Epoxy grouting material for filling and reinforcing gap between subway tunnel shield segment and steel ring and preparation method of epoxy grouting material

Abstract

The invention provides a grouting material for filling and reinforcing a gap between a subway tunnel shield segment and a steel ring and a preparation method of the grouting material, and belongs to the technical field of building materials. The epoxy grouting material comprises a component A and a component B, the component A is prepared from the following materials in parts by weight: 50 to 100 parts of epoxy resin, 1 to 15 parts of phenoxy resin, 10 to 50 parts of modified epoxy resin, 10 to 35 parts of reactive diluent and 1 to 5 parts of organic silicon defoaming agent; the component B is prepared from the following materials in parts by weight: 80 to 98 parts of a modified amine curing agent, 1 to 5 parts of functionally modified graphene and 0.5 to 1.5 parts of an accelerant; the mass ratio of the component A to the component B is (1-5): 1. According to the epoxy grouting material, the toughness of epoxy resin is improved, the characteristics of high compressive strength, high tensile strength, excellent adhesion and toughness are kept, the durability of the grouting material is improved, and the high requirement of the epoxy grouting material for filling and reinforcing the gap between the subway tunnel shield segment and the steel ring is met.

Description

Technical Field

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

[0002] With the development of economy and the expansion of cities, a large number of people have flocked to cities for employment and property. Urban traffic is becoming increasingly busy, and many cities choose to build underground rail transit (subway) to relieve the pressure of ground traffic. The subway tunnel lining is a complete circular tube body composed of prefabricated reinforced concrete arc-shaped segments assembled in a certain way, and the independent segments are fixed together by bolts. Due to various force majeure reasons, some segments are deformed and damaged, and cracks and water seepage may occur, which accelerates the aging of facilities and further endangers the safety and stable operation of the subway. Timely repair and reinforcement of the segments has become one of the key issues in subway construction and maintenance. At present, the commonly used method is to add arc-shaped thick steel plates in the tunnel, and the arc-shaped steel plates are laid along the inner wall of the tunnel and welded to form an annular structure. The steel ring is combined with the shield segment to form a superimposed structure to improve the bearing capacity of the tunnel and increase the safety reserve and durability of the tunnel. The gap space between the steel ring and the segment is filled and bonded with epoxy resin grouting material. After the grouting material is cured, the steel ring and the segment made of concrete are connected to form a dense whole.

[0003] Epoxy resin is an excellent thermosetting resin. After being mixed and cured with the corresponding curing agent, it has good bonding properties and easy operation. Its solid body has excellent mechanical properties, electrical insulation properties, acid and alkali resistance, and also has the advantage of low shrinkage, which has a very wide range of application scenarios. However, the other side of the excellent performance of epoxy resin is the disadvantages of large internal stress, large brittleness of the solid body, and poor impact resistance due to the high cross-linking density. Technical workers have modified epoxy resin and its corresponding curing agent, auxiliary materials, etc. to overcome the above shortcomings. In the project of filling and bonding reinforcement between subway concrete pipe segments and steel rings, higher requirements are put forward for the viscosity of grouting materials and the bonding strength of grouting materials to dry concrete and wet concrete, as well as the compressive strength, tensile strength, shear tensile strength, elongation at break, durability and other properties after consolidation. Therefore, it is necessary to develop epoxy grouting materials that meet these high requirements for filling and reinforcing the gaps between subway tunnel shield segments and steel rings. Summary of the invention

[0004] To achieve the above-mentioned purpose, the present invention provides an epoxy grouting material for filling and reinforcing the gap between the shield segment and the steel ring of a subway tunnel and a preparation method thereof. The toughness of the epoxy resin is increased by mixing epoxy resin, phenoxy resin and modified epoxy resin, and excellent bonding performance is achieved by using a Mannich-modified mixed amine curing agent and a functionally modified graphene material. The material also has the effects of low viscosity, high strength, high toughness and room temperature curing.

[0005] The first aspect of the present invention is to provide an epoxy grouting material for filling and reinforcing the gap between a shield segment and a steel ring in a subway tunnel, wherein the epoxy grouting material comprises a component A and a component B; wherein:

[0006] The 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; the component B comprises the following materials by weight: 80-98 parts of modified amine curing agent, 1-5 parts of functionalized modified graphene and 0.5-1.5 parts of accelerator.

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

[0008] The component A comprises 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; the component B comprises the following materials by weight: 90-98 parts of modified amine curing agent, 1-5 parts of functionalized modified graphene and 0.5-1.5 parts of accelerator.

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

[0010] The component A comprises 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; the component B comprises the following materials by weight: 94-98 parts of modified amine curing agent, 1-5 parts of functionalized modified 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, multifunctional 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 epoxy resin 6101 produced by Baling Petrochemical Company; the bisphenol F epoxy resin is Nan Ya NPEF 170; the multifunctional epoxy resin refers to an epoxy resin with a functional group number greater than or equal to 3, preferably a tetrafunctional epoxy resin AG-80; the alicyclic epoxy resin is selected from at least one of alicyclic epoxy resin S-100 and alicyclic epoxy resin S-28 produced by Nantong Synasia New Materials Co., Ltd.

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

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

[0015] More preferably, the epoxy equivalent of the epoxidized phenoxy resin is between 5000-20000 g / eq.

[0016] Preferably, the phenoxy resin brand 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] More preferably, the weight ratio of the epoxy resin to the phenoxy resin is 100:1-10.

[0019] 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 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 having an epoxy equivalent of 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 multifunctional reactive diluent.

[0025] Further preferably, the active diluent is selected from at least one of benzyl glycidyl ether, octyl glycidyl ether, carbon dodeca- to tetradecyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol glycidyl ether, N-(epoxypropyl)-N-phenyl-oxiranemethylamine and N,N-diglycidyl-4-glycidyloxyaniline.

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

[0027] Preferably, the modified amine curing agent is formed by modifying a phenolic compound, an aldehyde compound and an amine curing agent through a Mannich reaction.

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

[0029] Further preferably, the aldehyde compound is at least one selected from 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 polyether amine curing agents.

[0031] More preferably, the alicyclic amine curing agent is at least one selected from hydrogenated meta-xylylenediamine (1,3-BAC), isophoronediamine (IPDA) and N-aminoethylpiperazine (AEP).

[0032] 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 tripropylene glycol ether T-403.

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

[0034] More preferably, the 3-aminopropyltrimethoxysiloxane modified graphene oxide is XF315 produced by Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.

[0035] More preferably, the diethylenetriamine (DETA) modified graphene oxide is XF316 produced by Jiangsu Xianfeng Nanomaterial 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 comprises 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: Add 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 to obtain product B 1 ;

[0040] B2: to product B 1 Slowly add 20-600 parts of aldehyde compound in batches, increase the temperature, stir and reflux for 2-4 hours to obtain product B 2 ;

[0041] B3: Connect the reactor to a vacuum distillation device, increase the temperature, start vacuum dehydration, and cool down to obtain; or

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

[0043] C1: Add 80-350 parts of phenols and 130-350 parts of alicyclic amine curing agent into a reactor, stir and heat to obtain product C 1 ;

[0044] C2: to product C 1 Slowly add 20-300 parts of aldehyde compound in batches, raise the temperature, stir and reflux to react, and obtain product C 2 ;

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

[0046] C4: Connect the reactor to a vacuum distillation device, increase the temperature, start vacuum dehydration, and cool down to obtain.

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

[0048] B1: Add 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 to 60-80°C to obtain product B. 1 ;

[0049] B2: to product B 1 Slowly add 20-600 parts of aldehyde compound in batches, raise the temperature to 80-90°C, stir and reflux for 2-4h to obtain product B 2 ;

[0050] B3: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain; or

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

[0052] C1: Add 80-350 parts of phenols and 130-350 parts of alicyclic amine curing agent into a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, stir, and heat to 60-80°C to obtain product C 1 ;

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

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

[0055] C4: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain.

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

[0057] B1: Add 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 to 60-80°C to obtain product B. 1 ;

[0058] B2: Raise the temperature to 80-90°C. If the aldehyde compound is a liquid, slowly add 20-300 parts of it using a dropping funnel. If the aldehyde compound is a solid, add 20-300 parts of it to the product B.1 Slowly add ① part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, slowly add ② part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, slowly add ③ part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, the addition of aldehyde compound can be divided into multiple times, not limited to 3 times; solid aldehyde compound ①+②+③=20-300 parts, the total reaction time of aldehyde compound is 2-4h, and product B is obtained 2 ;

[0059] B3: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain; or

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

[0061] C1: Add 80-350 parts of phenols and 130-350 parts of alicyclic amine curing agent into a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, stir, and heat to 60-80°C to obtain product C 1 ;

[0062] C2: Raise the temperature to 80-90°C. If the aldehyde compound is a liquid, slowly add 20-300 parts of it using a dropping funnel. If the aldehyde compound is a solid, add 20-300 parts of it to the product C. 1 Slowly add ① part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, slowly add ② part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, slowly add ③ part of solid aldehyde compound, stir and reflux at 80-90°C for 0.5-1.5h, the addition of aldehyde compound can be divided into multiple times, not limited to 3 times; solid aldehyde compound ①+②+③=20-300 parts, the total reaction time of aldehyde compound is 2-4h, and product C is obtained 2 ;

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

[0064] C4: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain.

[0065] Preferably, the component A is prepared by the following method: 100 parts of epoxy resin and 1-15 parts of phenoxy resin are mixed and heated to 100-160°C, stirred for 0.5-3h until they are completely dissolved in each other, cooled to 40-60°C, 10-50 parts of modified epoxy resin, 10-35 parts of active diluent, 1-5 parts of silicone defoamer are added, mixed and stirred for 0.5h, and vacuumed for 0.5-2h to obtain component A.

[0066] Further preferably, the component A is prepared by the following method: 100 parts of epoxy resin and 1-12 parts of phenoxy resin are mixed and heated to 100-160°C, stirred for 0.5-3h until they are completely dissolved in each other, cooled to 40-60°C, 15-45 parts of modified epoxy resin, 10-30 parts of active diluent, 1-5 parts of silicone defoaming agent are added, mixed and stirred for 0.5h, and vacuumed for 0.5-2h to obtain component A.

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

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

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

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

[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 bonding properties, and also has the effects of low viscosity, high strength, high toughness, and room temperature curing, meeting the high requirements of epoxy grouting materials for filling and reinforcing the gaps between subway tunnel shield segments and steel rings. DETAILED DESCRIPTION

[0072] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0073] The methods are conventional methods unless otherwise specified. The materials are available from public commercial sources unless otherwise specified.

[0074] Embodiment 1:

[0075] An epoxy grouting material for filling and reinforcing the gap between a shield segment and a steel ring in a subway tunnel comprises a component A and a component B, wherein:

[0076] 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 Nan Ya NPEF 170, 30 parts of alicyclic epoxy resin S-28, 5 parts of phenoxy resin SQP40AXM40, 25 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840, 10 parts of carbon twelve to tetradecyl glycidyl ether, 10 parts of 1,6-hexanediol diglycidyl ether, and 3 parts of silicone defoamer BYK-A530;

[0077] 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.

[0078] Preparation method of component A: bisphenol A epoxy resin E51, bisphenol F epoxy resin Nan Ya NPEF 170, and alicyclic epoxy resin S-28 are mixed and stirred evenly, and phenoxy resin is added. After mixing, it is heated to 160°C and stirred for 3 hours until they are completely dissolved with each other. The temperature is lowered to 60°C, and liquid terminal carboxyl nitrile rubber (CTBN) modified epoxy resin 86840, carbon dodeca-tetradecyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and silicone defoamer BYK-A530 are added. The mixture is mixed and stirred for 0.5 hours. While stirring, vacuum is drawn at a vacuum degree of -0.1 MPa for 1 hour to obtain component A.

[0079] The modified amine curing agent is prepared by modifying phloroglucinol, benzaldehyde and hydrogenated meta-xylylenediamine through the Mannich reaction.

[0080] The preparation method of the modified amine curing agent is as follows: 126 parts of phloroglucinol and 284 parts of hydrogenated meta-xylylenediamine are added into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, and the temperature is heated to 60-80°C while stirring; 212 parts of benzaldehyde are slowly added dropwise by opening a liquid separation device, and the addition must be slow to avoid excessive reaction and explosion; after the addition is completed, the reaction is stirred and refluxed at 80-90°C for 2-4h, the reactor is connected to a vacuum distillation device, the temperature is raised to 115-125°C, vacuum dehydration is started for 1-2h, and the temperature is lowered to 40-60°C to obtain the modified amine curing agent.

[0081] Preparation method of component B: Modified amine curing agent, diethylenetriamine (DETA) modified graphene oxide XF316, and accelerator 2,4,6-tris (dimethylaminomethyl) phenol are mixed and stirred evenly to obtain component B.

[0082] Component A and component B are mixed in a mass ratio of 2:1 to obtain an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in subway tunnels.

[0083] Embodiment 2:

[0084] The invention discloses an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in a subway tunnel, comprising an A component and a B component.

[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 Nan Ya 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: bisphenol A epoxy resin E51, bisphenol F epoxy resin Nan Ya NPEF 170, and alicyclic epoxy resin S-100 are mixed and stirred evenly, phenoxy resin is added and mixed, heated to 160°C, stirred for 0.5-3h until they are completely dissolved with each other, and then cooled to 60°C; polythiol modified epoxy resin EPS70, N,N-diglycidyl-4-glycidyloxyaniline, and silicone defoamer BYK-A530 are added, mixed and stirred for 0.5h, and vacuumed at -0.1MPa for 1h while stirring to obtain component A.

[0088] The modified amine curing agent is prepared by modifying phloroglucinol, benzaldehyde, hydrogenated meta-phenylenediamine and amino-terminated polyoxyethylene ether D230 through Mannich reaction.

[0089] Preparation method of modified amine curing agent: 126 parts of phloroglucinol and 213 parts of hydrogenated meta-phenylenediamine are added to a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, and the temperature is heated to 60-80°C while stirring; 159 parts of benzaldehyde are slowly added dropwise by opening a liquid separation device, and the addition is slowly added dropwise to avoid excessive reaction and explosion. After the addition is completed, the reaction is stirred and refluxed at 80-90°C for 2-4h, cooled to 40-60°C, 115 parts of amino-terminated polyoxyethylene ether D230 are added, stirred evenly, and the temperature is raised to 80-90°C. During the heating process, 53 parts of benzaldehyde are gradually added dropwise again, and the reaction is continued for 1-2h. The reactor is connected to a vacuum distillation device, the temperature is raised to 115-125°C, and vacuum dehydration is started for 1-2h. The modified amine curing agent is obtained by cooling to 40-60°C.

[0090] Preparation method of component B: Modified amine curing agent, diethylenetriamine (DETA) modified graphene oxide XF316, and accelerator 2,4,6-tris (dimethylaminomethyl) phenol are mixed and stirred evenly to obtain component B.

[0091] Component A and component B are mixed in a mass ratio of 1.5:1 to obtain an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in subway tunnels.

[0092] Embodiment 3:

[0093] The invention discloses an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in a subway tunnel, comprising an A component and a B component.

[0094] Component A is composed of the following materials by weight: 80 parts of multifunctional 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 carbon twelve to tetradecyl 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 multifunctional epoxy resin AG-80, alicyclic epoxy resin S-28 and phenoxy resin, heat to 160°C, stir for 0.5-3h until they are completely dissolved in each other, and cool to 60°C; then add polyurethane modified epoxy resin EPU-300A, carbon 12 to 14 alkyl glycidyl ether, and silicone defoamer BYK-A530, mix and stir for 0.5h, and evacuate at -0.1MPa for 1h while stirring to obtain component A.

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

[0098] The preparation method of the modified amine curing agent is as follows: 126 parts of phloroglucinol and 460 parts of amino-terminated polyoxyethylene ether D230 are added into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel, and the temperature is heated to 60-80°C while stirring; 212 parts of benzaldehyde are slowly added dropwise by opening a liquid separation device, and the addition is slowly added dropwise to avoid excessive reaction and explosion. After the addition is completed, the reaction is stirred and refluxed at 80-90°C for 2-4h; the reactor is connected to a vacuum distillation device, the temperature is raised to 115-125°C, vacuum dehydration is started for 1-2h, and the temperature is lowered to 40-60°C to obtain the modified amine curing agent.

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

[0100] Component A and component B are mixed in a mass ratio of 1:1 to obtain an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in subway tunnels.

[0101] Embodiment 4:

[0102] The invention discloses an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in a subway tunnel, comprising an A component and a B component.

[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 Nan Ya NPEF 170, 20 parts of multifunctional epoxy resin AG-80, 10 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, and 3 parts of silicone defoamer BYK-A530;

[0104] 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.

[0105] Preparation method of component A: bisphenol A epoxy resin E44, bisphenol F epoxy resin Nan Ya NPEF 170, multifunctional epoxy resin AG-80, and alicyclic epoxy resin S-100 are mixed and stirred evenly, and phenoxy resin is added. After mixing, it is heated to 160°C and stirred for 3 hours until they are completely dissolved with each other. The temperature is lowered to 60°C, and liquid terminal carboxyl nitrile rubber (CTBN) modified epoxy resin 86840, 1,4-cyclohexanedimethanol diglycidyl ether, and silicone defoamer BYK-A530 are added. The mixture is mixed and stirred for 0.5 hours. While stirring, vacuum is drawn at a vacuum degree of -0.1 MPa for 1 hour to obtain component A.

[0106] The modified amine curing agent is prepared by modifying phloroglucinol, octadecyl aldehyde and hydrogenated meta-xylylenediamine through a Mannich reaction.

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

[0108] Preparation method of component B: According to weight, 96 parts of the prepared modified amine curing agent, 3 parts of 3-aminopropyltrimethoxysiloxane-modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol are mixed to obtain the above raw materials in the formula amount and stirred evenly to obtain component B.

[0109] The component A and the 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 segments and the steel rings of a subway tunnel.

[0110] Embodiment 5:

[0111] The invention discloses an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in a subway tunnel, comprising an A component and a B component.

[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, and 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-aminopropyltrimethoxysiloxane modified graphene oxide XF315, and 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, and then 5 parts of phenoxy resin are added and mixed, heated to 160°C, stirred for 0.5-3h until they are completely dissolved, and then cooled to 60°C. Then, 20 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840, 15 parts of 1,4-cyclohexanedimethanol diglycidyl ether, and 3 parts of silicone defoamer BYK-A530 are added, mixed and stirred for 0.5h, and vacuumed at -0.1MPa for 1h while stirring to obtain component A.

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

[0116] Preparation method of modified amine curing agent: Preparation method suitable for solid aldehyde compounds: Add 126 parts of phloroglucinol and 230 parts of terminal amino polyoxyethylene ether D230 into a reactor equipped with a stirrer, a reflux condenser and a thermometer, and heat to 60-80°C while stirring. Add 1 part of octadecyl aldehyde, stir and reflux at 80-90°C for 1h. Add 2 parts of octadecyl aldehyde, continue to reflux at 80-90°C for 1h. Add 3 parts of octadecyl aldehyde, continue to reflux at 80-90°C for 1h. The octadecyl aldehyde added in batches totals ①+②+③=268 parts. To avoid excessive reaction, octadecyl aldehyde can be added in batches multiple times, not limited to 3 times. Connect the reactor to a vacuum distillation device, heat to 115-125°C, and start vacuum dehydration for 1-2h. Cool down to 40-60°C to obtain a modified amine curing agent.

[0117] Preparation method of component B: According to weight, 96 parts of the prepared modified curing agent, 3 parts of 3-aminopropyltrimethoxysiloxane-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] The component A and the 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 segments and the steel rings of a subway tunnel.

[0119] Embodiment 6:

[0120] The invention discloses an epoxy grouting material for filling and reinforcing gaps between shield segments and steel rings in a subway tunnel, comprising an A component and a B component.

[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 nitrile 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-aminopropyltrimethoxysiloxane 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, and then 5 parts of phenoxy resin are added and mixed, heated to 160°C, stirred for 0.5-3h until they are completely dissolved, and then cooled to 60°C. Then, 20 parts of liquid carboxyl-terminated nitrile 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 0.5h, and vacuumed at -0.1MPa for 1h while stirring to obtain component A.

[0124] The modified amine curing agent is prepared by modifying phloroglucinol, octadecyl aldehyde, hydrogenated meta-phenylenediamine and amino-terminated polyoxyethylene ether D230 through Mannich reaction.

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

[0126] Preparation method of component B: According to weight, 96 parts of the prepared modified curing agent, 3 parts of 3-aminopropyltrimethoxysiloxane-modified graphene oxide XF315, and 1 part of accelerator 2,4,6-tris(dimethylaminomethyl)phenol are mixed and stirred evenly to obtain component B.

[0127] The component A and the 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 segments and the steel rings of a subway tunnel.

[0128] Comparative Example 1:

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

[0130] Comparative Example 2:

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

[0132] Comparative Example 3:

[0133] The difference between Comparative Example 3 and Example 1 is that in component A, the bisphenol A epoxy resin E51 is replaced with 40 parts of multifunctional epoxy resin AG-80, the bisphenol F epoxy resin Nan Ya NPEF 170 is reduced to 0 parts, and the alicyclic epoxy resin S-28 is reduced to 0 parts, and the rest is the same as Example 1.

[0134] Comparative Example 4:

[0135] The difference from Example 1 is that the liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 in the modified epoxy resin in component A is reduced to 5 parts, and the rest is the same as Example 1.

[0136] Comparative Example 5:

[0137] The difference from Example 1 is that the active diluent "10 parts of 1,6-hexanediol diglycidyl ether" in component A of Example 1 is replaced by "10 parts of inactive diluent benzyl alcohol", and the rest is the same as Example 1.

[0138] Comparative Example 6:

[0139] The difference from Example 1 is that the modified amine curing agent in component B is increased to 100 parts, and functionalized graphene oxide and accelerator are not contained. Others are the same as in Example 1.

[0140] Experimental results

[0141] The compressive strength, dry bond strength, wet bond strength and penetration pressure ratio are tested in accordance with the provisions of JC / T1041-2007, the tensile strength is tested in accordance with the provisions of GB / T 2567-2021, and the tensile shear strength is tested in accordance with the provisions of GB / T7124-2008. The test data are shown in Tables 1 and 2.

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

[0143]

[0144]

[0145] Table 2: Test data of 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 performance, and all have compressive strength, tensile strength, tensile shear strength, dry bonding strength, and wet bonding strength, and can highly meet the needs of filling and reinforcing the gaps between subway tunnel shield segments and steel rings.

[0149] In Examples 1-6, Example 1 is used as the basic formula. Compared with Example 1, Example 2 replaces the alicyclic epoxy resin S-28 with an equal amount of alicyclic epoxy resin S-100 with a lower viscosity. The modified epoxy resin replaces the toughening liquid carboxyl-terminated nitrile rubber modified epoxy resin 86840 with a flexible polythiol modified epoxy resin. The active diluent is replaced by 17 parts of N, N-diglycidyl-4-glycidyloxyaniline from 20 parts of two diluents. This makes Example 2 have the same toughness as Example 1. In component B, part of the alicyclic amine is replaced by polyetheramine, and the crosslinking density is reduced. Therefore, the compressive strength and tensile strength are slightly reduced.

[0150] Compared with Example 1, Example 3 mainly uses high-strength multifunctional epoxy resin AG-80 and standard alicyclic epoxy resin S-28, which have the effect of increasing the crosslinking density. In component B, the alicyclic amine is replaced by 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 and tensile strength are equivalent to those of Example 1. In addition, the modified epoxy resin is replaced by a high-elongation polyurethane modified epoxy resin EPU-300A in equal amounts, which improves the bonding performance to a certain extent, and the tensile shear strength and dry bonding strength are slightly increased, and the elongation at break is increased.

[0151] Example 4 uses four epoxy resins of different viscosities to mix, and the molar ratio of aldehyde compounds and amines in component B is reduced, the crosslinking density decreases, and the compressive strength, tensile strength, and tensile shear strength decrease accordingly. Liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 is reduced by 5 parts, the brittleness increases, and the elongation at break decreases.

[0152] Example 5 increases the amount of alicyclic epoxy resin S-28 by 20 parts, reduces the amount of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840 by 5 parts, and reduces toughness. Carbon twelve to tetradecyl glycidyl ether is reduced by 5 parts, all of which lead to increased rigidity. However, the introduction of bisphenol A epoxy resin E44 with a longer molecular chain reduces the molar ratio of aldehydes and amine compounds in component B, and reduces the crosslinking density. Overall, the hardness and brittleness decrease. The compressive strength and tensile strength decrease, and the elongation at break increases.

[0153] Compared with Example 1, Example 6 increases 20 parts of alicyclic epoxy resin S-28, introduces 10 parts of bisphenol A epoxy resin E44, reduces 5 parts of liquid carboxyl-terminated nitrile rubber (CTBN) modified epoxy resin 86840, and has a tendency to reduce toughness and increase hardness and brittleness. In component B, the molar ratio of some aldehyde compounds and mixed amine curing agents is reduced, the partial cross-linking density is reduced, and there is a tendency to reduce hardness and brittleness. Under the action of two phases, the overall hardness and brittleness decrease. The compressive strength and tensile strength decrease, and the elongation at break increases.

[0154] The difference between Comparative Example 1 and Example 1 is that the phenoxy resin SQP40AXM40 in component A is reduced to 0 parts, and the other formulas and methods are the same as those in Example 1. The molecular structure of phenoxy resin is extremely similar to that of bisphenol A epoxy resin, and has good compatibility with epoxy resin, and has a toughening effect on bisphenol A epoxy resin. After phenoxy resin is not added, the toughness of the system decreases. The compressive strength and tensile strength increase to a certain extent, the tensile shear strength remains the same, and the elongation at break decreases.

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

[0156] The difference between Comparative Example 3 and Example 1 is that: in component A, bisphenol A epoxy resin E51 is replaced with 40 parts of multifunctional epoxy resin AG-80, bisphenol F epoxy resin Nan Ya NPEF 170 is reduced to 0 parts, alicyclic epoxy resin S-28 is reduced to 0 parts, and other formulas and methods are the same as Example 1. The crosslinking density of the system decreases, and the compressive strength, tensile strength, and tensile shear strength decrease after curing. Since the multifunctional epoxy resin bisphenol A epoxy resin AG-80 has 2 more functional groups than E51, the decrease in Comparative Example 2 is less. Flexibility increases and elongation at break increases.

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

[0158] The difference between Comparative Example 5 and Example 1 is that 10 parts of the active diluent 1,6-hexanediol diglycidyl ether in component A is replaced by 10 parts of the inactive diluent benzyl alcohol, and the other formulas and methods are the same as those in Example 1. After the active diluent is replaced by the inactive diluent benzyl alcohol, the crosslinking 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 the modified amine curing agent in component B is increased to 100 parts, the functionalized modified graphene oxide and the accelerator are reduced to 0 parts, and the other formulas and methods are the same as the examples. The absence of functionalized modified graphene oxide reduces the toughness of the system, the compressive strength and tensile strength are increased, and the elongation at break is reduced.

[0160] Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An epoxy grouting material for filling and reinforcing the gap between the shield segment and the steel ring of a subway tunnel, characterized in that: It includes component A and component B; The 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 organosilicon defoamer; The B component comprises the following materials by weight: 80-98 parts of a modified amine curing agent, 1-5 parts of functionalized modified graphene, and 0.5-1.5 parts of an accelerator; The mass ratio of component A to component B is 1-5:

1.

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

3. The epoxy grouting material according to claim 1, characterized in that: The phenoxy resin is an epoxidized phenoxy resin, and the epoxy equivalent is between 5000-50000 g / eq.

4. The epoxy grouting material according to claim 1, characterized in that: 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 of 180-650 g / eq; The polythiol-modified epoxy resin is a polythiol-modified aliphatic epoxy resin.

5. The epoxy grouting material according to claim 1, characterized in that: The active diluent is a monofunctional active diluent or a multifunctional active diluent, and is selected from at least one of benzyl glycidyl ether, octyl glycidyl ether, carbon twelve to tetradecyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol glycidyl ether, N-(epoxypropyl)-N-phenyl-oxirane methylamine and N,N-diglycidyl-4-glycidyloxyaniline.

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

7. The epoxy grouting material according to claim 1, characterized in that: The modified amine curing agent is formed by modifying a phenolic compound, an aldehyde compound and an amine curing agent through a Mannich reaction; wherein, The phenolic compound is at least one selected from phenol, p-tert-butylphenol, phloroglucinol, pyrogallol, dodecylphenol and cardanol; The aldehyde compound is selected from at least one of formaldehyde, paraformaldehyde, dodecyl aldehyde, octadecyl aldehyde and benzaldehyde; The amine curing agent is selected from at least one of alicyclic amine curing agents and polyether amine curing agents.

8. The epoxy grouting material according to claim 1, characterized in that: The functionalized modified graphene is selected from at least one of 3-aminopropyltrimethoxysiloxane modified graphene oxide, diethylenetriamine modified graphene oxide and polyaniline modified graphene oxide.

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

10. The epoxy grouting material according to any one of claims 1 to 9, characterized in that: The modified amine curing agent is prepared by the following steps: B1: Add 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, a reflux condenser, a thermometer and a dropping funnel, stir, and heat to 60-80° C. to obtain product B1; B2: slowly add 20-600 parts of aldehyde compound to product B1 in batches, raise the temperature to 80-90° C., stir and reflux for 2-4 hours to obtain product B2; B3: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain; or The preparation steps of the modified amine curing agent are: C1: 80-350 parts of phenols and 130-350 parts of alicyclic amine curing agent are added to a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, stirred, and heated to 60-80° C. to obtain product C1; C2: slowly add 20-300 parts of aldehyde compound to product C1 in batches, raise the temperature to 80-90° C., stir and reflux for 1-2 hours to obtain product C2; C3: Cool to 40-60°C, add 100-4500 parts of polyetheramine into the reactor, stir evenly, slowly add 20-300 parts of aldehyde compound in batches again, heat to 80-90°C, and continue the reaction for 1-2h; C4: Connect the reactor to a vacuum distillation device, raise the temperature to 115-125°C, start vacuum dehydration for 1-2 hours, and then cool down to 40-60°C to obtain.

11. A method for preparing the epoxy grouting material according to any one of claims 1 to 10, characterized in that: The preparation method comprises the following steps: (1) 100 parts of epoxy resin and 1-15 parts of phenoxy resin are mixed and heated to 100-160° C., stirred for 0.5-3 hours until they are completely dissolved in each other, cooled to 40-60° C., 10-50 parts of modified epoxy resin, 10-35 parts of active diluent, and 1-5 parts of organosilicon defoamer are added, mixed and stirred for 0.5 hours, and vacuumed for 1-2 hours to obtain component A; (2) mixing 80-98 parts of a modified amine curing agent, 1-5 parts of a functionalized graphene, and 0.5-1.5 parts of an accelerator, and stirring the mixture to obtain a component B; (3) Component A and component B are mixed in a mass ratio of 1-5:1 to obtain an epoxy grouting material.

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