A grouting material based on surface modified fullerene and its preparation method and application

Abstract

The present invention discloses a grouting material based on surface-modified fullerene, a preparation method thereof and an application thereof. The grouting material comprises the following components in mass fractions: 15-18 parts of surface-modified fullerene, 1-2 parts of fluid loss reducing agent, 2-5 parts of reinforcing agent, 1-2 parts of water retaining agent, 1-2 parts of lubricant, 60 parts of magnesium phosphate cement clinker and 40 parts of aluminophosphate cement clinker. The present invention obtains a grouting material based on surface-modified fullerene by optimizing the formula composition of the grouting material. The grouting material has good fluidity, fluid loss reducing property and water retaining property, as well as good toughness and impact resistance; and the grouting material has a simple preparation process and low cost, and is particularly suitable for grouting reinforcement of water-softened mudstone tunnels in coal mines.

Description

Technical Field

[0001] The present invention belongs to the technical field of grouting materials, and in particular, the present invention relates to a grouting material based on surface-modified fullerene and a preparation method and application thereof. Background Art

[0002] my country's coal mines have formed a set of safe and efficient tunnel support technology based on geomechanical testing, with anchoring and grouting as the core. Grouting modification reinforces the broken tunnel surrounding rock into a whole with strength and bearing capacity, improves the integrity, strength and deformation resistance of the tunnel surrounding rock, and has achieved good control effect and application value in the control of coal mine tunnel surrounding rock. However, in the grouting of water-softened mudstone tunnels in coal mines, due to the softening characteristics of mudstone when exposed to water, the grouting liquid destroys the mudstone after being injected into the surrounding rock cracks, and does not play a good reinforcement role, which seriously affects the effect of grouting modification and is the most important restrictive factor for grouting reinforcement of water-softened mudstone tunnels in coal mines. Therefore, it is urgent to develop grouting materials suitable for water-softened mudstone tunnels in coal mines. Summary of the invention

[0003] The present invention aims to solve one of the technical problems in the related art at least to a certain extent. To this end, the present invention provides a grouting material based on surface-modified fullerene and a preparation method and application thereof.

[0004] In the first aspect, an embodiment of the present invention proposes a grouting material based on surface modified fullerene, comprising the following components in parts by weight: 15-18 parts of surface modified fullerene, 1-2 parts of fluid loss reducer, 2-5 parts of reinforcing agent, 1-2 parts of water retaining agent, 1-2 parts of lubricant, 60 parts of magnesium phosphate cement clinker, and 40 parts of aluminophosphate cement clinker.

[0005] In some embodiments, the surface modified fullerene is prepared by a method comprising the following steps: adding a fullerene material to a modifier mixture of selenocysteine, pyrrolysine, and isoleucine, heating and mixing, and then adding a composite catalyst and heating to react to obtain the surface modified fullerene.

[0006] In some embodiments, the fullerene material is a mixture of fullerene C20, fullerene C60, and fullerene C82, and the mass ratio of the fullerene C20, the fullerene C60, and the fullerene C82 is 1:1:1;

[0007] And / or, in the modifier mixture, the mass ratio of the selenocysteine, the pyrrolysine and the isoleucine is 1:1:(1.5-2.5), preferably 1:1:2;

[0008] And / or, the temperature of the heating and mixing is 30-50°C, and the mixing time is 5-15min;

[0009] And / or, the composite catalyst is a mixture of bismuth trioxide and antimony trioxide, and the mass ratio of the bismuth trioxide to the antimony trioxide is 1:(2-4), preferably 1:3;

[0010] And / or, the heating reaction is carried out under argon protection, the reaction temperature is 170-180° C., and the reaction time is 1-3 h.

[0011] In some embodiments, the fluid loss additive is a mixture of vinylformamide-vinylpyridine copolymer, N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer;

[0012] Preferably, the mass ratio of the vinylformamide-vinylpyridine copolymer to the N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer is (4-6):1, preferably 5:1.

[0013] In some embodiments, the enhancer is a mixture of 1-(4-vinylbenzyl)thymine and 1,8-naphthyridine-2,7-diamine;

[0014] Preferably, the mass ratio of the 1-(4-vinylbenzyl)thymine to the 1,8-naphthyridine-2,7-diamine is (1-3):1, preferably 2:1.

[0015] In some embodiments, the water retaining agent is a mixture of sodium lactate, hyaluronic acid, and sodium pyrrolidonecarboxylate;

[0016] Preferably, the mass ratio of the sodium lactate, the hyaluronic acid and the sodium pyrrolidonecarboxylate is 2:1:(5-8), preferably 2:1:6.

[0017] In some embodiments, the lubricant is a mixture of polytetrafluoroethylene nanoparticles, fluorinated ethylene propylene copolymer nanoparticles, molybdenum disulfide nanoparticles, and carbon black;

[0018] Preferably, the mass ratio of the polytetrafluoroethylene nanoparticles, the fluorinated ethylene propylene copolymer nanoparticles, the molybdenum disulfide nanoparticles and the carbon black is (2.5-4):2:1:2, preferably 3:2:1:2.

[0019] In a second aspect, an embodiment of the present invention further provides a method for preparing a grouting material based on surface-modified fullerene as described in the first aspect, comprising the following steps:

[0020] The surface-modified fullerene, fluid loss reducer, reinforcing agent, water retaining agent, lubricant, magnesium phosphate cement clinker and aluminophosphate cement clinker are weighed respectively according to their mass fractions, stirred and mixed, and the grouting material based on the surface-modified fullerene is obtained.

[0021] In some embodiments, the stirring and mixing time is 30-60 minutes.

[0022] In a third aspect, the embodiments of the present invention further propose the use of the grouting material based on surface-modified fullerene as described in the first aspect in water-softened mudstone tunnels in coal mines.

[0023] The advantages and beneficial effects of the embodiments of the present invention are as follows:

[0024] (1) The embodiment of the present invention optimizes the formula composition of the grouting material. By adding homemade surface-modified fullerene, fluid loss reducer, enhancer, water retention agent, and lubricant to magnesium phosphate cement clinker and aluminophosphate cement clinker, the grouting effect of the grouting material can be improved. The obtained grouting material is particularly suitable for grouting reinforcement of water-softened mudstone tunnels in coal mines.

[0025] (2) The surface-modified fullerene in the grouting material of the embodiment of the present invention has a stable structure, strong hardness and good ductility, which can significantly improve the strength and rigidity of the grouting material; and the surface-modified fullerene is spherical in shape, extremely hard and stable at the molecular level, and as a "molecular ball", it can significantly improve the fluidity of the grouting liquid.

[0026] (3) The surface-modified fullerene in the grouting material of the embodiment of the present invention has hydrophilic groups amino and carboxyl grafted on its surface, which improves its hydrophilicity and water retention properties, reduces water loss, and further improves the water loss reduction and water retention properties of the grouting material, which is beneficial to improving the solid performance of the grouting structure.

[0027] (4) The surface-modified fullerene in the grouting material of the embodiment of the present invention has a higher specific surface area, which increases the interface area between the fullerene and the matrix. When the grouting material is impacted, the interface can absorb the impact energy, which is beneficial to improving the toughness and impact resistance of the grouting material.

[0028] (5) The grouting material based on surface-modified fullerene in the embodiment of the present invention has a simple preparation process, convenient operation, low cost, good grouting effect, and is suitable for large-scale industrial application. DETAILED DESCRIPTION

[0029] Embodiments of the present invention are described in detail below. The embodiments are exemplary and intended to be used to explain the present invention, but should not be construed as limiting the present invention.

[0030] Where values ​​are described herein as a range, it should be understood that such disclosure includes disclosure of all possible sub-ranges within that range, as well as specific values ​​falling within that range, regardless of whether a specific value or a specific sub-range is explicitly stated.

[0031] Herein, the words "comprises" and "includes" and variations thereof mean that other elements or integers which are permitted but not specifically described may be included.

[0032] In this article, the term "and / or" is merely a term used to describe the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent three situations: A exists alone, A and B exist at the same time, and B exists alone.

[0033] In the first aspect, an embodiment of the present invention proposes a grouting material based on surface modified fullerene, comprising the following components in parts by weight: 15-18 parts of surface modified fullerene, 1-2 parts of fluid loss reducer, 2-5 parts of reinforcing agent, 1-2 parts of water retaining agent, 1-2 parts of lubricant, 60 parts of magnesium phosphate cement clinker, and 40 parts of aluminophosphate cement clinker.

[0034] The embodiment of the present invention optimizes the formula composition of the grouting material, and compounding the surface modified fullerene, the fluid loss reducing agent, the reinforcing agent, the water retaining agent, the lubricant with the magnesium phosphate cement clinker and the aluminophosphate cement clinker can improve the fluidity of the grouting material and improve the toughness and impact resistance of the grouting material, and is particularly suitable for grouting reinforcement of water-softened mudstone tunnels in coal mines.

[0035] In some embodiments, the surface modified fullerene is prepared by a method comprising the following steps: adding a fullerene material to a modifier mixture of selenocysteine, pyrrolysine, and isoleucine, heating and mixing, and then adding a composite catalyst and heating to react to obtain the surface modified fullerene.

[0036] In some embodiments, the fullerene material is a mixture of fullerene C20, fullerene C60, and fullerene C82, and the mass ratio of the fullerene C20, the fullerene C60, and the fullerene C82 is 1:1:1;

[0037] And / or, in the modifier mixture, the mass ratio of the selenocysteine, the pyrrolysine and the isoleucine is 1:1:(1.5-2.5), non-limiting examples include: 1:1:1.5, 1:1:1.8, 1:1:2, 1:1:2.5, etc.; preferably 1:1:2;

[0038] And / or, the temperature of the heating and mixing is 30-50° C. (non-limiting examples: 30° C., 35° C., 40° C., 50° C., etc.), and the mixing time is 5-15 min (non-limiting examples: 5 min, 10 min, 12 min, 15 min, etc.);

[0039] And / or, the composite catalyst is a mixture of bismuth trioxide and antimony trioxide, and the mass ratio of the bismuth trioxide to the antimony trioxide is 1:(2-4), non-limiting examples include: 1:2, 1:3, 1:4, etc.; preferably 1:3;

[0040] And / or, the heating reaction is carried out under argon protection, the reaction temperature is 170-180°C (non-limiting examples: 170°C, 175°C, 178°C, 180°C, etc.), and the reaction time is 1-3h (non-limiting examples: 1h, 2h, 2.5h, 3h, etc.).

[0041] In the embodiment of the present invention, a modifier composed of selenocysteine, pyrrolysine and isoleucine is used to modify the surface of the fullerene material under the action of a composite catalyst. The obtained surface-modified fullerene has a cage-like structure, is relatively stable, and is harder than diamond and 100 times more ductile than steel, which can significantly improve the strength and rigidity of the grouting material. The surface-modified fullerene is spherical in shape, the roundest of all molecules, and is extremely hard and stable at the molecular level. As a "molecular ball", it can significantly improve the fluidity of the grouting liquid.

[0042] The surface-modified fullerene prepared in the embodiment of the present invention has hydrophilic groups amino and carboxyl grafted on its surface, which improves its hydrophilicity and water retention properties, reduces water loss, and further improves the water loss reduction and water retention properties of the grouting material, which is beneficial to improving the solid performance of the grouting structure.

[0043] The self-made surface-modified fullerene in the embodiment of the present invention has a higher specific surface area, which increases the interface area between the fullerene and the substrate. When the grouting material is impacted, the interface can absorb the impact energy, which is beneficial to improving the toughness and impact resistance of the grouting material.

[0044] In some embodiments, the fluid loss additive is a mixture of vinylformamide-vinylpyridine copolymer, N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer;

[0045] Preferably, the mass ratio of the vinylformamide-vinylpyridine copolymer to the N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer is (4-6):1, non-limiting examples include: 4:1, 5:1, 6:1, etc.; preferably 5:1.

[0046] In some embodiments, the enhancer is a mixture of 1-(4-vinylbenzyl)thymine and 1,8-naphthyridine-2,7-diamine;

[0047] Preferably, the mass ratio of the 1-(4-vinylbenzyl)thymine to the 1,8-naphthyridine-2,7-diamine is (1-3):1, non-limiting examples include: 1:1, 2:1, 3:1, etc.; preferably 2:1.

[0048] In some embodiments, the water retaining agent is a mixture of sodium lactate, hyaluronic acid, and sodium pyrrolidonecarboxylate;

[0049] Preferably, the mass ratio of the sodium lactate, the hyaluronic acid and the sodium pyrrolidonecarboxylate is 2:1:(5-8), non-limiting examples include: 2:1:5, 2:1:6, 2:1:7, 2:1:8, etc.; preferably 2:1:6.

[0050] In some embodiments, the lubricant is a mixture of polytetrafluoroethylene nanoparticles, fluorinated ethylene propylene copolymer nanoparticles, molybdenum disulfide nanoparticles, and carbon black;

[0051] Preferably, the mass ratio of the polytetrafluoroethylene nanoparticles, the fluorinated ethylene propylene copolymer nanoparticles, the molybdenum disulfide nanoparticles and the carbon black is (2.5-4):2:1:2, non-limiting examples include: 2.5:2:1:2, 3:2:1:2, 3.6:2:1:2, 4:2:1:2, etc.; preferably 3:2:1:2.

[0052] In a second aspect, an embodiment of the present invention further provides a method for preparing a grouting material based on surface-modified fullerene as described in the first aspect, comprising the following steps:

[0053] The surface-modified fullerene, fluid loss reducer, reinforcing agent, water retaining agent, lubricant, magnesium phosphate cement clinker and aluminophosphate cement clinker are weighed respectively according to their mass fractions, stirred and mixed, and the grouting material based on the surface-modified fullerene is obtained.

[0054] In some embodiments, the stirring and mixing time is 30-60 min, non-limiting examples include: 30 min, 40 min, 45 min, 50 min, 60 min, etc.

[0055] The method for preparing a grouting material based on surface-modified fullerenes in the embodiment of the present invention has a simple process, is easy to operate, and has a low manufacturing cost. The prepared grouting material has excellent performance and is suitable for industrial large-scale production applications.

[0056] In a third aspect, the embodiments of the present invention further propose the use of the grouting material based on surface-modified fullerene as described in the first aspect in water-softened mudstone tunnels in coal mines.

[0057] When the grouting material based on surface-modified fullerene in the embodiment of the present invention is used in the water-softened mudstone tunnel of a coal mine, it has a good grouting reinforcement effect.

[0058] The following are non-limiting examples and comparative examples of the present invention. It should be noted that the schemes of the comparative examples are not prior art and are only provided for comparison with the schemes of the embodiments and are not intended to limit the present invention. Unless otherwise specified, the various raw materials used in the embodiments and comparative examples are conventional commercial products or can be prepared by known methods.

[0059] Example 1

[0060] The grouting material based on surface-modified fullerene of this embodiment includes the following components in parts by weight: 15 parts of surface-modified fullerene, 1 part of fluid loss reducer, 2 parts of reinforcing agent, 1 part of water retaining agent, 1 part of lubricant, 60 parts of magnesium phosphate cement clinker, and 40 parts of aluminophosphate cement clinker.

[0061] The surface-modified fullerene in this embodiment is prepared by a method comprising the following steps:

[0062] 5 parts of fullerene C20, 5 parts of fullerene C60 and 5 parts of fullerene C82 were weighed according to their mass proportions and added to a modifier mixture consisting of 10 parts of selenocysteine, 10 parts of pyrrolysine and 20 parts of isoleucine, and then auxiliary heated to 40°C and stirred for 10 minutes to promote uniform mixing; then 1 part of bismuth trioxide and 3 parts of antimony trioxide were added, and the mixture was reacted at 170°C for 2 hours under argon protection conditions. After filtering and drying, surface-modified fullerenes were obtained.

[0063] The fluid loss additive in this embodiment is a mixture of vinylformamide-vinylpyridine copolymer, N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer; and the mass ratio of vinylformamide-vinylpyridine copolymer to N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer is 5:1;

[0064] The enhancer is a mixture of 1-(4-vinylbenzyl)thymine and 1,8-naphthyridine-2,7-diamine; and the mass ratio of 1-(4-vinylbenzyl)thymine to 1,8-naphthyridine-2,7-diamine is 2:1;

[0065] The water retaining agent is a mixture of sodium lactate, hyaluronic acid and sodium pyrrolidonecarboxylate; and the mass ratio of sodium lactate, hyaluronic acid and sodium pyrrolidonecarboxylate is 2:1:6;

[0066] The lubricant is a mixture of polytetrafluoroethylene nanoparticles, fluorinated ethylene propylene copolymer nanoparticles, molybdenum disulfide nanoparticles and carbon black; and the mass ratio of polytetrafluoroethylene nanoparticles, fluorinated ethylene propylene copolymer nanoparticles, molybdenum disulfide nanoparticles and carbon black is 3:2:1:2.

[0067] The preparation method of the grouting material based on surface-modified fullerene in this embodiment comprises the following steps:

[0068] 15 parts of surface-modified fullerene, 1 part of fluid loss reducer, 2 parts of reinforcing agent, 1 part of water retaining agent, 1 part of lubricant, 60 parts of magnesium phosphate cement clinker and 40 parts of aluminophosphate cement clinker were weighed respectively according to their mass parts and mixed in a dry powder mixer for 50 minutes to obtain a grouting material based on surface-modified fullerene.

[0069] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 61MPa.

[0070] Example 2

[0071] This embodiment is basically the same as embodiment 1, except that in the preparation process of surface-modified fullerene in this embodiment, the reaction temperature of the heating reaction is 175°C.

[0072] The surface modified fullerene prepared in this embodiment has a particle size of 12 nm and a specific surface area of ​​24 m 2 / g, and a contact angle of 138 degrees; the compressive strength of the prepared grouting material based on surface-modified fullerene is 64MPa.

[0073] Example 3

[0074] This embodiment is basically the same as embodiment 1, except that in the preparation process of surface-modified fullerene in this embodiment, the reaction temperature of the heating reaction is 178°C.

[0075] The surface modified fullerene prepared in this embodiment has a particle size of 11 nm and a specific surface area of ​​27 m 2 / g, and a contact angle of 142 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 68MPa.

[0076] Example 4

[0077] This embodiment is basically the same as embodiment 1, except that in the preparation process of surface-modified fullerene in this embodiment, the reaction temperature of the heating reaction is 180°C.

[0078] The surface modified fullerene prepared in this embodiment has a particle size of 9 nm and a specific surface area of ​​30 m 2 / g, and a contact angle of 147 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 71MPa.

[0079] Example 5

[0080] This embodiment is basically the same as embodiment 1, except that: in the preparation process of surface-modified fullerene in this embodiment, the reaction temperature of the heating reaction is 180° C. and the reaction time is 2.5 h.

[0081] The surface modified fullerene prepared in this embodiment has a particle size of 8 nm and a specific surface area of ​​33 m 2 / g, and a contact angle of 154 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 73MPa.

[0082] Example 6

[0083] This embodiment is basically the same as embodiment 1, except that: in the preparation process of surface-modified fullerene in this embodiment, the reaction temperature of the heating reaction is 180° C. and the reaction time is 3 h.

[0084] The surface modified fullerene prepared in this embodiment has a particle size of 7 nm and a specific surface area of ​​35 m 2 / g, and a contact angle of 157 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 75MPa.

[0085] Example 7

[0086] This embodiment is basically the same as embodiment 1, except that: in the preparation process of surface-modified fullerene in this embodiment, the reaction time of the heating reaction is 1 hour.

[0087] The surface modified fullerene prepared in this embodiment has a particle size of 16 nm and a specific surface area of ​​20 m 2 / g, and a contact angle of 130 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 59 MPa.

[0088] Example 8

[0089] This embodiment is substantially the same as Embodiment 1, except that in this embodiment, the mass fraction of the surface-modified fullerene is 16 parts.

[0090] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface-modified fullerene is 63 MPa.

[0091] Example 9

[0092] This embodiment is substantially the same as Embodiment 1, except that in this embodiment, the mass fraction of the surface-modified fullerene is 17 parts.

[0093] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 65MPa.

[0094] Example 10

[0095] This embodiment is substantially the same as Embodiment 1, except that in this embodiment, the mass fraction of the surface-modified fullerene is 18 parts.

[0096] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 67MPa.

[0097] Embodiment 11

[0098] This embodiment is basically the same as Embodiment 1, except that: in this embodiment, the mass fraction of the reinforcing agent is 3 parts.

[0099] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 62MPa.

[0100] Example 12

[0101] This embodiment is substantially the same as Embodiment 1, except that in this embodiment, the weight fraction of the enhancer is 5 parts.

[0102] The surface modified fullerene prepared in this embodiment has a particle size of 14 nm and a specific surface area of ​​22 m 2 / g, and a contact angle of 133 degrees; the compressive strength of the prepared grouting material based on surface modified fullerene is 64MPa.

[0103] Comparative Example 1

[0104] This comparative example is substantially the same as Example 1, except that: in this comparative example, no surface-modified fullerene is added.

[0105] After testing, the compressive strength of the grouting material prepared in this comparative example is 33 MPa.

[0106] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" etc. mean 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 invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics 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.

[0107] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A grouting material based on surface-modified fullerene, characterized in that: The invention comprises the following components in parts by weight: 15-18 parts of surface modified fullerene, 1-2 parts of fluid loss reducing agent, 2-5 parts of reinforcing agent, 1-2 parts of water retaining agent, 1-2 parts of lubricant, 60 parts of magnesium phosphate cement clinker, and 40 parts of aluminophosphate cement clinker; The surface-modified fullerene is prepared by a method comprising the following steps: adding a fullerene material to a modifier mixture consisting of selenocysteine, pyrrolysine and isoleucine, heating and mixing, and then adding a composite catalyst to carry out a heating reaction to obtain the surface-modified fullerene; the composite catalyst is a mixture of bismuth trioxide and antimony trioxide, and the mass ratio of the bismuth trioxide to the antimony trioxide is 1:(2-4).

2. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The fullerene material is fullerene C 20 , Fullerene C 60 , Fullerene C 82 A mixture of the fullerene C 20 The fullerene C 60 With the fullerene C 82 The mass ratio is 1:1:

1.

3. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: In the modifier mixture, the mass ratio of the selenocysteine, the pyrrolysine and the isoleucine is 1:1:(1.5-2.5).

4. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The temperature of the heating and mixing is 30-50° C., and the mixing time is 5-15 min.

5. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The heating reaction is carried out under argon protection, the reaction temperature is 170-180° C., and the reaction time is 1-3 h.

6. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The fluid loss additive is a mixture of vinylformamide-vinylpyridine copolymer, N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer; the mass ratio of the vinylformamide-vinylpyridine copolymer to the N-methyl-N-vinylacetamide and N,N-dimethylacrylamide copolymer is (4-6):

1.

7. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The enhancer is a mixture of 1-(4-vinylbenzyl)thymine and 1,8-naphthyridine-2,7-diamine; the mass ratio of the 1-(4-vinylbenzyl)thymine to the 1,8-naphthyridine-2,7-diamine is (1-3):

1.

8. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The water-retaining agent is a mixture of sodium lactate, hyaluronic acid and sodium pyrrolidonecarboxylate; the mass ratio of the sodium lactate, the hyaluronic acid and the sodium pyrrolidonecarboxylate is 2:1:(5-8).

9. The grouting material based on surface-modified fullerene according to claim 1, characterized in that: The lubricant is a mixture of polytetrafluoroethylene nanoparticles, fluorinated ethylene propylene copolymer nanoparticles, molybdenum disulfide nanoparticles, and carbon black; the mass ratio of the polytetrafluoroethylene nanoparticles, the fluorinated ethylene propylene copolymer nanoparticles, the molybdenum disulfide nanoparticles, and the carbon black is (2.5-4):2:1:

2.

10. A method for preparing a grouting material based on surface-modified fullerene according to any one of claims 1 to 9, characterized in that: The steps include: The surface-modified fullerene, fluid loss reducer, reinforcing agent, water retaining agent, lubricant, magnesium phosphate cement clinker and aluminophosphate cement clinker are weighed respectively according to their mass fractions, stirred and mixed, and the grouting material based on the surface-modified fullerene is obtained.

11. The method for preparing a grouting material based on surface-modified fullerene according to claim 10, characterized in that: The stirring and mixing time is 30-60 minutes.

12. Use of the surface-modified fullerene-based grouting material according to any one of claims 1 to 9 in water-softened mudstone tunnels in coal mines.