A perfluorohexanone-based composite fire extinguishing agent

Abstract

The present application relates to a kind of based on perfluorohexanone composite fire extinguishing agent, mainly by perfluorohexanone and iron-based auxiliary agent composition;Wherein, perfluorohexanone in composite fire extinguishing agent The mass fraction is not less than 98%;Iron-based auxiliary agent in composite fire extinguishing agent The mass concentration is 1-1000ppm;The iron-based auxiliary agent is any one or combination in ferrocene additive, carbonyl iron additive.Wherein, ferrocene additive and carbonyl iron additive can realize high-efficiency fire extinguishing effect in high-temperature gas phase state, after pyrolysis with iron cycle to block chain combustion reaction, in low ppm level concentration can take effect, and perfluorohexanone synergistic effect forms based on perfluorohexanone composite fire extinguishing agent.Iron-based auxiliary agent concentration range is in 10-1000ppm, can effectively reduce the critical extinguishing concentration of perfluorohexanone, compared with traditional perfluorohexanone extinguishing agent, the extinguishing effect of composite fire extinguishing agent is improved;And for combustion-supporting phenomenon in perfluorohexanone extinguishing process, after adding iron-based auxiliary agent, combustion-supporting phenomenon can be significantly observed to be inhibited.

Description

Technical Field

[0001] This invention belongs to the field of fire extinguishing agent technology, specifically relating to a composite fire extinguishing agent based on perfluorohexanone. Background Technology

[0002] Over the past decade, developing novel fire extinguishing agents has become a crucial research direction in the fire protection field. Among these, perfluorohexanone (PFH) has gradually gained widespread attention due to its high fire extinguishing efficiency and good environmental performance. However, PFH exhibits combustion-supporting properties when used at low concentrations, significantly limiting its feasibility for low-dose applications and increasing the amount and cost of the agent used. Furthermore, it may produce toxic and corrosive gases during fire extinguishing, thus failing the aerosol explosion test conducted by the US Federal Aviation Administration (FAA). The fire extinguishing mechanism of PFH alone is primarily physical inhibition, with weaker chemical inhibition, making it difficult to further reduce the critical extinguishing concentration and limiting the potential for improving its fire extinguishing effectiveness.

[0003] Chinese patent CN105339052A discloses a fire extinguishing agent and a fire extinguishing method, which includes a metal cadmium and a dispersion medium. The metal cadmium is dispersed in the dispersion medium. The patent introduces the feasibility of using ferrocene as a fire extinguishing agent additive. By combining ferrocene with a dispersion medium (water, ammonium sulfate, magnesium sulfate, etc.) and then with a fire extinguishing agent, the fire extinguishing effect is achieved. This proves that ferrocene, as an additive, can improve the fire extinguishing effect of traditional fire extinguishing agents.

[0004] Chinese patent CN102179027A discloses a ferrocene-based fire extinguishing composition, which includes ferrocene, ferrocene derivatives, or a combination thereof. In use, a pyrotechnic agent is used as a heat and power source. By igniting the pyrotechnic agent, the high temperature of the combustion of the pyrotechnic agent causes the fire extinguishing composition to produce a large amount of fire extinguishing substance, which is sprayed out along with the pyrotechnic agent to achieve the purpose of extinguishing the fire.

[0005] The metal carbonyl fire extinguishing composition disclosed in Chinese patent CN103170084A confirms that carbonyl iron compounds can effectively enhance the chemical fire extinguishing efficiency of fire extinguishing agents, and can produce synergistic fire extinguishing effects with aerosols and traditional fire extinguishing agents, thus shortening the fire extinguishing time.

[0006] Based on existing technologies, it is known that although iron-based additives have been applied in the field of fire extinguishing agents, there are still many shortcomings and research gaps: Ferrocene or carbonyl iron are mostly used alone as additives or main materials in aerosol, dry powder, and water-based fire extinguishing agent systems. There is no research on using ferrocene and carbonyl iron as additives, nor on developing new composite fire extinguishing agents by combining the two additives with perfluorohexanone. The complementary properties of the two (ferrocene has good thermal stability, and carbonyl iron has strong activity) have not been utilized to achieve a synergistic improvement in the fire extinguishing efficiency of perfluorohexanone. In addition, if iron-based additives are directly mixed with perfluorohexanone, solid iron-based additives are prone to problems such as agglomeration, precipitation, and poor compatibility, which affect the stability of the composite fire extinguishing agent system. Summary of the Invention

[0007] The purpose of this invention is to provide a composite fire extinguishing agent based on perfluorohexanone, which effectively improves the fire extinguishing effect of traditional perfluorohexanone.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A composite fire extinguishing agent based on perfluorohexanone, mainly composed of perfluorohexanone and iron-based additives; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is not less than 98%; the mass concentration of the iron-based additives in the composite fire extinguishing agent is 1-1000 ppm; the iron-based additives are any one or a combination of ferrocene additives and carbonyl iron additives.

[0010] The perfluorohexanone-based composite fire extinguishing agent of this invention mainly consists of perfluorohexanone and iron-based additives, wherein the iron-based additives are any one or a combination of ferrocene additives and carbonyl iron additives. The components work synergistically to form a perfluorohexanone-based composite fire extinguishing agent. As the concentration ratio of the iron-based additives in the composite solution changes, the critical extinguishing concentration of perfluorohexanone can be effectively reduced. Compared with traditional perfluorohexanone fire extinguishing agents, the fire extinguishing effect of the composite fire extinguishing agent is improved. Furthermore, the combustion-supporting phenomenon during the perfluorohexanone fire extinguishing process is significantly suppressed after the addition of the iron-based additives. Both the ferrocene additive and the carbonyl iron additive are iron-based active additives, which can form a synergistic effect with the perfluorohexanone fire extinguishing agent. Ferrocene additives exhibit good thermal stability, while carbonyl iron additives demonstrate strong activity, rapidly decomposing at high temperatures to produce active iron components. These components efficiently capture H and OH free radicals in combustion chain reactions, interrupting the combustion chain. Carbonyl iron additives can also rapidly catalyze the decomposition of perfluorohexanone (PFH) extinguishing agents, enhancing their extinguishing effect and accelerating the extinguishing rate. Simultaneously, the iron-based active components in the additives can form a barrier layer on the surface of combustible materials, inhibiting reignition. Both types of iron-based additives improve extinguishing efficiency.

[0011] The aforementioned composite fire extinguishing agent based on perfluorohexanone is composed of perfluorohexanone, iron-based additives, and solvents; the solvent has a mass fraction of not less than 1% in the composite fire extinguishing agent.

[0012] The solvent is any one or a combination of perfluorohexane, toluene, xylene, acetone, butanone, ethyl acetate, ethylbenzene, diethyl ether, benzene, and dichloromethane.

[0013] Perfluorohexane is a perfluoroinert solvent, completely miscible with perfluorohexanone, and can stabilize ferrocene and iron carbonyl. Toluene, xylene, ethylbenzene, and benzene are weakly polar aromatic hydrocarbons with excellent chemical inertness, which can efficiently dissolve ferrocene and protect the iron carbonyl structure. Acetone and butanone are moderately polar ketones, which can be compounded in small amounts to assist in the solubilization of ferrocene, but pose a slight risk of decomposition to iron carbonyl. Ethyl acetate and diethyl ether are weakly polar esters and ethers with good solubility, which can improve the miscibility of the system. Various solvents can be compounded according to their complementary polarity and synergistic inertness to form a stable system that is perfectly compatible with perfluorohexanone composite fire extinguishing agents, ensuring the fire extinguishing activity of iron-based additives.

[0014] The perfluorohexanone-based composite fire extinguishing agent of this invention introduces a solvent for the solid iron-based additives, which improves the compatibility between the iron-based additives and the perfluorohexanone fire extinguishing agent, thereby enhancing the stability of the fire extinguishing agent system. The iron-based additives can exist in both liquid and solid forms at room temperature. The liquid iron-based additives are directly compatible with perfluorohexanone solutions without stratification or aggregation. Examples include alkyl ferrocene and vinyl ferrocene additives, which are liquid at room temperature and directly compatible with perfluorohexanone solutions without the need for a solvent. The solid iron-based additives, such as ferrocene additives and carbonyl iron additives containing polar functional groups (aldehydes, ketones, acids, hydroxyl groups, amines, phosphine), are not directly compatible with perfluorohexanone. Introducing a solvent ensures the compatibility of the solid iron-based additives with the perfluorohexanone fire extinguishing agent, thus guaranteeing the stability of the composite fire extinguishing agent system.

[0015] The ferrocene additive is any one or a combination of ferrocene, alkyl ferrocene, ferrocene aldehydes and ketones, ferrocene carboxylic acids and their derivatives, ferrocene alcohols, phenols and ethers, ferrocene hydrocarbons, ferrocene nitrogen-containing compounds, and ferrocene sulfur-containing and phosphorus-containing compounds.

[0016] The ferrocene additives used in this invention are all stable at room temperature and do not decompose, but rapidly volatilize at high temperatures, releasing iron-based core fire extinguishing particles. The selected ferrocene additives are generally non-toxic, environmentally friendly, and do not cause secondary pollution. Furthermore, the ferrocene additives exhibit a chemical inhibition effect during fire extinguishing, which, combined with the physical action of perfluorohexanone, creates a synergistic effect, significantly improving fire extinguishing efficiency and reducing the amount of perfluorohexanone extinguishing agent required.

[0017] The ferrocene additives selected in this invention, when formulated into a composite fire extinguishing agent, significantly enhance the ability to prevent fire reignition. This is reflected in the different types of ferrocene derivatives within the ferrocene additives, which have different functional groups and exhibit varying effects in a fire. For example, carboxylic acid and phosphorus-containing ferrocene compounds release CO2 and PO3- particles during the fire extinguishing process, which can act as flame retardants. Furthermore, based on the different functional groups of the ferrocene additives, composite fire extinguishing agents with different functional groups can be selected to suit various fire extinguishing scenarios. For instance, halogenated hydrocarbon ferrocene is suitable for hydrocarbon liquid fires in oil depots and petrochemical plants.

[0018] The ferrocene aldehydes and ketones are any one or a combination of ferrocene formaldehyde, 1,1'-ferrocene diformaldehyde, acetylferrocene, 1,1'-diacetylferrocene, benzoylferrocene, 1,1'-dibutyrylferrocene, and (hydrazylcarbonyl)ferrocene.

[0019] The ferrocene additive used in this invention can be an alkyl-based ferrocene. This alkyl-based ferrocene is liquid at room temperature and is directly compatible with perfluorohexanone fire extinguishing agents without stratification or aggregation. Examples include methylferrocene, ethylferrocene, butylferrocene, and tert-butylferrocene. Alkyl-based ferrocene exhibits excellent compatibility with perfluorohexanone; the alkyl group does not interfere with the release of iron particles, thus improving its fire extinguishing efficiency.

[0020] The alkyl ferrocene is any one or a combination of methyl ferrocene, ethyl ferrocene, butyl ferrocene, and tert-butyl ferrocene.

[0021] The ferrocene carboxylic acid and its derivatives are any one or a combination of ferrocene carboxylic acid, 1,1'-ferrocene dicarboxylic acid, ferrocene acetic acid, 3-ferrocene acyl propionic acid, ferrocene carboxyl chloride, and cyanoferrocene.

[0022] The ferrocene alcohol, phenol and ether compound are any one or a combination of ferrocene methanol, 1-hydroxyethylferrocene, and 1,1'-ferrocene dimethanol.

[0023] The ferrocene hydrocarbon compound is any one or a combination of 1,1'-dimethylferrocene, 1,1'-diethylferrocene, vinylferrocene, cyclopentenylferrocene, cyclohexenylferrocene, ferrocene acetylene, 1,1'-dibromoferrocene, and bis(pentamethylcyclopentadiene)ferro(II).

[0024] At room temperature, vinyl ferrocene is a liquid and is directly compatible with perfluorohexanone fire extinguishing agents without stratification or aggregation. The alkenylyl groups do not interfere with the release of iron particles, and the halogen atoms decompose at high temperatures to release halogen free radicals, which synergistically block chain reactions with iron particles, thus improving fire extinguishing efficiency.

[0025] The nitrogen-containing ferrocene compounds are any one or a combination of (dimethylaminomethyl)ferrocene, (S)-(-)-N,N-dimethyl-1-ferrocene ethylamine, (R)-(+)-N,N-dimethyl-1-ferrocene ethylamine, (ferrocenemethyl)trimethylammonium iodide, (ferrocenemethyl)dodecyl dimethylammonium bromide, N-(tert-butoxycarbonyl)aminoferrocene, (S)-N,N-dimethyl-1-ferrocene ethylamine (L)-tartrate, (R)-1-[(Sp)-2-(diphenylphosphino)ferrocene]ethylamine, (S)-(4-isopropyloxazoline-2-yl)ferrocene, and N-[(1S)-1-ferrocene-2-(diphenylphosphino)ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0026] The sulfur- and phosphorus-containing ferrocene compounds are 1,1'-bis(diphenylphosphine)ferrocene, 1,1'-bis(dicyclohexylphosphine)ferrocene, 1,1'-bis(dichlorophosphine)ferrocene, (1,1'-bis(diphenylphosphine)ferrocene)nickel dichloride, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, (R,R'')-2,2''-bis(diphenylphosphine)-1,1''-bisferrocene, (S)-(+)-N,N-dimethyl-1-(2-biphenylphosphine)ferrocene ethylamine, (R)-(-)-1-[(S)-2-(diphenylphosphine)ferrocene]benzylamine, (S)-1-[(RP)-2-(diphenylphosphine)ferrocene]ethylamine (R)-1-[(R)-2-(dicyclohexylphosphino)ferrocene]ethyldicyclohexylphosphino, (R)-1-[(S)-2-(diphenylphosphino)ferrocene]ethyldi-tert-butylphosphino, (Rp)-1-dicyclohexylphosphino-2-[(R)-α-(dimethylamino)-2-(dicyclohexylphosphino)benzyl]ferrocene, (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocene]ethyldicyclohexylphosphino, (R)-N-diphenylphosphino-N-methyl-(S)-2-(diphenylphosphino)ferrocene ethylamine, (R)-1-[(SP)-2-(di-tert-butylphosphino)ferrocene]ethyldiphenylphosphino 、(S)-1-[(RP)-2-(dicyclohexylphosphine)ferrocene]ethyl di-tert-butylphosphine, [1,1'-bis(di-phenylphosphine)ferrocene]palladium dichloride (II), dichloromethane complex (1:1), (R)-1-[(SP)-2-(diphenylphosphine)ferrocene]ethyl di(3,5-xylyl)phosphine, (S)-N,N-dimethyl-1-[(R)-1',2-bis(diphenylphosphine)ferrocene]ethylamine, (1S)-1-(diphenylphosphine)-2-[(1R)-1-(diphenylphosphine)ethyl]ferrocene, (di-2-norborneol polyphosphine chloride)(2-dimethylaminomethylferrocene-1-yl)palladium (II), (S P)-1-dicyclohexylphosphine-2-[(S)-α-(dimethylamino)-2-(dicyclohexylphosphine)benzyl]ferrocene, (S,Rp,SSPO)-1-tert-butylphosphine)-2-[1-(diphenylphosphine)ethyl]ferrocene, (R,Sp,RSPO-1-phenylphosphinoyl)-2-[1-(di-tert-butylphosphine)ethyl]ferrocene, 1,1'-bis(diphenylphosphine)ferrocene methanesulfonate)palladium(II), (R)-N,N-dimethyl-1-[(S)-1',2-bis(diphenylphosphine)ferrocene]ethylamine, 4-(tert-butyl)-1,2-bis(diphenylphosphine)-1'-(diisopropylphosphine)ferrocene, or any combination thereof.

[0027] The iron-based additives are any one or a combination of Fe-CO coordinated iron carbonyl compounds, organic acid salt iron carbonyl compounds, aromatic ring, heterocyclic, porphyrin iron carbonyl compounds, and alcohol or alkoxy iron carbonyl compounds.

[0028] The carbonyl iron compounds mentioned in this invention can all decompose and release metal ions at high temperatures. These metal ions can capture the O, OH, and H free radicals necessary for the chain combustion reaction, thereby interrupting the chain combustion reaction and achieving efficient fire extinguishing.

[0029] The Fe-CO coordinated carbonyl iron compounds used in this invention are solid at room temperature and readily soluble in perfluorohexanone, ensuring compatibility with perfluorohexanone extinguishing agents and enabling the formation of a stable system with the extinguishing agent. The Fe-CO coordination bonds in these compounds easily break at high temperatures, thereby catalyzing the decomposition of perfluorohexanone extinguishing agents, rapidly blocking the combustion chain reaction, and improving fire extinguishing efficiency. Simultaneously, the compounds exhibit moderate thermal stability and will not decompose or become inactive at room temperature, ensuring the storage stability and effectiveness of the extinguishing agent. In this patent, the preferred carbonyl iron additive is a Fe-CO coordinated carbonyl iron compound. The Fe-CO bond in the Fe-CO coordinated carbonyl iron breaks, releasing Fe ions, achieving a highly efficient fire extinguishing effect.

[0030] The Fe-CO coordinated carbonyl iron compound is any one or a combination of dodecyltriferrocarbonyl, cyclohexadienetricarbonyliron, cyclopentadienyldicarbonyliron dimer, N-(tert-butoxycarbonyl)aminoferrocene, hexafluorophosphate tricarbonyl(2-methoxycyclohexadieneon)iron, and dinonylcarbonyliron.

[0031] Dinonylcarbonyl iron is a low-temperature decomposition type with a rapid thermal response, releasing active iron atoms or iron oxides instantly upon contact with fire, enabling rapid extinguishing in the early stages of a fire. Dodecyltriferric iron is a medium-to-high temperature stable type with a slow and persistent decomposition, exhibiting outstanding high-temperature flame suppression and anti-reignition capabilities. The mixture formed by combining dinonylcarbonyl iron and dodecyltriferric iron creates a gradient fire extinguishing system that combines rapid low-temperature activation with long-term high-temperature suppression. Furthermore, the mixture exhibits superior compatibility and storage stability with perfluorohexanone, produces no corrosive byproducts during fire extinguishing, and can synergistically enhance the effects when combined with other iron-based additives.

[0032] The organic acid salt carbonyl iron compound is any one or a combination of ferric acetate, ferric stearate, ferric oleate, ferric oxalate (III) hexahydrate, ferric oxalate (II) hexahydrate, ferric p-toluenesulfonate, ferrous glycinate, ferrous fumarate, ferric gluconate (II), ferric citrate (III) hydrate, ferric ammonium citrate, ferric tartrate, ferric sodium ethylenediaminetetraacetate, and ferric sodium oxalate hydrate.

[0033] The aromatic, heterocyclic, and porphyrin-type carbonyl iron compounds are any one or a combination of tetra-p-tolylporphyrin iron, phthalocyanine iron (II), ferroin, 2-methyl-4-oxo-4H-pyran-3-ol iron (III), (S)-(-)-4-pyrrolidinepyridyl (pentamethylcyclopentadiene) iron, N,N'-bis(salicyl)ethylenediamine iron (II), and ferrocene chloroquine;

[0034] The alcohol and alkoxycarbonyl iron compound is any one or a combination of ferric ethoxide, ferric isopropoxy (III), ferric dextran, ferric heme, deferric methanesulfonate, ferric derarosilicate, ferric 1,3,5-benzenetricarboxylic acid (III) hydrate, ferric dichloro[1,3-bis(diphenylphosphino)propane] (II), and ferric dichloro[1,2-bis(diphenylphosphino)ethane] (II).

[0035] This invention provides a composite fire extinguishing agent based on perfluorohexanone, which can effectively improve the fire extinguishing effect of traditional perfluorohexanone. Simultaneously, it studies the combustion-supporting phenomenon that occurs during the fire extinguishing process of perfluorohexanone, ultimately determining the inhibitory effect of iron-based additives on the combustion-supporting effect of perfluorohexanone fire extinguishing agents. Experiments determine the effective range of iron-based additive concentrations, and examples demonstrate that within this effective range, the synergistic effect of iron-based additives on perfluorohexanone allows the fire extinguishing agent to achieve its optimal fire extinguishing effect while effectively suppressing the combustion-supporting phenomenon during the use of perfluorohexanone fire extinguishing agents.

[0036] The perfluorohexanone-based composite fire extinguishing agent of this invention mainly consists of perfluorohexanone and iron-based additives; the iron-based additives are any one or a combination of ferrocene additives and carbonyl iron additives. The ferrocene additives and carbonyl iron additives achieve highly efficient fire extinguishing in the high-temperature gas phase state. After pyrolysis, they use iron circulation to block the chain combustion reaction, and are effective even at low ppm concentrations. The synergistic effect of the components forms a perfluorohexanone-based composite fire extinguishing agent. When the concentration of the iron-based additives is in the range of 10-1000 ppm, it can effectively reduce the critical fire extinguishing concentration of perfluorohexanone. Compared with traditional perfluorohexanone fire extinguishing agents, the fire extinguishing effect of the composite fire extinguishing agent is improved. Furthermore, the combustion-supporting phenomenon during the perfluorohexanone fire extinguishing process is significantly suppressed after the addition of the iron-based additives. Ferrocene is low in toxicity, has wide applicability, and strong synergistic properties. Carbonyl iron has extremely high fire extinguishing efficiency, and both can effectively improve fire extinguishing performance. This invention selects ferrocene additives and carbonyl iron additives to formulate a novel perfluorohexanone composite fire extinguishing agent. The performance of the composite fire extinguishing agent is optimized compared with the traditional perfluorohexanone fire extinguishing agent in terms of both fire extinguishing effect and flame suppression effect.

[0037] The perfluorohexanone-based composite fire extinguishing agent of the present invention introduces a solvent for the solid compounds in the iron-based additives to ensure the compatibility of the iron-based additives with the perfluorohexanone fire extinguishing agent and to ensure the stability of the composite fire extinguishing agent system.

[0038] The present invention relates to a perfluorohexanone-based composite fire extinguishing agent. The iron-based additive is added to the perfluorohexanone fire extinguishing agent as an additive, and other solvents are used as the dispersion medium to form a composite fire extinguishing agent. There is no need to prepare a separate power source and heat source. At the same time, the addition of the iron-based additive further improves the fire extinguishing effect on the basis of the fire extinguishing effect of traditional fire extinguishing agents.

[0039] This invention relates to a novel composite fire extinguishing agent based on perfluorohexanone, which comprehensively considers the physicochemical properties of ferrocene-based and carbonyl iron additives. By introducing a solvent into the solid iron-based additive, and ensuring the compatibility of the additive with the perfluorohexanone solution, the possibility of combining the ferrocene additive with the carbonyl iron additive is proposed to form a novel fire extinguishing agent. The combination of these two substances improves the fire extinguishing efficiency of the agent.

[0040] This invention conducts experiments to verify the practicality of the novel composite fire extinguishing agent. During the experiment, the composite fire extinguishing agent is heated in an oil bath and extinguished in a vaporized state, achieving a highly efficient fire extinguishing effect and improving the utilization efficiency of perfluorohexanone fire extinguishing agent. At the same time, the addition of additives improves the fire extinguishing efficiency of perfluorohexanone fire extinguishing agent and inhibits the combustion-supporting phenomenon during the use of perfluorohexanone fire extinguishing agent. The selected iron-based additives ensure green environmental protection while improving the fire extinguishing effect, which is in line with the development concept of the new era. Attached Figure Description

[0041] Figure 1 This is a test platform for the fire extinguishing performance of a gas cup burner; including: 1-camera, 2-liquid storage tank (ethanol or n-heptane), 3-cup burner, 4-heating belt, 5-oil bath mixing chamber, 6-peristaltic pump, 7-fire extinguishing agent tank, 8-flow meter, 9-gas storage tank, 10-air compressor;

[0042] Figure 2 The curves show the changes in flame height and width during the combustion of anhydrous ethanol and the extinguishing effect of perfluorohexanone; the left side shows the change in flame width, and the right side shows the change in flame height. Detailed Implementation

[0043] The present invention will be further described below with reference to specific embodiments.

[0044] Example 1

[0045] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 75 ppm, and the remainder is solvent, which is toluene; the iron-based additives are ferrocene.

[0046] The preparation method of the perfluorohexanone-based composite fire extinguishing agent in this embodiment involves dissolving an iron-based additive in a solvent and then mixing it with perfluorohexanone.

[0047] Example 2

[0048] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives, and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 100 ppm, and the remainder is solvent, which is toluene; the iron-based additives are ferrocene.

[0049] The preparation method is the same as in Example 1.

[0050] Example 3

[0051] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 150 ppm, and the remainder is solvent, which is toluene; the iron-based additives are ferrocene.

[0052] The preparation method is the same as in Example 1.

[0053] Example 4

[0054] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 200 ppm, and the remainder is solvent, which is toluene; the iron-based additives are ferrocene.

[0055] The preparation method is the same as in Example 1.

[0056] Example 5

[0057] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives, and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 200 ppm, and the remainder is solvent; the solvent is a mixed solvent of toluene, xylene, and ethyl acetate in a volume ratio of 6:2:2; the iron-based additive is ferrocene.

[0058] The preparation method is the same as in Example 1.

[0059] Example 6

[0060] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives, and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 200 ppm, and the remainder is solvent; the solvent is a mixed solvent of xylene, butanone, and ethyl acetate in a volume ratio of 5:3:2; the iron-based additive is ferrocene.

[0061] The preparation method is the same as in Example 1.

[0062] Example 7

[0063] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives, and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 200 ppm, and the remainder is solvent; the solvent is a mixed solvent of toluene, acetone, butanone, and ethyl acetate in a volume ratio of 5:2:2:1; the iron-based additive is ferrocene.

[0064] The preparation method is the same as in Example 1.

[0065] Example 8

[0066] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 75 ppm, and the remainder is solvent, which is acetone; the iron-based additive is ferrocene formaldehyde.

[0067] The preparation method is the same as in Example 1.

[0068] Example 9

[0069] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 100 ppm, and the remainder is solvent, which is acetone; the iron-based additive is ferrocene formaldehyde.

[0070] The preparation method is the same as in Example 1.

[0071] Example 10

[0072] The perfluorohexanone-based composite fire extinguishing agent of this embodiment is composed of perfluorohexanone, iron-based additives and solvents; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is 98%; the mass concentration of iron-based additives in the composite fire extinguishing agent is 150 ppm, and the remainder is solvent, which is acetone; the iron-based additive is ferrocene formaldehyde.

[0073] The preparation method is the same as in Example 1.

[0074] The composition of the perfluorohexanone-based composite fire extinguishing agents in Examples 11-21 is shown in Table 1, and the rest is the same as in Example 1.

[0075] Table 1. Composition of the perfluorohexanone-based composite fire extinguishing agents in Examples 11-21

[0076]

[0077] The composition of the perfluorohexanone-based composite fire extinguishing agents in Examples 22-34 is shown in Table 2, and the rest is the same as in Example 1.

[0078] Table 2. Composition of the perfluorohexanone-based composite fire extinguishing agents in Examples 22-34

[0079]

[0080] Comparative Example 1

[0081] The extinguishing agent in this comparative example consists of 100% perfluorohexanone.

[0082] Experimental Example 1

[0083] This experimental example verifies the performance of the composite fire extinguishing agent in Examples 1-34, using a gas cup burner fire extinguishing performance testing platform, such as... Figure 1 The composite extinguishing agent enters the oil bath mixing chamber 5 from the extinguishing agent tank 7 via the peristaltic pump 6, and air enters the oil bath mixing chamber 5 from the air compressor 10 via the air storage tank 9 and the flow meter 8. The two are mixed in the oil bath mixing chamber 5 and heated by the oil bath before flowing into the cup burner 3 for extinguishing experiments. The ethanol or n-heptane required for the extinguishing experiment is supplied by the liquid storage tank 2. The oil bath mixing chamber 5 and the cup burner 3 are equipped with a winding heating belt 4. The peristaltic pump 6 and the flow meter 8 determine the amount of composite extinguishing agent (or perfluorohexanone) and air used, respectively. The camera 1 is used to observe and record the flame conditions.

[0084] The performance verification method is as follows:

[0085] Perfluorohexanone (PFH) composite extinguishing agent and air were introduced into an oil bath mixing chamber. Under oil bath heating conditions, the components were sublimated and fully mixed in the gaseous state. The sublimated gas was then introduced into a cup burner for extinguishing experiments. As the composite extinguishing agent was introduced, the critical extinguishing concentration of PPH was calculated based on the volume of the extinguishing agent and the volume of air introduced, and the relationship between the critical extinguishing concentration of PPH and the concentration of iron-based additives was observed. Therefore, the concentration range of iron-based additives when the extinguishing effect is optimized can be determined. During the experiment, the flame morphology was measured, that is, the changes in flame height, width and flame temperature were observed to observe the inhibitory effect of iron-based additives on the combustion-supporting phenomenon during the use of PPH extinguishing agent. To ensure the scientific nature of the experimental results, the flame images were digitized in this experiment.

[0086] The critical extinguishing concentration in the verification method is calculated using the following formula:

[0087]

[0088]

[0089]

[0090] in, Indicates the critical extinguishing concentration. For airflow, , where n represents the amount of extinguishing agent, R is the universal gas constant, T is the thermodynamic temperature, P is the atmospheric pressure of the experimental environment, and L is the calibrated flow rate of the peristaltic pump.

[0091] Examples 1-10 used anhydrous ethanol as flame fuel and were tested according to the above verification method. The test results of the critical extinguishing concentration are shown in Table 3 below.

[0092] Table 3 Performance Data of Anhydrous Ethanol Flame Extinguishing Agent

[0093]

[0094] Examples 11-21 used n-heptane flame fuel and were tested according to the above verification method. The test results of the critical extinguishing concentration are shown in Table 4 below.

[0095] Table 4 Performance Data of n-Heptane Flame Extinguishing Agent

[0096]

[0097] Examples 22-34 used anhydrous ethanol flame fuel and were tested according to the above verification method. The test results of the critical extinguishing concentration are shown in Table 5 below.

[0098] Table 5 Performance Data of Anhydrous Ethanol Flame Extinguishing Agent

[0099]

[0100] As can be seen from Tables 3, 4, and 5, the concentration ratio of the perfluorohexanone extinguishing agent base remained unchanged, with only the type and concentration of the added iron-based additives and the flame fuel being changed. Based on the extinguishing data of the two types of flames, it can be seen that compared with the perfluorohexanone extinguishing agent base, the critical extinguishing concentration of perfluorohexanone decreased after the addition of iron-based additives. The addition of iron-based additives improved the extinguishing efficiency of perfluorohexanone, and iron-based additives can enhance the extinguishing effect of perfluorohexanone.

[0101] Experimental Example 2

[0102] This experiment was used to test the effect of adding iron-based additives on inhibiting the combustion-supporting phenomenon during the extinguishing process of low-concentration perfluorohexanone. The volume fraction of perfluorohexanone was gradually increased (0-6%) during extinguishing, and the changes in flame morphology were observed during the extinguishing process.

[0103] Anhydrous ethanol flame fuel and the composite extinguishing agent of Examples 1-3 were selected, and the verification method of Experimental Example 1 was followed. Figure 1 The test platform was used to test the effect of adding iron-based additives to suppress combustion phenomena when using perfluorohexanone at low concentrations for fire extinguishing. The changes in flame morphology when adding additives to low-concentration perfluorohexanone for fire extinguishing were also tested. Figure 2 In the accompanying drawings, 0 ppm represents Comparative Example 1, 75 ppm represents Example 1, 100 ppm represents Example 2, and 150 ppm represents Example 3.

[0104] Figure 2 The curves show the changes in flame height and width during the combustion of anhydrous ethanol flame and the extinguishing effect of perfluorohexanone. Overall, without iron-based additives, the flame width and height of the perfluorohexanone extinguishing agent are larger. When different mass concentrations of ferrocene are added, with the increase of the volume fraction of perfluorohexanone (i.e., the change in the amount of perfluorohexanone used (0-6%)), the flame width does not change significantly, but the flame height decreases to varying degrees. It can be clearly observed that the combustion-supporting phenomenon of perfluorohexanone extinguishing agent under low concentration conditions is suppressed after the addition of iron-based additives.

Claims

1. A composite fire extinguishing agent based on perfluorohexanone, characterized in that, It is mainly composed of perfluorohexanone and iron-based additives; wherein, the mass fraction of perfluorohexanone in the composite fire extinguishing agent is not less than 98%; the mass concentration of the iron-based additives in the composite fire extinguishing agent is 1-1000 ppm; the iron-based additives are any one or a combination of ferrocene additives and carbonyl iron additives.

2. The composite fire extinguishing agent based on perfluorohexanone according to claim 1, characterized in that, It is composed of perfluorohexanone, iron-based additives and solvents; the solvent has a mass fraction of not less than 1% in the composite fire extinguishing agent.

3. The composite fire extinguishing agent based on perfluorohexanone according to claim 2, characterized in that, The solvent is any one or a combination of perfluorohexane, toluene, xylene, acetone, butanone, ethyl acetate, ethylbenzene, diethyl ether, benzene, and dichloromethane.

4. The composite fire extinguishing agent based on perfluorohexanone according to claim 1, characterized in that, The ferrocene additive is any one or a combination of ferrocene, alkyl ferrocene, ferrocene aldehydes and ketones, ferrocene carboxylic acids and their derivatives, ferrocene alcohols, phenols and ethers, ferrocene hydrocarbons, ferrocene nitrogen-containing compounds, and ferrocene sulfur-containing and phosphorus-containing compounds.

5. The composite fire extinguishing agent based on perfluorohexanone according to claim 4, characterized in that, The ferrocene aldehydes and ketones are any one or a combination of ferrocene formaldehyde, 1,1'-ferrocene diformaldehyde, acetylferrocene, 1,1'-diacetylferrocene, benzoylferrocene, 1,1'-dibutyrylferrocene, and (hydrazylcarbonyl)ferrocene.

6. The composite fire extinguishing agent based on perfluorohexanone according to claim 4, characterized in that, The alkyl ferrocene is any one or a combination of methyl ferrocene, ethyl ferrocene, butyl ferrocene, and tert-butyl ferrocene. The ferrocene carboxylic acid and its derivatives are any one or a combination of ferrocene carboxylic acid, 1,1'-ferrocene dicarboxylic acid, ferrocene acetic acid, 3-ferrocene acyl propionic acid, ferrocene carboxyl chloride, and cyanoferrocene. The ferrocene alcohol, phenol and ether compound are any one or a combination of ferrocene methanol, 1-hydroxyethylferrocene, and 1,1'-ferrocene dimethanol. The ferrocene hydrocarbon compound is any one or a combination of 1,1'-dimethylferrocene, 1,1'-diethylferrocene, vinylferrocene, cyclopentenylferrocene, cyclohexenylferrocene, ferrocene acetylene, 1,1'-dibromoferrocene, and bis(pentamethylcyclopentadiene)ferro(II).

7. The composite fire extinguishing agent based on perfluorohexanone according to claim 4, characterized in that, The nitrogen-containing ferrocene compounds are any one or a combination of (dimethylaminomethyl)ferrocene, (S)-(-)-N,N-dimethyl-1-ferrocene ethylamine, (R)-(+)-N,N-dimethyl-1-ferrocene ethylamine, (ferrocenemethyl)trimethylammonium iodide, (ferrocenemethyl)dodecyl dimethylammonium bromide, N-(tert-butoxycarbonyl)aminoferrocene, (S)-N,N-dimethyl-1-ferrocene ethylamine (L)-tartrate, (R)-1-[(Sp)-2-(diphenylphosphino)ferrocene]ethylamine, (S)-(4-isopropyloxazoline-2-yl)ferrocene, and N-[(1S)-1-ferrocene-2-(diphenylphosphino)ethyl]-3,5-bis(trifluoromethyl)benzamide.

8. The composite fire extinguishing agent based on perfluorohexanone according to claim 4, characterized in that, The sulfur- and phosphorus-containing ferrocene compounds are 1,1'-bis(diphenylphosphine)ferrocene, 1,1'-bis(dicyclohexylphosphine)ferrocene, 1,1'-bis(dichlorophosphine)ferrocene, (1,1'-bis(diphenylphosphine)ferrocene)nickel dichloride, [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride, (R,R'')-2,2''-bis(diphenylphosphine)-1,1''-bisferrocene, (S)-(+)-N,N-dimethyl-1-(2-biphenylphosphine)ferrocene ethylamine, (R)-(-)-1-[(S)-2-(diphenylphosphine)ferrocene]benzylamine, (S)-1-[(RP)-2-(diphenylphosphine)ferrocene]ethyldicyclohexylphosphine, (S... -(+)-1-[(R)-2-(dicyclohexylphosphino)ferrocene]ethyldicyclohexylphosphine, (R)-(-)-1-[(S)-2-(diphenylphosphino)ferrocene]ethyldi-tert-butylphosphine, (Rp)-1-dicyclohexylphosphine-2-[(R)-α-(dimethylamino)-2-(dicyclohexylphosphine)benzyl]ferrocene, (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocene]ethyldicyclohexylphosphine, (R)-N-diphenylphosphine-N-methyl-(S)-2-(diphenylphosphine)ferroceneethylamine, (R)-1-[(SP)-2-(di-tert-butylphosphino)ferrocene]ethyldiphenylphosphine, (S)-1-[(RP)-2-(dicyclohexylphosphine) [1,1'-bis(di-phenylphosphino)ferrocene]palladium dichloride (II), dichloromethane complex (1:1), (R)-1-[(SP)-2-(diphenylphosphino)ferrocene]ethylbis(3,5-dimethyl)phosphine, (S)-N,N-dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocene]ethylamine, (1S)-1-(diphenylphosphino)-2-[(1R)-1-(diphenylphosphino)ethyl]ferrocene, (2-dimethylaminomethylferrocene-1-yl)palladium (II), (SP)-1-dicyclohexylphosphine-2-[(S)-α-(dimethylamino)-2-(di-2- ... The following are any one or combination of the following: cyclohexylphosphine benzyl ferrocene, (S,Rp,SSPO)-1-tert-butylphosphine)-2-[1-(diphenylphosphine)ethyl]ferrocene, (R,Sp,RSPO-1-phenylphosphinoyl)-2-[1-(di-tert-butylphosphine)ethyl]ferrocene, (S,Rp,SSPO)-1-phenylphosphine)-2-[1-(tert-butylphosphine)ethyl]ferrocene, 1,1'-bis(diphenylphosphine)ferrocene methanesulfonate palladium(II), (R)-N,N-dimethyl-1-[(S)-1',2-bis(diphenylphosphine)ferrocene]ethylamine, and 4-(tert-butyl)-1,2-bis(diphenylphosphine)-1'-(diisopropylphosphine)ferrocene.

9. The composite fire extinguishing agent based on perfluorohexanone according to claim 1, characterized in that, The iron-based additives are any one or a combination of Fe-CO coordinated iron carbonyl compounds, organic acid salt iron carbonyl compounds, aromatic ring, heterocyclic, porphyrin iron carbonyl compounds, and alcohol or alkoxy iron carbonyl compounds.

10. The composite fire extinguishing agent based on perfluorohexanone according to claim 9, characterized in that, The Fe-CO coordinated carbonyl iron compound is any one or a combination of dodecyltriferrocarbonyl, cyclohexadienetricarbonyliron, cyclopentadienyldicarbonyliron dimer, N-(tert-butoxycarbonyl)aminoferrocene, hexafluorophosphate tricarbonyl(2-methoxycyclohexadieneon)iron, and dinonylcarbonyliron. The organic acid salt carbonyl iron compound is any one or a combination of ferric acetate, ferric stearate, ferric oleate, ferric oxalate (III) hexahydrate, ferric oxalate (II) hexahydrate, ferric p-toluenesulfonate, ferrous glycinate, ferrous fumarate, ferric gluconate (II), ferric citrate (III) hydrate, ferric ammonium citrate, ferric tartrate, ferric sodium ethylenediaminetetraacetate, and ferric sodium oxalate hydrate. The aromatic, heterocyclic, and porphyrin-type carbonyl iron compounds are any one or a combination of tetra-p-tolylporphyrin iron, phthalocyanine iron (II), ferroin, 2-methyl-4-oxo-4H-pyran-3-ol iron (III), (S)-(-)-4-pyrrolidinepyridyl (pentamethylcyclopentadiene) iron, N,N'-bis(salicyl)ethylenediamine iron (II), and ferrocene chloroquine; The alcohol and alkoxycarbonyl iron compound is any one or a combination of ferric ethoxide, ferric isopropoxy (III), ferric dextran, ferric heme, deferric methanesulfonate, ferric derarosilicate, ferric 1,3,5-benzenetricarboxylic acid (III) hydrate, ferric dichloro[1,3-bis(diphenylphosphino)propane] (II), and ferric dichloro[1,2-bis(diphenylphosphino)ethane] (II).

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