Solubility-resistant aqueous film-forming foam extinguishing agent and preparation method thereof

Abstract

The invention relates to the technical field of fire extinguishing agents, and discloses an anti-soluble aqueous film-forming foam fire extinguishing agent and a preparation method thereof.The anti-soluble aqueous film-forming foam fire extinguishing agent comprises a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl modified organosilicon surfactant, a foam stabilizer, a modified flame retardant, a cosolvent and a pH regulator; the carboxyl modified organic silicon surfactant is obtained by modifying a hydroxyl-containing organic silicon surfactant by using maleic anhydride; the modified flame retardant is obtained by carrying out surface modification treatment on a flame retardant by utilizing a silane coupling agent. According to the invention, the short-chain fluorocarbon surfactant and the carboxyl modified organosilicon surfactant are compounded, and the hydrocarbon surfactant, the foam stabilizer, the cosolvent, the modified flame retardant and the pH regulator are added, so that the synergistic interaction among the components is fully exerted; and the anti-soluble aqueous film-forming foam extinguishing agent which is high in surface activity, strong in foaming and foam stabilizing capability and excellent in fire extinguishing performance and does not contain PFOS is obtained.

Description

Technical Field

[0001] The invention relates to the technical field of fire extinguishing agents, and in particular to an anti-soluble aqueous film-forming foam fire extinguishing agent and a preparation method thereof. Background Art

[0002] Aqueous film-forming foam fire extinguishing agent, also known as "light water" foam fire extinguishing agent, refers to a fire extinguishing agent that can form a layer of water film on the fuel surface during the fire extinguishing process. This water film can not only isolate the fuel surface from oxygen, but also cool the fuel surface; at the same time, the liquid precipitated from the foam evaporates into water vapor at high temperature, diluting the oxygen concentration above the flammable liquid. Due to the synergistic fire extinguishing effect of water film and foam, aqueous film-forming foam is particularly suitable for large-scale flammable liquid fires. It is widely used in large ships, offshore oil and gas drilling platforms, and oil tank areas.

[0003] Perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonic acid (PFOA) are widely used in aqueous film-forming foam fire extinguishing agents (AFFF) due to their high surface activity, high chemical stability, and high thermal stability. However, because PFOS and PFOA are difficult to degrade and pose serious ecological hazards and environmental pollution problems, countries around the world have formulated increasingly stringent environmental regulations to restrict the use of PFOS. In addition, polar solvents are widely used in daily life and industrial production, and ordinary aqueous film-forming foam fire extinguishing agents are difficult to extinguish polar solvent fires.

[0004] Therefore, it is of great research significance to strengthen the control of PFOS and develop efficient and environmentally friendly PFOS-free anti-soluble aqueous film-forming foam fire extinguishing agents. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that the aqueous film-forming foam fire extinguishing agent in the prior art contains highly polluting raw material components such as PFOS and PFOA, and is difficult to extinguish polar solvent fires, and to provide an anti-soluble aqueous film-forming foam fire extinguishing agent and a preparation method thereof.

[0006] In order to achieve the above-mentioned object, the present invention provides an anti-soluble aqueous film-forming foam fire extinguishing agent on one hand, wherein the anti-soluble aqueous film-forming foam fire extinguishing agent contains: a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified silicone surfactant, a foam stabilizer, a modified flame retardant, a cosolvent and a pH regulator;

[0007] Wherein, the carboxyl-modified organosilicon surfactant is obtained by modifying a hydroxyl-containing organosilicon surfactant using maleic anhydride;

[0008] The modified flame retardant is obtained by surface-modifying the flame retardant with a silane coupling agent, and the flame retardant is selected from any one of ammonium polyphosphate, polyvinyl alcohol ammonium phosphate, tetra-n-butyl ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.

[0009] Preferably, the carboxyl-modified silicone surfactant is prepared according to the following process:

[0010] The hydroxyl-containing organosilicon surfactant, maleic anhydride and organic solvent are mixed, reacted at 60-90° C. for 2-8 hours, and then cooled and purified.

[0011] Preferably, the weight ratio of the organic silicon surfactant to maleic anhydride is 1:0.5-3.

[0012] Preferably, the hydroxyl-containing organosilicon surfactant is a hydroxyl polyether-modified organosiloxane.

[0013] Preferably, the ratio of the weight of the organic solvent to the total weight of the hydroxyl-containing organosilicon surfactant and maleic anhydride is 10-40:100.

[0014] Preferably, the organic solvent is selected from any one of isopropanol, n-propanol, propylene glycol, 1,3-butanediol and pentanediol.

[0015] Preferably, the modified flame retardant is prepared according to the following process:

[0016] The flame retardant is mixed with anhydrous ethanol, and then a silane coupling agent is added, and the mixture is reacted at 40 to 70° C. for 8 to 24 hours, followed by centrifugation and washing.

[0017] Preferably, the silane coupling agent is selected from one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-(2-methoxyethoxy)-silane, γ-glycidyloxypropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0018] Preferably, the weight ratio of the flame retardant to the silane coupling agent is 1:0.02-1.

[0019] Preferably, the weight ratio of the flame retardant to anhydrous ethanol is 1:1-10.

[0020] Preferably, the hydrocarbon surfactant is selected from at least two of anionic hydrocarbon surfactants, amphoteric hydrocarbon surfactants and nonionic surfactants.

[0021] Preferably, the anionic hydrocarbon surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium α-olefin sulfonate.

[0022] Preferably, the amphoteric hydrocarbon surfactant is selected from one or more of cocamidopropyl betaine, N-dodecyl dimethyl betaine and 2-undecyl-N-acetoxy-N(2-hydroxyethyl)imidazoline.

[0023] Preferably, the nonionic hydrocarbon surfactant is an alkyl glycoside.

[0024] Preferably, the short-chain fluorocarbon surfactant is selected from one or more of perfluoroalkylamine oxides, perfluoroalkyl polyoxyethylene ethers, perfluoroalkyl ether betaines, and hexafluoropropylene oxide trimer quaternary ammonium salts.

[0025] Preferably, the foam stabilizer is selected from one or more of xanthan gum, sodium carboxymethyl cellulose, polyethylene glycol and coconut oil diethanolamine.

[0026] Preferably, the co-solvent is selected from one or more of ethylene glycol, diethylene glycol butyl ether and isobutyl alcohol.

[0027] Preferably, the pH adjuster is selected from one or more of citric acid, lactic acid, tartaric acid, malic acid, phosphoric acid and acetic acid.

[0028] Preferably, the anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5wt% of short-chain fluorocarbon surfactant, 10-30wt% of hydrocarbon surfactant, 0.5-2wt% of carboxyl-modified silicone surfactant, 0.1-2wt% of foam stabilizer, 0.5-5wt% of modified flame retardant, 1-5wt% of cosolvent, 0.1-8wt% of pH adjuster, and 50-80wt% of water.

[0029] Preferably, the anti-soluble aqueous film-forming foam fire extinguishing agent further contains one or more of an antifreeze agent, a corrosion inhibitor, a chelating agent and a preservative.

[0030] Preferably, the antifreeze agent is selected from one or more of urea, ethylene glycol and propanol.

[0031] Preferably, the corrosion inhibitor is selected from one or more of sodium chromate, potassium chromate, sodium tripolyphosphate and sodium hexametaphosphate.

[0032] Preferably, the chelating agent is disodium ethylenediaminetetraacetate.

[0033] Preferably, the preservative is selected from one or more of sodium benzoate, potassium sorbate and methyl paraben.

[0034] Preferably, the anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5wt% of short-chain fluorocarbon surfactant, 10-30wt% of hydrocarbon surfactant, 0.5-2wt% of carboxyl-modified silicone surfactant, 0.1-2wt% of foam stabilizer, 0.5-5wt% of flame retardant, 1-5wt% of cosolvent, 0.1-8wt% of pH regulator, 2-10wt% of antifreeze agent, 0.1-1wt% of corrosion inhibitor, 0.1-1wt% of chelating agent, 0.1-1wt% of preservative, and 50-80wt% of water.

[0035] The second aspect of the present invention provides a method for preparing the anti-soluble aqueous film-forming foam fire extinguishing agent as described above, the method comprising: mixing a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified silicone surfactant, a foam stabilizer, a modified flame retardant, a cosolvent, a pH adjuster and water.

[0036] Preferably, the method comprises the following steps:

[0037] (1) mixing a hydrocarbon surfactant, a short-chain fluorocarbon surfactant, a carboxyl-modified silicone surfactant, a modified flame retardant, and water to obtain a first solution;

[0038] (2) mixing a foam stabilizer and a co-solvent to obtain a second solution;

[0039] (3) Mixing the first solution, the second solution and the pH adjuster.

[0040] In the technical scheme provided by the present invention, the organosilicon surfactant is modified by using maleic anhydride, thereby improving the water solubility of the organosilicon surfactant without affecting its surface activity; by introducing a silane coupling agent on the surface of a traditional flame retardant, the surface hydrophilic and hydrophobic groups can effectively improve the dispersion stability of the foam fire extinguishing agent and the wetting ability on the surface of flammable substances, thereby improving the flame retardant effect and fire extinguishing performance; at the same time, a short-chain fluorocarbon surfactant is compounded with a carboxyl-modified organosilicon surfactant, and a hydrocarbon surfactant, a foam stabilizer, a cosolvent, a modified flame retardant and a pH adjuster are added, so as to give full play to the synergistic effect of the various components, thereby obtaining a PFOS-free, anti-soluble aqueous film-forming foam fire extinguishing agent with high surface activity, strong foaming and stabilizing ability and excellent fire extinguishing performance.

[0041] The anti-soluble aqueous film-forming foam fire extinguishing agent provided by the present invention can be widely used in A and B class fires, and can especially effectively extinguish B class fuel fires mixed with oils and polar solvents. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is the UV-visible absorption spectrum of the carboxyl-modified organic silicon surfactant (a) and the hydroxyl polyether-modified organic silicon oxane (b) in Example 1 of the present invention. DETAILED DESCRIPTION

[0043] The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the present invention, and is not used to limit the present invention.

[0044] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0045] The present invention provides an anti-soluble aqueous film-forming foam fire extinguishing agent, which contains: a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified organic silicon surfactant, a foam stabilizer, a modified flame retardant, a cosolvent and a pH regulator;

[0046] The carboxyl-modified organic silicon surfactant is obtained by modifying a hydroxyl-containing organic silicon surfactant with maleic anhydride.

[0047] Organosilicon surfactants have silane groups and siloxane groups with strong hydrophobic effects, which make their organosilicon surfactants have high surface activity, thereby greatly reducing the surface tension of water. In addition, organosilicon surfactants also have obvious advantages in terms of stability, wettability, and spreadability, but their water solubility is poor, which limits their application. At present, the water solubility of organosilicon surfactants is improved by premixing with organic solvents, which will lead to the use of a large amount of organic solvents, and the use of a large amount of organic solvents is not conducive to efficient fire extinguishing, and will increase production costs and reduce environmental protection. In the present invention, the carboxyl-modified organosilicon surfactant is obtained by modifying the hydroxyl-containing organosilicon surfactant using maleic anhydride (maleic anhydride), so that not only the water solubility of the organosilicon surfactant is improved, but also its surface activity is not affected.

[0048] In a preferred embodiment, the carboxyl-modified silicone surfactant is prepared according to the following process: a hydroxyl-containing silicone surfactant, maleic anhydride and an organic solvent are mixed and reacted, and then cooled and purified. The reaction temperature is 60 to 90°C, and specifically, for example, it can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C; the reaction time is 2 to 8h, and specifically, for example, it can be 2h, 2.5h, 3h, 4h, 5h, 6h, 7h or 8h. In the present invention, the purification is carried out by vacuum distillation.

[0049] In the present invention, the weight ratio of the organic silicon surfactant to maleic anhydride is 1:0.5-3.

[0050] In a preferred embodiment, the organic solvent is selected from any one of isopropanol, n-propanol, propylene glycol, 1,3-butanediol and pentanediol.

[0051] In the present invention, the weight ratio of the organic solvent to the total weight of the hydroxyl-containing silicone surfactant and maleic anhydride is 10 to 40:100, specifically, for example, 10:100, 15:100, 20:100, 22:100, 25:100, 30:100, 33:100, 35:100 or 40:100.

[0052] In a preferred embodiment, the hydroxyl-containing organosilicon surfactant is a hydroxyl-containing polyether-modified organosiloxane.

[0053] The addition of flame retardant can play a certain role in blocking the spread of fire and play an effective auxiliary role in fire extinguishing. In order to achieve a better flame retardant effect, in the present invention, a modified flame retardant is added, and the modified flame retardant is obtained by surface modification of the flame retardant using a silane coupling agent, and the flame retardant is selected from any one of ammonium polyphosphate, polyvinyl alcohol ammonium phosphate, tetra-n-butyl ammonium phosphate, diammonium hydrogen phosphate and diammonium dihydrogen phosphate.

[0054] The present invention introduces a silane coupling agent on the surface of a conventional nitrogen-phosphorus-containing flame retardant so that the flame retardant surface has hydrophilic and hydrophobic groups, thereby effectively improving the dispersion stability of the foam fire extinguishing agent and the wetting ability on the surface of flammable substances. When used to extinguish a fire during combustion, the modified flame retardant is decomposed by heat to release non-combustible gases such as ammonia and water vapor, which can effectively reduce the oxygen concentration in the environment; and when the modified flame retardant is decomposed by heat, PO· free radicals are generated in the gas phase, and the PO· free radicals can capture high-energy free radicals HO· and H· in the flame area, thereby inhibiting the chain combustion reaction and playing a role in chemically inhibiting fire extinguishing; in addition, the generated phosphine not only consumes oxygen during the combustion process, but also the phosphoric acid and hypophosphorous acid generated by the oxidation of phosphine will cover the surface of the flammable substance in the form of a viscous semi-solid substance, further promoting the dehydration of the surface of the flammable substance to generate carbonized products, thereby exerting a flame retardant effect.

[0055] In a preferred embodiment, the silane coupling agent is selected from one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-(2-methoxyethoxy)-silane, γ-glycidyloxypropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0056] In a preferred embodiment, the modified flame retardant is prepared according to the following process: the flame retardant is mixed with anhydrous ethanol, and then a silane coupling agent is added, and the mixture is reacted at 40 to 70° C. for 8 to 24 hours, followed by centrifugation and washing.

[0057] Further preferably, the weight ratio of the flame retardant to the silane coupling agent is 1:0.02-1.

[0058] Further preferably, the weight ratio of the flame retardant to anhydrous ethanol is 1:1-10.

[0059] Hydrocarbon surfactants are environmentally friendly and have good foaming properties, and are mainly used as foaming components of fire extinguishing agents. In order to make the foaming properties of the hydrocarbon surfactants better, in the present invention, the hydrocarbon surfactants are selected from at least two of anionic hydrocarbon surfactants, amphoteric hydrocarbon surfactants and nonionic surfactants.

[0060] In a preferred embodiment, the anionic hydrocarbon surfactant may be one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium α-olefin sulfonate.

[0061] In a preferred embodiment, the amphoteric hydrocarbon surfactant may be one or more of cocamidopropyl betaine, N-dodecyl dimethyl betaine and 2-undecyl-N-acetoxy-N(2-hydroxyethyl)imidazoline.

[0062] In a preferred embodiment, the nonionic hydrocarbon surfactant is an alkyl glycoside.

[0063] The present invention does not limit the specific type of the short-chain fluorocarbon surfactant, as long as it is a fluorocarbon surfactant with a fluorocarbon chain length of ≤ 6. In a preferred embodiment, the short-chain fluorocarbon surfactant is selected from one or more of perfluoroalkylamine oxide, perfluoroalkyl polyoxyethylene ether, perfluoroalkyl ether betaine, and hexafluoropropylene oxide trimer quaternary ammonium salt.

[0064] The foam stabilizer can effectively increase the viscosity of the solution, and the adjacent surfactant molecules in the solution can form hydrogen bonds, slowing down the loss rate of the foam wall, thereby enhancing the stability of the foam and improving the anti-burning performance. The present invention does not limit the specific type of the foam stabilizer. In a specific embodiment, the foam stabilizer is selected from one or more of xanthan gum, sodium carboxymethyl cellulose, polyethylene glycol and coconut oil diethanolamine.

[0065] In the present invention, the co-solvent is selected from one or more of ethylene glycol, diethylene glycol butyl ether and isobutyl alcohol, so that it can not only play a dissolving effect, but also reduce the freezing point of the fire extinguishing agent product.

[0066] In the present invention, the pH adjuster is selected from one or more of citric acid, lactic acid, tartaric acid, malic acid, phosphoric acid and acetic acid, preferably citric acid, and most preferably a citric acid aqueous solution with a mass concentration of 40%.

[0067] In a preferred embodiment, the anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5wt% of a short-chain fluorocarbon surfactant, 10-30wt% of a hydrocarbon surfactant, 0.5-2wt% of a carboxyl-modified silicone surfactant, 0.1-2wt% of a foam stabilizer, 0.5-5wt% of a modified flame retardant, 1-5wt% of a cosolvent and 0.1-8wt% of a pH adjuster, and 50-80wt% of water.

[0068] In order to make the comprehensive performance of the anti-soluble aqueous film-forming foam fire extinguishing agent better, in the present invention, the anti-soluble aqueous film-forming foam fire extinguishing agent also contains one or more of an antifreeze agent, a corrosion inhibitor, a chelating agent and a preservative.

[0069] In a preferred embodiment, the antifreeze agent is selected from one or more of urea, ethylene glycol and propanol, preferably urea. Urea can not only reduce the freezing point of the fire extinguishing agent product, but also improve the burning resistance of the foam fire extinguishing agent.

[0070] The present invention does not limit the specific type of the corrosion inhibitor, for example, it can be chromate, polyethylene, polyphosphate or organophosphorus corrosion inhibitor. Preferably, the corrosion inhibitor is selected from one or more of sodium chromate, potassium chromate, sodium tripolyphosphate and sodium hexametaphosphate.

[0071] In order to reduce the cost of the chelating agent and make the raw materials readily available, in the present invention, the chelating agent is disodium ethylenediaminetetraacetate.

[0072] In the present invention, the preservative is selected from one or more of sodium benzoate, potassium sorbate and methyl parahydroxybenzoate.

[0073] In a preferred embodiment, the anti-soluble aqueous film-forming foam fire extinguishing agent contains a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified silicone surfactant, a foam stabilizer, a cosolvent, a pH regulator, an antifreeze agent, a corrosion inhibitor, a chelating agent, a flame retardant, a preservative and water.

[0074] Further preferably, the anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5wt% of short-chain fluorocarbon surfactant, 10-30wt% of hydrocarbon surfactant, 0.5-2wt% of carboxyl-modified silicone surfactant, 0.1-2wt% of foam stabilizer, 0.5-5wt% of modified flame retardant, 1-5wt% of cosolvent, 0.1-8wt% of pH regulator, 2-10wt% of antifreeze agent, 0.1-1wt% of corrosion inhibitor, 0.1-1wt% of chelating agent and 0.1-3wt% of preservative, and 50-80wt% of water.

[0075] In the present invention, firstly, based on a polyether silicone surfactant, a hydrophilic group carboxyl is introduced from the molecular structure, and the silicone surfactant is chemically modified to obtain a carboxyl-modified silicone surfactant with high surface activity, strong hydrophilicity and strong foam stabilizing ability; by introducing a silane coupling agent on the surface of a traditional flame retardant, the surface of the flame retardant has hydrophilic and hydrophobic groups, thereby effectively improving the dispersion stability of the foam fire extinguishing agent and the wetting ability of the surface of flammable substances, so that the flame retardant effect of the obtained modified flame retardant is good; then the carboxyl-modified silicone surfactant is compounded with a short-chain fluorocarbon surfactant and a hydrocarbon surfactant for use, and raw material components such as a hydrocarbon surfactant, a modified flame retardant, a foam stabilizer, a cosolvent and a pH adjuster are added, and the synergistic effect between the multiple components is utilized to obtain an anti-solubility water-forming film-forming foam fire extinguishing agent with excellent fire extinguishing performance and strong anti-burning ability.

[0076] The anti-soluble aqueous film-forming foam fire extinguishing agent provided by the present invention can not only avoid the use of PFOS, but also reduce the amount of short-chain fluorocarbon surfactants and co-solvents (organic solvents) while ensuring fire extinguishing performance and anti-burning ability, thereby making the fire extinguishing agent more cost-effective and more environmentally friendly. In addition, the anti-soluble aqueous film-forming foam fire extinguishing agent can effectively extinguish a variety of Class B fuel fires such as polar solvents and non-polar solvents.

[0077] In the present invention, the anti-soluble aqueous film-forming foam fire extinguishing agent needs to be mixed with water to prepare a foam solution for fire extinguishing. Further preferably, the content of the anti-soluble aqueous film-forming foam fire extinguishing agent in the foam solution is 3-8wt%, and most preferably 6wt%.

[0078] The present invention does not limit the specific preparation steps of the anti-solubility aqueous film-forming foam fire extinguishing agent, as long as the raw materials are mixed evenly.

[0079] The present invention also proposes a method for preparing the anti-soluble aqueous film-forming foam fire extinguishing agent as described above, the method comprising: mixing a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified silicone surfactant, a foam stabilizer, a modified flame retardant, a cosolvent, a pH adjuster and water.

[0080] In a preferred embodiment, the method comprises the following steps:

[0081] (1) mixing a hydrocarbon surfactant, a short-chain fluorocarbon surfactant, a carboxyl-modified silicone surfactant, a modified flame retardant, and water to obtain a first solution;

[0082] (2) mixing a foam stabilizer and a co-solvent to obtain a second solution;

[0083] (3) Mixing the first solution, the second solution and the pH adjuster.

[0084] It should be noted that, in other specific embodiments, step (2) may also be performed before step (1), or step (1) and step (2) may be performed simultaneously. It is only necessary to complete the preparation of the first solution and the second solution respectively before the next operation (i.e., before step (3)).

[0085] In the method of the present invention, preferably, the anti-soluble aqueous film-forming foam fire extinguishing agent further contains one or more of an antifreeze agent, a corrosion inhibitor, a chelating agent and a preservative. The present invention does not limit the specific steps of adding the above components, which can be added in step (1) or in step (3).

[0086] In a specific embodiment, the above components are added in step (1). In specific implementation, step (1) includes:

[0087] Under stirring, a hydrocarbon surfactant is mixed with a portion of water, and then a short-chain fluorocarbon surfactant and a carboxyl-modified silicone surfactant are added to obtain a mixed solution A;

[0088] The antifreeze agent, the corrosion inhibitor, the chelating agent, the modified flame retardant and the preservative are mixed with the remaining water and stirred to obtain a mixed solution B;

[0089] The mixed solution A and the mixed solution B are mixed and stirred.

[0090] The present invention will be described in detail below by way of examples, but the protection scope of the present invention is not limited thereto. The raw materials in the following examples are all commercially available unless otherwise specified.

[0091] In the following embodiments, perfluoroalkylamine oxides were purchased from DuPont, model FS-50 and 1157; hydroxy polyether modified organosiloxane was purchased from Zhejiang Runhe Silicone New Material Co., Ltd., model RH-288; maleic anhydride was purchased from Sane Chemical Technology (Shanghai) Co., Ltd.; cocamidopropyl betaine was purchased from Qingdao Huayuan Polymer Co., Ltd., model CAB-35; alkyl glycoside was purchased from Qingdao Huayuan Polymer Co., Ltd., model APG0810; sodium dodecyl sulfate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., batch number C2116183; ammonium polyphosphate and 3-aminopropyltriethoxysilane were purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0092] In the following examples, the pH value determination method is carried out with reference to 5.5 "pH value" in GB 15308-2006 "Foam Fire Extinguishing Agents".

[0093] Example 1

[0094] This example is used to illustrate the anti-soluble aqueous film-forming foam fire extinguishing agent and its preparation method of the present invention.

[0095] Insoluble aqueous film-forming foam fire extinguishing agent: short-chain fluorocarbon surfactant (formed by FS-50 and 1157 fluorocarbon surfactant in a weight ratio of 1:1) 2g, hydrocarbon surfactant (sodium dodecyl sulfate, cocamidopropyl betaine and alkyl glucoside) 20g, carboxyl modified silicone surfactant 1g, foam stabilizer (formed by xanthan gum and coconut oil diethanolamine in a weight ratio of 3:2) 0.5g, modified flame retardant 4g, cosolvent (butyl diethylene glycol) 4g, pH adjuster (20wt% citric acid aqueous solution) 3g, antifreeze agent (urea) 5g, corrosion inhibitor (sodium tripolyphosphate) 0.3g, chelating agent (disodium ethylenediaminetetraacetic acid) 0.5g, preservative (sodium benzoate) 1g and deionized water 58.7g;

[0096] The weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 4:5:7;

[0097] Preparation of the carboxyl-modified silicone surfactant: under stirring, hydroxy polyether-modified silicone siloxane and maleic anhydride are added to isopropanol in a weight ratio of 1:1.2, and reacted at 80°C for 4 hours to obtain a reaction solution, wherein the ratio of the weight of isopropanol to the total weight of the hydroxy polyether-modified silicone siloxane and maleic anhydride is 20:100; the reaction solution is cooled to room temperature, and then the solution is transferred to a rotary evaporator, and the product is purified and recovered by reduced pressure distillation to obtain a carboxyl-modified silicone surfactant.

[0098] Preparation of the modified flame retardant: 10g of ammonium polyphosphate and 50g of anhydrous ethanol were stirred and mixed, and magnetic stirring was performed; then 0.8g of 3-aminopropyltriethoxysilane was added and mixed, and the mixture was reacted at 60°C for 12h, and then centrifuged and washed.

[0099] Preparation of anti-soluble aqueous film-forming foam fire extinguishing agent:

[0100] (1) dissolving sodium dodecyl sulfate in 20 g of deionized water and stirring evenly, then adding cocamide betaine and alkyl glucoside, and then adding fluorocarbon surfactant and carboxyl-modified silicone surfactant to obtain a mixed solution A; mixing an antifreeze agent, a corrosion inhibitor, a chelating agent, a modified flame retardant, and a preservative with the remaining deionized water and stirring evenly to obtain a mixed solution B; adding the mixed solution B to the mixed solution A and stirring for 15 minutes to obtain a first solution;

[0101] (2) adding a foam stabilizer to the co-solvent and stirring the mixture to obtain a second solution;

[0102] (3) Add the second solution to the first solution and stir evenly, then add the pH adjuster and continue stirring for 30 minutes to obtain an anti-soluble aqueous film-forming foam fire extinguishing agent.

[0103] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0104] Example 2

[0105] This example is used to illustrate the anti-soluble aqueous film-forming foam fire extinguishing agent and its preparation method of the present invention.

[0106] The method described in Example 1 is used for implementation, except that the anti-soluble aqueous film-forming foam fire extinguishing agent includes: 1.5 g of short-chain fluorocarbon surfactant (FS-50), 22 g of hydrocarbon surfactant (sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside), 1 g of carboxyl-modified silicone surfactant, 0.7 g of foam stabilizer (formed by compounding xanthan gum and polyethylene glycol in a weight ratio of 2:5), 4 g of modified flame retardant, 2 g of cosolvent (butyl diethylene glycol), 1 g of pH regulator (20 wt % citric acid aqueous solution), 5 g of antifreeze agent (urea), 0.3 g of corrosion inhibitor (sodium tripolyphosphate), 0.15 g of chelating agent (disodium ethylenediaminetetraacetic acid), 1 g of preservative (sodium benzoate) and 61.35 g of deionized water; wherein the weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 4:9:9;

[0107] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0108] Example 3

[0109] The method described in Example 1 was used for implementation, except that the anti-soluble aqueous film-forming foam fire extinguishing agent: 2 g of short-chain fluorocarbon surfactant (formed by compounding FS-50 and 1157 fluorocarbon surfactants in a weight ratio of 1:1), 18 g of hydrocarbon surfactant (sodium dodecyl sulfate, cocamidopropyl betaine and alkyl glucoside), 1.2 g of carboxyl-modified silicone surfactant, and 1.2 g of foam stabilizer (formed by compounding xanthan gum and coconut oil diethanolamine in a weight ratio of 3:2). The invention discloses a compound preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following: a first-class preparation method comprising the following:

[0110] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0111] Example 4

[0112] Anti-soluble aqueous film-forming foam fire extinguishing agent: short-chain fluorocarbon surfactant (1157 fluorocarbon surfactant) 1g, hydrocarbon surfactant (sodium dodecyl sulfate and alkyl glycoside) 22g, carboxyl modified silicone surfactant 1.5g, foam stabilizer (xanthan gum) 2g, modified flame retardant 3g, cosolvent (diethylene glycol butyl ether) 3g, pH adjuster (20wt% citric acid aqueous solution) 2g, antifreeze agent (urea) 4g, corrosion inhibitor (sodium tripolyphosphate) 0.5g, chelating agent (disodium ethylenediaminetetraacetic acid) 0.5g, preservative (sodium benzoate) 1g and deionized water 59.5g;

[0113] The weight ratio of sodium lauryl sulfate to alkyl polyglycoside is 4:7;

[0114] The carboxyl-modified silicone surfactant and modified flame retardant were prepared according to the method described in Example 1.

[0115] Preparation of anti-soluble aqueous film-forming foam fire extinguishing agent:

[0116] (1) dissolving sodium dodecyl sulfate in deionized water under stirring, and then sequentially adding an alkyl polyglycoside, a fluorocarbon surfactant, a carboxyl-modified silicone surfactant, an antifreeze agent, a corrosion inhibitor, a chelating agent, a modified flame retardant and a preservative to obtain a first solution;

[0117] (2) adding a foam stabilizer to the co-solvent and stirring the mixture to obtain a second solution;

[0118] (3) Add the second solution to the first solution and stir evenly, then add the pH adjuster and continue stirring for 30 minutes to obtain an anti-soluble aqueous film-forming foam fire extinguishing agent.

[0119] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0120] Example 5

[0121] The method described in Example 1 is used for implementation, except that the anti-soluble aqueous film-forming foam fire extinguishing agent: 1 g of short-chain fluorocarbon surfactant (formed by compounding FS-50 and 1157 fluorocarbon surfactants in a weight ratio of 1:1), 25 g of hydrocarbon surfactant (sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside), 2 g of carboxyl-modified silicone surfactant, 1.5 g of foam stabilizer (formed by compounding xanthan gum and coconut oil diethanolamine in a weight ratio of 3:2), 5 g of modified flame retardant, 4 g of cosolvent (butyl diethylene glycol), 1 g of pH adjuster (20 wt % citric acid aqueous solution), 0.6 g of corrosion inhibitor (sodium tripolyphosphate), 0.6 g of chelating agent (disodium ethylenediaminetetraacetic acid), 1 g of preservative (sodium benzoate) and 58.3 g of deionized water; wherein the weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 1:2:2.

[0122] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0123] Example 6

[0124] The method described in Example 1 is used for implementation, except that the anti-soluble aqueous film-forming foam fire extinguishing agent includes: 1.8 g of short-chain fluorocarbon surfactant (FS-50 fluorocarbon surfactant), 18 g of hydrocarbon surfactant (sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside), 1 g of carboxyl-modified silicone surfactant, 2 g of foam stabilizer (formed by compounding xanthan gum and coconut oil diethanolamine in a weight ratio of 3:2), 3 g of modified flame retardant, 3 g of cosolvent (butyl diethylene glycol), 2 g of pH adjuster (20 wt % citric acid aqueous solution), 3 g of antifreeze agent (urea), 0.8 g of corrosion inhibitor (sodium tripolyphosphate), 0.3 g of chelating agent (disodium ethylenediaminetetraacetic acid), 0.5 g of preservative (sodium benzoate) and 64.9 g of deionized water; wherein the weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 1:1:4.

[0125] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0126] Example 7

[0127] The method described in Example 1 was used for implementation, except that the anti-soluble aqueous film-forming foam fire extinguishing agent: 1.5 g of short-chain fluorocarbon surfactant (formed by compounding FS-50 and 1157 fluorocarbon surfactants in a weight ratio of 1:1), 15 g of hydrocarbon surfactant (sodium dodecyl sulfate, cocamidopropyl betaine and alkyl glucoside), 2 g of carboxyl-modified silicone surfactant, and a foam stabilizer (formed by compounding xanthan gum and coconut oil diethanolamine in a weight ratio of 1:1). 2g of the preparation method, 4g of the modified flame retardant, 5g of the cosolvent (formed by compounding diethylene glycol butyl ether and ethylene glycol in a weight ratio of 1:1), 2g of the pH adjuster (20wt% citric acid aqueous solution), 5g of the antifreeze agent (urea), 1g of the corrosion inhibitor (sodium tripolyphosphate), 1g of the chelating agent (disodium ethylenediaminetetraacetic acid) and 61.5g of deionized water; wherein the weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 1:2:2.

[0128] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0129] Example 8

[0130] The method described in Example 1 was followed, except that no antifreeze agent, corrosion inhibitor, chelating agent and preservative were added (they were replaced with an equal amount of deionized water).

[0131] Specifically, the anti-soluble aqueous film-forming foam fire extinguishing agent: short-chain fluorocarbon surfactant (formed by compounding FS-50 and 1157 fluorocarbon surfactant in a weight ratio of 1:1) 2g, hydrocarbon surfactant (sodium dodecyl sulfate, cocamidopropyl betaine and alkyl glucoside) 20g, carboxyl modified silicone surfactant 1g, foam stabilizer (formed by compounding xanthan gum and coconut oil diethanolamine in a weight ratio of 3:2) 0.5g, modified flame retardant 4g, cosolvent (butyl diethylene glycol) 4g, pH adjuster (20wt% citric acid aqueous solution) 3g and deionized water 65.5g;

[0132] The weight ratio of sodium lauryl sulfate, cocamidopropyl betaine and alkyl glucoside is 4:5:7;

[0133] The carboxyl-modified silicone surfactant and modified flame retardant were prepared according to the method described in Example 1.

[0134] Preparation of anti-soluble aqueous film-forming foam fire extinguishing agent:

[0135] (1) dissolving sodium lauryl sulfate in deionized water, stirring evenly, then adding cocamide betaine and alkyl polyglycoside, and then adding fluorocarbon surfactant, carboxyl modified silicone surfactant and modified flame retardant, stirring evenly, to obtain a first solution;

[0136] (2) adding a foam stabilizer to the co-solvent and stirring the mixture to obtain a second solution;

[0137] (3) Add the second solution to the first solution and stir evenly, then add the pH adjuster and continue stirring for 30 minutes to obtain an anti-soluble aqueous film-forming foam fire extinguishing agent.

[0138] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0139] Example 9

[0140] The method described in Example 1 is used for implementation, except that the preparation method of the carboxyl-modified silicone surfactant and the modified flame retardant is as follows:

[0141] Under stirring, hydroxy polyether modified organosiloxane and maleic anhydride are added to isopropanol in a weight ratio of 1:1, and reacted at 85°C for 4 hours to obtain a reaction solution, wherein the ratio of the weight of isopropanol to the total weight of hydroxy polyether modified organosiloxane and maleic anhydride is 30:100; the reaction solution is cooled to room temperature, and then the solution is transferred to a rotary evaporator, and the product is purified and recovered by reduced pressure distillation to obtain a carboxyl modified organosilicon surfactant.

[0142] 10 g of ammonium polyphosphate and 60 g of anhydrous ethanol were stirred and mixed with a magnetic stirrer; then 1 g of vinyl triethoxysilane was added and mixed, and the mixture was reacted at 65° C. for 18 h, and then centrifuged and washed to obtain a modified flame retardant.

[0143] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 7.0 and 9.5.

[0144] Example 10

[0145] The method described in Example 1 is used for implementation, except that the preparation method of the carboxyl-modified silicone surfactant and the modified flame retardant is as follows:

[0146] Preparation of the carboxyl-modified silicone surfactant: under stirring, hydroxy polyether-modified silicone siloxane and maleic anhydride are added to isopropanol in a weight ratio of 1:2, and reacted at 70°C for 5 hours to obtain a reaction solution, wherein the weight ratio of isopropanol to the total weight of hydroxy polyether-modified silicone siloxane and maleic anhydride is 15:100; the reaction solution is cooled to room temperature, and then the solution is transferred to a rotary evaporator, and the product is purified and recovered by reduced pressure distillation to obtain a carboxyl-modified silicone surfactant.

[0147] Preparation of the modified flame retardant: 10 g of ammonium dihydrogen phosphate and 80 g of anhydrous ethanol were stirred and mixed, and then 0.5 g of 3-aminopropyltriethoxysilane was added and mixed, and the mixture was reacted at 60° C. for 18 h, and then centrifuged and washed.

[0148] According to the test, the pH value of the anti-soluble aqueous film-forming foam fire extinguishing agent is between 6.0 and 9.5.

[0149] Comparative Example 1

[0150] The method described in Example 1 was followed, except that the hydroxy polyether-modified organosiloxane was not modified (ie, when preparing the anti-soluble aqueous film-forming foam fire extinguishing agent, the carboxyl-modified organosilicon surfactant was replaced with the hydroxy polyether-modified organosiloxane).

[0151] Comparative Example 2

[0152] The method described in Example 1 was followed, except that the ammonium polyphosphate was not modified (ie, when preparing the anti-soluble aqueous film-forming foam fire extinguishing agent, the modified flame retardant was replaced with ammonium polyphosphate).

[0153] Test Example 1

[0154] The hydroxyl-containing organosilicon surfactant in Example 1 and the prepared carboxyl-modified organosilicon surfactant were subjected to ultraviolet absorption spectrum analysis. The results are as follows: Figure 1 As shown, Figure 1 In the above, a is a carboxyl-modified organic silicon surfactant, and b is a hydroxyl polyether-modified organic siloxane.

[0155] Depend on Figure 1 It can be seen that the UV spectrum peak of the carboxyl-modified silicone surfactant is significantly shifted to the long-wave direction, and the absorption peak intensity increases. This may be due to the formation of a conjugated system in the carboxyl-modified silicone surfactant molecules, which causes the UV absorption spectrum of the silicone surfactant to shift to the long-wave direction. This method further proves that the carboxyl-modified silicone surfactant molecules form a conjugated system, which changes the interaction force between molecules and thus plays a role in reducing the surface tension of the solution.

[0156] Test Example 2

[0157] The fire extinguishing agent products prepared in the above Examples 1-10 and Comparative Examples 1-2 were mixed with water at a ratio of 6:94 to prepare a foam solution for fire extinguishing. The fire extinguishing agent products were tested for foam performance, fire extinguishing performance and anti-burning performance, and the test results are shown in Table 1.

[0158] The foaming multiple and 25% liquid separation time are tested according to the standard GB15308-2006 "Foam Fire Extinguishing Agent";

[0159] The fire extinguishing capacity is based on the national standard GB15308-2006 "Foam Fire Extinguishing Agent" which stipulates that the fire extinguishing capacity should be 4.52m 2 The fire extinguishing time and 25% anti-burning time of the oil pan are required to be implemented. The test system is mainly composed of foam liquid storage tank, pressure gauge, standard gun, foam liquid delivery pipe, air compressor and pipeline. The flammable liquid fuel is #120 solvent oil for rubber industry. The area used is 4.52m 2 Oil pan to test fire extinguishing performance and burning resistance. 4.52m 2 The steps for the oil pan fire extinguishing time test are as follows: (1) Pour the foam solution into the foam liquid storage tank; (2) Use an air compressor to pressurize the foam liquid storage tank until the pressure reading reaches about 0.7 MPa, and adjust the foam gun flow rate to make the foam flow rate 11.4 L / min; (3) Pour 4.52 m 2 The oil pan is placed on the ground and kept level. The oil pan is located downwind of the standard foam gun. The foam gun is placed horizontally and 1.0m above the oil pan surface. The horizontal distance between the foam gun and the oil pan is adjusted so that the center of the foam jet falls to the center of the oil pan. (4) 90L of water is added to the oil pan to cover the entire bottom of the pan. 144L of fuel is added. (5) After adding the fuel, ignite the oil pan within 5 minutes and pre-burn for 60 seconds. Open the outlet valve of the low-multiple foam generation system, start supplying foam, and record the fire extinguishing time. Stop supplying foam after 180 seconds of spraying foam and wait for 300 seconds. Then place the anti-burning can containing 2L of gasoline in the center of the oil pan, ignite it, and start timing. When 25% of the fuel area of ​​the oil pan is ignited, the time interval at this time is recorded as the 25% anti-burning time.

[0160] Table 1

[0161]

[0162]

[0163] It can be seen from Table 1 that the aqueous film-forming foam fire extinguishing agent prepared in Examples 1-10 of the present invention has excellent foaming multiples, a long liquid separation time of 25%, and a fire extinguishing time (4.52m 2 The oil pan) is less than 126s, and the 25% anti-burning time is greater than 15min, which shows that the aqueous film-forming foam fire extinguishing agent provided by the present invention has excellent fire extinguishing performance and anti-burning performance.

[0164] Test Example 3

[0165] The foam fire extinguishing agent prepared in Example 1 was tested for its ability to extinguish a polar fuel (acetone). The ability to extinguish a polar fuel fire is based on the national standard GB15308-2006 "Foam Fire Extinguishing Agent" which states that the foam fire extinguishing agent can extinguish a 1.73 m 2The fire extinguishing time and 25% anti-burning time requirements of the oil pan are implemented, and the polar fuel is industrial acetone with a purity of not less than 99%.

[0166] Test method: Prepare a foam solution with fire extinguishing agent and water in a ratio of 6:94, and then perform the test according to the following steps: (1) Place the oil pan on the ground and keep it horizontal, so that the oil pan is downwind of the foam gun. Place the foam gun horizontally and 1m above the fuel surface, so that the center of the foam jet hits the central axis of the baffle and is 0.5m above the fuel surface; (2) Add 125L of fuel to the oil pan, ignite the oil pan within 5 minutes, pre-burn for 120s, and start to supply foam. And record the fire extinguishing time; (3) Supply foam through the foam solution for 180s, stop supplying foam and wait for 300s, place the anti-burn tank containing 2L of fuel in the center of the oil pan and ignite it. Record the 25% anti-burn time.

[0167] The results showed that the foam fire extinguishing agent prepared in Example 1 extinguished 1.73m 2 The extinguishing time of oil pan acetone fire is 108s, and the 25% anti-burning time is 830s, which shows that foam fire extinguishing agent can effectively extinguish polar fuel fire.

[0168] It should be noted that the preparation principles of Examples 2-10 are similar to those of Example 1, and therefore, the fire extinguishing agents prepared therefrom also have excellent anti-solvent properties and can effectively extinguish polar fuel fires.

[0169] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A solubility-resistant aqueous film-forming foam fire extinguishing agent, characterized in that: The anti-soluble aqueous film-forming foam fire extinguishing agent contains: a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified organic silicon surfactant, a foam stabilizer, a modified flame retardant, a cosolvent and a pH regulator; Wherein, the carboxyl-modified organosilicon surfactant is obtained by modifying a hydroxyl-containing organosilicon surfactant using maleic anhydride; The modified flame retardant is obtained by surface-modifying the flame retardant with a silane coupling agent, and the flame retardant is selected from any one of ammonium polyphosphate, polyvinyl alcohol ammonium phosphate, tetra-n-butyl ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.

2. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1, characterized in that: The carboxyl-modified silicone surfactant is prepared according to the following process: The hydroxyl-containing organosilicon surfactant, maleic anhydride and organic solvent are mixed, reacted at 60-90° C. for 2-8 hours, and then cooled and purified.

3. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1 or 2, characterized in that: The weight ratio of the organic silicon surfactant to maleic anhydride is 1:0.5-3; Preferably, the hydroxyl-containing organosilicon surfactant is a hydroxyl polyether-modified organosiloxane.

4. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 2, characterized in that: The weight ratio of the organic solvent to the total weight of the hydroxyl-containing organosilicon surfactant and maleic anhydride is 10-40:100; Preferably, the organic solvent is selected from any one of isopropanol, n-propanol, propylene glycol, 1,3-butanediol and pentanediol.

5. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1, characterized in that: The modified flame retardant is prepared according to the following process: The flame retardant is mixed with anhydrous ethanol, and then a silane coupling agent is added, and the mixture is reacted at 40 to 70° C. for 8 to 24 hours, followed by centrifugation and washing.

6. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1 or 5, characterized in that: The silane coupling agent is selected from one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-(2-methoxyethoxy)-silane, γ-glycidyloxypropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; Preferably, the weight ratio of the flame retardant to the silane coupling agent is 1:0.02-1.

7. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 5, characterized in that: The weight ratio of the flame retardant to anhydrous ethanol is 1:1-10.

8. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1, characterized in that: The hydrocarbon surfactant is selected from at least two of anionic hydrocarbon surfactants, amphoteric hydrocarbon surfactants and nonionic surfactants; Preferably, the anionic hydrocarbon surfactant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and sodium α-olefin sulfonate; Preferably, the amphoteric hydrocarbon surfactant is selected from one or more of cocamidopropyl betaine, N-dodecyl dimethyl betaine and 2-undecyl-N-acetoxy-N(2-hydroxyethyl)imidazoline; Preferably, the nonionic hydrocarbon surfactant is an alkyl glycoside.

9. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1, characterized in that: The short-chain fluorocarbon surfactant is selected from one or more of perfluoroalkylamine oxide, perfluoroalkyl polyoxyethylene ether, perfluoroalkyl ether betaine, and hexafluoropropylene oxide trimer quaternary ammonium salt; Preferably, the foam stabilizer is selected from one or more of xanthan gum, sodium carboxymethyl cellulose, polyethylene glycol and coconut oil diethanolamine; Preferably, the co-solvent is selected from one or more of ethylene glycol, diethylene glycol butyl ether and isobutyl alcohol; Preferably, the pH adjuster is selected from one or more of citric acid, lactic acid, tartaric acid, malic acid, phosphoric acid and acetic acid.

10. The anti-soluble aqueous film-forming foam fire extinguishing agent according to any one of claims 1 to 9, characterized in that: The anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5 wt % of a short-chain fluorocarbon surfactant, 10-30 wt % of a hydrocarbon surfactant, 0.5-2 wt % of a carboxyl-modified organic silicon surfactant, 0.1-2 wt % of a foam stabilizer, 0.5-5 wt % of a modified flame retardant, 1-5 wt % of a cosolvent, 0.1-8 wt % of a pH regulator, and 50-80 wt % of water.

11. The anti-solubility aqueous film-forming foam fire extinguishing agent according to any one of claims 1 to 9, characterized in that: The anti-soluble aqueous film-forming foam fire extinguishing agent also contains one or more of an antifreeze agent, a corrosion inhibitor, a chelating agent and a preservative.

12. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 11, characterized in that: The antifreeze agent is selected from one or more of urea, ethylene glycol and propanol; Preferably, the corrosion inhibitor is selected from one or more of sodium chromate, potassium chromate, sodium tripolyphosphate and sodium hexametaphosphate; Preferably, the chelating agent is disodium ethylenediaminetetraacetate; Preferably, the preservative is selected from one or more of sodium benzoate, potassium sorbate and methyl paraben.

13. The anti-solubility aqueous film-forming foam fire extinguishing agent according to claim 1 or 11, characterized in that: The anti-soluble aqueous film-forming foam fire extinguishing agent contains: 0.5-2.5wt% of a short-chain fluorocarbon surfactant, 10-30wt% of a hydrocarbon surfactant, 0.5-2wt% of a carboxyl-modified organic silicon surfactant, 0.1-3wt% of a foam stabilizer, 0.5-5wt% of a modified flame retardant, 1-5wt% of a cosolvent, 0.1-8wt% of a pH regulator, 2-10wt% of an antifreeze agent, 0.1-1wt% of a corrosion inhibitor, 0.1-1wt% of a chelating agent and 0.1-3wt% of a preservative.

14. A method for preparing the anti-soluble aqueous film-forming foam fire extinguishing agent according to any one of claims 1 to 13, characterized in that: The method comprises: mixing a short-chain fluorocarbon surfactant, a hydrocarbon surfactant, a carboxyl-modified organic silicon surfactant, a foam stabilizer, a modified flame retardant, a cosolvent, a pH regulator and water.

15. The method according to claim 14, characterized in that The method comprises the following steps: (1) mixing a hydrocarbon surfactant, a short-chain fluorocarbon surfactant, a carboxyl-modified silicone surfactant, a modified flame retardant, and water to obtain a first solution; (2) mixing a foam stabilizer and a co-solvent to obtain a second solution; (3) Mixing the first solution, the second solution and the pH adjuster.

Images