Phosphorene toughened grouting material applicable to large deformation roadways in coal mines and its preparation method

Abstract

The present invention provides a phosphorene toughened grouting material applicable to large-deformation roadways in coal mines and a preparation method thereof. Through "chemical scissors" intercalation treatment of phosphorite in an ionic solution, a monolayer phosphorene molecular toughening agent is prepared under the action of heating, stirring, ultrasonic waves and an electric field in a proton-inert solvent. The monolayer phosphorene molecular toughening agent, a fluid loss reducer and a dispersion promoter are added to a portland clinker cementitious material to prepare a novel phosphorene toughened grouting material, so as to improve the toughness, bonding strength and mechanical properties of the grouting material. The preparation method is simple, the cost is low, and the modification effect is good.

Description

Technical Field

[0001] The present invention relates to the technical field of grouting materials, and in particular to a phosphorene toughened grouting material suitable for coal mine large-deformation roadways and a preparation method thereof. Background Art

[0002] With the deepening of coal mining depth, roadways are facing problems such as bolt breakage, failure of support components, and large deformation of roadway surrounding rocks under the superposition of high ground stress and strong mining disturbance, which seriously affect the safe production of coal mines. Aiming at the problem of large deformation and failure of the surrounding rocks of roadways in coal mine kilometer deep wells, soft rocks, and strongly mined soft coal bodies, it is necessary to grout and modify the surrounding rocks of the roadways. Grouting modification refers to the continuous and coordinated modification from the surface to the inside of the surrounding rock, that is, grouting modification of the inside of the surrounding rock and shotcreting modification of the surface of the surrounding rock, so as to achieve the active modification of soft coal bodies, improve the "integrity", enhance the "strength performance", and control the "deformability". In the grouting reinforcement of continuously flowing and large-deformation roadways, the toughness problem of grouting materials cracking and breaking due to roadway deformation seriously affects the effect of grouting modification, which is the main restrictive factor for the grouting reinforcement of roadway surrounding rocks and has become a difficult problem in the grouting reinforcement of coal roadways. Therefore, it is urgent to develop new high-performance regulators to improve the toughness and bonding properties of grouting materials and promote their application. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an embodiment of the present invention provides a phosphorene toughened grouting material suitable for coal mine large-deformation roadways and a preparation method thereof, which can improve the toughness, bonding strength and mechanical properties of the grouting material.

[0004] An embodiment of the present invention provides a preparation method of a phosphorene toughened grouting material suitable for coal mine large-deformation roadways, including the following steps:

[0005] S1, prepare an ionic solution, which includes any one or a mixture of multiple of lithium ion solution, potassium ion solution, sodium ion solution, magnesium ion solution, aluminum ion solution, and calcium ion solution;

[0006] S2, weigh 5 parts of phosphorus blocks and 25 parts of ionic solution according to mass, add them to a proton-inert solvent composed of 2-3 parts of carbon tetrachloride and 1-3 parts of benzene, heat and stir, then perform ultrasonic treatment, apply a pulsed electric field, filter and dry to obtain a phosphorene molecular toughening agent;

[0007] S3, weigh 6 parts of phosphorene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter according to mass, add them to 100 parts of silicate clinker cementing material and mix and stir to obtain a phosphorene toughened grouting material.

[0008] In some embodiments, in the step S1, preparing the ionic solution includes the following steps: weighing 3 - 5 parts of lithium fluoride, 2 - 3 parts of lithium chloride, 3 - 5 parts of sodium fluoride, 1 - 3 parts of sodium chloride, 3 - 5 parts of aluminum fluoride, and 0.5 - 1 part of aluminum chloride by mass, adding them to 100 parts of water, heating with stirring, and mixing evenly to obtain the ionic solution.

[0009] In some embodiments, the fluid loss reducer includes poly(2 - acrylamido - 2 - methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number - average molecular weight of poly(2 - acrylamido - 2 - methylpropanesulfonic acid) is 1500 - 2000 g / mol, the number - average molecular weight of polyacrylamide is 2000 - 3000 g / mol, the number - average molecular weight of sodium polyacrylate is 3500 - 4000 g / mol, and the number - average molecular weight of magnesium polyacrylate is 3500 - 4000 g / mol.

[0010] In some embodiments, the dispersion promoter is a polyvinyl alcohol - polymethacrylate block copolymer, and its number - average molecular weight is 1200 - 2000 g / mol. Among them, the molar ratio of polyvinyl alcohol to polymethacrylate is (4 - 5):(1 - 1.5).

[0011] In some embodiments, in the step S1, when heating with stirring, the temperature is raised to 20°C, and the stirring time is 10 minutes.

[0012] In some embodiments, in the step S2, when heating with stirring, the temperature is raised to 100 - 120°C, the stirring rate is 5500 - 6000 revolutions per minute, and the stirring time is 10 minutes.

[0013] In some embodiments, in the step S2, the ultrasonic time is 5 - 7 minutes, and the ultrasonic power density is 20 - 23 W / cm 2 。

[0014] In some embodiments, in the step S2, the electric field strength of the pulsed electric field is 50 - 60 kV / cm, the pulse width is 90 - 120 μs, the pulse frequency is 1500 - 3000 Hz, and the pulse time is 5 minutes.

[0015] In some embodiments, in the step S3, the mixing and stirring is carried out using a dry powder mixer, and the stirring time is 15 minutes.

[0016] Another embodiment of the present invention provides a phosphorene - toughened grouting material prepared by the above - mentioned preparation method. Detailed Description of the Invention

[0017] The embodiments of the present invention will be described in detail below. The following described embodiments are exemplary and are intended to explain the present invention, and should not be construed as limiting the present invention.

[0018] The following describes a phosphorusene toughened grouting material applicable to large-deformation roadways in coal mines and its preparation method according to an embodiment of the present invention.

[0019] An embodiment of the present invention provides a preparation method of a phosphorusene toughened grouting material applicable to large-deformation roadways in coal mines, comprising the following steps:

[0020] S1, Prepare an ionic solution, which includes any one or a mixture of multiple of lithium ion solution, potassium ion solution, sodium ion solution, magnesium ion solution, aluminum ion solution, and calcium ion solution;

[0021] S2, Weigh 5 parts of phosphorus blocks and 25 parts of ionic solution by mass, add them to a proton-inert solvent composed of 2 - 3 parts of carbon tetrachloride and 1 - 3 parts of benzene, heat and stir, then perform ultrasonic treatment, apply a pulsed electric field, filter and dry to obtain a phosphorusene molecular toughening agent;

[0022] S3, Weigh 6 parts of phosphorusene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter by mass, add them to 100 parts of silicate clinker cementing material and mix and stir to obtain a phosphorusene toughened grouting material.

[0023] In the embodiment of the present invention, the phosphorus blocks are subjected to "chemical scissors" intercalation treatment in the ionic solution, and then a single-layer phosphorusene molecular toughening agent is prepared under heating, stirring, ultrasonic treatment, and electric field action in a proton-inert solvent. The single-layer phosphorusene molecular toughening agent, fluid loss reducer, and dispersion promoter are added to the silicate clinker cementing material to prepare a new type of phosphorusene toughened grouting material, improving the toughness, bond strength, and mechanical properties of the grouting material.

[0024] In the embodiment of the present invention, the phosphorusene molecular toughening agent is added to the grouting material. Since the phosphorusene molecular toughening agent has the flexibility and non-directionality of one-dimensional materials and the high specific surface area of two-dimensional materials, it has high dispersibility and specific surface area in the slurry, increasing the interfacial area of the phosphorusene / grouting stone body and enhancing the toughness of the grouting material. At the same time, the phosphorusene molecular toughening agent forms hydrogen bond forces with the slurry and π-π conjugation with the aromatic rings on the surface of the coal body, enhancing the bonding performance of the grouting material.

[0025] In the embodiment of the present invention, during the hydration process of the grouting cementing material, the phosphorusene molecules act as heterogeneous nucleation sites, promoting the hydration and hardening of the grouting material and improving the mechanical strength of the grouting material.

[0026] The preparation method of the embodiment of the present invention is simple, with low cost and good modification effect.

[0027] Furthermore, the concentration of the ionic solution is 12.5 - 22 g / ml.

[0028] In some embodiments, in step S1, preparing the ionic solution includes the following steps: weighing 3 - 5 parts of lithium fluoride, 2 - 3 parts of lithium chloride, 3 - 5 parts of sodium fluoride, 1 - 3 parts of sodium chloride, 3 - 5 parts of aluminum fluoride, and 0.5 - 1 part of aluminum chloride by mass, adding them to 100 parts of water, heating and stirring, and mixing evenly to obtain the ionic solution.

[0029] In some embodiments, the fluid loss additive includes poly(2 - acrylamido - 2 - methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number - average molecular weight of poly(2 - acrylamido - 2 - methylpropanesulfonic acid) is 1500 - 2000 g / mol, the number - average molecular weight of polyacrylamide is 2000 - 3000 g / mol, the number - average molecular weight of sodium polyacrylate is 3500 - 4000 g / mol, and the number - average molecular weight of magnesium polyacrylate is 3500 - 4000 g / mol.

[0030] Furthermore, the mass ratio of poly(2 - acrylamido - 2 - methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate is (1500 - 2000):(2000 - 3000):(3500 - 4000):(3500 - 4000).

[0031] In some embodiments, the dispersion promoter is a poly(vinyl alcohol - poly(methyl methacrylate)) block copolymer, and its number - average molecular weight is 1200 - 2000 g / mol. Among them, the molar ratio of poly(vinyl alcohol) to poly(methyl methacrylate) is (4 - 5):(1 - 1.5).

[0032] In some embodiments, in step S1, when heating and stirring, the temperature is raised to 20°C, and the stirring time is 10 minutes.

[0033] In some embodiments, in step S2, when heating and stirring, the temperature is raised to 100 - 120°C, the stirring rate is 5500 - 6000 revolutions per minute, and the stirring time is 10 minutes.

[0034] In some embodiments, in step S2, the ultrasonic time is 5 - 7 minutes, and the ultrasonic power density is 20 - 23 W / cm 2 。

[0035] In some embodiments, in step S2, the electric field strength of the pulsed electric field is 50 - 60 kV / cm, the pulse width is 90 - 120 μs, the pulse frequency is 1500 - 3000 Hz, and the pulse time is 5 minutes.

[0036] In some embodiments, in step S3, the mixing and stirring is carried out using a dry powder mixer, and the stirring time is 15 minutes.

[0037] Another embodiment of the present invention provides a phosphorene - toughened grouting material prepared by the above - mentioned preparation method.

[0038] The present invention will be further described below through specific embodiments.

[0039] Example 1

[0040] A preparation method of a phosphorene toughened grouting material applicable to large deformation roadways in coal mines includes the following steps:

[0041] S1, Weigh 3 parts of lithium fluoride, 2 parts of lithium chloride, 3 parts of sodium fluoride, 1 part of sodium chloride, 3 parts of aluminum fluoride, and 1 part of aluminum chloride by mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0042] S2, Weigh 5 parts of phosphate rock and 25 parts of the ionic solution by mass, add them to an aprotic inert solvent composed of 2 parts of carbon tetrachloride and 1 part of benzene, heat up to 100 °C and stir for 10 minutes, the stirring rate is 5500 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 5 minutes, and the ultrasonic power density is 20 W / cm 2 , Apply a pulsed electric field, the electric field strength of the pulsed electric field is 50 kV / cm, the pulse width is 90 μs, the pulse frequency is 2500 Hz, the pulse time is 5 minutes, then filter and dry to obtain a phosphorene molecular toughening agent.

[0043] S3, Weigh 6 parts of the phosphorene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter by mass, add them to 100 parts of silicate clinker cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorene toughened grouting material.

[0044] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1500 g / mol, the number average molecular weight of polyacrylamide is 2000 g / mol, the number average molecular weight of sodium polyacrylate is 3500 g / mol, and the number average molecular weight of magnesium polyacrylate is 3500 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer, its number average molecular weight is 1200 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 4:1.

[0045] After testing, the particle size of the prepared phosphorene molecular toughening agent is 45 nm, the compressive strength of the prepared phosphorene toughened grouting material is 66.5 MPa, the flexural strength is 11.3 MPa, and the bonding strength is 2.1 MPa.

[0046] Example 2

[0047] A preparation method of a phosphorene toughened grouting material applicable to large deformation roadways in coal mines includes the following steps:

[0048] S1, Weigh 5 parts of lithium fluoride, 3 parts of lithium chloride, 5 parts of sodium fluoride, 2 parts of sodium chloride, 5 parts of aluminum fluoride, and 0.5 part of aluminum chloride by mass fraction, add them to 100 parts of water, heat up to 20 °C, stir for 10 minutes, and mix evenly to obtain an ionic solution.

[0049] S2, Weigh 5 parts of phosphate rock and 25 parts of the ionic solution by mass fraction, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 100 °C, stir for 10 minutes, the stirring rate is 5800 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 7 minutes, and the ultrasonic power density is 23 W / cm 2 , Apply a pulsed electric field, the electric field strength of the pulsed electric field is 60 kV / cm, the pulse width is 120 μs, the pulse frequency is 1500 Hz, the pulse time is 5 minutes, then filter and dry to obtain a phosphorene molecular toughening agent.

[0050] S3, Weigh 6 parts of the phosphorene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter by mass fraction, add them to 100 parts of silicate clinker cementitious material, and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorene toughened grouting material.

[0051] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 2000 g / mol, the number-average molecular weight of polyacrylamide is 3000 g / mol, the number-average molecular weight of sodium polyacrylate is 3600 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3800 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer, its number-average molecular weight is 1600 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.5.

[0052] After testing, the particle size of the prepared phosphorene molecular toughening agent is 42 nm, the compressive strength of the prepared phosphorene toughened grouting material is 72.1 MPa, the flexural strength is 12.7 MPa, and the bond strength is 2.4 MPa.

[0053] Example 3

[0054] A preparation method of a phosphorene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0055] S1, Weigh 4 parts of lithium fluoride, 3 parts of lithium chloride, 4 parts of sodium fluoride, 3 parts of sodium chloride, 4 parts of aluminum fluoride, and 1 part of aluminum chloride by mass fraction, add them to 100 parts of water, heat up to 20 °C, stir for 10 minutes, and mix evenly to obtain an ionic solution.

[0056] S2, Weigh 5 parts of phosphate rock and 25 parts of ionic solution by mass fraction, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 120 °C and stir for 10 minutes, with a stirring rate of 5600 revolutions per minute, then perform ultrasonic treatment for 6 minutes, and the ultrasonic power density is 20 W / cm 2 , Apply a pulsed electric field with an electric field strength of 55 kV / cm, a pulse width of 100 μs, a pulse frequency of 1600 Hz, and a pulse time of 5 minutes, then filter and dry to obtain a phosphorene molecular toughening agent.

[0057] S3, Weigh 6 parts of phosphorene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter by mass fraction, add them to 100 parts of silicate clinker cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorene toughened grouting material.

[0058] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1800 g / mol, the number average molecular weight of polyacrylamide is 2300 g / mol, the number average molecular weight of sodium polyacrylate is 3700 g / mol, and the number average molecular weight of magnesium polyacrylate is 3700 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number average molecular weight of 1300 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.

[0059] After testing, the particle size of the prepared phosphorene molecular toughening agent is 40 nm, the compressive strength of the prepared phosphorene toughened grouting material is 73.8 MPa, the flexural strength is 13.9 MPa, and the bonding strength is 2.7 MPa.

[0060] Example 4

[0061] A preparation method of a phosphorene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0062] S1, Weigh 3 parts of lithium fluoride, 3 parts of lithium chloride, 4 parts of sodium fluoride, 2 parts of sodium chloride, 5 parts of aluminum fluoride, and 0.6 part of aluminum chloride by mass fraction, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, and mix evenly to obtain an ionic solution.

[0063] S2, Weigh 5 parts of phosphate rock and 25 parts of ionic solution by mass fraction, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 120 °C and stir for 10 minutes, with a stirring rate of 5800 revolutions per minute, then perform ultrasonic treatment for 6 minutes, and the ultrasonic power density is 22 W / cm 2, apply a pulsed electric field with an electric field strength of 56 kV / cm, a pulse width of 110 μs, a pulse frequency of 2800 Hz, and a pulse time of 5 minutes, then filter and dry to obtain a phosphorusene molecular toughening agent.

[0064] S3, weigh 6 parts of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersion promoter by mass, add them to 100 parts of the silicate clinker cementitious material, and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorusene toughened grouting material.

[0065] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1900 g / mol, the number-average molecular weight of polyacrylamide is 2800 g / mol, the number-average molecular weight of sodium polyacrylate is 3800 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3800 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1700 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.

[0066] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 39 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 74.4 MPa, the flexural strength is 14.1 MPa, and the bond strength is 2.7 MPa.

[0067] Example 5

[0068] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0069] S1, weigh 5 parts of lithium fluoride, 3 parts of lithium chloride, 4 parts of sodium fluoride, 3 parts of sodium chloride, 4 parts of aluminum fluoride, and 0.8 part of aluminum chloride by mass, add them to 100 parts of water, heat to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0070] S2, weigh 5 parts of phosphorus blocks and 25 parts of the ionic solution, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat to 120 °C and stir for 10 minutes, with a stirring rate of 6000 revolutions per minute, then perform ultrasonic treatment for 7 minutes, and the ultrasonic power density is 23 W / cm 2 , apply a pulsed electric field with an electric field strength of 60 kV / cm, a pulse width of 120 μs, a pulse frequency of 3000 Hz, and a pulse time of 5 minutes, then filter and dry to obtain a phosphorusene molecular toughening agent.

[0071] S3. Weigh 6 parts by mass of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersion promoter, add them to 100 parts of the silicate clinker cementitious material, and mix and stir with a dry powder mixer for 15 minutes to obtain the phosphorusene toughened grouting material.

[0072] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 2000 g / mol, the number-average molecular weight of polyacrylamide is 2900 g / mol, the number-average molecular weight of sodium polyacrylate is 3900 g / mol, and the number-average molecular weight of magnesium polyacrylate is 4000 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1900 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 4:1.

[0073] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 37 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 75.7 MPa, the flexural strength is 14.5 MPa, and the bond strength is 2.7 MPa.

[0074] Example 6

[0075] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines includes the following steps:

[0076] S1. Weigh 3 parts by mass of lithium fluoride, 2 parts of lithium chloride, 4 parts of sodium fluoride, 2 parts of sodium chloride, 3 parts of aluminum fluoride, and 0.8 part of aluminum chloride, add them to 100 parts of water, heat to 20 °C and stir for 10 minutes to mix evenly and obtain an ionic solution.

[0077] S2. Weigh 5 parts by mass of phosphorus blocks and 25 parts of the ionic solution, add them to a proton-inert solvent composed of 2 parts of carbon tetrachloride and 2 parts of benzene, heat to 110 °C and stir for 10 minutes at a stirring rate of 5700 revolutions per minute, then perform ultrasonic treatment for 7 minutes with an ultrasonic power density of 21 W / cm 2 , apply a pulsed electric field with an electric field strength of 56 kV / cm, a pulse width of 115 μs, a pulse frequency of 2800 Hz, and a pulse time of 5 minutes, then filter and dry to obtain the phosphorusene molecular toughening agent.

[0078] S3. Weigh 6 parts by mass of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersion promoter, add them to 100 parts of the silicate clinker cementitious material, and mix and stir with a dry powder mixer for 15 minutes to obtain the phosphorusene toughened grouting material.

[0079] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1900 g / mol, the number-average molecular weight of polyacrylamide is 2500 g / mol, the number-average molecular weight of sodium polyacrylate is 3800 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3600 g / mol. The dispersing agent is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1600 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.

[0080] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 36 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 76 MPa, the flexural strength is 14.5 MPa, and the bonding strength is 2.8 MPa.

[0081] Example 7

[0082] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines includes the following steps:

[0083] S1, Weigh 4 parts of lithium fluoride, 2 parts of lithium chloride, 5 parts of sodium fluoride, 2 parts of sodium chloride, 3 parts of aluminum fluoride, and 1 part of aluminum chloride by mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0084] S2, Weigh 5 parts of phosphorus block and 25 parts of ionic solution by mass, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 2 parts of benzene, heat up to 110 °C and stir for 10 minutes, the stirring rate is 5700 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 5 minutes, and the ultrasonic power density is 22 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 57 kV / cm, the pulse width is 100 μs, the pulse frequency is 2400 Hz, the pulse time is 5 minutes, and then filter and dry to obtain a phosphorusene molecular toughening agent.

[0085] S3, Weigh 6 parts of phosphorusene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersing agent by mass, add them to 100 parts of portland cement clinker-based cementitious material and mix with a dry powder mixer for 15 minutes to obtain a phosphorusene toughened grouting material.

[0086] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1600 g / mol, the number-average molecular weight of polyacrylamide is 2800 g / mol, the number-average molecular weight of sodium polyacrylate is 3700 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3600 g / mol. The dispersing agent is a poly(vinyl alcohol)-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1400 g / mol, and the molar ratio of poly(vinyl alcohol) to poly(methyl methacrylate) is 5:1.5.

[0087] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 34 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 79 MPa, the flexural strength is 14.7 MPa, and the bond strength is 2.8 MPa.

[0088] Example 8

[0089] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0090] S1, Weigh 4 parts of lithium fluoride, 3 parts of lithium chloride, 3 parts of sodium fluoride, 2 parts of sodium chloride, 3 parts of aluminum fluoride, and 0.5 part of aluminum chloride by mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0091] S2, Weigh 5 parts of phosphorus blocks and 25 parts of the ionic solution by mass, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 110 °C and stir for 10 minutes, the stirring rate is 5700 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 6 minutes, and the ultrasonic power density is 23 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 55 kV / cm, the pulse width is 95 μs, the pulse frequency is 2000 Hz, the pulse time is 5 minutes, then filter and dry to obtain the phosphorusene molecular toughening agent.

[0092] S3, Weigh 6 parts of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersing agent by mass, add them to 100 parts of the Portland cement clinker-based cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain the phosphorusene toughened grouting material.

[0093] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1700 g / mol, the number-average molecular weight of polyacrylamide is 2700 g / mol, the number-average molecular weight of sodium polyacrylate is 3600 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3600 g / mol. The dispersion promoter is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1500 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.5.

[0094] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 32 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 82 MPa, the flexural strength is 14.9 MPa, and the bond strength is 2.9 MPa.

[0095] Example 9

[0096] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0097] S1, Weigh 4 parts of lithium fluoride, 2 parts of lithium chloride, 3 parts of sodium fluoride, 1 part of sodium chloride, 3 parts of aluminum fluoride, and 0.6 parts of aluminum chloride according to mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0098] S2, Weigh 5 parts of phosphorus block and 25 parts of ionic solution according to mass, add them to a proton-inert solvent composed of 3 parts of carbon tetrachloride and 2 parts of benzene, heat up to 120 °C and stir for 10 minutes, the stirring rate is 5800 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 5 minutes, and the ultrasonic power density is 23 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 55 kV / cm, the pulse width is 100 μs, the pulse frequency is 2100 Hz, the pulse time is 5 minutes, then filter and dry to obtain a phosphorusene molecular toughening agent.

[0099] S3, Weigh 6 parts of phosphorusene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter according to mass, add them to 100 parts of portland clinker cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorusene toughened grouting material.

[0100] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1800 g / mol, the number-average molecular weight of polyacrylamide is 2600 g / mol, the number-average molecular weight of sodium polyacrylate is 3700 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3600 g / mol. The dispersing agent is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer, with a number-average molecular weight of 1600 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 5:1.

[0101] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 30 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 83 MPa, the flexural strength is 15.3 MPa, and the bond strength is 3.0 MPa.

[0102] Example 10

[0103] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0104] S1, Weigh 5 parts of lithium fluoride, 2 parts of lithium chloride, 4 parts of sodium fluoride, 1 part of sodium chloride, 5 parts of aluminum fluoride, and 0.6 parts of aluminum chloride by mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0105] S2, Weigh 5 parts of phosphorus blocks and 25 parts of the ionic solution by mass, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 2 parts of benzene, heat up to 120 °C and stir for 10 minutes, with a stirring rate of 5900 revolutions per minute, then perform ultrasonic treatment for 6 minutes, and the ultrasonic power density is 23 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 55 kV / cm, the pulse width is 100 μs, the pulse frequency is 2300 Hz, the pulse time is 5 minutes, then filter and dry to obtain the phosphorusene molecular toughening agent.

[0106] S3, Weigh 6 parts of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 parts of the dispersing agent by mass, add them to 100 parts of the silicate clinker cementing material and mix and stir with a dry powder mixer for 15 minutes to obtain the phosphorusene toughened grouting material.

[0107] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1900 g / mol, the number-average molecular weight of polyacrylamide is 2600 g / mol, the number-average molecular weight of sodium polyacrylate is 3700 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3700 g / mol. The dispersant is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1600 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 4:1.

[0108] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 27 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 84 MPa, the flexural strength is 15.4 MPa, and the bonding strength is 3.0 MPa.

[0109] Example 11

[0110] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines includes the following steps:

[0111] S1, Weigh 3 parts of lithium fluoride, 2 parts of lithium chloride, 5 parts of sodium fluoride, 3 parts of sodium chloride, 5 parts of aluminum fluoride, and 0.9 parts of aluminum chloride by mass, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0112] S2, Weigh 5 parts of phosphorus blocks and 25 parts of the ionic solution by mass, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 120 °C and stir for 10 minutes, the stirring rate is 5900 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 7 minutes, and the ultrasonic power density is 22 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 55 kV / cm, the pulse width is 100 μs, the pulse frequency is 2500 Hz, the pulse time is 5 minutes, then filter and dry to obtain a phosphorusene molecular toughening agent.

[0113] S3, Weigh 6 parts of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersant by mass, add them to 100 parts of the portland cement clinker-based cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorusene toughened grouting material.

[0114] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 2000 g / mol, the number-average molecular weight of polyacrylamide is 2000 g / mol, the number-average molecular weight of sodium polyacrylate is 3700 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3800 g / mol. The dispersant is a polyvinyl alcohol-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1700 g / mol, and the molar ratio of polyvinyl alcohol to poly(methyl methacrylate) is 4:1.

[0115] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 35 nm, the compressive strength of the prepared phosphorusene toughened grouting material is 86 MPa, the flexural strength is 15.6 MPa, and the bonding strength is 3.2 MPa.

[0116] Example 12

[0117] A preparation method of a phosphorusene toughened grouting material suitable for large-deformation roadways in coal mines, comprising the following steps:

[0118] S1, Weigh 5 parts of lithium fluoride, 2 parts of lithium chloride, 5 parts of sodium fluoride, 1 part of sodium chloride, 3 parts of aluminum fluoride, and 0.9 part of aluminum chloride according to mass parts, add them to 100 parts of water, heat up to 20 °C and stir for 10 minutes, mix evenly to obtain an ionic solution.

[0119] S2, Weigh 5 parts of phosphorus blocks and 25 parts of the ionic solution according to mass parts, add them to an aprotic inert solvent composed of 3 parts of carbon tetrachloride and 3 parts of benzene, heat up to 110 °C and stir for 10 minutes, the stirring rate is 5800 revolutions per minute, then perform ultrasonic treatment, the ultrasonic time is 7 minutes, and the ultrasonic power density is 22 W / cm 2 , apply a pulsed electric field, the electric field strength of the pulsed electric field is 55 kV / cm, the pulse width is 110 μs, the pulse frequency is 2600 Hz, the pulse time is 5 minutes, and then filter and dry to obtain a phosphorusene molecular toughening agent.

[0120] S3, Weigh 6 parts of the phosphorusene molecular toughening agent, 2 parts of the fluid loss reducer, and 0.5 part of the dispersant according to mass parts, add them to 100 parts of the Portland clinker cementitious material and mix and stir with a dry powder mixer for 15 minutes to obtain a phosphorusene toughened grouting material.

[0121] Among them, the fluid loss reducer includes poly(2-acrylamido-2-methylpropanesulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. The number-average molecular weight of poly(2-acrylamido-2-methylpropanesulfonic acid) is 1700 g / mol, the number-average molecular weight of polyacrylamide is 2200 g / mol, the number-average molecular weight of sodium polyacrylate is 3700 g / mol, and the number-average molecular weight of magnesium polyacrylate is 3800 g / mol. The dispersion promoter is a poly(vinyl alcohol)-poly(methyl methacrylate) block copolymer with a number-average molecular weight of 1700 g / mol, and the molar ratio of poly(vinyl alcohol) to poly(methyl methacrylate) is 4:1.

[0122] After testing, the particle size of the prepared phosphorusene molecular toughening agent is 23 nm. The compressive strength of the prepared phosphorusene toughened grouting material is 86 MPa, the flexural strength is 16.1 MPa, and the bond strength is 3.4 MPa.

[0123] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate the orientation or positional relationship based on the shown orientation or positional relationship, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.

[0124] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plural" is at least two, such as two, three, etc., unless otherwise specifically and clearly defined.

[0125] In the present invention, unless otherwise clearly specified and limited, the terms "installation", "connection", "connection", "fixation", etc. should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or integrated; it can be a mechanical connection, an electrical connection, or communication with each other; it can be directly connected, or indirectly connected through an intermediate medium, and can be the internal communication of two components or the interaction relationship between two components, unless otherwise clearly limited. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0126] In the present invention, unless otherwise clearly specified or limited, the first feature being "on" or "under" the second feature may be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature being "above", "over" and "on top of" the second feature may be that the first feature is directly above or obliquely above the second feature, or merely means that the horizontal height of the first feature is higher than that of the second feature. The first feature being "under", "below" and "beneath" the second feature may be that the first feature is directly below or obliquely below the second feature, or merely means that the horizontal height of the first feature is less than that of the second feature.

[0127] In the present invention, the terms "an embodiment", "some embodiments", "exemplifications", "specific exemplifications", or "some exemplifications", etc. mean that the specific features, structures, materials, or characteristics described in connection with the embodiment or exemplification are included in at least one embodiment or exemplification of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or exemplification. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or exemplifications in a suitable manner. In addition, without contradiction, those skilled in the art may combine and combine the different embodiments or exemplifications described in this specification and the features of the different embodiments or exemplifications.

[0128] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A preparation method of a phosphorene toughened grouting material applicable to large deformation roadways in coal mines, characterized in that, It includes the following steps: S1. Prepare an ionic solution. Weigh 3 - 5 parts of lithium fluoride, 2 - 3 parts of lithium chloride, 3 - 5 parts of sodium fluoride, 1 - 3 parts of sodium chloride, 3 - 5 parts of aluminum fluoride, and 0.5 - 1 part of aluminum chloride by mass fraction, add them to 100 parts of water, raise the temperature and stir until evenly mixed to obtain the ionic solution; S2. Weigh 5 parts of phosphate rock and 25 parts of the ionic solution by mass fraction, add them to an aprotic inert solvent composed of 2 - 3 parts of carbon tetrachloride and 1 - 3 parts of benzene, raise the temperature and stir, then perform ultrasonic treatment, apply a pulsed electric field, filter and dry to obtain a phosphorene molecular toughening agent; S3. Weigh 6 parts of the phosphorene molecular toughening agent, 2 parts of fluid loss reducer, and 0.5 part of dispersion promoter by mass fraction, add them to 100 parts of silicate clinker cementitious material and mix and stir to obtain a phosphorene - toughened grouting material. The dispersion promoter is a polyvinyl alcohol - polymethacrylate block copolymer with a number - average molecular weight of 1200 - 2000 g / mol, where the molar ratio of polyvinyl alcohol to polymethacrylate is (4 - 5):(1 - 1.5); In step S1, when raising the temperature and stirring, the temperature is raised to 20°C and the stirring time is 10 minutes; In step S2, when raising the temperature and stirring, the temperature is raised to 100 - 120°C, the stirring rate is 5500 - 6000 revolutions per minute, the stirring time is 10 minutes, the ultrasonic time is 5 - 7 minutes, the ultrasonic power density is 20 - 23 W / cm², the electric field strength of the pulsed electric field is 50 - 60 kV / cm, the pulse width is 90 - 120 μs, the pulse frequency is 1500 - 3000 Hz, and the pulse time is 5 minutes.

2. The preparation method of the phosphorene toughened grouting material applicable to large deformation roadways in coal mines according to claim 1, characterized in that, The fluid loss reducer includes poly(2 - acrylamido - 2 - methylpropane sulfonic acid), polyacrylamide, sodium polyacrylate, and magnesium polyacrylate. Among them, the number - average molecular weight of poly(2 - acrylamido - 2 - methylpropane sulfonic acid) is 1500 - 2000 g / mol, the number - average molecular weight of polyacrylamide is 2000 - 3000 g / mol, the number - average molecular weight of sodium polyacrylate is 3500 - 4000 g / mol, and the number - average molecular weight of magnesium polyacrylate is 3500 - 4000 g / mol.

3. The preparation method of the phosphorene toughened grouting material applicable to large deformation roadways in coal mines according to claim 1, characterized in that, In step S3, the mixing and stirring is carried out using a dry powder mixer, and the stirring time is 15 minutes.

4. A phosphorene - toughened grouting material prepared by the preparation method according to any one of claims 1 - 3.