Pumpable water-resistant anchoring agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of engineering materials, in particular to a pumpable water-resistant anchoring agent as well as a preparation method and application thereof. The anchoring agent is a two-component system, wherein a component A comprises a first sodium silicate solution, a second sodium silicate solution, a catalyst, a chain extender, a nano inorganic filler and a super-hydrophobic coupling agent; and the component B comprises an isocyanate substance, a plasticizer, hydrophobic isocyanate and polyether polyol. Hydrophobic components are introduced into a polyurethane curing network in a chemical bonding mode, a chemical crosslinking type water-resistant mechanism is constructed, and the long-term bonding strength retention rate and the impermeability of the anchoring agent in the underwater environment are remarkably improved by cooperating with the double effects of physical hole plugging and chemical hydrophobicity of the nanofiller subjected to hydrophobic modification. Meanwhile, by optimizing the component proportion and viscosity, the product has excellent pumpability, and is especially suitable for anchoring construction in wet or underwater environments such as deep tunnels and water conservancy projects.

Description

Technical Field

[0001] This invention relates to the field of engineering materials technology, and in particular to a pumpable water-resistant anchoring agent, its preparation method, and its application. Background Technology

[0002] In the field of engineering anchoring, polyurethane anchoring agents are widely used due to their advantages such as fast curing speed, high bonding strength, and resistance to chemical corrosion. As engineering construction expands into deeper, more humid environments, such as deep-buried tunnels, underwater tunnels, dam reinforcement in hydraulic engineering projects, and anchoring of damp rock slopes, higher requirements are placed on the water resistance performance of anchoring agents. In these scenarios, the anchoring agent is exposed to humid or underwater environments for extended periods, and its water resistance stability directly affects the safety and service life of the engineering structure.

[0003] However, traditional polyurethane anchoring agents have significant defects: (1) The urethane groups contained in the molecular structure are prone to hydrolysis reaction with water molecules, resulting in a significant decrease in bonding strength after long-term immersion. The bonding strength retention rate after 7 days underwater is usually less than 70%, which cannot meet the long-term anchoring requirements of humid environments; (2) Existing water-resistant modifications mostly involve adding hydrophobic nano-inorganic fillers (such as paraffin wax and silicone oil) in an attempt to form a physical covering layer on the surface of the anchoring agent to block water intrusion.

[0004] For two-component polyurethane anchors, typically only one component undergoes simple hydrophobic modification. This can easily lead to uneven distribution of hydrophobic segments after curing, resulting in weak water resistance in some areas and an inability to fully prevent moisture intrusion. Furthermore, the nano-inorganic fillers used in two-component polyurethane anchors are often ordinary nanomaterials that have not undergone hydrophobic modification, serving only a limited filling function. Because these nano-inorganic fillers cannot participate in curing and cross-linking, they are prone to detachment during construction or use, resulting in poor water resistance over time and reduced interfacial adhesion between the anchor and the substrate.

[0005] As engineering construction expands into deeper, more humid environments (such as deep-buried tunnels and underwater tunnels), the water resistance limitations of traditional polyurethane anchors are becoming increasingly apparent. For example, in the reinforcement of dams in water conservancy projects, the anchoring force of traditional polyurethane anchors decreases by more than 40% after being soaked underwater for three months, requiring frequent rework and maintenance. In the anchoring of damp rock slopes, due to insufficient water resistance, the anchor is easily affected by rainwater infiltration, leading to instability of the slope support structure and posing safety hazards.

[0006] In addition, traditional anchoring agents have not been optimized for pumpability requirements in terms of component ratio, viscosity and other performance parameters for large-scale and efficient construction projects, making it difficult to meet the construction efficiency requirements of deep and high-humidity engineering scenarios and lacking pumpability adaptability.

[0007] Therefore, developing a polyurethane anchoring agent that achieves synergistic enhancement of water resistance and anchoring performance through "crosslinking of hydrophobic components" has become the key to solving the anchoring problem in aquatic environments. Summary of the Invention

[0008] The technical problem this invention aims to solve is to overcome the shortcomings of existing technologies and provide a pumpable water-resistant anchoring agent, its preparation method, and its application. The pumpable water-resistant anchoring agent prepared by this invention constructs a "chemical cross-linking water-resistant" mechanism at the molecular design level, chemically bonding hydrophobic components to the polyurethane backbone, achieving deep binding between the hydrophobic components and the cured network. Combined with a two-component synergistic water-resistant design and the dual effects of "physical pore blocking + chemical hydrophobicity" from nano-inorganic fillers, it significantly improves the water-resistant performance and water-resistant duration of the anchoring agent while ensuring or even enhancing its anchoring performance. Furthermore, it makes the anchoring agent pumpable, adaptable to the construction and use needs of deep, high-humidity engineering scenarios, solving the problem of anchoring failure in aquatic environments, reducing rework and maintenance costs, and avoiding safety hazards.

[0009] The technical solution adopted by this invention to solve its technical problem is: A pumpable water-resistant anchoring agent, consisting of component A and component B, which are mixed in a 1:1 volume ratio before use; The A component, by mass, comprises: 50-80 parts of a first sodium silicate solution, 20-50 parts of a second sodium silicate solution, 0.3 parts of a catalyst, 5-10 parts of a chain extender, 3-5 parts of a nano-inorganic filler, and 2-4 parts of a superhydrophobic coupling agent. Component B, by mass, comprises: 90-110 parts isocyanate, 10-30 parts plasticizer, 3-8 parts hydrophobic isocyanate, and 2-6 parts polyether polyol. The mass ratio of hydrophobic isocyanate in component B to superhydrophobic coupling agent in component A is (1.2-2):1.

[0010] The total mass fraction of the first sodium silicate solution and the second sodium silicate solution is 100 parts.

[0011] Further, the first sodium silicate solution is a sodium silicate solution with a modulus of 2.1 to 2.8 and a Baume degree of 45 to 51°Bé; the second sodium silicate solution is a sodium silicate solution with a modulus of 2.8 to 3.5 and a Baume degree of 40 to 45°Bé.

[0012] The selected sodium silicate solution is a mixture of solutions with different Baume degrees and moduli. Baume degree and modulus are important properties of sodium silicate solutions. A higher modulus indicates a higher silica content and stronger adhesion, but it also makes the solution less soluble in water. Therefore, it is important to select an appropriate modulus range. Baume degree indicates the concentration of the solution; a higher concentration indicates a higher content of sodium silicate and silicates. By mixing sodium silicate solutions with different Baume degrees and moduli, the viscosity of component A can be controlled, resulting in a final anchoring agent with good pumpability and adhesion. Furthermore, in component A, the catalyst is selected from one or more of the following: a compound of organobismuth catalyst and organozinc catalyst, N,N-dimethylbenzylamine, tetramethyl-1,6-hexanediamine, dimethylaminoethoxyethanol, and tetramethyldipropylenetriamine; the role of the catalyst is to regulate the curing reaction rate after component A and component B are mixed, to ensure that curing is completed within a suitable time, and at the same time, without affecting the final performance of the anchoring agent. The chain extender is selected from one or more of glycerol, isophorone diamine, and methylallylpropanediamine. The chain extender can react with the isocyanate group of component B to increase the molecular chain length and improve the mechanical strength of the anchoring agent. The nano-inorganic filler is selected from one or more of alkyl-linked nano-silica, silane-modified nano-silica, hydrophobic nano-calcium carbonate, hydrophobic nano-zinc oxide, hydrophobic nano-titanium dioxide, hydrophobic nano-magnesium oxide, and hydrophobic carbon nanotubes. As a thixotropic agent, the nano-inorganic filler can impart good thixotropic properties to the anchoring agent, maintaining high viscosity when standing to prevent flow, and reducing viscosity during pumping and construction mixing to facilitate construction and ensure pumpability. At the same time, after hydrophobic modification, the nanomaterials can synergistically play multiple key roles of "waterproofing-reinforcement-toughening-adhesion" by constructing micro-nano composite hydrophobic structures in the polyurethane anchoring agent system, filling matrix voids, and achieving interfacial hydrophobic effects. It can not only significantly improve the material's bulk hydrophobicity, media resistance, and durability, but also effectively enhance mechanical strength and toughness. By repelling interfacial moisture, it ensures reliable anchoring on damp substrates, thereby comprehensively optimizing the overall performance and service life of the anchoring agent in harsh environments. The superhydrophobic coupling agent is selected from one or more of perfluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, hydroxyalkyl-terminated polydimethylsiloxane, and polydimethylsiloxane-diamino. This type of superhydrophobic coupling agent has a long-chain fluoroalkyl or silyl group (providing superhydrophobicity) at one end and an active functional group (such as -OH, -NH2) at the other end. It can react with isocyanate (-NCO) in component B and covalently link to the polyurethane molecular chain by forming chemical bonds (urethane bond, urea bond), introducing the hydrophobic segment into the system and making it part of the polymer backbone, thus achieving "anchored" hydrophobic function.

[0013] Furthermore, in component A, the nano-inorganic filler has a particle size of 20–50 nm and a contact angle ≥140°. The smaller particle size allows the nano-filler to be more uniformly dispersed in the polymer matrix, fully exerting its reinforcing effect and further improving the mechanical properties of the anchoring agent. The larger contact angle indicates that the filler surface has excellent superhydrophobicity, which better prevents moisture from contacting the filler, thereby effectively improving the water resistance of the anchoring agent and ensuring the reliability of the anchoring structure in humid environments.

[0014] Furthermore, in component B, the isocyanate is selected from one or more of triphenylmethane triisocyanate, trimer isocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate; the isocyanate contains active -NCO groups, which can crosslink with the catalyst, chain extender, and inorganic filler in component A to form a polyurethane network.

[0015] The plasticizer is selected from one or more of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dioctyl phthalate, and tributyl citrate; the plasticizer can improve the processing performance and flexibility of the anchoring agent, reduce the brittleness after curing, and adjust the viscosity of component B to meet pumpable requirements. The hydrophobic isocyanate is selected from one or more of octadecyl isocyanate, 4-(trifluoromethyl)benzyl isocyanate, 4-trifluoromethylphenyl isocyanate, and 2,4-difluorophenyl isocyanate. The hydrophobic isocyanate contains both hydrophobic functional groups and active -NCO groups, which can crosslink with the catalyst, chain extender and inorganic filler in component A to form a polyurethane network. At the same time, the hydrophobic functional group at the other end is also embedded in the polyurethane network, thus simultaneously realizing the formation of the anchoring agent crosslinking network and hydrophobic modification. The polyether polyol is selected from one or more of DL1000D, DL2000D, and silane-modified polyether polyol; as an important raw material for polyurethane synthesis, the polyether polyol reacts with isocyanate substances to form a polyurethane backbone, which affects the mechanical properties and curing speed of the anchoring agent.

[0016] The pumpable water-resistant anchoring agent provided by this invention possesses superior water-resistant properties due to its multi-level, synergistic water-resistant design from the molecular to the macroscopic level. Its water-resistant mechanism does not rely on a single physical barrier, but rather achieves simultaneous improvement in both water-resistant and anchoring performance through the combined action of three mechanisms: "chemical cross-linking anchoring hydrophobicity," "two-component synergistic hydrophobicity," and "nanofiller dual hydrophobicity."

[0017] First, the core mechanism of this invention is to use chemical crosslinking anchoring at the molecular level for hydrophobic design, aiming to solve the problem of easy migration and loss of traditional physical blending hydrophobic agents leading to the degradation of water resistance. It mainly includes: (1) bonding of superhydrophobic coupling agents: the superhydrophobic coupling agents contained in component A (such as hydroxyl-alkyl double-terminated polydimethylsiloxane, etc.) carry polysiloxane chains or long-chain fluoroalkyl groups at one end, providing extremely low surface energy and high hydrophobicity; the other end carries active functional groups (-OH, -NH2); after components A and B are mixed, these active ends can react chemically with the isocyanate groups (-NCO) in component B to form stable urethane bonds or urea bonds; through this chemical bonding method, the superhydrophobic segments are permanently and irreversibly anchored on the main chain of the polyurethane curing network, becoming part of the polymer skeleton; this realizes the "in-situ immobilization" of hydrophobic components, avoiding the decline in water resistance caused by molecular migration or leaching, thereby significantly improving the long-term effectiveness and durability of water resistance; (2) Introduction of hydrophobic isocyanates: The hydrophobic isocyanates selected in component B (such as octadecyl isocyanate, fluorinated phenyl isocyanate, etc.) have strong hydrophobic functional groups such as long alkyl chains and fluorine atoms in their molecular structure. When participating in the formation of polyurethane crosslinking network, these hydrophobic functional groups are directly embedded into the network structure, giving the entire curing system intrinsic hydrophobic properties from the molecular source.

[0018] Secondly, a two-component synergistic water-resistant design was implemented at the component level. Components A and B, while achieving rapid curing and providing anchoring force, inherently constitute a synergistic water-resistant system through their raw material selection. Component A: Based on a high-modulus, high-Baume-degree sodium silicate mixed solution, it forms an inorganic framework with certain water resistance after curing. Component B: As mentioned above, the polyurethane organic phase generated by the reaction of hydrophobic isocyanate and polyether polyol constitutes a hydrophobic polymer matrix. Synergistic effect: The final cured product forms an interpenetrating or hybrid "inorganic-organic" network structure. The continuous distribution of the hydrophobic polyurethane phase effectively encapsulates and shields the relatively hydrophilic silicate phase, preventing water erosion of the inorganic phase, achieving complementary advantages and synergistic effects between the organic and inorganic phases in terms of water resistance.

[0019] Finally, at the microstructural level, hydrophobically modified nano-inorganic fillers are used to achieve a dual mechanism of physical pore blocking and chemical hydrophobicity. Physical pore blocking and micro / nanostructure construction: The hydrophobically modified nano-inorganic fillers can be uniformly dispersed in the polyurethane system. Their nanoscale particles can effectively fill microscopic defects and pores in the polyurethane / silicate matrix, significantly reducing the channels for water penetration. Simultaneously, these nanoparticles construct a micro-nano composite rough structure on the matrix surface and inside. This structure can trap air, greatly reducing the actual contact area between water droplets and the solid surface, thus exhibiting a superhydrophobic effect and greatly improving the material's static water resistance. Interfacial hydrophobicity and chemical hydrophobicity: The nanofillers themselves are hydrophobically treated, and their surfaces are rich in hydrophobic groups. When they are distributed at the interface between the cured system and the external environment, they can form a hydrophobic barrier, effectively repelling interfacial moisture and preventing water molecules from penetrating along the interface, ensuring the reliability of anchoring on damp substrates. This interfacial hydrophobicity, combined with the chemical hydrophobicity of the filler itself, jointly enhances the system's anti-permeability performance.

[0020] In summary, this invention permanently anchors the superhydrophobic component to the polymer backbone through molecular-level chemical bonding, laying the foundation for long-term water resistance; achieves synergistic hydrophobicity between the organic and inorganic phases through component-level raw material design; and constructs a dense and hydrophobic microstructure through nanoscale physical filling and interface modification. These three interconnected and mutually reinforcing mechanisms not only endow the anchoring agent with excellent immediate water resistance but also ensure its durability in long-term aquatic environments. Furthermore, the reinforcing and toughening effect of the nanofillers ensures that the anchoring force remains unaffected or even improved, ultimately successfully solving the technical challenge of anchoring failure in aquatic environments.

[0021] A method for preparing the above-mentioned pumpable water-resistant anchoring agent specifically includes the following steps: Step S1: Preparation of component A: Weigh the materials according to the ratio, and add the first sodium silicate solution, the second sodium silicate solution, the catalyst, the chain extender, the nano-inorganic filler, and the superhydrophobic coupling agent into the stirring equipment in sequence. Stir and mix evenly to obtain component A. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add the isocyanate, plasticizer, and polyether polyol to another stirring device, and stir evenly to obtain Component B.

[0022] Anchoring agent application: Mix component A and component B at a volume ratio of 1:1 until homogeneous, and then use a pumping device to deliver the mixture to the required anchoring location.

[0023] When components A and B are mixed and cured in this ratio, the hydrophobic segments (long-chain fluoroalkyl or silane groups of the superhydrophobic coupling agent in component A and long alkyl chains, fluorine atoms, and other hydrophobic functional groups in the hydrophobic isocyanate of component B) can be uniformly distributed in the polyurethane (anchoring agent) curing network, ensuring water resistance uniformity. The nano-inorganic fillers (such as nano-silica, nano-calcium carbonate, and nano-zinc oxide) in component A need to be hydrophobically treated. The contact angle of the nano-inorganic fillers is ≥140°, and the particle size of the nano-inorganic fillers is 20-50nm. These parameters ensure that the nano-inorganic fillers can both refine the internal pores of the polyurethane through the nano-filling effect and reduce water adsorption through the hydrophobic surface, achieving a dual water-resistant effect of "physical pore blocking + chemical hydrophobicity".

[0024] Furthermore, the stirring speed of component A in step S1 is greater than that of component B in step S2. Component A contains various solid powders (nano-inorganic fillers) and liquids, requiring a higher stirring speed to achieve sufficient dispersion and uniform mixing. The stirring speed of component B is lower than that of component A because isocyanates are highly reactive, and a lower stirring speed reduces contact with air, avoids premature side reactions, and ensures the stability of component B.

[0025] Furthermore, in step S1, the stirring speed of component A is 280–620 rpm / min, and the stirring time is 28–62 min. This stirring speed and time can ensure that each component is evenly dispersed, avoid local performance differences caused by uneven mixing, and prevent excessive stirring from introducing too many air bubbles that affect the performance of the anchoring agent. In step S2, the stirring speed of component B is 90–320 rpm / min, and the stirring time is 28–62 min.

[0026] Further, in step S1, the stirring speed of component A is 300-600 rpm / min, and the stirring time is 30-60 min; in step S2, the stirring speed of component B is 100-300 rpm / min, and the stirring time is 30-60 min.

[0027] An application of the pumpable water-resistant anchoring agent as described above, wherein the anchoring agent is used in deep-buried tunnels, underwater tunnels, water conservancy projects or wet rock slope anchoring projects.

[0028] The beneficial effects of this invention are as follows: This invention has a reasonable design and a simple preparation method, and has the following advantages: (1) Significantly improved water resistance and long-lasting effect: The pumpable water-resistant anchoring agent prepared by this invention breaks through the limitations of traditional "passive waterproofing". Through the "chemical cross-linking water resistance" mechanism, the hydrophobic components (long-chain fluoroalkyl or silane of the superhydrophobic coupling agent in component A and long alkyl chain, fluorine atom and other hydrophobic functional groups in the hydrophobic isocyanate of component B) are chemically bonded to the polyurethane main chain (anchoring agent). Combined with the dual effect of the two-component synergistic water resistance and the "physical pore blocking + chemical hydrophobicity" of the nanofiller, the strength retention rate of the anchoring agent after 7 days in a 60℃ water bath is ≥90%, and the water absorption rate after 24 hours is ≤1.2%. This solves the problem of poor water resistance and short-lasting effect caused by hydrolysis of traditional anchoring agents. It can meet the long-term anchoring requirements in humid environments. For example, in the reinforcement of dikes in water conservancy projects, the decrease in anchoring force after long-term underwater immersion is greatly reduced, reducing rework and maintenance costs. (2) Water-resistant modification without sacrificing and improving anchoring performance: Abandoning the defects of traditional water-resistant modification that easily reduces strength, by using reactive hydrophobic components (superhydrophobic coupling agent and hydrophobic isocyanate) and nano-inorganic fillers in synergistic design, the 7d bonding strength of the anchor is guaranteed to be ≥4MPa and the compressive strength is ≥58MPa. Moreover, the superhydrophobic coupling agent improves the interface bonding between polyurethane and the substrate (concrete / rock layer), so that the interface bonding strength in humid environment is 30-40% higher than that of ordinary anchors, realizing the synergistic optimization of "water-resistant and mechanical" performance; (3) Good water resistance uniformity: In view of the two-component characteristics of polyurethane, complementary hydrophobic components are introduced into components A and B respectively, and the mass ratio of hydrophobic isocyanate in component B to superhydrophobic coupling agent in component A is limited to (1.2~2):1, to ensure that the hydrophobic segments are evenly distributed during mixed curing, avoiding the problem of uneven water resistance caused by single component modification, and fully resisting water intrusion. (4) Adapting to engineering construction requirements: This invention optimizes the selection and ratio of raw materials for components A and B, such as by rationally selecting thixotropic agents and plasticizers to adjust viscosity, so that the anchoring agent has the characteristic of being "pumpable". The viscosity of component A (25℃) is 200-300 mPa. The viscosity (25℃) of component B is 100–200 mPa. s, adapted to large-scale and efficient construction projects, especially suitable for deep and high-humidity engineering scenarios (such as deep-buried tunnels and water conservancy dams), improves industrialization and application adaptability, and avoids safety hazards such as slope instability. Attached Figure Description

[0029] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0030] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0031] Figure 1 These are contact angle diagrams of the anchoring agents prepared in Example 1 and Comparative Example 1, where a represents Example 1 and b represents Comparative Example 1. Figure 2 Here is a scanning electron microscope image of the anchoring agent prepared in Example 1; Figure 3 These are underwater 7-day compressive strength diagrams of the anchoring agents prepared in Examples 1 to 4; Figure 4 These are SEM images of the anchoring interface between Example 1 and Comparative Example 5 and coal / rock in a still water environment, where a is Example 1 and b is Comparative Example 5. Detailed Implementation

[0032] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. 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 application pertains.

[0033] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0034] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] In a first aspect, the present invention provides a pumpable water-resistant anchoring agent, which is composed of component A and component B, and is mixed in a volume ratio of 1:1 when used. Component A, by mass, includes: 50-80 parts of first sodium silicate solution, 20-50 parts of second sodium silicate solution, 0.3 parts of catalyst, 5-10 parts of chain extender, 3-5 parts of nano-inorganic filler, and 2-4 parts of superhydrophobic coupling agent. Component B, by mass, includes: 90-110 parts of isocyanate, 10-30 parts of plasticizer, 3-8 parts of hydrophobic isocyanate, and 2-6 parts of polyether polyol. The mass ratio of hydrophobic isocyanate in component B to superhydrophobic coupling agent in component A is (1.2-2):1.

[0036] This anchoring agent achieves a balance between water resistance and pumpability, and the limited volume ratio of 1:1 ensures that the two components can be mixed in a reasonable proportion and cured properly during on-site construction.

[0037] The first sodium silicate solution is a sodium silicate solution with a modulus of 2.1 to 2.8 and a Baume degree of 45 to 51°Bé; the second sodium silicate solution is a sodium silicate solution with a modulus of 2.8 to 3.5 and a Baume degree of 40 to 45°Bé.

[0038] In component A, the catalyst is selected from one or more of the following: a compound of organobismuth catalyst and organozinc catalyst, N,N-dimethylbenzylamine, tetramethyl-1,6-hexanediamine, dimethylaminoethoxyethanol, and tetramethyldipropylenetriamine; the chain extender is selected from one or more of the following: glycerol, isophorone diamine, and methylallylpropanediamine; the nano-inorganic filler is selected from one or more of the following: alkyl-linked nano-silica, silane-modified nano-silica, hydrophobic nano-calcium carbonate, hydrophobic nano-zinc oxide, hydrophobic nano-titanium dioxide, hydrophobic nano-magnesium oxide, and hydrophobic carbon nanotubes; and the superhydrophobic coupling agent is selected from one or more of the following: perfluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, hydroxyalkyl-terminated polydimethylsiloxane, and polydimethylsiloxane-diamino.

[0039] In component A above, the nano-inorganic filler has a particle size of 20–50 nm and a contact angle ≥140°.

[0040] In component B, the isocyanate is selected from one or more of triphenylmethane triisocyanate, trimer isocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate; the plasticizer is selected from one or more of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dioctyl phthalate, and tributyl citrate; the hydrophobic isocyanate is selected from one or more of octadecyl isocyanate, 4-(trifluoromethyl)benzyl isocyanate, 4-trifluoromethylbenzene isocyanate, and 2,4-difluorophenyl isocyanate; and the polyether polyol is selected from one or more of DL1000D, DL2000D, and silane-modified polyether polyol.

[0041] Secondly, the present invention provides a method for preparing the above-mentioned pumpable water-resistant anchoring agent, specifically including the following steps: Step S1: Preparation of component A: Weigh the materials according to the ratio, and add the first sodium silicate solution, the second sodium silicate solution, the catalyst, the chain extender, the nano-inorganic filler, and the superhydrophobic coupling agent into the stirring equipment in sequence. Stir and mix evenly to obtain component A. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add the isocyanate, plasticizer, and polyether polyol to another stirring device, and stir evenly to obtain Component B.

[0042] This invention abandons the complex multi-step prepolymerization process of traditional polyurethane anchoring agents and adopts a one-step mechanical blending process, which is simple, stable and easy to industrialize.

[0043] In step S1, the stirring speed of component A is greater than that of component B in step S2.

[0044] In step S1, the stirring speed of component A is 280–620 rpm / min, and the stirring time is 28–62 min; in step S2, the stirring speed of component B is 90–320 rpm / min, and the stirring time is 28–62 min.

[0045] Preferably, in step S1, the stirring speed of component A is 300-600 rpm / min and the stirring time is 30-60 min; in step S2, the stirring speed of component B is 100-300 rpm / min and the stirring time is 30-60 min.

[0046] Thirdly, this invention provides applications of the aforementioned pumpable, water-resistant anchoring agent. Specifically, this anchoring agent is used in deep-buried tunnels, underwater tunnels, hydraulic engineering projects, or anchoring projects on damp rock slopes. These engineering environments are typically characterized by high humidity and water pressure, placing extremely high demands on the water resistance and long-term stability of the anchoring agent. This anchoring agent, with its excellent water resistance, good mechanical properties, and pumpability, can well adapt to these harsh environments, effectively solving the problem of traditional anchoring agents easily failing in humid or underwater environments. It provides reliable anchoring protection for these important projects, ensuring the safety and stability of the engineering structure.

[0047] Example 1 The pumpable water-resistant anchoring agent of this embodiment is composed of component A and component B. When using it, component A and component B are mixed evenly in a 1:1 ratio and then transported to the anchoring site using a pumping device. Component A: 50 parts of primary sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of secondary sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), 5 parts of glycerol, 3 parts of alkyl-linked nano-silica (contact angle 142°, particle size 20nm), and 2 parts of perfluorooctyltriethoxysilane; Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, 3 parts octadecyl isocyanate, and 2 parts DL1000D polyether polyol.

[0048] The preparation method of the above-mentioned pumpable water-resistant anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organobismuth catalyst DY-20 and the organozinc catalyst DY-5350, glycerol, alkyl-linked nano-silica, and perfluorooctyltriethoxysilane are sequentially added to a stirring device. The stirring speed is 300 rpm / min and the stirring time is 60 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, octadecyl isocyanate, diethylene glycol ethyl ether acetate, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, and stir until uniform to obtain Component B.

[0049] Example 2 The pumpable water-resistant anchoring agent of this embodiment is composed of component A and component B. When using it, component A and component B are mixed evenly in a 1:1 ratio and then transported to the anchoring site using a pumping device. Component A: 65 parts of first sodium silicate solution (modulus 2.5, Baume degree 48°Bé), 35 parts of second sodium silicate solution (modulus 3.2, Baume degree 43°Bé), 0.3 parts of N,N-dimethylbenzylamine, 8 parts of isophorone diamine, 4 parts of silane-modified nano-silica (contact angle 145°, particle size 35nm), and 3 parts of heptadecafluorodecyltriethoxysilane; Component B: 100 parts of trimer isocyanate, 5 parts of 4-(trifluoromethyl)benzyl isocyanate, 20 parts of dioctyl phthalate, and 3 parts of DL2000D polyether polyol.

[0050] The preparation method of the above-mentioned pumpable water-resistant anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, N,N-dimethylbenzylamine, isophorone diamine, silane-modified nano silica, and heptadecafluorodecyltriethoxysilane are added sequentially to a stirring device. The stirring speed is 450 rpm / min and the stirring time is 45 min. The mixture is stirred until homogeneous to obtain component A. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add the trimer isocyanate, 4-(trifluoromethyl)benzyl isocyanate, dioctyl phthalate, and DL2000D polyether polyol to another stirring device, stir at 200 rpm / min for 45 min, stir until uniform, and then obtain Component B.

[0051] Example 3 The pumpable water-resistant anchoring agent of this embodiment is composed of component A and component B. When using it, component A and component B are mixed evenly in a 1:1 ratio and then transported to the anchoring site using a pumping device. Component A: 80 parts of primary sodium silicate solution (modulus 2.8, Baume degree 51°Bé), 20 parts of secondary sodium silicate solution (modulus 3.5, Baume degree 45°Bé), 0.3 parts of tetramethyl-1,6-hexanediamine, 10 parts of methylallylpropanediamine, 5 parts of hydrophobic carbon nanotubes (contact angle 148°, particle size 50nm), and 4 parts of hydroxyalkyl-terminated polydimethylsiloxane. Component B: 110 parts of triphenylmethane triisocyanate, 8 parts of 2,4-difluorophenyl isocyanate, 30 parts of tributyl citrate, and 4 parts of silane-modified polyether polyol.

[0052] The preparation method of the above-mentioned pumpable water-resistant anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, tetramethyl 1,6-hexanediamine, methylallylpropanediamine, hydrophobic carbon nanotubes, and hydroxyalkyl double-terminated polydimethylsiloxane are sequentially added to a stirring device. The stirring speed is 600 rpm / min and the stirring time is 30 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, 2,4-difluorophenyl isocyanate, tributyl citrate, and silane-modified polyether polyol to another stirring device, stir at 300 rpm / min for 30 min, stir until uniform, and then obtain Component B.

[0053] Example 4 The pumpable water-resistant anchoring agent of this embodiment is composed of component A and component B. When using it, component A and component B are mixed evenly in a 1:1 ratio and then transported to the anchoring site using a pumping device. Component A: 80 parts of primary sodium silicate solution (modulus 2.8, Baume degree 51°Bé), 20 parts of secondary sodium silicate solution (modulus 3.5, Baume degree 45°Bé), 0.3 parts of tetramethyl-1,6-hexanediamine, 10 parts of methylallylpropanediamine, 5 parts of hydrophobic carbon nanotubes (contact angle 148°, particle size 50nm), and 4 parts of polydimethylsiloxane-diamino. Component B: 100 parts of trimer isocyanate, 8 parts of diphenylmethane diisocyanate, 30 parts of dioctyl phthalate, and 4 parts of silane-modified polyether polyol.

[0054] The preparation method of the above-mentioned pumpable water-resistant anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, tetramethyl 1,6-hexanediamine, methylallylpropanediamine, hydrophobic carbon nanotubes, and polydimethylsiloxane-diamino were sequentially added to a stirring device. The stirring speed was 600 rpm / min and the stirring time was 30 min. After stirring and mixing evenly, component A was obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add the trimer isocyanate, diphenylmethane diisocyanate, dioctyl phthalate and silane-modified polyether polyol to another stirring device, stir at 300 rpm / min for 30 min, stir until uniform, and then obtain Component B.

[0055] Comparative Example 1 The anchoring agent in this comparative example includes: Component A: 50 parts of first sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of second sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), and 5 parts of glycerol; Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, and 2 parts DL1000D polyether polyol.

[0056] The preparation method of the above-mentioned anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organobismuth catalyst DY-20 and the organozinc catalyst DY-5350, and glycerol are added sequentially to a stirring device. The stirring speed is 300 rpm / min and the stirring time is 60 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, diethylene glycol ethyl ether acetate, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, stir until uniform, and then obtain Component B.

[0057] Comparative Example 2 The anchoring agent in this comparative example includes: Component A: 50 parts of first sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of second sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), 5 parts of glycerol, and 3 parts of alkyl-linked nano-silica (contact angle 142°, particle size 20nm); Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, 3 parts octadecyl isocyanate, and 2 parts DL1000D polyether polyol.

[0058] The preparation method of the above-mentioned anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organobismuth catalyst DY-20 and the organozinc catalyst DY-5350, glycerol, and alkyl-linked nano-silica were sequentially added to a stirring device. The stirring speed was 300 rpm / min and the stirring time was 60 min. After stirring and mixing evenly, component A was obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, diethylene glycol ethyl ether acetate, octadecyl isocyanate, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, stir until uniform, and then obtain Component B.

[0059] Comparative Example 3 The anchoring agent in this comparative example includes: Component A: 50 parts of primary sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of secondary sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), 5 parts of glycerol, and 2 parts of perfluorooctyltriethoxysilane; Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, 3 parts octadecyl isocyanate, and 2 parts DL1000D polyether polyol.

[0060] The preparation method of the above-mentioned anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organobismuth catalyst DY-20 and the organozinc catalyst DY-5350, glycerol, and perfluorooctyltriethoxysilane are sequentially added to a stirring device. The stirring speed is 300 rpm / min and the stirring time is 60 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, diethylene glycol ethyl ether acetate, octadecyl isocyanate, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, stir until uniform, and then obtain Component B.

[0061] Comparative Example 4 The anchoring agent in this comparative example includes: Component A: 50 parts of primary sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of secondary sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), 5 parts of glycerol, 3 parts of alkyl-linked nano-silica (contact angle 142°, particle size 20nm), and 2 parts of perfluorooctyltriethoxysilane; Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, and 2 parts DL1000D polyether polyol.

[0062] The preparation method of the above-mentioned anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organobismuth catalyst DY-20 and the organozinc catalyst DY-5350, glycerol, alkyl-linked nano-silica, and perfluorooctyltriethoxysilane are sequentially added to a stirring device. The stirring speed is 300 rpm / min and the stirring time is 60 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, diethylene glycol ethyl ether acetate, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, stir until uniform, and then obtain Component B.

[0063] Comparative Example 5 (Physical Blending Comparison) This comparative example is used to verify the performance difference between physically blended hydrophobic agents and the chemically bonded hydrophobic design of this invention.

[0064] The anchoring agent in this comparative example includes: Component A: 50 parts of first sodium silicate solution (modulus 2.1, Baume degree 45°Bé), 50 parts of second sodium silicate solution (modulus 2.8, Baume degree 40°Bé), 0.3 parts of organobismuth catalyst DY-20 and organozinc catalyst DY-5350 (combination ratio 1:10), 5 parts of glycerol, 3 parts of alkyl-linked nano-silica (contact angle 142°, particle size 20nm), and 2 parts of paraffin powder (as a non-reactive physical hydrophobic agent); Component B: 90 parts triphenylmethane triisocyanate, 10 parts diethylene glycol ethyl ether acetate, 3 parts liquid paraffin (as a non-reactive physical hydrophobic agent), and 2 parts DL1000D polyether polyol.

[0065] The preparation method of the above-mentioned anchoring agent specifically includes the following steps: Step S1: Preparation of component A: The first sodium silicate solution, the second sodium silicate solution, the organic bismuth catalyst DY-20 and the organic zinc catalyst DY-5350, glycerol, alkyl-linked nano-silica, and paraffin powder are sequentially added to a stirring device. The stirring speed is 300 rpm / min and the stirring time is 60 min. After stirring and mixing evenly, component A is obtained. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add triphenylmethane triisocyanate, diethylene glycol ethyl ether acetate, liquid paraffin, and DL1000D polyether polyol to another stirring device, stir at 100 rpm / min for 60 min, stir until uniform, and then obtain Component B.

[0066] Test case The anchoring agents prepared in Examples 1 to 4 were subjected to compressive strength tests, and the results are shown in Table 1.

[0067] Table 1. Test results of the anchoring agents prepared in Examples 1 to 4

[0068] The anchoring agents prepared in Comparative Examples 1 to 5 were subjected to compressive strength tests, and the results are shown in Table 2.

[0069] Table 2. Test results of the anchoring agents prepared in Comparative Examples 1 to 5.

[0070] As shown in Tables 1 and 2, Examples 1-4 are significantly superior to Comparative Examples 1-5 in all key performance indicators. Specifically: (1) Synergistic water resistance effect: Examples 1-4 showed the highest underwater 7-day bonding strength and compressive strength (e.g. Figure 3As shown in the figure, after accelerated aging in 60℃ warm water, the strength retention rate remained above 90%, which is much higher than all comparative examples; this fully demonstrates the long-lasting water resistance brought about by the "chemical cross-linking anchored hydrophobic" mechanism. (2) Advantages of chemical bonding: The properties of Comparative Example 5 (physically blended hydrophobic agent), especially its long-term water resistance (strength retention rate of only 58%) and water absorption rate (4.2%), were the worst among all samples. This directly indicates that physically blended hydrophobic agents are unstable in the solidified network and are prone to migration and loss. Not only can they not provide long-term protection, but they may also damage the integrity of the material structure, thus proving the necessity and superiority of the chemically bonded hydrophobic design adopted in this invention.

[0071] (3) Component integrity: The performance of Comparative Example 2 (lacking superhydrophobic coupling agent) and Comparative Example 4 (lacking hydrophobic isocyanate) is between that of the Example and the conventional comparative example, indicating that the hydrophobic components in components A and B are indispensable. Together they constitute a two-component synergistic water-resistant system. The absence of either component will lead to a decrease in water resistance.

[0072] In addition, the present invention controls the viscosity of component A to 350~390 mPa·s (Examples 1~Examples 4) through component ratio and thixotropic effect of nanofiller. This viscosity range ensures that it is resistant to flow when stationary and decreases in viscosity under pumping shear force, thereby realizing long-distance and high-efficiency pumping construction in complex engineering environments.

[0073] Figure 1 These are contact angle diagrams of the anchoring agents prepared in Example 1 and Comparative Example 1, where a represents Example 1 and b represents Comparative Example 1. Figure 1 As shown, the anchoring agent prepared by this invention has a surface contact angle as high as 137.9°, demonstrating its excellent superhydrophobic properties. This property stems from successful chemical hydrophobic modification, and it is precisely this dense hydrophobic network structure (such as...) Figure 2 As shown in Table 1, this effectively prevents the intrusion and erosion of water molecules, thus ensuring that the material can still maintain a high compressive strength of 59 MPa after 7 days underwater (see Table 1), achieving a synergistic improvement in water resistance and mechanical properties.

[0074] Figure 4 SEM images of the anchoring interface between Example 1 (a) and Comparative Example 5 (b) and coal / rock in a still water environment. Figure 4 As shown, Example 1 exhibits a dense morphology, indicating good bonding between the anchoring agent and the coal-rock interface; while Comparative Example 5 shows pores and interface gaps caused by the detachment of the hydrophobic agent. This provides a direct visual demonstration of the difference between "chemical bonding" and "physical blending" from a microscopic morphological perspective.

[0075] Application Example 1: Anchor Bolt Support for Water Inrush Sections in Deeply Buried Tunnels Application Scenario Description: During the excavation of a deep-buried tunnel, a water-rich fault zone was encountered. The rock mass was fractured, with continuous water inflow and significant seepage within the borehole, with a water pressure of approximately 0.3 MPa. The pumpable water-resistant anchoring agent of this invention (Formula of Example 1) was used for system anchor bolt support.

[0076] Construction process: First, a drilling rig is used to drill a hole with a diameter of 28mm. After the hole is drilled, a hollow grouting anchor cable with a diameter of 22mm is inserted into the hole. After the hollow grouting anchor cable is in place, a two-component grouting pump is used to pump components A and B in a volume ratio of 1:1.

[0077] Application performance data: (1) Pumpability: Components A and B are pumped smoothly without clogging. The slurry after mixing has good thixotropy and does not flow in vertical orifices; (2) Curing performance: The slurry solidifies within 3 to 5 minutes in continuously seeping holes; (3) Anchoring performance: Pull-out test is conducted 1 day after anchor installation; the anchoring force of a single anchor reaches 225 kN, which meets the design requirement of 200 kN; (4) Long-term stability: After 6 months of monitoring, the support structure is stable and there are no signs of loosening or corrosion of the anchor rods, indicating that the anchoring agent maintains excellent anchoring performance and sealing performance in a long-term high-humidity environment.

[0078] In summary, this invention introduces hydrophobic components into the polyurethane curing network via chemical bonding, constructing a "chemically cross-linked water-resistant" mechanism. This, combined with the "physical pore-blocking + chemical hydrophobicity" dual effect of hydrophobically modified nanofillers, significantly improves the long-term bond strength retention and impermeability of the anchoring agent in underwater environments. Furthermore, by optimizing the component ratio and viscosity, the product exhibits excellent pumpability, making it particularly suitable for anchoring construction in humid or underwater environments such as deep-buried tunnels and hydraulic engineering projects.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A pumpable, water-resistant anchoring agent, characterized in that: It consists of component A and component B, which should be mixed in a 1:1 volume ratio before use. The A component, by mass, comprises: 50-80 parts of a first sodium silicate solution, 20-50 parts of a second sodium silicate solution, 0.3 parts of a catalyst, 5-10 parts of a chain extender, 3-5 parts of a nano-inorganic filler, and 2-4 parts of a superhydrophobic coupling agent. Component B, by mass, comprises: 90-110 parts isocyanate, 10-30 parts plasticizer, 3-8 parts hydrophobic isocyanate, and 2-6 parts polyether polyol. The mass ratio of hydrophobic isocyanate in component B to superhydrophobic coupling agent in component A is (1.2-2):

1.

2. The pumpable water-resistant anchoring agent according to claim 1, characterized in that: In component A, the first sodium silicate solution is a sodium silicate solution with a modulus of 2.1 to 2.8 and a Baume degree of 45 to 51°Bé. The second sodium silicate solution is a sodium silicate solution with a modulus of 2.8 to 3.5 and a Baume degree of 40 to 45°Bé.

3. The pumpable water-resistant anchoring agent according to claim 1, characterized in that: In component A, the catalyst is selected from one or more of the following: a complex of organobismuth catalyst and organozinc catalyst, N,N-dimethylbenzylamine, tetramethyl-1,6-hexanediamine, dimethylaminoethoxyethanol, and tetramethyldipropylenetriamine. The chain extender is selected from one or more of glycerol, isophorone diamine, and allyl propylene diamine; The nano-inorganic filler is selected from one or more of the following: alkyl-linked nano-silica, silane-modified nano-silica, hydrophobic nano-calcium carbonate, hydrophobic nano-zinc oxide, hydrophobic nano-titanium dioxide, hydrophobic nano-magnesium oxide, and hydrophobic carbon nanotubes. The superhydrophobic coupling agent is selected from one or more of perfluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, hydroxyalkyl-terminated polydimethylsiloxane, and polydimethylsiloxane-diamino.

4. The pumpable water-resistant anchoring agent according to claim 3, characterized in that: In component A, the nano-inorganic filler has a particle size of 20–50 nm and a contact angle ≥140°.

5. The pumpable water-resistant anchoring agent according to claim 1, characterized in that: In component B, the isocyanate is selected from one or more of triphenylmethane triisocyanate, trimer isocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate; The plasticizer is selected from one or more of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dioctyl phthalate, and tributyl citrate; The hydrophobic isocyanate is selected from one or more of octadecyl isocyanate, 4-(trifluoromethyl)benzyl isocyanate, 4-trifluoromethylphenyl isocyanate, and 2,4-difluorophenyl isocyanate; The polyether polyol is selected from one or more of DL1000D, DL2000D, and silane-modified polyether polyols.

6. A method for preparing a pumpable water-resistant anchoring agent as described in any one of claims 1 to 5, characterized in that: Specifically, the steps include the following: Step S1: Preparation of component A: Weigh the materials according to the ratio, and add the first sodium silicate solution, the second sodium silicate solution, the catalyst, the chain extender, the nano-inorganic filler, and the superhydrophobic coupling agent into the stirring device in sequence. Stir and mix evenly to obtain component A. Step S2: Preparation of Component B: Weigh the materials according to the ratio, add the isocyanate, plasticizer, and polyether polyol to another stirring device, and stir evenly to obtain Component B.

7. The method for preparing a pumpable water-resistant anchoring agent according to claim 5, characterized in that: In step S1, the stirring speed of component A is greater than that of component B in step S2.

8. The method for preparing a pumpable water-resistant anchoring agent according to claim 7, characterized in that: In step S1, the stirring speed of component A is 280-620 rpm / min, and the stirring time is 28-62 min. In step S2, the stirring speed of component B is 90–320 rpm / min, and the stirring time is 28–62 min.

9. The method for preparing a pumpable water-resistant anchoring agent according to claim 8, characterized in that: In step S1, the stirring speed of component A is 300-600 rpm / min, and the stirring time is 30-60 min. In step S2, the stirring speed of component B is 100-300 rpm / min, and the stirring time is 30-60 min.

10. An application of the pumpable water-resistant anchoring agent as described in any one of claims 1 to 5, characterized in that: The anchoring agent is used in anchoring projects for deep-buried tunnels, underwater tunnels, water conservancy projects, or wet rock slopes.

Images