonding interface between the plugging material and the base material is easily damaged under the erosion of acidic medium, causing the plugging layer to fall off. The existing research on acid-resistant modification of inorganic plugging materials mainly adds acid-resistant aggregates (such as quartz sand) and selects acid-resistant cementitious materials (such as phosphate cement) to enhance the acid erosion resistance and mechanical strength, and the organic type optimizes the molecular structure (such as introducing acid-resistant groups into epoxy resin) to improve the chemical bond stability and acid resistance in acidic environment; although the durability of the plugging material in the acidic environment is improved, it cannot achieve firm bonding in the acidic environment. Therefore, it is an urgent problem to develop a new type of plugging material with acid-resistant matrix as the main body to achieve dynamic improvement of bonding performance in an environment with gradually increasing acidity and provide excellent mechanical properties. SUMMARY

[0007] The purpose of the present application is to provide a preparation method of acid-responsive dynamic bonding high-strength earth-rock dam plugging material, which solves the problems of interface bonding failure and insufficient mechanical properties of existing plugging materials in acidic medium.

[0008] Another purpose of the present application is to provide an acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0009] The technical scheme adopted by the present application is a preparation method of acid-responsive dynamic bonding high-strength earth-rock dam plugging material, which is implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl) boronic acid; Step 2, preparing an acid-responsive adhesive MPDA using 3-(methacrylamidophenyl) boronic acid, MAPBA and dopamine; Step 3, preparing a solid phase of high-strength earth-rock dam plugging material using the acid-responsive adhesive MPDA, PMMA and benzoyl peroxide; Step 4, preparing a liquid phase of high-strength earth-rock dam plugging material using DHPT, BHT and MMA; Step 5, mixing and stirring the solid phase and the liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0010] The present application also has the following characteristics: In step 1, specifically: 3-Aminophenylboronic acid and sodium bicarbonate are dissolved in a tetrahydrofuran solution to obtain a mixed solution, and then the mixed solution is stirred in an ice bath at 0°C-5°C for 10-60 minutes, followed by slow dropwise addition of methacryloyl chloride. After the addition is complete, the mixture is stirred for 2-12 hours. After the addition is complete, ethyl acetate is used as the organic extraction phase for extraction, and the organic phase MAPBA is collected and dried to obtain 3-(methacrylamidophenyl)boric acid.

[0011] The mass ratio of 3-aminophenylboronic acid to sodium bicarbonate is 5-8:5-10; the tetrahydrofuran solution is prepared by mixing water and tetrahydrofuran; and the volume ratio of methacryloyl chloride to the mixed solution is 1-5:1.5-7.

[0012] In step 2, specifically: Step 2.1, dissolving N-vinylacetamide, 3-(methacrylamidophenyl)boronic acid, and dopamine in glycerol and stirring for 12-24 hours to obtain a precursor mixture; The mass ratio of N-vinylacetamide, 3-(methacrylamidophenyl)boric acid, dopamine, and glycerol is 10-15:0.6-1.0:3-6:11.34-13.56; Step 2.2, dissolve MBA in deionized water and stir for 1-6 hours to form a crosslinker solution; Step 2.3, dissolving ammonium persulfate in deionized water to form an initiator solution; Step 2.4, add the crosslinker solution and the initiator solution to the precursor mixture in sequence, stir for 10-60 minutes, and then heat the mixture in a water bath under nitrogen at a temperature of 60-80°C for 6-12 hours. Filter the mixture, wash it with deionized water 2-5 times, and freeze-dry it at a temperature of -20 to -5°C, a vacuum degree of 10 to 40 Pa, and a freeze-drying time of 12 hours to 36 hours to obtain the acidic responsive adhesive MPDA.

[0013] In step 3, specifically: The following substances were weighed by mass percentage: 8%-15% acid-responsive adhesive MPDA, 83%-86% PMMA, and 2%-6% benzoyl peroxide (BPO), where the total mass percentage of the above components is 100%; MPDA and benzoyl peroxide were added to PMMA, which was then placed in a ball mill and milled on a ball mill for 4-10 hours to obtain a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0014] In step 4, specifically: Weigh the following substances by mass percentage: 0.3%-0.6% DHPT, 0.2%-0.4% BHT, 99%-99.5% MMA, the total mass percentage of the above components is 100%; DHPT and BHT are added into MMA and stirred for 20-60 minutes to mix evenly to obtain a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0015] In step 5, the solid-liquid ratio of the solid phase to the liquid phase is 2.0 g to 2.5 g: 1.0 mL to 1.5 mL.

[0016] Another technical solution adopted by the present invention is a high-strength earth-rock dam plugging material prepared by a method for preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0017] The beneficial effects of the present invention are: (1) MPDA acid-responsive adhesive uses 3-(methacrylamidophenyl)boronic acid (MAPBA) as the pH-responsive unit. In an acidic environment (pH range of 3-6.5), the adhesive reacts with H + As the concentration of DA increases, the acidity increases. The concentration of borate ester bonds formed through dynamic covalent interactions between the phenylboronic acid groups in MAPBA and the catechol groups in DA increases, forming numerous hydrogen bonds with polar groups such as hydroxyl and carboxyl groups on the soil and rock surfaces. DA's long hydrophobic chains repel the hydration layer, promoting a close fit between the adhesive and the substrate. The catechol groups, through hydrogen bonding, hydrophobic association, and π-π interactions, enhance adhesion to substrates such as soil and rock, achieving a dynamic improvement in bonding performance in an environment with gradually increasing acidity.

[0018] (2) As the acidity of the environment increases, the concentration of borate bonds in the MPDA in the acid-responsive dynamic bonding high-strength earth-rock dam plugging material increases, forming a large number of hydrogen bonds with polar groups such as hydroxyl and carboxyl groups on the surface of the earth and rock. Dopamine regulates expansion, and MAPBA strengthens the network. The expansion stress generated by MPDA's water absorption and expansion in an acidic environment, combined with the excellent compressive strength of PMMA, enhances its own mechanical properties, forming a solid support for the earth-rock dam and providing excellent mechanical properties in an environment with gradually increasing acidity to achieve high-strength plugging. DETAILED DESCRIPTION

[0019] The present invention is described in detail below with reference to specific embodiments.

[0020] The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); 3-aminophenylboronic acid (C6H8BNO2) and sodium bicarbonate (NaHCO3) are dissolved in a tetrahydrofuran solution to obtain a mixed solution, and then the mixed solution is stirred in an ice bath at a temperature of 0°C-5°C for 10-60 minutes. Methacryloyl chloride is then slowly added dropwise. After the addition is complete, the mixture is stirred at room temperature for 2-12 hours. After the reaction is completed, ethyl acetate is used as an organic extract phase for extraction, and the organic phase MAPBA is collected and dried in an oven to obtain 3-(methacrylamidophenyl)boronic acid (MAPBA); The mass ratio of 3-aminophenylboronic acid (C6H8BNO2) and sodium bicarbonate is 5-8:5-10; Tetrahydrofuran solution is a mixture of water and tetrahydrofuran (THF); The drying temperature is 50-80℃ and the drying time is 3-8h; The volume ratio of methacryloyl chloride to the mixed solution is 1-5:1.5-7; Step 2, preparing the acid-responsive adhesive MPDA, specifically: Step 2.1: Dissolve N-vinylacetamide (NVA), 3-(methacrylamidophenyl)boronic acid (MAPBA), and dopamine (DA) in glycerol and stir for 12-24 hours to ensure that all components are fully dissolved to form a homogeneous solution to obtain a precursor mixture. The mass ratio of N-vinylacetamide, 3-(methacrylamidophenyl)boric acid, dopamine, and glycerol is 10-15:0.6-1.0:3-6:11.34-13.56; Step 2.2, dissolve N,N'-methylenebisacrylamide (MBA) in deionized water and stir for 1-6 hours to completely dissolve it to form a crosslinker solution; The mass ratio of N,N'-methylenebisacrylamide to deionized water is 0.134-0.246:9.5-14.5; Step 2.3, dissolving ammonium persulfate (APS) in deionized water until it is completely dissolved to form an initiator solution; The mass ratio of ammonium persulfate to deionized water is 0.03-0.08:0.5-2.0; Step 2.4, adding the crosslinker solution and the initiator solution to the precursor mixture in sequence, stirring for 10-60 minutes, and then heating the mixture in a water bath under nitrogen at a temperature of 60-80° C. for 6-12 hours. Filtering, washing with deionized water 2-5 times, and freeze-drying to obtain the acid-responsive adhesive MPDA; The freeze-drying temperature is -20~-5℃, the vacuum degree is 10~40Pa, and the freeze-drying time is 12h~36h; Step 3, preparation of solid phase of acid-responsive dynamic bonding high-strength earth and rock dam plugging material; The following substances are weighed according to mass percentage: 8-15% acid-responsive adhesive MPDA, 83-86% PMMA, and 2-6% benzoyl peroxide (BPO), and the mass percentage of the above components is 100%. MPDA and benzoyl peroxide are added to PMMA, and then loaded into a ball mill tank and uniformly ball milled on a ball mill to obtain the solid phase of the acid-responsive dynamic bonding high-strength earth and rock dam plugging material. The rotation speed of the ball mill is 500-1200 r / min, the ball milling time is 4-10 h, and MPDA is subjected to particle size grading treatment using a 100-500 mesh test sieve.

[0021] Step 4, preparation of liquid phase of acid-responsive dynamic bonding high-strength earth and rock dam plugging material; The following substances are weighed according to mass percentage: 0.3-0.6% initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.2-0.4% polymerization inhibitor 2,6-di-tert-butyl-4-methyl phenol (BHT), and 99-99.5% methyl methacrylate (MMA), and the mass percentage of the above components is 100%. DHPT and BHT are added to MMA and stirred for 20-60 min to obtain the liquid phase of the acid-responsive dynamic bonding high-strength earth and rock dam plugging material. Step 5, preparation of acid-responsive dynamic bonding high-strength earth and rock dam plugging material; The solid phase and the liquid phase of the acid-responsive dynamic bonding high-strength earth and rock dam plugging material prepared in steps 3 and 4 are mixed and stirred at a solid-liquid ratio of 2.0-2.5 g:1.0-1.5 mL for 5-10 min to obtain the acid-responsive dynamic bonding high-strength earth and rock dam plugging material.

[0022] The acid-responsive dynamic bonding high-strength earth and rock dam plugging material of the present application uses PMMA as the matrix and MPDA as the acid-responsive adhesive, and 3-(methacrylamido phenyl) boronic acid (MAPBA) as the pH-responsive unit. In normal water environment, it effectively plugs cracks through covalent bonding and physical adsorption. In acidic environment (pH range of 3-6), H +As the concentration increases, the acidity increases. The concentration of borate ester bonds formed through dynamic covalent interactions between the phenylboronic acid groups in MAPBA and the catechol groups in DA increases, dynamically improving the bonding performance and providing excellent mechanical properties in the increasingly acidic environment. This results in a 150% increase in chemical bonding strength in acidic environments. Furthermore, MPDA, with NVA as its hydrophilic backbone, can absorb and swell in acidic environments, generating expansion stress through water absorption. Combined with the synergistic enhancement of PMMA's excellent compressive strength and water absorption expansion stress, this provides a solid support for the surrounding earth-rock dam, strengthens dynamic bonding strength and interfacial stability in acidic environments, and achieves high-strength leak plugging in acidic environments.

[0023] Example 1 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 5.0 g of 3-aminophenylboronic acid and 5.0 g of sodium bicarbonate in a mixture consisting of 30 mL of water and 15 mL of tetrahydrofuran (THF). Stir the solution in an ice bath at 0°C for 10 minutes, then slowly add 5 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 2 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 50°C to obtain 3-(methacrylamidophenyl)boronic acid (MAPBA). Step 2, preparing an acid-responsive adhesive MPDA; 10g N-vinylacetamide (NVA), 0.6g 3-(methacrylamidophenyl)boronic acid (MAPBA), and 3g dopamine (DA) were dissolved in 11.34g glycerol and stirred for 12 hours to ensure complete dissolution of the components to form a homogeneous precursor mixture. 0.134g N,N'-methylenebisacrylamide was dissolved in 9.5mL deionized water and stirred for 1 hour to completely dissolve. 0.03g ammonium persulfate (APS) was dissolved in 0.5mL deionized water. The crosslinker solution and initiator solution were added sequentially to the premixed solution and stirred for 10 minutes. After thorough mixing, the solution was placed in a three-necked flask at 60°C and purged with nitrogen for 6 hours. After completion of the reaction, the mixture was filtered and washed twice with deionized water. MPDA was then dried at -20°C under a vacuum of 10 Pa for 12 hours to obtain the acid-responsive adhesive MPDA.

[0024] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 15% of the acid-responsive adhesive MPDA, 83% of PMMA, and 2% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. The MPDA and benzoyl peroxide were added to the PMMA in a ball mill and milled for 4 hours. After mixing, a solid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding was obtained.

[0025] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; Weigh 0.6% of the initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.4% of the polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99% of methyl methacrylate (MMA) by mass, with the total mass percentage of these components being 100%. Add DHPT and BHT to MMA and mix uniformly for 20 minutes to obtain a liquid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding. Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.5 g:1.5 mL for 5 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0026] Example 2 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 5.0 g of 3-aminophenylboronic acid and 6.0 g of sodium bicarbonate in a mixture consisting of 35 mL of water and 20 mL of tetrahydrofuran. Stir the solution in an ice bath at 0°C for 12 minutes, then slowly add 5 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 3 hours. After the reaction is complete, extract with ethyl acetate. The organic phase, MAPBA, is collected and dried in an oven at 55°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0027] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 11g of N-vinylacetamide (NVA), 0.6g of 3-(methacrylamidophenyl)boronic acid (MAPBA), and 4g of dopamine (DA) in 11.38g of glycerol and stir for 13 hours to ensure complete dissolution of the components to form a homogeneous solution. Dissolve 0.141g of N,N'-methylenebisacrylamide (MBA) in 10mL of deionized water and stir for 2 hours to completely dissolve. Dissolve 0.04g of ammonium persulfate (APS) in 0.8mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 10 minutes. After thorough mixing, place the solution in a three-necked flask at 65°C in a water bath and allow nitrogen to flow for 7 hours. After completion of the reaction, filter and wash three times with deionized water. MPDA was dried at -15°C under a vacuum of 15 Pa for 14 hours to obtain the acid-responsive adhesive MPDA.

[0028] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 14% of the acid-responsive adhesive MPDA, 84% of PMMA, and 2% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA in a ball mill and milled for 5 hours. After mixing evenly, a high-strength earth-rock dam plugging material with an acid-responsive dynamic bond was obtained.

[0029] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.51% of the initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.49% of the polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99% of methyl methacrylate (MMA) were weighed by mass, with the total mass percentage of these components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 30 minutes to obtain a liquid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0030] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.5 g:1.4 mL for 6 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0031] Example 3 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 6.0 g of 3-aminophenylboronic acid and 7.0 g of sodium bicarbonate in a mixture consisting of 40 mL of water and 20 mL of tetrahydrofuran (THF). Cool the solution to 1°C in an ice bath with stirring for 30 minutes, then slowly add 10 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 4 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 58°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0032] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 13g of N-vinylacetamide (NVA), 1.0g of 3-(methacrylamidophenyl)boronic acid (MAPBA), and 4.5g of dopamine (DA) in 12.14g of glycerol and stir for 16 hours to ensure complete dissolution of the components to form a homogeneous solution. Dissolve 0.164g of N,N'-methylenebisacrylamide (MBA) in 11.5mL of deionized water and stir for 3 hours to completely dissolve. Dissolve 0.08g of ammonium persulfate (APS) in 1.0mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 20 minutes. After thorough mixing, place the solution in a three-necked flask at 68°C in a water bath and allow to react for 8 hours under nitrogen. After completion of the reaction, filter and wash four times with deionized water. MPDA was frozen at -10°C and dried under a vacuum of 10 Pa for 13 hours to obtain the acid-responsive adhesive MPDA.

[0033] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 13% of the acid-responsive adhesive MPDA, 85% of PMMA, and 2% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA in a ball mill and milled for 6 hours. After mixing, a high-strength solid phase of an acid-responsive, dynamically bonded earth-rock dam plugging material was obtained.

[0034] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.55% of the initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.45% of the polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99% of methyl methacrylate (MMA) were weighed by weight, with the total weight percentage of these components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 25 minutes to obtain a liquid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0035] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.4 g:1.3 mL for 7 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0036] Example 4 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 7.0 g of 3-aminophenylboronic acid and 8.0 g of sodium bicarbonate in a mixture of 45 mL of water and 30 mL of tetrahydrofuran. Cool the solution to 3°C in an ice bath with stirring for 40 minutes, then slowly add 15 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 6 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 60°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0037] Step 2, preparing an acid-responsive adhesive MPDA; 12g N-vinylacetamide (NVA), 0.8g 3-(methacrylamidophenyl)boronic acid (MAPBA), and 4g dopamine (DA) were dissolved in 12.64g glycerol and stirred for 16 hours to ensure complete dissolution of the components to form a homogeneous solution. 0.234g N,N'-methylenebisacrylamide (MBA) was dissolved in 11.5mL deionized water and stirred for 2 hours to completely dissolve. 0.03g ammonium persulfate (APS) was dissolved in 2.0mL deionized water. The crosslinker solution and initiator solution were added sequentially to the premixed solution and stirred for 40 minutes. After thorough mixing, the solution was placed in a three-necked flask at 80°C and purged with nitrogen for 6 hours. After completion of the reaction, the mixture was filtered and washed twice with deionized water. MPDA was frozen at -20°C and dried under a vacuum of 30 Pa for 24 hours to obtain the acid-responsive adhesive MPDA.

[0038] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 12% of the acid-responsive adhesive MPDA, 86% of PMMA, and 2% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA and placed in a ball mill. The mixture was then ball milled for 7 hours to obtain a high-strength earth-rock dam plugging material with an acid-responsive dynamic bond.

[0039] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.4% initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.1% polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.5% methyl methacrylate (MMA) were weighed by mass, with the total mass percentage of these components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 30 minutes to obtain a liquid phase of acid-responsive, dynamically bonded, high-strength earth-rock dam plugging material.

[0040] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.5 g:1.0 mL for 8 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0041] Example 5 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 8.0 g of 3-aminophenylboronic acid and 5.0 g of sodium bicarbonate in a mixture of 45 mL of water and 50 mL of tetrahydrofuran. Cool the solution to 5°C in an ice bath with stirring for 50 minutes, then slowly add 20 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 8 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 65°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0042] Step 2, preparing an acid-responsive adhesive MPDA; 11g N-vinylacetamide (NVA), 0.8g 3-(methacrylamidophenyl)boronic acid (MAPBA), and 6g dopamine (DA) were dissolved in 13g glycerol and stirred for 19 hours to ensure complete dissolution of the components to form a homogeneous solution. 0.187g N,N'-methylenebisacrylamide (MBA) was dissolved in 14.5mL deionized water and stirred for 5.5 hours to completely dissolve. 0.04g ammonium persulfate (APS) was dissolved in 1.5mL deionized water. The crosslinker solution and initiator solution were added sequentially to the premixed solution and stirred for 45 minutes. After thorough mixing, the solution was placed in a three-necked flask at 75°C and purged with nitrogen for 10 hours. After completion of the reaction, the mixture was filtered and washed three times with deionized water. MPDA was frozen at -15°C and dried under a vacuum of 25 Pa for 30 hours to obtain the acid-responsive adhesive MPDA.

[0043] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 10% of the acid-responsive adhesive MPDA, 85% of PMMA, and 5% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA and placed in a ball mill. The mixture was then ball milled for 8 hours to obtain a high-strength earth-rock dam plugging material with an acid-responsive dynamic bond.

[0044] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.45% of the initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.3% of the polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.25% of methyl methacrylate (MMA) were weighed by mass, with the total mass percentage of these components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 35 minutes to obtain a liquid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0045] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.5 g:1.2 mL for 5.5 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0046] Example 6 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 8.0 g of 3-aminophenylboronic acid and 9.0 g of sodium bicarbonate in a mixture of 80 mL of water and 60 mL of tetrahydrofuran. Stir the solution in an ice bath at 0°C for 55 minutes, then slowly add 25 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 10 hours. After the reaction is complete, extract with ethyl acetate. The organic phase, MAPBA, is collected and dried in an oven at 75°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0047] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 13g of N-vinylacetamide (NVA), 0.8g of 3-(methacrylamidophenyl)boronic acid (MAPBA), and 4g of dopamine (DA) in 13.34g of glycerol and stir for 20 hours to ensure complete dissolution of the components to form a homogeneous solution. Dissolve 0.211g of N,N'-methylenebisacrylamide (MBA) in 13.8mL of deionized water and stir for 4.5 hours to completely dissolve. Dissolve 0.03g of ammonium persulfate (APS) in 1.0mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 35 minutes. After thorough mixing, place the solution in a three-necked flask at 77°C in a water bath and allow nitrogen to flow for 11 hours. After completion of the reaction, filter and wash three times with deionized water. Dry MPDA at -8°C under a vacuum of 19 Pa for 19 hours to obtain the acid-responsive adhesive MPDA.

[0048] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 9% of the acid-responsive adhesive MPDA, 86% of PMMA, and 5% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA in a ball mill and milled for 5 hours. After mixing evenly, a high-strength earth-rock dam plugging material with an acid-responsive dynamic bond was obtained.

[0049] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.55% initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.2% polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.25% methyl methacrylate (MMA) were weighed by mass, with the total mass percentage of these components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 40 minutes to obtain a liquid phase of a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0050] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.0 g:1.5 mL for 7.5 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0051] Example 7 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 6.0 g of 3-aminophenylboronic acid and 8.0 g of sodium bicarbonate in a mixture of 80 mL of water and 15 mL of tetrahydrofuran. Stir the solution in an ice bath at 4°C for 55 minutes, then slowly add 15 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 10 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 78°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0052] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 13g of N-vinylacetamide (NVA), 1.0g of 3-(methacrylamidophenyl)boronic acid (MAPBA), and 3.5g of dopamine (DA) in 12.50g of glycerol and stir for 22 hours to ensure complete dissolution of all components to form a homogeneous solution. Dissolve 0.163g of N,N'-methylenebisacrylamide in 14.5mL of deionized water and stir for 3 hours to completely dissolve. Dissolve 0.03g of ammonium persulfate (APS) in 0.5mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 50 minutes. After thorough mixing, place the solution in a three-necked flask in a 75°C water bath and allow nitrogen to flow for 10 hours. After completion of the reaction, filter and wash twice with deionized water. Dry MPDA at -6°C under a vacuum of 35 Pa for 30 hours to obtain the acid-responsive adhesive MPDA.

[0053] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 9% of the acid-responsive adhesive MPDA, 85% of PMMA, and 6% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA in a ball mill and milled for 9 hours. After mixing, a high-strength solid phase of an acid-responsive, dynamically bonded earth-rock dam plugging material was obtained.

[0054] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.4% of initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.4% of inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.2% of methyl methacrylate (MMA) were weighed by mass fraction, with the total mass percentage of the above components being 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 50 minutes to obtain a liquid phase of acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0055] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.1 g:1.3 mL for 6.5 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0056] Example 8 The preparation method of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 8.0 g of 3-aminophenylboronic acid and 10.0 g of sodium bicarbonate in a mixture of 90 mL of water and 60 mL of tetrahydrofuran. Stir the solution in an ice bath at 5°C for 60 minutes, then slowly add 25 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 12 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 80°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0057] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 15g of N-vinylacetamide (NVA), 1.0g of 3-(methacrylamidophenyl)boronic acid (MAPBA), and 6g of dopamine (DA) in 13.56g of glycerol and stir for 24 hours to ensure complete dissolution of the components to form a homogeneous solution. Dissolve 0.246g of N,N'-methylenebisacrylamide in 14.5mL of deionized water and stir for 6 hours to completely dissolve. Dissolve 0.08g of ammonium persulfate (APS) in 2.0mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 60 minutes. After thorough mixing, place the solution in a three-necked flask in an 80°C water bath and allow nitrogen to flow for 12 hours. After completion of the reaction, filter and wash with deionized water five times. Dry MPDA at -5°C under a vacuum of 40 Pa for 36 hours to obtain the acid-responsive adhesive MPDA.

[0058] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 8% of the acid-responsive adhesive MPDA, 86% of PMMA, and 6% of benzoyl peroxide were weighed by mass, with the total mass percentage of these components being 100%. MPDA and benzoyl peroxide were added to PMMA in a ball mill and milled for 10 hours. After mixing evenly, a high-strength earth-rock dam plugging material with an acid-responsive dynamic bond was obtained.

[0059] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.3% of initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.2% of inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.5% of methyl methacrylate (MMA) were weighed by mass fraction, and the total mass percentage of the above components was 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 60 minutes to obtain a liquid phase of high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0060] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in steps 3 and 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.0 g:1.0 mL for 10 minutes to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

[0061] Comparative Example 1 (using Example 8 as a standard, without adding dopamine) The preparation method of the earth-rock dam plugging material is specifically implemented according to the following steps: Step 1, preparing 3-(methacrylamidophenyl)boronic acid (MAPBA); Dissolve 8.0 g of 3-aminophenylboronic acid and 10.0 g of sodium bicarbonate in a mixture of 90 mL of water and 60 mL of tetrahydrofuran. Stir the solution in an ice bath at 5°C for 60 minutes, then slowly add 25 mL of methacryloyl chloride dropwise. After the addition is complete, stir vigorously at room temperature for 12 hours. After the reaction is complete, extract with ethyl acetate. Collect the organic phase (MAPBA) and dry it in an oven at 80°C to yield 3-(methacrylamidophenyl)boronic acid (MAPBA).

[0062] Step 2, preparing an acid-responsive adhesive MPDA; Dissolve 15g of N-vinylacetamide (NVA) and 1.0g of 3-(methacrylamidophenyl)boronic acid (MAPBA) in 13.56g of glycerol and stir for 24 hours to ensure complete dissolution of all components to form a homogeneous solution. Dissolve 0.246g of N,N'-methylenebisacrylamide in 14.5mL of deionized water and stir for 6 hours to completely dissolve. Dissolve 0.08g of ammonium persulfate (APS) in 2.0mL of deionized water. Add the crosslinker solution and initiator solution sequentially to the premixed solution and stir for 60 minutes. After thorough mixing, place the solution in a three-necked flask in an 80°C water bath and allow nitrogen to flow for 12 hours. After completion of the reaction, filter and wash five times with deionized water. Dry MPDA at a freezing temperature of -5°C and a vacuum of 40 Pa for 36 hours to obtain the acid-responsive adhesive MPDA.

[0063] Step 3, preparing a solid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 8% of the acid-responsive adhesive MPDA, 86% of PMMA, and 6% of benzoyl peroxide were weighed according to mass fraction. MPDA and benzoyl peroxide were added to PMMA and placed in a ball mill jar. The mixture was ball milled on a ball mill for 10 hours. After mixing evenly, a high-strength earth-rock dam plugging material solid phase with acid-responsive dynamic bonding was obtained.

[0064] Step 4, preparing a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material; 0.3% of initiator N,N-dihydroxypropyl-p-toluidine (DHPT), 0.2% of inhibitor 2,6-di-tert-butyl-4-methylphenol (BHT), and 99.5% of methyl methacrylate (MMA) were weighed by mass fraction, and the total mass percentage of the above components was 100%. DHPT and BHT were added to MMA and uniformly mixed and stirred for 60 minutes to obtain a liquid phase of high-strength earth-rock dam plugging material with acid-responsive dynamic bonding.

[0065] Step 5, preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding; The solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material prepared in step 3 and step 4 were uniformly mixed and stirred at a solid-liquid ratio of 2.0 g:1.0 mL for 10 minutes to obtain the earth-rock dam plugging material.

[0066] The comparative test results of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material in Example 1-8 and the currently available epoxy resin plugging material and acrylate plugging material are shown in Table 1-3: Table 1 Comparison of the bonding strength between plugging materials and soil and rock in underwater dynamic acidic environment

[0067] Under normal water conditions with a pH of 7.0, the bonding strength between the present invention's plugging material and soil and rock is 9.25 MPa, the epoxy resin plugging material's bonding strength is 4.83 MPa, and the acrylic ester plugging material's bonding strength is 3.75 MPa. The bonding strength between the plugging material of Comparative Example 1 and soil and rock in an underwater dynamic acidic environment is 1.4 MPa.

[0068] Table 2 Expansion stress of the plugging material of the present invention under underwater dynamic acidic environment

[0069] The expansion stress of the plugging material of the present invention is 0.61 MPa when the pH value is 7.0 under normal water environment. The expansion stress of the plugging material of Comparative Example 1 under dynamic acidic environment under water is 0.23 MPa.

[0070] Table 3 Comparison of compressive strength of plugging materials in underwater dynamic acidic environment

[0071] Under normal water conditions with a pH of 7.0, the compressive strength of the plugging material of the present invention is 65.39 MPa, the compressive strength of the epoxy resin plugging material is 33.41 MPa, and the compressive strength of the acrylate plugging material is 26.51 MPa. The compressive strength of the plugging material of Comparative Example 1 under an underwater dynamic acidic environment is 23 MPa.

[0072] As shown in Table 1, compared with the existing epoxy resin plugging materials and acrylate plugging materials, the acid-responsive dynamic bonding high-strength earth-rock dam plugging material of the present invention can be seen from Table 1 that in an acidic environment (pH range of 3-6.5), as the H +As the concentration increases, the acidity increases, and the concentration of borate bonds formed by the dynamic covalent action of the phenylboronic acid groups in MAPBA and the catechol groups in DA increases, which continuously improves the adhesion of the material in an acidic environment, and increases the chemical bonding strength in an acidic environment by 150%. By comparing with epoxy resin plugging materials and acrylate plugging materials in the same acidic environment, it can be seen that the bonding strength of the material of the present invention to soil and stone is 2-3 times that of epoxy resin plugging materials and acrylate plugging materials, which significantly improves the bonding ability to soil and stone in an acidic environment.

[0073] MPDA acid-responsive adhesive, with a hydrophilic NVA backbone, enhances bonding performance through a synergistic "hydrophobic-adhesive" mechanism: The long hydrophobic chains of DA repel the hydrated layer, promoting close adhesion between the adhesive and the substrate. The catechol groups enhance adhesion to substrates such as soil and rock through hydrogen bonding, hydrophobic association, and π-π interactions. Simultaneously, DA optimizes the cross-linking network, imparting high compressive and tensile strengths, as well as elongation at break, ensuring bond stability under complex loads. In applications such as leak plugging in earth-rock dams, it effectively resists deformation and meets support requirements.

[0074] As shown in Table 2, the expansion stress of the material of the present invention in an underwater dynamic acidic environment (pH range of 3-6.5) increases with the increase of H + The expansion stress increases with increasing concentration, and the expansion stress generated by water absorption and expansion in an acidic environment enhances its own mechanical properties. It can adapt to a wider range of acidity and can still maintain a high expansion ratio and stably play a plugging role in a strong acid environment.

[0075] As shown in Table 3, the compressive strength of the material of the present invention in an underwater dynamic acidic environment (pH range of 3-6.5) increases with the increase of H + In an acidic environment, MPDA, with the help of the expansion stress generated by the increase in borate bond concentration and the regulation of MAPBA, cooperates with the PMMA matrix to improve the compressive strength, forming an "expansion filling-rigid support" mechanism, which together forms a firm support for the earth-rock dam, so that the pH is within the range of 3-6.5. + The higher the concentration, the stronger the compressive strength of the material, achieving high-strength plugging.

[0076] Comparative Example 1 lacks the introduction of catechol groups to form borate ester bonds. Due to the lack of dynamic covalent interaction between phenylboronic acid and catechol, hydrogen bonding with polar groups in the soil and rock is impossible, leading to a decrease in bonding strength. The loss of cross-linking control of the expansion network leads to a sharp decrease in expansion stress, disrupting the synergistic support between PMMA and MPDA and reducing compressive strength. This is primarily due to the lack of the borate ester-driven interface strengthening, expansion control, and rigid-flexible synergy mechanisms, ultimately resulting in a significant decline in the material's mechanical properties in acidic environments.

[0077] In summary, the acid-responsive dynamic bonding high-strength earth-rock dam bonding and leaking stopping material prepared by the application realizes the triple performance synergy of acid pH response regulation, dynamic bonding and water absorption expansion stress support through molecular design and interface regulation. Under normal water environment, the material blocks the cracks and prevents collapse through covalent bonding and physical adsorption, and in acidic water environment (pH range of 3-6.5), the concentration of acid-responsive group borate ester bond is regulated according to the change of pH, so that the pH is in the range of 3-6.5, H + The higher the concentration, the stronger the bonding force of the material and the soil and rock, and the bonding strength is improved by 150%. The material breaks through the limitations of traditional leaking stopping materials such as single function and poor underwater adaptability, integrates the functions of chemical bonding, physical filling and stress reinforcement, and provides an innovative solution for earth-rock dam leakage treatment and reinforcement.

Claims

1. A method for preparing a high-strength earth-rock dam plugging material with acid-responsive dynamic bonding, characterized in that: Please follow the steps below to implement: Step 1, preparing 3-(methacrylamidophenyl)boronic acid; Step 2, preparing an acidic responsive adhesive MPDA using 3-(methacrylamidophenyl)boronic acid, MAPBA, and dopamine; Step 3, using acid-responsive adhesives MPDA, PMMA and benzoyl peroxide to prepare a solid phase of a high-strength earth-rock dam plugging material; Step 4, preparing a liquid phase of a high-strength earth-rock dam plugging material using DHPT, BHT, and MMA; Step 5: Mixing and stirring the solid phase and liquid phase of the acid-responsive dynamic bonding high-strength earth-rock dam plugging material to obtain the acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

2. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 1, characterized in that: In the step 1, specifically: 3-Aminophenylboronic acid and sodium bicarbonate are dissolved in a tetrahydrofuran solution to obtain a mixed solution, and then the mixed solution is stirred in an ice bath at 0°C-5°C for 10-60 minutes, followed by slow dropwise addition of methacryloyl chloride. After the addition is complete, the mixture is stirred for 2-12 hours. After the addition is complete, ethyl acetate is used as the organic extraction phase for extraction, and the organic phase MAPBA is collected and dried to obtain 3-(methacrylamidophenyl)boric acid.

3. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 2, characterized in that: The mass ratio of 3-aminophenylboronic acid to sodium bicarbonate is 5-8:5-10; the tetrahydrofuran solution is prepared by mixing water and tetrahydrofuran; and the volume ratio of methacryloyl chloride to the mixed solution is 1-5:1.5-7.

4. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 1, wherein: In the step 2, specifically: Step 2.1, dissolving N-vinylacetamide, 3-(methacrylamidophenyl)boronic acid, and dopamine in glycerol and stirring for 12-24 hours to obtain a precursor mixture; The mass ratio of N-vinylacetamide, 3-(methacrylamidophenyl)boric acid, dopamine and glycerol is 10-15: 0.6-1.0：3-6：11.34-13.56； Step 2.2, dissolve MBA in deionized water and stir for 1-6 hours to form a crosslinker solution; Step 2.3, dissolving ammonium persulfate in deionized water to form an initiator solution; Step 2.4, add the crosslinker solution and the initiator solution to the precursor mixture in sequence, stir for 10-60 minutes, and then heat the mixture in a water bath under nitrogen at a temperature of 60-80°C for 6-12 hours. Filter the mixture, wash it with deionized water 2-5 times, and freeze-dry it at a temperature of -20 to -5°C, a vacuum degree of 10 to 40 Pa, and a freeze-drying time of 12 hours to 36 hours to obtain the acidic responsive adhesive MPDA.

5. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 1, characterized in that: In the step 3, specifically: The following substances were weighed by mass percentage: 8%-15% acid-responsive adhesive MPDA, 83%-86% PMMA, and 2%-6% benzoyl peroxide, where the total mass percentage of the above components is 100%; Acid-responsive adhesive MPDA and benzoyl peroxide are added to PMMA, which is then placed in a ball mill and ball-milled for 4-10 hours to obtain a solid phase of an acid-responsive dynamic-bonded high-strength earth-rock dam plugging material.

6. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 1, characterized in that: In the step 4, specifically: Weigh the following substances by mass percentage: 0.3%-0.6% DHPT, 0.2%-0.4% BHT, 99%-99.5% MMA, the total mass percentage of the above components is 100%; DHPT and BHT are added into MMA and stirred for 20-60 minutes to mix evenly to obtain a liquid phase of an acid-responsive dynamic bonding high-strength earth-rock dam plugging material.

7. The method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to claim 1, characterized in that: In step 5, the solid-liquid ratio of the solid phase to the liquid phase is 2.0 g to 2.5 g: 1.0 mL to 1.5 mL.

8. The high-strength earth-rock dam plugging material prepared by the method for preparing the acid-responsive dynamic bonding high-strength earth-rock dam plugging material according to any one of claims 1 to 7.

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