Foam extinguishing agent, its preparation method and application

Abstract

The application relates to the technical field of solid and liquid fire extinguishing, and discloses a foam extinguishing agent and a preparation method and application thereof. The foam extinguishing agent contains a flame retardant, a foaming agent, a foam stabilizer, a thickening agent and a preservative, wherein the flame retardant is a phosphorus-containing ferrocene derivative shown in formula I; and the foaming agent is a zwitterionic surfactant and / or an anionic surfactant. The foam extinguishing agent contains the phosphorus-containing ferrocene derivative with a specific structure, has excellent flame-retardant effect, and has excellent fire extinguishing performance as a single flame retardant without fluorocarbon surfactants.

Description

Technical Field

[0001] This invention relates to the field of solid and liquid fire fighting technology, specifically to a foam fire extinguishing agent, its preparation method, and its application. Background Technology

[0002] Fires are a serious problem facing human society. Even in sparsely populated areas, tens of thousands of fires occur every year, endangering human lives and property while also damaging the environment. Foam extinguishing agents are a type of foam extinguishing technology capable of rapidly extinguishing flammable liquid fires. During the extinguishing process, they form a physical barrier, separating the flames from the ignition source. Furthermore, they remain stable in the presence of oil, inhibiting the release of flammable vapors and providing protection against reignition. Since their invention in the 20th century, they have been widely used in oil fields, oil depots, ships, airports, and other locations prone to flammable liquid fires, and are considered effective extinguishing agents for oil tank fires and liquid fuel spills.

[0003] Traditional foam fire extinguishing agents use fluorocarbon surfactants as their core component. They are characterized by rapid spreading on burning oil surfaces and inhibition of flammable liquid volatilization, thus enabling them to quickly extinguish oil fires and are widely used in the petrochemical industry. Aqueous film-forming foam (AFFF), in particular, is widely recognized as the best-performing Class B fire extinguishing agent and enjoys a high market share. However, recent studies have found that perfluorooctane sulfonic acid (PFOS) and its salts used in AFFF are difficult to degrade, posing serious ecological damage and environmental problems. Therefore, it has been listed as a "persistent organic pollutant" (POPS) under the Stockholm Convention and its use is restricted worldwide.

[0004] To address the environmental problems associated with the long-chain fluorocarbon surfactant perfluorooctane sulfonic acid (PFOS) in traditional foam fire extinguishing agents, such as its difficulty in degradation, many researchers both domestically and internationally have begun to focus on developing novel, green, and environmentally friendly foam fire extinguishing agents. Currently, the preparation of foam fire extinguishing agents using short-chain fluorocarbon surfactants and organosilicon surfactants as core components represents two mainstream research directions. Meanwhile, research on smoke suppressants in foam fire extinguishing agents mainly focuses on alkaline earth metal salts, with insufficient research on other metal salts.

[0005] In addition, existing fire extinguishing agents are not very effective, or require the addition of various flame-retardant substances to achieve a better fire extinguishing effect.

[0006] Therefore, there is an urgent need to develop a new type of fluorine-free, environmentally friendly foam fire extinguishing agent. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of existing foam fire extinguishing agents containing fluorocarbon surfactants that harm the environment, the unsatisfactory fire extinguishing performance of non-fluorinated fire extinguishing agents, and the poor fire extinguishing effect of single flame retardants. This invention provides a foam fire extinguishing agent, its preparation method, and its application. The foam fire extinguishing agent of this invention contains a phosphorus-containing ferrocene derivative with a specific structure, which has excellent flame retardant properties. Using it as a single flame retardant, it can exhibit excellent fire extinguishing performance even without fluorocarbon surfactants.

[0008] To achieve the above objectives, the present invention provides a foam fire extinguishing agent containing a flame retardant, a foaming agent, a foam stabilizer, a thickener, and a preservative.

[0009] The flame retardant is a phosphorus-containing ferrocene derivative as shown in Formula I;

[0010] The foaming agent is an amphoteric surfactant and / or an anionic surfactant;

[0011]

[0012] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a ferrocene methylene group or sodium, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 At least one of them is a ferrocene methylene group, and at least one of R1 and R2 is sodium, at least one of R3 and R4 is sodium, at least one of R5 and R6 is sodium, at least one of R7 and R8 is sodium, and at least one of R9 and R 10 At least one of them is sodium, R 11 and R 12 At least one of them is sodium.

[0013] Preferably, the structure of the flame retardant is as shown in Formula II and / or Formula III:

[0014]

[0015] Preferably, the foam extinguishing agent also contains water.

[0016] Preferably, the foam extinguishing agent contains 2-8% by weight of flame retardant, 7-20% by weight of foaming agent, 2-8% by weight of foam stabilizer, 0.1-2% by weight of thickener, 2-5% by weight of preservative, and the remainder is water.

[0017] Preferably, the foam extinguishing agent contains 3-8% by weight of flame retardant, 10-20% by weight of foaming agent, 3-8% by weight of foam stabilizer, 0.1-2% by weight of thickener, 2-5% by weight of preservative, and the remainder is water.

[0018] Preferably, the foaming agent is selected from one or more of cocamidopropyl betaine, lauramidopropyl betaine, sodium lauroyl glutamate, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

[0019] Preferably, the foam stabilizer is urea and / or an alkyl glycoside surfactant.

[0020] Preferably, the thickener is a polysaccharide thickener.

[0021] Preferably, the thickener is selected from one or more of xanthan gum, sodium alginate, hydroxypropyl guar gum, and sodium carboxymethyl cellulose.

[0022] Preferably, the preservative is selected from one or more of potassium sorbate, sodium benzoate, and methylparaben.

[0023] A second aspect of the present invention provides a method for preparing the aforementioned foam fire extinguishing agent, the method comprising: mixing a flame retardant, a foaming agent, a foam stabilizer, a thickener, and a preservative.

[0024] Preferably, the specific operation process of this method includes:

[0025] S1. Add the foaming agent, flame retardant, preservative and foam stabilizer to water in sequence to dissolve them and obtain mixture A;

[0026] S2. Add the thickener to the mixture A and dissolve it.

[0027] A third aspect of the present invention provides the application of the foam extinguishing agent described above and the foam extinguishing agent prepared by the method described above in solid fires and liquid fires.

[0028] Compared with the prior art, the present invention has the following main advantages:

[0029] (1) The foam fire extinguishing agent provided by the present invention contains a phosphorus-containing ferrocene derivative, which has a phosphorus-containing flame retardant group and a ferrocene free radical quenching group, and has excellent flame retardant properties. In this process, iron atoms combine with water, air and other substances to generate active intermediates such as FeO and Fe2O3. These active intermediates can combine with key free radicals such as O·, O2 and OH· generated during combustion, and block the free radical chain reaction. As a single flame retardant in the fire extinguishing agent, the phosphorus element in the phosphorus-containing ferrocene derivative forms a char layer during the fire extinguishing process, which can reduce the heat conduction from the flame to the combustible and extinguish the fire quickly. Therefore, the phosphorus-containing ferrocene derivative does not need to be combined with other components with flame retardant effects to make the fire extinguishing agent have excellent fire extinguishing performance.

[0030] (2) Because the foam extinguishing agent provided by this invention contains phosphorus-containing ferrocene derivatives with excellent flame-retardant properties as flame retardants, the extinguishing efficiency of the foam extinguishing agent can be improved without using fluorocarbon surfactants. Therefore, the foam extinguishing agent of this invention is free of fluorocarbon surfactants and has low toxicity and is environmentally friendly. All raw materials used in this invention have good biodegradability, low environmental pollution, and no toxic side effects; moreover, after the extinguishing agent is released, it will not damage the ozone layer or produce a greenhouse effect, making it environmentally friendly and safe.

[0031] (3) Based on the use of phosphorus-containing ferrocene derivatives with excellent flame retardant properties as flame retardants, this invention combines amphoteric surfactants and / or anionic surfactants without silicon as foaming agents. The resulting fire extinguishing agent has rich and stable foam with low surface tension and good spreading performance on oil surfaces. This results in a short fire extinguishing time, long fire resistance time, and short fire control time for the foam fire extinguishing agent. It does not require the use of organosilicon surfactants and fluorocarbon surfactants.

[0032] (4) In a preferred embodiment, limiting the content of each component in the foam fire extinguishing agent of the present invention to a specific range can further improve the fire extinguishing effect.

[0033] (5) The method described in this invention is simple and easy to operate. Preferably, mixing the components in the foam extinguishing agent in a specific order can improve the performance of the prepared foam extinguishing agent.

[0034] (6) The foam extinguishing agent provided by the present invention has a wide range of applications and can be used in the fields of solid fires and liquid fires. Attached Figure Description

[0035] Figure 1 The infrared characterization spectrum of ferrocene phytate prepared in Example 1 is shown.

[0036] Figure 2 This is the phosphorus NMR spectrum of ferrocene phytate prepared in Example 1;

[0037] Figure 3 This is the primary mass spectrum of ferrocene phytate methyl ester prepared in Example 1;

[0038] Figure 4 This is the secondary mass spectrum of ferrocene phytate methyl ester prepared in Example 1;

[0039] Figure 5 This is the primary mass spectrum of the disubstituted ferrocene phytate prepared in Example 2;

[0040] Figure 6 This is the secondary mass spectrum of the disubstituted ferrocene phytate prepared in Example 2;

[0041] Figure 7 This is the phosphorus NMR spectrum of the disubstituted ferrocene phytate prepared in Example 2. Detailed Implementation

[0042] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0043] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0044] The first aspect of this invention provides a foam fire extinguishing agent, wherein the foam fire extinguishing agent contains a flame retardant, a foaming agent, a foam stabilizer, a thickener, and a preservative. The flame retardant is a phosphorus-containing ferrocene derivative of Formula I.

[0045]

[0046] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a ferrocene methylene group or sodium, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 At least one of them is a ferrocene methylene group, and at least one of R1 and R2 is sodium, at least one of R3 and R4 is sodium, at least one of R5 and R6 is sodium, at least one of R7 and R8 is sodium, and at least one of R9 and R 10 At least one of them is sodium, R11 and R 12 At least one of them is sodium. In this invention, the ferrocene methylene group is...

[0047] The foam fire extinguishing agent of this invention contains a phosphorus-containing ferrocene derivative with the structure shown in Formula I. The phosphorus content in the compound shown in Formula I is as high as about 21%. Because the iron atoms in the phosphorus-containing ferrocene derivative combine with water, air, etc. to generate active intermediates such as FeO and Fe2O3, these active intermediates can combine with key free radicals such as O·, O2 and OH· generated during combustion, blocking the free radical chain reaction, thus exhibiting excellent flame retardant properties. The phosphorus element in the phosphorus-containing ferrocene derivative forms a char layer during the fire extinguishing process, which can reduce the heat conduction from the flame to the combustible material and extinguish the fire quickly. Based on this, the phosphorus-containing ferrocene derivative does not need to be combined with other components with flame retardant effects to give the fire extinguishing agent excellent fire extinguishing performance.

[0048] The preparation method of the phosphorus-containing ferrocene derivatives described in this invention is simple. The inventors discovered through research that products with excellent flame-retardant properties can be prepared simply by subjecting specific reactants to an esterification reaction. Specifically, hydroxymethyl ferrocene containing transition metal iron is esterified with phytic acid to obtain phosphorus-containing ferrocene derivatives with excellent flame-retardant properties.

[0049] In a preferred embodiment, the structure of the flame retardant is as shown in Formula II and / or Formula III:

[0050]

[0051] In this invention, the method for preparing phosphorus-containing ferrocene derivatives includes: esterifying hydroxymethyl ferrocene with phytic acid in the presence of a catalyst to obtain an esterified product (ferrocene methyl phytate), and then reacting the esterified product with sodium hydroxide to generate the corresponding sodium salt.

[0052] In a specific embodiment, the molar ratio of the esterification product to sodium hydroxide is 1:9-11.

[0053] In a specific embodiment, the reaction temperature of the esterification product with sodium hydroxide is 20-40°C, and the reaction time is 0.2-1h.

[0054] In this invention, to obtain a compound with the structure shown in Formula I, the molar ratio of hydroxymethylferrocene to phytic acid needs to be limited to a specific range. In a preferred embodiment, the molar ratio of hydroxymethylferrocene to phytic acid can be 1.2-6.5:1, preferably 1.2-2.5:1, for example 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, or 2.5:1. When the molar ratio of hydroxymethylferrocene to phytic acid is small, the product with the structure of Formula II is obtained; when the molar ratio of hydroxymethylferrocene to phytic acid is large, phytic acid will undergo esterification with multiple hydroxymethylferrocene compounds, forming two or more phosphate ester bonds, that is, the resulting phosphorus-containing ferrocene derivative has two or more ferrocene groups.

[0055] In order to obtain a compound with the structure shown in Formula I, in a preferred embodiment, the esterification reaction conditions include a temperature of 70-90°C and a time of 4-6 hours.

[0056] In this invention, the catalyst can be a specific combination of dicyandiamide and urea, and dicyandiamide and urea need to be added simultaneously to obtain the target product of Formula I. In a specific embodiment, the molar ratio of urea to phytic acid can be 0.5-1.5:1. Specifically, the molar ratio of dicyandiamide to urea can be 0.4-1.2:1.

[0057] In a specific embodiment, the method includes: mixing hydroxymethyl ferrocene, phytic acid, a catalyst, a solvent, and a dehydrating agent to carry out an esterification reaction.

[0058] In a more specific embodiment, the method includes: dissolving hydroxymethyl ferrocene, phytic acid and catalyst in a solvent at room temperature (15-30°C), then adding a dehydrating agent, heating to 70-90°C and reacting for 4-6 hours, then cooling to room temperature (15-30°C), removing the solvent, dehydrating agent and excess hydroxymethyl ferrocene by multiple water washings and vacuum distillation to obtain ferrocene methyl phytate, and then reacting ferrocene methyl phytate with sodium hydroxide to generate the corresponding sodium salt.

[0059] In this invention, the dehydrating agent can be a conventional choice in the art. In a specific embodiment, the dehydrating agent can be selected from one or more of toluene, xylene, and cyclohexane, preferably toluene.

[0060] There are no particular restrictions on the amount of the dehydrating agent used; it can be added according to conventional requirements. In a specific embodiment, the weight ratio of the dehydrating agent to phytic acid can be 0.5-1:1.

[0061] In this invention, the solvent can be any conventional choice in the art. In a specific embodiment, the solvent can be selected from one or more of dimethyl sulfoxide, toluene, and cyclohexane, preferably dimethyl sulfoxide.

[0062] In the foam fire extinguishing agent described in this invention, the foaming agent used is a fluorine-free surfactant, specifically, an amphoteric surfactant and / or anionic surfactant. Because the foam fire extinguishing agent provided by this invention contains a phosphorus-containing ferrocene derivative with excellent flame-retardant properties as a flame retardant, the fire extinguishing efficiency of the foam fire extinguishing agent can be improved and environmental pollution reduced when using a fluorine-free surfactant. Simultaneously, the foaming agent is also a silicon-free amphoteric surfactant and / or anionic surfactant, resulting in a rich and stable foam with low surface tension and good spreading performance on oil surfaces, thus enabling the foam fire extinguishing agent to have a short extinguishing time, long anti-burning time, and short fire control time.

[0063] In a specific embodiment, the foaming agent may be selected from one or more of cocamidopropyl betaine CAB-35, lauroamide propyl betaine LAB-35, sodium lauroyl glutamate LG-95P, sodium dodecyl sulfate SDS, and sodium dodecylbenzene sulfonate SDBS.

[0064] In a specific embodiment, the foam extinguishing agent also contains water. A foam extinguishing agent can be obtained by dissolving components such as flame retardants and foaming agents in water.

[0065] In a specific embodiment, the foam extinguishing agent contains 2-8% flame retardant by weight, 7-20% foaming agent by weight, 2-8% foam stabilizer, 0.1-2% thickener, 2-5% preservative, and the remainder is water.

[0066] To improve the fire extinguishing effect, it is necessary to further control the content of each component in the foam fire extinguishing agent. In a preferred embodiment, the content of flame retardant in the foam fire extinguishing agent is 3-8% by weight, the content of foaming agent is 10-20% by weight, the content of foam stabilizer is 3-8%, the content of thickener is 0.1-2%, the content of preservative is 2-5%, and the balance is water.

[0067] In this invention, the foam stabilizer can be a conventional choice in the art. Specifically, the foam stabilizer can be urea and / or alkyl glycoside surfactants. In a more specific embodiment, the alkyl glycoside surfactant can be selected from one or more of alkyl glycoside APG-0810, alkyl glycoside APG-1214, and alkyl glycoside APG-0814.

[0068] In this invention, the thickener can be a conventional choice in the art. In a specific embodiment, the thickener can be a polysaccharide thickener. In a more specific embodiment, the thickener can be selected from one or more of xanthan gum, sodium alginate, hydroxypropyl guar gum, and sodium carboxymethyl cellulose.

[0069] In this invention, the preservative can be a conventional choice in the art. In a specific embodiment, the preservative can be selected from one or more of potassium sorbate, sodium benzoate, and methylparaben.

[0070] The foam fire extinguishing agent of the present invention significantly improves the performance of the foam fire extinguishing agent by using phosphorus-containing ferrocene derivatives as flame retardants and specific amphoteric surfactants and / or anionic surfactants as foaming agents, resulting in a short extinguishing time, long anti-burning time, and short fire control time.

[0071] A second aspect of the present invention provides a method for preparing the aforementioned foam fire extinguishing agent, the method comprising: mixing a flame retardant, a foaming agent, a foam stabilizer, a thickener, and a preservative.

[0072] The method for preparing foam fire extinguishing agent described in this invention is simple and easy to operate. The fire extinguishing agent can be obtained simply by mixing the various components in the fire extinguishing agent.

[0073] In a preferred embodiment, mixing the components of the foam extinguishing agent in a specific order allows for a more uniform and thorough dissolution of the components, thereby improving the performance of the prepared foam extinguishing agent. Preferably, the specific operation process includes: S1, adding the foaming agent, flame retardant, preservative, and foam stabilizer sequentially to water to obtain mixture A; S2, adding the thickener to mixture A to dissolve. Step S1 can be performed at room temperature (15-30℃), while step S2 can be performed under heating conditions at a temperature of 70-90℃.

[0074] A third aspect of this invention provides the application of the foam extinguishing agent described above and the foam extinguishing agent prepared by the method described above in solid and liquid fires. The foam extinguishing agent provided by this invention has excellent performance and wide applications.

[0075] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0076] In the following examples, the raw materials used were purchased from Shanghai Maclean.

[0077] Examples 1 and 2 illustrate the preparation process of phosphorus-containing ferrocene derivatives.

[0078] Example 1

[0079] Preparation of phosphorus-containing ferrocene derivatives:

[0080] At 20°C, hydroxymethyl ferrocene, phytic acid, and catalysts (dicyandiamide and urea) were dissolved in dimethyl sulfoxide (solvent). After complete dissolution, cyclohexane (a dehydrating agent) was added, and the mixture was heated to 70°C and reacted for 4 hours before being cooled to room temperature. The solvent, dehydrating agent, and excess hydroxymethyl ferrocene were removed by repeated washing with water and vacuum distillation to obtain ferrocene methyl phytate. Then, ferrocene methyl phytate and sodium hydroxide were reacted at 25°C for 0.2 hours to obtain phosphorus-containing ferrocene derivative A1. The molar ratio of hydroxymethyl ferrocene to phytic acid was 1.2:1; the molar ratio of phytic acid to urea was 1:1; the molar ratio of dicyandiamide to urea was 0.5:1; the mass ratio of the dehydrating agent to phytic acid was 0.5:1; and the molar ratio of ferrocene methyl phytate to sodium hydroxide was 1:11.

[0081] Figure 1 The image shows the infrared spectrum of the phosphorus-containing ferrocene derivative obtained in this embodiment. Figure 2 This is the phosphorus NMR spectrum of the phosphorus-containing ferrocene derivative obtained in this embodiment. From... Figure 1 It can be seen that 3415cm -1 The peak for phytic acid is the -OH peak at 2850 cm⁻¹. -1 This is a saturated CH peak, 1699 cm⁻¹ -1 The peak is P=O, at 1080 cm⁻¹. -1 The peak for the newly generated POC is at 1189 cm⁻¹. -1 It is the primary alcohol -OH on hydroxymethylferrocene. Additionally, 481 cm⁻¹ -1 The peak at this location represents the combination of cyclopentadiene and Fe. From... Figure 2 It can be seen that the absorption peak at 3.3 ppm is the phosphate monoester bond in phytic acid, and the shifted peak at -0.75 ppm is the absorption peak of the newly formed phosphate diester bond. According to... Figure 3 and Figure 4 The primary mass spectrometry showed a signal peak at 857.87, consistent with the molecular mass of the target product; the secondary mass spectrometry (858→793→737→672→659) indicated the gradual removal of the hydroxymethyl ferrocene group from ferrocene phytate. In summary, the phosphorus-containing ferrocene derivative A1 prepared in this embodiment possesses the structure of formula II.

[0082] Example 2

[0083] Preparation of phosphorus-containing ferrocene derivatives:

[0084] At 20°C, hydroxymethyl ferrocene, phytic acid, and catalysts (dicyandiamide and urea) were dissolved in dimethyl sulfoxide (solvent). After complete dissolution, toluene (a dehydrating agent) was added, and the mixture was heated to 90°C and reacted for 6 hours before being cooled to room temperature. The solvent, dehydrating agent, and excess hydroxymethyl ferrocene were removed by repeated washing with water and vacuum distillation to obtain disubstituted ferrocene methyl phytate. Then, the disubstituted ferrocene methyl phytate and sodium hydroxide were reacted at 25°C for 0.2 hours to obtain phosphorus-containing ferrocene derivative A2. The molar ratio of hydroxymethyl ferrocene to phytic acid was 2.5:1; the molar ratio of phytic acid to urea was 1:1.2; the molar ratio of dicyandiamide to urea was 0.5:1; the mass ratio of the dehydrating agent to phytic acid was 1:1; and the molar ratio of ferrocene methyl phytate to sodium hydroxide was 1:10.

[0085] The phosphorus-containing ferrocene derivative prepared in this embodiment has two phosphate diester bonds, that is, the phosphorus-containing ferrocene derivative has two ferrocene methylene groups. According to Figure 5 and Figure 6 The primary mass spectrometer showed a signal peak at 1055.89, consistent with the molecular mass of the target product; the secondary mass spectrometer showed a progressive removal of two hydroxymethyl ferrocene groups from 1056 to 658. According to... Figure 7 The absorption peaks at 2.08 ppm to 3.40 ppm represent the phosphate monoester bond in the phytic acid group; the absorption peaks at -1.43 ppm to -0.79 ppm represent the phosphate diester bond in the two symmetrical ferrocene methylene groups. The methylferrocene group increases the electronegativity of the O directly bonded to P, causing a low-field shift in the peak position. In summary, the phosphorus-containing ferrocene derivative A2 prepared in this embodiment has the structure of Formula III.

[0086] Examples 3-8 illustrate the preparation process of foam fire extinguishing agents.

[0087] Example 3

[0088] The foam extinguishing agent provided in this embodiment has the following composition by weight percentage: 5% cocamidopropyl betaine (CAB-35) (foaming agent), 5% sodium dodecyl sulfate (SDS) (foaming agent), 2% alkyl glycoside (APG-0810) (foam stabilizer), 1% urea (foam stabilizer), 0.1% xanthan gum (thickener), 3% ferrocene phosphorus derivative (flame retardant), 2% sodium benzoate (preservative), and the balance being water. The ferrocene phosphorus derivative is the ferrocene phosphorus derivative A1 prepared in Example 1.

[0089] The preparation method of foam fire extinguishing agent includes the following steps:

[0090] S1. Add the foaming agent, flame retardant, preservative and foam stabilizer to the water in sequence, and stir thoroughly at room temperature (20℃) until completely dissolved to form mixture A;

[0091] S2. Add the thickener to the mixture A in small amounts several times, and stir thoroughly at 80°C until completely dissolved.

[0092] Example 4

[0093] The foam fire extinguishing agent provided in this embodiment has the following composition by weight percentage: 10% cocamidopropyl betaine (CAB-35) (foaming agent), 10% sodium dodecyl sulfate (SDS) (foaming agent), 5% alkyl glycoside (APG-0810) (foam stabilizer), 3% urea (foam stabilizer), 0.5% xanthan gum (thickener), 8% ferrocene phosphorus derivative (flame retardant), 5% sodium benzoate (preservative), and the balance being water. The ferrocene phosphorus derivative is the ferrocene phosphorus derivative A1 prepared in Example 1.

[0094] The preparation method of the foam fire extinguishing agent is the same as in Example 3.

[0095] Example 5

[0096] The foam fire extinguishing agent provided in this embodiment has the following composition by weight percentage: 8% cocamidopropyl betaine (CAB-35) (foaming agent), 7% sodium dodecyl sulfate (SDS) (foaming agent), 3% alkyl glycoside (APG-0810) (foam stabilizer), 2% urea (foam stabilizer), 0.2% xanthan gum (thickener), 5% ferrocene phosphorus derivative (flame retardant), 2.5% sodium benzoate (preservative), and the balance being water. The ferrocene phosphorus derivative is the ferrocene phosphorus derivative A1 prepared in Example 1.

[0097] The preparation method of the foam fire extinguishing agent is the same as in Example 3.

[0098] Example 6

[0099] The foam extinguishing agent provided in this embodiment has the following composition by weight percentage: sodium lauroyl glutamate LG-95P 8% (foaming agent), sodium dodecylbenzenesulfonate SDBS 7% (foaming agent), alkyl glycoside APG-1214 3% (foam stabilizer), urea 2% (foam stabilizer), sodium alginate 1% (thickening agent), ferrocene phosphorus derivative 5% (flame retardant), sodium benzoate 2.5% (preservative), and the balance being water. The ferrocene phosphorus derivative is the ferrocene phosphorus derivative A2 prepared in Example 2.

[0100] The preparation method of the foam fire extinguishing agent is the same as in Example 1.

[0101] Example 7

[0102] The method of Example 5 was implemented, except that the content of the phosphorus-containing ferrocene derivative was 2.5%.

[0103] Example 8

[0104] The method of Example 5 was implemented, except that the content of cocamidopropyl betaine CAB-35 was 4% (foaming agent) and the content of sodium dodecyl sulfate SDS was 4% (foaming agent).

[0105] Comparative Example 1

[0106] The foam extinguishing agent provided in this comparative example does not contain flame retardants and its composition by weight percentage is as follows: sodium lauroyl glutamate LG-95P 8% (foaming agent), sodium dodecylbenzene sulfonate SDBS 7% (foaming agent), alkyl glycoside APG-1214 3% (foam stabilizer), urea 2% (foam stabilizer), sodium alginate 1% (thickening agent), sodium benzoate 2.5% (preservative), and the balance being water.

[0107] The preparation method of foam fire extinguishing agent includes the following steps:

[0108] S1. Add the foaming agent, preservative and foam stabilizer to the water in sequence, and stir thoroughly at room temperature (20℃) until completely dissolved to form mixture A;

[0109] S2. Add the thickener to the mixture A in small amounts several times, and stir thoroughly at 80°C until completely dissolved.

[0110] Comparative Example 2

[0111] The fire extinguishing agent was prepared according to the method of Example 5, except that ferrocene purchased from Shanghai McLean Company was used as a flame retardant instead of the phosphorus-containing ferrocene derivative in Example 1.

[0112] Comparative Example 3

[0113] The fire extinguishing agent was prepared according to the method in Example 5, except that the foaming agent was replaced by 8% polyether-modified polydimethylsiloxane (purchased from Shanghai Maclean, viscosity 2000 cst (25℃)) and 7% trisiloxane polyoxyethylene ether (purchased from Shanghai Maclean, purity 99%) instead of 8% cocamidopropyl betaine (CAB-35) and 7% sodium dodecyl sulfate (SDS).

[0114] Test case

[0115] The relevant properties and performance of the extinguishing agents prepared in Examples 3-8 and Comparative Examples 1-3 were tested, and the results are shown in Table 1.

[0116] Equipment used in the fire extinguishing agent performance testing process: pH meter, thermometer, freezing point tester, foam generation system, foam collector, liquid separation tester, balance, stopwatch, circular steel oil pan (inner diameter: ~565mm, depth: ~150mm, oil pan area: 0.25m²). 2 Steel fire-resistant tank (~inner diameter: 120mm, depth: ~80mm).

[0117] pH value determination method: (1) First, calibrate the pH meter with pH buffer; (2) Take 30 mL of foam extinguishing agent product, pour it into a dry and clean 50 mL beaker, immerse the electrode in the foam liquid, and measure the pH value at (20±2)℃; (3) Repeat the test once, and take the average value of the two test results, which is the pH value of the extinguishing agent.

[0118] Freezing point determination method: Follow the method specified in section 5.2.3 "Freezing point" of GB 15308-2006 "Foam Extinguishing Agents".

[0119] The foaming ratio and 25% separation time determination methods shall be carried out in accordance with section 5.8 "Foaming ratio and 25% separation time of low-expansion foam liquid" in GB 15308-2006 "Foam Extinguishing Agents".

[0120] 90% fire control time, fire extinguishing time, and fire resistance time: in accordance with 5.10 "Fire extinguishing performance" of GB 15308-2006 "Foam Extinguishing Agents".

[0121] Table 1

[0122]

[0123]

[0124] As shown in Table 1, the foam extinguishing agent prepared in the embodiments of the present invention has a pH value of around 7, a freezing point between -10 and -18, a foaming ratio between 7 and 9, and a 25% separation time between 3 and 4.5 minutes, exhibiting moderate properties that meet the usage requirements. Furthermore, the foam extinguishing agent prepared in the embodiments has a short 90% fire control time, a short extinguishing time, and a long fire resistance time, thus demonstrating excellent fire extinguishing performance.

[0125] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A foam fire extinguishing agent, characterized in that, This foam extinguishing agent contains flame retardants, foaming agents, foam stabilizers, thickeners, and preservatives. The flame retardant is a phosphorus-containing ferrocene derivative as shown in Formula I; The foaming agent is an amphoteric surfactant and / or an anionic surfactant; Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a ferrocene methylene group or sodium, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 At least one of them is a ferrocene methylene group, and at least one of R1 and R2 is sodium, at least one of R3 and R4 is sodium, at least one of R5 and R6 is sodium, at least one of R7 and R8 is sodium, and at least one of R9 and R 10 At least one of them is sodium, R 11 and R 12 At least one of them is sodium.

2. The foam extinguishing agent according to claim 1, characterized in that, The structure of the flame retardant is shown in Formula II and / or Formula III:

3. The foam extinguishing agent according to claim 1 or 2, characterized in that, The foam extinguishing agent also contains water.

4. The foam extinguishing agent according to claim 3, characterized in that, The foam extinguishing agent contains 2-8% flame retardant, 7-20% foaming agent, 2-8% foam stabilizer, 0.1-2% thickener, 2-5% preservative, and the remainder is water.

5. The foam extinguishing agent according to claim 3 or 4, characterized in that, The foam extinguishing agent contains 3-8% flame retardant, 10-20% foaming agent, 3-8% foam stabilizer, 0.1-2% thickener, 2-5% preservative, and the remainder is water.

6. The foam extinguishing agent according to any one of claims 1-5, characterized in that, The foaming agent is selected from one or more of cocamidopropyl betaine, lauramidopropyl betaine, sodium lauroyl glutamate, sodium dodecyl sulfate, and sodium dodecylbenzene sulfonate.

7. The foam extinguishing agent according to any one of claims 1-6, characterized in that, The foam stabilizer is urea and / or alkyl glycoside surfactants.

8. The foam extinguishing agent according to any one of claims 1-7, characterized in that, The thickener is a polysaccharide thickener; Preferably, the thickener is selected from one or more of xanthan gum, sodium alginate, hydroxypropyl guar gum, and sodium carboxymethyl cellulose.

9. The foam extinguishing agent according to any one of claims 1-8, characterized in that, The preservative is selected from one or more of potassium sorbate, sodium benzoate, and methylparaben.

10. A method for preparing the foam fire extinguishing agent according to any one of claims 1-9, characterized in that, The method includes mixing flame retardants, foaming agents, foam stabilizers, thickeners, and preservatives.

11. The method according to claim 10, characterized in that, The specific operation process of this method includes: S1. Add the foaming agent, flame retardant, preservative and foam stabilizer to water in sequence to dissolve them and obtain mixture A; S2. Add the thickener to the mixture A and dissolve it.

12. The use of the foam extinguishing agent according to any one of claims 1-9 and the foam extinguishing agent prepared by the method according to claim 10 or 11 in solid fires and liquid fires.

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