CN108421202A - A kind of fire extinguishant compositions - Google Patents

Abstract

A kind of fire extinguishant compositions, including ten difluoros, 2 methyl, 3 pentanone, 45 65wt%, 5 methyl, 2 octanone 15 30%, 10 30wt% of unsaturated oils and covering flavoring agent 1wt%；The unsaturation oils is selected from palmitoleic acid, leukotrienes or ricinoleic acid.Fire-fighting efficiency of the present invention is high, good environmental protection, non-toxic, can be effective for all kinds of fire.

Description

A fire extinguishing composition

technical field

The invention relates to a fire extinguishing agent composition and a preparation method thereof, belonging to the technical field of fire protection.

Background technique

To successfully prevent and extinguish a fire, two important factors must be considered: (1) isolating the burning material from the air, and (2) avoiding or reducing the temperature necessary for the combustion to proceed. Therefore, one approach is to extinguish small fires by covering the burning surface with fire extinguishers or foam to isolate the burning material from oxygen in the air. Usually, the main principle of pouring water on the burning surface for extinguishing the fire is to reduce the temperature to a point where the burning cannot continue. Obviously, in the case of water, some phenomenon of isolating the burning material from the air can also occur.

The method of fire extinguishing is determined by some conditions, such as the place where the fire occurs, the composition of the burning material, and the scale of the fire. Halocarbon fire extinguishing agents are often used in closed spaces such as computer rooms, warehouses, libraries with rare books, pipelines in gasoline stations and similar places. Halocarbon fire extinguishing agents not only extinguish fires, but also damage the room and its contents. more or less damaged. Correspondingly, when using water, sometimes floods can also exceed fires.

Among many types of fire extinguishing media, gaseous fire extinguishing agent is widely used because of its low fire extinguishing concentration, fast fire extinguishing speed, and no residue in fire extinguishing. The currently used fire extinguishing agents mainly include the following: Halon fire extinguishing agent, HFC fire extinguishing agent and other fire extinguishing agents.

Halon (transliteration of Halon) refers to chemicals belonging to halogenated alkanes. It achieves a good fire extinguishing effect by capturing free radicals and destroying the fire extinguishing agent on the flame contact surface to interrupt the combustion chain. The halon fire extinguishing agent widely used in the fire protection industry is an ozone-depleting substance and is one of the main culprits in the destruction of the ozone layer. When people use halon fire extinguishers to fight fires or train, halon gas is naturally released into the atmosphere. Halon contains chlorine and bromine. After being irradiated by sunlight in the atmosphere, free radicals of chlorine and bromine are decomposed. These chemically active groups combine with ozone to take away an oxygen atom in the ozone molecule, triggering a destructive chain reaction , so that the ozone layer is destroyed, thereby reducing the concentration of ozone, resulting in an ozone hole. Halons survive in the atmosphere for decades, and their damage to the ozone layer in the stratosphere will last for decades or even longer. Therefore, halons have a huge effect on the destruction of the ozone layer. In 1989, the Montreal Agreement was signed internationally, and developed countries began in 1995, and developing countries began in 2005 to ban the use of halon series fire extinguishing agents. Mainly the halon system will destroy the ozone layer in the atmosphere.

The fire extinguishing agents that replace halon are mainly HFC fire extinguishing agents. HFCs, such as heptafluoropropane (HFC227ea), hexafluoropropane, etc. Heptafluoropropane (HFC-227ea/FM200) is a clean gas fire extinguishing agent that mainly uses chemical fire extinguishing and also has physical fire extinguishing effects; it is colorless, odorless, low-toxic, non-conductive, and does not pollute the protected object It can cause damage to precision facilities; it can reliably extinguish class B and C fires and electrical fires with a low fire extinguishing concentration; it has small storage space, high critical temperature and low critical pressure, and can be liquefied and stored at room temperature; it does not contain particles after release Or oily residue, no damage to the atmospheric ozone layer (ODP value is zero), stay in the atmosphere for 31 to 42 years, not easy to degrade. Since heptafluoropropane does not contain chlorine or bromine, it will not damage the atmospheric ozone layer, so it is used to replace the halon fire extinguishing medium that is harmful to the environment. However, although heptafluoropropane is relatively stable at room temperature, it will still decompose at high temperature, and the decomposition will produce hydrogen fluoride, which will have a pungent smell. Other combustion products include carbon monoxide and carbon dioxide. That is to say, HFC series fire extinguishing agents have the problem of greenhouse effect, and developed countries have begun to gradually stop using them. In our country, although there is no regulation prohibiting the use. But in the long run, it will definitely be affected in terms of usage.

The 3M company of the United States has launched a fire extinguishing agent called "Fluorinated ketone" (Fluorinated ketone), which is called perfluorohexanone, and its commercial name is Novec1230. It has broad application prospects. Novec1230 is a new type of halon substitute, which overcomes the defects of global warming and climate change caused by the first generation of halon substitutes. Novec1230 fire extinguishing agent is stored in liquid form, and can quickly evaporate and cover when sprayed into protected areas The entire protected area uses heat absorption to extinguish the fire. It has the following advantages: it is a green and environmentally friendly substance, and its harm to the environment and human body is nearly zero; it is a colorless liquid at room temperature, easy to vaporize, normal temperature and pressure, easy to store, and its evaporation heat is only 1/25 of that of water. Strong; physical fire extinguishing, excellent fire extinguishing performance, can be used to protect precision and valuable equipment; clean fire extinguishing agent, not classified as dangerous goods, no residue left after release, easy to transport.

The inventors of the present application have developed a dodecafluoro-2-methyl-3-pentanone fire extinguishing agent composition on the basis of Novec1230 fire extinguishing agent. After searching, there is no relevant report of this composition at home and abroad. The applicant mixed dodecafluoro-2-methyl-3-pentanone, 5-methyl-2-octanone and unsaturated oil for the first time in the world. Excellent results were obtained. Compared with halon or HFC fire extinguishing agent, the fire extinguishing agent composition of the present invention is green and environment-friendly, clean fire extinguishing; compared with Novec1230 fire extinguishing agent, it has better fire extinguishing efficiency.

Contents of the invention

The invention provides a fire extinguishing agent composition, including dodecafluoro-2-methyl-3-pentanone 45-65wt%, 5-methyl-2-octanone 15-30%, unsaturated oil 10-30wt% % and covering flavoring agent 1wt%; the unsaturated oils are selected from palmitoleic acid, linolenic acid or ricinoleic acid. The masking flavoring is lemon oil. The fire extinguishing composition can fill a space around the fire source to absorb heat to smother the fire source. Unsaturated oils are helpful to the dispersion of fire extinguishing agent, thus effectively improving its fire extinguishing efficiency.

Inert gases may also be mixed in the composition. The inert gas is N ₂ , Ar or CO ₂ . The composition can be used as propellant of dry powder and foam fire extinguishing agent. Among them, the dry powder is sodium bicarbonate dry powder, potassium bicarbonate dry powder, potassium chloride dry powder, potassium sulfate dry powder, amino dry powder. The foam is protein foam, fluoroprotein foam, aqueous film-forming foam, and alcohol-resistant foam.

The composition preferably consists of dodecafluoro-2-methyl-3-pentanone 55-65wt%, 5-methyl-2-octanone 20-25wt%, unsaturated oils 10-15wt% and masking flavoring agent 1wt% , composed of 5wt% inert gas.

A method of preventing, controlling and extinguishing fire in an enclosed air area containing combustible materials of a non-self-supporting type, which comprises introducing into the air in the enclosed area an extinguishing agent composition as hereinbefore described in an amount sufficient to impart per mole The heat capacity of total oxygen thereby inhibits the combustion of combustible materials in the enclosed area where the extinguishing agent composition is maintained at 10%-25%.

The use of the above-mentioned fire extinguishing agent composition as a propellant in a portable fire extinguisher is characterized in that it is added in an amount sufficient to provide the portable fire extinguisher with a pressure of at least 150 psi at 21°C ^.

Perfluorohexanone mostly uses hexafluoropropylene as raw material. In an aprotic solvent, perfluorohexanone was synthesized under the catalysis of fluoride ions. The typical synthetic route known at present has: 1, hexafluoropropylene is prepared fluorinated ketone through oxidation reaction: this route generates corresponding hexafluoropropylene oxide by hexafluoropropylene earlier, then under the situation that cesium fluoride is made catalyst and other One molecule of hexafluoropropylene reacts to give perfluorohexanone. This method has poor reaction selectivity and many side reactions. 2. Reaction of hexafluoropropylene with perfluoropropionyl fluoride: This route is the production route of Nwvec1230 produced by 3M Company in the United States. It uses diglyme as solvent and activated potassium fluoride as catalyst at 70°C and 1MPa pressure The product is obtained by reacting hexafluoropropylene with perfluoropropionyl fluoride. This route has good yield and selectivity, but the main difficulty is that perfluoropropionyl fluoride, one of the raw materials, is difficult to prepare and preserve. 3. Epoxidative rearrangement of hexafluoropropylene dimer (perfluoroisohexene): This route uses hexafluoropropylene dimer as raw material, after oxidant epoxidation, under the catalysis of fluoride or triethylamine Obtain perfluorohexanone. In the first step of the epoxidation reaction, there are two possible epoxidation products I and II, but catalytic rearrangement can be performed without isolation to give a single final product. This route also starts from hexafluoropropylene in essence. The advantage is that the epoxidation product does not need to be separated, and the product can be obtained by in-situ reaction. The disadvantage is that there are many by-products in the polymerization reaction of hexafluoropropylene, and the epoxidation product passes through Physical methods cannot separate and the purity of the final product is limited. 4. Prepared by decomposing perfluorocarboxylic acid ester: Trifluoroacetic acid (2-methyl-3-pentanol) ester is fluorinated with fluorine gas to obtain perfluoroacetic acid (2-methyl-3-pentanol) in the presence of concentrated sulfuric acid with Freon 113 as solvent -3-pentanol) ester. Afterwards, potassium fluoride is used as a catalyst to react in diethylene glycol to remove trifluoroethanol fluorine, and then distilled to obtain fluorinated ketones. Since this synthetic route uses fluorine gas to fluorinate raw materials, the degree of fluorination is controlled by capsules, and the C-C bond may be interrupted by fluorine gas, resulting in an increase in by-products and a decrease in reaction selectivity. 5. Reaction of perfluoroisopropyl iodide and perfluoropropionyl chloride: this route uses phenylacetonitrile as solvent, at -196°C to normal temperature, uses tris(diethylamido)phosphorus as catalyst, and undergoes vacuum treatment to generate Fluorinated ketones.

This application adopts the reaction route of hexafluoropropylene and perfluoropropionyl fluoride, and the intermediate perfluoropropionyl fluoride is ring-opened by epoxide to obtain dodecafluoro-2-methyl-3-pentanone; it can also be purchased directly . 5-Methyl-2-octanone is commercially available.

At present, perfluorohexanone, that is, dodecafluoro-2-methyl-3-pentanone is considered as a new generation of green fire extinguishing agent replacing halon in the world. And the inventor is surprised to find through a large number of experiments, the fire extinguishing efficiency after dodecafluoro-2-methyl-3-pentanone mixed with 5-methyl-2-octanone and unsaturated oils is higher than that of dodecafluoro-2-methyl-3-pentanone alone. - 2-methyl-3-pentanone has higher fire extinguishing efficiency, thus a new fire extinguishing agent composition is proposed, which has higher fire extinguishing efficiency, leaves no residue after release, and is convenient for transportation.

Detailed ways

Example 1

Fire extinguishing agent composition 1 is composed of 55 wt% dodecafluoro-2-methyl-3-pentanone, 20 wt% 5-methyl-2-octanone, 24 wt% palmitoleic acid and 1 wt% lemon oil.

Example 2

Fire extinguishing agent composition 2 consists of 50 wt% dodecafluoro-2-methyl-3-pentanone, 30 wt% 5-methyl-2-octanone, 19 wt% linolenic acid and 1 wt% lemon oil.

Example 3

Fire extinguishing agent composition 3, composed of dodecafluoro-2-methyl-3-pentanone 61wt%, 5-methyl-2-octanone 20wt%, ricinoleic acid 13wt%, lemon oil 1wt% and nitrogen 5wt% .

Example 4

Fire extinguishing agent composition 4, composed of dodecafluoro-2-methyl-3-pentanone 65wt%, 5-methyl-2-octanone 19wt%, palmitoleic acid 10wt%, lemon oil 1wt% and carbon dioxide 5% .

Comparative example 5

Fire extinguishing agent composition 5 is composed of dodecafluoro-2-methyl-3-pentanone 75wt% and 5-methyl-2-octanone 25wt%.

Comparative example 6

Fire extinguishing agent composition 6 is composed of dodecafluoro-2-methyl-3-pentanone 100wt%.

Comparative example 7

Fire extinguishing agent composition 7 is composed of 100wt% of 5-methyl-2-octanone.

comparative experiment

In a specific experiment, seven standard crucible furnaces were flooded with overflow pipes with a total length of 3 meters in a laboratory measuring 0.5 x 3 x 3 meters. Adopt the composition of embodiment 1-4 and comparative example 5-7, all can make crucible stove extinguish in less than 10 seconds by pipeline, be respectively 7.2 seconds, 6.8 seconds, 4.9 seconds, 5.6 seconds, 7.9 seconds, 9.1 seconds and 9.4 seconds. Among them, the time used in Example 3 is the shortest.

The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present invention. Should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (9)

1. A fire extinguishing agent composition, comprising dodecafluoro-2-methyl-3-pentanone 45-65wt%, 5-methyl-2-octanone 15-30wt%, unsaturated oils 10-30wt% and 1 wt% of covering flavoring agent; the unsaturated oil is selected from palmitoleic acid, linolenic acid or ricinoleic acid. 2. The fire extinguishing agent composition according to claim 1, characterized in that 1-5% inert gas can also be mixed, and the covering flavoring agent is lemon oil. 3. fire extinguishing composition as claimed in claim 1, is characterized in that, composition is made of dodecafluoro-2-methyl-3-pentanone 55-65wt%, 5-methyl-2-octanone 20- 25 wt%, 10-15 wt% of unsaturated oil, 1 wt% of masking flavoring agent, and 5 wt% of inert gas. 4. fire extinguishing composition as claimed in claim 2 or 3 is characterized in that, composition is made of dodecafluoro-2-methyl-3-pentanone 61wt%, 5-methyl-2-octanone 20wt% , 13wt% of unsaturated oil, 1wt% of masking flavoring agent, 5wt% of inert gas, and the inert gas is N ₂ , Ar or CO ₂ . 5. the purposes of the propellant of fire extinguishing composition as described in one of claim 1-4 as dry powder, foam fire extinguishing agent. 6. purposes as claimed in claim 5, is characterized in that, dry powder is sodium bicarbonate dry powder, potassium bicarbonate dry powder, potassium chloride dry powder, potassium sulfate dry powder, amino dry powder. 7. purposes as claimed in claim 5, is characterized in that, foam is protein foam, fluoroprotein foam, aqueous film-forming foam, anti-solvent foam. 8. A method for preventing, controlling and extinguishing a fire in an enclosed air area, containing a non-self-supporting type of combustible material, comprising introducing the fire extinguishing agent combination as claimed in any one of claims 1-4 in the air in the enclosed area an amount sufficient to impart a heat capacity per mole of total oxygen to inhibit combustion of combustible materials in the enclosed area, the extinguishing agent composition being maintained at 10% to 25% in the enclosed area. 9. The use of the fire extinguishing agent composition as claimed in any one of claims 1-4 as a propellant for a portable fire extinguisher, characterized in that it is added in a sufficient amount to provide the portable fire extinguisher at 21°C , with a pressure of at least 150 ^psi .