An epoxy grouting material for filling and strengthening the gap between a shield segment of a subway tunnel and a steel ring and its preparation method

Abstract

The present invention provides a grouting material for filling and reinforcing the gap between a subway tunnel shield segment and a steel ring, and a preparation method thereof, belonging to the technical field of building materials. The epoxy grouting material comprises component A and component B; component A comprises the following materials by weight: 50-100 parts of epoxy resin, 1-15 parts of phenoxy resin, 10-50 parts of modified epoxy resin, 10-35 parts of active diluent and 1-5 parts of silicone defoamer; component B comprises the following materials by weight: 80-98 parts of modified amine curing agent, 1-5 parts of functionally modified graphene and 0.5-1.5 parts of accelerator; the mass ratio of component A to component B is 1-5:1. The present invention improves the toughness of epoxy resin while retaining the characteristics of high compressive strength, high tensile strength, excellent adhesion and toughness, improves the durability of the grouting material, and meets the high requirements of the epoxy grouting material for filling and reinforcing the gap between the subway tunnel shield segment and the steel ring.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and particularly relates to an epoxy grouting material for filling and reinforcing the gap between a shield segment of a subway tunnel and a steel ring, and a preparation method thereof. Background Art

[0002] With the development of the economy and the expansion of cities, a large number of people pour into cities for employment and housing purchase. Urban traffic is becoming increasingly busy, and many cities choose to build underground rail transit (subway) to relieve the pressure on ground traffic. The lining of a subway tunnel is a complete circular tube body assembled by precast reinforced concrete arc segments in a staggered joint method. The independent segments are fixed into a whole by bolts. Due to various force majeure reasons, some segments are deformed and damaged, and problems such as cracks and water seepage may occur, accelerating the aging of the facilities and further endangering the safety and stable operation of the subway. Timely repair and reinforcement of the segments have become one of the key issues in subway construction and maintenance. Currently, the commonly used method is to install arc-shaped thick steel plates in the tunnel. The arc-shaped steel plates are laid along the inner wall of the tunnel and welded at the joints to form a circular structure. The steel ring and the shield segment are combined to form a composite structure to improve the bearing capacity of the tunnel, increase the safety reserve and durability of the tunnel. The gap between the steel ring and the segment is filled and bonded with an epoxy resin grouting material. After the grouting material is cured, the steel ring and the segment made of concrete are connected into a dense whole.

[0003] Epoxy resin is an excellent thermosetting resin. After being mixed and cured with a corresponding curing agent, it has good bonding performance and operational convenience. Its solidified body has excellent mechanical properties, electrical insulation properties, acid and alkali resistance properties, and also has the advantage of low shrinkage rate, and has a very broad application scenario. However, on the other hand, due to the high crosslinking density of epoxy resin, it has disadvantages such as high internal stress, large brittleness of the solidified body, and poor impact resistance. Technical workers have carried out corresponding modification treatments on epoxy resin and its corresponding curing agents and auxiliary materials to overcome the above disadvantages. In the project of filling, bonding and reinforcing between subway concrete segments and steel rings, higher requirements are put forward for the viscosity of the grouting material, the bonding strength of the grouting material to dry concrete and wet concrete, and the compressive strength, tensile strength, shear tensile strength, fracture elongation rate, durability and other properties after consolidation. Therefore, it is very necessary to develop an epoxy grouting material for filling and reinforcing the gap between a shield segment of a subway tunnel and a steel ring that meets these high requirements. Summary of the Invention

[0004] To achieve the above object, the present invention provides an epoxy grouting material for filling and strengthening the gap between a subway tunnel shield segment and a steel ring, and a preparation method thereof. By mixing epoxy resin, phenoxy resin, and modified epoxy resin, the toughness of the epoxy resin is increased. By using a Mannich-modified mixed amine curing agent and a functionalized graphene material, excellent adhesion performance is achieved, and at the same time, there are effects of low viscosity, high strength, high toughness, and room temperature curing.

[0005] The first aspect of the present invention lies in providing an epoxy grouting material for filling and strengthening the gap between a subway tunnel shield segment and a steel ring. The epoxy grouting material includes component A and component B; wherein,

[0006] Component A includes the following materials by weight: 50 - 100 parts of epoxy resin, 1 - 15 parts of phenoxy resin, 10 - 50 parts of modified epoxy resin, 10 - 35 parts of active diluent, and 1 - 5 parts of silicone defoamer; Component B includes the following materials by weight: 80 - 98 parts of modified amine curing agent, 1 - 5 parts of functionalized graphene, and 0.5 - 1.5 parts of accelerator.

[0007] Preferably, the epoxy grouting material includes component A and component B; wherein,

[0008] Component A includes the following materials by weight: 80 - 100 parts of epoxy resin, 1 - 10 parts of phenoxy resin, 10 - 40 parts of modified epoxy resin, 15 - 30 parts of active diluent, and 1 - 5 parts of silicone defoamer; Component B includes the following materials by weight: 90 - 98 parts of modified amine curing agent, 1 - 5 parts of functionalized graphene, and 0.5 - 1.5 parts of accelerator.

[0009] Further preferably, the epoxy grouting material includes component A and component B; wherein,

[0010] Component A includes the following materials by weight: 90 - 100 parts of epoxy resin, 2 - 8 parts of phenoxy resin, 10 - 35 parts of modified epoxy resin, 15 - 25 parts of active diluent, and 1 - 5 parts of silicone defoamer; Component B includes the following materials by weight: 94 - 98 parts of modified amine curing agent, 1 - 5 parts of functionalized graphene, and 0.5 - 1.5 parts of accelerator.

[0011] Preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resin E51, bisphenol A epoxy resin E44, bisphenol F epoxy resin, multi-functional group epoxy resin, and alicyclic epoxy resin.

[0012] Further preferably, the bisphenol A epoxy resin E51 is selected from at least one of Hongchang GELR128 and Sanmu SM828; the bisphenol A epoxy resin E44 is the epoxy resin 6101 produced by Baling Petrochemical Company; the bisphenol F epoxy resin is South Asia NPEF 170; the multi-functional epoxy resin refers to an epoxy resin with a functional group number greater than or equal to 3, preferably the tetra-functional epoxy resin AG-80; the alicyclic epoxy resin is selected from at least one of the alicyclic epoxy resin S-100 and the alicyclic epoxy resin S-28 produced by Nantong Xinaxi New Materials Co., Ltd.

[0013] Preferably, the phenoxy resin is an epoxidized phenoxy resin with an epoxy equivalent between 5000 - 50000 g / eq.

[0014] Further preferably, the epoxidized phenoxy resin has an epoxy equivalent between 5000 - 30000 g / eq.

[0015] Even more preferably, the epoxidized phenoxy resin has an epoxy equivalent between 5000 - 20000 g / eq.

[0016] Preferably, the phenoxy resin grade is selected from at least one of Shandong Shengquan SQP-40AXM40, SQPB-40AXM40, SQPS-007A30, and SQP-50PM26.

[0017] Preferably, the weight ratio of the epoxy resin to the phenoxy resin is 50 - 100:1 - 15.

[0018] Further preferably, the weight ratio of the epoxy resin to the phenoxy resin is 100:1 - 10.

[0019] Even more preferably, the weight ratio of the epoxy resin to the phenoxy resin is 100:1 - 8.

[0020] Preferably, the modified epoxy resin is selected from at least one of nitrile rubber modified epoxy resin, polyurethane modified epoxy resin, and polythiol modified epoxy resin.

[0021] Preferably, the nitrile rubber modified epoxy resin is an adduct of bisphenol A glycidyl ether and a carboxyl-terminated liquid nitrile rubber (CTBN) elastomer.

[0022] Preferably, the polyurethane modified epoxy resin is selected from at least one of EPU-302, EPU-303, and EPU-300A with an epoxy equivalent between 180 - 650 g / eq.

[0023] Preferably, the polythiol modified epoxy resin is a polythiol modified aliphatic epoxy resin.

[0024] Preferably, the reactive diluent is a monofunctional reactive diluent or a polyfunctional reactive diluent.

[0025] More preferably, the reactive diluent is selected from at least one of benzyl glycidyl ether, octyl glycidyl ether, C12-C14 alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol glycidyl ether, N-(glycidyl)-N-phenyl-oxiranemethanamine, and N,N-diglycidyl-4-glycidyloxyaniline.

[0026] Preferably, the silicone defoamer is selected from at least one of BYK-A530, BKY-066N, and BYK-141.

[0027] Preferably, the modified amine curing agent is modified by Mannich reaction from phenolic compounds, aldehyde compounds, and amine curing agents.

[0028] More preferably, the phenolic compound is selected from at least one of phenol, p-tert-butylphenol, phloroglucinol, pyrogallol, dodecylphenol, and cashew phenol.

[0029] More preferably, the aldehyde compound is selected from at least one of formaldehyde, paraformaldehyde, dodecyl aldehyde, octadecyl aldehyde, and benzaldehyde.

[0030] More preferably, the amine curing agent is selected from at least one of alicyclic amine curing agents and polyetheramine curing agents.

[0031] Even more preferably, the alicyclic amine curing agent is selected from at least one of hydrogenated m-xylenediamine (1,3-BAC), isophorone diamine (IPDA), and N-(2-aminoethyl)piperazine (AEP).

[0032] Even more preferably, the polyetheramine curing agent is selected from at least one of amino-terminated polyoxyethylene ether D230, amino-terminated polyoxyethylene ether D400, amino-terminated polyoxyethylene ether D2000, and amino-terminated trimethylolpropane tripropyleneglycol ether T-403.

[0033] More preferably, the functionalized modified graphene is selected from at least one of 3-aminopropyltrimethoxysilane modified graphene oxide, diethylenetriamine (DETA) modified graphene oxide, and polyaniline modified graphene oxide.

[0034] Even more preferably, the 3-aminopropyltrimethoxysilane modified graphene oxide is XF315 produced by Jiangsu Xianfeng Nano Material Technology Co., Ltd.

[0035] Further preferably, the diethylenetriamine (DETA)-modified graphene oxide is XF316 produced by Jiangsu Xianfeng Nano Material Technology Co., Ltd.

[0036] Preferably, the accelerator is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), triethanolamine, and salicylic acid solution.

[0037] Further preferably, the salicylic acid solution includes benzyl alcohol and salicylic acid, and the mass ratio of benzyl alcohol to salicylic acid is 3:1.

[0038] Preferably, the modified amine curing agent is prepared by the following steps:

[0039] B1: Put 80 - 350 parts of phenols, 130 - 350 parts of alicyclic amine curing agent or 100 - 4500 parts of polyetheramine into the reactor, stir, and heat up to obtain product B1;

[0040] B2: Slowly add 20 - 600 parts of aldehyde compounds to product B1 in batches, heat up, and stir and reflux for 2 - 4 h to obtain product B2;

[0041] B3: Connect the reactor to a vacuum distillation device, heat up, turn on the vacuum to dehydrate, and cool down to obtain it; or

[0042] The preparation steps of the modified amine curing agent are as follows:

[0043] C1: Put 80 - 350 parts of phenols and 130 - 350 parts of alicyclic amine curing agent into the reactor, stir and heat up to obtain product C1;

[0044] C2: Slowly add 20 - 300 parts of aldehyde compounds to product C1 in batches, heat up, and stir and reflux to obtain product C2;

[0045] C3: Cool down to 40 - 60 °C, put 100 - 4500 parts of polyetheramine into the reactor, stir evenly, and then slowly add 20 - 300 parts of aldehyde compounds in batches again, heat up, and react;

[0046] C4: Connect the reactor to a vacuum distillation device, heat up, turn on the vacuum to dehydrate, and cool down to obtain it.

[0047] Further preferably, the modified amine curing agent is prepared by the following steps:

[0048] B1: Put 80 - 350 parts of phenols, 130 - 350 parts of alicyclic amine curing agent or 100 - 4500 parts of polyetheramine into the reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir, and heat up to 60 - 80 °C to obtain product B1;

[0049] B2: Slowly add 20 - 600 parts of aldehyde compound to product B1 in batches, heat up to 80 - 90 °C, stir and reflux for 2 - 4 h to obtain product B2;

[0050] B3: Connect the reactor to a vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, cool down to 40 - 60 °C, and that's it; or

[0051] The preparation steps of the modified amine curing agent are as follows:

[0052] C1: Put 80 - 350 parts of phenol and 130 - 350 parts of alicyclic amine curing agent into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir and heat up to 60 - 80 °C to obtain product C1;

[0053] C2: Slowly add 20 - 300 parts of aldehyde compound to product C1 in batches, heat up to 80 - 90 °C, stir and reflux for 1 - 2 h to obtain product C2;

[0054] C3: Cool down to 40 - 60 °C, put 100 - 4500 parts of polyetheramine into the reactor, stir evenly, and then slowly add 20 - 300 parts of aldehyde compound in batches again, heat up to 80 - 90 °C, and continue to react for 1 - 2 h;

[0055] C4: Connect the reactor to a vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, cool down to 40 - 60 °C, and that's it.

[0056] More preferably, the modified amine curing agent is prepared by the following steps:

[0057] B1: Put 80 - 350 parts of phenol, 130 - 350 parts of alicyclic amine curing agent or 100 - 4500 parts of polyetheramine into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir and heat up to 60 - 80 °C to obtain product B1;

[0058] B2: Heat up to 80 - 90 °C. If the aldehyde compound is liquid, slowly add 20 - 300 parts dropwise with a dropping funnel; if the aldehyde compound is a solid aldehyde compound, slowly add solid aldehyde compound ① parts to product B1, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h, slowly add solid aldehyde compound ② parts, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h, slowly add solid aldehyde compound ③ parts, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h. The addition of aldehyde compound can be carried out in multiple times, not limited to 3 - time feeding; solid aldehyde compound ① + ② + ③ = 20 - 300 parts, and the total reaction time of the aldehyde compound is 2 - 4 h to obtain product B2;

[0059] B3: Connect the reactor to the vacuum distillation device, heat it up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and then cool it down to 40 - 60 °C to obtain the product; or

[0060] The preparation steps of the modified amine curing agent are as follows:

[0061] C1: Put 80 - 350 parts of phenols and 130 - 350 parts of alicyclic amine curing agent into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir and heat up to 60 - 80 °C to obtain product C1;

[0062] C2: Heat up to 80 - 90 °C. If the aldehyde compound is a liquid, slowly add 20 - 300 parts dropwise using a dropping funnel; if the aldehyde compound is a solid aldehyde compound, slowly add ① part of the solid aldehyde compound to product C1, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h, slowly add ② part of the solid aldehyde compound, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h, slowly add ③ part of the solid aldehyde compound, stir and reflux at 80 - 90 °C for 0.5 - 1.5 h. The addition of the aldehyde compound can be carried out in multiple times, not limited to 3 - time feeding; ① + ② + ③ of the solid aldehyde compound = 20 - 300 parts, and the total reaction time of the aldehyde compound is 2 - 4 h to obtain product C2;

[0063] C3: Cool down to 40 - 60 °C, put 100 - 4500 parts of polyetheramine into the reactor, stir evenly, and then slowly add 20 - 300 parts of the aldehyde compound in batches again according to the method in C2, heat up to 80 - 90 °C, and continue to react for 1 - 2 h;

[0064] C4: Connect the reactor to the vacuum distillation device, heat it up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and then cool it down to 40 - 60 °C to obtain the product.

[0065] Preferably, the component A is prepared by the following method: Mix 100 parts of epoxy resin and 1 - 15 parts of phenoxy resin, heat to 100 - 160 °C, stir for 0.5 - 3 h until completely dissolved with each other, cool down to 40 - 60 °C, add 10 - 50 parts of modified epoxy resin, 10 - 35 parts of active diluent, and 1 - 5 parts of silicone defoamer, mix and stir for 0.5 h, and evacuate for 0.5 - 2 h to obtain component A.

[0066] Further preferably, the component A is prepared by the following method: Mix 100 parts of epoxy resin and 1 - 12 parts of phenoxy resin, heat to 100 - 160 °C, stir for 0.5 - 3 h until completely dissolved with each other, cool down to 40 - 60 °C, add 15 - 45 parts of modified epoxy resin, 10 - 30 parts of active diluent, and 1 - 5 parts of silicone defoamer, mix and stir for 0.5 h, and evacuate for 0.5 - 2 h to obtain component A.

[0067] Preferably, the component B is prepared by the following method: Mix 80-98 parts of a modified amine curing agent, 1-5 parts of functionalized graphene, and 0.5-1.5 parts of an accelerator, and stir evenly to obtain the component B.

[0068] More preferably, the component B is prepared by the following method: Mix 85-98 parts of a modified amine curing agent, 1-5 parts of functionalized graphene, and 0.5-1.5 parts of an accelerator, and stir evenly to obtain the component B.

[0069] Preferably, the epoxy grouting material is prepared by the following method: Mix the component A and the component B in a mass ratio of 1-5:1 to obtain the epoxy grouting material.

[0070] More preferably, the epoxy grouting material is prepared by the following method: Mix the component A and the component B in a mass ratio of 1-4:1 to obtain the epoxy grouting material.

[0071] Compared with the prior art, the present invention has the following beneficial effects: The epoxy grouting material obtained by the present invention has excellent adhesion performance, and at the same time has the effects of low viscosity, high strength, high toughness, and room temperature curing, meeting the high requirements of the epoxy grouting material for filling and reinforcing the gap between the shield segments and the steel rings in the subway tunnel. Detailed Embodiments

[0072] The following embodiments are used to further describe in detail the specific embodiments of the present invention. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0073] Unless otherwise specified, the methods are all conventional methods. Unless otherwise specified, the materials can all be obtained from public commercial channels.

[0074] Embodiment 1:

[0075] An epoxy grouting material for filling and reinforcing the gap between the shield segments and the steel rings in the subway tunnel, comprising a component A and a component B, wherein,

[0076] The component A is composed of the following materials by weight: 50 parts of bisphenol A epoxy resin E51, 20 parts of bisphenol F epoxy resin South Asia NPEF 170, 30 parts of alicyclic epoxy resin S-28, 5 parts of phenoxy resin SQP40AXM40, 25 parts of liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 10 parts of dodecyl to tetradecyl glycidyl ether, 10 parts of 1,6-hexanediol diglycidyl ether, and 3 parts of organosilicon defoamer BYK-A530;

[0077] Component B consists of the following materials by weight: 96 parts of modified amine curing agent, 3 parts of diethylenetriamine (DETA)-modified graphene oxide XF316, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0078] Preparation method of Component A: Mix bisphenol A epoxy resin E51, bisphenol F epoxy resin Nanya NPEF 170, and alicyclic epoxy resin S-28 evenly by stirring, add phenoxy resin, heat the mixture to 160 °C after mixing, stir for 3 h until completely dissolved with each other, cool down to 60 °C, then add liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN)-modified epoxy resin 86840, dodecyltetradecyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and silicone defoamer BYK-A530, mix and stir for 0.5 h, and while stirring, evacuate under a vacuum of -0.1 MPa for 1 h to obtain Component A.

[0079] The modified amine curing agent is modified by Mannich reaction from phloroglucinol, benzaldehyde, and hydrogenated m-xylenediamine.

[0080] Preparation method of the modified amine curing agent: Put 126 parts of phloroglucinol and 284 parts of hydrogenated m-xylenediamine into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, heat up to 60 - 80 °C while stirring; slowly add 212 parts of benzaldehyde through the liquid separation device, and it must be added slowly to avoid violent reaction and explosion polymerization; after the dropping is completed, stir and reflux at 80 - 90 °C for 2 - 4 h, connect the reactor to the vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and cool down to 40 - 60 °C to obtain the modified amine curing agent.

[0081] Preparation method of Component B: Mix the modified amine curing agent, diethylenetriamine (DETA)-modified graphene oxide XF316, and accelerator 2,4,6-tris(dimethylaminomethyl)phenol, and stir evenly to obtain Component B.

[0082] Mix Component A and Component B according to a mass ratio of 2:1 to obtain an epoxy grouting material for filling and strengthening the gap between the subway tunnel shield segment and the steel ring.

[0083] Example 2:

[0084] An epoxy grouting material for filling and strengthening the gap between the subway tunnel shield segment and the steel ring, including Component A and Component B.

[0085] Component A is composed of the following materials by weight: 50 parts of bisphenol A epoxy resin E51, 20 parts of bisphenol F epoxy resin Nanya NPEF 170, 30 parts of alicyclic epoxy resin S-100, 5 parts of phenoxy resin SQP40AXM40, 20 parts of polythiol-modified epoxy resin EPS70, 17 parts of N,N-diglycidyl-4-glycidyloxyaniline, and 3 parts of silicone defoamer BYK-A530;

[0086] Component B is composed of the following materials by weight: 96 parts of modified amine curing agent, 3 parts of diethylenetriamine (DETA)-modified graphene oxide XF316, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0087] Preparation method of Component A: Mix bisphenol A epoxy resin E51, bisphenol F epoxy resin Nanya NPEF 170, and alicyclic epoxy resin S-100 evenly by stirring, add phenoxy resin and heat to 160 °C, stir for 0.5 - 3 h until completely dissolved with each other, and then cool to 60 °C; then add polythiol-modified epoxy resin EPS70, N,N-diglycidyl-4-glycidyloxyaniline, and silicone defoamer BYK-A530, mix and stir for 0.5 h, and while stirring, evacuate under a vacuum of -0.1 MPa for 1 h to obtain Component A.

[0088] The modified amine curing agent is modified by Mannich reaction from phloroglucinol, benzaldehyde, hydrogenated m-xylenediamine, and terminal amino polyoxyethylene ether D230.

[0089] Preparation method of the modified amine curing agent: Put 126 parts of phloroglucinol and 213 parts of hydrogenated m-xylenediamine into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, heat up to 60 - 80 °C while stirring; open the liquid separation device and slowly drop 159 parts of benzaldehyde, and add it drop by drop slowly to avoid violent reaction and explosive polymerization. After dropping, stir and reflux at 80 - 90 °C for 2 - 4 h, cool to 40 - 60 °C, add 115 parts of terminal amino polyoxyethylene ether D230, stir evenly, heat up to 80 - 90 °C, and gradually drop 53 parts of benzaldehyde again during the heating process, and continue to react for 1 - 2 h. Connect the reactor to the vacuum distillation device, heat up to 115 - 125 °C, and start evacuating for dehydration for 1 - 2 h. Cool to 40 - 60 °C to obtain the modified amine curing agent.

[0090] Preparation method of Component B: Mix the modified amine curing agent, diethylenetriamine (DETA)-modified graphene oxide XF316, and accelerator 2,4,6-tris(dimethylaminomethyl)phenol evenly by stirring to obtain Component B.

[0091] Mix component A and component B in a mass ratio of 1.5:1 to obtain an epoxy grouting material for filling and reinforcing the gap between the shield segment of the subway tunnel and the steel ring.

[0092] Example 3:

[0093] An epoxy grouting material for filling and reinforcing the gap between the shield segment of the subway tunnel and the steel ring, comprising component A and component B.

[0094] Component A is composed of the following materials by weight: 80 parts of polyfunctional epoxy resin AG-80, 20 parts of alicyclic epoxy resin S-28, 5 parts of phenoxy resin SQP40AXM40, 25 parts of polyurethane-modified epoxy resin EPU-300A, 20 parts of dodecyltetradecyl glycidyl ether, and 3 parts of silicone defoamer BYK-A530;

[0095] Component B is composed of the following materials by weight: 96 parts of modified amine curing agent, 3 parts of diethylenetriamine (DETA)-modified graphene oxide XF316, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0096] Preparation method of component A: Mix polyfunctional epoxy resin AG-80, alicyclic epoxy resin S-28 and phenoxy resin, heat to 160 °C, stir for 0.5 - 3 h until completely dissolved with each other, and cool to 60 °C; then add polyurethane-modified epoxy resin EPU-300A, dodecyltetradecyl glycidyl ether, and silicone defoamer BYK-A530, mix and stir for 0.5 h, and while stirring, evacuate under a vacuum of -0.1 MPa for 1 h to obtain component A.

[0097] The modified amine curing agent is modified by Mannich reaction from phloroglucinol, benzaldehyde and amino-terminated polyoxyethylene ether D230.

[0098] Preparation method of the modified amine curing agent: Put 126 parts of phloroglucinol and 460 parts of amino-terminated polyoxyethylene ether D230 into a reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel, heat up to 60 - 80 °C while stirring; slowly drop 212 parts of benzaldehyde through the separation device, and drop it slowly to avoid violent reaction and explosive polymerization. After dropping, stir and reflux at 80 - 90 °C for 2 - 4 h; connect the reactor to the vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and cool to 40 - 60 °C to obtain the modified amine curing agent.

[0099] Preparation method of component B: Mix the prepared modified amine curing agent, diethylenetriamine (DETA)-modified graphene oxide XF316, and accelerator 2,4,6-tris(dimethylaminomethyl)phenol and stir evenly to obtain component B.

[0100] Mix component A and component B in a mass ratio of 1:1 to obtain an epoxy grouting material for filling and strengthening the gap between the shield segment of the subway tunnel and the steel ring.

[0101] Example 4:

[0102] An epoxy grouting material for filling and strengthening the gap between the shield segment of the subway tunnel and the steel ring, comprising component A and component B.

[0103] Component A is composed of the following materials by weight: 20 parts of bisphenol A epoxy resin E44, 50 parts of bisphenol F epoxy resin South Asia NPEF 170, 20 parts of polyfunctional epoxy resin AG-80, 10 parts of alicyclic epoxy resin S-100, 5 parts of phenoxy resin SQP40AXM40, 20 parts of liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 15 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 3 parts of organosilicon defoamer BYK-A530;

[0104] Component B is composed of the following materials by weight: 96 parts of modified amine curing agent, 3 parts of graphene oxide XF316 modified by diethylenetriamine (DETA), 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0105] Preparation method of component A: Mix bisphenol A epoxy resin E44, bisphenol F epoxy resin South Asia NPEF 170, polyfunctional epoxy resin AG-80, and alicyclic epoxy resin S-100 evenly by stirring, add phenoxy resin, heat to 160 °C after mixing, stir for 3 h until completely dissolved with each other, cool down to 60 °C, then add liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 1,4-cyclohexanedimethanol diglycidyl ether, and organosilicon defoamer BYK-A530, mix and stir for 0.5 h, and evacuate under a vacuum of -0.1 MPa for 1 h while stirring to obtain component A.

[0106] The modified amine curing agent is modified by the Mannich reaction of phloroglucinol, octadecyl aldehyde, and hydrogenated m-xylenediamine.

[0107] Preparation method of modified amine curing agent: Preparation method applicable to solid aldehyde compounds: Put 126 parts of phloroglucinol and 142 parts of hydrogenated m-xylenediamine into a reactor equipped with a stirrer, reflux condenser and thermometer, and heat up to 60-80 °C while stirring. Add ① part of octadecyl aldehyde, and stir and reflux at 80-90 °C for 1 h. Add ② part of octadecyl aldehyde, and continue to reflux at 80-90 °C for 1 h. Add ③ part of octadecyl aldehyde, and continue to reflux at 80-90 °C for 1 h. The total amount of octadecyl aldehyde added in batches is ①+②+③ = 268 parts. In order to avoid too violent reaction, octadecyl aldehyde can be added in multiple batches, and it is not limited to adding in 3 batches. Connect the reactor to a vacuum distillation device, heat up to 115-125 °C, and start vacuum dehydration for 1-2 h. Cool down to 40-60 °C to obtain the modified amine curing agent.

[0108] Preparation method of component B: By weight, mix 96 parts of the prepared modified amine curing agent, 3 parts of 3-aminopropyltrimethoxysilane modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol, and stir the above raw materials with the obtained formula dosage evenly to obtain component B.

[0109] Mix component A and component B according to a mass ratio of 1:1 to obtain an epoxy grouting material for filling and reinforcing the gap between the subway tunnel shield segment and the steel ring.

[0110] Example 5:

[0111] An epoxy grouting material for filling and reinforcing the gap between the subway tunnel shield segment and the steel ring, including component A and component B.

[0112] Component A is composed of the following materials by weight: 40 parts of bisphenol A epoxy resin E51, 10 parts of bisphenol A epoxy resin E44, 50 parts of alicyclic epoxy resin S-100, 5 parts of phenoxy resin SQP40AXM40, 20 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840, 15 parts of 1,4-cyclohexanedimethanol diglycidyl ether, 3 parts of silicone defoamer BYK-A530;

[0113] Component B is composed of the following materials by weight: 96 parts of modified curing agent, 3 parts of 3-aminopropyltrimethoxysilane modified graphene oxide XF315, 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0114] Preparation method of Component A: By weight, 40 parts of bisphenol A epoxy resin E51, 10 parts of bisphenol A epoxy resin E44, and 50 parts of alicyclic epoxy resin S-100 are mixed and stirred evenly, then 5 parts of phenoxy resin are added and the mixture is heated to 160 °C and stirred for 0.5 - 3 h until completely dissolved with each other, and then cooled to 60 °C. Then 20 parts of liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 15 parts of 1,4-cyclohexanedimethanol diglycidyl ether, and 3 parts of silicone defoamer BYK-A530 are added, and the mixture is stirred for 0.5 h and vacuumized at a vacuum degree of -0.1 MPa for 1 h while stirring to obtain Component A.

[0115] The modified amine curing agent is modified by Mannich reaction from phloroglucinol, octadecyl aldehyde, and amino-terminated polyoxyethylene ether D230.

[0116] Preparation method of the modified amine curing agent: Preparation method applicable to solid aldehyde compounds: 126 parts of phloroglucinol and 230 parts of amino-terminated polyoxyethylene ether D230 are put into a reactor equipped with a stirrer, a reflux condenser, and a thermometer, and the temperature is raised to 60 - 80 °C while stirring. ① part of octadecyl aldehyde is added, and the mixture is stirred and refluxed at 80 - 90 °C for 1 h. ② part of octadecyl aldehyde is added, and the mixture continues to reflux at 80 - 90 °C for 1 h. ③ part of octadecyl aldehyde is added, and the mixture continues to reflux at 80 - 90 °C for 1 h. The total amount of octadecyl aldehyde added in batches is ① + ② + ③ = 268 parts. To avoid too violent reaction, octadecyl aldehyde can be added in multiple batches, and it is not limited to adding in 3 batches. The reactor is connected to a vacuum distillation device, the temperature is raised to 115 - 125 °C, and vacuum dehydration is carried out for 1 - 2 h. The temperature is cooled to 40 - 60 °C to obtain the modified amine curing agent.

[0117] Preparation method of Component B: By weight, 96 parts of the prepared modified curing agent, 3 parts of 3-aminopropyltrimethoxysilane modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol are mixed and stirred evenly to obtain Component B.

[0118] Component A and Component B are mixed in a mass ratio of 1:1 to obtain an epoxy grouting material for filling and reinforcing the gap between the shield segment of the subway tunnel and the steel ring.

[0119] Example 6:

[0120] An epoxy grouting material for filling and reinforcing the gap between the shield segment of the subway tunnel and the steel ring, comprising Component A and Component B.

[0121] Component A is composed of the following materials by weight: 40 parts of bisphenol A epoxy resin E51, 10 parts of bisphenol A epoxy resin E44, 50 parts of alicyclic epoxy resin S-28, 5 parts of phenoxy resin SQP40AXM40, 20 parts of liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 10 parts of octyl glycidyl ether, 10 parts of N,N-diglycidyl-4-glycidyloxyaniline, and 3 parts of silicone defoamer BYK-A530;

[0122] Component B is composed of the following materials by weight: 96 parts of modified curing agent, 3 parts of 3-aminopropyltrimethoxysilane modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol.

[0123] Preparation method of Component A: By weight, 40 parts of bisphenol A epoxy resin E51, 10 parts of bisphenol A epoxy resin E44, and 50 parts of alicyclic epoxy resin S-100 are mixed and stirred evenly, then 5 parts of phenoxy resin are added and heated to 160 °C, and stirred for 0.5 - 3 h until completely dissolved with each other, and then cooled to 60 °C. Then 20 parts of liquid carboxyl-terminated butadiene acrylonitrile rubber (CTBN) modified epoxy resin 86840, 10 parts of octyl glycidyl ether, 10 parts of N,N-diglycidyl-4-glycidyloxyaniline, and 3 parts of silicone defoamer BYK-A530 are added, mixed and stirred for 0.5 h, and vacuumized at -0.1 MPa vacuum for 1 h while stirring to obtain Component A.

[0124] The modified amine curing agent is modified by Mannich reaction with phloroglucinol, octadecyl aldehyde, hydrogenated m-xylenediamine, and terminal amino polyoxyethylene ether D230.

[0125] Preparation method of modified amine curing agent: Preparation method applicable to solid aldehyde compounds: Put 126 parts of phloroglucinol and 142 parts of hydrogenated m-xylenediamine into a reactor equipped with a stirrer, reflux condenser and thermometer, and heat up to 60-80 °C while stirring. Add ① part of octadecyl aldehyde, and stir and reflux at 80-90 °C for 1 h. Add ② part of octadecyl aldehyde, and continue to reflux at 80-90 °C for 1 h. Add ③ part of octadecyl aldehyde, and continue to reflux at 80-90 °C for 1 h. The total amount of octadecyl aldehyde added in batches is ①+②+③ = 268 parts. To avoid too violent reaction, octadecyl aldehyde can be added in multiple batches, and it is not limited to adding in 3 batches. Cool to 40-60 °C, add 115 parts of amino-terminated polyoxyethylene ether D230, and stir evenly. Add ④ part of octadecyl aldehyde, and stir and reflux at 80-90 °C for 1 h. Add ⑤ part of octadecyl aldehyde, and stir and reflux at 80-90 °C for 1 h. Add ⑥ part of octadecyl aldehyde, and stir and reflux at 80-90 °C for 1 h. The total amount of octadecyl aldehyde added in the second batch in batches is ④+⑤+⑥ = 134 parts. To avoid too violent reaction, octadecyl aldehyde can be added in multiple batches, and it is not limited to adding in 3 batches. Connect the reactor to a vacuum distillation device, heat up to 115-125 °C, and start vacuum dehydration for 1-2 h. Cool to 40-60 °C to obtain the modified amine curing agent.

[0126] Preparation method of component B: By weight, mix 96 parts of the prepared modified curing agent, 3 parts of 3-aminopropyltrimethoxysilane modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol, and stir evenly after mixing the above raw materials in the formula dosage to obtain component B.

[0127] Mix component A and component B according to a mass ratio of 1:1 to obtain an epoxy grouting material for filling and strengthening the gap between subway tunnel shield segments and steel rings.

[0128] Comparative example 1:

[0129] The difference from Example 1 is that: component A does not contain phenoxy resin SQP40AXM40, and the others are the same as Example 1.

[0130] Comparative example 2:

[0131] The difference between Comparative example 2 and Example 1 is that: in component A, bisphenol A epoxy resin E51 is reduced to 40 parts, bisphenol F epoxy resin South Asia NPEF 170 is reduced to 0 parts, and alicyclic epoxy resin S-28 is reduced to 0 parts, and the others are the same as Example 1.

[0132] Comparative example 3:

[0133] The difference between Comparative Example 3 and Example 1 is as follows: In Component A, 40 parts of bisphenol A epoxy resin E51 is replaced with 40 parts of multi-functional epoxy resin AG-80, 170 parts of bisphenol F epoxy resin South Asia NPEF is reduced to 0 part, and alicyclic epoxy resin S-28 is reduced to 0 part. Other conditions are the same as those in Example 1.

[0134] Comparative Example 4:

[0135] The difference from Example 1 is as follows: In Component A, 86840 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin in the modified epoxy resin is reduced to 5 parts. Other conditions are the same as those in Example 1.

[0136] Comparative Example 5:

[0137] The difference from Example 1 is as follows: In Component A of Example 1, the active diluent "10 parts of 1,6-hexanediol diglycidyl ether" is replaced with "10 parts of non-active diluent benzyl alcohol". Other conditions are the same as those in Example 1.

[0138] Comparative Example 6:

[0139] The difference from Example 1 is as follows: In Component B, the modified amine curing agent is increased to 100 parts, without functionalized graphene oxide and accelerator. Other conditions are the same as those in Example 1.

[0140] Experimental results

[0141] The compressive strength, dry bonding strength, wet bonding strength, and osmotic pressure ratio are detected according to the regulations in "JC / T 1041-2007", the tensile strength is detected according to the regulations in "GB / T 2567-2021", and the tensile shear strength is detected according to the regulations in "GB / T 7124-2008". The test data are shown in Table 1 and Table 2.

[0142] Table 1: Test data of the epoxy grouting materials prepared in Examples 1-6

[0143]

[0144]

[0145] Table 2: Test data of the epoxy grouting materials prepared in Comparative Examples 1-6

[0146]

[0147]

[0148] The test data of the above Examples 1-6 show that they have excellent comprehensive properties, including compressive strength, tensile strength, tensile shear strength, dry bonding strength, and wet bonding strength, and can well meet the requirements for filling and reinforcing the gaps between subway tunnel shield segments and steel rings.

[0149] In Examples 1-6, taking Example 1 as the base formulation, in Example 2, the alicyclic epoxy resin S-28 with a lower viscosity was replaced with an equal amount of the alicyclic epoxy resin S-100. The modified epoxy resin replaced the liquid carboxyl-terminated nitrile rubber modified epoxy resin 86840 with toughening effect with a flexible polythiol modified epoxy resin, and the reactive diluent was replaced from a total of 20 parts of two diluents to 17 parts of N,N-diglycidyl-4-glycidyloxyaniline. As a result, the toughness of Example 2 is comparable to that of Example 1. In Component B, part of the alicyclic amine was replaced with polyetheramine, and the crosslinking density decreased. Therefore, the compressive strength and tensile strength decreased slightly.

[0150] Compared with Example 1, in Example 3, the epoxy resin mainly used the high-strength multi-functional epoxy resin AG-80 and the standard alicyclic epoxy resin S-28, which has the effect of increasing the crosslinking density. In Component B, the alicyclic amine was replaced with polyetheramine D230, which has the effect of reducing the crosslinking density to a certain extent. The effects of the two offset each other, and the compressive strength, tensile strength are comparable to those of Example 1. In addition, the modified epoxy resin was replaced with an equal amount of the polyurethane modified epoxy resin EPU-300A with a high elongation rate, which improved the adhesion performance to a certain extent, and the tensile shear strength and dry adhesion strength increased slightly, and the elongation at break increased.

[0151] In Example 4, four epoxy resins with different viscosities were mixed. In Component B, the molar ratio of aldehyde compounds and amines was reduced, the crosslinking density decreased, and the compressive strength, tensile strength, and tensile shear strength decreased accordingly. The amount of the liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 was reduced by 5 parts, the brittleness increased, and the elongation at break decreased.

[0152] In Example 5, the amount of the alicyclic epoxy resin S-28 was increased by 20 parts, the amount of the liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 was reduced by 5 parts, and the toughness decreased. The amount of dodecyl to tetradecyl glycidyl ether was reduced by 5 parts, all of which led to an increase in rigidity. However, the bisphenol A type epoxy resin E44 with a longer molecular chain was introduced. In Component B, the molar ratio of aldehyde and amine compounds was reduced, and the crosslinking density was reduced. Generally, the hard brittleness decreased. The compressive strength and tensile strength decreased, and the elongation at break increased.

[0153] In Example 6, compared with Example 1, 20 parts of alicyclic epoxy resin S-28 were added, 10 parts of bisphenol A epoxy resin E44 were introduced, and 5 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 were reduced, showing a tendency to reduce toughness and increase brittleness. In Component B, the molar ratio of some aldehyde compounds and mixed amine curing agents was reduced, resulting in a decrease in some crosslinking density and a tendency to reduce brittleness. Under the interaction of the two phases, the overall brittleness decreased. The compressive strength and tensile strength decreased, while the elongation at break increased.

[0154] The difference between Comparative Example 1 and Example 1 is that in Component A, the phenoxy resin SQP40AXM40 was reduced to 0 parts, and the other formulations and methods were the same as those in Example 1. The molecular structure of the phenoxy resin is extremely similar to that of bisphenol A epoxy resin and has good compatibility with epoxy resin, showing a toughening effect on bisphenol A epoxy resin. Without adding the phenoxy resin, the toughness of the system decreased. The compressive strength and tensile strength increased to a certain extent, the tensile shear strength remained the same, and the elongation at break decreased.

[0155] The difference between Comparative Example 2 and Example 1 is that in Component A, the bisphenol A epoxy resin E51 was reduced to 40 parts, the bisphenol F epoxy resin South Asia NPEF 170 was reduced to 0 parts, and the alicyclic epoxy resin S-28 was reduced to 0 parts, and the other formulations and methods were the same as those in Example 1. The crosslinking density of the system decreased, and the compressive strength, tensile strength, and tensile shear strength decreased after curing, while the flexibility increased and the elongation at break increased.

[0156] The difference between Comparative Example 3 and Example 1 is that in Component A, the bisphenol A epoxy resin E51 was replaced with 40 parts of polyfunctional epoxy resin AG-80, the bisphenol F epoxy resin South Asia NPEF 170 was reduced to 0 parts, and the alicyclic epoxy resin S-28 was reduced to 0 parts, and the other formulations and methods were the same as those in Example 1. The crosslinking density of the system decreased, and the compressive strength, tensile strength, and tensile shear strength decreased after curing. Since the polyfunctional epoxy resin bisphenol A epoxy resin AG-80 has 2 more functional groups than E51, the decrease amplitude in Comparative Example 2 is less. The flexibility increased and the elongation at break increased.

[0157] The difference between Comparative Example 4 and Example 1 is that in Component A, the liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 in the modified epoxy resin was reduced to 5 parts, and the other formulations and methods were the same as those in Example 1. The toughness of the system decreased, the ability to disperse stress decreased, the elongation at break decreased accordingly, and the compressive strength and tensile strength increased.

[0158] The difference between Comparative Example 5 and Example 1 is that: in Component A, 10 parts of the active diluent 1,6 - hexanediol diglycidyl ether are replaced with 10 parts of the non - active diluent benzyl alcohol, and the other formulations and methods are the same as those in Example 1. After the active diluent is replaced with the non - active diluent benzyl alcohol, the cross - linking density of the system is reduced, and the compressive strength and tensile strength decrease accordingly.

[0159] The difference between Comparative Example 6 and Example 1 is that: in Component B, the modified amine curing agent is increased to 100 parts, and the functionalized modified graphene oxide and the accelerator are reduced to 0 parts, and the other formulations and methods are the same as those in Example 1. The absence of the functionalized modified graphene oxide reduces the toughness of the system, the compressive strength and tensile strength increase to some extent, and the elongation at break decreases.

[0160] Finally, the method of the present invention is only a preferred implementation scheme and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An epoxy grouting material for filling and reinforcing the gap between the shield segment of a subway tunnel and a steel ring, characterized in that: It includes Component A and Component B; The Component A includes the following materials by weight parts: 50 - 100 parts of epoxy resin, 1 - 15 parts of phenoxy resin, 10 - 50 parts of modified epoxy resin, 10 - 35 parts of active diluent, and 1 - 5 parts of silicone defoamer; The Component B includes the following materials by weight parts: 80 - 98 parts of modified amine curing agent, 1 - 5 parts of functionalized graphene, and 0.5 - 1.5 parts of accelerator; The mass ratio of Component A to Component B is 1 - 5:1; The phenoxy resin is epoxidized phenoxy resin with an epoxy equivalent between 5000 - 50000 g / eq; The modified epoxy resin is selected from at least one of nitrile rubber modified epoxy resin, polyurethane modified epoxy resin, and polythiol modified epoxy resin; wherein, The nitrile rubber modified epoxy resin is an adduct of bisphenol A glycidyl ether and carboxyl - terminated liquid nitrile rubber elastomer; The polyurethane modified epoxy resin is selected from at least one of EPU - 302, EPU - 303, and EPU - 300A with an epoxy equivalent between 180 - 650 g / eq; The polythiol modified epoxy resin is an aliphatic epoxy resin modified by polythiol.

2. The epoxy grouting material according to claim 1, characterized in that: The epoxy resin is selected from one or more of bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E44, bisphenol F type epoxy resin, multi - functional group epoxy resin, and alicyclic epoxy resin.

3. The epoxy grouting material according to claim 1, characterized in that: The active diluent is a mono - functional group active diluent or a multi - functional group active diluent, and is selected from at least one of benzyl glycidyl ether, octyl glycidyl ether, dodecyl - tetradecyl glycidyl ether, 1,4 - butanediol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4 - cyclohexanedimethanol glycidyl ether, N - (glycidyl) - N - phenyl - epoxyethanamine, and N,N - diglycidyl - 4 - glycidyloxyaniline.

4. The epoxy grouting material according to claim 1, characterized in that: The silicone defoamer is selected from at least one of BYK - A530, BKY - 066N, and BYK - 141.

5. The epoxy grouting material according to claim 1, characterized in that: The modified amine curing agent is modified by Mannich reaction from phenolic compounds, aldehyde compounds, and amine curing agents; wherein, The phenolic compounds are selected from at least one of phenol, p - tert - butylphenol, phloroglucinol, pyrogallol, dodecylphenol, and cashew phenol; The aldehyde compounds are selected from at least one of formaldehyde, paraformaldehyde, dodecyl aldehyde, octadecyl aldehyde, and benzaldehyde; The amine curing agents are selected from at least one of alicyclic amine curing agents and polyetheramine curing agents.

6. The epoxy grouting material according to claim 1, wherein: The functionalized graphene is selected from at least one of 3 - aminopropyltrimethoxysilane modified graphene oxide, diethylenetriamine modified graphene oxide, and polyaniline modified graphene oxide.

7. The epoxy grouting material according to claim 1, wherein: The accelerator is selected from at least one of 2,4,6 - tris(dimethylaminomethyl)phenol, triethanolamine, and salicylic acid solution.

8. The epoxy grouting material according to any one of claims 1-7, characterized in that, The modified amine curing agent is prepared by the following steps: B1: Charge 80 - 350 parts of phenols, 130 - 350 parts of alicyclic amine curing agent or 100 - 4500 parts of polyetheramine into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir, and heat up to 60 - 80 °C to obtain product B1; B2: Slowly add 20 - 600 parts of aldehyde compounds to product B1 in batches, heat up to 80 - 90 °C, and carry out a stirring reflux reaction for 2 - 4 h to obtain product B2; B3: Connect the reactor to a vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and cool down to 40 - 60 °C to obtain the product; or The preparation steps of the modified amine curing agent are as follows: C1: Charge 80 - 350 parts of phenols and 130 - 350 parts of alicyclic amine curing agent into a reactor equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, stir and heat up to 60 - 80 °C to obtain product C1; C2: Slowly add 20 - 300 parts of aldehyde compounds to product C1 in batches, heat up to 80 - 90 °C, and carry out a stirring reflux reaction for 1 - 2 h to obtain product C2; C3: Cool down to 40 - 60 °C, charge 100 - 4500 parts of polyetheramine into the reactor, stir evenly, and then slowly add 20 - 300 parts of aldehyde compounds in batches again, heat up to 80 - 90 °C, and continue the reaction for 1 - 2 h; C4: Connect the reactor to a vacuum distillation device, heat up to 115 - 125 °C, start vacuum dehydration for 1 - 2 h, and cool down to 40 - 60 °C to obtain the product.

9. A method for preparing the epoxy grouting material according to any one of claims 1-8, characterized in that, The preparation method includes the following steps: (1) Mix 100 parts of epoxy resin and 1 - 15 parts of phenoxy resin, heat to 100 - 160 °C, stir for 0.5 - 3 h until completely dissolved with each other, cool down to 40 - 60 °C, add 10 - 50 parts of modified epoxy resin, 10 - 35 parts of active diluent, and 1 - 5 parts of silicone defoamer, mix and stir for 0.5 h, and carry out vacuum for 1 - 2 h to obtain component A; (2) Mix 80 - 98 parts of modified amine curing agent, 1 - 5 parts of functionally modified graphene, and 0.5 - 1.5 parts of accelerator, and stir evenly to obtain component B; (3) Mix component A and component B according to a mass ratio of 1 - 5:1 to obtain the epoxy grouting material.

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