Flexible anti-vibration tunnel waterproof curtain grouting material and construction method thereof

Abstract

The application belongs to the technical field of tunnel and underground engineering plugging materials, and provides a flexible anti-vibration tunnel waterproof curtain grouting material and a construction method thereof, which comprises: component A and component B; the mass ratio of component A to component B is 1:1-3:1; the component A comprises isocyanate-terminated polyurethane, divalent acid ester and phosphoric acid; the component B is composed of the following raw materials in parts by weight: divalent acid ester 50-80 parts, curing agent 10-20 parts, catalyst 1-5 parts and dynamic water anti-dispersing agent 1-5 parts; the curing agent is IPDA and zinc dimethyl dithiocarbamate, and the molar ratio of the two is 2: (1-1.5). The grouting material provided by the application has a high-multiple foaming and expanding function, can fill cracks in a strong vibration environment such as a tunnel excavated by the drill-and-blast method, and the setting time can be accurately controlled, the water gushing plugging efficiency is improved, and the problem of the fragility of rigid water plugging materials in a blasting vibration environment is solved.

Description

Technical Field

[0001] This invention belongs to the technical field of tunnel and underground engineering sealing materials, and relates to a flexible vibration-resistant tunnel waterproof curtain grouting material and its construction method. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Tunnel and underground engineering projects often employ the drill-and-blast method, where the intense and frequent vibrations generated by blasting have a significant destructive impact on the engineering structure and ancillary facilities. Traditional grouting and sealing materials such as cement grout, water glass, and single-component polyurethane typically form rigid or brittle stone bodies after curing. Under continuous blasting vibration loads, these rigid stone bodies are highly susceptible to cracking, fragmentation, or detachment from the rock mass interface. This causes previously sealed leakage channels to reopen due to material fracture, creating new and unpredictable leakage points. Furthermore, the bonding interface between the rigid stone body and the rock mass, which has fissures or a tendency to deform, is prone to micro-cracks or debonding due to vibration stress concentration, compromising the integrity and sealing of the waterproofing curtain and causing structural interface instability. These problems not only significantly reduce waterproofing effectiveness and increase subsequent maintenance costs but also pose a serious threat to construction safety and structural durability. Therefore, it is urgent to address the vulnerability of rigid sealing materials under blasting vibration environments. Summary of the Invention

[0004] To address the aforementioned problems, this invention provides a flexible, vibration-resistant, waterproof curtain grouting material for tunnels and its construction method. The grouting material provided by this invention is particularly suitable for drill-and-blast tunnels, forming a flexible, vibration-resistant, and waterproof curtain. The core characteristic of this material lies in the high elasticity of the solidified rock mass it forms after curing. Even after undergoing significant deformation with a compression deformation of up to 50%, it can almost completely recover its original shape after the external force is removed, maintaining excellent waterproof sealing performance. This effectively resists repeated deformation caused by blasting vibrations without cracking, peeling, or leakage.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a flexible vibration-resistant tunnel waterproof curtain grouting material, comprising: component A and component B; the mass ratio of component A to component B is 1:1 to 3:1;

[0007] Component A includes: isocyanate-terminated polyurethane, divalent ester, and phosphoric acid;

[0008] The B component is composed of the following raw materials in parts by weight: 50-80 parts of divalent ester, 10-20 parts of curing agent, 1-5 parts of catalyst, and 1-5 parts of hydrophobic anti-dispersant.

[0009] The curing agent is IPDA and zinc dimethyl dithiocarbamate, with a molar ratio of 2:(1-1.5).

[0010] Unlike existing rigid water-blocking materials, this invention, based on a polyurethane prepolymer, introduces a divalent ester (diluent) and phosphoric acid (polymerization inhibitor) into component A, and a divalent ester (diluent), isophorone diamine (IPDA), and zinc dimethyl dithiocarbamate (binary curing agent) into component B. This optimizes the structure and stability of the prepolymer, resulting in a highly elastic three-dimensional cross-linked network structure of the cured polyurethane. The divalent ester in both components A and B acts as a diluent, reducing the system viscosity and facilitating the dispersion of the prepolymer molecular chains. The combined addition of both components ensures stable system viscosity after mixing components A and B. The phosphoric acid (polymerization inhibitor) suppresses the side reactions of residual isocyanate (-NCO) in the prepolymer, ensuring its stability and enabling it to form a regular cross-linked structure when reacting with component B, thus guaranteeing elastic properties. A combination of alicyclic amines and dynamic bond modifiers is used as the curing agent. The main curing agent is isophorone diamine (IPDA), whose alicyclic structure provides rigidity similar to aromatic rings, but steric hindrance facilitates molecular chain resilience. A sulfur-containing dynamic crosslinking agent, zinc dimethyl dithiocarbamate, is added as an auxiliary curing agent. Dynamic disulfide bonds enhance vibrational energy dissipation, resulting in superior compressive strength at a suitable expansion ratio. The catalyst is bismorpholino diethyl ether (DMDEE). Containing two morpholino rings, DMDEE exhibits high catalytic efficiency for the addition reaction of -NCO with active hydrogen, effectively catalyzing polyurethane reactions even at low temperatures. Compared to other monofunctional catalysts (such as triethylamine), its bifunctional groups significantly improve the reaction rate of the mixed system while maintaining low odor emissions. Simultaneously, DMDEE significantly reduces viscosity fluctuations after mixing components A and B. This is because its specific molecular structure allows for uniform distribution throughout the system in the initial reaction phase, ensuring that the diffusion rate of component B is consistent with the viscoelasticity of the system, making it particularly suitable for two-component grouting construction.

[0011] Therefore, the grouting material of this invention forms a stone body that, during the instantaneous strong impact and subsequent reciprocating vibration generated by blasting, can deform like an "elastic body" and absorb vibration energy, rather than accumulating internal stress until fracture like a brittle material. Even if the rock mass develops minor displacements or cracks under vibration, the material's strong recovery force after deformation allows it to remain tightly attached to the crack walls, maintaining the integrity of the seal and preventing new leakage channels from being created by vibration. Compared to rigid materials, flexible stone bodies are more tolerant of minor differential deformations inherent in the rock mass itself, reducing the risk of debonding caused by interfacial shear forces.

[0012] A second aspect of the present invention provides a construction method for a flexible vibration-resistant tunnel waterproof curtain grouting material, comprising:

[0013] Mixing component A with component B yields a flexible, vibration-resistant, waterproof curtain grouting material for tunnels.

[0014] The flexible vibration-resistant tunnel waterproof curtain grouting material is injected using the orifice two-liquid mixing grouting method to obtain the grout.

[0015] Beneficial effects of the present invention

[0016] (1) The stone body formed by this invention has excellent elastic recovery ability, which completely solves the global problem of rigid water-blocking materials breaking and debonding due to blasting vibration during drilling and blasting construction, thus creating new leakage points. It significantly improves the durability and reliability of waterproofing effect.

[0017] (2) The grouting material of the present invention is controlled by two components, and the setting time can be adjusted in real time according to the site requirements. Compared with single-component oil-based polyurethane materials, it is easy to construct and can meet the precise operation requirements of different site conditions.

[0018] (3) The grouting material provided by the present invention has a high expansion ratio, short setting time, dynamic water anti-dispersion effect, and gelation and curing strength > 5MPa. It is a grouting material specially developed for the high-speed dynamic water disaster in the wide fissures of underground engineering.

[0019] (4) The grouting material preparation process provided by the present invention is simple, convenient on-site operation, greatly improves grouting efficiency, is highly practical, and has a high water blocking rate. Attached Figure Description

[0020] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. Exemplary embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0021] Figure 1 This is a schematic diagram of the method for using the two-liquid mixed grouting method at the orifice of the grouting material in Embodiment 1 of the present invention.

[0022] Figure 2 This is a diagram showing the foaming of the grouting material in Embodiment 1 of the present invention upon contact with water.

[0023] Figure 3 This is a composition diagram of the grouting material in Embodiment 1 of the present invention. Detailed Implementation

[0024] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. The reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they are used in accordance with conventional methods in the art or product instructions. Similarly, unless otherwise specified, the test methods of this invention are performed in accordance with conventional methods in the art or industry-standard methods or practices. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0026] As described in the background section, the drill-and-blast method is commonly used for tunnel excavation. Blasting generates severe vibrations, and traditional water-blocking materials, being rigid, are prone to secondary damage, creating new leakage points. This invention provides a flexible, vibration-resistant tunnel waterproof curtain grouting material. This grouting material is flexible and highly tough; even after 50% compression deformation, it can still return to its original shape after the external force is removed, effectively solving the aforementioned problems.

[0027] Therefore, the present invention provides a flexible vibration-resistant tunnel waterproof curtain grouting material, comprising: component A and component B; the mass ratio of component A to component B is 1:1-3:1;

[0028] Component A includes: isocyanate-terminated polyurethane, divalent ester, and phosphoric acid;

[0029] The B component is composed of the following raw materials in parts by weight: 50-80 parts of divalent ester, 10-20 parts of curing agent, 1-5 parts of catalyst, and 1-5 parts of hydrophobic anti-dispersant.

[0030] The curing agent is IPDA and zinc dimethyl dithiocarbamate, with a molar ratio of 2:(1-1.5).

[0031] The grouting material provided by this invention has the function of resisting cyclic stress, strong self-sealing ability, better structural adaptability, and improved efficiency of water inrush sealing. The grouting material of this invention can adapt to strong vibration environment, and the rock mass has excellent elastic recovery ability and is not easily damaged by vibration, which is the key to solving the problem of continuous waterproofing in drill-and-blast tunnels.

[0032] This invention does not impose any particular limitation on the preparation method of isocyanate-terminated polyurethane, as long as the -NCO% (molar percentage of isocyanate groups) content is controlled to be 10%-15%. Therefore, in some embodiments, the preparation method of component A includes:

[0033] Mix 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, preheat to 50℃-60℃, add polyether polyol in batches to react and obtain a semi-prepolymer, cool, add divalent ester and phosphoric acid, mix evenly to obtain the final product.

[0034] The type of polyether polyol affects the mechanical and elastic properties of polyurethane elastomers. Therefore, this invention has studied the types of polyether polyols. In some embodiments, the polyether polyol is polyether 330 or polyether 330N to obtain better elasticity and toughness.

[0035] The ratio of isocyanate to polyol directly affects the mechanical properties and process stability of polyurethane elastomers. Therefore, in some embodiments, the mass ratio of the polyether polyol to 2,4-toluene diisocyanate is 65-75:5-7 to obtain better elasticity and toughness.

[0036] The type and ratio of isocyanates affect the mechanical and elastic properties of polyurethane elastomers. Therefore, this invention has studied the type and ratio of isocyanates. In some embodiments, the mass ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate is 5-7:20-24 to obtain a highly elastic three-dimensional cross-linked network structure.

[0037] In some embodiments, the mass ratio of divalent ester to phosphoric acid in component A is 50-100:1. In component A, the divalent ester acts as an active diluent, reducing the viscosity of the system when mixed with the prepolymer, making the prepolymer molecular chains easier to disperse. During subsequent reaction with component B, it reduces molecular chain aggregation, helping to form a more uniform three-dimensional cross-linked network. This uniform network structure avoids stress concentration, allowing the molecular chains to deform and recover more orderly when the material is subjected to vibration and compression, indirectly improving elastic recovery. Phosphoric acid inhibits the side reactions of residual isocyanate (-NCO) in the prepolymer, ensuring a stable molecular structure during storage and construction, guaranteeing the formation of a regular cross-linked structure when reacting with component B, thereby ensuring elastic properties.

[0038] Catalysts can affect the reaction rate of polyurethane. Therefore, the present invention has studied the types of catalysts. In some embodiments, the catalyst is bismorpholino diethyl ether, which accelerates the crosslinking reaction between the prepolymer and the curing agent.

[0039] The type of water-resistant anti-dispersant affects the cohesiveness and anti-separation properties of grouting materials. Therefore, this invention studies the types of water-resistant anti-dispersants. In some embodiments, the water-resistant anti-dispersant is liquid polyacrylamide, whose core function is to prevent grout dispersion in a high-speed water environment. Its molecular chains can form temporary adsorption structures with prepolymers and curing agents, ensuring that components A and B can still fully react in water to form a complete stone body. If the grout disperses, it will lead to incomplete cross-linking and breakage of the elastic structure. Therefore, the water-resistant anti-dispersant is a "guarantee" for the effectiveness of elastic properties in actual engineering.

[0040] In some embodiments, component B is prepared by uniformly mixing divalent ester, IPDA, zinc dimethyl dithiocarbamate, catalyst, and dynamic water-dispersant. The divalent ester in component B acts as a diluent, consistent with component A. Adding a divalent ester to a single component only adjusts its own viscosity; adding both components together achieves "stable viscosity of the mixed system," avoiding localized poor elasticity due to uneven mixing. The alicyclic amine + dynamic bond approach as a curing agent shows greater potential in elasticity recovery and durability. IPDA, as a cycloaliphatic diamine curing agent, undergoes nucleophilic addition of its primary amine group (-NH2) with the epoxy group of the epoxy resin to form a crosslinking network. The thiocarbamate group of zinc dimethyl dithiocarbamate can capture oxidative free radicals and inhibit polymer chain degradation. IPDA provides the main crosslinking network, while zinc salt acts as an auxiliary stabilizer, improving the hydrolysis resistance of the epoxy coating under humid and hot environments. The decomposition of IPDA carbamates (such as B-IPDA) generates CO2 foaming, and zinc salt can regulate the cell structure. After components A and B are mixed, the curing agent can react efficiently with pure -NCO. When the two are combined, the prepolymer can crosslink with the curing agent with the "optimal molecular structure," avoiding impurities generated by side reactions from damaging the network.

[0041] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are explanations of the present invention and not limitations thereof.

[0042] In the following examples and comparative examples, the diluent is a divalent ester; the curing agent is IPDA and zinc dimethyl dithiocarbamate (molar ratio 2:1, mixed thoroughly before use); the catalyst is bismorpholino diethyl ether; and the hydrodynamic anti-dispersant is liquid polyacrylamide.

[0043] Setting time, expansion ratio and compressive strength were tested according to industry standard T / CECS 10313-2023, where compressive strength is the immediate strength after final setting.

[0044] The test method for the recovery rate after 50% compression deformation is as follows: record the initial volume of the material, compress the material to 50% of its volume, then remove the external force, and after the material volume no longer changes, test the final volume and calculate the recovery rate after deformation.

[0045] Deformation recovery rate = (final volume / initial volume) × 100%.

[0046] Example 1

[0047] like Figure 3 As shown, the composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0048] (1) Preparation of component A:

[0049] In this embodiment, the -NCO% content is designed to be 10;

[0050] Take 5 parts of 2,4-toluene diisocyanate and 20 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0051] Take 75 parts of polyether polyol with brand name 330 and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85°C. The reaction should be continued for 2 hours.

[0052] The -NCO% content was tested by titration and verified three times until -NCO% reached 10. Heating was then stopped and the mixture was cooled to room temperature.

[0053] Add 100 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store it in a dry, airtight container, taking care to avoid light, rain and direct sunlight.

[0054] (2) Preparation of component B:

[0055] Take 50 parts of diluent, 10 parts of curing agent, 1 part of catalyst, and 2 parts of dynamic water anti-dispersant and mix them evenly to obtain component B. Store it in a dry and airtight container, and take care to avoid light, rain and direct sunlight.

[0056] During use, component A and component B are mixed at the orifice for grouting, such as... Figure 1 As shown in the table below, various performance indicators were tested, and the results are as follows.

[0057] Table 1. Structural Performance Tests

[0058]

[0059] Component A is pale yellow in appearance, has a viscosity of 1200 Pa•s, and has a light ester aroma. Component B is dark brown in appearance, has a viscosity of 400 Pa•s, and has an amine odor.

[0060] The flexible vibration-resistant tunnel waterproof curtain grouting material is injected into water, and the foaming process is as follows: Figure 2 As shown, the slurry status is recorded every 10 seconds.

[0061] Example 2

[0062] The composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0063] (1) Preparation of component A:

[0064] In this embodiment, the -NCO% content is designed to be 11;

[0065] Take 5 parts of 2,4-toluene diisocyanate and 22 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0066] Take 73 parts of polyether polyol with brand name 330 and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85°C. The reaction should be continued for 2 hours.

[0067] The -NCO% content was tested by titration and verified three times until -NCO% reached 11. Heating was then stopped and the mixture was cooled to room temperature.

[0068] Add 50 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store in a dry, airtight container, avoiding light, rain and direct sunlight.

[0069] (2) Preparation of component B:

[0070] Mix 80 parts of diluent, 20 parts of curing agent, 5 parts of catalyst, and 5 parts of dynamic water anti-dispersion agent evenly to obtain component B. Store in a dry, airtight container, and avoid light, rain, and direct sunlight.

[0071] During use, component A and component B are mixed and injected through the orifice, and various performance indicators are tested. The results are shown in the table below.

[0072] Table 2. Structural Performance Tests

[0073]

[0074] Component A is pale yellow in appearance, has a viscosity of 2000 Pa•s, and a faint ester aroma. Component B is dark brown in appearance, has a viscosity of 1100 Pa•s, and an amine odor.

[0075] Example 3

[0076] The composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0077] (1) Preparation of component A:

[0078] In this embodiment, the -NCO% content is designed to be 12%;

[0079] Take 7 parts of 2,4-toluene diisocyanate and 22 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0080] Take 72 parts of polyether polyol with brand name 330 and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85°C. The reaction should be continued for 2 hours.

[0081] The -NCO% content was tested by titration and verified three times until -NCO% reached 12. Heating was then stopped and the mixture was cooled to room temperature.

[0082] Add 100 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store in a dry, airtight container, taking care to avoid light, rain and direct sunlight.

[0083] (2) Preparation of component B:

[0084] Take 80 parts of diluent, 18 parts of curing agent, 1 part of catalyst, and 1 part of dynamic water anti-dispersant and mix them evenly to obtain component B. Store it in a dry and airtight container, and take care to avoid light, rain and direct sunlight.

[0085] During use, component A and component B are mixed and injected through the orifice, and various performance indicators are tested. The results are shown in the table below.

[0086] Table 3. Structural Performance Tests

[0087]

[0088] Component A is pale yellow in appearance, has a viscosity of 1300 Pa•s, and a faint ester aroma. Component B is dark brown in appearance, has a viscosity of 220 Pa•s, and an amine odor.

[0089] Example 4

[0090] The composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0091] (1) Preparation of component A:

[0092] In this embodiment, the -NCO% content is designed to be 13%;

[0093] Take 7 parts of 2,4-toluene diisocyanate and 24 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0094] Take 70 parts of polyether polyol with brand name 330N and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85℃. The reaction should be continued for 2 hours.

[0095] The -NCO% content was tested by titration and verified three times until -NCO% reached 13. Heating was then stopped and the mixture was cooled to room temperature.

[0096] Add 100 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store in a dry, airtight container, taking care to avoid light, rain and direct sunlight.

[0097] (2) Preparation of component B:

[0098] Take 80 parts of diluent, 20 parts of curing agent, 2 parts of catalyst, and 5 parts of dynamic water anti-dispersion agent and mix them evenly to obtain component B. Store it in a dry and airtight container, and take care to avoid light, rain and direct sunlight.

[0099] During use, component A and component B are mixed and injected through the orifice. Component A is pale yellow in appearance, has a viscosity of 1420 Pa•s, and a faint ester aroma. Component B is dark brown in appearance, has a viscosity of 1050 Pa•s, and an amine odor. The performance indicators were tested, and the results are shown in the table below.

[0100] Table 4. Structural Performance Tests

[0101]

[0102] Example 5

[0103] The composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0104] (1) Preparation of component A:

[0105] In this embodiment, the -NCO% content is designed to be 14%;

[0106] Take 10 parts of 2,4-toluene diisocyanate and 23 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0107] Take 68 parts of polyether polyol with brand name 330N and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85℃. The reaction should be continued for 2 hours.

[0108] The -NCO% content was tested by titration and verified three times until -NCO% reached 14. Heating was then stopped and the mixture was cooled to room temperature.

[0109] Add 50 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store in a dry, airtight container, avoiding light, rain and direct sunlight.

[0110] (2) Preparation of component B:

[0111] Take 80 parts of diluent, 20 parts of curing agent, 2 parts of catalyst, and 5 parts of dynamic water anti-dispersion agent and mix them evenly to obtain component B. Store it in a dry and airtight container, and take care to avoid light, rain and direct sunlight.

[0112] During use, component A and component B are mixed and injected through the orifice, and various performance indicators are tested. The results are shown in the table below.

[0113] Table 5. Structural Performance Tests

[0114]

[0115] Component A is pale yellow in appearance, has a viscosity of 1480 Pa•s, and a faint ester aroma. Component B is dark brown in appearance, has a viscosity of 1130 Pa•s, and an amine odor.

[0116] Example 6

[0117] The composition of the flexible vibration-resistant tunnel waterproof curtain grouting material is as follows:

[0118] (1) Preparation of component A:

[0119] In this embodiment, the -NCO% content is designed to be 15%;

[0120] Take 10 parts of 2,4-toluene diisocyanate and 24 parts of 2,6-toluene diisocyanate, add them to a flask, mix thoroughly, and preheat the mixture to 50°C;

[0121] Take 65 parts of polyether polyol with brand name 330N and add it to the flask in two portions. The whole process must be carried out under vacuum, and the reaction temperature should be controlled at 85℃. The reaction should be continued for 2 hours.

[0122] The -NCO% content was tested by titration and verified three times until -NCO% reached 15. Heating was then stopped and the mixture was cooled to room temperature.

[0123] Add 50 parts of divalent ester and 1 part of phosphoric acid to the above mixture, stir thoroughly to obtain component A, and store in a dry, airtight container, avoiding light, rain and direct sunlight.

[0124] (2) Preparation of component B:

[0125] Take 80 parts of diluent, 20 parts of curing agent, 5 parts of catalyst, and 1 part of dynamic water anti-dispersant and mix them evenly to obtain component B. Store it in a dry and airtight container, and take care to avoid light, rain and direct sunlight.

[0126] During use, component A and component B are mixed and injected through the orifice, and various performance indicators are tested. The results are shown in the table below.

[0127] Table 6. Structural Performance Tests

[0128]

[0129] Component A is pale yellow in appearance, has a viscosity of 1580 Pa•s, and a faint ester aroma. Component B is dark brown in appearance, has a viscosity of 260 Pa•s, and an amine odor.

[0130] Comparative Example 1

[0131] The difference from Example 1 is that no divalent ester and phosphoric acid were added to component A.

[0132] Comparative Example 2

[0133] The difference from Example 1 is that phosphoric acid was not added to component A.

[0134] Comparative Example 3

[0135] The difference from Example 1 is that in component B, 3,3'-dichloro-4,4'-diaminodiphenylmethane is used instead of IPDA and zinc dimethyl dithiocarbamate.

[0136] Comparative Example 4

[0137] The difference from Example 1 is that in component B, triethylamine is used instead of bismorpholino diethyl ether.

[0138] Comparative Example 5

[0139] The difference from Example 1 is that the amount of catalyst used is 0.5 parts.

[0140] Comparative Example 6

[0141] The difference from Example 1 is that the amount of catalyst used is 5.5 parts.

[0142] Table 7 Structural Performance Tests

[0143]

[0144] As shown in Table 7, Comparative Example 1, due to the absence of divalent ester and phosphoric acid, resulted in an incomplete cross-linking network structure, manifested as a short setting time, significantly reduced expansion ratio, and low compressive strength. Comparative Example 2, lacking only phosphoric acid, showed improved compressive strength, but the expansion ratio remained insufficient, indicating that phosphoric acid plays a crucial role in suppressing side reactions and ensuring the regularity of the cross-linking structure. Comparative Example 3, after replacing IPDA and zinc dimethyl dithiocarbamate with 3,3'-dichloro-4,4'-diaminodiphenylmethane, exhibited performance indicators such as compressive strength, expansion ratio, and setting time that were inferior to those of Example 1, demonstrating that IPDA and zinc dimethyl dithiocarbamate, as specific curing agents, have irreplaceable advantages in constructing cross-linking networks with both rigidity and toughness. Comparative Example 4, using triethylamine instead of bismorpholino diethyl ether, significantly reduced the catalytic efficiency of the polyurethane reaction, resulting in decreased mechanical strength and elasticity of the material, along with a significant reduction in flowability. As can be seen from the records of Comparative Examples 5 and 6, if the amount of catalyst is too large or too small, it will affect the reaction of polyurethane, resulting in a decrease in the mechanical strength and elasticity of the material.

[0145] The experimental data above fully verify the synergistic effect achieved by the present invention through specific component ratios, especially the synergistic effect of divalent esters, phosphoric acid, IPDA and zinc dimethyl dithiocarbamate, which is of decisive significance for ensuring that the material has excellent elastic recovery properties, controllable curing characteristics and vibration resistance.

[0146] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A flexible vibration-resistant tunnel waterproof curtain grouting material, characterized in that, include: Component A, Component B; The mass ratio of component A to component B is 1:1 to 3:1; Component A includes: isocyanate-terminated polyurethane, divalent ester, and phosphoric acid; The B component is composed of the following raw materials in parts by weight: 50-80 parts of divalent ester, 10-20 parts of curing agent, 1-5 parts of catalyst, and 1-5 parts of hydrophobic anti-dispersant. The curing agent is IPDA and zinc dimethyl dithiocarbamate, with a molar ratio of 2:(1-1.5). The catalyst is bismorpholino diethyl ether; The isocyanate-terminated polyurethane contains 10%-15% molar percentage of isocyanate groups. The water-dispersing agent is liquid polyacrylamide.

2. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 1, characterized in that, The preparation method of component A includes: Mix 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, preheat to 50℃-60℃, add polyether polyol in batches to react and obtain a semi-prepolymer, cool, add divalent ester and phosphoric acid, mix evenly to obtain the final product.

3. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 2, characterized in that, The polyether polyol is polyether 330 or polyether 330N.

4. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 2, characterized in that, The mass ratio of the polyether polyol to 2,4-toluene diisocyanate is 65-75:5-7.

5. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 2, characterized in that, The mass ratio of the 2,4-toluene diisocyanate to the 2,6-toluene diisocyanate is 5-7:20-24.

6. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 1, characterized in that, In component A, the mass ratio of divalent ester to phosphoric acid is 50-100:

1.

7. The flexible vibration-resistant tunnel waterproof curtain grouting material as described in claim 1, characterized in that, The preparation method of component B is as follows: the divalent ester, IPDA, zinc dimethyl dithiocarbamate, catalyst, and hydrophobic anti-dispersant are mixed evenly to obtain the final product.

8. A construction method for a flexible vibration-resistant tunnel waterproof curtain grouting material as described in any one of claims 1-7, characterized in that, include: Component A and component B are mixed to obtain the grouting material; The grouting material is injected using the orifice two-liquid mixing grouting method to obtain the grouting material.

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