Permeable epoxy grouting material and preparation method thereof

Abstract

The invention provides a permeable epoxy grouting material and a preparation method thereof, and belongs to the technical field of building materials.The permeable epoxy grouting material comprises a component A and a component B. When the permeable epoxy grouting material is used, the component A and the component B are mixed according to the mass ratio of 2: 1-5: 1; the component A comprises the following components in 100 parts by mass: 35-60 parts of epoxy resin, 5-25 parts of a non-active diluent, 10-30 parts of an active diluent, 1-10 parts of a silane coupling agent and 3-15 parts of a nonionic surfactant; the component B comprises the following components in 100 parts by mass: 70-90 parts of a phenolic aldehyde amine modified curing agent, 5-20 parts of a non-active diluent and 1-10 parts of an accelerant; wherein the reactive diluent is selected from a diluent which has one or more than two epoxy groups and can react with the phenolic aldehyde amine modified curing agent; the non-active diluent is selected from at least one of phthalic acid C1-C8 dibasic ester, benzyl alcohol, ethylene glycol, diformate and N-methyl pyrrolidone.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and in particular relates to a permeable epoxy grouting material and a preparation method thereof, and more specifically to an environmentally friendly high-permeability epoxy grouting material and a preparation method thereof that can be used in applications such as crack repair and reinforcement of concrete structures such as housing construction, rail transit, and highway tunnels. Background Art

[0002] Concrete structures, such as buildings, rail transit systems, and highway tunnels, are prone to structural defects such as deformation and cracking over long periods of use. These defects can lead to localized or widespread water seepage, potentially endangering the structure and causing significant damage. Grouting reinforcement is a highly effective and widely used method for repairing concrete cracks, primarily for deep and penetrating cracks in concrete.

[0003] Epoxy grouting material is a chemical grouting material. Due to its excellent mechanical properties, chemical resistance, and bonding properties, as well as its ability to cure at room temperature and minimal shrinkage upon curing, it is commonly used for concrete crack repair, leak prevention, and reinforcement. However, the high viscosity of epoxy resin results in poor fluidity, making it difficult to inject into micro-cracks less than 1 mm, limiting its application in grouting reinforcement. To reduce the viscosity of epoxy resin, a large amount of reactive or inactive diluent is usually added, but both types of diluents will reduce the physical and mechanical properties of the epoxy grouting material to varying degrees.

[0004] In order to resolve this contradiction, the epoxy grouting materials used in engineering usually adopt furfural-acetone as diluent. Furfural and acetone have good viscosity-reducing properties, and under certain conditions, they can act as active diluents to participate in the construction of the three-dimensional network structure of epoxy resin. While obtaining a lower initial viscosity of the slurry, it can also ensure that the consolidated body has excellent physical and mechanical properties.

[0005] However, this system suffers from the drawback that furfural, a volatile, highly toxic chemical raw material with a pungent odor, is used in high concentrations in the formulation, posing a serious threat to construction workers and the surrounding environment during grout preparation and application. With increasing attention to environmental protection and material safety, the use of the furfural-acetone diluent system in epoxy grouting materials is becoming increasingly limited. Summary of the Invention

[0006] In response to the above technical problems, the present invention provides a permeable epoxy grouting material and a preparation method thereof, in order to at least partially solve the above technical problems.

[0007] As a first aspect of the present invention, a permeable epoxy grouting material is provided, comprising component A and component B. When used, component A and component B are mixed in a mass ratio of 2:1-5:1; component A comprises, based on 100 parts by mass: 35-60 parts of epoxy resin, 5-25 parts of inactive diluent, 10-30 parts of active diluent, 1-10 parts of silane coupling agent, and 3-15 parts of non-ionic surfactant; component B comprises, based on 100 parts by mass: 70-90 parts of phenalkamine-modified curing agent, 5-20 parts of inactive diluent, and 1-10 parts of accelerator; wherein the active diluent is selected from a diluent having one or more epoxy groups and capable of reacting with the phenalkamine-modified curing agent; and the inactive diluent is selected from at least one of C1-C8 dibasic phthalate, benzyl alcohol, ethylene glycol, diformate, and N-methylpyrrolidone.

[0008] As a second aspect of the present invention, a method for preparing the above-mentioned penetrating epoxy grouting material is provided, comprising: stirring and mixing 5-25 parts of an inactive diluent, 10-30 parts of an active diluent, 1-10 parts of a silane coupling agent and 3-15 parts of a nonionic surfactant per 100 parts by mass to obtain a penetrating mixed diluent; stirring and mixing 35-75 parts of an epoxy resin and 25-65 parts of the penetrating mixed diluent per 100 parts by mass to obtain a component A grouting raw material; subjecting a phenolic compound, an aldehyde compound and an amine compound to a Mannich reaction to obtain a phenalkamine modified curing agent; mixing 5-20 parts of an inactive diluent, 1-10 parts of an accelerator and 70-90 parts of a phenalkamine modified curing agent per 100 parts by mass to obtain a component B grouting raw material; and mixing the component A grouting raw material and the component B grouting raw material in a mass ratio of 2:1-5:1 to obtain a penetrating epoxy grouting material.

[0009] Based on the above technical solution, the present invention provides a permeable epoxy grouting material and a preparation method thereof, which has at least one of the following beneficial effects:

[0010] (1) In the technical solution of the present invention, in order to solve the problems of the current penetrating epoxy grouting materials such as strong odor, high toxicity, and easy harm to the environment and construction workers, it is proposed to use an inactive diluent with a higher boiling point, lower volatility, and non-toxic components to mix with an active diluent containing a monofunctional group (or bifunctional group) to obtain a mixed diluent; among them, some active diluents have the characteristics of small molecular weight, small steric hindrance and low viscosity, and some active diluents have good mechanical properties, which can reduce the viscosity of epoxy grouting materials while ensuring the strength of the grouting body; inactive diluents have the advantages of low viscosity and promoting the curing reaction of epoxy resin. Different types of inactive diluents and active diluents are compounded, and the resulting mixed diluent can not only effectively reduce the viscosity of epoxy resin, but also participate in the construction of a three-dimensional network structure of the solid body formed by the curing of epoxy resin and the surrounding concrete, thereby overcoming the problem of the difficult balance between the viscosity, solid body rigidity and toughness of the existing epoxy grouting materials.

[0011] (2) In the technical solution of the present invention, the phenalkamine modified curing agent of the present invention is obtained by modifying an amine compound by a phenolic compound and an aldehyde compound through a Mannich reaction. The molecular structure of the phenalkamine modified curing agent contains phenolic hydroxyl groups, primary amino groups (-NH2) and secondary amino groups (-NH-), which can increase the curing speed of amino groups and epoxy groups.

[0012] (3) In the technical solution of the present invention, the penetrating epoxy grouting material of the present invention has the advantages of being green and environmentally friendly, having low viscosity, high permeability, and being able to cure quickly in a humid environment and underwater. Moreover, the grouting material can easily penetrate into the cracks of the concrete structure due to its low viscosity (higher fluidity). After curing, the solid body formed with the concrete has strong mechanical properties, which can play a role in overall strengthening and reinforcement, and achieve a long-term and stable waterproof and anti-seepage effect. DETAILED DESCRIPTION

[0013] Below, embodiments of the present invention will be described. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present invention. In the detailed description below, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of embodiments of the present invention. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessarily confusing the concept of the present invention.

[0014] The terms used herein are only for describing specific embodiments and are not intended to limit the present invention. The term "comprising" used herein indicates the existence of features, steps, operations, but does not exclude the existence or addition of one or more other features.

[0015] When expressions such as “at least one of A, B, and C, etc.” are used, they should generally be interpreted in accordance with the meaning commonly understood by those skilled in the art (for example, “a system having at least one of A, B, and C” should include but is not limited to systems having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, and C, etc.). When expressions such as “at least one of A, B, or C, etc.” are used, they should generally be interpreted in accordance with the meaning commonly understood by those skilled in the art (for example, “a system having at least one of A, B, or C” should include but is not limited to systems having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, and C, etc.).

[0016] Most current grouting materials still use furfural-acetone as a diluent. Furfural-acetone's high permeability and low viscosity allow it to penetrate deep into concrete structures, forming a "rooted" interlaced structure with inorganic concrete materials, strengthening the overall structure and providing long-term waterproofing and anti-seepage. Furthermore, under certain conditions, it can act as a reactive diluent in the construction of the epoxy resin's three-dimensional network, achieving a low initial slurry viscosity while also ensuring excellent physical and mechanical properties. However, the furfural in this system is a volatile, highly toxic chemical raw material with a pungent odor, posing serious hazards to construction workers and the environment. Its application is increasingly restricted by environmental protection requirements. While environmentally friendly, high-permeability epoxy grouting materials have been developed, these efforts primarily focus on modified furfural-acetone systems, such as replacing furfural with less toxic solvents such as α,β-furanpropenal and benzaldehyde. However, achieving a green and non-toxic high-permeability epoxy grouting material remains elusive. To this end, the present invention proposes to use a non-toxic, higher boiling point and lower volatility inactive diluent mixed with an active diluent to replace the traditional furfural-acetone system, so that the obtained permeable grouting material has lower viscosity while having higher permeability and mechanical properties.

[0017] As a first aspect of the present invention, a permeable epoxy grouting material is provided, comprising component A and component B. When used, component A and component B are mixed in a mass ratio of 2:1-5:1. Component A comprises, based on 100 parts by mass, 35-60 parts of epoxy resin, 5-25 parts of inactive diluent, 10-30 parts of active diluent, 1-10 parts of silane coupling agent, and 3-15 parts of nonionic surfactant. Component B comprises, based on 100 parts by mass, 70-90 parts of phenalkamine-modified curing agent, 5-20 parts of inactive diluent, and 1-10 parts of accelerator. The active diluent is selected from a diluent having one or more epoxy groups and capable of reacting with the phenalkamine-modified curing agent. The inactive diluent is selected from at least one of C1-C8 dibasic phthalate, benzyl alcohol, ethylene glycol, diformate, and N-methylpyrrolidone.

[0018] In an embodiment of the present invention, epoxy resin needs to add other diluents to reduce its viscosity because it has a large viscosity. The present invention adopts an inactive diluent with lower volatility, higher boiling point and lower viscosity, and mixes it with a reactive diluent containing an epoxy group and capable of reacting with a phenolic amine modified curing agent to obtain a non-toxic, low-viscosity mixed diluent, which can reduce the viscosity of the epoxy resin in the grouting material. In addition, different types of inactive diluents and reactive diluents are compounded, and the resulting mixed diluent can not only effectively reduce the viscosity of the epoxy resin, but also participate in the construction of the three-dimensional network structure of the epoxy resin solidification, thereby overcoming the problem that the viscosity, solid rigidity and toughness of the existing epoxy grouting material are difficult to balance. Further, coupling agent and surfactant are added to the mixed diluent, and the obtained A component can improve the bonding performance, mechanical properties and durability of the grouting material and the concrete structure, and can also improve the permeability of the grouting material, promote penetration, reduce surface tension, so that the grouting material flows into the slit of the concrete structure and realizes solidification repair. Component B is formed by mixing a phenalkamine-modified curing agent, an inactive diluent, and an accelerator. The phenalkamine-modified curing agent's molecular structure contains phenolic hydroxyl groups, primary amino groups (-NH2), and secondary amino groups (-NH-), which can accelerate the curing speed of amines and epoxy resins, and maintains significant curing effectiveness in humid or underwater environments. Finally, when used, components A and B are mixed in appropriate proportions. The resulting grouting material is environmentally friendly, has low viscosity, high permeability, and cures quickly in humid or underwater environments. It can easily penetrate cracks in concrete structures and, after curing, forms a bond with the concrete with strong mechanical properties, providing overall reinforcement and long-term, stable waterproofing and anti-seepage properties. Excessive or insufficient component A can result in a low crosslink density in the epoxy resin bond, thus affecting the mechanical properties and strength of the grouting material.

[0019] According to an embodiment of the present invention, the epoxy resin is selected from bisphenol A and / or bisphenol F epoxy resins, such as one or a mixture of at least two of epoxy resins selected from the group consisting of E-42, E-44, E-51, E55, and 170. The epoxy resin in the present invention is primarily used to construct a cured structure with higher strength and toughness, enhance interfacial strength, achieve bonding with concrete materials, and thereby repair concrete structures.

[0020] According to an embodiment of the present invention, the reactive diluent is selected from diluents having one or more epoxy groups and capable of reacting with the phenalkamine-modified curing agent, for example, at least one selected from the group consisting of C3-C8 alkyl or alkenyl glycidyl ether, C6-C7 phenyl glycidyl ether, benzyl glycidyl ether, poly-C2-C3 glycol diglycidyl ether, and butanediol diglycidyl ether. Specifically, the C3-C8 alkyl or alkenyl glycidyl ether is selected from at least one of n-butyl glycidyl ether, allyl glycidyl ether, and 2-ethyl-hexyl glycidyl ether; the C6-C7 phenyl glycidyl ether is selected from at least one of phenyl glycidyl ether and cresyl glycidyl ether; and the poly-C2-C3 glycol diglycidyl ether is selected from at least one of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether. The reactive diluent in the present invention is primarily used to reduce the viscosity of the epoxy resin in component A and improve the permeability of the grouting material. Furthermore, the reactive diluent's molecular structure contains epoxy groups, which participate in the epoxy resin's curing reaction, optimizing its structure and regulating its curing time, providing a foundation for the injection and application of the grouting material. Furthermore, some of the reactive diluents described herein also contain a rigid benzene ring structure, which not only reduces the viscosity of the epoxy resin but also improves the mechanical properties (such as strength) of the grouting material after it penetrates cracks in the concrete structure and cures to form a bond with the concrete.

[0021] According to embodiments of the present invention, the inactive diluent is primarily a high-boiling-point organic solvent (above 120°C). This organic solvent has low volatility, low viscosity, and both viscosity-reducing properties, along with environmental benefits. Alcohol-based inactive diluents also promote epoxy resin curing and are environmentally friendly. For example, the inactive diluent may be selected from at least one of C1-C8 dibasic phthalates, benzyl alcohol, ethylene glycol, diformate esters, and N-methylpyrrolidone. The C1-C8 dibasic phthalate ester may include at least one of dimethyl phthalate, dibutyl phthalate, and dioctyl phthalate. The inactive diluent in embodiments of the present invention primarily reduces the viscosity of the epoxy resin and improves the permeability of the grouting material through physical dilution. While the inactive diluent does not react with the epoxy resin or the phenalkamine-modified curing agent, it can promote the curing reaction of the epoxy resin.

[0022] According to an embodiment of the present invention, the amount of the active diluent is greater than the amount of the inactive diluent. The inactive diluents in component A and component B may be the same or different, preferably the same.

[0023] According to an embodiment of the present invention, the silane coupling agent is selected from silane coupling agents containing epoxy and / or amino functional groups. Specifically, the epoxy-functional silane coupling agent is selected from γ-glycidoxypropyltrimethoxysilane; the amino-functional silane coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, and N,N-diethyl-3-aminopropyltrimethoxysilane. The silane coupling agent in the present invention is a low- or high-molecular-weight compound containing functional groups at both ends that react with inorganic and organic substances, respectively. In other words, one end reacts with the surface of an inorganic substance, while the other reacts with an organic molecule, firmly connecting the two materials through a chemical bond. This improves the bonding between the grouting material and the concrete, and enhances the mechanical properties of the bond formed after the grouting material cures.

[0024] According to an embodiment of the present invention, the nonionic surfactant is selected from at least one of butynediol, dimethylhexynediol, dimethyloctynediol, and tetramethyldecynediol; and the accelerator is selected from at least one of triethylamine, triethanolamine, 2,4,6-tris(dimethylaminomethyl)phenol, and o-hydroxybenzyldimethylamine. In this invention, the nonionic surfactant is primarily used to improve the permeability of the grouting material, promote penetration, and reduce the surface tension of the grouting material. This environmentally friendly, highly permeable grouting material, thanks to its low viscosity and excellent permeability, can penetrate 2-3 mm into C30 concrete blocks. Furthermore, the nonionic surfactant exhibits excellent storage stability.

[0025] According to an embodiment of the present invention, the accelerator is selected from at least one of triethylamine, triethanolamine, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), and o-hydroxybenzyldimethylamine (DMP-10), and mainly promotes the curing of epoxy resin.

[0026] According to an embodiment of the present invention, a phenalkamine-modified curing agent (also known as a Mannich-modified amine curing agent) is formed by a Mannich reaction of a phenolic compound, an aldehyde compound, and an amine compound; wherein the molar ratio of the amine compound to the aldehyde compound and the phenolic compound is 1:1:1-3:1.5:1. Furthermore, the phenolic compound is selected from at least one of phenol, nonylphenol, cardanol, m-cresol, and bisphenol A, preferably a mixture of two phenolic compounds, such as cardanol and phenol, wherein cardanol is preferably mixed with other phenolic compounds, which can slow down the operability time of the grouting material and is applicable to more scenarios; the aldehyde compound is selected from benzaldehyde or formaldehyde; the amine compound is selected from at least one of diethylenetriamine, triethylenetetramine, m-phenylenediamine, hexamethylenediamine, diaminodiphenylmethane, polyetheramine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 2-aminodiphenylsulfone, and N-aminoethylpiperazine, for example, the amine compound is selected from a mixture of diethylenetriamine, polyetheramine, and isophoronediamine. In the present invention, the phenolic compound and the aldehyde compound modify the amine compound through a Mannich reaction to introduce phenolic hydroxyl groups into the amine compound, thereby increasing the curing speed of the amine group and the epoxy group in the amine compound, and also having good curing advantages in humid or underwater environments. Furthermore, C4-C8 short-chain fatty amines, C10-C16 long-chain fatty amines and alicyclic amines respectively have the advantages of fast curing speed, high toughness and high heat resistance. In order to integrate and balance the performance of different types of curing agents, different types of amine compounds are selected as modification targets, so as to effectively balance the curing agent product viscosity, amine value and impact resistance and other indicators.

[0027] As a second aspect of the present invention, a method for preparing a penetrating epoxy grouting material is provided, comprising: stirring and mixing, based on 100 parts by mass, 5-25 parts of an inactive diluent, 10-30 parts of an active diluent, 1-10 parts of a silane coupling agent, and 3-15 parts of a nonionic surfactant to obtain a penetrating mixed diluent; subsequently, stirring and mixing, based on 100 parts by mass, 35-75 parts of an epoxy resin and 25-65 parts of the penetrating mixed diluent to obtain a component A grouting raw material; subjecting a phenolic compound, an aldehyde compound, and an amine compound to a Mannich reaction to obtain a phenalkamine-modified curing agent; further, mixing, based on 100 parts by mass, 5-20 parts of an inactive diluent, 1-10 parts of an accelerator, and 70-90 parts of a phenalkamine-modified curing agent to obtain a component B grouting raw material; finally, mixing the component A grouting raw material and the component B grouting raw material in a mass ratio of 2:1-5:1 to obtain a penetrating epoxy grouting material.

[0028] In the embodiments of the present invention, the grouting material prepared using the method and formula provided by the present invention has good permeability and low viscosity, can penetrate into the narrow cracks of concrete, and after solidification, the solid body formed with the concrete has excellent physical and mechanical properties, which can play an overall reinforcement role on the concrete structure, effectively reducing the risk of leakage caused by the enlargement of cracks due to deformation of the concrete structure. In addition, the permeable grouting material of the present invention also has the characteristics of low odor and green environmental protection, which makes up for the shortcomings of traditional furfural-acetone system permeable grouting materials such as high toxicity and environmental pollution, and takes into account the environmental performance of high-permeability epoxy grouting materials and the physical and mechanical properties of the solid body, effectively expanding the application range of epoxy grouting materials in the field of grouting reinforcement.

[0029] Below in conjunction with specific embodiment, the technical scheme in the present invention is clearly and completely described, and it is obvious that described embodiment is only a part of embodiment of the present invention, rather than whole embodiment. Based on the embodiment in the present invention, every other embodiment that those of ordinary skill in the art obtains, all belong to the scope of protection of the present invention. In addition, reagent of the present invention or medicine can be purchased through commercial channels and obtain, or synthesize and obtain.

[0030] Example 1

[0031] (1) In parts by mass, 5 parts of polyethylene glycol diglycidyl ether, 10 parts of allyl glycidyl ether, 15 parts of benzyl glycidyl ether, and 5 parts of benzyl alcohol were added to a reactor in sequence and stirred to mix evenly; 2 parts of γ-aminopropyltrimethoxysilane and 3 parts of butynediol were added to the above reactor in sequence and continued to stir and mix evenly to prepare an environmentally friendly high-penetration mixed diluent.

[0032] (2) Based on 100 parts by mass, epoxy resin E-51 was preheated at 70°C, and then 60 parts of epoxy resin E-51 and 40 parts of environmentally friendly high-penetration mixed diluent were stirred and mixed evenly. After the stirring was stopped, the mixed slurry was allowed to cool naturally to room temperature to obtain a low-viscosity epoxy resin A component grouting raw material.

[0033] (3) According to the molar ratio of cardanol to cresol of n(cardanol):n(cresol)=1:5, the weighed cardanol and cresol were placed in a reactor and stirred.

[0034] Subsequently, a small molecule amine compound was weighed according to a molar ratio of diethylenetriamine, polyetheramine and isophoronediamine of n(diethylenetriamine):n(polyetheramine):n(isophoronediamine)=3:1:2, and then the weighed diethylenetriamine, polyetheramine and isophoronediamine were added to the above-mentioned reactor at a molar ratio of small molecule amine compound to phenolic compound of n(amine):n(phenol)=2:1, and the temperature was raised to 40°C and stirred for 20-40 minutes.

[0035] According to the ratio of n(amine):n(aldehyde):n(phenol)=2:1.2:1, weighed paraformaldehyde was slowly added to the above-mentioned reactor, and the temperature was raised to 80°C and stirred for reaction for 3 hours. After the reaction was completed, vacuum dehydration was carried out at a vacuum degree of -0.096~0.098MPa and 110°C for 2 hours, and the Mannich modified amine curing agent was obtained after cooling to room temperature.

[0036] (4) Based on 100 parts by mass, 90 parts of Mannich modified amine curing agent, 8 parts of benzyl alcohol and 2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were stirred and mixed uniformly to prepare the grouting raw material of component B of environmentally friendly high permeability epoxy grouting material.

[0037] (5) The grouting raw material of component A in step (2) and the grouting raw material of component B in step (4) are mixed and stirred evenly in a mass ratio of 3:1 to prepare an environmentally friendly high-permeability epoxy grouting material.

[0038] Example 2

[0039] (1) In parts by mass, 5 parts of butanediol diglycidyl ether, 10 parts of n-butyl glycidyl ether, and 5 parts of ethylene glycol were added to a reactor in sequence and stirred to mix evenly; 2 parts of γ-aminopropyltrimethoxysilane and 3 parts of butynediol were added to the above reactor in sequence and continued to stir and mix evenly to prepare an environmentally friendly high-penetration mixed diluent.

[0040] (2) Based on 100 parts by mass, epoxy resin 170 is preheated at 70°C, and then 75 parts of epoxy resin 170 and 25 parts of environmentally friendly high-permeability mixed diluent are stirred and mixed evenly. After stirring is stopped, the mixed slurry is allowed to cool naturally to room temperature to obtain a low-viscosity epoxy resin A component grouting raw material.

[0041] (3) According to the molar ratio of nonylphenol to phenol being n(nonylphenol):n(phenol)=1:2, weighed nonylphenol and phenol are placed in a reactor and stirring is started.

[0042] Subsequently, small molecule amine compounds were weighed according to a molar ratio of triethylenetetramine, polyetheramine and 1,3-bis(aminomethyl)cyclohexane of n(triethylenetetramine):n(polyetheramine):n(1,3-bis(aminomethyl)cyclohexane)=3:1:2, and then the weighed triethylenetetramine, polyetheramine and 1,3-bis(aminomethyl)cyclohexane were added to the above-mentioned reactor at a molar ratio of small molecule amine compounds to phenolic compounds of n(amine):n(phenol)=2:1, and the temperature was raised to 40°C and stirred for 20-40 minutes.

[0043] According to the ratio of n(amine):n(aldehyde):n(phenol)=2:1.2:1, weighed paraformaldehyde was slowly added to the above-mentioned reactor, and the temperature was raised to 80°C and stirred for reaction for 3 hours. After the reaction was completed, vacuum dehydration was carried out at a vacuum degree of -0.096~0.098MPa and 110°C for 2 hours, and the Mannich modified amine curing agent was obtained after cooling to room temperature.

[0044] (4) Based on 100 parts by mass, 90 parts of Mannich modified amine curing agent, 8 parts of benzyl alcohol and 2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were stirred and mixed uniformly to prepare a grouting raw material of component B of an environmentally friendly high-permeability epoxy grouting material;

[0045] (5) The grouting material of component A in step (2) and the grouting material of component B in step (4) are mixed and stirred in a ratio of 2:1 to prepare an environmentally friendly high-permeability epoxy grouting material.

[0046] Example 3

[0047] (1) In parts by mass, 10 parts of polyethylene glycol diglycidyl ether, 5 parts of n-butyl glycidyl ether, 15 parts of benzyl glycidyl ether, and 5 parts of dimethyl phthalate were added to a reactor in sequence and stirred to mix evenly; 2 parts of γ-aminopropyltrimethoxysilane and 3 parts of butynediol were added to the above reactor in sequence and continued to stir and mix evenly to prepare an environmentally friendly high-penetration mixed diluent.

[0048] (2) Based on 100 parts by mass, epoxy resin E-51 was preheated at 70°C, and then 60 parts of epoxy resin E-51 and 40 parts of environmentally friendly high-penetration mixed diluent were stirred and mixed evenly. After the stirring was stopped, the mixed slurry was allowed to cool naturally to room temperature to obtain a low-viscosity epoxy resin A component grouting raw material.

[0049] (3) According to the molar ratio of cardanol to phenol of n(cardanol):n(phenol)=1:5, weighed cardanol and phenol were placed in a reactor and stirred.

[0050] Subsequently, small molecule amine compounds were weighed according to the molar ratio of hexamethylenediamine, polyetheramine and meta-phenylenediamine being n(hexamethylenediamine):n(polyetheramine):n(meta-phenylenediamine)=3:1:2, and then the weighed hexamethylenediamine, polyetheramine and meta-phenylenediamine were added to the above-mentioned reactor at a molar ratio of small molecule amine compounds and phenolic compounds being n(amine):n(phenol)=2:1, and the temperature was raised to 40°C and stirred for 20-40 minutes.

[0051] According to the ratio of n(amine):n(aldehyde):n(phenol)=2:1.2:1, weighed paraformaldehyde was slowly added to the above-mentioned reactor, and the temperature was raised to 85°C and stirred for reaction for 3 hours. After the reaction was completed, vacuum dehydration was carried out at a vacuum degree of -0.096~0.098MPa and 110°C for 2 hours, and the Mannich modified amine curing agent was obtained after cooling to room temperature.

[0052] (4) Based on 100 parts by mass, 90 parts of Mannich modified amine curing agent, 8 parts of benzyl alcohol and 2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were stirred and mixed uniformly to prepare the grouting raw material of component B of environmentally friendly high permeability epoxy grouting material.

[0053] (5) The grouting material of component A in step (2) and the grouting material of component B in step (4) are mixed and stirred in a ratio of 4:1 to prepare an environmentally friendly high-permeability epoxy grouting material.

[0054] Example 4

[0055] (1) Add 5 parts of polypropylene glycol diglycidyl ether, 25 parts of benzyl glycidyl ether, and 5 parts of benzyl alcohol to a reactor in sequence, and stir and mix them evenly; add 2 parts of γ-aminopropyltrimethoxysilane and 3 parts of butynediol to the above reactor in sequence, and continue to stir and mix them evenly to prepare an environmentally friendly high-penetration mixed diluent.

[0056] (2) Based on 100 parts by mass, epoxy resin E-51 was preheated at 70°C, and then 60 parts of epoxy resin E-51 and 40 parts of environmentally friendly high-penetration mixed diluent were stirred and mixed evenly. After the stirring was stopped, the mixed slurry was allowed to cool naturally to room temperature to obtain a low-viscosity epoxy resin A component grouting raw material.

[0057] (3) According to the molar ratio of cardanol to phenol of n(cardanol):n(phenol)=1:5, weighed cardanol and phenol were placed in a reactor and stirred.

[0058] Subsequently, a small molecule amine compound was weighed according to a molar ratio of hexamethylenediamine, polyetheramine and isophoronediamine of n(hexamethylenediamine):n(polyetheramine):n(isophoronediamine)=3:1:2, and then the weighed hexamethylenediamine, polyetheramine and isophoronediamine were added to the above-mentioned reaction kettle at a molar ratio of small molecule amine compound to phenolic compound of n(amine):n(phenol)=2:1, and the temperature was raised to 40°C and stirred for 20-40 minutes.

[0059] According to the ratio of n(amine):n(aldehyde):n(phenol)=2:1.2:1, weighed paraformaldehyde was slowly added to the above-mentioned reactor, and the temperature was raised to 85°C and stirred for reaction for 3 hours. After the reaction was completed, vacuum dehydration was carried out at a vacuum degree of -0.096~0.098MPa and 110°C for 2 hours, and the Mannich modified amine curing agent was obtained after cooling to room temperature.

[0060] (4) Based on 100 parts by mass, 90 parts of Mannich modified amine curing agent, 8 parts of benzyl alcohol and 2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were stirred and mixed uniformly to prepare the grouting raw material of component B of environmentally friendly high permeability epoxy grouting material.

[0061] (5) The grouting material of component A in step (2) and the grouting material of component B in step (4) are mixed and stirred in a ratio of 2:1 to prepare an environmentally friendly high-permeability epoxy grouting material.

[0062] Comparative Example 1

[0063] (1) 30 parts by mass of cardanol glycidyl ether and 5 parts by mass of furfural were added to a reactor in sequence and stirred to mix evenly; 2 parts by mass of γ-aminopropyltrimethoxysilane and 3 parts by mass of butynediol were added to the reactor in sequence and stirred to mix evenly to prepare an environmentally friendly high-penetration mixed diluent.

[0064] (2) Based on 100 parts by mass, epoxy resin E-51 was preheated at 70°C, and then 60 parts of epoxy resin E-51 and 40 parts of environmentally friendly high-penetration mixed diluent were stirred and mixed evenly. After the stirring was stopped, the mixed slurry was allowed to cool naturally to room temperature to obtain a low-viscosity epoxy resin A component grouting raw material.

[0065] (3) According to the molar ratio of cardanol to phenol of n(cardanol):n(phenol)=1:5, weighed cardanol and phenol were placed in a reactor and stirred.

[0066] Subsequently, a small molecule amine compound was weighed according to a molar ratio of hexamethylenediamine, polyetheramine and isophoronediamine of n(hexamethylenediamine):n(polyetheramine):n(isophoronediamine)=3:1:2, and then the weighed hexamethylenediamine, polyetheramine and isophoronediamine were added to the above-mentioned reaction kettle at a molar ratio of small molecule amine compound to phenolic compound of n(amine):n(phenol)=2:1, and the temperature was raised to 40°C and stirred for 20-40 minutes.

[0067] According to the ratio of n(amine):n(aldehyde):n(phenol)=2:1.2:1, weighed paraformaldehyde was slowly added to the above-mentioned reactor, and the temperature was raised to 85°C and stirred for reaction for 3 hours. After the reaction was completed, vacuum dehydration was carried out at a vacuum degree of -0.096~0.098MPa and 110°C for 2 hours, and the Mannich modified amine curing agent was obtained after cooling to room temperature.

[0068] (4) Based on 100 parts by mass, 90 parts of Mannich modified amine curing agent, 8 parts of benzyl alcohol and 2 parts of 2,4,6-tris(dimethylaminomethyl)phenol were stirred and mixed uniformly to prepare the grouting raw material of component B of environmentally friendly high permeability epoxy grouting material.

[0069] (5) The grouting material of component A in step (2) and the grouting material of component B in step (4) are mixed and stirred in a ratio of 2:1 to prepare an environmentally friendly high-permeability epoxy grouting material.

[0070] The environmentally friendly, high-permeability epoxy grouting materials prepared in Examples 1-4 and Comparative Example 1 were subjected to physical and mechanical performance tests, including initial viscosity, workable time, compressive strength, adhesive strength, and penetration depth. Initial viscosity refers to the viscosity of the slurry immediately after the two components A and B are evenly mixed, measured using a single-cylinder rotational viscometer according to GB / T 2794-2013. Workable time refers to the time elapsed from mixing the two components until the viscosity reaches 200 mPa·s, measured according to GB / T 2794-2013. Compressive strength refers to GB / T 2567-2008, adhesive strength refers to DL / T 5150-2001, penetration depth refers to JC / T 2217-2014, and environmental performance refers to DB11 / 1983-2022. The main performance indicators of the environmentally friendly, high-permeability epoxy grouting materials are shown in Table 1.

[0071] Table 1

[0072]

[0073] As shown in Table 1, increasing the proportion of component A in the grouting material can increase the initial viscosity of the grouting material, extend the operable time of the grouting material, and increase the compressive strength. In addition, using cardanol to prepare a phenalkamine-modified curing agent and applying it to the grouting material can significantly extend the operable time of the grouting material, such as in Examples 2 and 4 of the present invention.

[0074] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A permeable epoxy grouting material, characterized in that: The penetrating epoxy grouting material comprises component A and component B, which are mixed at a mass ratio of 2:1-5:1 during use; Based on 100 parts by mass, the component A comprises: 35-60 parts of epoxy resin, 5-25 parts of inactive diluent, 10-30 parts of active diluent, 1-10 parts of silane coupling agent, and 3-15 parts of nonionic surfactant; Based on 100 parts by mass, the component B comprises: 70-90 parts of phenalkamine modified curing agent, 5-20 parts of inactive diluent, and 1-10 parts of accelerator; Wherein, the reactive diluent is selected from diluents having one or more epoxy groups and capable of reacting with the phenalkamine modified curing agent; The inactive diluent is selected from at least one of phthalic acid C1-C8 dibasic esters, benzyl alcohol, ethylene glycol, diformate, and N-methylpyrrolidone.

2. The permeable epoxy grouting material according to claim 1, characterized in that: The epoxy resin is bisphenol A and / or bisphenol F epoxy resin; The active diluent is selected from at least one of C3-C8 alkyl or alkenyl glycidyl ether, C6-C7 phenyl glycidyl ether, benzyl glycidyl ether, poly C2-C3 glycol diglycidyl ether, and butanediol diglycidyl ether.

3. The permeable epoxy grouting material according to claim 1, characterized in that: The silane coupling agent is selected from silane coupling agents containing epoxy functional groups and / or amino functional groups.

4. The permeable epoxy grouting material according to claim 3, characterized in that: The silane coupling agent containing epoxy functional groups is selected from γ-glycidyloxypropyltrimethoxysilane; The silane coupling agent containing an amino functional group is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, and N,N-diethyl-3-aminopropyltrimethoxysilane.

5. The permeable epoxy grouting material according to claim 1, characterized in that: The nonionic surfactant is selected from at least one of butynediol, dimethylhexynediol, dimethyloctynediol, and tetramethyldecynediol; The accelerator is selected from at least one of triethylamine, triethanolamine, 2,4,6-tris(dimethylaminomethyl)phenol, and o-hydroxybenzyldimethylamine.

6. The permeable epoxy grouting material according to claim 1, characterized in that: Phenolic amine modified curing agent is prepared by Mannich reaction of phenolic compounds, aldehyde compounds and amine compounds; Wherein, the molar ratio of the amine compound to the aldehyde compound and the phenol compound is 1:1:1-3:1.5:

1.

7. The permeable epoxy grouting material according to claim 6, characterized in that: The phenolic compound is at least one selected from phenol, nonylphenol, cardanol, m-cresol, and bisphenol A; The aldehyde compound is selected from benzaldehyde or formaldehyde; The amine compound is selected from at least one of diethylenetriamine, triethylenetetramine, m-xylenediamine, hexamethylenediamine, diaminodiphenylmethane, polyetheramine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 2-aminodiphenylsulfone, and N-aminoethylpiperazine.

8. The permeable epoxy grouting material according to claim 1, characterized in that: The C3-C8 alkyl or alkenyl glycidyl ether is selected from at least one of n-butyl glycidyl ether, allyl glycidyl ether, and 2-ethyl-hexyl glycidyl ether; The C6-C7 phenyl glycidyl ether is selected from at least one of phenyl glycidyl ether and cresyl glycidyl ether; The poly C2-C3 glycol diglycidyl ether is selected from at least one of polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; The C1-C8 dibasic phthalate is selected from dimethyl phthalate, dibutyl phthalate, and dioctyl phthalate.

9. A method for preparing the permeable epoxy grouting material according to any one of claims 1 to 8, characterized in that: The method comprises: Based on 100 parts by mass, 5-25 parts of an inactive diluent, 10-30 parts of an active diluent, 1-10 parts of a silane coupling agent, and 3-15 parts of a nonionic surfactant are stirred and mixed uniformly to obtain a penetrating mixed diluent; Based on 100 parts by mass, 35-75 parts of epoxy resin and 25-65 parts of the penetrating mixed diluent are stirred and mixed uniformly to obtain a grouting raw material of component A; A phenolic compound, an aldehyde compound and an amine compound are subjected to a Mannich reaction to obtain a phenalkamine modified curing agent; Based on 100 parts by mass, 5-20 parts of an inactive diluent, 1-10 parts of an accelerator, and 70-90 parts of the phenalkamine-modified curing agent are mixed to obtain a component B grouting raw material; The A component grouting raw material and the B component grouting raw material are mixed in a mass ratio of 2:1-5:1 to obtain a penetrating epoxy grouting material.

10. The method according to claim 9, characterized in that The time for stirring and mixing to form the osmotic mixed diluent is 10-30 minutes; The epoxy resin is preheated at 60-80°C before mixing; The time for stirring and mixing to form the A component grouting raw material and the B component grouting raw material is 30-60 minutes.

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