A two-component polymer grouting material for cable tunnels and its preparation method

Abstract

This application belongs to the field of grouting materials and provides a two-component polymer grouting material for cable tunnels and its preparation method. The preparation method includes the following steps: mixing a polyisocyanate with a carbodiimide stabilizer and heating to obtain an isocyanate intermediate; then adding an amine modifier to the isocyanate intermediate and continuing heating to obtain a modified isocyanate; mixing an epoxy compound with a tertiary amine compound and heating to obtain an epoxy intermediate; then adding a haloalkane to the epoxy intermediate and continuing heating to obtain a modified epoxy compound; mixing a polyether polyol with a sulfonating agent and a catalyst and heating to obtain a modified polyether polyol; mixing the modified isocyanate with an accelerator to obtain component A; and mixing the modified epoxy compound, the modified polyether polyol, and a crown ether polymerization inhibitor to obtain component B. The two-component polymer grouting material prepared by the above method can effectively resist salt erosion and improve the salt corrosion resistance of the grouting material.

Description

Technical Field

[0001] This application relates to the field of grouting materials, specifically to a two-component polymer grouting material for cable tunnels and its preparation method. Background Technology

[0002] In cable tunnel engineering, after the segment lining is assembled, voids inevitably form between its outer wall and the surrounding rock. These voids are filled and reinforced by injecting grouting material, which can effectively prevent serious problems such as ground loosening, uneven tunnel settlement, and groundwater leakage. To meet the requirements of controllable setting time during on-site construction, the grouting material is usually a two-component system (such as a polyether-type polyurethane system), that is, two components, A and B, are stored independently—component A is the main agent, and component B is the curing agent. When used, they are mixed in a precise ratio, and the two components undergo a rapid chemical reaction to form a highly dense solidified body in the voids behind the wall. This not only effectively fills the voids and restricts the deformation of the surrounding rock, but also seals the groundwater seepage channels, forming a three-in-one synergistic load-bearing structure of "lining-grouting body-surrounding rock", thereby ensuring the long-term stability and waterproof safety of the tunnel structure.

[0003] However, in nearshore areas, seawater is rich in high concentrations of chloride, sulfate, and magnesium ions. These corrosive ions, using groundwater as a transport carrier, continuously penetrate the surface of polyurethane solids, causing severe salt erosion. Chloride ions, with their strong nucleophilicity, can directly attack the ester bonds in the polyurethane molecular chains, initiating nucleophilic substitution reactions, leading to molecular chain breakage, disintegration of the cross-linked network, and a decrease in the mechanical properties of the solid. Sulfate and magnesium ions coordinate with polar groups in the polyurethane, weakening intermolecular forces, accelerating chain segment movement, causing plasticization and softening of the material, and reducing its cohesive strength. The synergistic effect of these three corrosive ions leads to a continuous deterioration of the mechanical properties of cement-based grouting materials, a significant decrease in bond strength, and gradual cracking and loosening of the solid from the inside out, ultimately resulting in a decline in the long-term durability of the grout. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a two-component polymer grouting material for cable tunnels and its preparation method, aiming to solve the problem of reduced durability of grouting materials caused by salt erosion in cable tunnels in coastal areas.

[0005] To address the aforementioned technical problems, a method for preparing a two-component polymer grouting material for cable tunnels is proposed. The preparation method includes the following steps: S1. Mix polyisocyanate with carbodiimide stabilizer and heat to react to obtain isocyanate intermediate. Then add amine modifier to isocyanate intermediate and continue heating to react to obtain modified isocyanate. S2. Mix the epoxy compound with the tertiary amine compound and heat to react to obtain an epoxy intermediate. Then add a haloalkane to the epoxy intermediate and continue to heat to react to obtain a modified epoxy compound, wherein the modified epoxy compound contains a quaternary ammonium cation. S3. Mix the polyether polyol with the sulfonating agent and the catalyst, and heat to react to obtain the modified polyether polyol, wherein the modified polyether polyol contains sulfonic acid groups. S4. Mix the modified isocyanate with the accelerator to obtain the A component polymer grouting material. Mix the modified epoxy compound, the modified polyether polyol and the crown ether polymerization inhibitor to obtain the B component polymer grouting material.

[0006] In addition, a two-component polymer grouting material for cable tunnels is proposed, which is prepared by the above-described preparation method of a two-component polymer grouting material for cable tunnels. The two-component polymer grouting material is composed of component A polymer grouting material and component B polymer grouting material mixed at a mass ratio of 1:(1.05~1.1). The operation method is as follows: after measuring component A polymer grouting material and component B polymer grouting material according to the mass ratio, they are mixed evenly by a two-liquid grouting pump through a mixer and injected into the joint of cable tunnel segments. The grouting pressure is controlled at 0.2~0.8MPa and the grouting flow rate is controlled at 10~30L / min. During the grouting process, the grouting situation at the seepage points of the tunnel wall is observed. Grouting is stopped when grouting begins to appear at adjacent grouting holes or joints.

[0007] As can be seen from the above technical solutions, the exemplary embodiments disclosed herein possess at least the following advantages and positive effects: On the one hand, by employing modified isocyanates containing isocyanate groups, covalently linked carbodiimide-urea ketimide structures, and amine groups, and combining them with modified epoxy compounds containing residual epoxy groups and modified polyether polyols containing residual hydroxyl groups, the isocyanate groups react with hydroxyl groups to form a polyurethane network, and the amine groups open the epoxy groups to form an epoxy crosslinking network, thus constructing a highly dense polymer interpenetrating network structure. At the same time, the carbodiimide groups on the main chain react with the carboxylic acid produced by polyurethane hydrolysis and are converted into a stable acylurea structure. This solves the problem in the prior art that polyurethane grouting materials are prone to acid-catalyzed hydrolysis of urethane bonds in nearshore high-humidity environments, leading to a decrease in material durability. This achieves the effect of blocking the hydrolysis chain reaction and significantly improving the service life and long-term stability of the material in nearshore high-humidity environments.

[0008] On the other hand, by introducing crown ether polymerization inhibitors into the system and combining modified epoxy compounds containing quaternary ammonium cations and modified polyether polyols containing sulfonic acid groups, the crown ether polymerization inhibitors shield the electrostatic pre-pairing between quaternary ammonium cations and sulfonic acid groups during storage. After grouting, the active sites are released in situ through competitive replacement by metal ions in the salt solution. This solves the problem that traditional grouting materials are susceptible to penetration and corrosion by chloride ions, sulfate ions, and magnesium ions in nearshore high-salt environments. This achieves efficient adsorption of chloride and sulfate ions by quaternary ammonium cations and stable complexation and fixation of magnesium ions by sulfonic acid groups. A dense and stable ion cross-linked hardened layer is formed at the material-formation interface, further enhancing the salt penetration resistance and long-term durability of the grouting consolidation body. Attached Figure Description

[0009] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure. It is obvious that the drawings described below are merely some embodiments of this disclosure, and those skilled in the art can obtain other drawings based on these drawings without any inventive effort. In the drawings: Figure 1 This is a schematic diagram of a method for preparing a two-component polymer grouting material for cable tunnels in one embodiment; Figure 2 This is a schematic diagram of step S1 in a method for preparing a two-component polymer grouting material for cable tunnels in one embodiment; Figure 3 This is a schematic diagram of step S2 in a method for preparing a two-component polymer grouting material for cable tunnels in one embodiment; Figure 4 This is a schematic diagram of step S3 in a method for preparing a two-component polymer grouting material for cable tunnels in one embodiment. Detailed Implementation

[0010] Exemplary embodiments will now be described more fully with reference to the accompanying drawings. However, these exemplary embodiments can be implemented in many forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be more thorough and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art.

[0011] Furthermore, the described features or characteristics may be combined in any suitable manner in one or more embodiments. Numerous specific details are provided in the following description to give a thorough understanding of embodiments of this disclosure. However, those skilled in the art will recognize that the technical solutions of this disclosure may be practiced without one or more of the specific details, or other method steps may be employed. In other instances, well-known methods, implementations, or operations are not shown or described in detail to avoid obscuring various aspects of this disclosure.

[0012] The flowcharts shown in the accompanying drawings are merely illustrative and do not necessarily include all content and operations / steps, nor do they necessarily need to be performed in the described order. For example, some operations / steps can be broken down, while others can be combined or partially combined; therefore, the actual execution order may change depending on the specific circumstances.

[0013] Please refer to Figure 1 This invention proposes a method for preparing a two-component polymer grouting material for cable tunnels, the method comprising the following steps: S1. Mix polyisocyanate with carbodiimide stabilizer and heat to react to obtain isocyanate intermediate. Then add amine modifier to isocyanate intermediate and continue heating to react to obtain modified isocyanate.

[0014] By reacting polyisocyanates with carbodiimide stabilizers, a carbodiimide-urea ketimide structure is introduced into the modified isocyanate molecule. Furthermore, an active amine group is introduced using an amine modifier, resulting in a modified isocyanate that simultaneously possesses isocyanate reactivity, hydrolysis resistance, and subsequent crosslinking enhancement capabilities. The carbodiimide group can react with the carboxylic acid generated during polyurethane hydrolysis during material service, transforming it into a stable acylurea structure. This effectively inhibits the acid-catalyzed hydrolysis of urethane bonds by the carboxylic acid, blocking the chain degradation process of polyurethane in high-humidity and high-salt environments. The introduced amine group can further undergo ring-opening crosslinking reactions with epoxy groups, improving the density of the material's network structure.

[0015] Reference Figure 2 Step S1 includes: S1.1 Add the polyisocyanate to the reaction vessel, heat it to 60~70℃ in an inert atmosphere, add the carbodiimide stabilizer, stir and react for 2~4h to obtain the isocyanate intermediate, wherein the molar ratio of the isocyanate group in the polyisocyanate to the carbodiimide group in the carbodiimide stabilizer is 1:(0.01~0.05).

[0016] In step S1.1, the polyisocyanate is an aliphatic isocyanate and / or an aromatic isocyanate. The aliphatic isocyanate includes at least one of hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate trimer (IPDI trimer), and hexamethylene diisocyanate biuret (HDI biuret). The aromatic isocyanate is polymethylene polyphenyl polyisocyanate (PAPI) or / and toluene diisocyanate trimer (TDI trimer). The carbodiimide stabilizer includes at least one of polycarbodiimide, monomeric carbodiimide, and bis(2,6-diisopropylphenyl)carbodiimide.

[0017] By controlling the reaction of polyisocyanate and carbodiimide stabilizer under an inert atmosphere at 60-70℃, and limiting the molar ratio of isocyanate groups to carbodiimide groups to 1:(0.01-0.05), the carbodiimide structure can be stably introduced into the isocyanate molecular system while ensuring the main reactivity of polyisocyanate, thus obtaining an isocyanate intermediate with both high reactivity and hydrolysis resistance. Among them, aliphatic isocyanates can improve the weather resistance, flexibility and yellowing resistance of the material, while aromatic isocyanates can enhance the mechanical strength and crosslinking density of the material. The combination of the two is beneficial to balance the construction performance and service performance of the grouting material. The introduced carbodiimide groups can react with the carboxylic acid produced by hydrolysis during the subsequent service of the material, inhibiting the acid-catalyzed degradation process. Therefore, it helps to improve the hydrolysis resistance, structural stability and long-term durability of the obtained isocyanate intermediate in the high humidity and high salinity environment of the nearshore.

[0018] In one embodiment, the polyisocyanate is an aromatic isocyanate, which is a polymethylene polyphenyl polyisocyanate (PAPI) or / and toluene diisocyanate trimer (TDI trimer).

[0019] Compared to aliphatic isocyanates, aromatic isocyanates, due to the presence of rigid benzene ring structures in their molecular structure, result in polyurethane materials with higher crosslinking density, chain segment rigidity, and intermolecular forces. This allows for the formation of a denser polymer network structure, effectively reducing the diffusion rate of chloride ions, sulfate ions, and moisture within the material and mitigating the corrosive effect of salt penetration on the polyurethane network. Simultaneously, the higher content of hard segments formed by aromatic isocyanates improves the material's mechanical strength, dimensional stability, and interfacial adhesion. Under long-term immersion conditions in high-salt nearshore environments, they are less prone to swelling, softening, and microcrack propagation, thus further enhancing the salt erosion resistance and long-term service stability of polyurethane grouting materials.

[0020] S1.2 Add the amine modifier to the isocyanate intermediate and continue stirring at 60~70℃ for 1~3h to obtain amino isocyanate, wherein the molar ratio of isocyanate group in polyisocyanate to amino group in amine modifier is 1:(0.1~0.2).

[0021] The amine modifier in step S1.2 includes at least one of 1-methylpiperazine, N-methylmonoethanolamine, diethanolamine, N,N-dimethylethylenediamine, and 4,4'-diaminodiphenylmethane.

[0022] By adding an amine modifier to the isocyanate intermediate and controlling the molar ratio of isocyanate groups to amine groups to be 1:(0.1~0.2), a functional structure containing active amine groups can be stably introduced into the isocyanate molecule while retaining some of the isocyanate activity, thereby obtaining an amine isocyanate with both high crosslinking reactivity and interface enhancement ability. The introduced amine groups can subsequently undergo ring-opening addition reactions with epoxy groups to further construct a polyurethane / epoxy interpenetrating network structure, improve the crosslinking density, structural compactness, and impermeability of the material, and help inhibit the migration of salt and moisture into the material interior.

[0023] S1.3 Add benzoyl chloride to amino isocyanate and stir at 50~70℃ for 20~30 min to obtain modified isocyanate, wherein the amount of benzoyl chloride added is 0.1~0.5wt% of the mass of polyisocyanate.

[0024] By adding benzoyl chloride to amino isocyanates and controlling its addition amount to 0.1~0.5wt% of the polyisocyanate mass, residual trace amounts of moisture and highly reactive free amine groups in the system can be precisely removed while retaining the subsequent reactivity of the amine groups, thereby obtaining modified isocyanates with significantly improved storage stability. Specifically, benzoyl chloride preferentially reacts with moisture to generate benzoic acid and hydrogen chloride, preventing moisture from reacting with isocyanate groups during storage or curing to generate carbon dioxide bubbles, ensuring the density and mechanical strength of the grouting material after curing. At the same time, benzoyl chloride undergoes an acylation reaction with unreacted free amine groups, converting them into a stable benzamide structure, inhibiting uncontrollable side reactions (such as excessive formation of urea bonds or abnormal increase in viscosity) between free amine groups and isocyanate groups during storage, and preventing problems such as gelation, thickening, or foaming of component A during long-term storage.

[0025] S2. Mix the epoxy compound with the tertiary amine compound and heat to react, to obtain an epoxy intermediate. Then add a haloalkane to the epoxy intermediate and continue heating to react, to obtain a modified epoxy compound, wherein the modified epoxy compound contains a quaternary ammonium cation.

[0026] By reacting epoxy compounds with tertiary amine compounds to generate epoxy intermediates, followed by quaternization treatment with haloalkanes, quaternary ammonium cations are introduced into the epoxy compound molecules. This results in modified epoxy compounds possessing both epoxy group reactivity and permanently positively charged ionic functional groups. The quaternary ammonium cations can actively capture high concentrations of corrosive anions in seawater through strong electrostatic adsorption during the service life of the grouting material, forming a dense ion-crosslinked hardened layer in situ on the material surface. This hardened layer acts as a physical barrier, further blocking salt and moisture penetration. Furthermore, when this layer is damaged, the exposed quaternary ammonium cations can recombine with anions, achieving self-healing continuous protection. In addition, the residual epoxy groups that did not participate in the quaternization reaction can undergo ring-opening addition reactions with the amine groups introduced in step S1 during subsequent curing, further constructing a polyurethane / epoxy interpenetrating network structure. This improves the material's crosslinking density, structural compactness, and impermeability, thereby synergistically enhancing the grouting material's resistance to salt erosion and its long-term service life in near-shore high-salt-spray, high-humidity cable tunnel environments.

[0027] Reference Figure 3 Step S2 includes: S2.1 Add the epoxy compound and the tertiary amine compound to an organic solvent, and under an inert atmosphere, heat to 60~100℃ and stir for 2~6 hours to obtain an epoxy intermediate. The molar ratio of the epoxy group in the epoxy compound to the amine group in the tertiary amine compound is 1:(0.45~0.55), and the mass ratio of the epoxy compound to the organic solvent is 1:(1~2).

[0028] In step S2.1, the epoxy compound includes at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, polyethylene glycol diglycidyl ether, butyl glycidyl ether, and allyl glycidyl ether, and the tertiary amine compound includes at least one of triethylamine, N-methyldiethanolamine, pyridine, N,N-dimethylaniline, and triethylenediamine.

[0029] By adding an epoxy compound and a tertiary amine compound to an organic solvent under an inert atmosphere and stirring the reaction at 60–100 °C for 2–6 h, and limiting the molar ratio of epoxy group to tertiary amine group to 1:(0.45–0.55) and the mass ratio of epoxy compound to organic solvent to 1:(1–2), the nucleophilicity of the nitrogen atom in the tertiary amine compound can attack the three-membered ring in the epoxy group, resulting in a ring-opening addition reaction to generate a hydroxyalkylated epoxy intermediate containing a tertiary ammonium structure. This process ensures the complete conversion of the epoxy group and the introduction of the tertiary ammonium structure while avoiding the introduction of excess tertiary amine residue that could lead to the introduction of free amine in subsequent reactions. Amine impurities are removed to obtain epoxy intermediates with well-defined structures, high purity, and controllable reactivity. By controlling the reaction temperature within the range of 60-100℃, a sufficient reaction rate for the ring-opening reaction is ensured while avoiding excessively high temperatures that could trigger self-polymerization of epoxy groups or decomposition of tertiary amines. The addition of organic solvents reduces the viscosity of the system, promotes uniform mixing of reactants, and effectively absorbs the exothermic reaction, preventing local overheating and side reactions. An inert atmosphere protects the reaction system from oxidation interference and hydrolysis side reactions caused by oxygen and moisture, providing an ideal precursor for the subsequent quaternization reaction to prepare modified epoxy compounds.

[0030] S2.2 Cool the epoxy intermediate to 50~70℃, add haloalkanes under stirring, and keep the mixture at the temperature and stir for 3~6h to obtain a quaternary ammonium intermediate, wherein the amount of haloalkanes added is 10~30wt% of the mass of the epoxy compound.

[0031] The haloalkane in step S2.2 includes at least one of bromoethane, chlorohexadecane, chlorobutane, benzyl chloride, and bromobutane.

[0032] By cooling the epoxy intermediate to 50-70°C under stirring conditions and then adding haloalkanes, controlling the amount of haloalkanes added to be 10-30 wt% of the epoxide compound mass, and maintaining the reaction temperature for 3-6 hours, the halogen atoms (Cl, Br) in the haloalkanes can be used as leaving groups to undergo nucleophilic substitution reactions (quaternization reactions) with the tertiary ammonium structure in the epoxy intermediate, converting the tertiary ammonium into stable quaternary ammonium cations. This process ensures the quaternization reaction proceeds fully while avoiding the introduction of excessive haloalkanes that could lead to the introduction of free halogenated impurities or side reactions in subsequent systems, thus obtaining quaternary ammonium cations. A quaternary ammonium intermediate with high ion content and stable structure is obtained. By controlling the reaction temperature within the range of 50~70℃, a sufficient reaction rate is ensured for the quaternization reaction to achieve a high conversion rate within 3~6h, while avoiding the decomposition or side reactions of haloalkanes caused by excessive temperature. The temperature-maintaining and stirring conditions ensure sufficient contact and uniform reaction between haloalkanes and epoxy intermediates, which helps to obtain quaternary ammonium intermediates with controllable degree of quaternization, uniform cation distribution and good storage stability. This lays a key ionic functional group foundation for the final preparation of modified epoxy compounds with the ability to actively capture aggressive anions.

[0033] S2.3 Cool the quaternary ammonium intermediate to 30~50℃, add a neutralizing agent aqueous solution to adjust the pH of the quaternary ammonium intermediate to 6~8, stir, let stand, collect the organic phase, wash with deionized water, and distill to obtain the modified epoxy compound. The distillation temperature is 50~80℃ and the vacuum degree is -0.08~-0.095 MPa.

[0034] The neutralizing agent in step S2.3 includes at least one of sodium bicarbonate aqueous solution, sodium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium carbonate aqueous solution.

[0035] The quaternary ammonium intermediate was cooled to 30-50°C, and then a neutralizing agent aqueous solution was added to adjust the pH to 6-8. The mixture was then stirred, allowed to stand, the organic phase was collected, washed with deionized water, and then subjected to a process at 50-80°C and a vacuum degree of -0.08 to -0.095. Distillation under MPa conditions utilizes a neutralizing agent to neutralize unreacted haloalkanes, free tertiary amines, or acidic / basic impurities such as hydrogen halides generated in the quaternary ammonium intermediate, converting them into water-soluble salts that enter the aqueous phase. Water-soluble impurities are then separated from the organic phase through settling and deionized water washing. Finally, residual organic solvents and trace amounts of water are removed by vacuum distillation, yielding a modified epoxy compound with high purity, neutral pH, and low ionic impurity content. Controlling the temperature to 30–50°C avoids thermal decomposition or side reactions of the quaternary ammonium cation under high-temperature conditions. Adjusting the pH to a neutral range of 6–8 ensures sufficient neutralization and removal of acidic / basic impurities while preventing excessively acidic or alkaline environments from damaging the structural stability of the quaternary ammonium cation. The deionized water washing step effectively removes inorganic salts generated in the neutralization reaction and residual water-soluble impurities. Vacuum distillation is performed at 50–80°C and a vacuum degree of -0.08 to -0.095. The process is carried out under MPa conditions, which can efficiently remove organic solvents and moisture at lower temperatures, avoid thermal degradation of quaternary ammonium cations, and ensure that the residual solvent in the product is minimized. Therefore, it helps to obtain modified epoxy compounds with high purity, good stability, no corrosive impurities, and long shelf life.

[0036] S3. Mix the polyether polyol with the sulfonating agent and catalyst, and heat to react to obtain the modified polyether polyol, wherein the modified polyether polyol contains sulfonic acid groups.

[0037] By heating and reacting polyether polyols with sulfonating agents under the action of a catalyst, sulfonic acid groups are covalently introduced into the polyether polyol molecular chain, giving the resulting modified polyether polyol both hydroxyl reactivity and permanently negatively charged ionic functional groups. The sulfonic acid groups can actively capture high concentrations of corrosive cations in seawater through strong coordination complexation during the service life of the grouting material, forming a dense ion-crosslinked hardened layer in situ on the material surface. This hardened layer acts as a physical barrier, further blocking salt and moisture penetration. Furthermore, after this layer is damaged, the exposed sulfonic acid groups can re-bind cations, achieving self-healing continuous protection. In addition, the residual hydroxyl groups that did not participate in the sulfonation reaction can undergo addition polymerization with the isocyanate groups in component A during subsequent curing, forming a polyurethane network structure. This ensures the mechanical strength and structural integrity of the material. The covalently linked sulfonic acid groups do not migrate or bleed during long-term service, continuously and stably performing their ion-capturing function. This, in conjunction with quaternary ammonium cations, achieves bidirectional capture and fixation of anions and cations in seawater, significantly enhancing the grouting material's resistance to salt erosion and its long service life in near-shore high-salt-spray and high-humidity cable tunnel environments.

[0038] Reference Figure 4 Step S3 includes: S3.1 Add the polyether polyol to the reactor, heat it to 110~120℃ in an inert atmosphere, stir and dehydrate for 1.5~2.5h to obtain the pretreated polyol, wherein the hydroxyl value of the polyether polyol is 30~150mgKOH / g.

[0039] The polyether polyol in step S3.1 includes at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, and polyoxypropylene triol.

[0040] By heating polyether polyols to 110-120℃ and stirring for 1.5-2.5 hours in an inert atmosphere, the high temperature and vacuum conditions can efficiently remove free water and low-boiling-point volatiles from the polyether polyols, reducing the water content of the system to below 0.05%, thereby obtaining dry, pure, and hydroxyl-value-stable pretreated polyols. Controlling the dehydration temperature within the range of 110-120℃ ensures rapid evaporation of water under boiling conditions, avoiding incomplete dehydration due to excessively low temperatures, while also preventing thermal oxidative degradation or molecular chain breakage of the polyether polyols due to excessively high temperatures. The inert atmosphere effectively isolates the polyether polyols from air. The process involves removing oxygen and moisture to prevent oxidation and discoloration of the polyether polyol or the introduction of new moisture during dehydration. Stirring increases the surface area of ​​the liquid and promotes the diffusion of internal moisture to the surface, thus improving dehydration efficiency. A dehydration time of 1.5 to 2.5 hours ensures sufficient removal of moisture while avoiding the negative impact of prolonged heating on the performance of the polyether polyol. The hydroxyl value of the polyether polyol is controlled within the range of 30 to 150 mg KOH / g to ensure sufficient hydroxyl reaction sites during subsequent reactions with sulfonating agents. This avoids insufficient sulfonic acid group grafting density due to an excessively low hydroxyl value or excessive crosslinking due to an excessively high hydroxyl value, which would affect the flexibility of the material.

[0041] S3.2 Add sulfonic acid reagent and catalyst to the pretreated polyol, and stir the reaction at 70~100℃ for 6~12h in an inert atmosphere to obtain pre-modified polyol. The molar ratio of hydroxyl groups of polyether polyol to sulfonic acid reagent is 1:(0.2~0.3), and the amount of catalyst added is 1~2wt% of the mass of polyether polyol.

[0042] The sulfonic acid reagent in step S3.2 includes at least one of 2-chloroethylsulfonic acid, chloromethanesulfonic acid, and 2-bromoethylsulfonic acid, and the catalyst includes at least one of sodium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and triethanolamine.

[0043] By adding sulfonic acid reagent and catalyst to pretreated polyols under an inert atmosphere and stirring the reaction at 70-100℃ for 6-12 hours, and limiting the molar ratio of hydroxyl groups in the polyether polyol to the sulfonic acid reagent to 1:(0.2-0.3) and the amount of catalyst added to 1-2 wt% of the polyether polyol mass, the alkaline environment provided by the catalyst can promote the deprotonation of the terminal hydroxyl groups of the polyether polyol, enhance the nucleophilic reactivity of the hydroxyl groups, and enable the hydroxyl groups to act as nucleophiles to attack the reaction sites in the sulfonic acid reagent, resulting in a nucleophilic substitution reaction. This covalently introduces sulfonic acid groups into the ends of the polyether polyol molecular chains, ensuring that the grafting density of the sulfonic acid groups meets the requirements. While meeting the requirements for ion capture, it is necessary to avoid excessive residual sulfonic acid reagent, which could lead to difficulties in subsequent purification or the introduction of side reactions, thereby obtaining pre-modified polyols with uniform sulfonic acid group grafting and partial retention of hydroxyl groups. Among these measures, controlling the reaction temperature within the range of 70~100℃ ensures that the nucleophilic substitution reaction has a sufficient reaction rate to achieve a high hydroxyl conversion rate within 6~12h, while avoiding excessive temperature that could cause thermal decomposition of sulfonic acid reagents or oxidative degradation of polyether polyols. The inert atmosphere effectively prevents oxygen from interfering with the oxidation of the reaction system and water from competitively hydrolyzing the sulfonic acid reagents. The appropriate addition of a catalyst can significantly reduce the reaction activation energy and shorten the reaction time.

[0044] S3.3 Cool the pre-modified polyol to 40~60℃, first add an alkaline neutralizing agent to adjust the pH of the pre-modified polyol to 6.5~7.5, then add activated carbon and stir for 20~30 min, filter and dry to obtain modified polyether polyol. The alkaline neutralizing agent includes at least one of triethanolamine, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and sodium carbonate aqueous solution. The amount of activated carbon added is 1~5 wt% of the mass of the polyether polyol.

[0045] By cooling the pre-modified polyol to 40-60℃, adding an alkaline neutralizing agent to adjust the pH to 6.5-7.5, then adding activated carbon and stirring for 20-30 minutes, followed by filtration and drying, the alkaline neutralizing agent can neutralize acidic impurities such as hydrogen halides generated in the pre-modified polyol, converting them into water-soluble salts. Simultaneously, the sulfonic acid groups are converted to sulfonate forms, improving their stability and ion-binding activity in the polyether system. This results in a pH-neutralized, sulfonate-stable modified polyether polyol. Controlling the temperature to 40-60℃ avoids the formation of sulfonic acid groups under high-temperature conditions. The thermal decomposition of the group or the oxidative degradation of the polyether polyol, adjusting the pH to a neutral range of 6.5~7.5 ensures that acidic impurities are fully neutralized and removed, and that sulfonic acid groups are completely converted into sulfonate forms. It also prevents the ether bonds of the polyether polyol from breaking or new alkaline impurities from being broken due to an overly alkaline environment. The addition of activated carbon can effectively capture organic impurities and some colored substances in the system through physical and chemical adsorption. Stirring the reaction for 20~30 minutes ensures that the activated carbon and the system are in full contact and adsorption balance. The filtration operation removes the activated carbon loaded with impurities, and the drying process removes residual moisture and volatile organic compounds from the system.

[0046] S4. Mix the modified isocyanate with the accelerator to obtain the A component polymer grouting material. Mix the modified epoxy compound, the modified polyether polyol and the crown ether polymerization inhibitor to obtain the B component polymer grouting material.

[0047] In step S4, the accelerator is composed of a mixture of organotin catalyst and tertiary amine catalyst in a mass ratio of 1:(2~5). The organotin catalyst includes at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dioctyltin dilaurate. The tertiary amine catalyst includes at least one of triethylenediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N-dimethylbenzylamine, and N-ethylmorpholine. The mass ratio of modified isocyanate to accelerator is 100:(0.3~1.5). The crown ether polymerization inhibitor includes at least one of 18-crown ether-6, 15-crown ether-5, cyclodextrin, and dibenzo-18-crown ether-6. The mass ratio of modified epoxy compound, modified polyether polyol, and crown ether polymerization inhibitor is 100:(120~130):(1~3).

[0048] In component A, the composite accelerator is composed of organotin catalysts and tertiary amine catalysts in a mass ratio of 1:(2~5). The organotin catalyst preferentially catalyzes the addition polymerization reaction of isocyanate groups with hydroxyl groups in the modified polyether polyol, rapidly forming the polyurethane main network. The tertiary amine catalyst simultaneously catalyzes the ring-opening addition reaction of the amine groups introduced in step S1 with the residual epoxy groups in the modified epoxy compound, constructing an epoxy crosslinking network. The two work synergistically to achieve efficient and simultaneous construction of the polyurethane / epoxy interpenetrating network, improving the crosslinking density, structural compactness, and impermeability of the material. Secondly, in component B, the crown ether polymerization inhibitor selectively complexes quaternary ammonium cations through its cyclic cavity structure, effectively shielding the electrostatic interaction between quaternary ammonium cations and sulfonic acid groups during storage, preventing premature formation of ion pairs that could lead to increased viscosity or sedimentation and stratification in component B, thus ensuring the long-term storage stability and construction fluidity of component B. After grouting, the crown ether reacts with Mg in seawater. 2+ Ca 2+ Competitive complexation occurs, and the released quaternary ammonium cations bind Cl through electrostatic adsorption. - SO4 2- The sulfonic acid group binds to Mg through coordination complexation. 2+ Ca 2+ A dense ion-crosslinked hardened layer is formed in situ on the material surface. This hardened layer acts as a physical barrier to prevent the penetration of salt and moisture and has self-healing properties, which significantly improves the salt corrosion resistance and long-term service life of the grouting material in the near-shore high salt spray and high humidity cable tunnel environment.

[0049] In addition, a two-component polymer grouting material for cable tunnels is proposed, which is prepared by the above-described preparation method of a two-component polymer grouting material for cable tunnels. The two-component polymer grouting material is composed of component A polymer grouting material and component B polymer grouting material mixed at a mass ratio of 1:(1.05~1.1). The operation method is as follows: after measuring component A polymer grouting material and component B polymer grouting material according to the mass ratio, they are mixed evenly by a two-liquid grouting pump through a mixer and injected into the joint of cable tunnel segments. The grouting pressure is controlled at 0.2~0.8MPa and the grouting flow rate is controlled at 10~30L / min. During the grouting process, the grouting situation at the seepage points of the tunnel wall is observed. Grouting is stopped when grouting begins to appear at adjacent grouting holes or joints.

[0050] The preferred mixing mass ratio of the polymer grouting material of component A to that of component B is 1:1.08. Before grouting, the amount of accelerator should be adjusted according to the tunnel ambient temperature. When the ambient temperature is below 10℃, the amount of accelerator can be increased appropriately or the polymer grouting materials of components A and B can be preheated to 20~30℃. If a large flow of water seepage occurs during the grouting process, the grouting pressure can be increased to 1.0MPa. After grouting is completed, the grouting pump and pipeline should be cleaned with a cleaning agent in a timely manner to prevent residual materials from solidifying and clogging the equipment.

[0051] For example, the present invention provides the following specific embodiments to illustrate the specific preparation method: Example 1: S1.1 Add HDI trimer to a reaction vessel, heat to 65°C in an inert atmosphere, add polycarbodiimide, stir and react for 3 hours to obtain an isocyanate intermediate, wherein the molar ratio of isocyanate groups in HDI trimer to carbodiimide groups in polycarbodiimide is 1:0.03. S1.2 Add 1-methylpiperazine to the isocyanate intermediate and continue stirring at 65°C for 2 hours to obtain amino isocyanate, wherein the molar ratio of isocyanate group to amino group of 1-methylpiperazine in HDI trimer is 1:0.15. S1.3. Benzoyl chloride is added to the amino isocyanate and stirred at 60°C for 25 min to obtain the modified isocyanate. The amount of benzoyl chloride added is 0.3 wt% of the mass of the HDI trimer. S2.1. Bisphenol A diglycidyl ether and triethylamine are added to toluene. Under an inert atmosphere, the mixture is heated to 80°C and stirred for 4 hours to obtain an epoxy intermediate. The molar ratio of the epoxy group in bisphenol A diglycidyl ether to the amino group in triethylamine is 1:0.5, and the mass ratio of bisphenol A diglycidyl ether to toluene is 1:1.5. S2.2. Cool the epoxy intermediate to 60℃, add bromoethane under stirring, and maintain the temperature and stir for 4.5 h to obtain the quaternary ammonium intermediate. The amount of bromoethane added is 20 wt% of the mass of bisphenol A diglycidyl ether. S2.3 Cool the quaternary ammonium intermediate to 40℃, add sodium carbonate aqueous solution to adjust the pH of the quaternary ammonium intermediate to 6~8, stir, let stand, collect the organic phase, wash with deionized water, and distill to obtain the modified epoxy compound. The distillation temperature is 65℃ and the vacuum degree is -0.09MPa. S3.1. Polyethylene glycol is added to a reaction vessel, heated to 115°C in an inert atmosphere, and stirred to dehydrate for 2 hours to obtain a pretreated polyol, wherein the hydroxyl value of the polyethylene glycol is 80 mg KOH / g. S3.2. Add 2-chloroethylsulfonic acid and a 20wt% sodium hydroxide aqueous solution to the pretreated polyol. Stir and react at 85℃ for 9 hours under an inert atmosphere to obtain a pre-modified polyol. The molar ratio of the hydroxyl groups of polyethylene glycol to 2-chloroethylsulfonic acid is 1:0.25, and the amount of sodium hydroxide aqueous solution added is 1.5wt% of the mass of polyethylene glycol. S3.3. Cool the pre-modified polyol to 50℃, first add triethanolamine to adjust the pH of the pre-modified polyol to 6.5~7.5, then add activated carbon and stir for 25 min, filter and dry to obtain modified polyether polyol, wherein the amount of activated carbon added is 3wt% of the mass of polyethylene glycol; S4. The modified isocyanate and the accelerator are mixed at a mass ratio of 100:0.8 to obtain the polymer grouting material of component A. The modified epoxy compound, the modified polyether polyol and 18-crown ether-6 are mixed at a mass ratio of 100:125:2 to obtain the polymer grouting material of component B. The accelerator is composed of dibutyltin dilaurate and triethylenediamine mixed at a mass ratio of 1:3.5.

[0052] Example 2: The process is basically the same as in Example 1, except that in step S1.1, TDI trimer is used instead of HDI trimer, that is, the polyisocyanate is an aromatic isocyanate.

[0053] Comparative Example 1: It is basically the same as Example 1, except that polycarbodiimide was not added in step S1.1, that is, no carbodiimide stabilizer was used in step S1.

[0054] Comparative Example 2: It is basically the same as Example 1, except that 1-methylpiperazine is not added in step S1.2, that is, no amine modifier is used in step S1.

[0055] Comparative Example 3: It is basically the same as Example 1, except that triethylamine is not added in step S2.1, that is, no tertiary amine compound is used in step S2.

[0056] Comparative Example 4: It is basically the same as Example 1, except that bromoethane is not used in step S2.2, that is, no haloalkane is used in step S2.

[0057] Comparative Example 5: It is basically the same as Example 1, except that 2-chloroethylsulfonic acid is not used in step S3.1, that is, no sulfonating agent is used in step S3.

[0058] Comparative Example 6: The process is basically the same as in Example 1, except that the polymer grouting material of component B in step S4 does not contain 18-crown ether-6, that is, it does not contain crown ether polymerization inhibitor.

[0059] Comparative Example 7: 1-Methylpiperazine was added to the HDI trimer, and the reaction was continued at 65°C for 2 hours to obtain amino isocyanate. The molar ratio of isocyanate groups to amino groups of 1-methylpiperazine in the HDI trimer was 1:0.15. Aminoisocyanate and accelerator are mixed at a mass ratio of 100:0.8 to obtain component A polymer grouting material. Bisphenol A diglycidyl ether and polyethylene glycol are mixed at a mass ratio of 100:125 to obtain component B polymer grouting material. The accelerator is composed of dibutyltin dilaurate and triethylenediamine mixed at a mass ratio of 1:3.5.

[0060] Performance testing: Salt corrosion resistance test: The two-component polymer grouting materials prepared in Examples 1-2 and Comparative Examples 1-7 were prepared into standard samples of 50mm×50mm×5mm with a mass ratio of polymer grouting material A to polymer grouting material B of 1:1.08. After curing at room temperature (23±2℃) and relative humidity of 50±5% for 7 days, the salt corrosion resistance test was carried out.

[0061] A simulated seawater erosion solution was prepared with the following components: NaCl 24.5 g / L, MgCl2·6H2O 11.0 g / L, Na2SO4 4.1 g / L, CaCl2 1.2 g / L, and KCl 0.7 g / L. The pH of the solution was adjusted to 7.5–8.0. The sample was completely immersed in the above erosion solution and removed after 28 days. The following methods were used for testing: (1) Mass change rate test: After the sample is taken out of the etching solution, the surface is gently rinsed with deionized water to remove the attached salt, and then the surface moisture is absorbed with filter paper. After drying in an oven at 105±2℃ until constant weight, the sample is weighed and the mass change rate is calculated according to the formula (initial mass - mass after soaking) / initial mass × 100%. (2) Mechanical property testing: The tensile strength retention rate and elongation at break retention rate of the specimen were determined using a universal testing machine; (3) Surface hardness test: The surface hardness of the sample after immersion for 28 days was tested using a Shore D hardness tester.

[0062] The test results are shown in Table 1.

[0063] Table 1. Performance Tests of Two-Component Polymer Grouting Materials: According to the results in Table 1, compared with Comparative Example 7 (unmodified polyurethane), Examples 1 and 2 both showed lower mass loss (negative values ​​indicate corrosion weight loss) and higher mechanical property retention and surface hardness. Among them, Example 2 (aromatic TDI trimer) was slightly better than Example 1 (aliphatic HDI trimer) in terms of tensile strength retention and surface hardness, but Example 1 performed better in terms of elongation at break retention. Further observation of Examples 1 and Comparative Examples 1-6 showed that, compared with Example 1, Comparative Examples 1-6 lacked carbodiimide stabilizer, amine modifier, tertiary amine compound, haloalkanes, sulfonating agent, and crown ether polymerization inhibitor, respectively, resulting in a decrease in the salt erosion resistance of the final two-component polymer grouting material.

[0064] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein. The specification and examples are to be considered exemplary only, and the true scope and spirit of this disclosure are indicated by the following claims.

[0065] It should be understood that this disclosure is not limited to the precise structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of this disclosure is limited only by the appended claims.

Claims

1. A method for preparing a two-component polymer grouting material for cable tunnels, characterized in that, The preparation method includes the following steps: S1. Mix polyisocyanate with carbodiimide stabilizer and heat to react to obtain isocyanate intermediate. Then add amine modifier to isocyanate intermediate and continue heating to react to obtain modified isocyanate. S2. Mix the epoxy compound with the tertiary amine compound and heat to react to obtain an epoxy intermediate. Then add a haloalkane to the epoxy intermediate and continue to heat to react to obtain a modified epoxy compound, wherein the modified epoxy compound contains a quaternary ammonium cation. S3. Mix the polyether polyol with the sulfonating agent and the catalyst, and heat to react to obtain the modified polyether polyol, wherein the modified polyether polyol contains sulfonic acid groups. S4. Mix the modified isocyanate with the accelerator to obtain the A component polymer grouting material. Mix the modified epoxy compound, the modified polyether polyol and the crown ether polymerization inhibitor to obtain the B component polymer grouting material.

2. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 1, characterized in that, Step S1 includes: S1.1 Add the polyisocyanate to the reaction vessel, heat it to 60~70℃ in an inert atmosphere, add the carbodiimide stabilizer, stir and react for 2~4h to obtain the isocyanate intermediate, wherein the molar ratio of the isocyanate group in the polyisocyanate to the carbodiimide group in the carbodiimide stabilizer is 1:(0.01~0.05). S1.2 Add the amine modifier to the isocyanate intermediate and continue stirring at 60~70℃ for 1~3h to obtain amino isocyanate, wherein the molar ratio of isocyanate group in polyisocyanate to amino group in amine modifier is 1:(0.1~0.2). S1.3 Add benzoyl chloride to amino isocyanate and stir at 50~70℃ for 20~30 min to obtain modified isocyanate, wherein the amount of benzoyl chloride added is 0.1~0.5wt% of the mass of polyisocyanate.

3. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 2, characterized in that, In step S1.1, the polyisocyanate is an aliphatic isocyanate and / or an aromatic isocyanate. The aliphatic isocyanate includes at least one of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and hexamethylene diisocyanate biuret. The aromatic isocyanate is polymethylene polyphenyl polyisocyanate or / and toluene diisocyanate trimer. The carbodiimide stabilizer includes at least one of polycarbodiimide, monomeric carbodiimide, and bis(2,6-diisopropylphenyl)carbodiimide. In step S1.2, the amine modifier includes at least one of 1-methylpiperazine, N-methylmonoethanolamine, diethanolamine, N,N-dimethylethylenediamine, and 4,4'-diaminodiphenylmethane.

4. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 3, characterized in that, The polyisocyanate is an aromatic isocyanate, which is a polymethylene polyphenyl polyisocyanate or / and toluene diisocyanate trimer.

5. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 1, characterized in that, Step S2 includes: S2.1 Add the epoxy compound and the tertiary amine compound to an organic solvent, and under an inert atmosphere, heat to 60~100℃ and stir for 2~6 hours to obtain an epoxy intermediate. The molar ratio of the epoxy group in the epoxy compound to the amine group in the tertiary amine compound is 1:(0.45~0.55), and the mass ratio of the epoxy compound to the organic solvent is 1:(1~2). S2.2 Cool the epoxy intermediate to 50-70℃, add haloalkanes under stirring, and maintain the temperature and stir for 3-6 hours to obtain a quaternary ammonium intermediate, wherein the amount of haloalkanes added is 10-30 wt% of the mass of the epoxy compound; S2.3 Cool the quaternary ammonium intermediate to 30~50℃, add a neutralizing agent aqueous solution to adjust the pH of the quaternary ammonium intermediate to 6~8, stir, let stand, collect the organic phase, wash with deionized water, and distill to obtain the modified epoxy compound. The distillation temperature is 50~80℃ and the vacuum degree is -0.08~-0.095 MPa.

6. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 5, characterized in that, In step S2.1, the epoxy compound includes at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, polyethylene glycol diglycidyl ether, butyl glycidyl ether, and allyl glycidyl ether; the tertiary amine compound includes at least one of triethylamine, N-methyldiethanolamine, pyridine, N,N-dimethylaniline, and triethylenediamine; the organic solvent includes at least one of acetone, butanone, ethyl acetate, toluene, xylene, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran; in step S2.2, the halogenated alkane includes at least one of bromoethane, hexadecane chloride, chlorobutane, benzyl chloride, and n-butane bromide; and in step S2.3, the neutralizing agent includes at least one of sodium bicarbonate aqueous solution, sodium carbonate aqueous solution, sodium hydroxide aqueous solution, and potassium carbonate aqueous solution.

7. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 1, characterized in that, Step S3 includes: S3.1 Add the polyether polyol to the reactor, heat it to 110~120℃ in an inert atmosphere, stir and dehydrate for 1.5~2.5h to obtain the pretreated polyol, wherein the hydroxyl value of the polyether polyol is 30~150mgKOH / g; S3.2 Add sulfonic acid reagent and catalyst to the pretreated polyol, and stir the reaction at 70~100℃ for 6~12h in an inert atmosphere to obtain pre-modified polyol. The molar ratio of hydroxyl groups of polyether polyol to sulfonic acid reagent is 1:(0.2~0.3), and the amount of catalyst added is 1~2wt% of the mass of polyether polyol. S3.3 Cool the pre-modified polyol to 40~60℃, first add an alkaline neutralizing agent to adjust the pH of the pre-modified polyol to 6.5~7.5, then add activated carbon and stir for 20~30 min, filter and dry to obtain modified polyether polyol. The alkaline neutralizing agent includes at least one of triethanolamine, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and sodium carbonate aqueous solution. The amount of activated carbon added is 1~5 wt% of the mass of the polyether polyol.

8. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 7, characterized in that, In step S3.1, the polyether polyol includes at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, and polyoxypropylene triol; in step S3.2, the sulfonic acid reagent includes at least one of 2-chloroethylsulfonic acid, chloromethanesulfonic acid, and 2-bromoethylsulfonic acid; and the catalyst includes at least one of sodium hydroxide aqueous solution, sodium bicarbonate aqueous solution, and triethanolamine.

9. The method for preparing a two-component polymer grouting material for cable tunnels according to claim 1, characterized in that, In step S4, the accelerator is composed of a mixture of organotin catalyst and tertiary amine catalyst in a mass ratio of 1:(2~5). The organotin catalyst includes at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and dioctyltin dilaurate. The tertiary amine catalyst includes at least one of triethylenediamine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N-dimethylbenzylamine, and N-ethylmorpholine. The mass ratio of modified isocyanate to accelerator is 100:(0.3~1.5). The crown ether polymerization inhibitor includes at least one of 18-crown ether-6, 15-crown ether-5, cyclodextrin, and dibenzo-18-crown ether-6. The mass ratio of modified epoxy compound, modified polyether polyol, and crown ether polymerization inhibitor is 100:(120~130):(1~3).

10. A two-component polymer grouting material for cable tunnels, characterized in that, The two-component polymer grouting material is prepared by the preparation method of a two-component polymer grouting material for cable tunnels as described in any one of claims 1-9; The two-component polymer grouting material is composed of component A polymer grouting material and component B polymer grouting material mixed at a mass ratio of 1:(1.05~1.1). The operation method is as follows: after measuring component A polymer grouting material and component B polymer grouting material according to the mass ratio, they are mixed evenly by a two-liquid grouting pump through a mixer and injected into the joint of cable tunnel segments. The grouting pressure is controlled at 0.2~0.8MPa and the grouting flow rate is controlled at 10~30L / min. During the grouting process, the grouting situation at the seepage points of the tunnel wall is observed. Grouting is stopped when grouting begins to appear at adjacent grouting holes or joints.

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