Anti-flowing water polymer grouting material and preparation method thereof

Abstract

The invention relates to the technical field of grouting materials, and particularly discloses an anti-flowing water polymer grouting material and a preparation method thereof. Comprising the following raw materials in parts by weight: 30-50 parts of a polymer main agent, 15-25 parts of a composite curing agent, 5-10 parts of an anti-dispersing agent, 3-8 parts of a thixotropic agent, 2-5 parts of a coupling agent, 0.5-2 parts of a defoaming agent, 1-3 parts of a nanoscale inorganic reinforcing agent and 2-5 parts of a low-viscosity reactive diluent, the preparation method comprises the following steps: S1, pretreating the macromolecular main agent; s2, mixing functional additives; s3, preparing a modification system; and S4, curing and forming. The technical effect of remarkably improving the anti-dispersion stability and interface bonding capacity of the slurry in a flowing water environment is achieved by adopting a synergistic process technical scheme of combining vacuum dehydration pretreatment of a macromolecular main agent, heating step-by-step mixing of a functional auxiliary agent and dropwise adding forming of a curing agent; the problems that the adhesive is easy to disperse under the action of water flow and is not firmly bonded with a base material are solved.

Description

Technical Field

[0001] This invention relates to the field of grouting materials technology, specifically to a water-resistant polymer grouting material and its preparation method. Background Technology

[0002] Anti-dynamic water polymer grouting material is a type of functional engineering material specifically adapted to dynamic water environments. Its core purpose is to quickly solidify and reinforce engineering structures, prevent seepage and plug leaks after the grout is injected into the rock and soil or structural gaps. It is a key material to ensure the safety of engineering construction in dynamic water environments and to improve the stability and durability of structures.

[0003] The effectiveness of this type of material depends directly on the grout's resistance to dispersion under the action of flowing water, as well as the interfacial bonding strength with concrete, soil and rock substrates after curing. It is widely used in engineering scenarios with stringent requirements for the resistance of grouting materials to flowing water, such as tunnel construction, water conservancy facility maintenance, and underground space development.

[0004] Most existing anti-dynamic water grouting materials adopt a crude preparation method of directly mixing and stirring raw materials, without systematic optimization for the special needs of dynamic water scenarios. They often ignore the impact of water flow on the stability of grout components, neither taking effective pretreatment measures to improve the compatibility of raw materials nor strengthening the anti-dispersion ability of grout through reasonable mixing processes and feeding sequences. As a result, after the grout is injected into a dynamic water environment, it is easy for components to separate and disperse under the scouring of water flow, making it difficult to form a continuous and dense solidified body in the target area. At the same time, due to the insufficient bonding force between the grout and the substrate interface, peeling and detachment are prone to occur after solidification, which seriously affects the grouting reinforcement and seepage prevention effect. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a water-resistant polymer grouting material and its preparation method, which solves the problems of simple mixing and unoptimized grout preparation schemes in existing technologies, resulting in easy dispersion of the grouting material under water flow and weak adhesion to the substrate.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: a water-resistant polymer grouting material, comprising the following raw materials in parts by weight: 30-50 parts of polymer main agent, 15-25 parts of composite curing agent, 5-10 parts of anti-dispersion agent, 3-8 parts of thixotropic agent, 2-5 parts of coupling agent, 0.5-2 parts of defoamer, 1-3 parts of nano-scale inorganic reinforcing agent, 2-5 parts of low-viscosity reactive diluent, 0.3-1 part of hindered anti-aging agent, 0.5-2 parts of nitrogen-containing heterocyclic crosslinking accelerator, and 0.2-1 part of nonionic wetting agent.

[0007] By adopting the above technical solution, due to the use of multi-component synergistic formulation, which covers functional components such as main agent, curing agent, anti-dispersant agent and thixotropic agent, each component has a clear division of labor and complements each other, and specifically strengthens the core performance requirements in dynamic water environment. Therefore, the slurry achieves a comprehensive effect that takes into account anti-dispersibility, adhesion, mechanical strength and stability.

[0008] Preferably, the polymeric main agent is a compound of epoxy acrylate and polyurethane acrylate, with a mass ratio of 1:0.3-0.7; The composite curing agent is a mixture of modified aliphatic amine and polythiol, with a mass ratio of 1:0.2-0.4; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 50,000-80,000 Da, a solid content of ≥90%, and a degree of hydrolysis of 20-30%.

[0009] By adopting the above technical solution, the use of epoxy acrylate and polyurethane acrylate as the main agent balances crosslinking reactivity and flexibility. The modified aliphatic amine and polythiol compound curing agent are adapted to the reaction characteristics of the main agent, improving curing efficiency. Acrylamide and sodium acrylate copolymer with specific molecular weight and degree of hydrolysis are specifically enhanced to strengthen anti-dispersion ability. The three form a core functional synergy. Therefore, the slurry is not easily dispersed under dynamic water conditions, and the curing rate and strength development are adapted to engineering requirements.

[0010] Preferably, the thixotropic agent is a compound of organobentonite and fumed silica in a mass ratio of 2:1-3:1, with a specific surface area ≥150 m². 2 / g, the particle size of organic bentonite is ≤2μm, and the particle size of fumed silica is 10-20nm.

[0011] By adopting the above technical solution, the organic bentonite and fumed silica are compounded in a specific ratio, with different particle sizes and specific surface areas. The organic bentonite provides basic thixotropy, while the fumed silica enhances the structural stability of the system through nanoscale dispersion. The two work together to improve the shear dilution and scour resistance of the slurry. Therefore, the slurry can maintain the integrity of the system under the flushing of flowing water and quickly restore its consistency after injection to avoid loss.

[0012] Preferably, the coupling agent is γ-aminopropyltriethoxysilane KH550 or γ-glycidoxypropyltrimethoxysilane KH560.

[0013] By adopting the above technical solution, due to the use of two highly active silane coupling agents, the functional groups in their molecular structure can interact with both inorganic substrates and organic components to build a stable interfacial bonding network. Therefore, the interfacial bonding force between the slurry and substrates such as concrete and soil is significantly improved, and the slurry is less likely to peel off after curing.

[0014] Preferably, the defoamer is a compound of silicone defoamer and polyether defoamer, with a mass ratio of 1:0.5-1:1; the silicone defoamer is polydimethylsiloxane, and the polyether defoamer is polyoxyethylene polyoxypropylene glycerol ether.

[0015] By adopting the above technical solution, the synergistic combination of rapid defoaming by silicone-based defoamers and long-lasting foam suppression by polyether-based defoamers can effectively eliminate bubbles generated during slurry preparation and construction. Therefore, a dense and uniform cured body structure is obtained, avoiding the reduction in anti-dispersion and mechanical strength caused by bubble defects.

[0016] Preferably, the epoxy value of the epoxy acrylate in the polymer main agent is 0.2-0.4 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 50-100mgKOH / g.

[0017] By adopting the above technical solution, the main component with epoxy value and hydroxyl value within a specific range can be used to accurately match the reactivity of the composite curing agent, ensuring that the crosslinking reaction is sufficient and the rate can be controlled. Therefore, the effect of stable slurry curing process and high-strength, high-stability crosslinking network is obtained after curing.

[0018] A method for preparing a water-resistant polymer grouting material includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in proportion and dehydrated for a set time under a set temperature and a set vacuum degree to obtain the pretreated main agent. S2, Functional Additive Mixing: Add the anti-dispersant and thixotropic agent to the pretreatment main agent in S1, heat to the set temperature, stir at the set speed for the set time to form a mixed system A; S3, Preparation of modified system: Add coupling agent and defoamer to the mixture system A of S2, cool to the set temperature, stir at the set speed for the set time to obtain the mixture system B; S4. Curing and molding: Add the composite curing agent to the mixture system B of S3, stir at a set temperature and a set speed for a set time, and after a set reaction time, obtain the water-resistant polymer grouting material.

[0019] By adopting the above technical solution, the process route of pretreatment, step feeding, temperature adaptation and curing is adopted. Each step specifically solves key problems such as raw material compatibility, additive dispersibility and reaction controllability. Therefore, the slurry system is uniform and stable, and the anti-dispersion and adhesion are synergistically improved.

[0020] Preferably, in step S1, the temperature is set to 40-60℃, the vacuum degree is set to -0.08~-0.06MPa, the dehydration time is set to 30-60min, and the moisture content of the pretreatment agent is ≤0.5%, the dehydration temperature is set to 45-55℃, and the dehydration time is set to 40-50min.

[0021] By adopting the above technical solution, the main agent is dehydrated and pretreated using specific temperature, vacuum and time parameters, which can effectively remove residual moisture from the raw materials and avoid moisture affecting the crosslinking reaction and system stability. Therefore, the main agent compatibility is improved, the subsequent reaction is easier to control, and the slurry anti-dispersion ability is more stable.

[0022] Preferably, in step S2, the final temperature of the heating is set to 50-70℃, the stirring speed is set to 300-500 rpm, and the stirring time is set to 60-90 min; The heating rate should be controlled at 2-3℃ / min to avoid local overheating that could cause premature cross-linking of the main agent.

[0023] By adopting the above technical solution, the use of a mild heating rate and appropriate temperature and rotation speed parameters can ensure that the anti-dispersant and thixotropic agent are fully dissolved and uniformly dispersed in the main agent, avoiding local aggregation or premature cross-linking of the main agent. Therefore, the functional additives can play their full role, and the uniformity and stability of the mixed system A are significantly improved.

[0024] Preferably, in step S3, the final cooling temperature is set to 30-40℃, the stirring speed is set to 200-300 rpm, and the stirring time is set to 30-45 min. In step S4, the temperature is set to 25-35℃, the stirring speed is set to 150-200 rpm, the stirring time is set to 10-15 min, and the reaction time is set to 40-60 min. The composite curing agent is added by dripping at a rate of 0.5-1.0 parts / min, and the system temperature is kept stable at 28-32℃ during the dripping process.

[0025] By adopting the above technical solution, the crosslinking reaction is adapted to the temperature of the crosslinking agent, thus avoiding the failure of the agent due to high temperature. At the same time, the curing agent is added dropwise and the temperature and speed are controlled to ensure that the crosslinking reaction is uniform and sufficient, and to avoid the system defects caused by excessive local reaction. Therefore, the slurry modification effect is excellent, the curing process is stable and controllable, and the cured body has a dense structure and strong interfacial bonding.

[0026] This invention provides a water-resistant polymer grouting material and its preparation method. It has the following beneficial effects: 1. This invention employs a synergistic process technology that combines vacuum dehydration pretreatment of polymer main agent, stepwise mixing of functional additives with heating, and dropwise addition of curing agent to achieve a significant improvement in the anti-dispersion stability and interfacial bonding ability of slurry under dynamic water conditions. Compared with the existing technology of simple mixing and slurry preparation schemes that are not optimized for dynamic water scenarios, this invention solves the problems of easy dispersion and weak adhesion to the substrate under water flow.

[0027] 2. This invention adopts a technical solution of staged addition of coupling agent, temperature adaptation of modified system, and precise control of parameters throughout the process. It achieves the technical effect of synergistic optimization of slurry system uniformity, construction fluidity and sufficient cross-linking reaction. Compared with the existing technology of adding additives at one time and not controlling reaction temperature and feeding sequence, it solves the problems of uneven system dispersion, difficult construction operation and insufficient cross-linking reaction.

[0028] 3. The present invention adopts a gradient formula design and a technical solution with flexible adaptation of key process parameters, which achieves the technical effect of being compatible with multiple scenarios such as laboratory research and development, small and medium-sized customized production and large-scale mass production. Compared with the preparation scheme with fixed parameters and single adaptability in the existing technology, it solves the problem that it is difficult to meet the needs of different production scales and has limited adaptability to application conditions. Attached Figure Description

[0029] Figure 1 This is a flowchart illustrating the steps of a method for preparing a water-resistant polymer grouting material according to the present invention. Detailed Implementation

[0030] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. 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.

[0031] This invention provides a water-resistant polymer grouting material, comprising the following raw materials in parts by weight: 30-50 parts of polymeric main agent, 15-25 parts of composite curing agent, 5-10 parts of anti-dispersion agent, 3-8 parts of thixotropic agent, 2-5 parts of coupling agent, 0.5-2 parts of defoamer, 1-3 parts of nano-scale inorganic reinforcing agent, 2-5 parts of low-viscosity reactive diluent, 0.3-1 part of hindered anti-aging agent, 0.5-2 parts of nitrogen-containing heterocyclic crosslinking accelerator, and 0.2-1 part of nonionic wetting agent.

[0032] Specifically, the raw material components are selected and proportioned based on the core requirements of anti-dispersion, strong adhesion, stable construction, and long durability under dynamic water conditions. In the polymer main agent, epoxy acrylate provides a rigid cross-linking framework, while polyurethane acrylate introduces flexible segments; the combination of the two balances strength and crack resistance. The composite curing agent is adjusted by modifying the ratio of aliphatic amines to polythiols to adapt to different construction windows under varying water flow rates. The molecular chain structure of the anti-dispersion agent is optimized to form a three-dimensional network adsorption structure in the slurry, capturing free components. The thixotropic agent, with its nano-sized particle size and high specific surface area, constructs a reversible shear-dilution system. The coupling agent acts as a bridging molecule, realizing the organic slurry... The chemical bonding between the liquid and the inorganic substrate, the defoamer targets and eliminates different types of bubbles generated during the mixing and pumping of the slurry, and the nano-scale inorganic reinforcing agent fills the internal pores of the slurry to improve the density of the cured body. The low-viscosity active diluent adjusts the initial viscosity of the slurry to match the grouting equipment without reducing performance. The hindered anti-aging agent delays the degradation of the cured body in complex environments by capturing free radicals. The nitrogen-containing heterocyclic crosslinking accelerator precisely activates the reactivity of the curing agent to ensure sufficient crosslinking. The non-ionic wetting agent reduces the surface tension of the slurry to achieve rapid wetting of the substrate. The components form a multi-dimensional system with complementary functions and synergistic effects.

[0033] The main polymer is a compound of epoxy acrylate and polyurethane acrylate, with a mass ratio of 1:0.3-0.7; The composite curing agent is a mixture of modified aliphatic amine and polythiol, with a mass ratio of 1:0.2-0.4; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 50,000-80,000 Da, a solid content of ≥90%, and a degree of hydrolysis of 20-30%.

[0034] Specifically, the anti-dispersant is selected from copolymers with this molecular weight and degree of hydrolysis because when the molecular weight is below 50,000 Da, the molecular chains are too short to form a stable three-dimensional network structure, resulting in weak anti-dispersion effect. When the molecular weight is above 80,000 Da, the molecular chains are severely entangled, causing the slurry viscosity to soar and affecting the flowability of the work. The hydrolysis degree of 20-30% optimizes the ratio of hydrophilic to hydrophobic groups on the molecular chains. The hydrophilic groups can form hydrogen bonds with water molecules, enhancing the compatibility of the slurry with water and preventing stratification. The hydrophobic groups interact to form physical cross-linking points, improving shear resistance. The modified aliphatic amine in the composite curing agent has room temperature curing activity, while the polythiol undergoes an addition reaction with the double bond of the main agent through the thiol group. This avoids the defects of a single curing agent. When the modified aliphatic amine is used alone, it cures too quickly, resulting in insufficient workable time for the slurry. When the polythiol is used alone, it cures too slowly, resulting in slow strength development. The compound ensures both the workable time required for construction and the rapid achievement of the design strength of the cured body.

[0035] The thixotropic agent is a compound of organobentonite and fumed silica in a mass ratio of 2:1-3:1, with a specific surface area ≥150 m². 2 / g, the particle size of organic bentonite is ≤2μm, and the particle size of fumed silica is 10-20nm.

[0036] Specifically, after organic modification, the organic bentonite exhibits enhanced interlayer oleophilicity and improved compatibility with polymeric agents. Its particle size design (≤2μm) prevents agglomeration, ensuring uniform dispersion in the slurry. A basic thixotropic structure is formed through interlayer sliding and adsorption. The fumed silica, a nano-sized amorphous powder, has a particle size of 10-20nm, resulting in a specific surface area of ​​150-200m². 2 / g, with a large number of hydroxyl groups on the surface, can form a three-dimensional network structure through hydrogen bonding interactions, acting as a reinforcing agent for organobentonite and improving the stability of the thixotropic system. The mass ratio of 2:1-3:1 is set because organobentonite provides the main thixotropic strength, while fumed silica helps to regulate the thixotropic recovery rate. When the ratio is lower than 2:1, the proportion of fumed silica is too high and it is easy to agglomerate, resulting in abnormal initial viscosity of the slurry. When the ratio is higher than 3:1, the thixotropic recovery rate is too slow, and it is difficult for the slurry to quickly resist the scouring of moving water after injection. This ratio can achieve the ideal effect of rapid viscosity reduction during shearing and rapid viscosity recovery after shearing stops.

[0037] The coupling agent is γ-aminopropyltriethoxysilane KH550 or γ-glycidoxypropyltrimethoxysilane KH560.

[0038] Specifically, both coupling agents belong to the silane coupling agent class. Their molecular structure is amphiphilic. The siloxane group at one end can hydrolyze in water to generate silanol groups. The silanol groups can undergo condensation reactions with hydroxyl groups on the surface of inorganic substrates such as concrete and soil to form stable Si-O-Si chemical bonds. The organic functional groups at the other end are the amino group of KH550 and the epoxy group of KH560. They can react chemically with the double bonds and hydroxyl groups in the polymer main agent to form chemical crosslinks. The amino functional group of KH550 has mild reactivity and is suitable for conventional working conditions with moderate reaction rate requirements. The epoxy functional group of KH560 has higher reactivity and is suitable for emergency repair scenarios that require rapid interface bonding. Compared with physical adsorption coupling agents, the chemical bonding layer formed by this type of coupling agent is stronger and can effectively resist the effects of harsh environments such as water erosion and moisture corrosion, avoiding gaps or peeling at the interface between the cured body and the substrate.

[0039] The defoamer is a compound of silicone defoamer and polyether defoamer, with a mass ratio of 1:0.5-1:1; the silicone defoamer is polydimethylsiloxane, and the polyether defoamer is polyoxyethylene polyoxypropylene glycerol ether.

[0040] Specifically, polydimethylsiloxane, as an organosilicon defoamer, has a surface tension of only 20-21 mN / m, far lower than that of the slurry system. It can quickly spread on the surface of bubbles, destroying their stability and causing them to burst instantly, thus achieving rapid defoaming. Polyoxyethylene polyoxypropylene glycerol ether, as a polyether defoamer, forms a uniform adsorption film in the slurry by adjusting the ratio of ethylene oxide to propylene oxide in the molecular chain, preventing the generation, merging, and growth of bubbles, thus achieving long-lasting foam suppression. The design with a mass ratio of 1:0.5-1:1 can cover the entire process of slurry preparation and construction. During the stirring stage, polydimethylsiloxane is relied upon for rapid defoaming, while during the pumping and grouting stages, polyether defoamers are relied upon for long-lasting foam suppression, avoiding bubble residue caused by the functional defects of a single defoamer. This prevents the formation of structural defects such as pores and cracks in the cured body, ensuring the uniformity of anti-dispersion properties and mechanical strength.

[0041] The epoxy value of the epoxy acrylate in the polymer main agent is 0.2-0.4 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 50-100mgKOH / g.

[0042] Specifically, the epoxy value of epoxy acrylate directly determines the number of crosslinking reaction sites. When the epoxy value is below 0.2 eq / 100g, there are insufficient crosslinking sites, resulting in low crosslinking density of the cured body and poor mechanical strength and anti-dispersion properties. When it is above 0.4 eq / 100g, the crosslinking density is too high, increasing the brittleness of the cured body and making it prone to cracking due to dynamic water pressure impact. The hydroxyl value of polyurethane acrylate reflects the number of hydroxyl groups on the molecular chain. When the hydroxyl value is below 50 mg KOH / g, there are few reaction sites with the curing agent, resulting in incomplete curing reaction and residual unreacted components affecting performance. When it is above 100 mg KOH / g, the reaction rate is too fast, shortening the working time of the grout to less than 10 seconds, making it impossible to complete grouting, diffusion, and other construction steps. When the epoxy value and hydroxyl value of both are precisely matched within the above range, it can ensure that the crosslinking reaction rate can be controlled and fully utilized, enabling the cured body to form a composite structure of rigid skeleton and flexible chain segments, which has both high strength to resist dynamic water erosion and flexibility to adapt to substrate deformation.

[0043] Please see the appendix Figure 1 A method for preparing a water-resistant polymer grouting material includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in proportion and dehydrated for a set time under a set temperature and a set vacuum degree to obtain the pretreated main agent. In S1, the set temperature is 40-60℃, the set vacuum degree is -0.08~-0.06MPa, the set dehydration time is 30-60min, and the moisture content of the pretreatment agent is ≤0.5%. The set dehydration temperature is 45-55℃, and the set dehydration time is 40-50min.

[0044] S2, Functional Additive Mixing: Add the anti-dispersant and thixotropic agent to the pretreatment main agent in S1, heat to the set temperature, stir at the set speed for the set time to form a mixed system A; In S2, the final temperature of the heating is set to 50-70℃, the stirring speed is set to 300-500rpm, and the stirring time is set to 60-90min. The heating rate should be controlled at 2-3℃ / min to avoid local overheating that could cause premature cross-linking of the main agent.

[0045] S3, Preparation of modified system: Add coupling agent and defoamer to the mixture system A of S2, cool to the set temperature, stir at the set speed for the set time to obtain the mixture system B; In S3, the cooling endpoint temperature is set to 30-40℃, the stirring speed is set to 200-300rpm, and the stirring time is set to 30-45min.

[0046] S4. Curing and molding: Add the composite curing agent to the mixture system B of S3, stir at a set temperature and a set speed for a set time, and after a set reaction time, obtain the water-resistant polymer grouting material; In S4, the temperature is set to 25-35℃, the stirring speed is set to 150-200 rpm, the stirring time is set to 10-15 min, and the reaction time is set to 40-60 min. The composite curing agent is added by dripping at a rate of 0.5-1.0 parts / min, and the system temperature is kept stable at 28-32℃ during the dripping process.

[0047] Specifically, the vacuum dehydration pretreatment of S1, with a temperature of 40-60℃, ensures rapid evaporation of moisture while avoiding thermal and oxidative aging of the main agent. The vacuum degree of -0.08~-0.06MPa can lower the boiling point of moisture and shorten the dehydration time. The control standard of moisture content ≤0.5% can completely eliminate the inhibitory effect of moisture on the activity of the curing agent, while avoiding the formation of micropores in the cured body. During the heating and stirring stage of S2, a gentle heating rate of 2-3℃ / min can prevent local temperature surges from causing premature polymerization of the double bonds in the main agent. The final temperature of 50-70℃ is suitable for the dissolution and dispersion requirements of the anti-dispersant and thixotropic agent. The rotation speed of 300-500rpm can generate sufficient shear force to break the initial agglomeration state of the thixotropic agent. The stirring time of 60-90min ensures that it is evenly distributed in the main agent and forms an initial functional network. During the cooling modification stage of S3, the temperature range of 30-40℃ can prevent the epoxy groups of coupling agents, especially KH560, from self-polymerizing due to high temperature. The low-speed stirring of 200-300rpm can achieve uniform mixing of coupling agents, defoamers and other additives without destroying the thixotropic network formed by S2. The stirring time of 30-45min ensures that the additives are fully dissolved and play their role. In the curing and molding stage of S4, the dropwise addition method allows for precise control of the addition rate of the composite curing agent, avoiding violent reactions and heat accumulation caused by excessively high local concentrations. A dropwise acceleration rate of 0.5-1.0 parts / min, matched with a system temperature of 28-32℃, ensures uniform cross-linking reaction. A stirring speed of 150-200 rpm ensures thorough mixing of the curing agent and the system while avoiding the introduction of excessive air. A reaction time of 40-60 minutes ensures complete cross-linking, ultimately forming a dense and stable anti-dynamic water grouting material. The entire process deeply integrates raw material characteristics and parameter control, avoiding performance shortcomings caused by single-step optimization, and achieving full-chain synergy of raw materials, process, and performance.

[0048] The following is a description with reference to specific embodiments: Example 1: A water-resistant polymer grouting material, comprising the following raw materials in parts by weight: 30 parts of polymeric main agent, 15 parts of composite curing agent, 5 parts of anti-dispersant agent, 3 parts of thixotropic agent, 2 parts of coupling agent, 0.3 parts of defoamer, 1 part of nano-scale inorganic reinforcing agent, 2 parts of low viscosity reactive diluent, 0.3 parts of hindered anti-aging agent, 0.5 parts of nitrogen-containing heterocyclic crosslinking accelerator, and 0.2 parts of nonionic wetting agent; The polymer main agent consists of 18.75 parts epoxy acrylate and 6.25 parts polyurethane acrylate, with a compounding mass ratio of 1:0.3. The composite curing agent is composed of 12.5 parts modified aliphatic amine and 2.5 parts polythiol, with a compounding mass ratio of 1:0.2; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 50,000 Da, a solid content of 90%, and a degree of hydrolysis of 20%. The thixotropic agent is composed of 2 parts organobentonite and 1 part fumed silica, with a mass ratio of 2:1 and a specific surface area of ​​150 m². 2 / g; The coupling agent is γ-aminopropyltriethoxysilane KH550; the defoamer is 0.2 parts polydimethylsiloxane and 0.1 parts polyoxyethylene polyoxypropylene glycerol ether, with a compounding mass ratio of 1:0.5. The hindered anti-aging agent is 2,6-di-tert-butyl-p-cresol; The nano-scale inorganic reinforcing agent is nano-calcium carbonate with a particle size of 50nm, the low-viscosity reactive diluent is propylene glycol methyl ether acetate, the nitrogen-containing heterocyclic crosslinking accelerator is 2-methylimidazole, and the non-ionic wetting agent is polyoxyethylene fatty alcohol ether. The epoxy value of the epoxy acrylate is 0.2 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 50 mg KOH / g; the particle size of the organobentonite is 2 μm, and the particle size of the fumed silica is 10 nm.

[0049] A method for preparing a water-resistant polymer grouting material includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in the above proportion, placed in a vacuum drying oven, and the temperature is set to 40℃ and the vacuum degree to -0.08MPa. The mixture is dehydrated for 30 minutes to obtain a pretreated main agent with a water content of 0.5%. S2. Mixing of functional additives: Add anti-dispersant, thixotropic agent and nano calcium carbonate to the pretreatment main agent, heat to 50°C at a heating rate of 2°C / min, and stir at 300 rpm for 60 min to form mixed system A; S3. Preparation of modified system: Add coupling agent KH550, defoamer, propylene glycol methyl ether acetate and polyoxyethylene fatty alcohol ether to mixed system A, cool to 30℃, stir at 200 rpm for 30 min to obtain mixed system B. S4. Curing and molding: Mix the composite curing agent and 2-methylimidazole evenly, and add it dropwise to the mixture system B at a rate of 0.5 parts / min. Keep the system temperature at 28℃, stir at 150 rpm for 10 min, and continue to react for 40 min to obtain the water-resistant polymer grouting material.

[0050] Example 2: A water-resistant polymer grouting material, comprising the following raw materials in parts by weight: The composition includes: 40 parts polymer base agent, 21 parts composite curing agent, 7.5 parts anti-dispersant agent, 4.2 parts thixotropic agent, 3.5 parts coupling agent, 1.31 parts defoamer, 2 parts nano-scale inorganic reinforcing agent, 3.5 parts low viscosity reactive diluent, 0.65 parts hindered anti-aging agent, 1.25 parts nitrogen-containing heterocyclic crosslinking accelerator, and 0.6 parts nonionic wetting agent. The polymer main agent consists of 20 parts epoxy acrylate and 10 parts polyurethane acrylate, with a compounding mass ratio of 1:0.5. The composite curing agent is composed of 17.5 parts modified aliphatic amine and 5.25 parts polythiol, with a compounding mass ratio of 1:0.3; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 65,000 Da, a solid content of 95%, and a degree of hydrolysis of 25%. The thixotropic agent is composed of 3 parts organobentonite and 1.2 parts fumed silica, with a mass ratio of 2.5:1 and a specific surface area of ​​180 m². 2 / g; The coupling agent is γ-glycidyl oxypropyltrimethoxysilane KH560; The defoamer is composed of 0.75 parts polydimethylsiloxane and 0.56 parts polyoxyethylene polyoxypropylene glycerol ether, with a compounding mass ratio of 1:0.75; The nano-sized inorganic reinforcing agent is nano-silica with a particle size of 40nm; the low-viscosity reactive diluent is propylene glycol methyl ether acetate. The nitrogen-containing heterocyclic crosslinking accelerator is 2-methylimidazole; the nonionic wetting agent is polyoxyethylene fatty alcohol ether. The epoxy value of the epoxy acrylate is 0.3 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 75 mg KOH / g; the particle size of the organobentonite is 1.5 μm, and the particle size of the fumed silica is 15 nm.

[0051] A method for preparing a water-resistant polymer grouting material includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in the above proportion, placed in a vacuum drying oven, and the temperature is set to 50℃ and the vacuum degree to -0.07MPa. The mixture is dehydrated for 45 minutes to obtain a pretreated main agent with a water content of 0.3%.

[0052] S2. Mixing of functional additives: Add anti-dispersant, thixotropic agent and nano silica to the pretreatment main agent, heat to 60℃ at a heating rate of 2.5℃ / min, and stir at 400rpm for 75min to form mixed system A.

[0053] S3. Preparation of modified system: Add coupling agent KH560, defoamer, propylene glycol methyl ether acetate and polyoxyethylene fatty alcohol ether to mixed system A, cool to 35℃, and stir at 250 rpm for 37.5 min to obtain mixed system B.

[0054] S4. Curing and molding: Mix the composite curing agent and 2-methylimidazole evenly, and add it dropwise to the mixture system B at a rate of 0.75 parts / min. Keep the system temperature at 30℃, stir at 175 rpm for 12.5 min, and continue to react for 50 min to obtain the water-resistant polymer grouting material.

[0055] Example 3: A water-resistant polymer grouting material, comprising the following raw materials in parts by weight: 50 parts of polymeric main agent, 25 parts of composite curing agent, 10 parts of anti-dispersant agent, 7.11 parts of thixotropic agent, 5 parts of coupling agent, 2.66 parts of defoamer, 3 parts of nano-scale inorganic reinforcing agent, 5 parts of low viscosity reactive diluent, 1 part of hindered anti-aging agent, 2 parts of nitrogen-containing heterocyclic crosslinking accelerator, and 1 part of nonionic wetting agent; The polymer main agent consists of 29.41 parts epoxy acrylate and 20.59 parts polyurethane acrylate, with a compounding mass ratio of 1:0.7. The composite curing agent is composed of 17.86 parts modified aliphatic amine and 7.14 parts polythiol, with a compounding mass ratio of 1:0.4; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 80,000 Da, a solid content of 98%, and a degree of hydrolysis of 30%. The thixotropic agent is composed of 5.33 parts organobentonite and 1.78 parts fumed silica, with a mass ratio of 3:1 and a specific surface area of ​​200 m². 2 / g; The coupling agent is γ-aminopropyltriethoxysilane KH550; The defoamer is composed of 1.33 parts polydimethylsiloxane and 1.33 parts polyoxyethylene polyoxypropylene glycerol ether, with a compound mass ratio of 1:1; The nano-scale inorganic reinforcing agent is nano-calcium carbonate with a particle size of 30 nm; The low-viscosity reactive diluent is propylene glycol methyl ether acetate; The nitrogen-containing heterocyclic crosslinking accelerator is 2-methylimidazole; The nonionic wetting agent is polyoxyethylene fatty alcohol ether; The epoxy value of the epoxy acrylate is 0.4 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 100 mg KOH / g; the particle size of the organobentonite is 1 μm, and the particle size of the fumed silica is 20 nm.

[0056] A method for preparing a water-resistant polymer grouting material includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in the above proportion, placed in a vacuum drying oven, and the temperature is set to 60℃ and the vacuum degree to -0.06MPa. The mixture is dehydrated for 60min to obtain a pretreated main agent with a water content of 0.2%.

[0057] S2. Mixing of functional additives: Add anti-dispersant, thixotropic agent and nano calcium carbonate to the pretreatment main agent, heat to 70°C at a heating rate of 3°C / min, and stir at 500 rpm for 90 min to form mixed system A.

[0058] S3. Preparation of modified system: Add coupling agent KH550, defoamer, propylene glycol methyl ether acetate and polyoxyethylene fatty alcohol ether to mixed system A, cool to 40℃, and stir at 300 rpm for 45 min to obtain mixed system B.

[0059] S4. Curing and molding: Mix the composite curing agent and 2-methylimidazole evenly, and add it dropwise to the mixture system B at a rate of 1.0 parts / min. Keep the system temperature at 32℃, stir at 200 rpm for 15 min, and continue to react for 60 min to obtain the water-resistant polymer grouting material.

[0060] Comparative Example 1: Unlike Example 2, coupling agent KH560 was added to the pretreatment main agent along with anti-dispersant, thixotropic agent and nano silica in the S2 functional additive mixing stage. No additional coupling agent was added in the S3 modified system preparation stage. All other process parameters were the same as in Example 2.

[0061] Comparative Example 2: Unlike Example 2, the S1 polymer main agent pretreatment step only mixed the epoxy acrylate and polyurethane acrylate in proportion and did not perform vacuum dehydration treatment. It directly entered the S2 functional additive mixing stage. The remaining process parameters were the same as those in Example 2.

[0062] Comparative Example 3: Unlike Example 2, in the S4 curing stage, the uniformly mixed composite curing agent and 2-methylimidazole were poured into the mixing system B in one go, instead of being added dropwise. All other process parameters were the same as in Example 2.

[0063] Comparative Example 4: Unlike Example 2, the S3 modified system was prepared first, and then the S2 functional additive was mixed. All other process parameters were the same as in Example 2.

[0064] Comparative Example 5: Unlike Example 2, no heating was performed during the mixing stage of the S2 functional additive. The mixture was stirred at 400 rpm for 75 minutes while maintaining room temperature. All other process parameters were the same as in Example 2.

[0065] Table 1, Performance Test Data Table ; Based on the differences in Examples 1-3, Comparative Examples 1-5, and the performance test data table, it can be seen that the core advantage of this invention stems from the synergistic effect of six key processes: vacuum dehydration pretreatment of polymer main agent, stepwise mixing of functional additives at elevated temperature, staged addition of coupling agent, cooling adaptation of modified system, dripping and molding of curing agent, and precise adaptation of parameters throughout the entire process. In addition, the parameters of each step are deeply matched with the characteristics of raw materials. This has a significant positive impact on the dynamic water dispersion resistance, compressive strength, bonding stability, construction adaptability, and storage consistency of grouting materials. Furthermore, it achieves triple synergistic optimization of raw material dispersion uniformity, crosslinking efficiency and interfacial bonding force, and construction adaptability and environmental adaptability.

[0066] Comparative Examples 1-5 all exhibited targeted performance declines due to the absence or improper adjustment of a single core process: Comparative Example 1 reversed the order of coupling agent addition, resulting in a decrease in the interfacial bonding force between the polymer main agent and the functional additives, with the dynamic water dispersion rate dropping to 93.2% and the 24-hour compressive strength to only 33.5 MPa; Comparative Example 2 omitted the vacuum dehydration step of the polymer main agent, and the residual moisture disrupted the system homogeneity, resulting in a dynamic water dispersion rate of only 91.8% and a bond strength to only 4.3 MPa; Comparative Example 3 added the composite curing agent all at once instead of dropwise, causing excessively rapid local crosslinking. The system was uneven, with a dynamic water dispersion rate of 92.5% and a compressive strength of 32.8 MPa. In Comparative Example 4, the process order of mixing and modifying the functional additives was reversed, resulting in insufficient dispersion of the additives and crosslinking defects. The dynamic water dispersion rate dropped to 90.7%, the slurry viscosity increased to 510 mPa·s, and the construction fluidity deteriorated. In Comparative Example 5, the heating operation in the S2 stage was omitted, and stirring at room temperature led to uneven dispersion of the functional additives. The gel time was extended to 32 s and the bonding strength was only 4.5 MPa. This fully demonstrates the indispensability of each process step and the rationality of the sequence.

[0067] Examples 1-3 all exhibit excellent comprehensive performance: dynamic water dispersion resistance of 95.0%-98.5%, gel time of 10-30s, 24-hour compressive strength of 30.2-38.6MPa, 24-hour concrete substrate bond strength of 4.5-5.8MPa, and slurry viscosity of 350-480mPa·s. Example 2 achieves the optimal performance balance, with a dynamic water dispersion resistance of 98.5%, bond strength of 5.8MPa, and compressive strength of 38.6MPa, achieving optimal fit between dispersion resistance, mechanical properties, and construction compatibility. Example 1 maintains process stability with minimal parameters, achieving a dynamic water dispersion resistance of 95.0% and a compressive strength of 30.2MPa, suitable for small-scale laboratory preparation and low-cost scenarios. Example 3 achieves large-scale production adaptability with maximum parameters, balancing production capacity and product consistency, with a dynamic water dispersion resistance of 97.2% and a compressive strength of 35.8MPa. Both examples jointly verify the rationality and application flexibility of the parameter range of this invention.

[0068] Precise matching of parameters in each step is key to performance assurance: S1 vacuum dehydration temperature of 40-60℃ and vacuum degree of -0.08~-0.06MPa match the swelling characteristics of the polymer main agent, avoiding cross-linking defects caused by residual moisture; S2 heating rate of 2-3℃ / min and target temperature of 50-70℃ match the dispersion requirements of functional additives, and stirring rate of 300-500rpm ensures system homogeneity; S3 cooling temperature of 30-40℃ and stirring rate of 200-300rpm match the reactivity of crosslinking agents, avoiding additive failure caused by high temperature; S4 curing temperature of 28-32℃ and dropping rate of 0.5-1.0 parts / min match the cross-linking efficiency of the curing agent, preventing performance fluctuations caused by excessively rapid local reactions; the compounding ratio of each raw material is 1:0.3-0.7 for polymer main agent and 1:0.2-0.4 for composite curing agent to synergistically improve anti-dispersion and mechanical properties.

[0069] Example 2 achieves the optimal balance between water resistance, mechanical strength and construction adaptability through precise adaptation of parameters throughout the entire process; the process collaboration system of Examples 1-3 not only avoids performance loss or cost waste caused by parameter boundaries, but also covers the needs of multiple scenarios such as laboratory research and development, small and medium-sized customized production and large-scale mass production.

[0070] In summary, this invention effectively addresses the shortcomings of traditional water-resistant grouting materials, such as insufficient resistance to dispersion in water, low bond strength, weak compressive strength, poor construction fluidity, and limited environmental adaptability, significantly improving the overall performance of grouting materials. Example 2 offers optimal cost-effectiveness and scalable production potential, enabling direct application in grouting reinforcement for tunnels, water conservancy projects, and underground structures in water-resistant environments. The parameter flexibility of Examples 1-3 adapts to various scenarios, including laboratory research, customized solutions for special working conditions, and low-cost projects, providing a standardized and replicable technical solution for the efficient application of polymer grouting materials in water-resistant environments. It also offers a new path for the industrial production of water-resistant functional materials.

[0071] Table 2, GB Testing Standards ; Dynamic water anti-dispersion rate: Prepare standard slurry, build a dynamic water simulation device, control the water flow rate to 1-3 m / s, inject the slurry into the dynamic water flow field, let it stand for 3 minutes and collect the undispersed solid phase, calculate the ratio of the solid phase residue to the initial slurry solid phase mass, which is the dynamic water anti-dispersion rate.

[0072] Gel time: The Vicat apparatus method was used. The slurry was poured into a standard mold and the ambient temperature was controlled at 25°C. The penetration resistance was measured every 1 minute. When the penetration resistance reached 3.5 MPa, the time from the completion of slurry preparation to that moment was recorded, which is the gel time.

[0073] 24h compressive strength: Prepare 40mm×40mm×160mm specimens according to the standard ratio, vibrate to form, cure for 24h at a temperature of 20±1℃ and humidity ≥90%, and conduct a compressive test using a pressure testing machine with a loading rate of 5kN / s. Record the maximum load at failure and calculate the compressive strength.

[0074] 24-hour concrete substrate bond strength: Prepare 100mm×100mm×100mm concrete substrate specimens, grind the surface to a smooth finish, apply grout evenly to the substrate surface, attach the same type of concrete specimens, and after standard curing for 24 hours, perform tensile tests using a tensile testing machine at a rate of 1mm / min, record the failure load, and calculate the bond strength.

[0075] Slurry viscosity: A rotational viscometer was used. A suitable rotor was selected, and the slurry was placed in a constant temperature water bath at 25℃ for 30 minutes. The viscometer was started, and the rotation speed was set to 60 r / min. After the reading stabilized, the value was recorded. The unit is expressed in mPa·s.

[0076] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A polymer grouting material resistant to dynamic water flow, characterized in that, The raw materials include the following parts by weight: 30-50 parts of polymeric main agent, 15-25 parts of composite curing agent, 5-10 parts of anti-dispersant agent, 3-8 parts of thixotropic agent, 2-5 parts of coupling agent, 0.5-2 parts of defoamer, 1-3 parts of nano-scale inorganic reinforcing agent, 2-5 parts of low viscosity reactive diluent, 0.3-1 part of hindered anti-aging agent, 0.5-2 parts of nitrogen-containing heterocyclic crosslinking accelerator, and 0.2-1 part of nonionic wetting agent.

2. The anti-dynamic water polymer grouting material according to claim 1, characterized in that: The polymeric main agent is a compound of epoxy acrylate and polyurethane acrylate, with a mass ratio of 1:0.3-0.7; The composite curing agent is a mixture of modified aliphatic amine and polythiol, with a mass ratio of 1:0.2-0.4; The anti-dispersant is a copolymer of acrylamide and sodium acrylate, with a molecular weight of 50,000-80,000 Da, a solid content of ≥90%, and a degree of hydrolysis of 20-30%.

3. The anti-dynamic water polymer grouting material according to claim 1, characterized in that: The thixotropic agent is a compound of organobentonite and fumed silica in a mass ratio of 2:1-3:1, with a specific surface area ≥150m². 2 / g, the particle size of organic bentonite is ≤2μm, and the particle size of fumed silica is 10-20nm.

4. The anti-dynamic water polymer grouting material according to claim 1, characterized in that: The coupling agent is γ-aminopropyltriethoxysilane KH550 or γ-glycidoxypropyltrimethoxysilane KH560.

5. The anti-dynamic water polymer grouting material according to claim 1, characterized in that: The defoamer is a compound of silicone defoamer and polyether defoamer, with a mass ratio of 1:0.5-1:1; the silicone defoamer is polydimethylsiloxane, and the polyether defoamer is polyoxyethylene polyoxypropylene glycerol ether.

6. The anti-dynamic water polymer grouting material according to claim 1, characterized in that: The epoxy value of the epoxy acrylate in the polymer main agent is 0.2-0.4 eq / 100g, and the hydroxyl value of the polyurethane acrylate is 50-100mgKOH / g.

7. A method for preparing a water-resistant polymer grouting material, characterized in that, The method for using a water-resistant polymer grouting material according to any one of claims 1-6 includes the following steps: S1. Pretreatment of polymer main agent: Epoxy acrylate and polyurethane acrylate are mixed in proportion and dehydrated for a set time under a set temperature and a set vacuum degree to obtain the pretreated main agent. S2, Functional Additive Mixing: Add the anti-dispersant and thixotropic agent to the pretreatment main agent in S1, heat to the set temperature, stir at the set speed for the set time to form a mixed system A; S3, Preparation of modified system: Add coupling agent and defoamer to the mixture A of S2, cool to the set temperature, stir at the set speed for the set time to obtain mixture B; S4. Curing and molding: Add the composite curing agent to the mixture system B of S3, stir at a set temperature and a set speed for a set time, and after a set reaction time, obtain the water-resistant polymer grouting material.

8. The method for preparing a water-resistant polymer grouting material according to claim 7, characterized in that: In S1, the temperature is set to 40-60℃, the vacuum degree is set to -0.08~-0.06MPa, the dehydration time is set to 30-60min, and the moisture content of the pretreatment agent is ≤0.5%, the dehydration temperature is set to 45-55℃, and the dehydration time is set to 40-50min.

9. The method for preparing a water-resistant polymer grouting material according to claim 7, characterized in that: In step S2, the final temperature of the heating is set to 50-70℃, the stirring speed is set to 300-500 rpm, and the stirring time is set to 60-90 min. The heating rate should be controlled at 2-3℃ / min to avoid local overheating that could cause premature cross-linking of the main agent.

10. The method for preparing a water-resistant polymer grouting material according to claim 7, characterized in that: In step S3, the final cooling temperature is set to 30-40℃, the stirring speed is set to 200-300 rpm, and the stirring time is set to 30-45 min. In step S4, the temperature is set to 25-35℃, the stirring speed is set to 150-200 rpm, the stirring time is set to 10-15 min, and the reaction time is set to 40-60 min. The composite curing agent is added by dripping at a rate of 0.5-1.0 parts / min, and the system temperature is kept stable at 28-32℃ during the dripping process.

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