An inorganic quick-setting filling material and its preparation method

Abstract

An inorganic quick-setting filling material and its preparation method, including material A and material B. Material A is made from the following components by weight: 25-35 parts of sulfoaluminate cement, 30-40 parts of blast furnace slag, 10-20 parts of waste gypsum, 1-3 parts of recycled alumina fiber, 5-10 parts of volcanic ash, 0.8-1.2 parts of (3,6-diaminoacridin-9-yl)boronic acid; Material B is made from the following raw materials by weight: 4-6 parts of functional water-soluble resin, 1-2 parts of 3-(N-morpholino)-2-hydroxypropanesulfonate sodium, 0.5-0.8 parts of sucralose, 0.1-1 part of sodium lignosulfonate, 0.8-1.2 parts of 1,3,5-triglycidyl-S-triazine trione, 0.1-0.5 parts of N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid sodium salt. This material has good quick-setting effect, high compressive strength, excellent flame retardant and antistatic properties, and long service life.

Description

Technical Field

[0001] The present invention relates to the technical field of filling materials, and particularly relates to an inorganic quick-setting filling material and a preparation method thereof. Background Art

[0002] With the increase in coal mining volume and mining scope, the gob areas and underground cavities are increasing continuously, posing a serious threat to the safe production of mines, engineering construction, and people's lives and property. At present, the measure adopted in China is to fill and reinforce the gob areas and underground cavities. The key to the success of this measure lies in the filling material. Developing filling materials with excellent comprehensive performance and performance stability is crucial for ensuring the quality of the filling project.

[0003] At present, the commonly used filling materials include injecting cement slurry, injecting organic foaming materials, hydraulic filling, etc. Among them, for injecting cement slurry filling, due to the solidification of the cement slurry, the volume shrinks, the setting is slow and water separation is easy, and it is easy to have insufficient filling and poor compaction in the filling area; the effect of injecting organic foaming materials is good, but it is easy to generate heat, the material itself is flammable, the price is high, the treatment cost is high, increasing the enterprise investment and cost; the hydraulic filling material is transported by pipeline, which has certain limitations on the maximum particle size of the filling material, is easy to cause pipeline blockage, and has complex operation procedures, high working intensity and high cost.

[0004] To solve the above problems, a Chinese invention patent with the authorization announcement number of CN105198346B discloses an inorganic filling material, including material A and material B. Material A is composed of the following mass parts: 70 - 80 bauxite powder, 1 - 2 calcium formate, 15 - 20 alumina, 2 - 5 gypsum, 15 - 20 fly ash, 2 - 5 calcium powder; Material B is composed of the following mass parts: 30 - 40 gypsum, 20 - 25 lime, 1 - 2 composite quick-setting agent, 0.1 - 1 water reducing agent, 1 - 5 expanding agent, 0.1 - 1 sodium dodecyl sulfate, 1 - 5 polyolefins, 0.1 - 1 alkali lignin. The filling body constructed by this invention is in close contact with the surrounding of the roadway, forming a well-integrated sealed body, with strong integrity and good compressive performance. The filling body has expansibility, improving the underground safety condition; it is non-combustible and non-supporting combustion, with outstanding explosion-proof and anti-static properties, and good effects on plugging gas and preventing fire; it has a higher filling rate and is easier to control the roof, and can effectively control the roof of the gob area and limit the surface subsidence. However, the quick-setting effect of this inorganic filling material needs to be further improved, and the compressive strength needs to be further increased.

[0005] It can be seen that developing an inorganic quick-setting filling material and a preparation method thereof with good quick-setting effect, high compressive strength, excellent flame retardant and antistatic properties, and long service life meets the market demand, has broad market value and application prospects, and has very important significance for promoting the development of the field of thermal insulation materials for RVs. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide an inorganic quick-setting filling material with good quick-setting effect, high compressive strength, excellent flame retardant and antistatic properties, and long service life, and a preparation method thereof.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] An inorganic quick-setting filling material, comprising material A and material B, and the mass ratio of material A to material B is 1:1; material A is made of the following components by weight: 25-35 parts of sulfoaluminate cement, 30-40 parts of blast furnace slag, 10-20 parts of waste gypsum, 1-3 parts of recycled alumina fiber, 5-10 parts of volcanic ash, 0.8-1.2 parts of (3,6-diaminoacridin-9-yl)boronic acid; material B is made of the following raw materials by weight: 4-6 parts of functional water-soluble resin, 1-2 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.5-0.8 parts of sucralose, 0.1-1 part of sodium lignosulfonate, 0.8-1.2 parts of 1,3,5-triglycidyl-S-triazine trione, 0.1-0.5 parts of N-(trimethoxysilylpropyl)ethylenediamine triacetic acid sodium salt; the functional water-soluble resin comprises structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt.

[0009] Preferably, the preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and initiator into a high-boiling solvent, stirring and reacting at 60-70 °C for 4-6 h in an inert gas atmosphere, rotary evaporating to remove the solvent, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 20-30 h, and finally taking the supernatant in the dialysis bag and rotary evaporating to remove water to obtain the functional water-soluble resin.

[0010] Preferably, the mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, initiator, and high-boiling solvent is 2:2:(0.5-0.8):0.3:(0.05-0.06):(15-25).

[0011] Preferably, there is no special requirement for the source of the reactive β-cyclodextrin quaternary ammonium salt. In an embodiment of the present invention, the reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B.

[0012] Preferably, the initiator is azobisisobutyronitrile; the high-boiling solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon, and argon.

[0013] Preferably, the waste gypsum is waste anhydrite with a fineness of 200-400 mesh.

[0014] Preferably, the fineness of the blast furnace slag is 40-300 mesh.

[0015] Preferably, the sulfoaluminate cement is rapid hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa.

[0016] Preferably, the particle size of the pozzolan is 400-800 mesh.

[0017] Preferably, the recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7-10 microns.

[0018] Another object of the present invention is to provide a method for preparing the inorganic rapid-setting filling material, comprising the following steps: preparing raw materials and components according to the ratio, mixing each component of material A evenly to obtain material A; mixing each raw material of material B evenly to obtain material B; packaging them separately; during use, mixing material A and material B evenly according to a mass ratio of 1:1, and then adding water, controlling the water-cement ratio to be (0.5-0.75):1 to obtain the inorganic rapid-setting filling material.

[0019] The beneficial effects of adopting the above technical solutions are as follows:

[0020] (1) For the method for preparing the inorganic rapid-setting filling material provided by the present invention, after mixing each raw material and component evenly by weight, it is ready, with convenient and easy operation, little environmental impact, low energy consumption, no need for special equipment and production lines, high preparation efficiency and finished product qualification rate, suitable for continuous large-scale production, and having high popularization and application value.

[0021] (2) The inorganic quick-setting filling material provided by the present invention includes material A and material B, and the mass ratio of material A to material B is 1:1. Material A is made from the following components by weight: 25-35 parts of sulfoaluminate cement, 30-40 parts of blast furnace slag, 10-20 parts of waste gypsum, 1-3 parts of recycled alumina fiber, 5-10 parts of volcanic ash, and 0.8-1.2 parts of (3,6-diaminoacridin-9-yl)boronic acid. Material B is made from the following raw materials by weight: 4-6 parts of functional water-soluble resin, 1-2 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.5-0.8 parts of sucralose, 0.1-1 part of sodium lignosulfonate, 0.8-1.2 parts of 1,3,5-triglycidyl-S-triazine trione, and 0.1-0.5 parts of N-(trimethoxysilylpropyl)ethylenediamine triacetic acid sodium salt. Through the interaction of each component, the prepared inorganic quick-setting filling material has good quick-setting effect, high compressive strength, excellent flame retardant and antistatic properties, and long service life.

[0022] (3) The inorganic quick-setting filling material provided by the present invention, the functional water-soluble resin includes the structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt. Sulfonic acid group, phenylphosphonium bromide, β-cyclodextrin quaternary ammonium salt, hydroxymethyl, and amide group structures are simultaneously introduced into the molecular structure of the functional water-soluble resin. Under the multiple effects of electronic effect, steric effect and conjugation effect, these structures can effectively improve the quick-setting effect. After the material is poured into the broken coal rock mass and goaf, it has good diffusion and penetration properties. While ensuring high water retention, it can form a dense consolidation body with the coal body, with high compressive strength, good filling effect, pressure-bearing densification, and good plugging performance. The use of blast furnace slag, waste gypsum and recycled alumina fiber belongs to the recycling and reuse of waste, turning waste into treasure, which can not only save resources but also be beneficial to environmental protection. And through the combined use of the above components, excellent mechanical strength and plugging performance can be given to the product; by cooperating with other components and raw materials, it can resolve the destructive influence of the external environment on the structure of the filling material, improve the internal structure density, and further improve the comprehensive performance and performance stability of the filling material. Detailed implementation mode

[0023] In order to enable those skilled in the art to better understand the technical solutions of the present invention and make the above features, purposes and advantages of the present invention clearer and easier to understand, the present invention will be further described below in conjunction with embodiments. The embodiments are only used to illustrate the present invention and not to limit the scope of the present invention.

[0024] Example 1

[0025] An inorganic rapid-setting filling material, comprising material A and material B, with the mass ratio of material A to material B being 1:1; Material A is made from the following components by weight: 25 parts of sulfoaluminate cement, 30 parts of blast furnace slag, 10 parts of waste gypsum, 1 part of recycled alumina fiber, 5 parts of volcanic ash, 0.8 part of (3,6-diaminoacridin-9-yl)boronic acid; Material B is made from the following raw materials by weight: 4 parts of functional water-soluble resin, 1 part of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.5 part of sucralose, 0.1 part of sodium lignosulfonate, 0.8 part of 1,3,5-triglycidyl-S-triazine trione, 0.1 part of N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid sodium salt; The functional water-soluble resin comprises structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt.

[0026] The preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and initiator into a high-boiling-point solvent, stirring and reacting at 60 °C for 4 h in an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 20 - 30 h, and finally taking the supernatant in the dialysis bag and removing water by rotary evaporation to obtain the functional water-soluble resin; The mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, initiator, and high-boiling-point solvent is 2:2:0.5:0.3:0.05:15; The reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B; The initiator is azobisisobutyronitrile; The high-boiling-point solvent is dimethyl sulfoxide; The inert gas is nitrogen; Through GPC test, the number-average molecular weight of this resin is 18110 g / mol, M W / M n = 1.313; Through elemental analysis and calculation of weight change, the mass ratio of the structural units introduced by 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, and reactive β-cyclodextrin quaternary ammonium salt is 1.98:2:0.49:0.27;

[0027] The waste gypsum is waste anhydrous gypsum with a fineness of 200 meshes; The fineness of the blast furnace slag is 40 meshes; The sulfoaluminate cement is fast-hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa; The particle size of the volcanic ash is 400 meshes; The recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7 - 10 microns.

[0028] A preparation method of the inorganic quick-setting filling material comprises the following steps: preparing raw materials and components according to the ratio, mixing each component of material A evenly to obtain material A; mixing each raw material of material B evenly to obtain material B; and then packaging them respectively. When in use, mixing material A and material B evenly according to the mass ratio of 1:1, then adding water, and controlling the water-cement ratio to be 0.75:1 to obtain the inorganic quick-setting filling material.

[0029] Example 2

[0030] An inorganic quick-setting filling material comprises material A and material B, and the mass ratio of material A to material B is 1:1. Material A is made of the following components by weight: 27 parts of sulfoaluminate cement, 33 parts of blast furnace slag, 12 parts of waste gypsum, 1.5 parts of recycled alumina fiber, 6 parts of volcanic ash, and 0.9 part of (3,6-diaminoacridin-9-yl)boronic acid. Material B is made of the following raw materials by weight: 4.5 parts of functional water-soluble resin, 1.2 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.6 part of sucralose, 0.5 part of sodium lignosulfonate, 0.9 part of 1,3,5-triglycidyl-s-triazine trione, and 0.2 part of N-(trimethoxysilylpropyl)ethylenediamine triacetic acid sodium salt. The functional water-soluble resin comprises structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, and reactive β-cyclodextrin quaternary ammonium salt.

[0031] The preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and initiator into a high-boiling solvent, stirring and reacting at 63°C for 4.5 h in an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 23 h, and finally taking the supernatant in the dialysis bag and removing water by rotary evaporation to obtain the functional water-soluble resin. The mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, initiator, and high-boiling solvent is 2:2:0.6:0.3:0.053:17. The reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B. The initiator is azobisisobutyronitrile. The high-boiling solvent is N,N-dimethylformamide. The inert gas is helium.

[0032] The waste gypsum is waste anhydrous anhydrite with a fineness of 250 meshes; the fineness of the blast furnace slag is 150 meshes; the sulfoaluminate cement is rapid hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa; the particle size of the pozzolan is 500 meshes; the recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7-10 microns.

[0033] A preparation method of the inorganic rapid-setting filling material comprises the following steps: preparing raw materials and components according to the ratio, mixing each component of the A material evenly to obtain the A material; mixing each raw material of the B material evenly to obtain the B material; and packaging them separately. During use, mixing the A material and the B material evenly according to a mass ratio of 1:1, then adding water, and controlling the water-cement ratio to be 0.7:1 to obtain the inorganic rapid-setting filling material.

[0034] Example 3

[0035] An inorganic rapid-setting filling material comprises an A material and a B material, and the mass ratio of the A material to the B material is 1:1; the A material is made of the following components by weight: 30 parts of sulfoaluminate cement, 35 parts of blast furnace slag, 15 parts of waste gypsum, 2 parts of recycled alumina fiber, 7 parts of pozzolan, and 1 part of (3,6-diaminoacridin-9-yl)boronic acid; the B material is made of the following raw materials by weight: 5 parts of functional water-soluble resin, 1.5 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.65 parts of sucralose, 0.7 parts of sodium lignosulfonate, 1 part of 1,3,5-triglycidyl-S-triazine trione, and 0.35 parts of N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid sodium salt; the functional water-soluble resin comprises structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, and reactive β-cyclodextrin quaternary ammonium salt.

[0036] The preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and an initiator into a high-boiling solvent, stirring and reacting at 65 °C for 5 h under an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 25 h, and finally taking the supernatant inside the dialysis bag and removing water by rotary evaporation to obtain the functional water-soluble resin; the mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyltriphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, the initiator, and the high-boiling solvent is 2:2:0.65:0.3:0.055:20; the reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B; the initiator is azobisisobutyronitrile; the high-boiling solvent is N-methylpyrrolidone; the inert gas is neon.

[0037] The waste gypsum is waste anhydrous gypsum with a fineness of 300 meshes; the fineness of the blast furnace slag is 200 meshes; the sulfoaluminate cement is rapid hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa; the particle size of the pozzolan is 600 meshes; the recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7-10 microns.

[0038] A preparation method of the inorganic rapid-setting filling material comprises the following steps: preparing raw materials and components according to the ratio, mixing each component of the A material evenly to obtain the A material; mixing each raw material of the B material evenly to obtain the B material; and then packaging them separately; during use, mixing the A material and the B material evenly according to a mass ratio of 1:1, and then adding them into water, controlling the water-cement ratio to be 0.6:1 to obtain the inorganic rapid-setting filling material.

[0039] Example 4

[0040] An inorganic rapid-setting filling material, comprising material A and material B, with the mass ratio of material A to material B being 1:1; material A is made from the following components by weight: 33 parts of sulfoaluminate cement, 38 parts of blast furnace slag, 18 parts of waste gypsum, 2.5 parts of recycled alumina fiber, 9 parts of volcanic ash, 1.1 parts of (3,6-diaminoacridin-9-yl)boronic acid; material B is made from the following raw materials by weight: 5.5 parts of functional water-soluble resin, 1.8 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.75 parts of sucralose, 0.9 parts of sodium lignosulfonate, 1.1 parts of 1,3,5-triglycidyl-s-triazine trione, 0.4 parts of N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid sodium salt; the functional water-soluble resin includes the structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt.

[0041] The preparation method of the functional water-soluble resin includes the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and initiator into a high-boiling solvent, stirring and reacting at 68°C for 5.5 h under an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 28 h, and finally taking the supernatant inside the dialysis bag and removing water by rotary evaporation to obtain the functional water-soluble resin; the mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, initiator, and high-boiling solvent is 2:2:0.75:0.3:0.058:23; the reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B; the initiator is azobisisobutyronitrile; the high-boiling solvent is a mixture of dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone in a mass ratio of 1:2:3; the inert gas is nitrogen.

[0042] The waste gypsum is waste anhydrous anhydrite with a fineness of 350 mesh; the fineness of the blast furnace slag is 280 mesh; the sulfoaluminate cement is fast-hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa; the particle size of the volcanic ash is 750 mesh; the recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7-10 microns.

[0043] A preparation method of the inorganic rapid-setting filling material comprises the following steps: preparing raw materials and components according to the ratio, mixing the components of material A evenly to obtain material A; mixing the raw materials of material B evenly to obtain material B; and then packaging them respectively. When in use, mixing material A and material B evenly according to the mass ratio of 1:1, and then adding water, controlling the water-cement ratio to be 0.55:1 to obtain the inorganic rapid-setting filling material.

[0044] Example 5

[0045] An inorganic rapid-setting filling material comprises material A and material B, and the mass ratio of material A to material B is 1:1. Material A is made of the following components by weight: 35 parts of sulfoaluminate cement, 40 parts of blast furnace slag, 20 parts of waste gypsum, 3 parts of recycled alumina fiber, 10 parts of volcanic ash, and 1.2 parts of (3,6-diaminoacridin-9-yl)boronic acid. Material B is made of the following raw materials by weight: 6 parts of functional water-soluble resin, 2 parts of 3-(N-morpholino)-2-hydroxypropanesulfonic acid sodium salt, 0.8 part of sucralose, 1 part of sodium lignosulfonate, 1.2 parts of 1,3,5-triglycidyl-S-triazine trione, and 0.5 part of N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid sodium salt. The functional water-soluble resin comprises structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, and reactive β-cyclodextrin quaternary ammonium salt.

[0046] The preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, and an initiator into a high-boiling solvent, stirring and reacting at 70 °C for 6 h in an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialyzing in water for 30 h, and finally taking the supernatant in the dialysis bag and removing water by rotary evaporation to obtain the functional water-soluble resin. The mass ratio of 2-acrylamido-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive β-cyclodextrin quaternary ammonium salt, initiator, and high-boiling solvent is 2:2:0.8:0.3:0.06:25. The reactive β-cyclodextrin quaternary ammonium salt is prepared by the method of Example 6 of the Chinese invention patent with the authorization announcement number CN106008755B. The initiator is azobisisobutyronitrile. The high-boiling solvent is dimethyl sulfoxide. The inert gas is neon.

[0047] The waste gypsum is waste anhydrous anhydrite with a fineness of 400 mesh; the fineness of the blast furnace slag is 300 mesh; the sulfoaluminate cement is rapid hardening sulfoaluminate cement with a 3-day strength of 42.5 MPa; the particle size of the pozzolan is 800 mesh; the recycled alumina fiber is recycled alumina continuous fiber F-72 with a single filament diameter of 7-10 microns.

[0048] A preparation method of the inorganic rapid-setting filling material comprises the following steps: preparing raw materials and components according to the ratio, mixing each component of the A material evenly to obtain the A material; mixing each raw material of the B material evenly to obtain the B material; and then packaging them separately; when in use, mixing the A material and the B material evenly according to a mass ratio of 1:1, and then adding water, and controlling the water-cement ratio to be 0.5:1 to obtain the inorganic rapid-setting filling material.

[0049] Comparative Example 1

[0050] An inorganic rapid-setting filling material and its preparation method are basically the same as those in Example 1, except that the functional water-soluble resin and the recycled alumina fiber are not added.

[0051] Comparative Example 2

[0052] An inorganic rapid-setting filling material and its preparation method are basically the same as those in Example 1, except that (3,6-diaminoacridin-9-yl)boronic acid and 3-(N-morpholinyl)-2-hydroxypropanesulfonic acid sodium are not added.

[0053] The inorganic rapid-setting filling materials described in Examples 1-5 and Comparative Examples 1-2 were subjected to performance tests, and the test results are shown in Table 1. The test methods refer to the current national standards and industry conventional methods in China: among them, the antistatic performance test is the surface resistance of the material after curing for 7 days, laboratory temperature: 22 °C; relative humidity: 64%; the flame retardancy is measured by the flaming combustion time in the alcohol burner combustion experiment, and the smaller the value, the better the flame retardancy.

[0054] As can be seen from Table 1, compared with the comparative examples, the inorganic rapid-setting filling material disclosed in the embodiments of the present invention has better compressive strength, rapid-setting performance, flame retardancy and antistatic property; the combined use of the functional water-soluble resin, the recycled alumina fiber, (3,6-diaminoacridin-9-yl)boronic acid and 3-(N-morpholinyl)-2-hydroxypropanesulfonic acid sodium is beneficial to improving the above properties.

[0055] Table 1

[0056]

[0057] The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification is only the principle of the present invention. Without departing from the spirit and scope of the present invention, various changes and improvements will occur to the present invention, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection required by the present invention is defined by the appended claims and their equivalents.

Claims

1. An inorganic quick-setting filling material, characterized in that: The invention is composed of material A and material B, wherein the mass ratio of material A to material B is 1:1; the material A is made of the following components in parts by weight: 25-35 parts of sulphoaluminate cement, 30-40 parts of blast furnace slag, 10-20 parts of waste gypsum, 1-3 parts of recycled alumina fiber, 5-10 parts of volcanic ash, and 0.8-1.2 parts of (3,6-diaminoacridine-9-yl)boric acid; the material B is made of the following raw materials in parts by weight: 4-6 parts of functional water-soluble resin, 3-(N-morpholinyl)-2 1-2 parts of sodium hydroxypropanesulfonate, 0.5-0.8 parts of sucralose, 0.1-1 parts of sodium lignin sulfonate, 0.8-1.2 parts of 1,3,5-triglycidyl-S-triazinetrione, 0.1-0.5 parts of sodium N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid; the functional water-soluble resin includes structural units introduced by the following monomers: 2-acrylamido-2-methylpropanesulfonic acid, N-trihydroxymethyl methacrylamide, allyl triphenylphosphine bromide, reactive β-cyclodextrin quaternary ammonium salt; The preparation method of the functional water-soluble resin comprises the following steps: adding 2-acrylamide-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive beta-cyclodextrin quaternary ammonium salt and initiator to a high boiling point solvent, stirring and reacting at 60-70°C for 4-6 hours in an inert gas atmosphere, removing the solvent by rotary evaporation, then dissolving the obtained crude product in water, taking the supernatant and placing it in a dialysis bag, dialysing it in water for 20-30 hours, finally taking the supernatant in the dialysis bag, removing water by rotary evaporation, and obtaining the functional water-soluble resin; the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid, N-trimethylolmethylacrylamide, allyl triphenylphosphonium bromide, reactive beta-cyclodextrin quaternary ammonium salt, initiator and high boiling point solvent is 2:2:(0.5-0.8):0.3:(0.05-0.06):(15-25).

2. The inorganic quick-setting filling material according to claim 1, characterized in that: The initiator is azobisisobutyronitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone; and the inert gas is any one of nitrogen, helium, neon, and argon.

3. The inorganic quick-setting filling material according to claim 1, characterized in that: The waste gypsum is waste anhydrous gypsum with a fineness of 200-400 meshes.

4. The inorganic quick-setting filling material according to claim 1, characterized in that: The fineness of the blast furnace slag is 40-300 meshes.

5. The inorganic quick-setting filling material according to claim 1, characterized in that: The sulphoaluminate cement is a fast-hardening sulphoaluminate cement, and its 3-day strength is 42.5 MPa.

6. The inorganic quick-setting filling material according to claim 1, characterized in that: The particle size of the volcanic ash is 400-800 meshes.

7. The inorganic quick-setting filling material according to claim 1, characterized in that: The recycled alumina fiber is recycled alumina continuous fiber F-72, and the single fiber diameter is 7-10 microns.

8. A method for preparing the inorganic quick-setting filling material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: preparing raw materials and components according to a ratio, mixing the components of material A evenly to obtain material A; mixing the raw materials of material B evenly to obtain material B; and packaging them respectively; When in use, material A and material B are evenly mixed in a mass ratio of 1:1, and then added into water, and the water-cement ratio is controlled to be (0.5-0.75):1 to obtain an inorganic quick-setting filling material.

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