CN105727825A - Compounding of carbon-4 fluoride surfactant and application of compound system preparation method of carbon-4 fluoride surfactant to aqueous film forming foam extinguishing agent - Google Patents

Compounding of carbon-4 fluoride surfactant and application of compound system preparation method of carbon-4 fluoride surfactant to aqueous film forming foam extinguishing agent Download PDF

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CN105727825A
CN105727825A CN201610129840.7A CN201610129840A CN105727825A CN 105727825 A CN105727825 A CN 105727825A CN 201610129840 A CN201610129840 A CN 201610129840A CN 105727825 A CN105727825 A CN 105727825A
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肖进新
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
    • 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
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    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant

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Abstract

The invention discloses a preparation method of the compound system of a short fluorocarbon chain (the length of the fluorocarbon chain is equal to that of 4 carbons, short for carbon-4) ampholytic nonionic fluorinated surfactant and application thereof to an aqueous film forming foam extinguishing agent, wherein the ampholytic fluorinated surfactant is one of a series of carbon-4 sulfamine alkyl dimethyl betaine or carbon-4 sulfamine sulphobetaine; the nonionic fluorinated surfactant is one of a series of carbon-4 sulfamine amine oxide; the total mass fraction of the two types of fluorinated surfactant is 0.2-10% and the mass ratio of the ampholytic fluorinated surfactant to the nonionic fluorinated surfactant is (10:1)-(1:10) (carbon-4 sulfamine alkyl dimethyl betaine to carbon-4 sulfamine amine oxide or carbon-4 sulfamine sulphobetaine to carbon-4 sulfamine amine oxide), good surface activity, spreading performance and flame extinguishing ability are achieved, and the aqueous film forming foam extinguishing agent formed based on the compound system of the ampholytic nonionic fluorinated surfactant is excellent in fire extinguishing performance.

Description

Carbon 4 fluorine surfactant is compounding and in the application of aqueous film-forming foam extinguishing agent
Technical field
The present invention relates to a kind of carbon fluorine chain length short carbon fluorine chain amphoteric fc-surfactant-non-less than 4 carbon The preparation method of ion-type fc-surfactant compound system and the application in aqueous film-forming foam extinguishing agent thereof.
Background technology
Organic fluorine chemistry product are the big class chemicals being applied to numerous industry and commercial use, including binding agent, cleaning Agent, coating, electronic device etc..Wherein, fluorine surfactant has high surface, high physics and chemical stability, carbon fluorine Chain not only hydrophobic but also hate the feature of oil, has irreplaceable purposes in a lot of fields, such as aqueous film-forming foam extinguishing agent, unique fabric Finishing agent, sapecial coating etc..
Long carbon fluorine chain contained in the fluorine surfactant of large-scale production recent decades in past and application, has been found to Having environmental persistence and bioaccumulation, it produces and application receives restriction in various degree.Full-fluorine octyl sulfuryl fluoride, complete Fluorine octyl sulfonic acid, perfluoro octyl sulfonic acid salt and related chemicals (being referred to as PFOS) thereof are " organic about persistency in quilt in 2009 The Convention of Stockholm of pollutant " (Stockholm Convention on Persistent Organic Pollutants) include persistence organic pollutant (POPs) category in, produce and use severely limited.
PFOS is aqueous film-forming foam extinguishing agent core component, such as Minnesota Mining and Manufacturing Company FC-203CF type aqueous film-forming foam extinguishing agent (Journal of Environmental Monitoring 4 (2002) 90-95).Along with various countries honour an agreement the propelling of degree, anxious The short carbon fluorine chain fluorine surfactant of aqueous film-forming foam extinguishing agent need to be applicable to.Existing result of study shows, when carbon fluorine chain is 4 During carbon, its harm the most substantially can consider.
CN103446943A proposes the double type cationic fluorocarbon surfactant with perfluoro butyl sulfonic acid fluoride as raw material Preparation method and application in aqueous film-forming foam extinguishing agent field, but this surfactant structure is complicated, production difficulty and one-tenth This is the highest.JP2007252731A proposes with F (CF2)3SO2NH(CH2)3N(CH3)CH2CH(OH)-OSO3 -、F(CF2)5SO2NH(CH2)3NHCH2CH(OH)CH2-SO3Na、F(CF2)5CH2CH2SO2NH(CH2)3N+(CH3)2-CH2O-COO-For core group The aqueous film-forming foam extinguishing agent divided, with ISO-7203 standard evaluation, extinguishing property reaches I-A level, but prepared by this surfactant Flow process is complicated, is prone to oxidation deterioration during storage, relatively costly.It is F (CF that JPH09173498A proposes structure2)c-X-R5- N (R6R7) nonionic surfactant of (=O), wherein c be 3-21, X be-SO2-or-CO-, R5For-(CH2)r-, r is 1- 10, R6、R7For-CsH2s+1, s is 1-5；With the aqueous film-forming foam extinguishing agent that this structure is core component, there is certain fire extinguishing Can, but resume combustion problem can not be solved.
Research shows, compounding by different surfaces activating agent, both can reduce the concentration of surfactant, it is possible to carry The performance of high surfactant.The amphoteric of a length of 4 carbon of carbon fluorine chain prepared by the present invention-nonionic carbon fluorine surface activity Agent compound system has the highest surface activity, and surfactant total concentration is 0.2-10%, and the two mass ratio is at 10:1 to 1:10 In the range of time, aqueous solution can become water membrane in pasta upper berth spread, thus can be used for preparing aqueous film-forming foam extinguishing agent.By Only have 4 fluorine carbon atoms in its carbon fluorine chain, do not possess the feature of persistence organic pollutant, thus can be as the replacement of PFOS Product.
Coefficient of foaming is one of key index of aqueous film-forming foam extinguishing agent.Research shows, amphoteric surfactant rises Bubble better performances, but foam stability is low, and foam duration is short；Nonionic surfactant frothing capacity is poor, but bubble Foam stability is higher, and foam duration is longer.Thus, if both fluorine surfactants are used alone, it is difficult to reach water Foaming properties required by film-forming foam extinguishing chemical.If but by amphoteric surfactant with nonionic surfactant with one Certainty ratio compounds, and gets final product the two advantage comprehensive, reaches foaming characteristic good, the purpose that foam stability is high.In the present invention, short carbon fluorine chain The nonionic fc-surfactant of amphoteric fc-surfactant and short carbon fluorine chain compound, frothing capacity is good, foam Stability is higher, and coefficient of foaming is higher.
Aqueous film-forming foam extinguishing agent with this compound system as core is through country's fixed fire extinguishing system and fire retarding component quality The qualification of Supervision Test Center, attack time reaches I A level.
Summary of the invention
The present invention is with the amphoteric fc-surfactant of a length of 4 carbon of carbon fluorine chain, nonionic carbon fluorine surface activity Based on agent, obtain, by compounding, amphoteric-nonionic fc-surfactant compound system that surface activity is excellent.With Time, this compound system can be applicable to aqueous film-forming foam extinguishing agent field.
Amphoteric fc-surfactant structure such as formula 1(F4HnN (R1)(R2) C), formula 2(F4HnN (R1)(R2) S) shown in:
Wherein n is 1-4, R1、R2For-CpH2p+1, p is 1-4, R1、R2Can identical also can be different.Preferred structure is F4H3N (CH3) (CH3) C, F4H4N (C2H5)(CH3) C, F4H4N (CH3)(CH3)S。
Nonionic fc-surfactant structure such as formula 3(F4HbN (R3)(R4) O) shown in:
Wherein b is 1-4, R3、R4For-CqH2q+1, q is 1-4, R3、R4Can identical also can be different.Preferred structure is F4H3N (CH3) (CH3) O, F4H2N (CH3)(C3H7) O, F4H3N (C4H9)(C4H9)O。
The preparation method of above-mentioned amphoteric-nonionic fc-surfactant compound system, comprises the steps:
(1) F4HnN (R is configured with deionized water1)(R2) C solution；
(2) F4HnN (R is configured with deionized water1)(R2) S solution；
(3) F4HbN (R is configured with deionized water3)(R4) O solution；
(4) by a certain percentage by F4HnN (R1)(R2) C solution (or F4HnN (R1)(R2) S solution) and F4HbN (R3)(R4) O solution Mixing, constant volume, obtain concentration, form the amphoteric/nonionic carbon fluoro-fc-surfactant compound system determined.
Above-mentioned amphoteric-nonionic fc-surfactant compound system application in aqueous film-forming foam extinguishing agent. A kind of aqueous film-forming foam extinguishing agent, comprises above-mentioned amphoteric-nonionic fc-surfactant compound system.
The present invention has the advantage that relative to prior art and effect:
The present invention with amphoteric fc-surfactant, the nonionic fc-surfactant of a length of 4 carbon of carbon fluorine chain is Basis, obtains, by compounding, amphoteric-nonionic fc-surfactant compound system that surface activity is excellent, without persistently Property organic pollution；Without obvious bioaccumulation effect, safety and environmental protection；Surface activity is excellent, and frothing capacity performance is good, foam stabilization Property is higher, and coefficient of foaming is higher.
AFFF fire extinguishing prepared by amphoteric based on the present invention-nonionic fc-surfactant compound system Agent, has MJPZ spreading rate fast, the feature that extinguishing property is excellent.
Detailed description of the invention
In amphoteric-nonionic fc-surfactant compound system that the present invention provides, live in amphoteric carbon fluorine surface Property agent has a structure that
Wherein n is 1-4, R1、R2For-CpH2p+1, p is 1-4, R1、R2Can identical also can be different.
Nonionic fc-surfactant has a structure that
Wherein b is 1-4, R3、R4For-CqH2q+1, q is 1-4, R3、R4Can identical also can be different.
The invention provides the method for fluorine surfactant used by the preparation present invention.
In the present invention, amphoteric fc-surfactant preparation flow is: N, N-dialkyl group-alkyl diamine (NH2(CH2)nNR1R2, molal quantity is 1.05 to 1.50 times of perfluoro butyl sulfonic acid fluoride) and triethylamine (molal quantity is perfluoro butyl sulfonic acid fluoride 1.20 to 2.00 times) add in the reactor with reflux, add isopyknic oxolane, stirring is lower instills perfluor fourth Base sulfuryl fluoride (F (CF2)4SO2F), it is warming up to 70-110 DEG C after all adding, reacts 6-12 hour, remove solvent and mistake under reduced pressure Amount amine, washing and drying obtains F (CF2)4SO2NH(CH2)nN(R1)(R2)。
By F (CF2)4SO2NH(CH2)nN(R1)(R2) be dissolved in ethanol, add in the reactor with reflux, add (molal quantity is F (CF to sodium chloroacetate2)4SO2NH(CH2)nN(R1)(R2) 1.02 to 1.20 times) aqueous solution, 60-80 after mixing DEG C reaction 3-8 hour, removes organic solvent under reduced pressure, and crystallisation by cooling filters, and dry filtering residue obtains F4HnN (R1)(R2)C。
By F (CF2)4SO2NH(CH2)nN(R1)(R2) be dissolved in ethanol, add in the reactor with reflux, add (molal quantity is F (CF to propane sultone2)4SO2NH(CH2)nN(R1)(R2) 1.02 to 1.30 times) ethanol solution, after mixing 70-100 DEG C is reacted 5-8 hour, and crystallisation by cooling filters, and dry filtering residue obtains F4HnN (R1)(R2)S。
In the present invention, nonionic fc-surfactant preparation flow is: N, N-dialkyl group-alkyl diamine (NH2 (CH2)bNR3R4, molal quantity is 1.05 to 1.50 times of perfluoro butyl sulfonic acid fluoride) and triethylamine (molal quantity is perfluoro butyl sulphonyl 1.20 to 2.00 times of fluorine) add in the reactor with reflux, add isopyknic oxolane, stirring is lower to be instilled entirely Fluorine butyl sulfuryl fluoride, is warming up to 70-110 DEG C after all dripping off, react 6-12 hour, removes solvent and excess amine under reduced pressure, washing It is dried to obtain F (CF2)4SO2NH(CH2)bN(R3)(R4).By F (CF2)4SO2NH(CH2)bN(R3)(R4) be dissolved in ethanol, add band Having in the reactor of reflux, (molal quantity is F (CF to 35% hydrogen peroxide2)4SO2NH(CH2)bN(R3)(R4) 1.50 to 2.30 times) aqueous solution is added thereto, and is warming up to 60-80 DEG C and reacts 3-6 hour, removes ethanol, crystallisation by cooling under reduced pressure, filters, dry Dry filtering residue obtains F4HbN (R3)(R4)O。
The invention provides above-mentioned amphoteric fc-surfactant, nonionic fc-surfactant with certain mass Than the method being mixed with amphoteric-nonionic fc-surfactant compound system, and test this compound system in combustion Oil meter face spreading property and coefficient of foaming.
Present invention also offers with above-mentioned amphoteric/nonionic carbon fluoro-fc-surfactant compound system as core The preparation method of 6% type aqueous film-forming foam extinguishing agent of component, it is characterised in that: fc-surfactant total concentration is 1-10%； Amphoteric fc-surfactant and nonionic fc-surfactant quality are 10:1 to 1:10 than scope；Live in hydrocarbon surface Property agent is any one in following compound: CkH2k+1OSO3M、CkH2k+1SO3M、CkH2k+1-PhSO3M、CkH2k+1N+(CH3)2CH2COO-、CkH2k+1N+(CH3)2CH2CH2SO3 -、CkH2k+1N(CH3)2O, wherein k is 6-14, M=Li+、Na+、K+、Cs+、H+、 NH4 +、N(CtH2t+1)4 +、NH(CtH2t+1)3 +(t=1-4), NH3CH2CH2OH+、NH2(CH2CH2OH)2 +、NH(CH2CH2OH)3 +；Foam Stabilizer is xanthan gum or sodium alginate；Thickening agent is xanthan gum；Anti-burning agent is xanthan gum；Cosolvent be ethylene glycol monobutyl ether, One or several mixture in butyl, diethylene glycol ether, carbamide；Buffer solution is trishydroxymethylaminomethane Aqueous solution；Antifreeze is ethylene glycol or glycerol；Metal inhibitor is BTA；Antibacterial is formaldehyde；Chelating agen is second Sodium ethylene diamine tetracetate.
The present invention tests the extinguishing property of above-mentioned aqueous film-forming foam extinguishing agent.
Embodiment 1.
224.4 kg N, N-dimethyl-propane diamine (2200 moles), 404.0 kg triethylamines (4000 moles) add In the reactor of 2500 L band backflows, adding 700 L oxolanes, mechanical agitation is uniform.604.0 kg perfluoro butyl sulfonic acid fluorides (2000 moles) are added thereto, and be warming up to 80 DEG C, react 8 hours, remove solvent and excess amine, water under reduced pressure after all adding Washing, filter, filtering residue is dried and is obtained C4F9SO2NH(CH2)3N(CH3)2702.0 kg, productivity 91.4%.By 192 kg C4F9SO2NH (CH2)3N(CH3)2(500 moles) are placed in 2500 L reactors, add 200 L ethanol and stirring is allowed to dissolve, 60.6 kg chlorine Sodium acetate (520 moles) is dissolved in 240.0 kg deionized waters and adds in reactor, is warming up to 80 DEG C after stirring and evenly mixing, reacts 4 Hour, cooling.Remove ethanol, crystallisation by cooling under reduced pressure, filter, dry filtering residue and obtain F4H3N (CH3)(CH3) C 203.6 kg, produce Rate 92.1%.Take 1.00 kg F4H3N (CH3)(CH3) C, add 4.00 kg deionized waters, being uniformly mixed so as to obtain mass fraction is 20% F4H3N(CH3)(CH3) C solution, weighing this solution 18.00 g, addition deionized water is to 1 kg, and obtaining mass fraction is 0.36% F4H3N (CH3)(CH3) C diluent.
Embodiment 2.
278.4kg N, N-dimethyl-butanediamine (2400 moles), 242.4 kg triethylamines (2400 moles) add 2500 In the reactor of L band backflow, adding 600 L oxolanes, mechanical agitation is uniform.604.0 kg perfluoro butyl sulfonic acid fluorides (2000 Mole) be added thereto, it is warming up to 100 DEG C after all adding, reacts 12 hours, remove solvent and excess amine under reduced pressure, washing, mistake Filter, filtering residue is dried and is obtained C4F9SO2NH(CH2)4N(CH3)2666.2 kg, productivity 83.7%.By 99.5 kg C4F9SO2NH (CH2)4N(CH3)2(250 moles) are placed in 1000 L reactors, add 120 L ethanol and stirring is allowed to dissolve, 33.6 kg third Sultones (275 moles) is dissolved in 200 L ethanol and adds in reactor, is warming up to 90 DEG C after stirring and evenly mixing, reacts 7 hours, Cooling, crystallization, filter, dry filtering residue and obtain F4H4N (CH3)(CH3) S 98.3 kg, productivity 75.6%.Take 1.00 kg F4H4N (CH3)(CH3) S, add 4.00 kg deionized waters, be uniformly mixed so as to obtain the F4H4N (CH that mass fraction is 20%3)(CH3) S solution, claim Taking this solution 30.00 g, addition deionized water, to 1 kg, obtains the F4H4N (CH that mass fraction is 0.60%3)(CH3) S dilution Liquid.
Embodiment 3.
224.4 kg N, N-dimethyl-propane diamine (2200 moles), 323.2 kg triethylamines (3200 moles) add 2500 In the reactor of L band backflow, adding 650 L oxolanes, mechanical agitation is uniform.604.0 kg perfluoro butyl sulfonic acid fluorides (2000 Mole) be added thereto, it is warming up to 70 DEG C after all adding, reacts 10 hours, remove solvent and excess amine under reduced pressure, washing, mistake Filter, filtering residue is dried and is obtained C4F9SO2NH(CH2)3N(CH3)2696.5 kg, productivity 90.7%.By 192 kg C4F9SO2NH(CH2)3N(CH3)2(500 moles) are placed in 2500 L reactors, add 200 L ethanol and stirring is allowed to dissolve, 102.0 kg 35% mistakes Hydrogen oxide (1050 moles) aqueous solution adds in reactor, and stirring heats up 70 DEG C, reacts 5 hours, cooling.Remove second under reduced pressure Alcohol, crystallisation by cooling, filters, dries filtering residue and obtain F4H3N (CH3)(CH3) O 176.2 kg, productivity 88.1%.Take 1.00 kg F4H3N(CH3)(CH3) O, add 4.00 kg deionized waters, be uniformly mixed so as to obtain the F4H3N (CH that mass fraction is 20%3)(CH3) O is molten Liquid, weighs this solution 18.00 g, and addition deionized water, to 1 kg, obtains the F4H3N (CH that mass fraction is 0.36%3)(CH3)O Diluent；Weigh the F4H3N (CH of 20%3)(CH3) O solution 30.00 g, addition deionized water is to 1 kg, and obtaining mass fraction is F4H3N (the CH of 0.60%3)(CH3) O diluent.
Embodiment 4.
F4H3N (the CH of 16.36 g 20%3)(CH3) C solution and the F4H3N (CH of 1.64 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (10:1) mixed liquor.
F4H3N (the CH of 15.00 g 20%3)(CH3) C solution and the F4H3N (CH of 3.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (5:1) mixed liquor.
F4H3N (the CH of 12.00 g 20%3)(CH3) C solution and the F4H3N (CH of 6.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (2:1) mixed liquor.
F4H3N (the CH of 9.00 g 20%3)(CH3) C solution and the F4H3N (CH of 9.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (1:1) mixed liquor.
F4H3N (the CH of 6.00 g 20%3)(CH3) C solution and the F4H3N (CH of 12.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (1:2) mixed liquor.
3.00 the F4H3N (CH of g 20%3)(CH3) C solution and the F4H3N (CH of 15.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (1:5) mixed liquor.
F4H3N (the CH of 1.64 g 20%3)(CH3) C solution and the F4H3N (CH of 16.36 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H3N (CH of 0.36%3)(CH3)C-F4H3N(CH3)(CH3) O (1:10) mixed liquor.
Test the spreading property of above-mentioned mixed liquor (i.e. compound system).Reference literature (Chemical Research and Application 20 (2008) 569-572) method: in 500 mL beakers, add 100 mL hexamethylene；By above-mentioned mixed liquor Take 10 mL after being blown into air foaming in 1 minute and add in the beaker filling hexamethylene, observe moisture film and sprawl situation.Result such as table 1 institute Showing, all compound systems have the spreading property of excellence.
Table 1 F4H3N (CH3)(CH3)C-F4H3N(CH3)(CH3) O compound system spreading property.
The most quickly sprawl finger and sprawl the time less than 1 second, it is difficult to accurately timing.
Embodiment 5.
F4H4N (the CH of 27.27 g 20%3)(CH3) S solution and the F4H3N (CH of 2.73 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (10:1) mixed liquor.
F4H4N (the CH of 25.00 g 20%3)(CH3) S solution and the F4H3N (CH of 5.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (5:1) mixed liquor.
F4H4N (the CH of 20.00 g 20%3)(CH3) S solution and the F4H3N (CH of 10.00 g 20%3)(CH3) O solution, Add deionized water to 1 kg, obtain the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (2:1) mixed liquor.
F4H4N (the CH of 15.00 g 20%3)(CH3) S solution and the F4H3N (CH of 15.00 g 20%3)(CH3) O solution, Add deionized water to 1 kg, obtain the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) OO (1:1) mixed liquor.
F4H4N (the CH of 10.00 g 20%3)(CH3) S solution and the F4H3N (CH of 20.00 g 20%3)(CH3) O solution, Add deionized water to 1 kg, obtain the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (1:2) mixed liquor.
F4H4N (the CH of 5.00 g 20%3)(CH3) S solution and the F4H3N (CH of 25.00 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (1:5) mixed liquor.
F4H4N (the CH of 2.73 g 20%3)(CH3) S solution and the F4H3N (CH of 27.27 g 20%3)(CH3) O solution, add Deionized water, to 1 kg, obtains the F4H4N (CH of 0.60%3)(CH3)S-F4H3N(CH3)(CH3) O (1:10) mixed liquor.
Test the spreading property of above-mentioned mixed liquor (i.e. compound system).
Result is as shown in table 1, and all compound systems have the spreading property of excellence.
Table 2 F4H4N (CH3)(CH3)S-F4H3N(CH3)(CH3) O compound system spreading property.
The most quickly sprawl finger and sprawl the time less than 1 second, it is difficult to accurately timing.
Embodiment 6.
With reference to GB15308-2006 " fire foam " described mode, detect F4H3N (CH3)(CH3)C-F4H3N(CH3) (CH3) O compound system, F4H4N (CH3)(CH3)S-F4H3N(CH3)(CH3) coefficient of foaming of O compound system, result such as table 3 institute Show.Individually F4H3N (CH3)(CH3)C、F4H3N(CH3)(CH3) O and F4H4N (CH3)(CH3) S all cannot form a large amount of the most steady Fixed foam；But compound system coefficient of foaming result is preferable, the most especially with F4H3N (CH3)(CH3)C-F4H3N(CH3)(CH3)O (1:1) best results.
Table 3 compound system coefficient of foaming.
Embodiment 7.
A kind of amphoteric/nonionic carbon fluoro-fc-surfactant compound system with short carbon fluorine chain is for core component 6% type aqueous film-forming foam extinguishing agent, consisting of as shown in table 4.
Table 4 6% type aqueous film-forming foam extinguishing agent composition table.
* foam stabiliser, thickening agent, anti-burning agent are doubled as.
Above-mentioned 6% type aqueous film-forming foam extinguishing agent is through country's fixed fire extinguishing system and fire retarding component Quality Supervision and Inspection Center With reference to GB15308-2006 " fire foam " inspection, result is as shown in table 5.
Table 5 aqueous film-forming foam extinguishing agent consignment result.
From testing result, aforementioned 6% type aqueous film-forming foam extinguishing agent attack time reaches I A grade standard, can not only be used for Fresh water type can act also as sea water resistance type aqueous film-forming foam extinguishing agent use, wherein freezing point, anti-freeze melting, than mobility, The indexs such as table/interfacial tension, diffusion coefficient, rate of corrosion, 25% drainage time are all up to state standards requirement, only in pH value, anti-burning The minority indexs such as time are slightly inferior to standard-required.
Embodiment 8.
For the deficiency of embodiment 7, necessarily improving 6% type fire foam, formula is as shown in table 6.
Table 6 modified model 6% type aqueous film-forming foam extinguishing agent composition table.
Above-mentioned modified model 6% type aqueous film-forming foam extinguishing agent is according to GB15308-2006 " fire foam " self-inspection, and result is such as Shown in table 7.
Table 7 modified model 6% type aqueous film-forming foam extinguishing agent self-detection result.
Above-mentioned modified model 6% type aqueous film-forming foam extinguishing agent is according to GB15308-2006 " fire foam " self-inspection, and indices is equal Qualified, fire extinguishing grade reaches I A level, can not only be used for fresh water type and can act also as sea water resistance type aqueous film-forming foam extinguishing agent.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify, All should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (7)

1. class amphoteric fc-surfactant-nonionic based on the short carbon fluorine chain of a length of 4 carbon of carbon fluorine chain Fc-surfactant compound system, amphoteric fc-surfactant structural formula such as formula 1(F4HnN (R1)(R2) C), formula 2 (F4HnN (R1)(R2) S) shown in, nonionic fc-surfactant structural formula such as formula 3(F4HbN (R3)(R4) O) shown in:
Wherein, n is 1-4, R1、R2For-CpH2p+1, p is 1-4, R1、R2Can identical also can be different；B is 1-4, R3、R4For-CqH2q+1, Q is 1-4, R3、R4Can identical also can be different.
2. F4HnN (R described in claim 11)(R2) C and F4HnN (R1)(R2) preparation method of S:
(1) prepared by sulfonamide: it is characterized in that: F (CF2)4SO2F、NH2(CH2)nNR1R2, the mol ratio of triethylamine be 1:1.05- 1.50:1.20-2.00, solvent for use is oxolane, 70-110 DEG C, reacts 6-12 hour, removes solvent and excess under reduced pressure Amine, washing and drying obtains F (CF2)4SO2NH(CH2)nNR1R2；
(2) F4HnN (R1)(R2) prepared by C: F (CF2)4SO2NH(CH2)nNR1R2It is 1:1.02-1.20 with sodium chloroacetate mol ratio, Being dissolved in respectively in second alcohol and water, after mixing, 60-80 DEG C is reacted 3-8 hour, removes organic solvent, crystallisation by cooling under reduced pressure, filters, Dry filtering residue obtains F4HnN (R1)(R2)C；
(3) F4HnN (R1)(R2) prepared by S: F (CF2)4SO2NH(CH2)nNR1R2It is 1:1.02-with propane sultone mol ratio 1.30, it is dissolved in ethanol, 60-80 DEG C is reacted 3-8 hour, and crystallisation by cooling filters, and dry filtering residue obtains F4HnN (R1)(R2)S；
(4) F4HbN (R3)(R4) prepared by O: F (CF2)4SO2F、NH2(CH2)bNR3R4, the mol ratio of triethylamine be 1:1.05-1.50: 1.20-2.00,70-110 DEG C, react 6-12 hour, remove solvent and excess amine under reduced pressure, and washing and drying obtains F (CF2)4SO2NH (CH2)bNR1R2；F(CF2)4SO2NH(CH2)bNR3R4It is 1:1.50-2.30 with hydrogen peroxide mol ratio, is dissolved in ethanol, 60-80 DEG C reaction 3-6 hour, removes ethanol under reduced pressure, and crystallisation by cooling filters, and dry filtering residue obtains F4HbN (R3)(R4)O。
3. a class is by the amphoteric fc-surfactant described in claim 1, nonionic fc-surfactant mixing system Standby both sexes-nonionic fc-surfactant compound system, it is characterised in that in compound system, live in amphoteric carbon fluorine surface Property agent and nonionic fc-surfactant mass ratio in the range of 10:1 to 1:10.
4. a class is by the purposes of the both sexes described in claim 3-nonionic fc-surfactant compound system, and its feature exists In, it is used for preparing aqueous film-forming foam extinguishing agent.
5. a class is the AFFF of key component by the both sexes described in claim 3-nonionic fc-surfactant The preparation method of extinguishing chemical, it is characterised in that: fc-surfactant 2-100 part, hc-surfactant 1-3 part, foam is steady Determine agent 1-5 part, thickening agent 1-5 part, anti-burning agent 1-5 part, cosolvent 5-35 part, organic solvent 20-250 part, buffer solution 1-5 Part, antifreeze 40-100 part, metal inhibitor 1-5 part, antibacterial 2-5 part, chelating agen 1-5 part, water 477-916 part.
Aqueous film-forming foam extinguishing agent the most according to claim 5, it is characterised in that: hc-surfactant used is following Any one in compound: CkH2k+1OSO3M、CkH2k+1SO3M、CkH2k+1-PhSO3M、CkH2k+1N+(CH3)2CH2COO-、 CkH2k+1N+(CH3)2CH2CH2SO3 -、CkH2k+1N(CH3)2O, wherein k is 6-14, M=Li+、Na+、K+、Cs+、H+、NH4 +、N (CtH2t+1)4 +、NH(CtH2t+1)3 +(t=1-4), NH3CH2CH2OH+、NH2(CH2CH2OH)2 +、NH(CH2CH2OH)3 +。
Aqueous film-forming foam extinguishing agent the most according to claim 5, it is characterised in that: foam stabiliser is xanthan gum or Sargassum Acid sodium；Thickening agent is xanthan gum；Anti-burning agent is xanthan gum；Organic solvent is the one in normal propyl alcohol, n-butyl alcohol, n-amyl alcohol；Help Solvent is one or several mixture in ethylene glycol monobutyl ether, butyl, diethylene glycol ether, carbamide；Buffer molten Liquid is trishydroxymethylaminomethane aqueous solution；Antifreeze is ethylene glycol or glycerol；Metal inhibitor is BTA；Antibacterial Agent is formaldehyde；Chelating agen is sodium ethylene diamine tetracetate.
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CN106955450B (en) * 2017-03-22 2020-05-19 中国民用航空飞行学院 Environment-friendly aqueous film-forming foam extinguishing agent
CN106955450A (en) * 2017-03-22 2017-07-18 中国民用航空飞行学院 A kind of environment-friendly type aqueous film-forming foam extinguishing agent
CN107497091A (en) * 2017-09-15 2017-12-22 浙江睦田消防科技开发有限公司 Aqueous film-forming foam extinguishing agent based on C4 twin type fluorine surfactants
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CN109851529B (en) * 2017-11-30 2021-09-03 中国科学院上海有机化学研究所 Amphoteric fluorine-containing surfactant and preparation method and application thereof
CN109851529A (en) * 2017-11-30 2019-06-07 中国科学院上海有机化学研究所 A kind of amphoteric fluorine-containing surfactant and the preparation method and application thereof
CN108837370A (en) * 2018-06-01 2018-11-20 厦门泰消防科技开发有限公司 A kind of sea water resistance fire foam
CN111454183A (en) * 2019-01-22 2020-07-28 华为技术有限公司 Lithium negative electrode pretreatment protective agent, lithium negative electrode pretreatment protection method and lithium negative electrode with protective layer
CN113398522A (en) * 2021-06-17 2021-09-17 海南飞浪消防科技有限公司 Seawater-resistant environment-friendly aqueous film-forming foam extinguishing agent and preparation method and application thereof
CN114404859A (en) * 2021-12-21 2022-04-29 程潇 Preparation method of lithium battery fire extinguishing agent and lithium battery fire extinguishing test device
CN114874783A (en) * 2022-06-07 2022-08-09 浙江睦田消防科技开发有限公司 Fluorine-containing surfactant, application and preparation method thereof, and fire extinguishing agent comprising fluorine-containing surfactant
CN115350437A (en) * 2022-06-28 2022-11-18 宁波能林消防器材有限公司 Environment-friendly anti-solubility foam extinguishing agent with wide adaptability and preparation method thereof
CN115350437B (en) * 2022-06-28 2024-06-11 宁波能林消防器材有限公司 Widely-applicable environment-friendly type anti-soluble foam extinguishing agent and preparation method thereof
CN115650884A (en) * 2022-10-10 2023-01-31 中科永安(铜陵)科技有限公司 Ionic ammonium salt short-chain fluorocarbon surfactant and synthesis method thereof

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