In-situ cross-linking modified grouting material and preparation method thereof

Abstract

The application provides an in-situ cross-linking modified grouting material and a preparation method thereof. The grouting material comprises the following components in mass fractions: 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 coagulants, 3-5 parts of reinforcing agents and 80-100 parts of cementing materials. The grouting material provided by the application can significantly increase the grouting amount and obviously improve the grouting reinforcement effect. The preparation method of the grouting material has the characteristics of simple process, low cost and easy popularization and application.

Description

TECHNICAL FIELD

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

[0002] With the increase of coal mining depth, under the influence of high ground stress and strong mining, under the impact of deep well, soft, broken and impact, continuous dilatancy deformation and sustained deformation of the surrounding rock of the coal mine roadway occur, which leads to the destruction of the roadway supporting member, roof falling, rib spalling and other problems, seriously affecting the mining of the working face and the roadway excavation. In view of the large deformation of the surrounding rock of the roadway, grouting modification is an important part, which is to prepare a slurry by mixing certain or certain materials in a certain proportion, and then to inject the slurry capable of curing the injected medium into the cracks or broken zones or pores of the surrounding rock by using a pressurizing device through a grouting drill hole or a grouting guide pipe, so as to diffuse, gel and solidify, improve the physical and mechanical properties and bearing capacity, and achieve the purpose of stratum reinforcement or anti-seepage and leakage prevention.

[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, the reinforcement effect on the roadway is limited, which seriously affects the effect of grouting modification, and is the most important restricting factor of the roadway surrounding rock grouting reinforcement. Therefore, it is urgent to develop a new in-situ crosslinking modified grouting material and a preparation method thereof and promote its application. SUMMARY

[0004] The present application aims to at least solve one of the technical problems in the related art. The present application provides an in-situ crosslinking modified grouting material and a preparation method thereof. The preparation method has the characteristics of simple process, low cost and easy popularization 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 the embodiments of the first aspect of the present application, an in-situ crosslinking modified grouting material is provided, which comprises the following components in mass fraction: 18-20 parts of in-situ crosslinking macromolecule, 3-5 parts of in-situ crosslinking agent, 1-2 parts of in-situ crosslinking catalyst, 1-2 parts of in-situ crosslinking accelerator, 1-3 parts of coagulant, 3-5 parts of reinforcing agent, and 80-100 parts of cementing material.

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

[0007] In some embodiments, the in-situ crosslinking agent comprises 1,3-dimethyl imidazole nitrate and 1-ethyl-2,3-dimethyl imidazole in a mass ratio of 1:3.

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

[0009] In some embodiments, the in-situ cross-linking promoter comprises benzenehexacarboxylic acid and triethylenetetramine hexaacetic acid with a mass ratio of 2:1.

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

[0011] In some embodiments, the reinforcing agent comprises titanium carbide (Ti2C x ) MXene multi-layer nanosheet, titanium carbide (Ti3C2T x ) MXene multi-layer nanosheet.

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

[0013] According to the embodiments of the second aspect of the present application, a preparation method of an in-situ cross-linking modified grouting material is provided, comprising the following steps:

[0014] According to the stoichiometry, the in-situ cross-linking macromolecule, the coagulant, the reinforcing agent, and the cementitious material are uniformly mixed to obtain a mixed material A;

[0015] According to the stoichiometry, the in-situ cross-linking agent, the in-situ cross-linking catalyst, and the in-situ cross-linking promoter are added to the mixed material A, and the mixed material A is subjected to ultrasonic treatment at a power density of 10-13 W / cm 2 After ultrasonic treatment for 10-15 min, the dry powder is stirred for 20-25 min to obtain the grouting material according to any one of the above embodiments.

[0016] The present application forms a high-molecular three-dimensional space network macromolecular cross-linking network in the cementitious material system through in-situ cross-linking reaction of the in-situ cross-linking macromolecule and the in-situ cross-linking promoter benzenehexacarboxylic acid and triethylenetetramine hexaacetic acid. The cross-linking points between the chains generated by cross-linking inhibit the sliding between the high-molecular chains, and the modulus and hardness increase with the increase of the cross-linking density. In addition, the high-molecular three-dimensional space network macromolecular cross-linking network 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, improves the grouting reinforcement effect, and enables the cementitious material to resist damage under external forces such as impact and collision, so that the grouting material can resist damage such as energy absorption, deformation, and fracture, and the durability of the grouting material is improved.

[0017] Therefore, the application forms a macromolecular three-dimensional space network macromolecular crosslinking network in situ, accelerates the setting time of the cementing material, prevents the slurry from flowing out of the roadway cracks and holes, prevents slurry leakage, significantly increases the grouting amount, and improves the grouting reinforcement effect.

[0018] Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will become apparent to those having ordinary skill in the art upon examination of the following or can be learned from practice of the application. BRIEF DESCRIPTION OF DRAWINGS

[0019] The above and / or additional aspects and advantages of the application will become apparent and be well understood from a review of the description of an embodiment, taken in conjunction with the drawings.

[0020] Figure 1 It is a flow chart of the method for preparing the grouting material according to one embodiment of the application. DETAILED DESCRIPTION

[0021] Embodiments of the application are described in detail below with reference to the attached drawing figures, wherein the same or like reference numerals are used throughout the drawing figures to refer to the same or like elements or elements having the same or similar functionality. The embodiments described below are merely examples for explaining the application, and cannot be understood as limiting the application. On the contrary, the application includes all changes, modifications and equivalents falling within the spirit and scope of the appended claims.

[0022] The ranges disclosed herein are defined by their lower and upper limits. Ranges created by combining these upper and lower limits are also within the scope of the application. For example, if a range is from 1 to 10, then 5-9 also falls within the range. Moreover, it is specifically intended that the description of the application set forth herein include all such possibilities.

[0023] In the description of the embodiments of the present application, the term "and / or" is merely an association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B, which can represent the three cases of A existing alone, A and B existing together, and B existing alone. In addition, the character " / " in this paper generally represents that the front and rear associated objects are in an "or" relationship.

[0024] To achieve the above-mentioned purpose, according to the first aspect of the embodiment of the present application, a modified in-situ cross-linking grouting material is provided, which comprises the following components in mass fraction: 18-20 parts of in-situ cross-linking macromolecule, 3-5 parts of in-situ cross-linking agent, 1-2 parts of in-situ cross-linking catalyst, 1-2 parts of in-situ cross-linking accelerator, 1-3 parts of coagulant, 3-5 parts of reinforcing agent, and 80-100 parts of cementitious material.

[0025] In the present embodiment, the modified in-situ cross-linking grouting material comprises 18-20 parts of in-situ cross-linking macromolecule, wherein the in-situ cross-linking macromolecule comprises polyethylene glycol diglycidyl ether (CAS: 26403-72-5). In some embodiments, the mass fraction of the in-situ cross-linking macromolecule can be 18 parts, 19 parts, or 20 parts, etc. If the fraction of the in-situ cross-linking macromolecule 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 fraction of the in-situ cross-linking macromolecule 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 the present embodiment, the modified in-situ cross-linking grouting material comprises 3-5 parts of in-situ cross-linking agent, wherein the in-situ cross-linking agent comprises 1,3-dimethyl imidazole nitrate (CAS: 941584-21-0) and 1-ethyl-2,3-dimethyl imidazole (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 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 fraction of the in-situ cross-linking agent is large, such as greater than 5 parts, the cross-linking density of the grouting material is large, and the flexibility decreases.

[0027] In the present embodiment, the modified in-situ cross-linking grouting material comprises 1-2 parts of in-situ cross-linking catalyst, wherein the in-situ cross-linking catalyst comprises 2,2'-bis(4,5-dimethylimidazole) (CAS: 69286-06-2) and 1-benzyl-2,3-dimethyl imidazole 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 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 not sufficient, the cross-linking is not sufficient, and the mechanical properties of the grouting material are insufficient.

[0028] The in-situ cross-linking modified grouting material in the embodiment includes 1-2 parts of in-situ cross-linking promoters by mass fraction, wherein the in-situ cross-linking promoters include benzenehexacarboxylic acid (CAS: 517-60-2) and triethylenetetramine hexaacetic acid (CAS: 869-52-3) in a mass ratio of 2:1. In some embodiments, the mass fraction of the in-situ cross-linking promoters is 1 part or 2 parts, etc. If the fraction of the in-situ cross-linking promoters is smaller, 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 fraction of the in-situ cross-linking promoters is larger, such as greater 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 not uniform.

[0029] The in-situ cross-linking modified grouting material in the embodiment includes 1-3 parts of coagulants by mass fraction, wherein the coagulants include rubidium hydroxide and strontium hydroxide in a mass ratio of 4:1. In some embodiments, the mass fraction of the coagulants is 1 part, 2 parts, or 3 parts, etc. If the fraction of the coagulants is smaller, such as less than 1 part, the setting time of the grouting material is slow, and grouting leakage is prone to occur. If the fraction of the coagulants is larger, such as greater than 3 parts, the setting time of the grouting material is fast, and pipe and pump blockage is prone to occur.

[0030] The in-situ cross-linking modified grouting material in the embodiment includes 3-5 parts of reinforcing agents by mass fraction, wherein the reinforcing agents include titanium carbide (Ti2CT x ) MXene multi-layer nanosheets (CAS: 12363-89-2) and titanium carbide (Ti3C2T x ) MXene multi-layer nanosheets (CAS: 12316-56-2) in a mass ratio of 2:1. In some embodiments, the mass fraction of the reinforcing agents is 3 parts, 4 parts, or 5 parts, etc. If the fraction of the reinforcing agents is smaller, such as less than 3 parts, the reinforcing effect of the grouting material is not good, and the strength of the grouting material is insufficient. If the fraction of the reinforcing agents is larger, such as greater than 5 parts, the rigidity of the grouting material is high, and the toughness is insufficient.

[0031] The in-situ cross-linking modified grouting material in the embodiment includes 80-100 parts of cementitious materials by mass fraction, wherein the cementitious materials include tricalcium aluminate, calcium titanate, calcium phosphate, calcium formate, and tetracalcium aluminoferrite in a mass ratio of 2:1:1:1:3. In some embodiments, the mass fraction of the cementitious materials is 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 fraction of the cementitious materials is smaller, such as less than 80 parts, the compressive strength of the grouting material is insufficient. If the fraction of the cementitious materials is larger, 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 preparation method of in-situ cross-linking modified grouting material is provided as shown in the following steps. Figure 1

[0033] S1: uniformly mix in-situ cross-linking macromolecule, coagulant, reinforcing agent and cementitious material according to stoichiometry to obtain mixed material A;

[0034] S2: add in-situ cross-linking agent, in-situ cross-linking catalyst and in-situ cross-linking promoter into mixed material A according to stoichiometry, and ultrasonic treat mixed material A at a power density of 10-13 W / cm 2 After ultrasonic treatment for 10-15 minutes, dry powder is stirred for 20-25 minutes to obtain the grouting material in any of the above embodiments.

[0035] Specifically, in step S1, in-situ cross-linking macromolecule 18-20 parts, coagulant 1-3 parts, reinforcing agent 3-5 parts and cementitious material 80-100 parts are weighed according to mass fraction, and uniformly mixed to obtain mixed material A. In step S2, in-situ cross-linking agent 3-5 parts, in-situ cross-linking catalyst 1-2 parts and in-situ cross-linking promoter 1-2 parts are weighed according to mass fraction, and added into mixed material A, and ultrasonic treated at a power density of 10-13 W / cm 2 After ultrasonic treatment for 10 minutes, dry powder is stirred for 20 minutes to obtain the in-situ cross-linking modified grouting material in any of the above embodiments.

[0036] In order to further understand the present application, the scheme of the present application will be further described in combination with embodiments. Those skilled in the art will understand that only some examples are described in the present application, and any other suitable specific examples are within the scope of the present application.

[0037] Example 1

[0038] The present embodiment provides an in-situ cross-linking modified grouting material, a preparation method and specific operation parameters thereof are as follows: in-situ cross-linking macromolecule 18 parts, coagulant 3 parts, reinforcing agent 5 parts and cementitious material 99 parts are weighed according to mass fraction, and uniformly mixed to obtain mixed material A. In-situ cross-linking agent 5 parts, in-situ cross-linking catalyst 1 part and in-situ cross-linking promoter 1 part are weighed according to mass fraction, and added into mixed material A, and ultrasonic treated at a power density of 13 W / cm 2 After ultrasonic treatment for 10 minutes, dry powder is stirred for 20 minutes to obtain the in-situ cross-linking modified grouting material in any of the above embodiments.

[0039] Example 2

[0040] ​The embodiment has the following differences compared with embodiment 1: the in-situ crosslinking macromolecule 19 parts, the coagulant 1 part, the reinforcing agent 3 parts, and the cementing material 90 parts are weighed according to the mass fraction, uniformly mixed to obtain a mixed material A. The in-situ crosslinking agent 4 parts, the in-situ crosslinking catalyst 2 parts, and the in-situ crosslinking promoter 2 parts are weighed according to the mass fraction, added to the mixed material A, and ultrasonic treatment is performed at a power density of 12 W / cm 2 for 10 minutes.

[0041] Example 3

[0042] The embodiment has the following differences compared with embodiment 1: the in-situ crosslinking macromolecule 20 parts, the coagulant 1 part, the reinforcing agent 3 parts, and the cementing material 100 parts are weighed according to the mass fraction, uniformly mixed to obtain a mixed material A. The in-situ crosslinking agent 3 parts, the in-situ crosslinking catalyst 1 part, and the in-situ crosslinking promoter 2 parts are weighed according to the mass fraction, added to the mixed material A, and ultrasonic treatment is performed at a power density of 11 W / cm 2 for 10 minutes.

[0043] Example 4

[0044] The embodiment has the following differences compared with embodiment 1: the in-situ crosslinking macromolecule 18 parts, the coagulant 2 parts, the reinforcing agent 4 parts, and the cementing material 86 parts are weighed according to the mass fraction, uniformly mixed to obtain a mixed material A. The in-situ crosslinking agent 5 parts, the in-situ crosslinking catalyst 2 parts, and the in-situ crosslinking promoter 2 parts are weighed according to the mass fraction, added to the mixed material A, and ultrasonic treatment is performed at a power density of 10 W / cm 2 for 10 minutes.

[0045] Example 5

[0046] The embodiment has the following differences compared with embodiment 1: the in-situ crosslinking macromolecule 20 parts, the coagulant 1 part, the reinforcing agent 3 parts, and the cementing material 80 parts are weighed according to the mass fraction, uniformly mixed to obtain a mixed material A. The in-situ crosslinking agent 4 parts, the in-situ crosslinking catalyst 1 part, and the in-situ crosslinking promoter 1 part are weighed according to the mass fraction, added to the mixed material A, and ultrasonic treatment is performed at a power density of 13 W / cm 2 for 10 minutes.

[0047] Experimental Example

[0048] The grouting materials in each embodiment are detected after use, and the results are shown in Table 1.

[0049] Table 1 Performance results table of grouting materials in embodiments

[0050]

[0051] From the results in Table 1, it can be seen that the grouting material provided by the application significantly improves the grouting reinforcement effect.

[0052] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the 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 is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and the person skilled in the art can make changes, modifications, replacements and variations to the above-described embodiments within the scope of the present application.

Claims

1. An in-situ crosslinking modified grouting material, characterized in that, The components include the following mass fractions: in-situ crosslinking macromolecule 18-20 parts, in-situ crosslinking agent 3-5 parts, in-situ crosslinking catalyst 1-2 parts, in-situ crosslinking promoter 1-2 parts, coagulant aid 1-3 parts, reinforcing agent 3-5 parts, cementitious material 80-100 parts; the in-situ crosslinking macromolecule includes polyethylene glycol diglycidyl ether; the in-situ crosslinking agent includes 1,3-dimethyl imidazole nitrate and 1-ethyl-2,3-dimethyl imidazole in a mass ratio of 1:3; the in-situ crosslinking promoter includes benzenhexanoic acid and triethylenetetramine hexaacetic acid in a mass ratio of 2:

1.

2. The grouting material as set forth in claim 1, wherein The in-situ crosslinking catalyst includes 2,2'-bis(4,5-dimethyl imidazole) and 1-benzyl-2,3-dimethyl imidazole chloride in a mass ratio of 1:

1.

3. The grouting material as set forth in claim 1, wherein The coagulant aid includes rubidium hydroxide and strontium hydroxide in a mass ratio of 4:

1.

4. The grouting material according to any one of claims 1 to 3, characterized in that The enhancer includes Ti2C at a mass ratio of 2:1 x MXene multilayer nanosheets, Ti3C2T x MXene multilayer nanosheets.

5. The grouting material according to claim 4, 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.

6. A method for producing an in-situ crosslinking modified grouting material, characterized by, The method includes the following steps: The in-situ crosslinking macromolecule, coagulant aid, reinforcing agent and cementitious material are mixed according to stoichiometry to obtain mixed material A; The in-situ crosslinking agent, in-situ crosslinking catalyst and in-situ crosslinking promoter are added to the mixed material A according to stoichiometry, the mixed material A is ultrasonically treated at a power density of 10-13 W / cm² for 10-15 min, and the dry powder is stirred for 20-25 min to obtain the grouting material according to any one of claims 1-5.

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