CN106955450B - Environment-friendly aqueous film-forming foam extinguishing agent - Google Patents
Environment-friendly aqueous film-forming foam extinguishing agent Download PDFInfo
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- CN106955450B CN106955450B CN201710180150.9A CN201710180150A CN106955450B CN 106955450 B CN106955450 B CN 106955450B CN 201710180150 A CN201710180150 A CN 201710180150A CN 106955450 B CN106955450 B CN 106955450B
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0064—Gels; Film-forming compositions
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Abstract
An environment-friendly aqueous film-forming foam extinguishing agent comprises the following components: betaine surfactant, polyether, diethylene glycol butyl ether, hydrophilic polymer, formaldehyde, triazole, urea, water and a compound shown in formula (I). The preparation method comprises the following steps: adding 80-100 parts by weight of a compound shown in formula (I) and 0-50 parts by weight of sodium hexanesulfonate into a reaction kettle, adding 500-700 parts by weight of water, fully stirring and preheating, adding 50-70 parts by weight of betaine surfactant, 50-70 parts by weight of polyether, 40-60 parts by weight of diethylene glycol butyl ether, 1-4 parts by weight of hydrophilic polymer, 0.1-1 part by weight of formaldehyde, 0.1-1 part by weight of triazole and 20-40 parts by weight of urea under stirring; after stirring evenly, adjusting the pH value to 7 by fresh water or acetic acid, then adding water to the total amount of 1000 parts by weight, and stirring evenly to obtain the product.
Description
Technical Field
The invention relates to the field of fire extinguishing agent materials, in particular to an environment-friendly aqueous film-forming foam extinguishing agent and a preparation method thereof.
Background
Fluorine is the element with the highest electronegativity in nature, so a covalent bond of a carbon-fluorine (C-F) bond has the performance of an ionic bond, the bond energy is very high and can reach 452kJ/mol, and because the atomic radius of the covalently bonded fluorine atom is larger than that of an oxygen atom, the perfluorinated C-C bond can be effectively shielded and protected, so that the fluorine-containing surfactant has good chemical stability and thermal stability compared with the fluorine-containing surfactant.
Due to the unique property of fluorosurfactant that aqueous solutions spread on the oil surface, it is most attractive as the principal ingredient of aqueous film-forming foam extinguishants (AFFFs) in many fluorosurfactant applications. The fire extinguishing function of the water film-forming foam extinguishing agent is mainly performed by the foam layer floating on the oil surface and the water film layer together. When the formulated aqueous film-forming foam is sprayed onto the surface of a fuel, the foam spreads rapidly over the oil surface, while the foam gradually separates out liquid to cool the oil surface. The separated liquid also spreads to form a water film on the oil surface, and the water film and the foam layer jointly inhibit the evaporation of the fuel oil. And the spreading action of the aqueous solution can also drive the foam to rapidly flow to the area which is not extinguished so as to further extinguish the fire. Therefore, the double fire extinguishing capability of the aqueous film-forming foam extinguishing agent makes the aqueous film-forming foam extinguishing agent the most favored one for oil fire extinguishment. The aqueous film-forming foam extinguishing agent consists of a fluorine-containing surfactant, a hydrocarbon surfactant, additives (a foam stabilizer, a conditioning agent, an anti-burning agent, an anti-freezing agent, a cosolvent, a buffer solution, a bacteriostatic agent and the like) for improving the foam performance and water.
However, the fluorine surfactant is difficult to synthesize and expensive, so that the aqueous film-forming foam extinguishing agent is difficult to popularize. The existing aqueous film-forming foam extinguishing agent is limited by the environmental planning administration of the united nations because of containing sustainable organic pollutants (POPs). The use of the foam extinguishing agent containing POPs has been completely prohibited in 2015 in western countries such as the United states, and China will gradually decrease in the coming years and finally completely prohibit the use of the foam extinguishing agent containing POPs. Corresponding substitutes have been developed in the United states, but the technology is strictly confidential, and the product price is very high and is ten times higher than that of the existing aqueous film-forming foam extinguishing agent.
Disclosure of Invention
In order to solve the problems of the prior art, the first aspect of the invention provides an environment-friendly aqueous film-forming foam extinguishing agent, which comprises the following components: betaine surfactant, polyether, diethylene glycol butyl ether, hydrophilic polymer, formaldehyde, triazole, urea, water and a compound shown in formula (I), wherein the compound shown in formula (I) is:
In some embodiments, in the compound of formula (I), n is 3.
In some embodiments, in the compound of formula (I), X is bromine or iodine.
In some embodiments, in the compound of formula (I), R is methyl or hydroxyethyl.
In some embodiments, the compound of formula (I) is:
in some embodiments, the compound of formula (I) is:
in some embodiments, the betaine surfactant is selected from one of coconut oil fatty acid amide propyl dimethylamino acetic acid betaine, palm kernel oil fatty acid amide propyl dimethylamino acetic acid betaine, tallow fatty acid amide propyl dimethylamino acetic acid betaine, lauric acid amide propyl dimethylamino acetic acid betaine, myristic acid amide propyl dimethylamino acetic acid betaine, palmitic acid amide propyl dimethylamino acetic acid betaine, stearic acid amide propyl dimethylamino acetic acid betaine, oleic acid amide propyl dimethylamino acetic acid betaine, and cocamidopropyl betaine.
In some embodiments, the environmentally friendly aqueous film forming foam fire suppressant further comprises sodium hexanesulfonate.
In some embodiments, the water is industrial soft water.
The second aspect of the invention provides a preparation method of the environment-friendly aqueous film-forming foam extinguishing agent, which comprises the following steps: adding 80-100 parts by weight of a compound shown in formula (I) and 0-50 parts by weight of sodium hexanesulfonate into a reaction kettle, adding 500-700 parts by weight of water, fully stirring and preheating, adding 50-70 parts by weight of betaine surfactant, 50-70 parts by weight of polyether, 40-60 parts by weight of diethylene glycol butyl ether, 1-4 parts by weight of hydrophilic polymer, 0.1-1 part by weight of formaldehyde, 0.1-1 part by weight of triazole and 20-40 parts by weight of urea under stirring; after stirring evenly, adjusting the pH value to 7 by fresh water or acetic acid, then adding water to the total amount of 1000 parts by weight, and stirring evenly to obtain the product.
The environment-friendly aqueous film-forming foam extinguishing agent provided by the invention has the characteristics of low production cost and biodegradability, has low toxicity to the environment and organisms, does not produce any pollution, and can solve the problem that domestic aqueous film-forming foam extinguishing agents contain sustainable organic pollutants.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from … …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The invention provides an environment-friendly aqueous film-forming foam extinguishing agent, which comprises the following components: betaine surfactant, polyether, diethylene glycol butyl ether, hydrophilic polymer, formaldehyde, triazole, urea, water and a compound shown in formula (I), wherein the compound shown in formula (I) is:
In some embodiments, in the compound of formula (I), n is 3.
In some embodiments, in the compound of formula (I), X is bromine or iodine.
In some embodiments, in the compound of formula (I), R is methyl or hydroxyethyl.
The preparation method of the compound shown in the formula (I) comprises the following steps:
(1) adding a mixed solution of perfluoroalkyl sulfonyl fluoride and a first organic solvent into N, N' -dimethyl-1, 3-propane diamine, reacting for 1-3h in an ice bath, then heating to 30-60 ℃, reacting for 2-6h, and draining the first organic solvent after the reaction is finished to obtain an intermediate product;
(2) adding a mixed solution of a halogenated organic matter and a second organic solvent into the intermediate product, heating to 70-100 ℃, reacting for 5-15h, draining the second organic solvent after the reaction is finished, recrystallizing and drying to obtain the compound.
The structural formula of the intermediate product is
Wherein n is 1 to 3.
In some embodiments, the compound of formula (I) is:
in some embodiments, the compound of formula (I) is:
the diethylene glycol butyl ether in the environment-friendly aqueous film-forming foam extinguishing agent provided by the invention can play a role in foam increasing and stabilizing.
In some embodiments, the hydrophilic polymer is selected from one of xanthan gum, peach gum, gelatin, guar gum.
Because the fluorocarbon chain has strong hydrophobicity, the foam liquid drainage speed of the single fluorocarbon surfactant is high. In actual fire fighting, however, slow discharge rates of the foam are required. The hydrophilic polymer dilutes the hydrophobicity of the fluorocarbon chain and increases the viscosity of the foam liquid, thereby increasing the stability of the foam and delaying the time of foam liquid separation. In addition, the hydrophilic polymer can also enhance the burn resistance and the re-ignition resistance of the foam.
In some embodiments, the betaine surfactant is selected from one of coconut oil fatty acid amide propyl dimethylamino acetic acid betaine, palm kernel oil fatty acid amide propyl dimethylamino acetic acid betaine, tallow fatty acid amide propyl dimethylamino acetic acid betaine, lauric acid amide propyl dimethylamino acetic acid betaine, myristic acid amide propyl dimethylamino acetic acid betaine, palmitic acid amide propyl dimethylamino acetic acid betaine, stearic acid amide propyl dimethylamino acetic acid betaine, oleic acid amide propyl dimethylamino acetic acid betaine, and cocamidopropyl betaine.
In some preferred embodiments, the betaine surfactant is CAB.
In some preferred embodiments, the polyether is a PAG.
In some embodiments, the environmentally friendly aqueous film forming foam fire suppressant further comprises sodium hexanesulfonate.
In some embodiments, the water is industrial soft water.
The second aspect of the invention provides a preparation method of the environment-friendly aqueous film-forming foam extinguishing agent, which comprises the following steps: adding 80-100 parts by weight of a compound shown in formula (I) and 0-50 parts by weight of sodium hexanesulfonate into a reaction kettle, adding 500-700 parts by weight of water, fully stirring and preheating, adding 50-70 parts by weight of betaine surfactant, 50-70 parts by weight of polyether, 40-60 parts by weight of diethylene glycol butyl ether, 1-4 parts by weight of hydrophilic polymer, 0.1-1 part by weight of formaldehyde, 0.1-1 part by weight of triazole and 20-40 parts by weight of urea under stirring; after stirring evenly, adjusting the pH value to 7 by fresh water or acetic acid, then adding water to the total amount of 1000 parts by weight, and stirring evenly to obtain the product.
The components of the environment-friendly aqueous film-forming foam extinguishing agent provided by the invention have a synergistic effect, so that the environment-friendly aqueous film-forming foam extinguishing agent has better surface activity and fire extinguishing performance while reducing the cost and the biotoxicity.
The invention is further illustrated by the following specific examples.
Example 1
An environment-friendly aqueous film-forming foam extinguishing agent comprises the following components: betaine surfactant CAB, polyether PAG, diethylene glycol monobutyl ether, xanthan gum, formaldehyde, triazole, urea, industrial soft water and a compound shown in a formula (I), wherein the compound shown in the formula (I) is:
the preparation method of the environment-friendly aqueous film-forming foam extinguishing agent comprises the following steps: adding 100 parts by weight of a compound shown in a formula (I) into a reaction kettle, adding 600 parts by weight of industrial soft water, fully stirring and preheating, and adding 60 parts by weight of CAB, 60 parts by weight of PAG, 50 parts by weight of diethylene glycol butyl ether, 2 parts by weight of xanthan gum, 0.5 part by weight of formaldehyde, 0.25 part by weight of triazole and 30 parts by weight of urea under stirring; after uniformly stirring, adjusting the pH value to 7 by using fresh water, then processing the industrial soft water to the total amount of 1000 parts by weight, and uniformly stirring to obtain the finished product.
The preparation method of the compound shown in the formula (I) comprises the following steps:
(1) under magnetic stirring, dropwise adding a mixed solution of 30mmol of perfluorobutanesulfonyl fluoride and 30mL of toluene into 30mmol of N, N' -dimethyl-1, 3-propane diamine, reacting for 2h in an ice bath after dropwise adding for about 20min, then heating to 45 ℃, reacting for 4h, and draining the toluene after the reaction is finished to obtain an intermediate product;
(2) under magnetic stirring, adding a mixed solution of 15.5mmol of methyl iodide and 20mL of acetonitrile into 13mmol of intermediate product under the protection of nitrogen, heating to 80 ℃, reacting for 10h, draining acetonitrile after the reaction is finished, dissolving the product with a small amount of ethanol, adding a large amount of diethyl ether for recrystallization, and drying to obtain the product. The yield was 90%.
Example 2
An environment-friendly aqueous film-forming foam extinguishing agent comprises the following components: betaine surfactant CAB, polyether PAG, diethylene glycol monobutyl ether, xanthan gum, formaldehyde, triazole, urea, industrial soft water and a compound shown in a formula (I), wherein the compound shown in the formula (I) is:
the preparation method of the environment-friendly aqueous film-forming foam extinguishing agent comprises the following steps: adding 80 parts by weight of a compound shown in a formula (I) and 50 parts by weight of sodium hexane sulfonate into a reaction kettle, adding 600 parts by weight of industrial soft water, fully stirring and preheating, and adding 60 parts by weight of CAB, 60 parts by weight of PAG, 50 parts by weight of diethylene glycol monobutyl ether, 2 parts by weight of xanthan gum, 0.5 part by weight of formaldehyde, 0.25 part by weight of triazole and 30 parts by weight of urea under stirring; after uniformly stirring, adjusting the pH value to 7 by using acetic acid, then processing the industrial soft water to 1000 parts by weight of the total amount, and uniformly stirring to obtain the finished product.
The preparation method of the compound shown in the formula (I) comprises the following steps:
(1) under magnetic stirring, dropwise adding a mixed solution of 30mmol of perfluorobutanesulfonyl fluoride and 30mL of toluene into 30mmol of N, N' -dimethyl-1, 3-propane diamine, reacting for 2h in an ice bath after dropwise adding for about 20min, then heating to 45 ℃, reacting for 4h, and draining the toluene after the reaction is finished to obtain an intermediate product;
(2) under magnetic stirring, adding a mixed solution of 15mmol of 2-bromoethanol and 20mL of tetrahydrofuran into 13mmol of intermediate product under the protection of nitrogen, heating to 80 ℃, reacting for 10 hours, draining the tetrahydrofuran after the reaction is finished, dissolving the product with a small amount of ethanol, adding a large amount of diethyl ether for recrystallization, and drying to obtain the product. The yield was 92%.
In the invention, the water film-forming foam extinguishing agent is 6 wt% in the example 1 and the example 2.
Examples 1 and 2 were tested according to GB 15308-2006 and the results are given in the table below.
The foregoing examples are merely illustrative and are provided to illustrate some of the features of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutes not currently contemplated for reasons of inaccuracy in language representation, and such changes should also be construed where possible to be covered by the appended claims.
Claims (4)
1. The environment-friendly aqueous film-forming foam extinguishing agent is characterized by comprising the following components in 1000 parts by weight: 60 parts of betaine surfactant, 60 parts of polyether, 50 parts of diethylene glycol monobutyl ether, 2 parts of xanthan gum, 0.5 part of formaldehyde, 0.25 part of triazole, 30 parts of urea, the balance of water, 80 parts of compound shown in formula (I) and 50 parts of sodium hexane sulfonate;
the compound shown in the formula (I) is:
2. the environmentally friendly aqueous film-forming foam fire extinguisher according to claim 1, wherein the betaine surfactant is selected from one of coconut oil fatty acid amide propyl dimethylamino acetic acid betaine, palm kernel oil fatty acid amide propyl dimethylamino acetic acid betaine, tallow fatty acid amide propyl dimethylamino acetic acid betaine, lauric acid amide propyl dimethylamino acetic acid betaine, myristic acid amide propyl dimethylamino acetic acid betaine, palmitic acid amide propyl dimethylamino acetic acid betaine, stearic acid amide propyl dimethylamino acetic acid betaine, oleic acid amide propyl dimethylamino acetic acid betaine, and cocamide propyl betaine.
3. The environmentally friendly aqueous film-forming foam fire extinguishing agent of claim 1, wherein the water is industrial soft water.
4. The method for preparing environment-friendly aqueous film-forming foam fire extinguishing agent as claimed in any one of claims 1-3, which comprises the following steps: adding 80 parts by weight of a compound shown in a formula (I) and 50 parts by weight of sodium hexane sulfonate into a reaction kettle, adding 600 parts by weight of water, fully stirring and preheating, and adding 60 parts by weight of betaine surfactant, 60 parts by weight of polyether, 50 parts by weight of diethylene glycol butyl ether, 2 parts by weight of xanthan gum, 0.5 part by weight of formaldehyde, 0.25 part by weight of triazole and 30 parts by weight of urea under stirring; after stirring evenly, adjusting the pH value to 7 by fresh water or acetic acid, then adding water to the total amount of 1000 parts by weight, and stirring evenly to obtain the product.
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| WO2020033255A1 (en) | 2018-08-09 | 2020-02-13 | Carrier Corporation | Fire extinguishing composition and method of making |
| CN109966689A (en) * | 2019-04-09 | 2019-07-05 | 中国民用航空飞行学院 | A kind of solid foam extinguishing chemical |
| CN112619023B (en) * | 2020-12-21 | 2022-03-18 | 国网电力科学研究院有限公司 | Diluted and tackified type aqueous film-forming foam extinguishing agent and preparation method thereof |
| CN112675469A (en) * | 2020-12-28 | 2021-04-20 | 成都科宏达化学有限责任公司 | Environment-friendly water-based fire extinguishing agent for fire fighting |
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