KARST CHANNEL TYPE WATER INRUSH EFFICIENT-BLOCKING ULTRA-HIGH EXPANSION GROUTING MATERIAL AND PREPARATION AND USING METHODS AND APPLICATION THEREOF

Abstract

A karst channel type water inrush efficient-blocking ultra-high expansion grouting material, preparation, methods and application thereof, the grouting material includes macromolecule polymer particles A and a cross-linking solidifying fluid B, wherein the macromolecule polymer particles A are an inlaid type core-shell structure, primary macromolecule water-absorbent resin serves as an inner core, part of a gelling catalyzer is attached to an the inner core surface forming a shell, and the gelling catalyzer permeates the inner core forming an inlaid structure; before use, the macromolecule polymer particle A and the cross-linking solidifying fluid B are stirred; and then obtained mixed liquid is used as the grouting material to be injected into a fracture of a rock mass fracture zone. By means of the grouting material, high-pressure large-flow karst water inrush can be efficiently treated, the blocking efficiency of water inrush is improved, and major underground engineering construction of China is further facilitated.

Claims

1-15. (canceled)

16. A preparation method of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material, the method comprising: (1) adding a cross-linking agent into an acrylic acid solution, and then adding an active substance containing a hydrophilic group for polymerization reaction to obtain a precursor; (2) adding an initiator into the precursor obtained in step (1), heating for reaction to obtain a colloidal polymer, and smashing and drying the colloidal polymer to obtain primary macromolecule water-absorbent resin particles; and (3) uniformly spraying a gelling catalyzer onto the primary macromolecule water-absorbent resin particles, then performing drying, thus forming a shell structure with gel formed by catalyzing a cross-linking solidifying fluid B on a surface of the gelling catalyzer through cross-linking, and making part of the gelling catalyzer permeate into the primary macromolecule water-absorbent resin particles to obtain macromolecule polymer particles A of an inlaid type core-shell structure, wherein the gelling catalyzer is a composition of polyethylene glycol, 4,4′-methylene bis(o-chloroaniline) and polyether polyol; and the cross-linking solidifying fluid B is a substance capable of reacting with water.

17. The preparation method according to claim 16, wherein a mass fraction of the acrylic acid solution is 10% to 80%; or in step (1), the active substance containing the hydrophilic group comprises: any one or a mixture of several of starch, polyvinyl alcohol, polyacrylamide, acrylamide, and the like or any one or a mixture of several of solutions of the above substances; or in step (1), the cross-linking agent comprises any one or a composition of several of N,N-methylene bisacrylamide, divinyl benzene, isocyanate, dipentaerythritol hexaacrylate and pentaerythrityl tetraethylhexanoate; or in step (1), an adding ratio of the cross-linking agent is 0.3% to 2% of the mass of the acrylic acid in step (1); or in step (2), the initiator is an inorganic peroxide initiator; or in step (2), a use amount, namely an adding ratio, of the initiator is 0.1% to 0.7% of the mass of the acrylic acid in step (1); or in step (3), a use amount of a gelling catalyzer solution accounts for 1% to 10% of the total mass of the particles.

18. The preparation method according to claim 16, wherein in step (3), a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol in the gelling catalyzer is (1-5):(1-5):(2-5); or in step (2), a drying condition is: aeration-drying at 100° C. to 200° C. for 20 min to 120 min; or in step (2), a temperature of the polymerization reaction is 65° C. to 90° C., and a reaction time is 23 min to 119 min; or the gelling catalyzer is prepared into an aqueous solution.

19. The preparation method according to claim 18, wherein the gelling catalyzer is prepared into the aqueous solution with a mass fraction of 50% to 90%.

20. The preparation method according to claim 16, wherein a preparation method of the cross-linking solidifying fluid B comprises: S1, dehydrating polyether polyol: uniformly mixing metered polyether polyol and a plasticizer, then performing dehydration under a vacuum heating condition, cooling after dehydration is completed to obtain dehydrated polyether polyol and then putting the dehydrated polyether polyol in a dry container and sealing for standby application; S2, synthesizing a prepolymer: dropwise adding polyisocyanate into the dehydrated polyether polyol under a heating condition, then heating for polymerization reaction, after reaching a reaction endpoint, cooling and discharging, and storing an obtained prepolymer in an airtight and dry container; and S3, adding a diluent into the prepolymer, and uniformly stirring to obtain the cross-linking solidifying fluid B.

21. The preparation method according to claim 20, wherein in S1, the vacuum heating condition is that: dehydration is performed for 2.5 h to 4 h at 110° C. to 120° C. and a vacuum degree of −0.080 MPa to 0.1 MPa, and after dehydration is completed, cooling to reach 50° C. or below; or in S1, the polyether polyol is low-molecular-weight hydrophilic polyether with di-functionality or tri-functionality; or in S1, the plasticizer comprises any one or a mixture of several of phthalate ester, terephthalate, isophthalate, and the like; or in S1, an adding mass ratio of the polyether polyol to the plasticizer is (2.94-5.88):(1-2.05); or in S2, the isocyanate is toluene diisocyanate or polymethylene polyphenyl polyisocyanate or methylene diphenyl diisocyanate or combination thereof; or in S2, the heating condition is heating to no more than 50° C., controlling a temperature to be constant, completing dropwise adding within 30 min, and after dropwise adding is completed, uniformly stirring; or in S2, a temperature for heating for the polymerization reaction is 80° C. to 85° C.; or in S3, the diluent is acetone.

22. The preparation method according to claim 20, wherein an adding amount of the diluent is 15% to 35% of mass of the prepolymer.

23. The preparation method according to claim 20, wherein the adding amount of the diluent is 25% to 35% of mass of the prepolymer.

24. A preparation method of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material, wherein in the preparation method according to claim 16, during preparation of the precursor in step (1), first, acrylic acid is incompletely neutralized with alkaline liquor to obtain an incompletely-neutralized solution containing the acrylic acid, the incompletely-neutralized solution is mixed with a cross-linking agent, and then subjected to polymerization reaction with an active substance containing a hydrophilic group to obtain the precursor, and subsequent steps are consistent with steps (2) and (3) in the preparation method according to claim 16.

25. The preparation method according to claim 24, wherein a neutralization degree of the incompletely-neutralized solution is controlled to be 60% to 90%; or the alkaline liquor comprises any one or a mixture of several of sodium hydroxide, calcium hydroxide and potassium hydroxide; or the alkaline liquor is slowly added into the acrylic acid solution in an ice-water bath for neutralization.

26. An ultra-high expansion grouting material prepared by the method according to claim 16, wherein the grouting material comprises macromolecule polymer particles A and a cross-linking solidifying fluid B, the macromolecule polymer particles A are of an inlaid type core-shell structure, the grouting material is of an inlaid type core-shell structure, primary macromolecule water-absorbent resin obtained in step (2) serves as an inner core, part of a gelling catalyzer added in step (3) is attached to a surface of the inner core to form a shell, and meanwhile part of the gelling catalyzer permeates into the inner core to form an inlaid structure.

27. The ultra-high expansion grouting material prepared by the method according to claim 26, wherein a using method of the ultra-high expansion grouting material specifically comprises: stirring the macromolecule polymer particles A and the cross-linking solidifying fluid B for full mixing; and then injecting obtained mixed liquid as the grouting material into a fracture of a rock mass fracture zone.

28. The ultra-high expansion grouting material prepared by the method according to claim 26, wherein a mass ratio of the macromolecule polymer particles A to the cross-linking solidifying fluid B is (1-3):(1-5); or before use, a catalyzer or a retarder is added into the cross-linking solidifying fluid B, and a solidifying rate of the cross-linking solidifying fluid B after meeting water is controlled; or the catalyzer is formed by compounding of meta-toluenediamine, triethylenediamine and dibutyltin dilaurate; or an adding amount of the catalyzer is 2%-5% of mass of the cross-linking solidifying fluid B; or the retarder is an organic weak acid type compound.

29. The ultra-high expansion grouting material prepared by the method according to claim 28, wherein the retarder is tartaric acid or citric acid.

30. The ultra-high expansion grouting material prepared by the method according to claim 26, wherein a use amount of the retarder is controlled to be 8% to 12%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The accompanying drawings constituting a part of this application are used for providing further understanding for this application. Exemplary examples of this application and descriptions thereof are used for explaining this application and do not constitute any inappropriate limitation to this application.

[0066] FIG. 1 is an effect diagram of actual macromolecule polymer particles A prepared according to Example 1 of the present invention.

[0067] FIG. 2 is an effect diagram of actual cross-linking solidifying fluid B prepared according to Example 1 of the present invention.

[0068] FIG. 3 is an effect diagram of an actual expansion macromolecule grouting material prepared from the macromolecule polymer particles A and cross-linking solidifying fluid B prepared according to Example 1 of the present invention.

[0069] FIG. 4 is an effect diagram of an actual expansion macromolecule grouting material in FIG. 3 after expanding when meeting water.

[0070] FIG. 5 is an SEM graph of macromolecule polymer particles A prepared according to Example 1 of the present invention.

[0071] FIG. 6 is an SEM graph of a solidified body formed by cross-linking of the macromolecule polymer particles A prepared according to Example 1 of the present invention.

DETAILED DESCRIPTION

[0072] It should be noted that the following detailed descriptions are all exemplary and are intended to provide a further understanding of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which this application belongs.

[0073] It should be noted that terms used herein are only for describing specific implementations and are not intended to limit exemplary implementations according to the present application. As used herein, the singular form is also intended to include the plural form unless the context clearly dictates otherwise. In addition, it should further be understood that, terms “comprise” and/or “include” used in this application indicate that there are features, steps, operations, devices, components, and/or combinations thereof.

[0074] As mentioned above, as for problems in the prior art, in order to further improve a blocking effect of a grouting material on karst water inrush, the present invention provides a karst channel type water inrush efficient-blocking ultra-high expansion grouting material and preparation and using methods thereof. The present invention is further described below in conjunction with the accompanying drawings and the detailed description.

Example 1

[0075] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0076] 1. Preparation of macromolecule polymer particles A:

[0077] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 10% and 5 parts of an acrylamide co-polymer solution with a mass fraction of 20% are prepared with ice water, and 12 parts of alkaline liquor with a mass fraction of 10% is added, so that an acrylic acid neutralized solution with a neutralization degree of 60% is obtained.

[0078] (2) A polymerization reaction initiating stage: 0.072 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50%, added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.025 part of potassium persulfate is added and heated to 80° C., and the reaction lasts for 23 min, so that a colloidal polymer is generated.

[0079] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 100° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0080] (4) 5 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed in a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0081] 2. Preparation of the cross-linking solidifying fluid B:

[0082] (1) Polyether polyol dehydration: 50 parts of polypropylene oxide glycol N204 (a hydroxyl value being 255 mgKOH/g, and a functionality degree being 2) and 17 parts of phthalate ester are added into a container with a stirrer and a thermometer, heated and stirred, then heated and vacuumized, dehydrated at 110° C. and a vacuum degree of −0.08 MPa for 3 h, then cooled to reach 50° C. or below, and put in a dry container and airtightly preserved for standby application.

[0083] (2) Prepolymer synthesis: 100 parts of the dehydrated polyether polyol is accurately added into a dry there-necked flask, heated to 50° C., and stirred, 28 parts of toluene diisocyanate (TDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 80° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 7.0%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0084] (3) 20 parts of an acetone diluent and 4 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate being 1:1:2 are added to 80 parts of the prepolymer synthesized in step (2), and uniformly stirred, so as to obtain the cross-linking solidifying fluid B.

[0085] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are uniformly mixed at a mass ratio of 1:1, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 1.1 to 1.3.

[0086] A test method of a swelling ratio of the macromolecule polymer particles A is (the same method is adopted in other examples): 1 g of the macromolecule polymer particles A are put in a 400-mesh gauze and immersed in an aqueous solution, after the particles fully absorb water and expand, residual water on the surfaces of the particles is filtered out with filter paper, and the change of water-absorbing mass of the particles is recorded. A swelling ratio Sw (unit: (g/g)) is calculated by a following formula:

[00001]$\mathrm{SW}=\frac{M_n-M_0}{M_0}\times 100\%$

[0087] where M.sub.0 and M.sub.n respectively represent a mass of dry macromolecule polymer particles A and a mass of water-absorbed macromolecule polymer particles A.

[0088] A test method of an average gelling time of reaction between the cross-linking solidifying fluid B and tenfold water is (the same method is adopted in other examples): 10 g of the cross-linking solidifying fluid B is accurately weighed and put in a beaker, 100 ml of water is added, time t.sub.1 at which the water is added is recorded, the mixture is uniformly stirred rapidly (for about 10 s), and then allowed for still standing, so that white emulsion is obtained, and then the change of the viscosity is constantly detected with a glass rod. When the glass rod leaves a liquid level and a drawing phenomenon occurs, it indicates that the sample has already been gelled, time t.sub.2 is recorded, the gelling time t=t.sub.2−t.sub.1, an average value of repeated experiments is used as the average gelling time of reaction between B and the tenfold water.

[0089] A test method of a maximum swelling ratio of the expansion macromolecule grouting material is (the same method is adopted in other examples): grout is prepared according to a ratio, 1 part of the expansion macromolecule grouting material is put in 100 parts of pure water, after the material fully absorbs water and expands, residual water on the surface of the material is filtered out with filter paper, and the change of water-absorbing mass of the material is recorded. A swelling ratio Sw (unit: (g/g)) is calculated by a following formula:

[00002]$S_{A+B}=\frac{M_2-M_1}{M_1}\times 100\%$

[0090] where M.sub.2 and M.sub.1 respectively represent masses of the expansion macromolecule grouting material before and after meeting water (unit: g).

[0091] Gelling time of the grouting material is recorded, and an average value of repeated tests is used.

[0092] A test method of average gelling time of reaction between the expansion macromolecule grouting material and tenfold water is (the same method is adopted in other examples): 10 g of the expansion macromolecule grouting material is accurately weighed and put in a beaker, 100 ml of water is added, time t.sub.3 at which the water is added is recorded, the mixture is uniformly stirred rapidly, and then allowed for still standing, so that white emulsion is obtained, then a volume of the expansion macromolecule grouting material increases continuously, and the water in the beaker is completely absorbed and gel is formed is recorded, at the moment, time t.sub.4 is recorded, gelling time t=t.sub.4−t.sub.3, an average value of repeated experiments is used as the average gelling time of reaction between the expansion macromolecule grouting material and the tenfold water.

TABLE-US-00001 TABLE 1.1 Macromolecule polymer particle A property test Maximum swelling ratio Sw of Swelling ratio Sw in a NaCl solution with A in pure water.sup.Sw Cl ion concentration of 0.5 g/L 204 g/g 72.8 g/g

TABLE-US-00002 TABLE 1.2 Cross-linking solidifying fluid B property test Relative Average gelling time of reaction Appearance.sup.Sw density between B and tenfold water Light yellow liquid 1.05 86.5 s

TABLE-US-00003 TABLE 1.3 Expansion macromolecule grouting material property test Maximum swelling Average gelling time ratio S.sub.A+B of A + B of reaction between A:B Appearance in pure water.sup.Sw A + B and tenfold water 1:1 Light yellow 108 g/g 65.2 s liquid

Example 2

[0093] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0094] 1. Preparation of macromolecule polymer particles A:

[0095] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 80% and 5 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 24 parts of alkaline liquor with a mass fraction of 60% is added, so that an acrylic acid neutralized solution with a neutralization degree of 90% is obtained.

[0096] (2) A polymerization reaction initiating stage: 0.09 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50%, 5 parts of a gelling catalyzer (a ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, the solutions are added into the acrylic acid neutralized solution prepared in step (1), uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.03 part of potassium persulfate is added and heated to 80° C., and the reaction lasts for 57 min, so that a colloidal polymer is generated.

[0097] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 200° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0098] (4) 10 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed in a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0099] 2. Preparation of the cross-linking solidifying fluid B:

[0100] (1) Polyether polyol dehydration: 25 parts of polyether polyol PEG1000 (a hydroxyl value being 112 mgKOH/g, and a functionality degree being 2), 75 parts of polyether polyol 505S (a hydroxyl value being 56.3 mgKOH/g, and a functionality degree being 3) and 35 parts of phthalate ester are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 120° C. and a vacuum degree of −0.1 MPa for 2.5 h, then cooled to 50° C. or below, and put in a dry container and airtightly preserved for standby application.

[0101] (2) Prepolymer synthesis: 100 parts of the dehydrated polyether polyol is accurately added into a dry there-necked flask, heated to 50° C., and stirred, 56 parts of methylene diphenyl diisocyanate (MDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 8.2%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0102] (3) 35 parts of an acetone diluent and 2 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate being 1:1:2 are added to 65 parts of the prepolymer, and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0103] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 3:5, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 2.1 to 2.3.

TABLE-US-00004 TABLE 2.1 Macromolecule polymer particle A property test Maximum swelling ratio Swelling ratio Sw in a NaCl solution Sw of A in pure water.sup.Sw with Cl ion concentration of 0.5 g/L 161.7 g/g 34.5 g/g

TABLE-US-00005 TABLE 2.2 Cross-linking solidifying fluid B property test Relative Average gelling time of reaction Appearance.sup.Sw density between B and tenfold water Light yellow liquid 1.08 104.5 s

TABLE-US-00006 TABLE 2.3 Expansion macromolecule grouting material property test Maximum swelling Average gelling time ratio S.sub.A+B of A + B of reaction between A:B Appearance in pure water.sup.Sw A + B and tenfold water 3:5 Light yellow 72.6 g/g 29.8 s liquid

Example 3

[0104] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0105] 1. Preparation of macromolecule polymer particles A:

[0106] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 40% and 5 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 12 parts of alkaline liquor with a mass fraction of 50% is added, so that an acrylic acid neutralized solution with a neutralization degree of 75% is obtained.

[0107] (2) A polymerization reaction initiating stage: 0.05 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.025 part of ammonium persulfate is added, and heated to 80° C., and the reaction lasts for 88 min, so that a colloidal polymer is generated.

[0108] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 200° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0109] (4) 10 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 1:1:4) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0110] 2. Preparation of the cross-linking solidifying fluid B:

[0111] (1) Polyether polyol dehydration: 35 parts of polyether polyol PEG1000 (a hydroxyl value being 112 mgKOH/g, and a functionality degree being 2), 65 parts of polyether polyol 505S (a hydroxyl value being 56.3 mgKOH/g, and a functionality degree being 3) and 35 parts of isophthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 110° C. and a vacuum degree of −0.095 MPa for 3 h, then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0112] (2) Prepolymer synthesis: 100 parts of the dehydrated polyether polyol is accurately added into a dry container, heated to 50° C., and stirred, 56 parts of polymethylene polyphenyl polyisocyanate (PAPI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 9.8%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0113] (3) 30 parts of an acetone diluent and 3 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate of 1:1:2 are added to 70 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0114] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 2:3, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 3.1 to 3.3.

TABLE-US-00007 TABLE 3.1 Macromolecule polymer particle A property test Maximum swelling ratio Sw Swelling ratio Sw in a NaCl solution of A in pure water.sup.Sw with Cl ion concentration of 0.5 g/L 183.6 g/g 56.4 g/g

TABLE-US-00008 TABLE 3.2 Cross-linking solidifying fluid B property test Relative Average gelling time of reaction Appearance.sup.Sw density between B and tenfold water Light yellow liquid 1.12 98.7 s

TABLE-US-00009 TABLE 3.3 Expansion macromolecule grouting material property test Maximum swelling Average gelling time ratio S.sub.A+B of A + B of reaction between A:B Appearance in pure water.sup.Sw A + B and tenfold water 2:3 Light yellow 85.4 g/g 46.5 s liquid

Example 4

[0115] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0116] 1. Preparation of macromolecule polymer particles A:

[0117] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 30% and 8 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 9.6 parts of alkaline liquor with a mass fraction of 50% is added, so that an acrylic acid neutralized solution with a neutralization degree of 80% is obtained.

[0118] (2) A polymerization reaction initiating stage: 0.05 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.05 part of ammonium persulfate is added, and heated to 80° C., and the reaction lasts for 119 min, so that a colloidal polymer is generated.

[0119] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 200° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0120] (4) 5 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 1:2:3) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained.

[0121] 2. Preparation of the cross-linking solidifying fluid B:

[0122] (1) Polyether polyol dehydration: 25 parts of polyether polyol N330 (a hydroxyl value being 57 mgKOH/g, and a functionality degree being 2), 75 parts of polyether polyol N310 (a hydroxyl value being 165 mgKOH/g, and a functionality degree being 3) and 35 parts of terephthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 115° C. and a vacuum degree of −0.095 MPa for 2.5 h, then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0123] (2) Prepolymer synthesis: 100 parts of the dehydrated polyether polyol is accurately added into a dry container, heated to 50° C., and stirred, 50 parts of polymethylene polyphenyl polyisocyanate (PAPI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 10.2%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0124] (3) 30 parts of an acetone diluent and 8 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate being 1:1:2 are added to 70 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0125] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 2:1, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 4.1 to 4.3.

TABLE-US-00010 TABLE 4.1 Macromolecule polymer particle A property test Maximum swelling Swelling ratio Sw in a ratio Sw of NaCl solution with Cl ion A in pure waterSw concentration of 0.5 g/L 195.2 g/g 66.8 g/g

TABLE-US-00011 TABLE 4.2 Cross-linking solidifying fluid B property test Average gelling time of reaction AppearanceSw Relative density between B and tenfold water Light yellow liquid 1.09 84.2 s

TABLE-US-00012 TABLE 4.3 Expansion macromolecule grouting material property test Maximum swelling ratio Average gelling time of S.sub.A+B of A + B in reaction between A + B A:B Appearance pure waterSw and tenfold water 2:1 Light yellow 94.3 g/g 57.3 s liquid

Example 5

[0126] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0127] 1. Preparation of macromolecule polymer particles A:

[0128] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 50% and 10 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 14 parts of alkaline liquor with a mass fraction of 50% is added, so that an acrylic acid neutralized solution with a neutralization degree of 75% is obtained.

[0129] (2) A polymerization reaction initiating stage: 0.27 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.09 part of ammonium persulfate is added, and heated to 80° C., and the reaction lasts for 119 min, so that a colloidal polymer is generated.

[0130] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 100° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0131] (4) 5 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0132] 2. Preparation of the Cross-Linking Solidifying Fluid B:

[0133] (1) Polyether polyol dehydration: 30 parts of polyether polyol N210 (a hydroxyl value being 117 mgKOH/g, and a functionality degree being 2), 70 parts of polyether polyol N220 (a hydroxyl value being 57 mgKOH/g, and a functionality degree being 3) and 30 parts of isophthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 120° C. and a vacuum degree of −0.095 MPa for 2.5 h, then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0134] (2) Prepolymer synthesis: the dehydrated polyether polyol is accurately added into a dry container according to the amount of a formula, heated to 50° C., and stirred, 56 parts of toluene diisocyanate (TDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 11.3%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0135] (3) 25 parts of an acetone diluent and 5 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate being 1:1:2 are added to 75 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0136] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 3:2, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 5.1 to 5.3.

TABLE-US-00013 TABLE 5.1 Macromolecule polymer particle A property test Maximum swelling Swelling ratio Sw in a NaCl ratio Sw of solution with Cl ion A in pure waterSw concentration of 0.5 g/L 174.5 g/g 46.5 g/g

TABLE-US-00014 TABLE 5.2 Cross-linking solidifying fluid B property test Average gelling time of reaction AppearanceSw Relative density between B and tenfold water Light yellow liquid 1.10 83.5 s

TABLE-US-00015 TABLE 5.3 Expansion macromolecule grouting material property test Maximum Average gelling swelling ratio time of reaction S.sub.A+B of A + B between A + B A:B Appearance in pure waterSw and tenfold water 3:2 Light yellow 78.3 g/g 40.1 s liquid

Example 6

[0137] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0138] 1. Preparation of macromolecule polymer particles A:

[0139] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 30% and 5 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 8.4 parts of alkaline liquor with a mass fraction of 30% is added, so that an acrylic acid neutralized solution with a neutralization degree of 70% is obtained.

[0140] (2) A polymerization reaction initiating stage: 0.1 part of a cross-linking agent, i.e., N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.05 part of potassium persulfate is added, and heated to 80° C., and the reaction lasts for 105 min, so that a colloidal polymer.

[0141] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 100° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0142] (4) 5 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction being 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0143] 2. Preparation of the cross-linking solidifying fluid B:

[0144] (1) Polyether polyol dehydration: 30 parts of polyether polyol N303 (a hydroxyl value being 560 mgKOH/g, and a functionality degree being 2), 70 parts of polyether polyol N240 (a hydroxyl value being 28 mgKOH/g, and a functionality degree being 3) and 30 parts of isophthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 110° C. and a vacuum degree of −0.08 MPa for 4 h, and then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0145] (2) Prepolymer synthesis: the dehydrated polyether polyol is accurately added into a dry container according to the amount of a formula, heated to 50° C., and stirred, 56 parts of toluene diisocyanate (TDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 10.9%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0146] (3) 25 parts of an acetone diluent and 4 parts of a catalyzer with a ratio of toluenediamine to triethylenediamine to dibutyltin dilaurate being 1:1:2 are added to 75 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0147] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 1:1, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 6.1 to 6.3.

TABLE-US-00016 TABLE 6.1 Macromolecule polymer particle A property test Maximum swelling Swelling ratio Sw in a NaCl ratio Sw of solution with Cl ion A in pure waterSw concentration of 0.5 g/L 185.1 g/g 52.9 g/g

TABLE-US-00017 TABLE 6.2 Cross-linking solidifying fluid B property test Average gelling time of reaction AppearanceSw Relative density between B and tenfold water Light yellow liquid 1.11 91.5 s

TABLE-US-00018 TABLE 6.3 Expansion macromolecule grouting material property test Maximum swelling Average gelling ratio S.sub.A+B time of reaction of A + B between A + B A:B Appearance in pure waterSw and tenfold water 1:1 Light yellow 84.2 g/g 41.8 s liquid

Example 7

[0148] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0149] 1. Preparation of macromolecule polymer particles A:

[0150] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 50% and 10 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 14 parts of alkaline liquor with a mass fraction of 50% is added, so that an acrylic acid neutralized solution with a neutralization degree of 75% is obtained.

[0151] (2) A polymerization reaction initiating stage: 0.31 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.11 part of ammonium persulfate is added, and heated to 80° C., and the reaction lasts for 119 min, so that a colloidal polymer is generated.

[0152] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 100° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0153] (4) 2 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 2:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction being 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0154] 2. Preparation of the cross-linking solidifying fluid B:

[0155] (1) Polyether polyol dehydration: 30 parts of polyether polyol N210 (a hydroxyl value being 117 mgKOH/g, and a functionality degree being 2), 70 parts of polyether polyol N220 (a hydroxyl value being 57 mgKOH/g, and a functionality degree being 3) and 20 parts of isophthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 115° C. and a vacuum degree of −0.095 MPa for 3.5 h, then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0156] (2) Prepolymer synthesis: the dehydrated polyether polyol is accurately added into a dry container according to the amount of a formula, heated to 50° C., and stirred, 56 parts of toluene diisocyanate (TDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 12.0%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0157] (3) 25 parts of an acetone diluent and 8 parts of a retarder tartaric acid are added to 75 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0158] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 3:4, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 7.1 to 7.3.

TABLE-US-00019 TABLE 7.1 Macromolecule polymer particle A property test Maximum swelling Swelling ratio Sw in a ratio Sw of A NaCl solution with Cl ion in pure waterSw concentration of 0.5 g/L 186.2 g/g 43.2 g/g

TABLE-US-00020 TABLE 7.2 Cross-linking solidifying fluid B property test Average gelling time of reaction between AppearanceSw Relative density B and tenfold water Light yellow liquid 1.11 256.5 s

TABLE-US-00021 TABLE 7.3 Expansion macromolecule grouting material property test Maximum Average gelling swelling ratio time of reaction S.sub.A+B of A + B between A + B A:B Appearance in pure waterSw and tenfold water 3:4 Light yellow 75.3 g/g 187.5 s liquid

Example 8

[0159] Preparation of a karst channel type water inrush efficient-blocking ultra-high expansion grouting material includes the following steps:

[0160] 1. Preparation of macromolecule polymer particles A:

[0161] (1) An acrylic acid neutralizing stage: firstly, 36 parts of an acrylic acid solution with a mass fraction of 50% and 10 parts of an acrylamide co-polymer solution with a mass fraction of 10% are prepared with ice water, and 14 parts of alkaline liquor with a mass fraction of 50% is added, so that an acrylic acid neutralized solution with a neutralization degree of 75% is obtained.

[0162] (2) A polymerization reaction initiating stage: 0.23 part of a cross-linking agent N,N-methylene bisacrylamide is prepared into a solution with a mass fraction of 50% and added into the acrylic acid neutralized solution prepared in step (1), and uniformly stirred for 1 h, then an initiator solution with a mass fraction of 50% prepared from 0.1 part of ammonium persulfate is added, and heated to 80° C., and the reaction lasts for 119 min, so that a colloidal polymer is generated.

[0163] (3) A drying and smashing stage: the colloidal polymer obtained in step (2) is smashed and put in a drying furnace at 100° C. for drying to reach a constant weight, and particles are smashed and screened, so that primary macromolecule water-absorbent resin particles are obtained.

[0164] (4) 3 parts of a gelling catalyzer (a mass ratio of polyethylene glycol to 4,4′-methylene bis(o-chloroaniline) to polyether polyol being 1:1:2) of a cross-linking solidifying fluid B is prepared into a solution with a mass fraction of 50%, and the solution is uniformly sprayed onto the primary macromolecule water-absorbent resin particles obtained in step (3), which are then placed a drying oven at 160° C. for forced air drying, so that macromolecule polymer particles A are obtained for standby application.

[0165] 2. Preparation of the cross-linking solidifying fluid B:

[0166] (1) Polyether polyol dehydration: 30 parts of polyether polyol N210 (a hydroxyl value being 117 mgKOH/g, and a functionality degree being 2), 70 parts of polyether polyol N220 (a hydroxyl value being 57 mgKOH/g, and a functionality degree being 3) and 20 parts of isophthalate are added into a container with a stirrer and a thermometer and heated and stirred, then heated and vacuumized, dehydrated at 120° C. and a vacuum degree of −0.095 MPa for 3 h, then cooled to 50° C. or below, and an obtained product is put in a dry container and airtightly preserved for standby application.

[0167] (2) Prepolymer synthesis: dehydrated polyether polyol is accurately added into a dry container according to the amount of a formula, heated to 50° C., and stirred, 60 parts of toluene diisocyanate (TDI) is slowly and dropwise added, and a temperature is controlled so that dropwise adding is finished within 30 min. After dropwise adding is finished, the mixture is uniformly stirred, and heated to 85° C. for reaction, a —NCO % content is measured by sampling every 30 min during reaction (detection by a hydrochloric acid-di-n-butylamine method) till the —NCO mass % content is stabilized at 10.9%, i.e., a reaction endpoint is reached. Cooling and discharging are performed, and an obtained prepolymer is stored in an airtight and dry container.

[0168] (3) 30 parts of an acetone diluent and 12 parts of a retarder namely citric acid are added to 70 parts of the prepolymer synthesized in step (2), and uniformly stirred, so that the cross-linking solidifying fluid B is obtained.

[0169] The macromolecule polymer particles A and the cross-linking solidifying fluid B prepared according to this example are mixed uniformly at a mass ratio of 3:4, so that the expansion macromolecule grouting material is obtained, various performance indexes of the grouting material are tested, and results are shown in tables 8.1 to 8.3.

TABLE-US-00022 TABLE 8.1 Macromolecule polymer particle A property test Maximum swelling ratio Swelling ratio Sw in a NaCl solution Sw of A in pure waterSw with Cl ion concentration of 0.5 g/L 191.2 g/g 55 g/g

TABLE-US-00023 TABLE 8.2 Cross-linking solidifying fluid B property test Average gelling time of reaction between AppearanceSw Relative density B and tenfold water Light yellow liquid 1.08 341.5 s

TABLE-US-00024 TABLE 8.3 Expansion macromolecule grouting material property test Maximum swelling Average gelling ratio S.sub.A+B of time of reaction A + B in between A + B A:B Appearance pure waterSw and tenfold water 3:4 Light yellow 95.8 g/g 287.5 s liquid

[0170] With reference to FIG. 1 to FIG. 6 and in conjunction with test data in tables 1-8, it can be seen that the swelling ratio of the macromolecule polymer particles A is up to 55-204 times or above when the particles meet water. That is because the cross-linking solidifying fluid B reacts with water in the stratum under the action of the surface catalyzer of the macromolecule polymer particles A, so that the expanded macromolecule polymer particles A are effectively bonded, the macromolecule polymer particles A are bonded more firmly to form an elastic solidified body, water inrush treatment in the karst area is more facilitated, and the technical problem that the grouting material is difficult to remain under the water inrush condition is effectively solved in a mode of ‘expanding while meeting water and blocking water with water’.

[0171] Besides, the setting time of the grouting material prepared by the present invention may be controlled by the adding amount of the catalyzer and may be effectively regulated according to the demands of the engineering, and thus it is guaranteed that the grout is good in operability and engineering applicability. Full composition of multi-component materials is achieved, a purpose of a super-superposition effect of all components is achieved, and an effect of effective blocking of water inrush in the water-rich karst area is achieved. Moreover, the grouting material has the technical advantages of being convenient to operate and more efficient.

[0172] The above descriptions are merely preferred examples of this application and are not intended to limit this application. For those skilled in the art, this application may have various modifications and changes. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of this application shall fall within the protection scope of this application.