A composite modified polyurethane grouting reinforcement material and its preparation method and application

Abstract

The present invention relates to the technical field of grouting materials, and in particular to a composite modified polyurethane grouting reinforcement material and its preparation method and application. The composite modified polyurethane grouting reinforcement material comprises component A and component B; in terms of mass fractions, the raw materials of component A comprise 60 to 80 parts of polymer polyol, 5 to 10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5 to 2 parts of catalyst, and 20 to 30 parts of diluent; in terms of mass fractions, the component B comprises 90 to 100 parts of organic polyisocyanate, 0.5 to 1.5 parts of foam stabilizer, and 3 to 5 parts of plasticizer. The grouting reinforcement material of the present invention has low initial viscosity, good fluidity, good surface tension and permeability, timely cementation, and high bonding strength and toughness after solidification. It is suitable for reinforcement construction with complex on-site application conditions such as rapid and effective reinforcement of Class IV or Class V surrounding rocks such as siltstone or quicksand layers, rapid consolidation reinforcement of large falling blocks in the roof area, etc.

Description

Technical Field

[0001] The invention relates to the technical field of grouting materials, and in particular to a composite modified polyurethane grouting reinforcement material and a preparation method and application thereof. Background Art

[0002] Polyurethane grouting material is a chemical slurry composed of polyurethane prepolymer and additives (solvents, catalysts, retarders, surfactants, plasticizers, etc.). Its main component is the terminal isocyanate (NCO) prepolymer obtained by the reaction of excess diisocyanate (or polyisocyanate) and polyether polyol.

[0003] At present, the -NCO end groups in polyurethane reinforcement agents can react with water in coal and rock mines. The generated urea bonds and metal oxides are chelated by hydrogen bonds to form urea-metal oxide complexes, and can also form covalent bonds with metal hydrates. They can form a bonding layer with high surface tension on the surface of the rock formation, achieving a good reinforcement effect; and the higher the -NCO content, the better the bonding strength of the polyurethane reinforcement agent. However, too high a -NCO content will increase the toxicity of the slurry and reduce the toughness of the consolidated body. In order to achieve green environmental protection and ensure its toughness, it is currently common to add stabilizers and introduce more polar groups to improve the bonding properties of the consolidated body. However, for reinforcement construction with complex on-site application conditions such as rapid and effective reinforcement of Class IV or Class V surrounding rocks such as siltstone or quicksand layers, effective penetration reinforcement of pulverized coal seams, and rapid consolidation reinforcement of large caving blocks in the roof, the material performance still needs to be improved. Summary of the invention

[0004] In view of the contradiction between the bonding strength and toughness of current polyurethane grouting reinforcement materials, and the problem that it is difficult to meet the reinforcement requirements of complex working conditions, the present invention provides a composite modified polyurethane grouting reinforcement material and a preparation method and application thereof.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention is a composite modified polyurethane grouting reinforcement material, comprising component A and component B;

[0007] The raw materials of component A include 60-80 parts of polymer polyol, 5-10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5-2 parts of catalyst, and 20-30 parts of diluent, by weight.

[0008] Calculated by weight, the B component includes 90 to 100 parts of organic polyisocyanate, 0.5 to 1.5 parts of foam stabilizer and 3 to 5 parts of plasticizer.

[0009] The second technical solution of the present invention is a method for preparing the above-mentioned composite modified polyurethane grouting reinforcement material, comprising the following steps:

[0010] Component A and component B are stirred separately into homogeneous liquids, and when in use, the components A and B are poured into the positions that need to be reinforced.

[0011] The third technical solution of the present invention is the application of the above-mentioned composite modified polyurethane grouting reinforcement material in the reinforcement of surrounding rock, pulverized coal seam and the reinforcement of large caving block areas on the roof.

[0012] The present invention discloses the following technical effects:

[0013] (1) The grouting reinforcement material of the present invention has a low initial viscosity (about 150-200cp), good fluidity, good surface tension and permeability, timely bonding, and high bonding strength and toughness after solidification. It is suitable for reinforcement construction with complex on-site application conditions such as rapid and effective reinforcement of Class IV or Class V surrounding rocks such as siltstone or quicksand layers, effective penetration reinforcement of pulverized coal seams, and rapid consolidation reinforcement of large caving blocks in the roof.

[0014] (2) The preparation method of the present invention is simple, low-cost, universal, and easy to scale up for production. DETAILED DESCRIPTION

[0015] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0016] It should be understood that the terms described in the present invention are only for describing a particular embodiment and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0017] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention.

[0018] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to the skilled artisan. The present invention description and examples are exemplary only.

[0019] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0020] The "parts" described in the present invention, unless otherwise specified, all represent parts by mass.

[0021] One of the technical solutions of the present invention is a composite modified polyurethane grouting reinforcement material, comprising component A and component B;

[0022] The raw materials of component A include 60-80 parts of polymer polyol, 5-10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5-2 parts of catalyst, and 20-30 parts of diluent, by weight.

[0023] Calculated by weight, the B component includes 90 to 100 parts of organic polyisocyanate, 0.5 to 1.5 parts of foam stabilizer and 3 to 5 parts of plasticizer.

[0024] The present invention has been repeatedly tested, and the results show that the amount of each raw material of the above-mentioned component A and component B exceeding the range recorded above will more or less affect the toughness, compressive strength or bonding strength of the solidified body after curing. Therefore, the present invention preferably limits the amount of each raw material to the parameter range recorded above.

[0025] In a preferred embodiment of the present invention, the carboxymethyl cellulose / silicon dioxide mixture is an alcohol solution in which nano-silicon dioxide and carboxymethyl cellulose are dispersed; the mass concentration of carboxymethyl cellulose in the carboxymethyl cellulose / silicon dioxide mixture is 1-3%, and the mass concentration of nano-silicon dioxide is 3-15%. The particle size of nano-silicon dioxide in the carboxymethyl cellulose / silicon dioxide mixture is 15-50nm, and the specific surface area is 150-280m 2 / g, purity not less than 98%.

[0026] On the one hand, the carboxymethyl cellulose / silicon dioxide mixture can reduce the initial viscosity of the grouting reinforcement material, increase the injectability, and enable the grouting reinforcement material to be injected into very small pores; on the other hand, the nano-silicon dioxide in the carboxymethyl cellulose / silicon dioxide mixture can also serve as a reaction site and play a connecting role, thereby enhancing the toughness and strength of the consolidated body after solidification.

[0027] If the particle size of nano-silicon dioxide is too large or too small and the specific surface area is too small, it will affect its effect as a reaction site and its bonding effect, and then affect the toughness and strength of the grouting reinforcement material after curing. Therefore, the preferred particle size of nano-silicon dioxide in the present invention is 15-50nm and the specific surface area is 150-280m 2 / g.

[0028] In a further preferred embodiment of the present invention, the mass ratio of carboxymethyl cellulose to silicon dioxide is 1:(3-5); and the alcohol may be glycerol.

[0029] In a preferred embodiment of the present invention, the polymer polyol is polyethylene glycol.

[0030] In a preferred embodiment of the present invention, the catalyst is at least one of diethylenetriamine, N,N-dimethylcyclohexylamine, tetramethylethylenediamine, stannous octoate and lead isooctanoate.

[0031] In a preferred embodiment of the present invention, the diluent is at least one of butyl ester, toluene, xylene and ethylene oxide.

[0032] In a preferred embodiment of the present invention, the organic polyisocyanate is cyclohexyl diisocyanate and / or naphthalene diisocyanate.

[0033] In a preferred embodiment of the present invention, the foam stabilizer is silicone oil; and the plasticizer is at least one of phthalic acid esters, aliphatic diacid esters, phosphate esters and chlorinated paraffin.

[0034] In a preferred embodiment of the present invention, the volume ratio of the component A to the component B is (0.1-1):1.

[0035] The second technical solution of the present invention is a method for preparing the above-mentioned composite modified polyurethane grouting reinforcement material, comprising the following steps:

[0036] Component A and component B are stirred separately into homogeneous liquids, and when in use, the components A and B are poured into the positions that need to be reinforced.

[0037] The third technical solution of the present invention is the application of the above-mentioned composite modified polyurethane grouting reinforcement material in the reinforcement of surrounding rock, pulverized coal seam and the reinforcement of large caving block areas on the roof.

[0038] Unless otherwise specified, the raw materials used in the embodiments of the present invention can be obtained through commercial sources.

[0039] The carboxymethyl cellulose used in the examples of the present invention is commercially available medium-viscosity carboxymethyl cellulose with a viscosity of 100-1000 mPa·s.

[0040] The carboxymethyl cellulose / silicon dioxide mixed solution used in the embodiment of the present invention is prepared by the following steps: 1.5% (mass concentration) carboxymethyl cellulose is dissolved in glycerol, and then 3% (mass concentration) nano-silicon dioxide (particle size 20nm, specific surface area 280m2) is added thereto. 2 / g, SiO2 purity not less than 99%, purchased from Jiangsu Tianxing New Materials Co., Ltd.) was evenly dispersed to obtain a carboxymethyl cellulose / silicon dioxide mixed solution.

[0041] Example 1

[0042] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0043] Component A is composed of the following raw materials in parts by weight: 70 parts of polyethylene glycol-400, 7.5 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 1 part of diethylenetriamine, and 25 parts of butyl ester;

[0044] Component B is composed of the following raw materials in parts by weight: 95 parts of cyclohexyl diisocyanate, 51 parts of silicone oil-880 and 4 parts of phthalate;

[0045] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0046] Component A and component B are mixed and stirred to become two homogeneous liquids. When in use, component A and component B are mixed in a volume ratio of 1:1 through a dual-liquid pump and poured into the position that needs to be reinforced.

[0047] Example 2

[0048] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0049] Component A is composed of the following raw materials in parts by weight: 60 parts of polyethylene glycol-400, 5 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5 parts of diethylenetriamine, and 20 parts of butyl ester;

[0050] Component B is composed of the following raw materials in parts by weight: 90 parts of cyclohexyl diisocyanate, 0.5 parts of silicone oil-8805 and 3 parts of phthalate;

[0051] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0052] Component A and component B are mixed and stirred to become two homogeneous liquids. When used, component A and component B are mixed in a volume ratio of 1:1 through a double liquid pump and poured into the position that needs to be reinforced.

[0053] Example 3

[0054] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0055] Component A is composed of the following raw materials in parts by weight: 80 parts of polyethylene glycol-400, 10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 2 parts of diethylenetriamine, and 30 parts of butyl ester;

[0056] Component B is composed of the following raw materials in parts by weight: 100 parts of cyclohexyl diisocyanate, 1.5 parts of silicone oil-8805 and 5 parts of phthalate;

[0057] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0058] Component A and component B are mixed and stirred to become two homogeneous liquids. When used, component A and component B are mixed in a volume ratio of 1:1 through a double liquid pump and poured into the position that needs to be reinforced.

[0059] Example 4

[0060] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0061] Component A is composed of the following raw materials in parts by weight: 70 parts of polyethylene glycol-400, 7.5 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 1 part of N,N-dimethylcyclohexylamine, and 25 parts of toluene;

[0062] Component B is composed of the following raw materials in parts by weight: 95 parts of naphthalene diisocyanate, 51 parts of silicone oil-880 and 4 parts of aliphatic diacid ester;

[0063] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0064] Component A and component B are mixed and stirred to become two homogeneous liquids. When used, component A and component B are mixed in a volume ratio of 1:1 through a double liquid pump and poured into the position that needs to be reinforced.

[0065] Example 5

[0066] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0067] Component A is composed of the following raw materials in parts by weight: 60 parts of polyethylene glycol-400, 5 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5 parts of N,N-dimethylcyclohexylamine, and 20 parts of toluene;

[0068] Component B is composed of the following raw materials in parts by weight: 90 parts of naphthalene diisocyanate, 0.5 parts of silicone oil-8805 and 3 parts of aliphatic diacid ester;

[0069] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0070] Component A and component B are mixed and stirred to become two homogeneous liquids. When used, component A and component B are mixed in a volume ratio of 1:1 through a double liquid pump and poured into the position that needs to be reinforced.

[0071] Example 6

[0072] A composite modified polyurethane grouting reinforcement material, the raw material of which is composed of component A and component B in a volume ratio of 1:1;

[0073] Component A is composed of the following raw materials in parts by weight: 80 parts of polyethylene glycol-400, 10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 2 parts of N,N-dimethylcyclohexylamine, and 30 parts of toluene;

[0074] Component B is composed of the following raw materials in parts by weight: 100 parts of naphthalene diisocyanate, 1.5 parts of silicone oil-8805 and 5 parts of aliphatic diacid ester;

[0075] The preparation method of the composite modified polyurethane grouting reinforcement material comprises the following steps:

[0076] Component A and component B are mixed and stirred to become two homogeneous liquids. When used, component A and component B are mixed in a volume ratio of 1:1 through a double liquid pump and poured into the position that needs to be reinforced.

[0077] Table 1 shows the main performance indicators of the composite modified polyurethane grouting reinforcement materials prepared in Examples 1-6 (refer to the "General Safety Technical Specifications for Polymer Materials for Coal Mine Reinforcement, Water Blockage, Filling and Spraying" and "Polymer Materials for Coal Mine Reinforcement").

[0078] Table 1

[0079]

[0080] It can be seen from Table 1 that the composite modified polyurethane grouting reinforcement material prepared in Examples 1-6 of the present invention cures quickly and has high bonding strength and flexural strength, and can be used for rapid and effective reinforcement of Class IV or Class V surrounding rocks such as siltstone or quicksand layers, effective penetration reinforcement of pulverized coal seams, rapid consolidation reinforcement of large caving blocks in the roof, and other reinforcement constructions with complex on-site application conditions.

[0081] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A composite modified polyurethane grouting reinforcement material for surrounding rock reinforcement, pulverized coal seam reinforcement and roof large caving block area reinforcement, characterized in that: It includes component A and component B; The raw materials of component A include 60-80 parts of polymer polyol, 5-10 parts of carboxymethyl cellulose / silicon dioxide mixed solution, 0.5-2 parts of catalyst, and 20-30 parts of diluent, by weight. Calculated by weight, the B component includes 90 to 100 parts of an organic polyisocyanate, 0.5 to 1.5 parts of a foam stabilizer, and 3 to 5 parts of a plasticizer; The carboxymethyl cellulose / silicon dioxide mixed solution is an alcohol solution in which nano-silicon dioxide and carboxymethyl cellulose are dispersed; the mass concentration of carboxymethyl cellulose in the carboxymethyl cellulose / silicon dioxide mixed solution is 1-3%, and the mass concentration of nano-silicon dioxide is 3-15%; wherein the particle size of the nano-silicon dioxide is 15-50nm, and the specific surface area is 150-280m 2 / g; The volume ratio of the component A to the component B is (0.1-1):1; The polymer polyol is polyethylene glycol; The catalyst is at least one of diethylenetriamine, N,N-dimethylcyclohexylamine, tetramethylethylenediamine, stannous octoate and lead isooctanoate; The diluent is at least one of butyl ester, toluene, xylene and ethylene oxide; The organic polyisocyanate is cyclohexyl diisocyanate and / or naphthalene diisocyanate; The foam stabilizer is silicone oil; the plasticizer is at least one of phthalic acid ester, aliphatic diacid ester, phosphate ester and chlorinated paraffin.

2. A method for preparing the composite modified polyurethane grouting reinforcement material according to claim 1, characterized in that: The following steps are involved: Component A and component B are stirred separately into homogeneous liquids, and when in use, the components A and B are poured into the positions that need to be reinforced.

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