Reinforced grouting material for mine and preparation method thereof
By constructing an organic-inorganic interpenetrating network for the reinforcement grouting material, the problems of slow solidification speed, strength decay, and poor flame retardant properties of existing chemical grouting materials are solved, achieving efficient and safe mine reinforcement.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- INNER MONGOLIA BEILIANDIAN GAOTOUYAO MINING INDUSTRY CO LTD
- Filing Date
- 2026-05-12
- Publication Date
- 2026-06-09
Smart Images
Figure CN122167129A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of reinforcement materials technology, specifically to a mine reinforcement grouting material and its preparation method. Background Technology
[0002] During mineral mining, fracture zones often form at the working face and support face due to differences in density and strength, affecting mining progress and posing safety hazards. Grouting reinforcement of fracture zones in underground coal mine working faces can solidify the fractured surrounding rock within the fracture zone into a dense solid with a certain strength, increasing the strength of the ore layer, improving the overall strength and integrity of the working face roof, artificially improving the stress condition of the working face roof, achieving the purposes of seepage prevention, leakage plugging, and reinforcement, creating conditions for safe and efficient mining. Compared with traditional methods of working faces through faults, this method can improve work efficiency and reduce the danger to workers. Currently, mines mostly use chemical grouting materials. However, existing chemical grouting materials have disadvantages during use, such as slow solidification speed and strength decay leading to roadway re-fracture and water leakage, posing certain safety hazards. Currently, polyurethane is the most commonly used chemical grouting reinforcement material. Its disadvantages include poor flame retardancy, making it difficult to meet the GB8624-97 standard's flame-retardant B1 rating; low strength; high cost; and, in the event of a fire, high smoke density, accompanied by liquid dripping and the release of toxic cyanide ions, easily causing environmental pollution. Furthermore, at low ambient temperatures, polyurethane requires 1-2 minutes to cure after mixing, during which liquid drips. Summary of the Invention
[0003] To address the shortcomings of existing technologies, this invention proposes a mine reinforcement grouting material and its preparation method.
[0004] This invention is achieved through the following technical solution: A mine reinforcement grouting material, the raw materials for which are prepared include the following components in parts by weight: polyethyleneimine grafted silane coupling agent KH560 modified nano-silica (abbreviated as PEI-KH-SiO2). 10-15 parts, triglycidyl isocyanate-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-polypropylene glycol composite prepolymer (abbreviated as TGIC-DOPO-PPG) 30-50 parts, water glass 40-60 parts, dimethylaminoethoxyethanol 0.2-0.3 parts, dibutyl phthalate 10-16 parts.
[0005] Furthermore, the modulus of the water glass is preferably 2.2-2.3.
[0006] Furthermore, the preparation method of the PEI-KH-SiO2 includes the following steps: L1. Nano-silica was added to ethanol and ultrasonically dispersed. Silane coupling agent KH560 was added, and the mixture was refluxed at 80℃ for 8 h. After centrifugation, the precipitate was washed with anhydrous ethanol and dried under vacuum to obtain nano-silica modified with silane coupling agent KH560, abbreviated as KH-SiO2. L2. Take the KH-SiO2 obtained in step L1, add it to deionized water and disperse it by ultrasonication. Add polyethyleneimine (PEI), react at 70-80℃ for 5 h, cool to room temperature, centrifuge at 3000 rpm for 10-15 min, wash the precipitate with anhydrous ethanol, and dry it under vacuum to obtain PEI-KH-SiO2.
[0007] Furthermore, in step L1, the diameter of the nano-silica is preferably 50-70 nm.
[0008] Furthermore, in step L1, the mass concentration of the nano-silica in ethanol is 20-30 mg / mL.
[0009] Further, in step L1, the mass ratio of the KH560 silane coupling agent to nano-silica is 1:8-10.
[0010] Furthermore, in step L2, the mass concentration of KH-SiO2 in deionized water is 20 mg / mL.
[0011] Furthermore, in step L2, the mass ratio of KH-SiO2 to polyethyleneimine is 10:1.
[0012] Furthermore, the preparation method of the TGIC-DOPO-PPG includes the following steps: V1. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was heated to 135 °C until completely melted. Triglycidyl isocyanate (TGIC) was added to it at a rate of 10 mmol / 20 min. The temperature was raised to 170 °C within 30 min, and the reaction was stirred for 3 h. The mixture was then cooled to room temperature, ground, washed with toluene, and dried under vacuum to obtain triglycidyl isocyanate-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as TGIC-DOPO. V2. Polypropylene glycol (PPG400) was dehydrated under vacuum at 110°C for 2-3 h and then cooled to obtain dehydrated PPG. Toluene diisocyanate (TDI) was added dropwise to the dehydrated PPG at 40-50°C under N2 protection. After the addition was completed, the mixture was stirred for 30 min, heated to 80°C, and stirred for 5-6 h to obtain polypropylene glycol-toluene diisocyanate, abbreviated as PPG-TDI. V3. Take the PPG-TDI obtained in step V2, and under N2 protection at 40-50℃, add the TGIC-DOPO obtained in step V1 while stirring. Raise the temperature to 70-80℃ and stir the reaction for 6-8 hours to obtain TGIC-DOPO-PPG.
[0013] Furthermore, in step V1, the molar ratio of DOPO to TGIC is 2.95:1.
[0014] Furthermore, in step V2, the molar ratio of TDI to PPG400 is 2:1.
[0015] Furthermore, in step V3, the mass ratio of TGIC-DOPO to PPG-TDI is 1:2.4.
[0016] Furthermore, the present invention also provides a method for preparing the aforementioned mine reinforcement grouting material, comprising the following steps: While stirring, dimethylaminoethoxyethanol was added dropwise to water glass, followed by PEI-KH-SiO2. The mixture was stirred until homogeneous to obtain component A. Dibutyl phthalate was then mixed with TGIC-DOPO-PPG to obtain component B. Before use, components A and B were thoroughly mixed to obtain a mine reinforcement grouting material.
[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a mine reinforcement grouting material and its preparation method. PEI-KH-SiO2 and TGIC-DOPO-PPG are prepared to construct an organic-inorganic interpenetrating network, improving the material's compressive and shear strength and exhibiting high flame retardancy. This invention prepares PEI-KH-SiO2 by reacting a silane coupling agent KH560 with the surface of nano-silica, grafting epoxy groups onto the SiO2 surface to obtain KH-SiO2. Through a ring-opening reaction between the amino groups in PEI and the epoxy groups in KH-SiO2, long molecular chains are successfully grafted onto the silica surface to obtain PEI-KH-SiO2. This not only functions as a filler but also provides multifunctional chemical crosslinking. The amino groups on the surface of PEI-KH-SiO2 can react with the isocyanate groups (-NCO) in TGIC-DOPO-PPG to form urea bonds, which are then integrated into the organic polyurethane / polyurea network. This chemically connects the organic and inorganic phases, forming a three-dimensional organic-inorganic interpenetrating network structure, thus improving the dispersibility of nano-SiO2. This invention prepares TGIC-DOPO-PPG by using a ring-opening reaction between the PH bond of DOPO and the epoxy group of TGIC to covalently graft TGIC molecules with DOPO. TGIC contains three epoxy groups, which increases the DOPO content and enhances the flame-retardant effect. The nitrogen-containing triazine ring in the TGIC structure also has a flame-retardant effect. After the ring-opening reaction of TGIC and DOPO, hydroxyl groups are generated. These hydroxyl groups react with the isocyanate groups of the polyurethane prepolymer PPG-TDI to graft phosphorus-containing flame-retardant groups onto the polyurethane molecular backbone. During the curing process, the isocyanate groups of TGIC-DOPO-PPG can react with PEI-KH-SiO2 for linkage and can also react with water molecules in liquid water glass to generate substituted urea groups. The isocyanate groups can continue to react with the substituted urea groups. Ultimately, a copolymer with alternating rigid and flexible segments is formed, and the organic and inorganic components are crosslinked. The flexible segments are composed of irregularly oriented, compliant molecules of polypropylene glycol polyether, while the rigid segments are composed of chain-like molecules such as aromatic groups, urethane groups, and substituted urea groups in isocyanates that are not easily altered. The resulting reinforced grouting material exhibits good curing performance and superior mechanical properties. Attached Figure Description
[0018] Figure 1 The mechanical properties of the grouting materials described in Examples 1-3 and Comparative Examples 1-3 of this invention; Figure 2 This demonstrates the flame-retardant effect of the grouting materials described in Examples 1-3 and Comparative Examples 1-3 of the present invention. Detailed Implementation
[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments. However, this invention is not limited to the following embodiments. It should be noted that, unless otherwise specified, all chemical reagents involved in this invention are purchased through commercial channels.
[0020] Example 1: A mine reinforcement grouting material, the raw materials for which are prepared include the following components in parts by weight: 15 parts PEI-KH-SiO2, 50 parts TGIC-DOPO-PPG, 60 parts water glass, 0.3 parts dimethylaminoethoxyethanol, and 16 parts dibutyl phthalate.
[0021] The preparation method of PEI-KH-SiO2 includes the following steps: L1. Take 3 g of 70 nm diameter nano-silica and add it to 100 mL of ethanol for ultrasonic dispersion. Add 0.3 g of silane coupling agent KH560, reflux at 80 °C for 8 h, centrifuge, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain KH-SiO2. L2. Take 2 g of KH-SiO2 obtained in step L1 and add it to 100 mL of deionized water for ultrasonic dispersion. Add 0.2 g of polyethyleneimine (PEI), react at 80℃ for 5 h, cool to room temperature, centrifuge at 3000 rpm for 15 min, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain PEI-KH-SiO2.
[0022] The preparation method of TGIC-DOPO-PPG includes the following steps: V1. 0.295 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was heated at 135 °C until completely melted. 0.1 mol of triglycidyl isocyanate (TGIC) was added to the mixture at a rate of 10 mmol / 20 min. The temperature was raised to 170 °C within 30 min, and the mixture was stirred for 3 h. After cooling to room temperature, the mixture was ground, washed with toluene, and dried under vacuum to obtain TGIC-DOPO. V2. Polypropylene glycol (PPG400) 0.1 mol was dehydrated under vacuum at 110 °C for 3 h and then cooled to obtain dehydrated PPG. Under N2 protection at 50 °C, toluene diisocyanate (TDI) 0.2 mol was added dropwise to the dehydrated PPG. After the addition was completed, the mixture was stirred for 30 min, heated to 80 °C, and stirred for 6 h to obtain PPG-TDI. V3. Take 24 g of PPG-TDI obtained in step V2, add 10 g of TGIC-DOPO obtained in step V1 to it while stirring at 50℃ and under N2 protection, heat to 80℃ and stir for 8 h to obtain TGIC-DOPO-PPG.
[0023] This embodiment also provides a method for preparing the aforementioned mine reinforcement grouting material, including the following steps: Dimethylaminoethoxyethanol was added dropwise to water glass with a modulus of 2.3 while stirring, and PEI-KH-SiO2 was added. The mixture was stirred until homogeneous to obtain component A. Dibutyl phthalate was mixed with TGIC-DOPO-PPG to obtain component B. Before use, components A and B were thoroughly mixed to obtain a mine reinforcement grouting material.
[0024] Example 2: A mine reinforcement grouting material, the raw materials for which are prepared include the following components in parts by weight: 10 parts PEI-KH-SiO2, 30 parts TGIC-DOPO-PPG, 40 parts water glass, 0.2 parts dimethylaminoethoxyethanol, and 10 parts dibutyl phthalate.
[0025] The preparation method of PEI-KH-SiO2 includes the following steps: L1. Take 2 g of 50 nm diameter nano-silica and add it to 100 mL of ethanol for ultrasonic dispersion. Add 0.25 g of silane coupling agent KH560 and reflux at 80 °C for 8 h. Centrifuge, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain KH-SiO2. L2. Take 2 g of KH-SiO2 obtained in step L1 and add it to 100 mL of deionized water for ultrasonic dispersion. Add 0.2 g of polyethyleneimine (PEI), react at 70℃ for 5 h, cool to room temperature, centrifuge at 3000 rpm for 10 min, wash the precipitate with anhydrous ethanol, and dry under vacuum to obtain PEI-KH-SiO2.
[0026] The preparation method of TGIC-DOPO-PPG includes the following steps: V1. 0.295 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was heated at 135 °C until completely melted. 0.1 mol of triglycidyl isocyanate (TGIC) was added to the mixture at a rate of 10 mmol / 20 min. The temperature was raised to 170 °C within 30 min, and the mixture was stirred for 3 h. After cooling to room temperature, the mixture was ground, washed with toluene, and dried under vacuum to obtain TGIC-DOPO. V2. Polypropylene glycol (PPG400) 0.1 mol was dehydrated under vacuum at 110 °C for 2 h and then cooled to obtain dehydrated PPG. Toluene diisocyanate (TDI) 0.2 mol was added dropwise to the dehydrated PPG at 40 °C under N2 protection. After the addition was completed, the mixture was stirred for 30 min, heated to 80 °C, and stirred for 5 h to obtain PPG-TDI. V3. Take 24 g of PPG-TDI obtained in step V2, add 10 g of TGIC-DOPO obtained in step V1 to it while stirring at 40℃ and under N2 protection, heat to 70℃, stir and react for 6 h to obtain TGIC-DOPO-PPG.
[0027] This embodiment also provides a method for preparing the aforementioned mine reinforcement grouting material, including the following steps: Dimethylaminoethoxyethanol was added dropwise to water glass with a modulus of 2.2 while stirring, and PEI-KH-SiO2 was added. The mixture was stirred until homogeneous to obtain component A. Dibutyl phthalate was mixed with TGIC-DOPO-PPG to obtain component B. Before use, components A and B were thoroughly mixed to obtain a mine reinforcement grouting material.
[0028] Example 3: A mine reinforcement grouting material, the raw materials for which are prepared include the following components in parts by weight: 12 parts PEI-KH-SiO2, 40 parts TGIC-DOPO-PPG, 50 parts water glass, 0.25 parts dimethylaminoethoxyethanol, and 12 parts dibutyl phthalate.
[0029] The preparation method of PEI-KH-SiO2 includes the following steps: L1. Take 2.5 g of 60 nm diameter nano-silica and add it to 100 mL of ethanol for ultrasonic dispersion. Add 0.3 g of silane coupling agent KH560 and reflux at 80 °C for 8 h. Centrifuge, wash the precipitate with anhydrous ethanol, and vacuum dry to obtain KH-SiO2. L2. Take 2 g of KH-SiO2 obtained in step L1 and add it to 100 mL of deionized water for ultrasonic dispersion. Add 0.2 g of polyethyleneimine (PEI), react at 75℃ for 5 h, cool to room temperature, centrifuge at 3000 rpm for 12 min, wash the precipitate with anhydrous ethanol, and dry under vacuum to obtain PEI-KH-SiO2.
[0030] The preparation method of TGIC-DOPO-PPG includes the following steps: V1. 0.295 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was heated at 135 °C until completely melted. 0.1 mol of triglycidyl isocyanate (TGIC) was added to the mixture at a rate of 10 mmol / 20 min. The temperature was raised to 170 °C within 30 min, and the mixture was stirred for 3 h. After cooling to room temperature, the mixture was ground, washed with toluene, and dried under vacuum to obtain TGIC-DOPO. V2. Polypropylene glycol (PPG400) 0.1 mol was dehydrated under vacuum at 110 °C for 2.5 h and then cooled to obtain dehydrated PPG. Under N2 protection at 40-50 °C, toluene diisocyanate (TDI) 0.2 mol was added dropwise to the dehydrated PPG. After the addition was completed, the mixture was stirred for 30 min, heated to 80 °C, and stirred for 5.5 h to obtain PPG-TDI. V3. Take 24 g of PPG-TDI obtained in step V2, add 10 g of TGIC-DOPO obtained in step V1 to it while stirring at 45°C and under N2 protection, heat to 75°C and stir for 7 h to obtain TGIC-DOPO-PPG.
[0031] This embodiment also provides a method for preparing the aforementioned mine reinforcement grouting material, including the following steps: Dimethylaminoethoxyethanol was added dropwise to water glass with a modulus of 2.25 while stirring, according to the weight ratio. PEI-KH-SiO2 was added and stirred evenly to obtain component A. Dibutyl phthalate and TGIC-DOPO-PPG were stirred and mixed evenly to obtain component B. Before use, components A and B were thoroughly mixed to obtain the mine reinforcement grouting material.
[0032] The only difference between Comparative Example 1 and Example 1 is that nano-silica was modified with silane coupling agent KH550, and the resulting product was used to replace PEI-KH-SiO2.
[0033] The only difference between Comparative Example 2 and Example 1 is that polyethyleneimine is used instead of PEI-KH-SiO2.
[0034] The only difference between Comparative Example 3 and Example 1 is that PPG-TDI is used instead of TGIC-DOPO-PPG.
[0035] Experimental Example 1: Following the methods of Examples 1-3 and Comparative Examples 1-2, grouting material was prepared and injected into a mold. After initial solidification, it was placed in a temperature-controlled chamber with an ambient temperature of 23℃ and a relative humidity of 50% for 24 hours before demolding. The compressive strength and shear strength were tested according to the method of AQ / T 1089-2020. The results are as follows: Figure 1 As shown.
[0036] Figure 1 The results showed that the compressive strength and shear strength of Examples 1-3 were better than those of Comparative Examples 1-3. Comparative Example 1 used silane coupling agent KH550 to modify nano-silica without adding polyethyleneimine, resulting in reduced crosslinking strength and decreased mechanical properties. Comparative Example 2 used polyethyleneimine instead of PEI-KH-SiO2 without adding nano-silica, resulting in decreased mechanical properties. Comparative Example 3 used PPG-TDI instead of TGIC-DOPO-PPG, resulting in decreased mechanical strength.
[0037] Experimental Example 2: Following the methods of Examples 1-3 and Comparative Examples 1-2, grouting material was prepared and injected into a mold. After initial solidification, it was placed in a temperature-controlled chamber with an ambient temperature of 23℃ and a relative humidity of 50% for 24 hours before demolding. The oxygen index was measured according to the method of AQ / T 1089-2020, and the results are as follows. Figure 2 As shown.
[0038] Figure 2 The results showed that the oxygen index of Examples 1-3 was higher than that of Comparative Examples 1-3. Comparative Example 1 used silane coupling agent KH550 to modify nano-silica without adding polyethyleneimine, resulting in a certain degree of decrease in flame retardant performance. Comparative Example 2 used polyethyleneimine to replace PEI-KH-SiO2 without adding nano-silica, resulting in a decrease in flame retardant effect. Comparative Example 3 used PPG-TDI to replace TGIC-DOPO-PPG without adding DOPO, resulting in a decrease in oxygen index and a reduction in flame retardant effect.
[0039] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
Claims
1. A mine reinforcement grouting material, characterized in that, The raw materials for preparation include the following components in parts by weight: 10-15 parts of polyethyleneimine-grafted silane coupling agent KH560 modified nano silica, 30-50 parts of triglycidyl isocyanurate-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-polypropylene glycol composite prepolymer, 40-60 parts of water glass, 0.2-0.3 parts of dimethylaminoethoxyethanol, and 10-16 parts of dibutyl phthalate; The abbreviation for modified nano-silica with polyethyleneimine grafted silane coupling agent KH560 is PEI-KH-SiO2, and the abbreviation for triglycidyl isocyanurate-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-polypropylene glycol composite prepolymer is TGIC-DOPO-PPG. The preparation method of PEI-KH-SiO2 includes the following steps: L1. Nano-silica was added to ethanol and ultrasonically dispersed. Silane coupling agent KH560 was added, and the mixture was refluxed at 80°C. After centrifugation, the precipitate was washed with anhydrous ethanol and vacuum dried to obtain nano-silica modified with silane coupling agent KH560, abbreviated as KH-SiO2. L2. Take the KH-SiO2 obtained in step L1, add it to deionized water and disperse it by ultrasonication, add polyethyleneimine, react at 70-80℃, cool, centrifuge, wash the precipitate, and dry to obtain PEI-KH-SiO2; The preparation method of TGIC-DOPO-PPG includes the following steps: V1. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was heated to 135 °C until completely melted, and triglycidyl isocyanurate was added to it. The temperature was raised to 170 °C within 30 min, and the reaction was stirred. The mixture was then cooled, ground, washed with toluene, and dried to obtain triglycidyl isocyanurate-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as TGIC-DOPO. V2. Polypropylene glycol is dehydrated under vacuum and then cooled to obtain dehydrated PPG. Toluene diisocyanate is added dropwise to the dehydrated PPG at 40-50℃ under N2 protection. After the addition is complete, the mixture is stirred for 30 min, then heated to 80℃ and stirred for 5-6 h to obtain polypropylene glycol-toluene diisocyanate, abbreviated as PPG-TDI. V3. Take the PPG-TDI obtained in step V2, and under N2 protection at 40-50℃, add the TGIC-DOPO obtained in step V1 while stirring. Raise the temperature to 70-80℃ and stir the reaction for 6-8 hours to obtain TGIC-DOPO-PPG.
2. The mine reinforcement grouting material according to claim 1, characterized in that, The modulus of the water glass is 2.2-2.
3.
3. The mine reinforcement grouting material according to claim 1, characterized in that, In step L1, the diameter of the nano-silica is 50-70 nm.
4. The mine reinforcement grouting material according to claim 1, characterized in that, In step L1, the mass ratio of the KH560 silane coupling agent to nano-silica is 1:8-10.
5. The mine reinforcement grouting material according to claim 1, characterized in that, In step L2, the mass ratio of KH-SiO2 to polyethyleneimine is 10:
1.
6. The mine reinforcement grouting material according to claim 1, characterized in that, In step V1, the molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to triglycidyl isocyanurate is 2.95:
1.
7. The mine reinforcement grouting material according to claim 1, characterized in that, In step V2, the molar ratio of toluene diisocyanate to polypropylene glycol is 2:
1.
8. The mine reinforcement grouting material according to claim 1, characterized in that, In step V3, the mass ratio of TGIC-DOPO to PPG-TDI is 1:2.
4.
9. A method for preparing a mine reinforcement grouting material as described in any one of claims 1-8, characterized in that, Includes the following steps: While stirring, dimethylaminoethoxyethanol was added dropwise to water glass, followed by PEI-KH-SiO2. The mixture was stirred until homogeneous to obtain component A. Dibutyl phthalate was then mixed with TGIC-DOPO-PPG to obtain component B. Before use, components A and B were thoroughly mixed to obtain a mine reinforcement grouting material.