In-situ crosslinking modified grouting material and preparation method thereof

Abstract

The invention provides an in-situ cross-linking modified grouting material and a preparation method thereof. The in-situ cross-linking modified grouting material comprises the following components in parts by mass: 18-20 parts of in-situ cross-linking macromolecules, 3-5 parts of an in-situ cross-linking agent, 1-2 parts of an in-situ cross-linking catalyst, 1-2 parts of an in-situ cross-linking accelerant, 1-3 parts of a coagulant aid, 3-5 parts of a reinforcing agent and 80-100 parts of a cementing material. According to the grouting material provided by the invention, the grouting amount is obviously increased, and the grouting reinforcement effect is obviously improved. The invention also provides a preparation method of the grouting material, and the preparation method has the characteristics of simple process, low cost and easiness in popularization and application.

Description

Technical Field

[0001] The present application relates to the technical field of preparation of new grouting materials, and in particular to an in-situ cross-linked modified grouting material and a preparation method thereof. Background Art

[0002] With the increase in the depth of coal mining, under the influence of high ground stress and strong mining, deep wells, softness, crushing and impact, the surrounding rock of coal mine tunnels undergoes continuous expansion deformation and continuous deformation, leading to problems such as damage to tunnel support components, roof collapse and spalling, which seriously affect the mining of the working face and tunnel excavation. In response to the problem of large deformation of tunnel surrounding rock. Grouting modification is an important part of it. It is to prepare a certain material or some materials into slurry in a certain proportion, and then use a pressure device with the help of grouting drilling or grouting pipe to inject the slurry that can solidify the injected medium into the cracks or broken zones or pores of the surrounding rock, so that it can diffuse, gel and solidify, so as to improve its physical and mechanical properties and bearing capacity, so as to achieve the purpose of strengthening the formation or preventing seepage and plugging leaks.

[0003] However, in the continuous rheological large deformation roadway grouting reinforcement, the mechanical properties of the grouting material are difficult to meet the actual requirements, and the reinforcement effect on the roadway is limited, which seriously affects the effect of grouting modification and is the main constraint factor for the roadway surrounding rock grouting reinforcement. Therefore, it is urgent to develop new in-situ cross-linked modified grouting materials and their preparation methods and promote their application. Summary of the invention

[0004] The present application aims to solve at least one of the technical problems in the related art to a certain extent. The present application proposes an in-situ cross-linked modified grouting material and a preparation method thereof, the preparation method has the characteristics of simple process, low cost and easy promotion and application; the grouting material provided by the present application significantly increases the grouting amount and significantly improves the grouting reinforcement effect.

[0005] According to an embodiment of the first aspect of the present application, an in-situ cross-linked modified grouting material is proposed, comprising the following components in parts by mass: 18-20 parts of in-situ cross-linking macromolecules, 3-5 parts of in-situ cross-linking agents, 1-2 parts of in-situ cross-linking catalysts, 1-2 parts of in-situ cross-linking accelerators, 1-3 parts of coagulant aids, 3-5 parts of reinforcing agents, and 80-100 parts of gelling materials.

[0006] In some embodiments, the in situ cross-linking macromolecule comprises polyethylene glycol diglycidyl ether.

[0007] In some embodiments, the in-situ cross-linking agent includes 1,3-dimethylimidazole nitrate and 1-ethyl-2,3-dimethylimidazole in a mass ratio of 1:3.

[0008] In some embodiments, the in-situ cross-linking catalyst includes 2,2'-bis(4,5-dimethylimidazole) and 1-benzyl-2,3-dimethylimidazole chloride in a mass ratio of 1:1.

[0009] In some embodiments, the in-situ cross-linking accelerator includes mellitic acid and triethylenetetraaminehexaacetic acid in a mass ratio of 2:1.

[0010] In some embodiments, the coagulant aid includes rubidium hydroxide and strontium hydroxide in a mass ratio of 4:1.

[0011] In some embodiments, the reinforcing agent includes titanium carbide (Ti2CT x )MXene multilayer nanosheets, titanium carbide (Ti3C2T x )MXene multilayer nanosheets.

[0012] In some embodiments, the cementitious material includes tricalcium aluminate, calcium titanate, calcium phosphate, calcium formate, and tetracalcium aluminoferrite in a mass ratio of 2:1:1:1:3.

[0013] According to an embodiment of the second aspect of the present application, a method for preparing an in-situ cross-linked modified grouting material is proposed, comprising the following steps:

[0014] Mixing the in-situ cross-linking macromolecule, the coagulant, the reinforcing agent and the gelling material according to the stoichiometric ratio to obtain a mixed material A;

[0015] The in-situ crosslinking agent, the in-situ crosslinking catalyst and the in-situ crosslinking accelerator are added to the mixed material A according to the stoichiometric amount, and the mixed material A is heated to 10-13 W / cm 2 After ultrasonication for 10-15 minutes, the dry powder is stirred for 20-25 minutes to obtain the grouting material described in any of the above embodiments.

[0016] The invention of the present application forms a macromolecular cross-linked network of three-dimensional space mesh in the cementitious material system through in-situ cross-linking reaction of in-situ cross-linking macromolecules with in-situ cross-linking promoters such as benzyl hexachloride and triethylenetetraaminehexaacetic acid. The cross-linking points between chains generated by cross-linking inhibit the sliding between macromolecular chains, and the modulus and hardness increase with the increase of cross-linking density. In addition, the macromolecular cross-linked network of three-dimensional space mesh makes the molecular arrangement of the cementitious material more regular, reduces the energy barrier of hydration and crystallization of the cementitious material, promotes the crystal nucleation and crystal growth of the grouting material, increases the hydration degree of the grouting stone body, improves the grouting reinforcement effect, and enables the cementitious material to resist damage under the action of external forces such as impact and collision, so that the grouting material can resist damage such as energy absorption, deformation, and fracture, thereby improving the durability of the grouting material.

[0017] Therefore, the present application forms a macromolecular cross-linked network of three-dimensional space mesh in situ to accelerate the setting time of the cementitious material, prevent the slurry from flowing out of the cracks and holes in the tunnel, prevent leakage of slurry, significantly increase the grouting volume, and improve the grouting reinforcement effect.

[0018] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0020] Figure 1 It is a flow chart of the method for preparing grouting materials proposed in one embodiment of the present application. DETAILED DESCRIPTION

[0021] Embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present application, and cannot be construed as limiting the present application. On the contrary, the present application includes all changes, modifications and equivalents that fall within the spirit and connotation of the appended claims.

[0022] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0023] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0024] To achieve the above-mentioned purpose, according to an embodiment of the first aspect of the present application, an in-situ cross-linked modified grouting material is proposed, comprising the following components in parts by weight: 18-20 parts of in-situ cross-linking macromolecules, 3-5 parts of in-situ cross-linking agents, 1-2 parts of in-situ cross-linking catalysts, 1-2 parts of in-situ cross-linking accelerators, 1-3 parts of coagulant aids, 3-5 parts of reinforcing agents, and 80-100 parts of gelling materials.

[0025] Among them, in this embodiment, the in-situ cross-linked modified grouting material includes 18-20 parts by mass of in-situ cross-linked macromolecules, wherein the in-situ cross-linked macromolecules include polyethylene glycol diglycidyl ether (CAS: 26403-72-5). In some embodiments, the mass fraction of the in-situ cross-linked macromolecules can be 18 parts, 19 parts or 20 parts, etc. If the mass fraction of the in-situ cross-linked macromolecules is small, such as less than 18 parts, the modification effect is not good, and the mechanical properties of the grouting material are insufficient. If the mass fraction of the in-situ cross-linked macromolecules is large, such as greater than 20 parts, the mechanical properties of the cementitious material matrix are affected, and the compressive strength of the grouting material is insufficient.

[0026] In this embodiment, the in-situ cross-linked modified grouting material includes 3-5 parts by mass of an in-situ cross-linking agent, wherein the in-situ cross-linking agent includes 1,3-dimethylimidazole nitrate (CAS: 941584-21-0) and 1-ethyl-2,3-dimethylimidazole (CAS: 92507-97-6) in a mass ratio of 1:3. In some embodiments, the mass fraction of the in-situ cross-linking agent is 3 parts, 4 parts or 5 parts, etc. If the mass fraction of the in-situ cross-linking agent is small, such as less than 3 parts, the cross-linking density of the grouting material is low, the cross-linking effect is not good, and the mechanical properties and durability are affected. If the mass fraction of the in-situ cross-linking agent is large, such as more than 5 parts, the cross-linking density of the grouting material is large and the flexibility is reduced.

[0027] In this embodiment, the in-situ cross-linked modified grouting material includes 1-2 parts by weight of an in-situ cross-linking catalyst, wherein the in-situ cross-linking catalyst includes 2,2'-bis(4,5-dimethylimidazole) (CAS: 69286-06-2) and 1-benzyl-2,3-dimethylimidazole chloride (CAS: 36443-79-5) in a mass ratio of 1:1. In some embodiments, the mass fraction of the in-situ cross-linking catalyst is 1 part or 2 parts, etc. If the mass fraction of the in-situ cross-linking catalyst is small, such as less than 1 part, the cross-linking reaction of the grouting material is insufficient, the cross-linking is insufficient, and the mechanical properties of the grouting material are insufficient.

[0028] In this embodiment, the in-situ cross-linked modified grouting material includes 1-2 parts by mass of an in-situ cross-linking accelerator, wherein the in-situ cross-linking accelerator includes benzyl hexachloride (CAS: 517-60-2) and triethylenetetraaminehexaacetic acid (CAS: 869-52-3) in a mass ratio of 2:1. In some embodiments, the mass fraction of the in-situ cross-linking accelerator is 1 part or 2 parts, etc. If the mass fraction of the in-situ cross-linking accelerator is small, such as less than 1 part, the in-situ cross-linking rate of the grouting material is slow, the cross-linking degree is low, and the mechanical strength of the grouting material is insufficient. If the mass fraction of the in-situ cross-linking accelerator is large, such as more than 2 parts, the cross-linking rate of the grouting material is too fast, the cross-linking is uneven, and the performance of the grouting material is uneven.

[0029] In this embodiment, the in-situ cross-linked modified grouting material includes 1-3 parts by weight of a coagulant, wherein the coagulant includes rubidium hydroxide and strontium hydroxide in a mass ratio of 4:1. In some embodiments, the mass fraction of the coagulant is 1 part, 2 parts or 3 parts, etc. If the mass fraction of the coagulant is small, such as less than 1 part, the grouting material solidifies slowly and leakage is likely to occur. If the mass fraction of the coagulant is large, such as more than 3 parts, the grouting material solidifies quickly and pipe and pump blockage are likely to occur.

[0030] In this embodiment, the in-situ cross-linked modified grouting material includes 3-5 parts by weight of a reinforcing agent, wherein the reinforcing agent includes titanium carbide (Ti2CT x )MXene multilayer nanosheets (CAS: 12363-89-2), titanium carbide (Ti3C2T x )MXene multilayer nanosheets (CAS: 12316-56-2). In some embodiments, the weight fraction of the reinforcing agent is 3, 4 or 5. If the weight fraction of the reinforcing agent is small, such as less than 3, the reinforcing effect of the grouting material is poor and the strength of the grouting material is insufficient. If the weight fraction of the reinforcing agent is large, such as more than 5, the rigidity of the grouting material is high and the toughness is insufficient.

[0031] In this embodiment, the in-situ cross-linked modified grouting material includes 80-100 parts by mass of a cementitious material, wherein the cementitious material includes tricalcium aluminate, calcium titanate, calcium phosphate, calcium formate and tetracalcium aluminoferrate in a mass ratio of 2:1:1:1:3. In some embodiments, the mass fractions of the cementitious material are 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, etc. If the mass fraction of the cementitious material is small, such as less than 80 parts, the compressive strength of the grouting material is insufficient. If the mass fraction of the cementitious material is large, such as greater than 100 parts, the toughness of the grouting material decreases.

[0032] According to the embodiment of the second aspect of the present application, a method for preparing an in-situ cross-linked modified grouting material is proposed. Figure 1 As shown, the following steps are included:

[0033] S1: mixing the in-situ cross-linking macromolecule, the coagulant, the reinforcing agent and the gelling material according to the stoichiometric ratio to obtain a mixed material A;

[0034] S2: Add the in-situ crosslinking agent, in-situ crosslinking catalyst and in-situ crosslinking accelerator to the mixed material A according to the stoichiometric amount, and mix the mixed material A at a power density of 10-13W / cm 2 After ultrasonic treatment for 10-15 minutes, the dry powder is stirred for 20-25 minutes to obtain the grouting material in any of the above embodiments.

[0035] Specifically, in step S1, 18-20 parts of in-situ crosslinking macromolecules, 1-3 parts of coagulant, 3-5 parts of reinforcing agent, and 80-100 parts of gelling material are weighed in parts by mass, and uniformly mixed to obtain mixed material A. In step S, 3-5 parts of in-situ crosslinking agent, 1-2 parts of in-situ crosslinking catalyst, and 1-2 parts of in-situ crosslinking accelerator are weighed in parts by mass, added to the mixed material A, and heated to a power density of 10-13 W / cm 2 The dispersion is carried out by ultrasonication for 10 minutes, and then stirred for 20 minutes using a dry powder mixer to prepare the in-situ cross-linked modified grouting material in any of the above embodiments.

[0036] To facilitate further understanding of the present application, the scheme of the present application is further described below in conjunction with the embodiments. Those skilled in the art will understand that the description in the present application is only part of the examples, and any other suitable specific examples are within the scope of the present application.

[0037] Example 1

[0038] This embodiment provides an in-situ cross-linked modified grouting material, and its preparation method and specific operating parameters are as follows: 18 parts of in-situ cross-linked macromolecules, 3 parts of coagulant, 5 parts of reinforcing agent, and 99 parts of gelling material are weighed by weight, and uniformly mixed to obtain mixed material A. 5 parts of in-situ cross-linking agent, 1 part of in-situ cross-linking catalyst, and 1 part of in-situ cross-linking accelerator are weighed by weight, and added to the mixed material A, and heated at a power density of 13W / cm 2 Ultrasonic treatment was performed for 10 minutes, and then stirring was performed using a dry powder mixer for 20 minutes to prepare an in-situ cross-linked modified grouting material.

[0039] Example 2

[0040] Compared with Example 1, this embodiment has the following differences: 19 parts of in-situ cross-linking macromolecules, 1 part of coagulant, 3 parts of reinforcing agent, and 90 parts of gelling material are weighed by weight and uniformly mixed to obtain mixed material A. 4 parts of in-situ cross-linking agent, 2 parts of in-situ cross-linking catalyst, and 2 parts of in-situ cross-linking accelerator are weighed by weight and added to mixed material A, and heated to 12 W / cm 2 Sonicate for 10 min.

[0041] Example 3

[0042] Compared with Example 1, this embodiment has the following differences: 20 parts of in-situ cross-linking macromolecules, 1 part of coagulant, 3 parts of reinforcing agent, and 100 parts of gelling material are weighed by weight and uniformly mixed to obtain mixed material A. 3 parts of in-situ cross-linking agent, 1 part of in-situ cross-linking catalyst, and 2 parts of in-situ cross-linking accelerator are weighed by weight and added to the mixed material A, and heated at a power density of 11 W / cm 2 Sonicate for 10 min.

[0043] Example 4

[0044] Compared with Example 1, this embodiment has the following differences: 18 parts of in-situ cross-linking macromolecules, 2 parts of coagulant, 4 parts of reinforcing agent, and 86 parts of gelling material are weighed by weight and uniformly mixed to obtain mixed material A. 5 parts of in-situ cross-linking agent, 2 parts of in-situ cross-linking catalyst, and 2 parts of in-situ cross-linking accelerator are weighed by weight and added to mixed material A, and heated to 100 W / cm 2 Sonicate for 10 min.

[0045] Example 5

[0046] Compared with Example 1, this embodiment has the following differences: 20 parts of in-situ cross-linking macromolecules, 1 part of coagulant, 3 parts of reinforcing agent, and 80 parts of gelling material are weighed by weight and uniformly mixed to obtain mixed material A. 4 parts of in-situ cross-linking agent, 1 part of in-situ cross-linking catalyst, and 1 part of in-situ cross-linking accelerator are weighed by weight and added to the mixed material A, and the mixture is heated at a power density of 13 W / cm 2 Sonicate for 10 min.

[0047] Experimental example

[0048] The grouting materials in each example were tested after use, and the results are shown in Table 1.

[0049] Table 1 Performance results of the grouting materials in the embodiment

[0050]

[0051] It can be seen from the results in Table 1 that the grouting material provided in this application significantly improves the grouting reinforcement effect.

[0052] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0053] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. An in-situ cross-linked modified grouting material, characterized in that: The invention comprises the following components in parts by weight: 18-20 parts of in-situ crosslinking macromolecules, 3-5 parts of in-situ crosslinking agents, 1-2 parts of in-situ crosslinking catalysts, 1-2 parts of in-situ crosslinking accelerators, 1-3 parts of coagulants, 3-5 parts of reinforcing agents and 80-100 parts of gelling materials.

2. The grouting material according to claim 1, characterized in that: The in-situ cross-linking macromolecule comprises polyethylene glycol diglycidyl ether.

3. The grouting material according to claim 1, characterized in that: The in-situ cross-linking agent includes 1,3-dimethylimidazole nitrate and 1-ethyl-2,3-dimethylimidazole in a mass ratio of 1:

3.

4. The grouting material according to claim 1, characterized in that: The in-situ cross-linking catalyst comprises 2,2'-bis(4,5-dimethylimidazole) and 1-benzyl-2,3-dimethylimidazole chloride in a mass ratio of 1:

1.

5. The grouting material according to claim 1, characterized in that: The in-situ cross-linking accelerator comprises mellitic acid and triethylenetetraaminehexaacetic acid in a mass ratio of 2:

1.

6. The grouting material according to claim 1, characterized in that: The coagulant aid comprises rubidium hydroxide and strontium hydroxide in a mass ratio of 4:

1.

7. The grouting material according to any one of claims 1 to 6, characterized in that: The reinforcing agent includes titanium carbide (Ti2CT x )MXene multilayer nanosheets, titanium carbide (Ti3C2T x )MXene multilayer nanosheets.

8. The grouting material according to claim 7, characterized in that: The cementitious material includes tricalcium aluminate, calcium titanate, calcium phosphate, calcium formate and tetracalcium aluminoferrite in a mass ratio of 2:1:1:1:

3.

9. A method for preparing an in-situ cross-linked modified grouting material, characterized in that: The following steps are involved: Mixing the in-situ cross-linking macromolecule, the coagulant, the reinforcing agent and the gelling material according to the stoichiometric ratio to obtain a mixed material A; The in-situ crosslinking agent, the in-situ crosslinking catalyst and the in-situ crosslinking accelerator are added to the mixed material A according to the stoichiometric amount, and the mixed material A is heated to 10-13 W / cm 2 After ultrasonication for 10-15 minutes, the dry powder is stirred for 20-25 minutes to obtain the grouting material according to any one of claims 1-8.

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