Foam extinguishing agent multi-component composition as well as preparation method and application thereof

Abstract

The invention provides a foam extinguishing agent multi-component composition as well as a preparation method and application thereof. The foam extinguishing agent multi-component composition comprises the following components: 31-150 parts of a short-chain fluorocarbon surfactant, 26-52 parts of an organic silicon surfactant, 35-100 parts of a foaming agent, 12-32 parts of a cross-linking agent, 15-20 parts of a gelling agent and 5-20 parts of a foam stabilizer. The range and grade of fire or explosion accidents caused by battery thermal runaway of the lithium iron phosphate battery energy storage system are reduced to the maximum extent, and casualties and property loss are reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of fire extinguishing materials, and more specifically, to a foam fire extinguishing agent multi-component composition and a preparation method and application thereof. Background Art

[0002] Traditional water-based flame retardant products are mainly foaming products, which include the following three components: 1) acid source; 2) carbon source; 3) gas source. The substances used as acid sources mainly include: halides, ammonium phosphate, ammonium polyphosphate, urea phosphate, sulfate, boric acid, etc.; the substances used as gas sources mainly include urea, ammonium bicarbonate, melamine, dicyanamide and its derivatives; the carbon sources mainly include polyols, starch, etc. The biggest problem with traditional water-based flame retardants is that most substances are not water-soluble. For this reason, dispersants and anti-settling agents have to be added, which makes the surface of the treated products opaque and has serious precipitation and crystallization, which greatly affects the surface quality of the products. In addition, some components are highly hygroscopic and have a great impact on the mechanical properties of the products. In addition, some components are non-degradable and bring harm to the ecological environment.

[0003] Battery thermal runaway is an important factor causing safety hazards in lithium iron phosphate batteries. During thermal runaway, the battery generally undergoes high-temperature capacity decay, decomposition of the solid electrolyte interface film, reaction between the negative electrode and the electrolyte, melting of the diaphragm, decomposition of the positive electrode, decomposition of the organic electrolyte, reaction between the negative electrode and the binder, and combustion of the electrolyte.

[0004] When a lithium iron phosphate battery energy storage system catches fire or explodes due to thermal runaway of the battery, if fire-fighting measures can be taken promptly and efficiently, the scope and level of the accident can be minimized, and casualties and property losses can be reduced. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a foam fire extinguishing agent multi-component composition and a preparation method and application thereof.

[0006] In a first aspect, the present invention provides a foam fire extinguishing agent multi-component composition, comprising the following components: 31-150 parts of short-chain fluorocarbon surfactant, 26-52 parts of silicone surfactant, 35-100 parts of foaming agent, Crosslinking agent 12-32 parts, 15-20 parts of gelling agent, 5-20 parts of foam stabilizer.

[0007] Preferably, the following components are included: 55-108 parts of short-chain fluorocarbon surfactant, 33-45 parts of silicone surfactant, 52-78 parts of foaming agent, Cross-linking agent 18-28 parts, 16-18 parts of gelling agent, 12-16 parts of foam stabilizer.

[0008] Preferably, the following components are included: 69-102 parts of short-chain fluorocarbon surfactant, 38-42 parts of organic silicon surfactant, 55-70 parts of foaming agent, Crosslinking agent 20-25 parts, 16-18 parts of gelling agent, 12-16 parts of foam stabilizer.

[0009] Preferably, the following components are included: 55-108 parts of short-chain fluorocarbon surfactant, 33-45 parts of silicone surfactant, 52-78 parts of foaming agent, Cross-linking agent 18-28 parts, 16-18 parts of gelling agent, 12-16 parts of foam stabilizer.

[0010] Preferably, the following components are included: 88 parts of short-chain fluorocarbon surfactant, 40 parts of silicone surfactant, 68 parts of foaming agent, 22 parts of cross-linking agent, 17 parts of gelling agent, 15 parts of foam stabilizer.

[0011] Preferably, the short-chain fluorocarbon surfactant is prepared by perfluorobutylsulfonyl fluoride, N,N-dimethyl-1,3-propylenediamine, 2-bromoethanol, triethylamine, dichloromethane and ethanol. The specific process is: N,N-dimethyl-1,3-propylenediamine and triethylamine are mixed with dichloromethane under a nitrogen atmosphere, and then perfluorobutylsulfonyl fluoride is added in an ice bath, stirred at room temperature, and then ethanol and 2-bromoethanol are added, and stirred at 80-120°C to prepare the short-chain fluorocarbon surfactant.

[0012] Preferably, the gelling agent comprises sodium alginate and fly ash, and the mass ratio of sodium alginate to fly ash is 1-5:2-8.

[0013] Preferably, the organosilicon surfactant is a lactobionic acid-modified organosilicon surfactant, which is synthesized by a two-step reaction using 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, n-octyltrimethoxysilane, tetramethylammonium hydroxide and lactobionic acid as raw materials.

[0014] Preferably, the foaming agent is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium laurate, dodecyltrimethylammonium chloride, sodium fatty alcohol polyoxyethylene ether sulfate, sodium α-olefin sulfonate, and hexadecyltrimethylammonium bromide.

[0015] Preferably, the crosslinking agent is one of N,N-methylenebisacrylamide, 1,4-butanediol diglycidyl ether and polyethylene glycol diglycidyl ether.

[0016] Preferably, the foam stabilizer is one or more of starch, glycerol, polyvinyl alcohol, polyacrylamide, hydroxyethyl cellulose, and carboxymethyl cellulose.

[0017] In a second aspect, the present invention provides a method for preparing a foam fire extinguishing agent multi-component composition, comprising the following steps: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stirring to form solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent, add them to solution A, and stir to form solution B; (3) Mix the foaming agent, gelling agent and foam stabilizer and add them to solution B, stir, introduce into a stirring tank and stir for 20-30 min, adjust the pH value of the reaction liquid to between 6.9 and 7.5, let it stand to defoam, and obtain a multi-component foam fire extinguishing agent composition.

[0018] In a third aspect, the present invention provides an application of a foam fire extinguishing agent multi-component composition, wherein the foam fire extinguishing agent multi-component composition described in claim 1 is used as a fire extinguishing agent in a lithium iron phosphate battery energy storage system, and the foam fire extinguishing agent multi-component composition is uniformly mixed by a resonance atomization foam generating device.

[0019] In summary, the present invention has the following beneficial effects: After the gel foam liquid of the present invention forms foam under the action of the foaming agent, the gelling agent and the cross-linking agent uniformly present in the foam wall undergo a cross-linking reaction to form a gel body containing gas in a three-dimensional network structure. The liquid phase of the gel foam is water, and the gas phase is generally selected from inert gas nitrogen. The gel foam has good plugging performance. When the foam is broken, the gel in the foam continues to play a plugging and covering role, thereby ensuring the durability and effectiveness of the plugging; The foam fire extinguishing agent of the short-chain perfluoroalkyl sulfonic acid surfactant of the present invention can change the polarity and hydrophilicity of the surfactant molecule by introducing specific functional groups, such as amino groups, hydroxyl groups, etc., into the sulfonic acid group or the alkyl end, thereby affecting its dispersion and stability in the foam. Secondly, adjusting the number of ether bonds in the molecule can adjust the overall structure and properties of the surfactant. Adding an appropriate amount of ether bonds can improve its wettability and dispersibility, which helps to improve the stability and wettability of the foam. In the present invention, after the gelling agent and the foaming agent are dissolved and stirred evenly, a cross-linking agent and a foam stabilizer are added, and foam is rapidly formed by mechanical foaming. The gelling agent and the cross-linking agent in the foam wall undergo a cross-linking reaction to form a three-dimensional network space structure constituting the skeleton of the foam, so that the gel foam has stability and strength that are difficult to match with ordinary water-based foams. The invention adopts the fire-proofing material with advantages of gel and three-phase foam, namely the gel foam fire-proofing material, which has excellent coal spontaneous combustion resistance and goaf area air leakage blocking performance.

[0020] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the scope of protection of the present invention. DETAILED DESCRIPTION

[0021] The present invention is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the reactions are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources. Example Example 1

[0022] This embodiment provides a foam fire extinguishing agent multi-component composition, including the following components by weight: Short-chain fluorocarbon surfactant 35g, 28g of silicone surfactant, Foaming agent 40g, Cross-linking agent 24g, Gelling agent 16g, Foam stabilizer 12g.

[0023] Among them, the short-chain fluorocarbon surfactant is prepared by mixing 50g of N,N-dimethyl-1,3-propylenediamine and 50g of triethylamine with 100g of dichloromethane under a nitrogen atmosphere, adding 120g of perfluorobutylsulfonyl fluoride in an ice bath, stirring at room temperature, and then adding 100mL of ethanol and 50mL of 2-bromoethanol, stirring at 120°C to obtain a short-chain fluorocarbon surfactant.

[0024] The gelling agent comprises sodium alginate and fly ash, and the mass ratio of the sodium alginate to the fly ash is 1-5:2-8.

[0025] The organic silicon surfactant is synthesized into a lactobionic amide-modified organic silicon surfactant by using 100 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 52 g of n-octyltrimethoxysilane, 32 g of tetramethylammonium hydroxide and 66 g of lactobionic acid as raw materials through a two-step reaction.

[0026] The foaming agent is sodium laurate.

[0027] The crosslinking agent is N,N-methylenebisacrylamide.

[0028] The foam stabilizer is a mixture of polyacrylamide and hydroxyethyl cellulose in a mass ratio of 1:2.

[0029] A method for preparing a multi-component composition of a foam fire extinguishing agent comprises the following steps: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stirring to form solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent, add them to solution A, and stir to form solution B; (3) Mix the foaming agent, gelling agent and foam stabilizer and add them to solution B, stir, introduce them into a stirring tank and stir for 30 minutes, adjust the pH value of the reaction solution to 6.9, let it stand to defoam, and obtain a multi-component foam fire extinguishing agent composition. Example 2

[0030] This embodiment provides a foam fire extinguishing agent multi-component composition, including the following components by weight: Short-chain fluorocarbon surfactant 45g, 35g of silicone surfactant, Foaming agent 66g, Cross-linking agent 22g, Gelling agent 17g, 15g foam stabilizer.

[0031] Among them, the short-chain fluorocarbon surfactant is prepared by mixing 50g of N,N-dimethyl-1,3-propylenediamine and 50g of triethylamine with 50g of dichloromethane in a nitrogen atmosphere, adding 100g of perfluorobutylsulfonyl fluoride in an ice bath, stirring at room temperature, and then adding 100mL of ethanol and 50mL of 2-bromoethanol, stirring at 120°C to obtain a short-chain fluorocarbon surfactant.

[0032] The gelling agent comprises sodium alginate and fly ash, and the mass ratio of the sodium alginate to the fly ash is 1:3.

[0033] The organic silicon surfactant is synthesized into a lactobionic amide-modified organic silicon surfactant by using 100 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 52 g of n-octyltrimethoxysilane, 32 g of tetramethylammonium hydroxide and 66 g of lactobionic acid as raw materials through a two-step reaction.

[0034] The foaming agent is sodium laurate.

[0035] The crosslinking agent is N,N-methylenebisacrylamide.

[0036] The foam stabilizer is a mixture of polyacrylamide and hydroxyethyl cellulose in a mass ratio of 1:2.

[0037] A method for preparing a multi-component composition of a foam fire extinguishing agent comprises the following steps: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stirring to form solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent, add them to solution A, and stir to form solution B; (3) Mix the foaming agent, gelling agent and foam stabilizer and add them to solution B, stir, introduce them into a stirring tank and stir for 30 minutes, adjust the pH value of the reaction liquid to 7.1, let it stand to defoam, and obtain a multi-component foam fire extinguishing agent composition. Example 3

[0038] This embodiment provides a foam fire extinguishing agent multi-component composition, including the following components by weight: Short-chain fluorocarbon surfactant 120g, 42g of silicone surfactant, Foaming agent 62g, Cross-linking agent 25g, Gelling agent 18g, Foam stabilizer 13g.

[0039] Among them, the short-chain fluorocarbon surfactant is prepared by mixing 50g of N,N-dimethyl-1,3-propylenediamine and 100g of triethylamine with 100g of dichloromethane in a nitrogen atmosphere, adding 120g of perfluorobutylsulfonyl fluoride in an ice bath, stirring at room temperature, and then adding 100mL of ethanol and 50mL of 2-bromoethanol, stirring at 100°C to obtain a short-chain fluorocarbon surfactant.

[0040] The gelling agent comprises sodium alginate and fly ash, and the mass ratio of the sodium alginate to the fly ash is 2:5.

[0041] The organic silicon surfactant is synthesized into a lactobionic amide-modified organic silicon surfactant by using 100 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 52 g of n-octyltrimethoxysilane, 32 g of tetramethylammonium hydroxide and 66 g of lactobionic acid as raw materials through a two-step reaction.

[0042] The foaming agent is sodium laurate.

[0043] The crosslinking agent is N,N-methylenebisacrylamide.

[0044] The foam stabilizer is a mixture of polyacrylamide and hydroxyethyl cellulose in a mass ratio of 1:3.

[0045] A method for preparing a multi-component composition of a foam fire extinguishing agent comprises the following steps: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stirring to form solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent, add them to solution A, and stir to form solution B; (3) Mix the foaming agent, gelling agent and foam stabilizer and add them to solution B, stir, introduce them into a stirring tank and stir for 30 minutes, adjust the pH value of the reaction solution to 7.2, let it stand to defoam, and obtain a multi-component foam fire extinguishing agent composition. Example 4

[0046] This embodiment provides a foam fire extinguishing agent multi-component composition, including the following components by weight: Short-chain fluorocarbon surfactant 150g, Silicone surfactant 52g, Foaming agent 100g, Cross-linking agent 32g, Gelling agent 20g, 20g foam stabilizer.

[0047] Among them, the short-chain fluorocarbon surfactant is prepared by mixing 50g of N,N-dimethyl-1,3-propylenediamine and 50g of triethylamine with 100g of dichloromethane under a nitrogen atmosphere, adding 150g of perfluorobutylsulfonyl fluoride in an ice bath, stirring at room temperature, and then adding 100mL of ethanol and 50mL of 2-bromoethanol, stirring at 120°C to obtain a short-chain fluorocarbon surfactant.

[0048] The gelling agent comprises sodium alginate and fly ash, and the mass ratio of the sodium alginate to the fly ash is 5:8.

[0049] The organic silicon surfactant is synthesized into a lactobionic amide-modified organic silicon surfactant by using 100 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 52 g of n-octyltrimethoxysilane, 32 g of tetramethylammonium hydroxide and 66 g of lactobionic acid as raw materials through a two-step reaction.

[0050] The foaming agent is sodium laurate.

[0051] The crosslinking agent is N,N-methylenebisacrylamide.

[0052] The foam stabilizer is a mixture of polyacrylamide and hydroxyethyl cellulose in a mass ratio of 2:1.

[0053] A method for preparing a multi-component composition of a foam fire extinguishing agent comprises the following steps: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stirring to form solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent, add them to solution A, and stir to form solution B; (3) Mix the foaming agent, gelling agent and foam stabilizer and add them to solution B, stir, introduce them into a stirring tank and stir for 30 minutes, adjust the pH value of the reaction solution to 7.5, let it stand to defoam, and obtain a multi-component foam fire extinguishing agent composition.

[0054] Comparative Example 1 Compared with Example 1, the difference is that no short-chain fluorocarbon surfactant is added, and the other ingredients are the same.

[0055] Comparative Example 2 Compared with Example 1, the difference is that the short-chain fluorocarbon surfactant is replaced by perfluorooctane sulfonic acid, and the other ingredients are the same.

[0056] For this example 3 Compared with Example 1, the difference is that no silicone surfactant is added, and other ingredients are the same.

[0057] Comparative Example 4 Compared with Example 1, the difference is that no cross-linking agent is added, and other components are the same.

[0058] Comparative Example 5 Compared with Example 1, the difference is that no gelling agent is added, and the other ingredients are the same.

[0059] Performance Testing Table 1 Performance test results From the above performance test results, it can be seen that the foam fire extinguishing agent multi-component composition prepared in Examples 1-4, especially the fire extinguishing agent in Example 2, has increased surface tension and decreased foaming multiple, but the comprehensive performance of better fire extinguishing performance and anti-burning performance is the most outstanding. This is mainly because the foam fire extinguishing agent of the short-chain perfluoroalkyl sulfonic acid surfactant can change the polarity and hydrophilicity of the surfactant molecule by introducing specific functional groups, such as amino group, hydroxyl group, etc., into the sulfonic acid group or the alkyl end, thereby affecting its dispersion and stability in the foam.

[0060] However, because the necessary technical solutions were not adopted in Comparative Examples 1-5, the corresponding performance tests were significantly worse than those of Examples 1-4. In Comparative Example 1, no short-chain fluorocarbon surfactant was added, and it can be seen that the foaming multiple of the multi-component composition of the foam fire extinguishing agent decreased, proving that the short-chain perfluoroalkyl sulfonic acid surfactant has an important influence on the fire extinguishing effect. In Comparative Example 2, the short-chain fluorocarbon surfactant was replaced with perfluorooctane sulfonic acid. From the results, it can be seen that the perfluorooctane sulfonic acid was further affected, resulting in a decrease in the foaming multiple. After the gelling agent and the foaming agent were dissolved and stirred evenly, a cross-linking agent and a foam stabilizer were added, and foam was quickly formed by mechanical foaming. The gelling agent and the cross-linking agent in the foam wall underwent a cross-linking reaction to form a three-dimensional network space structure to form the skeleton of the foam, so that the gel foam has stability and strength that are difficult to match with ordinary water-based foams. The above experimental results further prove the importance of the technical solution defined in the present invention for its technical effect.

[0061] The above is only an exemplary embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A foam fire extinguishing agent multicomponent composition, characterized in that: The invention comprises the following components: 31-150 parts of a short-chain fluorocarbon surfactant, 26-52 parts of an organic silicon surfactant, 35-100 parts of a foaming agent, 12-32 parts of a cross-linking agent, 15-20 parts of a gelling agent and 5-20 parts of a foam stabilizing agent.

2. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The invention comprises the following components: 55-108 parts of a short-chain fluorocarbon surfactant, 33-45 parts of an organic silicon surfactant, 52-78 parts of a foaming agent, 18-28 parts of a cross-linking agent, 16-18 parts of a gelling agent and 12-16 parts of a foam stabilizer.

3. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The short-chain fluorocarbon surfactant is prepared from perfluorobutylsulfonyl fluoride, N,N-dimethyl-1,3-propylenediamine, 2-bromoethanol, triethylamine, dichloromethane and ethanol. The specific process is: N,N-dimethyl-1,3-propylenediamine and triethylamine are mixed with dichloromethane under a nitrogen atmosphere, and then perfluorobutylsulfonyl fluoride is added in an ice bath, and stirred at room temperature, and then ethanol and 2-bromoethanol are added, and stirred at 80-120°C to prepare the short-chain fluorocarbon surfactant.

4. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The gelling agent comprises sodium alginate and fly ash, and the mass ratio of the sodium alginate to the fly ash is 1-5:2-8.

5. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The organosilicon surfactant is a lactobionic acid modified organosilicon surfactant, which is synthesized by a two-step reaction using 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, n-octyltrimethoxysilane, tetramethylammonium hydroxide and lactobionic acid as raw materials.

6. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The foaming agent is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium laurate, dodecyltrimethylammonium chloride, sodium fatty alcohol polyoxyethylene ether sulfate, sodium α-olefin sulfonate, and hexadecyltrimethylammonium bromide.

7. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The cross-linking agent is one of N,N-methylenebisacrylamide, 1,4-butanediol diglycidyl ether and polyethylene glycol diglycidyl ether.

8. The foam fire extinguishing agent multi-component composition according to claim 1, characterized in that: The foam stabilizer is one or more of starch, glycerol, polyvinyl alcohol, polyacrylamide, hydroxyethyl cellulose and carboxymethyl cellulose.

9. The method for preparing the multi-component composition of a foam fire extinguishing agent according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Weigh a short-chain fluorocarbon surfactant and add it to water, stir to form a solution A; (2) Weigh an organosilicon surfactant and a cross-linking agent and add them to solution A, stir to form a solution B; (3) Mix a foaming agent, a gelling agent and a foam stabilizer and add them to solution B, stir, introduce it into a stirring tank and stir for 20-30 minutes, adjust the pH value of the reaction solution to between 6.9 and 7.5, let it stand to defoam, and obtain a foam fire extinguishing agent multi-component composition.

10. An application of a foam fire extinguishing agent multi-component composition, wherein the foam fire extinguishing agent multi-component composition according to claim 1 is used as a fire extinguishing agent in a lithium iron phosphate battery energy storage system, and the foam fire extinguishing agent multi-component composition is uniformly mixed by a resonance atomization foam generating device.