A high-permeability grouting material based on hydrophobic association principle modification and a preparation method thereof

Abstract

The application discloses a high-permeability grouting material based on hydrophobic association principle modification and a preparation method thereof, and belongs to the technical field of grouting materials. The high-permeability grouting material comprises A liquid and B liquid; the A liquid comprises 30-70 parts of acrylic acid salt, 1-6 parts of a hydrophobic association monomer, 0.1-2.0 parts of a hydrophobic association promoter, 2-5 parts of a cosolvent, 1-6 parts of a crosslinking agent and 15-30 parts of water according to mass fraction; and the B liquid comprises 0.1-1.0 parts of an initiator and 25-40 parts of water. The application modifies the acrylic acid salt grouting material based on the hydrophobic association principle, significantly improves the bearing strength, rigidity and impermeability of the consolidated body while maintaining the high permeability of the slurry, and solves the core technical problem that the strength improvement and the injectability of the existing material are difficult to be considered simultaneously.

Description

Technical Field

[0001] This invention relates to the field of grouting materials technology, and in particular to a high-permeability grouting material modified based on the principle of hydrophobic association and its preparation method. Background Technology

[0002] In the field of tunnel and underground engineering, acrylate materials possess characteristics such as low initial viscosity, controllable gelation time, and environmental friendliness. Compared with granular materials such as cement and polyurethane and epoxy resin-based materials with higher viscosity, they are more suitable for the penetration grouting requirements of dense and weak strata. However, existing acrylate grouting materials form a highly flexible three-dimensional network structure after polymerization. In addition, the solid content of the gel system is relatively low and the cross-linked skeleton is not dense enough, resulting in weak rigidity and low load-bearing strength of the solidified body, which makes it difficult to meet the reinforcement and load-bearing requirements of dense and weak strata.

[0003] Existing modification technologies for acrylate grouting materials mostly employ methods such as adding inorganic fillers and adjusting the crosslinking system. These technologies generally suffer from the drawback of difficulty in simultaneously improving strength and ensuring injectability. Furthermore, they are characterized by complex preparation processes and significantly increased costs, making it difficult to meet the requirements for effective anti-seepage reinforcement of dense and weak strata. Summary of the Invention

[0004] In view of this, the present invention provides a high-permeability grouting material modified based on the principle of hydrophobic association and its preparation method. The present invention modifies acrylate grouting materials based on the principle of hydrophobic association, significantly improving the load-bearing strength, rigidity, and long-term service stability of the solidified body in a water environment while maintaining the high permeability of the grout, thus solving the core technical problem of simultaneously improving strength and injectability in existing materials.

[0005] In a first aspect, the present invention provides a high-permeability grouting material modified based on the principle of hydrophobic association, comprising liquid A and liquid B; By mass fractions, solution A comprises: 20-30 parts of acrylate, 1-6 parts of hydrophobic associating monomer, 0.1-2.0 parts of hydrophobic associating promoter, 2-5 parts of cosolvent, 1-6 parts of crosslinking agent, and 30-40 parts of water; solution B comprises: 0.1-1.0 parts of initiator and 10-50 parts of water. The hydrophobic associating monomer is a glycidyl ether monomer and / or glycidyl ester monomer that simultaneously contains carbon-carbon double bonds and epoxy groups. The hydrophobic association promoter is tris(2-hydroxyethyl)amine; The cosolvents include polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether.

[0006] Preferably, the solute in the acrylate aqueous solution is one or more of the following: alkali metal salt of acrylic acid, alkaline earth metal salt of acrylic acid, alkali metal salt of methacrylic acid, and alkaline earth metal salt of methacrylic acid.

[0007] Furthermore, the acrylate includes one or more of magnesium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, zinc acrylate, magnesium methacrylate, sodium methacrylate, zinc methacrylate, and calcium methacrylate.

[0008] Preferably, the hydrophobic associating monomer is one or more of allyl alcohol glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.

[0009] Preferably, the mass ratio of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol and propylene glycol methyl ether is (1.2~5): (1.2~5): (40~50): (10~30).

[0010] Preferably, the crosslinking agent includes one or more of N,N-methylenebisacrylamide, polyethylene glycol diacrylate, and pentaerythritol diacrylate.

[0011] Preferably, the initiator is an inorganic peroxide initiator.

[0012] Furthermore, the initiator includes one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0013] Secondly, the present invention provides a method for preparing the above-mentioned high-permeability acrylate grouting material modified based on the principle of hydrophobic association, comprising the following steps: The preparation method of solution A is as follows: add crosslinking agent, hydrophobic association promoter, cosolvent and hydrophobic association monomer to acrylate aqueous solution, and stir to obtain solution A; The preparation method of solution B is as follows: Dissolve the initiator in water to obtain solution B.

[0014] Thirdly, the present invention provides the application of the above-mentioned high-permeability grouting material modified based on the principle of hydrophobic association or the high-permeability grouting material prepared by the above-mentioned preparation method, which is used for grouting treatment of strata in tunnels and underground engineering.

[0015] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) This invention introduces a specific ratio of acrylate, a hydrophobic associating monomer containing polymerizable carbon-carbon double bonds and epoxy groups, tris(2-hydroxyethyl)amine, a compound cosolvent and a crosslinking agent into liquid A, and forms a complete polymerization and crosslinking system with liquid B containing an initiator. While maintaining the ultra-low initial viscosity, excellent injectability and controllable gel time of the grouting material, a stable covalent crosslinking network and a reversible hydrophobic associating physical crosslinking structure are simultaneously constructed. This significantly improves the rigidity and load-bearing strength of the grouting material solid, effectively inhibits the swelling and softening behavior of the solid in a water-rich environment, improves the long-term service stability of the material, and overcomes the inherent defects of existing acrylate grouting materials that are difficult to balance strength improvement and high permeability.

[0016] (2) The hydrophobic associating monomer used in this invention can undergo free radical copolymerization with acrylate monomers through carbon-carbon double bonds, stably embedding into the polymer backbone structure. The epoxy groups contained therein can undergo nucleophilic ring-opening reaction with the hydroxyl groups of tris(2-hydroxyethyl)amine, forming a secondary covalent cross-linking structure outside the basic cross-linking network, further improving the cross-linking density and structural integrity of the polymer system. The hydrophobic segments formed after ring opening can spontaneously form a reversible hydrophobic associating structure in the aqueous system. Under the action of external force, the impact energy can be dissipated through the association-dissociation process, which can improve the strength of the solidified body while taking into account the toughness of the material, avoiding the problem that the existing cross-linking modification technology can easily lead to a significant increase in the brittleness of the material. At the same time, the epoxy groups of the hydrophobic associating monomer can undergo ring-opening reaction with the silanol groups in the stratum soil and rock to form covalent ether bonds, which strengthens the interfacial bonding force between the grouting solidified body and the stratum medium, and improves the overall effect of stratum reinforcement and water erosion resistance.

[0017] (3) The present invention uses a compound cosolvent system composed of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol and propylene glycol methyl ether, which can effectively adjust the polarity of the aqueous system, improve the solubility and dispersion uniformity of hydrophobic associating monomers in the aqueous phase, avoid the problem of increased slurry viscosity and decreased injectability caused by hydrophobic monomer aggregation, and ensure that the grouting material can stably penetrate the tiny pores of dense and weak strata.

[0018] (4) The two-component system of the present invention enables the separate storage of reducing accelerator and oxidizing initiator, which can effectively avoid premature polymerization reaction during storage and improve the storage stability of the material. At the same time, the preparation process and usage method of the material are simple to operate, without the need for complex production equipment and harsh reaction conditions, and can be directly adapted to the on-site construction conditions of tunnels and underground engineering. Attached Figure Description

[0019] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention and do not constitute an undue limitation thereof. Obviously, those skilled in the art can obtain other drawings based on these drawings without any inventive effort.

[0020] Figure 1 These are images of the injectability test results of the grouting materials in Embodiment 1, Comparative Example 5, and Comparative Example 6 of the present invention; Figure 2 These are the contact angle test results of the grouting materials of Embodiment 1 and Comparative Example 5 of the present invention in dense and weak strata, from 0 to 10 seconds. Detailed Implementation

[0021] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0022] This invention provides a high-permeability acrylate grouting material, comprising liquid A and liquid B; By mass fractions, solution A comprises: 20-30 parts of acrylate, 1-6 parts of hydrophobic associating monomer, 0.1-2.0 parts of hydrophobic associating promoter, 2-5 parts of cosolvent, 1-6 parts of crosslinking agent, and 30-40 parts of water; solution B comprises: 0.1-1.0 parts of initiator and 10-50 parts of water.

[0023] This invention, through the synergistic combination of a specific two-component system and modified components, significantly improves the load-bearing strength and toughness of the solidified body while maintaining the ultra-low initial viscosity and high permeability of the grouting material. It overcomes the inherent defects of existing acrylate grouting materials, which cannot simultaneously achieve high strength and high injectability, and is suitable for the grouting treatment needs of dense and weak strata in tunnels and underground engineering.

[0024] In this invention, acrylate is the main polymer monomer of the grouting material. Its molecules contain negatively charged carboxylate groups. The electrostatic repulsion between these negative charges causes the monomer molecules to tend to disperse uniformly in the aqueous solution, resulting in an aqueous solution viscosity close to that of pure water, which is the core basis for the high permeability of the grouting material. Simultaneously, the polymerizable carbon-carbon double bonds contained in the acrylate molecules can participate in free radical copolymerization reactions, forming the polymer backbone of the grouting material's solidified structure. In optional embodiments of this invention, the acrylate can be 20 parts, 22 parts, 25 parts, 27 parts, 30 parts, or any other part number within the range of 20-30 parts.

[0025] In optional embodiments of the present invention, the acrylate is one or more selected from alkali metal salts of acrylic acid, alkaline earth metal salts of acrylic acid, alkali metal salts of methacrylic acid, and alkaline earth metal salts of methacrylic acid. Further, the acrylate includes one or more selected from magnesium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, zinc acrylate, magnesium methacrylate, sodium methacrylate, zinc methacrylate, and calcium methacrylate. Different cationic types of acrylate can achieve different performance controls: divalent magnesium and calcium ions can form ionic crosslinks with carboxylate groups on the polymer chain, further increasing the crosslinking density and solid strength of the system, while reducing system toxicity; monovalent sodium and potassium salts can adjust the system viscosity and improve the water solubility of the monomer. The blending ratio of different acrylates can be adjusted according to the pore characteristics and hydrological conditions of the target strata to adapt to different engineering requirements.

[0026] The hydrophobic associating monomer of this invention is a glycidyl ether monomer and / or glycidyl ester monomer containing both carbon-carbon double bonds and epoxy groups. Specifically, the hydrophobic associating monomer is preferably one or more of allyl alcohol glycidyl ether, glycidyl acrylate, and glycidyl methacrylate. The dual active groups in the molecular structure of the hydrophobic associating monomer achieve multi-dimensional performance enhancement. The specific working principle is as follows: First, the carbon-carbon double bonds in the molecule can undergo free radical copolymerization with the acrylate monomer, stably embedding into the polymer backbone structure, so that the hydrophobic groups are uniformly distributed in the polymer network; Second, the epoxy groups in the molecule can undergo nucleophilic ring-opening reaction with the hydroxyl groups of the hydrophobic associating promoter tris(2-hydroxyethyl)amine, constructing a secondary covalent cross-linking network outside the basic cross-linking network, significantly increasing the cross-linking density of the polymer system, thereby improving the rigidity and load-bearing strength of the solidified body; Third, the epoxy groups can undergo ring-opening reaction with the silanol groups (-Si-OH) on the surface of silica in the geological formation to form -CO-Si- covalent ether bonds. Permanently anchoring polymer chains to the surface of soil and rock particles achieves organic-inorganic integrated reinforcement of loose strata, significantly improving the grouting reinforcement effect and interfacial bonding force; Fourth, the hydrophobic segments formed after partial ring opening can spontaneously aggregate in the aqueous system to form reversible hydrophobic association physical cross-linking points. Under external force, they can dissipate impact energy through association-dissociation processes, improving the strength of the solidified body while taking into account the toughness of the material, avoiding the problem of significantly increased material brittleness caused by conventional cross-linking modification; Fifth, the local hydrophobic micro-regions formed by the hydrophobic segments can form "hydrophobic islands" in the polymer network, resisting the entry of excessive water molecules into the gel network, effectively inhibiting the swelling and softening of the solidified body in a water-rich environment, and improving the water environment stability and long-term service performance of the material.

[0027] In optional embodiments of the present invention, the hydrophobic associating monomer can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, etc., or any other part value in the range of 1 to 6; preferably 2 to 5 parts, more preferably 2 to 4 parts.

[0028] The hydrophobic association promoter of this invention is tris(2-hydroxyethyl)amine, which has one tertiary nitrogen atom and three ethanol groups with hydroxyl groups at the ends. It possesses the following functions: First, as a reducing component in a redox initiation system, it works in conjunction with the peroxide initiator in solution B to undergo a redox reaction at room temperature, continuously generating free radicals to initiate the free radical copolymerization and crosslinking reactions of acrylate monomers, hydrophobic association monomers, and crosslinking agents. Simultaneously, by adjusting its dosage, the gel time of the grouting slurry can be flexibly controlled to adapt to different engineering conditions. Second, as a crosslinking agent for the ring-opening reaction of epoxy groups, its molecular structure contains... The three terminal hydroxyl groups of the ethanol group can nucleophilically attack the epoxy groups of the hydrophobic associating monomer, causing the epoxy ring to open and forming ester bonds while generating new secondary hydroxyl groups. This constructs a secondary covalent cross-linked network outside the main polymer network of acrylate-hydrophobic associating monomer, further increasing the cross-linking density of the polymer system, limiting the swelling and expansion of the polymer network in water, and improving the material's resistance to deformation. At the same time, the multiple ester bonds formed by the ring-opening reaction are also hydrophobic structural units, which can further enhance the hydrophobic association effect of the system, reduce the overall hydrophilicity of the polymer network, and further improve the material's water environment stability.

[0029] In optional embodiments of the present invention, the hydrophobic association promoter can be 0.1 parts, 0.5 parts, 1.0 parts, 1.5 parts, 2.0 parts, etc., or any other part value in the range of 0.1 to 2.0; preferably 0.5 to 1.8 parts, more preferably 1.0 to 1.5 parts.

[0030] In this invention, the co-solvent includes polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether. Preferably, the mass ratio of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether is (1.2~5):(1.2~5):(40~50):(10~30), and more preferably (1.5~4):(1.5~4):(42~48):(15~25), etc. The co-solvent is a key component for ensuring uniform dispersion of hydrophobic associating monomers in an aqueous system and preventing abnormal increases in slurry viscosity. This invention employs a co-solvent system composed of a nonionic surfactant and an alcohol ether organic solvent. Isopropanol, a polar organic solvent, significantly reduces the polarity of the aqueous system, improves the solubility of hydrophobic associating monomers in aqueous solution, and prevents the agglomeration and stratification of hydrophobic monomers due to poor water solubility. Propylene glycol methyl ether acts as a coupling agent, regulating the evaporation rate of the system and preventing excessively high local concentrations and agglomeration of hydrophobic associating monomers due to rapid local solvent evaporation. It also improves the compatibility between components. Polysorbate and fatty alcohol polyoxyethylene ether are both nonionic surfactants. Their synergistic effect forms a dense and stable interfacial film on the surface of hydrophobic associating monomer droplets, providing strong steric hindrance and electrostatic repulsion, further inhibiting the agglomeration of hydrophobic monomer droplets, ensuring the dispersion stability of the system, and without significantly increasing the initial viscosity of the slurry, maintaining the high permeability of the material.

[0031] In optional embodiments of the present invention, the co-solvent can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc., or any other part value in the range of 2 to 5; preferably 2.5 to 4.5 parts, more preferably 3 to 4 parts.

[0032] In this invention, the crosslinking agent includes one or more of N,N-methylenebisacrylamide, polyethylene glycol diacrylate, and pentaerythritol diacrylate; wherein the number average molecular weight of the polyethylene glycol diacrylate is 200-1000, more preferably 200-600. The crosslinking agent is a bifunctional polymerizable monomer containing two carbon-carbon double bonds that can participate in free radical copolymerization. During the polymerization reaction, it can graft copolymerize with different polymer backbones, forming chemical crosslinking bridges between polymer molecular chains to construct a basic three-dimensional network polymer structure, providing basic strength and elasticity to the solidified body. This invention uses a bifunctional crosslinking agent, which can form a relatively loose and uniform elastic three-dimensional network structure, allowing external forces to be effectively dispersed throughout the network. This avoids the problem of excessively high crosslinking density and significantly increased material brittleness caused by multifunctional crosslinking agents, balancing the strength and toughness of the material. Among them, N,N-methylenebisacrylamide is a short-chain crosslinking agent, which can increase the density of crosslinking points and enhance the rigidity of the material; polyethylene glycol diacrylate is a medium- to long-chain flexible crosslinking agent, which can improve the toughness and elongation at break of the material. The compounding ratio of different crosslinking agents can be adjusted according to engineering requirements to achieve precise control of the rigidity and toughness of the material.

[0033] In optional embodiments of the present invention, the crosslinking agent can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, etc., or any other part value in the range of 1 to 6; preferably 2 to 5 parts, more preferably 3 to 4 parts.

[0034] In this invention, the initiator is an inorganic peroxide initiator, which can form a room-temperature redox initiation system with tris(2-hydroxyethyl)amine in solution A. After the two are mixed, a stable redox reaction can occur at room temperature, continuously generating active free radicals. The system can efficiently initiate free radical copolymerization and cross-linking reactions without additional heating or ultraviolet irradiation. The grouting process is simple and easy to implement, while ensuring that the grouting material can be normally gelled and cured in the formation under normal / high temperature conditions.

[0035] In an optional embodiment of the present invention, the substance comprises one or more of ammonium persulfate, potassium persulfate, and sodium persulfate, which have good water solubility and are peroxide-based strong oxidizing free radical initiators that form a redox initiation system with reducing tri(2-hydroxyethyl)amine.

[0036] By adjusting the dosage of the initiator, it can be combined with a hydrophobic association promoter to control the gel time of the grout within a wide range. A higher initiator dosage results in a faster polymerization rate and a shorter gel time, and vice versa. Ammonium persulfate and potassium persulfate are both water-soluble initiators, exhibiting good solubility in aqueous solutions, stable decomposition, and excellent environmental friendliness and storage stability, making them suitable for underground engineering applications. In optional embodiments of this invention, the initiator can be 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, or any other part value within the range of 0.1 to 2.0 parts; preferably 0.5 to 2 parts.

[0037] It should be noted that the A and B solutions of this invention need to be sealed, protected from light, and stored at room temperature. The preferred storage temperature is 5~35℃. Avoid high temperature exposure or low temperature freezing. The storage period can reach more than 6 months, which solves the problems of short storage period and easy self-polymerization failure of existing single-component acrylate slurry.

[0038] This invention also provides a method for preparing the above-mentioned high-permeability acrylate grouting material, including a preparation step of liquid A and a preparation step of liquid B, as detailed below: The preparation method of solution A is as follows: add crosslinking agent, hydrophobic association promoter, cosolvent and hydrophobic association monomer to acrylate aqueous solution, and stir to obtain solution A; The preparation method of solution B is as follows: Dissolve the initiator in water to obtain solution B.

[0039] In an optional embodiment of the present invention, the preparation of liquid A can be further refined into the following steps: Add a crosslinking agent, a hydrophobic association promoter, and a cosolvent to an aqueous acrylate solution and stir to obtain a first mixture; Add the hydrophobic associating monomer to the first mixture and keep stirring or sonicating until a homogeneous solution A is obtained.

[0040] In an optional embodiment of the present invention, in the step of stirring to obtain the first mixture, the stirring speed is 200~600 rpm; after adding the hydrophobic associating monomer, the stirring speed is 800~1000 rpm, and the hydrophobic associating monomer is preferably added dropwise to ensure its uniform distribution in the system.

[0041] This invention does not impose any particular limitation on the preparation method of acrylate aqueous solution, and various methods known in the art can be used to obtain it. For example, it can be prepared by neutralizing acrylic acid with a corresponding alkali (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, etc.); alternatively, qualified acrylate aqueous solution products can be directly purchased. Regardless of the method used, as long as the desired concentration and composition of the acrylate aqueous solution can be obtained, it is applicable to this invention.

[0042] In this invention, liquid A and liquid B are stored separately and then mixed before use. This two-component design avoids premature contact between the initiator and the accelerator, preventing polymerization reactions and ensuring the storage stability of the slurry, while also facilitating control of the gelation time.

[0043] The high-permeability acrylate grouting material provided by this invention can be applied using either two-component or single-component grouting methods.

[0044] As a preferred embodiment, a two-liquid grouting process is employed. Liquid A and liquid B are placed in two separate tanks and transported via a two-liquid grouting pump in the grouting system. In-hole mixing can be used before injection into the target formation. This method fully utilizes the characteristics of the redox initiation system of this invention, achieving precise control of gelation time, avoiding the risk of pipe blockage, and facilitating construction and control of the diffusion reinforcement range.

[0045] As an alternative implementation method, a single-component grouting process can also be used. This involves first uniformly mixing liquid A and liquid B, and then injecting the mixed grout into the target formation. This method is suitable for shallow, short-distance, and small-volume grouting projects.

[0046] The present invention also provides the application of the above-mentioned high-permeability acrylate grouting material or the high-permeability acrylate grouting material prepared by the above-mentioned preparation method, which is used for grouting treatment of strata in tunnels and underground engineering.

[0047] Furthermore, the grouting treatment includes reinforcement treatment of dense and weak strata, seepage prevention and water stopping treatment of strata, leakage plugging treatment of strata with moving water, reinforcement treatment of fractured surrounding rock zones, and sealing treatment of seepage from cracks in underground structures; wherein, the dense and weak strata include ultra-fine porous strata such as siltstone strata, mudstone strata, silty clay strata, silty soil strata, and completely weathered rock strata, which are difficult for existing conventional grouting materials to penetrate effectively.

[0048] The grouting material of this invention has an initial viscosity as low as 8~10 mPa·s, which can completely penetrate ultra-fine pores with a diameter of 0.01 mm, perfectly meeting the penetration and reinforcement requirements of dense and weak strata; at the same time, the uniaxial compressive strength of the consolidated body can reach 3~5MPa, far exceeding the industry standard requirements, which can effectively improve the bearing capacity and stability of weak strata; the gelation time is adjustable over a wide range, which can simultaneously adapt to various engineering scenarios such as reinforcement, seepage prevention, and leakage plugging, and has broad application prospects in underground engineering such as tunnels, subways, mines, and water conservancy and hydropower.

[0049] The technical solution of the present invention will be further described below with reference to specific embodiments. The present invention does not impose any special restrictions on the source of reagents used in the following embodiments; commercially available products well known to those skilled in the art can be used.

[0050] In the following examples, the acrylate aqueous solution was prepared using conventional methods in the art. Magnesium acrylate was obtained by neutralizing acrylic acid with magnesium oxide, sodium acrylate was obtained by neutralizing acrylic acid with sodium hydroxide, and calcium acrylate was obtained by neutralizing acrylic acid with calcium oxide. In each example, unless otherwise specified, "acrylate aqueous solution" refers to the acrylate aqueous solution prepared in advance using the above methods, and subsequent steps directly add other components to this aqueous solution.

[0051] Example 1 This embodiment provides a high-permeability acrylate grouting material and its preparation method.

[0052] The recipe is as follows: Solution A: 25 parts magnesium acrylate, 2 parts glycidyl methacrylate, 1 part tri(2-hydroxyethyl)amine, 2 parts co-solvent, 3 parts N,N-methylenebisacrylamide, and 37.5 parts deionized water; wherein, the co-solvent is a mixture of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether in a mass ratio of 2:3:45:20.

[0053] Solution B: 1 part ammonium persulfate, 20 parts deionized water.

[0054] The preparation method is as follows: (1) The preparation method of solution A is as follows: i) Add N,N-methylenebisacrylamide, tris(2-hydroxyethyl)amine, and co-solvent to a 40% magnesium acrylate aqueous solution (containing 25 parts magnesium acrylate and 37.5 parts water) according to the formula, and stir at 300 rpm for 15 min until the system is homogeneous and transparent to obtain the first mixture. ii) Weigh glycidyl methacrylate according to the ratio, put it into a constant pressure dropping funnel, and add it dropwise to the first mixture at a dropping rate of 1.0 mL / min. During the dropping process, start a high-speed stirrer at 900 rpm. iii) After the addition is complete, continue stirring at 900 rpm for 60 minutes until the system is homogeneous, without layering or visible oil droplets, and liquid A is obtained. Store in a sealed container.

[0055] (2) Preparation of solution B: Weigh ammonium persulfate and deionized water according to the ratio, add them to a container, stir at 200 rpm until the ammonium persulfate is completely dissolved, and obtain clear and transparent solution B. Seal and store in the dark.

[0056] Example 2 This embodiment provides a high-permeability acrylate grouting material and its preparation method.

[0057] The recipe is as follows: Solution A: 22 parts magnesium acrylate, 3 parts calcium acrylate, 1.5 parts glycidyl methacrylate, 1.5 parts glycidyl acrylate, 1 part tri(2-hydroxyethyl)amine, 4 parts co-solvent, 5 parts polyethylene glycol diacrylate (average molecular weight approximately 400), and 37.5 parts deionized water; wherein, the co-solvent is a mixture of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether in a mass ratio of 3:3:48:16.

[0058] Solution B: 2 parts ammonium persulfate, 20 parts deionized water.

[0059] The preparation method is as follows: (1) The preparation method of solution A is as follows: i) Add polyethylene glycol diacrylate, tris(2-hydroxyethyl)amine, and co-solvent to a 40% (w / w) aqueous solution of acrylate (containing 22 parts magnesium acrylate, 3 parts calcium acrylate, and 37.5 parts water) according to the specified ratio. Stir at 300 rpm for 15 min until the system is homogeneous and transparent to obtain the first mixture. ii) Weigh glycidyl methacrylate and glycidyl acrylate according to the ratio, put them into a constant pressure dropping funnel, and add them dropwise to the first mixture at a dropping rate of 1.0 mL / min. During the dropping process, turn on the high-speed stirrer at 900 rpm simultaneously. iii) After the addition is complete, continue stirring at 900 rpm for 60 minutes until the system is homogeneous, without layering or visible oil droplets, and liquid A is obtained. Store in a sealed container.

[0060] (2) Preparation of solution B: Weigh ammonium persulfate and deionized water according to the ratio, add them to a container, stir at 200 rpm until the ammonium persulfate is completely dissolved, and obtain clear and transparent solution B. Seal and store in the dark.

[0061] Example 3 This embodiment provides a high-permeability acrylate grouting material and its preparation method.

[0062] The recipe is as follows: Solution A: 25 parts magnesium acrylate, 2 parts glycidyl methacrylate, 1 part allyl alcohol glycidyl ether, 1 part tri(2-hydroxyethyl)amine, 3 parts co-solvent, 4 parts N,N-methylenebisacrylamide, and 37.5 parts deionized water; wherein, the co-solvent is a mixture of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether in a mass ratio of 2:3:40:25.

[0063] Solution B: 0.5 parts ammonium persulfate, 28 parts deionized water.

[0064] The preparation method is as follows: (1) The preparation method of solution A is as follows: i) Add N,N-methylenebisacrylamide, tris(2-hydroxyethyl)amine, and co-solvent to a 40% magnesium acrylate aqueous solution (containing 25 parts magnesium acrylate and 37.5 parts water) according to the formula, and stir at 300 rpm for 15 min until the system is homogeneous and transparent to obtain the first mixture. ii) Weigh glycidyl methacrylate and allyl alcohol glycidyl ether according to the ratio, put them into a constant pressure dropping funnel, and add them dropwise to the first mixture at a dropping rate of 1.0 mL / min. During the dropping process, turn on the high-speed stirrer at 900 rpm. iii) After the addition is complete, continue stirring at 900 rpm for 60 minutes until the system is homogeneous, without layering or visible oil droplets, and liquid A is obtained. Store in a sealed container.

[0065] (2) Preparation of solution B: Weigh ammonium persulfate and deionized water according to the ratio, add them to a container, stir at 200 rpm until the ammonium persulfate is completely dissolved, and obtain clear and transparent solution B. Seal and store in the dark.

[0066] Example 4 This embodiment provides a high-permeability acrylate grouting material and its preparation method.

[0067] The recipe is as follows: Solution A: 22 parts magnesium acrylate, 3 parts sodium acrylate, 1 part glycidyl methacrylate, 3 parts tri(2-hydroxyethyl)amine, 3 parts co-solvent, 5 parts polyethylene glycol diacrylate (average molecular weight approximately 400), and 37.5 parts deionized water; wherein, the co-solvent is a mixture of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether in a mass ratio of 4:4:42:20.

[0068] Solution B: 2 parts potassium persulfate, 40 parts deionized water.

[0069] The preparation method is as follows: (1) The preparation method of solution A is as follows: i) Add polyethylene glycol diacrylate, tris(2-hydroxyethyl)amine, and co-solvent to a 40% (w / w) acrylate aqueous solution (containing 22 parts magnesium acrylate, 3 parts sodium acrylate, and 37.5 parts water) according to the specified ratio. Stir at 300 rpm for 15 min until the system is homogeneous and transparent to obtain the first mixture. ii) Weigh glycidyl methacrylate according to the ratio, put it into a constant pressure dropping funnel, and add it dropwise to the first mixture at a dropping rate of 1.0 mL / min. During the dropping process, start a high-speed stirrer at 900 rpm. iii) After the addition is complete, continue stirring at 900 rpm for 60 minutes until the system is homogeneous, without layering or visible oil droplets, and liquid A is obtained. Store in a sealed container.

[0070] (2) Preparation of solution B: Weigh ammonium persulfate and deionized water according to the ratio, add them to a container, stir at 200 rpm until the ammonium persulfate is completely dissolved, and obtain clear and transparent solution B. Seal and store in the dark.

[0071] Comparative Example 1 The difference between this comparative example and Example 1 is that solution A in this comparative example does not contain glycidyl methacrylate, while the other conditions and preparation process are the same.

[0072] Comparative Example 2 The difference between this comparative example and Example 1 is that solution A in this comparative example does not contain tris(2-hydroxyethyl)amine.

[0073] Comparative Example 3 The difference between this comparative example and Example 1 is that the solution A in this comparative example does not contain a co-solvent, while the other conditions and preparation process are the same.

[0074] Comparative Example 4 This comparative example provides a traditional water glass-based grouting material. (1) Preparation of grouting fluid Solution A (water glass main agent): uses industrial-grade sodium silicate with a content of 70%.

[0075] Liquid B (curing agent): Mix water and water glass curing agent at a mass ratio of 20:50 and stir evenly to obtain a composite curing agent.

[0076] (2) Preparation of grouting fluid When using, mix liquid A and liquid B at a volume ratio of 4:1 and stir until homogeneous to obtain the water glass grouting solution.

[0077] Comparative Example 5 This comparative example provides a traditional ultrafine cement-based grouting material.

[0078] Prepare an ultrafine cement material with a water-cement ratio of 1:1. Weigh out the ultrafine silicate cement and water according to the ratio, add the water to the mixing container, and slowly add the ultrafine cement while stirring. Continue stirring to fully disperse the cement and obtain the ultrafine cement grout.

[0079] Test case The performance test results of the examples and comparative examples are summarized in Table 1.

[0080] Table 1 Test results of the examples and comparative examples

[0081] Note: In Table 1, the uniaxial compressive strength test of the consolidated body was performed by mixing liquid A and liquid B, then mixing the mixture with the dense, weak formation medium in a specific ratio, injecting it into a mold, curing it at room temperature to the specified age, and then determining the uniaxial compressive strength using a universal testing machine. Injectability was tested using the simulated porosity method: a dense, weak formation medium column model (Φ20mm×200mm) was prepared, and liquid A and liquid B were mixed evenly and immediately injected into the sand column model. The grouting pressure was controlled at 0.2MPa, and the penetration of the grout into the sand column was observed. In Comparative Example 2, due to the excessively long gelation time and low strength, it was difficult to determine the strength and impermeability coefficient parameters.

[0082] As can be seen from the performance comparison analysis in Table 1, in the field of dense and weak strata treatment, the grouting materials of Examples 1-4 of this invention have better applicability than those of Comparative Examples 1-5. They have advantages such as low viscosity, controllable gelation time, and good permeability to dense and weak strata media. Moreover, the uniaxial compressive strength of the consolidated body is higher than 2.5 MPa and the permeability coefficient is low, indicating that the consolidated body has good anti-seepage reinforcement performance.

[0083] Images of the injectability test of the grouting materials in Example 1, Comparative Example 4, and Comparative Example 5 are shown below. Figure 1 As shown, it can be seen that the material of Embodiment 1 of the present invention has strong applicability in dense and weak strata, no particulate or flocculent sedimentation, and good compatibility with dense and weak strata.

[0084] Grouting materials from Examples 1 and 4 were dripped onto the surface of compacted, dense, and weak strata (siltstone), and the contact angles from 0 s to 10 s were tested. Figure 2 As shown, the grouting material of Embodiment 1 of the present invention has stronger wettability.

[0085] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high-permeability grouting material modified based on the principle of hydrophobic association, characterized in that, Includes liquid A and liquid B; By mass fractions, solution A comprises: 20-30 parts of acrylate, 1-6 parts of hydrophobic associating monomer, 0.1-2.0 parts of hydrophobic associating promoter, 2-5 parts of cosolvent, 1-6 parts of crosslinking agent, and 30-40 parts of water; solution B comprises: 0.1-1.0 parts of initiator and 10-50 parts of water. The hydrophobic associating monomer is a glycidyl ether monomer and / or glycidyl ester monomer that simultaneously contains carbon-carbon double bonds and epoxy groups. The hydrophobic association promoter is tris(2-hydroxyethyl)amine; The cosolvents include polysorbate, fatty alcohol polyoxyethylene ether, isopropanol, and propylene glycol methyl ether.

2. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 1, characterized in that, The solute in the acrylate aqueous solution is one or more of the following: alkali metal salt of acrylic acid, alkaline earth metal salt of acrylic acid, alkali metal salt of methacrylic acid, and alkaline earth metal salt of methacrylic acid.

3. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 2, characterized in that, The acrylates include one or more of magnesium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, zinc acrylate, magnesium methacrylate, sodium methacrylate, zinc methacrylate, and calcium methacrylate.

4. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 1, characterized in that, The hydrophobic associating monomer is one or more of allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.

5. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 1, characterized in that, The mass ratio of polysorbate, fatty alcohol polyoxyethylene ether, isopropanol and propylene glycol methyl ether is (1.2~5): (1.2~5): (40~50): (10~30).

6. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 1, characterized in that, The crosslinking agent includes one or more of N,N-methylenebisacrylamide, polyethylene glycol diacrylate, and pentaerythritol diacrylate.

7. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 1, characterized in that, The initiator is an inorganic peroxide initiator.

8. The high-permeability grouting material modified based on the principle of hydrophobic association as described in claim 7, characterized in that, The initiator includes one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

9. The method for preparing a high-permeability grouting material modified based on the principle of hydrophobic association as described in any one of claims 1 to 8, characterized in that, Includes the following steps: The preparation method of solution A is as follows: add crosslinking agent, hydrophobic association promoter, cosolvent and hydrophobic association monomer to acrylate aqueous solution, and stir to obtain solution A; The preparation method of solution B is as follows: Dissolve the initiator in water to obtain solution B.

10. The application of the high-permeability grouting material modified based on the hydrophobic association principle as described in any one of claims 1 to 8, or the high-permeability grouting material modified based on the hydrophobic association principle prepared by the preparation method described in claim 9, characterized in that... Grouting treatment for tunnels and underground engineering.

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