Two-component inorganic flame-retardant filling retention covering agent and preparation method thereof

Abstract

The invention discloses a two-component inorganic flame-retardant filling retention covering agent and a preparation method thereof.The covering agent comprises a component A and a component B. The component A comprises deionized water, sodium silicate, silica sol, an accelerant, a foam stabilizer, a surfactant and flame-retardant silicone oil; the component B comprises a polyurethane prepolymer, silicone oil, a catalyst and a solvent; the preparation method of the coating comprises the following steps: obtaining the two-component inorganic flame-retardant filling retention covering agent, and applying the two-component inorganic flame-retardant filling retention covering agent to a lower corner, an upper corner and a goaf of a coal mine. Compared with the prior art, the inorganic flame-retardant filling retention covering agent is divided into the component A and the component B, the component A and the component B are quickly foamed in a short time to form a 20-fold flame-retardant elastomer, and the flame-retardant elastomer has the advantages of high temperature resistance, 1000 DEG C fire test resistance, good flame retardance and good compression resistance.

Description

Technical Field

[0001] The invention relates to the technical field of mining foaming filling, and in particular to a two-component inorganic flame retardant filling retention covering agent and a preparation method thereof. Background Art

[0002] During coal mining, tunnel excavation and mine construction, the lower corners, upper corners and goaf are key areas for gas accumulation and outflow. Cracks are very likely to occur in this area, causing dangers such as gas outflow. Therefore, a filling material for coal mines with the functions of filling, plugging air leaks and good load-bearing capacity is needed; furthermore, flammable materials such as coal dust and gas in mines are very likely to cause fires, so the filling material for coal mines needs to have high flame retardant properties.

[0003] At present, traditional inorganic curing foam has the problems of small foaming multiple, long curing time, shrinkage after foaming, resulting in gaps, and it is difficult to achieve good filling and plugging effect. The use of polyurethane foam filler can have better elasticity, good bonding ability with coal rock, closed-cell structure, and better sealing effect, but the foaming amount of polyurethane foam is low and the flame retardant effect is poor, resulting in high plugging cost and poor flame retardant effect.

[0004] The two-component inorganic flame retardant filling retention covering agent of the present invention is made of component A and component B. When in use, component A and component B are sprayed and rapidly foamed to form a flame retardant elastomer, thereby improving construction efficiency and construction progress. The flame retardant elastomer formed by foaming does not shrink and is resistant to high temperatures, and can completely fill and cover the lower corners, upper corners, goafs and other filled areas, thereby achieving the effects of plugging air leakage and flame retardancy. Summary of the invention

[0005] The purpose of the present invention is to provide a two-component inorganic flame retardant filling retention covering agent and a preparation method thereof, aiming to overcome the problems of slow foaming speed, small foaming amount, foaming shrinkage, and poor flame retardant effect of existing foaming filling materials used in coal mines, resulting in poor plugging of air leakage, filling and flame retardant effects.

[0006] A two-component inorganic flame retardant filling retention covering agent, the covering agent comprises component A and component B, wherein:

[0007] The component A comprises deionized water, sodium silicate, silica sol, accelerator, foaming agent, surfactant and flame retardant silicone oil;

[0008] The component B comprises polyurethane prepolymer, silicone oil, catalyst and solvent.

[0009] Preferably, in the above technical solution, the covering agent is a mixture of component A and component B in a weight ratio of 1:1-3.

[0010] Preferably, in the above technical solution, in percentage, the component A consists of 30-70% deionized water, 10-30% sodium silicate, 10-30% silica sol, 5-20% accelerator, 1-10% uniform foaming agent, 1-10% surfactant, and 0.1-5% flame retardant silicone oil.

[0011] Preferably, in the above technical solution, in percentage, the component B consists of 70-90% polyurethane prepolymer, 0.1-8% cell opening aid, 0.1-5% silicone oil, 0.1-5% catalyst and 10-30% solvent.

[0012] Preferably, in the above technical scheme, the preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 600-700r / min and a temperature of 100-110°C, the hydrophilic polyester resin and the high-activity polyether are evacuated for 1-2h and then cooled; at a temperature of 75-80°C, isocyanate is added and reacted at a constant temperature for 3-4h to obtain a polyurethane prepolymer.

[0013] Preferably, in the above technical solution, the polyurethane prepolymer is composed of a hydrophilic polyester resin, a highly active polyether and an isocyanate in a weight ratio of 2-3:1-2:6-8.

[0014] Preferably, in the above technical solution, the isocyanate is one or more of 1,3-toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0015] Preferably, in the above technical solution, the flame retardant silicone oil is one or more of BL-999, BL-5638, BL-824EU, BL-677, and BL-8333.

[0016] Preferably, in the above technical solution, the silicone oil is HGD-607H, HGD-8802H or silicone oil 901.

[0017] Preferably, in the above technical scheme, the isocyanate is one or more of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), and 1,6-hexamethylene diisocyanate trimer (THDI).

[0018] A method for preparing the above-mentioned two-component inorganic flame retardant filling retention covering agent, the preparation method comprising:

[0019] The preparation method comprises:

[0020] S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100-200 r / min, mixing and packaging to obtain component A;

[0021] S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 55-60°C, stirring for 20-40 minutes, cooling, and packaging at room temperature to obtain component B.

[0022] An application of the above-mentioned two-component inorganic flame retardant filling retention covering agent is to quickly mix component A and component B in a ratio of 1:1-3 and then spray them on the lower corner, upper corner and goaf of the coal mine.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] The method of the present invention is used to prepare a two-component inorganic flame retardant filling retention covering agent with fast foaming speed, no shrinkage after foaming and good flame retardant effect. The principle is as follows: (1) a hydrophilic polyester resin, a high-activity polyether and an isocyanate are first reacted to obtain a polyurethane prepolymer, a surfactant improves the dispersibility and fluidity of each component when the two components are mixed, and a promoter and a catalyst increase the reaction rate, so as to achieve rapid foaming in a short time to form a polyurethane elastomer that is more than 20 times larger; (2) sodium silicate can absorb the heat released during the polyurethane foaming process, pyrolyze and lose water to form anhydrous sodium silicate, and the sodium silicate, anhydrous sodium silicate and silica sol are uniformly mixed in the polyurethane foam to enhance the high temperature resistance and compressive strength of the polyurethane elastomer; during synergistic combustion, the flame retardant silicone oil and silicone oil accelerate the carbonization of the polyurethane elastomer to achieve a high temperature 1000°C fire test. DETAILED DESCRIPTION

[0025] Although not otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as those commonly understood by those skilled in the art. Terms with definitions in dictionaries should be interpreted as having the same meaning as those disclosed in the relevant technical literature and this article, and should not be interpreted in an idealized or overly formal sense.

[0026] Azodicarbonamide AC is used as the foam leveling agent;

[0027] The accelerator is triethanolamine;

[0028] The surfactant is sodium dodecyl sulfate;

[0029] The flame retardant silicone oil is dimethyl silicone oil, methyl silicone oil or polydimethylsiloxane;

[0030] The hydrophilic polyester resin is CAPA3050 (3050), MD-2000 (2000) or ESUN1000C (1000);

[0031] The highly active polyether is SEP-330N (330N), polyetheramine D-400 (ED400), JH-360N (360N) or GEP-551C (551C);

[0032] The silicone oil is HGD-8802H, HGD-607H or 901, the HGD-8802H and HGD-607H are purchased from Hengguang New Materials Suzhou Co., Ltd., and the 901 is purchased from Shanghai Ruibin New Energy Technology Co., Ltd.;

[0033] The catalyst is HGD-DPA or HGDV-33, and both HGD-DPA and HGDV-33 are purchased from Hengguang New Materials Suzhou Co., Ltd.;

[0034] The solvent includes one or more of dichloromethane, dichloroethane, cyclohexane, ethyl acetate, isopropanol, ethyl acetate, and ethylene glycol monomethyl ether.

[0035] Example 1

[0036] A two-component inorganic flame retardant filling retention covering agent, wherein, by percentage, component A is composed of 30% deionized water, 20% sodium silicate, 20% silica sol, 7% accelerator, 6% uniform foaming agent, 4% surfactant and 3% flame retardant silicone oil; component B is composed of 69% polyurethane prepolymer, 8% opening agent (FLA-320L), 2% silicone oil (HGD-607H), 1% catalyst (HGD-DPA) and 20% solvent, wherein the uniform foaming agent is azodicarbonamide AC, the accelerator is triethanolamine, the surfactant is sodium dodecyl sulfate, and the flame retardant silicone oil is methyl silicone oil;

[0037] The preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 600 r / min and a temperature of 110° C., 2 parts of hydrophilic polyester resin (CAPA3050) and 1 part of high-activity polyether (SEP-330N) are evacuated for 1 hour and then cooled; at a temperature of 75° C., 6 parts of 4,4′-dicyclohexylmethane diisocyanate are added and reacted at a constant temperature for 3 hours to obtain a polyurethane prepolymer.

[0038] A method for preparing the above-mentioned two-component inorganic flame retardant filling retention covering agent, the specific steps of the preparation method are as follows:

[0039] S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100 r / min, mixing and packaging to obtain component A;

[0040] S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 60°C, stirring for 40 minutes, cooling, and packaging at room temperature to obtain component B.

[0041] An application of the two-component inorganic flame retardant filling retention covering agent as described above is to mix component A and component B in a ratio of 1:1 and then quickly spray them to the area that needs to be filled and covered.

[0042] Example 2

[0043] A two-component inorganic flame retardant filling retention covering agent, wherein, by percentage, component A is composed of 55% deionized water, 10% sodium silicate, 10% silica sol, 15% accelerator, 3% uniform foaming agent, 6% surfactant and 1% flame retardant silicone oil; component B is composed of 75% polyurethane prepolymer, 5% opening agent (FLA-320L), 5% silicone oil (HGD-8802H), 5% catalyst (HGD-DPA) and 10% solvent, wherein the uniform foaming agent is azodicarbonamide AC, the accelerator is triethanolamine, the surfactant is sodium dodecyl sulfate, and the flame retardant silicone oil is methyl silicone oil;

[0044] The preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 650 r / min and a temperature of 100° C., 3 parts of hydrophilic polyester resin (CAPA3050) and 1 part of high-activity polyether (ED400) are evacuated for 2 hours and then cooled; at a temperature of 80° C., 6 parts of 4,4′-dicyclohexylmethane diisocyanate are added and reacted at a constant temperature for 4 hours to obtain a polyurethane prepolymer.

[0045] A method for preparing the above-mentioned two-component inorganic flame retardant filling retention covering agent, the specific steps of the preparation method are as follows:

[0046] S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100 r / min, mixing and packaging to obtain component A;

[0047] S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 55°C, stirring for 20 minutes, cooling, and packaging at room temperature to obtain component B.

[0048] An application of the two-component inorganic flame retardant filling retention covering agent as described above is to mix component A and component B in a ratio of 1:2 and then quickly spray them to the area that needs to be filled and covered.

[0049] Example 3

[0050] A two-component inorganic flame retardant filling retention covering agent, wherein, by percentage, component A is composed of 35% deionized water, 30% sodium silicate, 20% silica sol, 7% accelerator, 6% uniform foaming agent, 1% surfactant and 1% flame retardant silicone oil; component B is composed of 90% polyurethane prepolymer, 3% pore opening aid (FLA-320L), 2% silicone oil (901), 5% catalyst (HGD-DPA) and 10% solvent, wherein the uniform foaming agent is azodicarbonamide AC, the accelerator is triethanolamine, the surfactant is sodium dodecyl sulfate, and the flame retardant silicone oil is dimethyl silicone oil;

[0051] The preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 700 r / min and a temperature of 100° C., 2 parts of a hydrophilic polyester resin (CAPA3050) and 2 parts of a highly active polyether (SEP-330N) are evacuated for 1 hour and then cooled; at a temperature of 80° C., 8 parts of 4,4′-dicyclohexylmethane diisocyanate are added and reacted at a constant temperature for 3 hours to obtain a polyurethane prepolymer.

[0052] A method for preparing the above-mentioned two-component inorganic flame retardant filling retention covering agent, the specific steps of the preparation method are as follows:

[0053] S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100 r / min, mixing and packaging to obtain component A;

[0054] S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 60°C, stirring for 40 minutes, cooling, and packaging at room temperature to obtain component B.

[0055] An application of the two-component inorganic flame retardant filling retention covering agent as described above is to mix component A and component B in a ratio of 1:1 and then quickly spray them to the area that needs to be filled and covered.

[0056] Example 4

[0057] A two-component inorganic flame retardant filling retention covering agent, wherein, by percentage, component A is composed of 30% deionized water, 20% sodium silicate, 20% silica sol, 7% accelerator, 6% uniform foaming agent, 4% surfactant and 3% flame retardant silicone oil; component B is composed of 69% polyurethane prepolymer, 8% pore opening aid (FLA-320L), 2% silicone oil (HGD-8802H), 1% catalyst (HGD-DPA) and 20% solvent, wherein the uniform foaming agent is azodicarbonamide AC, the accelerator is triethanolamine, the surfactant is sodium dodecyl sulfate, and the flame retardant silicone oil is dimethyl silicone oil;

[0058] The preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 600 r / min and a temperature of 110° C., 2 parts of hydrophilic polyester resin (MD-2000) and 1 part of high-activity polyether (ED400) are evacuated for 1 hour and then cooled; at a temperature of 75° C., 6 parts of 4,4′-dicyclohexylmethane diisocyanate are added and reacted at a constant temperature for 3 hours to obtain a polyurethane prepolymer.

[0059] A method for preparing the above-mentioned two-component inorganic flame retardant filling retention covering agent, the specific steps of the preparation method are as follows:

[0060] S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100 r / min, mixing and packaging to obtain component A;

[0061] S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 60°C, stirring for 40 minutes, cooling, and packaging at room temperature to obtain component B.

[0062] An application of the two-component inorganic flame retardant filling retention covering agent as described above is to mix component A and component B in a ratio of 1:2 and then quickly spray them to the area that needs to be filled and covered.

[0063] Comparative Example 1

[0064] The method is basically the same as Example 1, except that component A lacks sodium silicate and silica sol, and component B lacks silicone oil. In terms of percentage, component A is composed of 80% deionized water, 7% accelerator, 6% uniform foaming agent, 4% surfactant and 3% flame retardant silicone oil; component B is composed of 71% polyurethane prepolymer, 8% cell opening agent (FLA-320L), 1% catalyst (HGD-DPA) and 20% solvent.

[0065] Comparative Example 2

[0066] It is basically the same as Example 1, except that component A lacks sodium silicate, flame retardant silicone oil and surfactant, component B lacks pore opening aid, and component A lacks uniform foaming agent. In percentage, component A is composed of 67% deionized water, 20% silica sol, 7% accelerator and 6% uniform foaming agent; component B is composed of 77% polyurethane prepolymer, 2% silicone oil, 1% catalyst (HGD-DPA) and 20% solvent.

[0067] Comparative Example 3

[0068] The method is basically the same as Example 1, except that the polyurethane prepolymer preparation method is different. The polyurethane prepolymer preparation method is as follows: 2 parts of resin and 1 part of polyether are vacuumed for 1 hour at a temperature of 150°C and then cooled; 6 parts of 4,4′-dicyclohexylmethane diisocyanate are added at a temperature of 75°C and reacted at a constant temperature for 3 hours to obtain a polyurethane prepolymer.

[0069] The two-component inorganic flame retardant filling retention covering agent obtained in Examples 1-4 and Comparative Examples 1-3 was subjected to a foaming test and a temperature resistance test. The foaming test was performed by mixing component A and component B prepared in each group and spraying the same amount of covering agent in a container of the same specification. The foaming condition was observed during spraying, and the shrinkage condition was observed after curing for three days. The test results are shown in Table 1 below.

[0070] Table 1 Foaming and heat resistance test results

[0071] Group Foaming test Temperature resistance test (℃) Example 1 Large amount of foaming, no shrinkage 1000 Example 2 Large amount of foaming, no shrinkage 1000 Example 3 Large amount of foaming, no shrinkage 1000 Example 4 Large amount of foaming, no shrinkage 1000 Comparative Example 1 Large amount of foaming, micro-shrinkage after foaming 500 Comparative Example 2 Large amount of foaming, micro-shrinkage after foaming 700 Comparative Example 3 Small amount of foaming, micro-shrinkage after foaming 800

[0072] The two-component inorganic flame retardant filling retention covering agent obtained in Examples 1-4 and Comparative Examples 1-3 was tested with reference to AQ / T1090-2020 polymer foaming material for coal mine filling and sealing. The test results are shown in Tables 2 and 3 below.

[0073] Table 2 Basic properties of fillers in each group

[0074]

[0075] Table 3 Compressive strength of each group

[0076]

[0077] The present invention can be implemented in various ways and is not limited to the embodiments described. A person skilled in the art can understand that the present invention can be implemented in other specific ways without changing the technical concept or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary and are not intended to limit the present invention.

Claims

1. A method for preparing a two-component inorganic flame retardant filling retention covering agent, characterized in that: The covering agent comprises component A and component B, wherein: The component A comprises deionized water, sodium silicate, silica sol, accelerator, foaming agent, surfactant and flame retardant silicone oil; The component B comprises polyurethane prepolymer, silicone oil, catalyst and solvent.

2. The two-component inorganic flame retardant filling retention covering agent according to claim 1, characterized in that: The covering agent is a mixture of component A and component B in a weight ratio of 1:1-3.

3. The two-component inorganic flame retardant filling retention covering agent according to claim 2, characterized in that: In percentage, the component A is composed of 30-70% deionized water, 10-30% sodium silicate, 10-30% silica sol, 5-20% accelerator, 1-10% uniform foaming agent, 1-10% surfactant, and 0.1-5% flame retardant silicone oil.

4. The two-component inorganic flame retardant filling retention covering agent according to claim 2, characterized in that: In terms of percentage, the component B is composed of 70-90% of polyurethane prepolymer, 0.1-8% of cell-opening aid, 0.1-5% of silicone oil, 0.1-5% of catalyst and 10-30% of solvent.

5. The two-component inorganic flame retardant filling retention covering agent according to claim 3, characterized in that: The preparation method of the polyurethane prepolymer is as follows: under the conditions of a rotation speed of 600-700 r / min and a temperature of 100-110° C., a hydrophilic polyester resin and a high-activity polyether are evacuated for 1-2 hours and then cooled; at a temperature of 75-80° C., isocyanate is added and reacted at a constant temperature for 3-4 hours to obtain a polyurethane prepolymer.

6. The two-component inorganic flame retardant filling retention covering agent according to claim 5, characterized in that: The polyurethane prepolymer is composed of hydrophilic polyester resin, high-activity polyether and isocyanate in a weight ratio of 2-3:1-2:6-8.

7. The two-component inorganic flame retardant filling retention covering agent according to claim 3, characterized in that: The isocyanate is one or more of 1,3-tolyl diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

8. The two-component inorganic flame retardant filling retention covering agent according to claim 3, characterized in that: The silicone oil is HGD-607H, HGD-8802H or silicone oil 901.

9. A method for preparing the two-component inorganic flame retardant filling retention covering agent as claimed in claims 1-8, characterized in that: The preparation method comprises: S1, preparing component A: taking deionized water and placing it in a reaction kettle, adding sodium silicate, silica sol, accelerator, foaming agent, surfactant, and flame retardant silicone oil at a speed of 100-200 r / min, mixing and packaging to obtain component A; S2, preparing component B: adding silicone oil, catalyst and solvent to the polyurethane prepolymer at a temperature of 55-60°C, stirring for 20-40 minutes, cooling, and packaging at room temperature to obtain component B.

10. An application of the two-component inorganic flame retardant filling retention covering agent as claimed in claims 1-8, characterized in that: Mix component A and component B in a ratio of 1:1-3, quickly mix and spray on the lower corner, upper corner and goaf of the coal mine.

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