WO1999029373A1 - Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure - Google Patents

Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure Download PDF

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Publication number
WO1999029373A1
WO1999029373A1 PCT/US1997/022746 US9722746W WO9929373A1 WO 1999029373 A1 WO1999029373 A1 WO 1999029373A1 US 9722746 W US9722746 W US 9722746W WO 9929373 A1 WO9929373 A1 WO 9929373A1
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WIPO (PCT)
Prior art keywords
alkyl
fire
composition
substituted
fighting
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PCT/US1997/022746
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English (en)
Inventor
Richard M. Stern
Pavel L. Blagev
Wei-Qiang Fan
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Minnesota Mining And Manufacturing Company
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Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Priority to BR9714908-0A priority Critical patent/BR9714908A/pt
Priority to CA002312067A priority patent/CA2312067A1/fr
Priority to KR1020007006264A priority patent/KR20010032921A/ko
Priority to AU55221/98A priority patent/AU5522198A/en
Priority to EP97951631A priority patent/EP1037693A1/fr
Priority to PCT/US1997/022746 priority patent/WO1999029373A1/fr
Priority to JP2000524040A priority patent/JP2001525234A/ja
Publication of WO1999029373A1 publication Critical patent/WO1999029373A1/fr

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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
    • 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
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0035—Aqueous solutions
    • A62D1/0042—"Wet" water, i.e. containing surfactant
    • 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
    • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components

Definitions

  • the invention provides high performance, aqueous film forming foam agents that contain low surface tension producing fluorinated amine oxide surfactants.
  • the fluorinated amine oxide surfactants adsorb strongly onto nutrient sludge, soil and clay, and other substrates.
  • the invention also provides methods of fighting fires using these compositions.
  • Fire extinguishing foams of various types are known for use against fires of polar and non-polar flammable liquids such as hydrocarbon solvents, gasoline, kerosene, crude oil, and the like. Often these foams additionally provide the ability to form a film on the surface of a liquid. Such a film not only helps to extinguish the fire but can inhibit re-ignition of the flammable liquid once the fire has been extinguished by the foam.
  • Aqueous film forming foam (AFFF) concentrates are concentrated aqueous solutions that can be diluted and used to extinguish flammable liquids (i.e., Class B) fires. These concentrates can contain fluorinated surfactants, fluorine-free surfactants, foam stabilizers, and other various additives. Based on industrial convention, these concentrates are generally designated as 1%, 3%, or 6% concentrates. The significance of this numerical designation is that the concentrate can be formed into a fire-fighting premix composition by diluting the designated parts by volume concentrate (i.e., 1 , 3, or 6) with sufficient water such that the parts water plus the parts concentrate will equal 100.
  • flammable liquids i.e., Class B
  • a 3% concentrate is diluted with 97 parts of fresh or sea water to form a premix.
  • water is typically delivered through a fire hose and from 1 to 6 parts by volume of the premix are inducted by venturi effect into 94 to 99 parts of water, to form a premix.
  • the premix is then converted into a foam by use of an air-aspirating nozzle located at the outlet of the fire hose.
  • the resulting thick, mobile foam blanket achieves rapid knockdown, control, extinguishment and resistance to reignition of the flammable liquid.
  • a vapor-sealing film drains from the foam to rapidly spread over the flammable fuel surface, acting as a barrier between the fuel surface and the oxygen-containing air.
  • Amine oxide surfactants having a fluorocarbon moiety are generally known in the art.
  • British Patent Specification 1,302,612 discloses amine oxides of the general formula:
  • Rf is a saturated fluorinated non-aromatic radical in which the carbon atoms are substituted only by fluorine, chlorine or hydrogen atoms with no more than one hydrogen or chlorine atom for every two adjacent carbon atoms.
  • aqueous concentrate composition useful for suppressing vaporization of a liquid hydrocarbon
  • a film-forming component comprising a water soluble fluorinated surfactant;
  • a water-soluble stabilizer selected from the group consisting of alkyl ethers of alkylene glycol and glycerol; and (d) up to 95 weight percent water.
  • C n F2n+l is a straight or branched perfluorinated chain
  • n is a whole number from 1 to 20
  • a is a whole number from 2 to 10
  • Ri is either a hydrogen atom or an alkyl group
  • p is a whole number from 2 to 10.
  • the invention provides a fire-fighting composition made up of:
  • Q is SO 2 or CO
  • Rl is H; C,. 6 alkyl or C,. 6 alkyl substituted by halogen, OH, SH, C,_ 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C,. 6 alkyl;
  • R2 and R3 are independently C,. 6 alkyl; C,. 6 alkyl substituted by halogen, OH, SH, C,. 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C, .6 alkyl; or R2 and R3 may join to form a 5 to 7 membered heterocyclic ring that may contain one or more additional hetero atoms and that may be substituted by one or more C,_. 6 alkyl groups; n is 2 to 6; and R j is a substantially fluorinated C g . 18 alkyl group;
  • Q is SO 2 or CO
  • R4 is H; C,_ 6 alkyl or C,_ 6 alkyl substituted by halogen, OH, SH, C,. 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C,. 6 alkyl; R5 and R6 are independently C,. 6 alkyl; C,. 6 alkyl substituted by halogen, OH, SH,
  • R5 and R6 may join to form a 5 to 7 membered heterocyclic ring that may contain one or more additional hetero atoms and that may be substituted by one or more C,. 6 alkyl groups; n is 2 to 6; and
  • R f is a substantially fluorinated C 10 . 20 cycloalkyl, or a C 8 . 18 alkyl interrupted by one or more -O- or -S- atoms;
  • a concentrate of the fire-fighting composition preferably contains from about 0.5 to 12 wt-% of one or more compounds of formulas (I) or (II).
  • This concentrate composition can be diluted with salt or fresh water, typically 1, 3, or 6 parts by volume of the fire-fighting concentrate per 99, 97, or 94 parts water, respectively, to form a premix composition that preferably contains from about
  • the invention further provides methods of fighting fires by diluting with water, aerating, and applying to the surface of a liquid fire, an effective amount of a fire-fighting composition as described above.
  • Fluorinated amine oxide surfactants useful in the fire fighting compositions of this invention adsorb strongly from an aqueous solution onto materials commonly encountered in the ground, for instance nutrient sludge, various types of soil, sand, clay, bacteria surfaces, and the like. This adsorption is so strong that in some cases virtually no fluorinated surfactant can be detected in the water that remains after use, as measured indirectly by surface tension reduction or directly by chromatographic or by fluorine analysis. Thus, nearly quantitative removal of the fluorinated amine oxide surfactants from the environment can be accomplished, potentially preventing the fluorinated surfactant from contacting subsurface groundwater, greatly reducing groundwater contamination and foaming problems.
  • alkyl includes both straight-chain and branched alkyl groups of all sizes.
  • alkyl groups include straight chain groups such as methyl, ethyl, n-propyl n-octyl, n-nonyl etc., as well as branched groups such as i-propyl, sec-butyl, i-butyl, tert-butyl, iso-octyl, t-octyl, n- decyl, etc.
  • the alkyl group is interrupted by one or more -O- or -S- atoms, this interruption can take place in a branch or at a branching point, as well as in the long chain of the alkyl group.
  • This definition applies both to fluorinated and non- fluorinated alkyl groups.
  • substantially fluorinated indicates that at least about 75 percent, preferably at least about 85 percent, more preferably at least about 95 percent of the hydrogen atoms of the hydrocarbon moiety are replaced by fluorine atoms.
  • remaining hydrogen atoms can be replaced by other halogen atoms, such as by chlorine atoms.
  • the fluorinated amine oxide surfactants useful in the fire-fighting compositions of the invention have formulas (I) and (II):
  • Q is SO 2 or CO
  • Rl is H; C,. 6 alkyl or C,. 6 alkyl substituted by halogen, OH, SH, C,. 6 alkoxy, C,_ 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C, .6 alkyl; R2 and R3 are independently C,. 6 alkyl; C,. 6 alkyl substituted by halogen, OH, SH, C,. 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C,.
  • R2 and R3 may join to form a 5 to 7 membered heterocyclic ring that may contain one or more additional hetero atoms and that may be substituted by one or more C,. 6 alkyl groups; n is 2 to 6; and
  • R f is a substantially fluorinated C 8 . 18 alkyl group
  • Q is SO 2 or CO
  • R4 is H; C,. 6 alkyl or C,. 6 alkyl substituted by halogen, OH, SH, C,. 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C,. 6 alkyl;
  • R5 and R6 are independently C,_ 6 alkyl; C,. 6 alkyl substituted by halogen, OH, SH, C,_ 6 alkoxy, C,. 6 alkylthio, NO 2 , CN or NRR' wherein R and R' are independently H or C
  • heterocyclic ring When R2 and R3 or R5 and R6 join to form a heterocyclic ring, that ring may be saturated or unsaturated and may contain one or more additional hetero atoms in the ring, such as O, S, or N.
  • suitable heterocyclic rings include morpholine, thiomorpholine, piperidine, piperazine, pyridine, 1,2- diazine, 1,3-diazine, 1,4-diazine, pyrrole, pyrrolidine, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, triazole, tetrazole, and the like. These rings may be unsubstituted or substituted by one or more C,_ 6 alkyl groups.
  • the fluorinated amine oxide surfactants useful in the invention may be prepared by treating an alcoholic solution of the appropriate fluorinated carboxamidoamine or sulfonamidoamine precursor with hydrogen peroxide. This reaction may be carried out at elevated temperatures, for example at about 60° to 70°C. After reaction, excess hydrogen peroxide may be decomposed with activated carbon, palladium/carbon or manganese dioxide, followed by filtering to remove the unconsumed solids.
  • the fluorinated carboxamido- or sulfonamido- amine precursor may be commercially available or may be prepared by reaction of the appropriate perfluorinated sulfonyl or carbonyl fluoride with a diamine that contains both a primary nitrogen and a tertiary nitrogen in the presence of an acid scavenging tertiary amine such as triethylamine.
  • the reaction is preferably carried out in an organic solvent such as an aromatic or aliphatic hydrocarbon or ether solvent. Examples of appropriate solvents include toluene, heptane, isopropyl ether, tetrahydrofuran and the like.
  • the solvent is removed before the precursor is reacted to form the amine oxide surfactant used in the invention.
  • the fluorinated amine oxide can be present in the fire-fighting composition of the present invention in any amount that will provide a composition capable of effectively extinguishing and securing a flammable liquid fire (e.g., in the case of a premix composition) or, in the case of a concentrate composition, the amine oxide can be present in an amount that when diluted and foamed, will provide such a fire-fighting composition.
  • the fire-fighting concentrate compositions of the invention contains from about 0.5 to 12 wt-%> fluorinated amine oxide surfactant, based on the total weight of the concentrate.
  • the amount of fluorinated amine oxide surfactant in a concentrate composition will of course depend on the designated concentration of the concentrate (i.e., whether it is a 1, 3, or 6%> concentrate).
  • a 1%> concentrate can preferably contain from about 3 to 12 wt-%> fluorinated amine oxide surfactant.
  • the premix composition (the diluted concentrate) contains from about 0.01 to 0.12 wt-%, more preferably from about 0.03 to 0.1 wt-% fluorinated amine oxide surfactant, based on the total weight of the premix composition.
  • M is an alkali metal or alkaline earth metal, preferably a or K.
  • M is an alkali metal or alkaline earth metal, preferably a or K.
  • the amount of each ionic form of the fluorinated amine oxide surfactant found in an aqueous composition varies with the pH of the composition. At a pH of about 4.6 or below, there is essentially no metal salt formation. The amount of salt increases to about 50%> at a pH of about 6.5, and at a pH of 9.3 or above the fluorinated amine oxide surfactant exists almost entirely in the salt form. At the preferred pH of about 8, the surfactant is about 70% in the salt form.
  • compositions of the invention also include an effective amount of a fluorine-free surfactant.
  • fluorine-free surfactants may be nonionic, anionic, amphoteric, or a mixture of these types, with amphoteric and anionic surfactants being generally preferred.
  • fluorine-free surfactants useful in the inventive compositions have a hydrophilic/lipophilic balance (HLB) greater than or equal to about 10.
  • Non-fluorinated surfactants can be added to the fire-fighting compositions of the present invention for a number of reasons.
  • the presence of non-fluorinated hydrocarbon surfactant is desired to make clear, stable sea water premixes, because in the absence of non-fluorinated surfactants, sea water premixes tend to foam poorly and can precipitate or phase out the fluorinated surfactant.
  • nonionic fluorine-free surfactants include ethylene oxide- based nonionic surfactants, for example ethoxylated alcohols such as CkH2k+lO(C2H4O) m H wherein k is an integer between about 8 and 18 and m is greater than or equal to about 10; ethoxylated alkylphenols such as
  • p is an integer between about 4 and 12 and m is greater than or equal to about 10
  • TritonTM X-305 a 30-mole ethoxylate of a branched chain octylphenol, commercially available from Union Carbide Corp., Danbury, Connecticut
  • block copolymers of ethylene oxide and propylene oxide e.g., PluronicTM F-77 surfactant, which contains about 30% by weight of polymerized ethylene oxide, commercially available from BASF Corp., Parsippany, New Jersey.
  • anionic fluorine-free surfactants include alkyl sulfates, for example, sodium n-octyl sulfate (e.g., Sipex OLS, commercially available from Rhone-Poulenc Corp., Cranbury. New Jersey) and sodium decyl sulfate (e.g., PolystepTM B-25, commercially available from Stepan Co. of Northfield, 111.); alkyl ether sulfates of the general formula
  • Useful amphoteric surfactants include those which comprise a hydrocarbon chain with a length in the range from about 8 to 14 carbon atoms. Examples of such hydrocarbon chains include caprylo (C 8 ), capro (C 10 ), lauro (C 12 ), or coco (C 12 . 14 ).
  • amphoteric surfactants include hydroxysultaines (e.g., cocoamidopropyl hydroxysultaines; alkyl ether hydroxypropylsultaines); dipropionates (e.g., disodium cocoampho dipropionates, disodium capryloampho dipropionates, sodium laurimino dipropionates); diacetates (e.g., disodium cocoampho diacetates); acetates (e.g., sodium lauroampho acetates, sodium cocoampho acetates); propionates (e.g., sodium cocoampho propionates, sodium capryloampho propionates; capro amphocarboxy propionates, amino propionates); betaines (e.g., lauramidopropyl betaines, cocamidopropyl betaines); amidopropylsultaines (e.g., cocoamidopropyl sultaines
  • Preferred commercially available amphoteric surfactants include the following:
  • H2C-HA sodium laurimino dipropionate, C 12 H 25 N + (H)(CH 2 CH 2 COO-)(CH 2 CH 2 COO- Na + )
  • MiranolTM C2M-SF Cone (sodium cocoampho propionate, C 11.13 H 23 . 27 CONHCH 2 CH 2 N + (CH 2 CH 2 COO-)(CH 2 CH 2 COOH)(CH 2 CH 2 OH));
  • MirataineTM CB (cocamidopropyl betaine, C ⁇ .13 H 23 . 27 CONHCH 2 CH 2 CH 2 N + (CH 3 ) 2 CH 2 COO )); MirataineTM CBS (cocoamidopropyl hydroxysultaine,
  • MiranolTM JS Cone (sodium caprylampho hydroxypropyl sulfonate, C 7 H 15 CONHCH 2 CH 2 N(CH 2 CH 2 OH) (CH 2 CH(OH)CH 2 SO 3 " ) Na + ); MiranolTM JAS-50%> (sodium capryloampho propionate, C 7 H 15 CONHCH 2 CH 2 N + (CH 2 CH 2 COO ' )(CH 2 CH 2 COOH)(CH 2 CH 2 OH)); MiranolTM J2M-SF Cone, (disodium capryloampho dipropionate, C 7 H ]5 CONHCH 2 CH 2 N + (CH 2 CH 2 COO ' )(CH 2 CH 2 COO- Na + )(CH 2 CH 2 OH));
  • Mirataine BB lauramidopropyl betaine, C ⁇ H 23 N(CH 3 ) 2 CH 2 COO " ; and RewotericTM AM CAS- 15 (cocoamidopropyl sultaine, C ⁇ . 13 H 23 . 27 CONHCH 2 CH 2 CH 2 N + (CH 3 ) 2 (CH 2 ) n COO ).
  • MirataineTM, MiranolTM, and MiraponTM hydrocarbon surfactants are all commercially available from Rhone-Poulenc Corp., Cranberry, New Jersey; RewotericTM hydrocarbon surfactants are commercially available from Witco Corp., Greenwich, Connecticut.
  • the above mentioned preferred amphoteric surfactants are especially effective in combination with the fluorinated amine oxide surfactants of this invention to formulate superior AFFF agents. Not only is the foamability of the agents greatly improved, but the surface tensions of the premixes made from the concentrate compositions are very low, for example below about 17 dynes/cm, and the interfacial tension at about 2.0 to 3.5 dynes/cm is optimum for film formation. This allows the fire-fighting compositions to form thick and stable non-emulsified aqueous films which spread well over the fuel or other liquid, leading to exceptional fire-fighting performance.
  • the fluorine-free surfactant can preferably be present in the fire-fighting concentrate composition of the invention in an amount from about 1 to 30 wt-%), based on the total weight of the concentrate. Additional non-surfactant components may optionally be added to the fire-fighting compositions of the present invention.
  • Solvents may be present to facilitate solubilization of the fluorinated amine oxide surfactant and/or the fluorine-free surfactant in water. Suitable solvents include, ethylene glycol, glycerol, diethylene glycol monobutyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, and hexylene glycol. These solvents may also act as foam stabilizers and freeze-protection agents. The amount of solvent used is typically between about 5 wt-% to 50 wt-%> of the concentrate composition.
  • Stabilizers and thickeners may also be added to the fire-fighting concentration to further enhance foam stability after aeration of the premix.
  • useful stabilizers and thickeners include partially hydrolyzed proteins, starches, polyvinyl resins (e.g., polyvinyl alcohols, polyvinylpyrrolidone, polyacrylamides and carboxyvinyl resins), alkanolamide surfactants, long chain alcohols, polyethylene glycol, guar gum, and locust bean gum.
  • polysaccharide resins and biogums such as xanthan gum can be incorporated as foam stabilizers in fire-fighting compositions intended to be used on polar solvent fires such as alcohols, ketones, esters and ethers.
  • other additives may be useful to improve polar solvent resistance, including fluorochemically modified oligomeric acrylates or polymers.
  • Corrosion inhibitors may also be employed. Additional components that may be added to the fire-fighting compositions of this invention are detailed in U.S. Pat. Nos. 5,085,786 (Aim et al.) and 3,772,195 (Francen), both of which are incorporated herein by reference.
  • the total amount of solids attributable to non-surfactant components, if such components are present, should be such that the concentrate composition maintains its foamability, and that the density of the foam prepared is less than 0.5g/ cc , preferably less than 0.2g/ cc .
  • the amount of solids attributable to non-surfactant components such as stabilizers, thickeners, corrosion inhibitors, buffers, antimicrobial agents, and divalent ion salts will be less than about 20%) by weight, preferably less than about 10%> by weight, of the concentrate.
  • the concentrate compositions of the invention are highly storage stable. They pass U.S. Government specification MIL-F-24385C, which requires that foaming and film-forming properties of concentrates not be adversely affected if the concentrate and its fresh and sea water premixes are stored at 65 °C for 10 days. These conditions are designed to simulate a room temperature storage period of approximately 10 years.
  • the fire-fighting compositions of the invention are generally provided as 1%, 3% or 6%> concentrates, which, as described above means they can be diluted with 99%, 97%, or 94%> by volume water respectively, to form a fire- fighting premix composition.
  • the concentrates are conventional within the industry, fire-fighting compositions of any useful concentration may be prepared.
  • the fire-fighting concentrates of the invention are used by diluting an appropriate amount of the concentrate with water, forming a foam, and applying the foam to a burning liquid.
  • sea water or fresh water is typically delivered through a fire hole under pressure, to induct or inject from about 1% to 6%> by volume of the fire-fighting concentrate into the hose by venturi effect to form a premix.
  • This premix is aerated by use of an air aspirating nozzle located at the outlet of the hose, forming foam.
  • the foam is applied to a body of burning fuel or another flammable liquid and spreads quickly to blanket the surface for rapid extinguishment of the fire.
  • Fire-fighting compositions that contain the fluorinated amine oxide surfactants of the invention strongly adsorb to substrates comprising sludge, various types of soils, sand, clay and other substrates.
  • substrates comprising sludge, various types of soils, sand, clay and other substrates.
  • the aqueous solution that drains from the substrate can have a very low concentration of fluorinated amine oxide surfactant, for example from about 0 to 50 ppm (parts per million).
  • the balance of the fluorinated amine oxide surfactant has adsorbed onto the substrate, and can be recovered, for example, by removing that portion of the substrate that has adsorbed surfactant, drying the substrate, and extracting the fluorinated amine oxide surfactant with organic solvents.
  • the fluorinated amine oxide surfactants can then be isolated and recovered. This feature, which allows the surfactant to be removed from the ground and prevents the surfactant from reaching groundwater, minimizes the potential effects that these compounds, if not collected, would have on the environment.
  • Foam Expansion and Drain Time Foam expansion, defined as the volume of foam produced divided by the volume of liquid used to produce the foam, is determined as described in U.S. Government Military Specification MIL-
  • the 25%) drain time for the foam is defined as the amount of time after foam collection for 25%) of the weight (i.e., volume) of foam to drain to the bottom of the graduate (read as milliliters in the graduated cylinder, assuming a specific gravity of 1.0).
  • the Film-Forming and Sealing Test determines whether an AFFF premix is capable of forming a stable film on n- heptane.
  • An aqueous film is generated on the n-heptane surface by gently applying dropwise 0.75 mL of test premix solution from a 1 mL disposable syringe to the tip of the inverted screw over an approximately 30 to 60 second time period.
  • the surface tension should be as low as possible for the premix to have its maximum film-forming effectiveness.
  • the interfacial tension should be as high as possible to produce thick, stable films and to avoid emulsification of the fuel, yet should be sufficiently low to allow for a positive spreading coefficient.
  • the Spreading Coefficient (in dynes/cm), is calculated from the surface and interfacial tension values measured with the premixes as follows:
  • a positive Spreading Coefficient is a minimum requirement for the premix to form a vapor sealing aqueous film on the surface of the fuel.
  • CMC Critical Micelle Concentration
  • F-2 to F-15 The following fluorinated amine oxide surfactants were made using the same general procedure as with F-l :
  • F-2 C ⁇ oF2lS ⁇ 2NHC3H6N(CH3)2 ⁇ >O
  • H-l SipexTM OLS, 33%> active solution of sodium «-octyl sulfate. commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-2 MiranolTM C2M-SF, 39%) active solution of disodium cocoampho dipropionate, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-3 MiranolTM JS, 49% active solution of sodium caproampho hydroxypropyl sulfonate, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-4 MiranolTM S2M-SF, 39% active solution of caproampho carboxypropionate, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-5 MirataineTM CBS, 43.5%> active solution of cocoamidopropyl hydroxysultaine, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-6 MirataineTM CB, 30%> active solution of cocoamidopropyl betaine, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-7 MirataineTM COB, 30%> active coco/oleamidopropyl betaine, commercially available from Rhone-Poulenc Corp., Cranbury, New Jersey.
  • H-8 TritonTM X-305, 70% active polyethoxylated (30) octylphenol, commercially available from Union Carbide Corp., Danbury, Connecticut.
  • H-9 MiranolTM C2M-Conc. NP, 50%> active disodium cocoampho diacetate, commercially available from Rhone-Poulenc Corp.
  • H-10 MiranolTM HMA, 38% sodium lauroampho acetate, commercially available from Rhone-Poulenc Corp.
  • H-ll RewotericTM AM CAS- 15, 50% cocoamidopropyl sulfobetaine, commercially available from Witco Corp., Greenwich, Connecticut.
  • H-12 MiranolTM Ultra C-32, 39%) sodium cocoampho acetate, commercially available from Rhone-Poulenc Corp.
  • H-13 RewotericTM AM HC, 50%) coco sulfobetaine, commercially available from Witco Corp.
  • H-14 MiraponTM Excel 825, 30.5% sodium cocoampho acetate, commercially available from Rhone-Poulenc Corp.
  • H-15 MiranolTM CM-SF Cone, 37%> sodium cocoampho propionate, commercially available from Rhone-Poulenc Corp.
  • H-16 MiranolTM JAS-50, 50% sodium capryloampho propionate, commercially available from Rhone-Poulenc Corp.
  • H-17 MiranolTM J2M-SF Cone, 38.5% disodium capryloampho dipropionate, commercially available from Rhone-Poulenc Corp.
  • H-18 MirataineTM BB, 30%> lauramidopropyl betaine, commercially available from Rhone-Poulenc Corp.
  • H-19 MirataineTM JC-HA, 42% proprietary aminopropionate, commercially available from Rhone-Poulenc Corp.
  • H-20 MirataineTM BET O-30, 30% oleamidopropyl betaine, commercially available from Rhone-Poulenc Corp.
  • H-21 MirataineTM ASC, 42.5% alkylether hydroxypropyl sultaine, commercially available from Rhone-Poulenc Corp.
  • H-22 MirataineTM H2C-HA, 30%> sodium laurimino dipropionate, commercially available from Rhone-Poulenc Corp.
  • H-23 MiranolTM J2M Cone, 49%o disodium capryloampho diacetate, commercially available from Rhone-Poulenc Corp.
  • H-24 MiranolTM BM Cone, 38%) disodium lauroampho diacetate, commercially available from Rhone-Poulenc Corp.
  • fluorinated amine oxide surfactants F-1 through F-15 were dissolved in deionized water at various solids concentrations and the surface tension of each resulting aqueous surfactant solution was measured. Then the critical micelle concentration (CMC) was determined for each surfactant.
  • the CMC for each surfactant and the corresponding surface tension are presented in Table 1; an asterisk (*) indicates low surfactant water solubility (i.e., a solubility of 500 ppm or less).
  • Adsorption of each fluorinated amine oxide surfactant to nutrient sludge was measured using the following test procedure, which is a modification of the USEPA Aerobic aquatic biodegradation inoculum medium.
  • a large batch of test nutrient sludge having a suspended solids count in the range of 1700-2100 mg/L was allowed to aerated for one day.
  • the molecular weight for each fluorinated amine oxide was calculated to determine the proper amount of each surfactant (mg) to add to 500 mL of nutrient sludge to give a concentration of approximately 1 millimolar.
  • This calculated amount of surfactant was weighed into a glass vial, and 20-25 mL of water that was purified through a MilliQTM Ultra Purification System (available from Millipore, of Bedford, MA) was then added. The vial was then capped and was shaken until the surfactant dissolved or overnight (about 16 hours), whichever was sooner. The resulting aqueous surfactant solution was then quantitatively transferred to a NalgeneTM 1 -L Erlenmeyer flask along with 500 mL of the aerated nutrient sludge. The flask with its contents was placed for 2 minutes on an orbital shaker set at 100-130 rpm. After shaking, the suspended solids were allowed to settle for about 2 minutes.
  • the liquid was then separated from the solids using one of two equivalent techniques: (1) After shaking, the suspended solids were allowed to settle for about 2 minutes, and a 5-1 OmL aliquot of the supernatant liquid was filtered using a plastic syringe equipped with a 45 micron filter;
  • the concentration of fluorinated amine oxide surfactant F-1 in aqueous solution with the sludge was reduced from the initial concentration of about 600 ppm, to a measured concentration of less than 5 ppm, thus effectively removing the fluorinated compound from the aqueous solution and minimizing its potential effect on the environment.
  • the nutrient sludge-fluorochemical complex was found to be quite stable, even after autoclaving.
  • the measured surface tension of solution from a one-day complex sample, before autoclaving was 66 dynes/cm, indicating an aqueous surfactant concentration of under 1 ppm.
  • the samples were autoclaved at 121 °C and 15 psi (776 Torr), for 15 minutes (total of one hour cycle time which includes warmup, autoclaving, and cool down), was 50 dynes/cm, indicating an aqueous surfactant concentration of approximately 1 ppm. This is in contrast to the surfactant concentration before contacting with the nutrient sludge, where the measured surface tension was 15.6 dynes/cm, at an aqueous surfactant concentration of approximately 600 ppm.
  • Examples 8-15 formulated to be 3%> fire-fighting concentrate compositions contained the following ingredients, including 1 wt-%> of hydrocarbon surfactants H-1 (short chain ionic surfactant), H-2 through H-7 (amphoteric surfactants) or H-8 (nonionic surfactant):
  • H-1 short chain ionic surfactant
  • H-2 through H-7 amphoteric surfactants
  • H-8 nonionic surfactant
  • Example 16 a 3% AFFF concentrate containing fluorinated amine oxide surfactant F-1, short chain ionic hydrocarbon surfactant H-1, and anionic hydrocarbon surfactant H-2 was formulated as follows (%> solids by weight):
  • hydrocarbon surfactant H-2 25.0% - dipropylene glycol n-propyl ether remainder - water pH adjusted to 8.3 with 25%> aqueous sodium hydroxide.
  • Examples 17 and Comparative Examples C12-C13 fire tests were run to compare the fire-fighting performance of 3% sea water premixes made from AFFF concentrates containing fluorinated amine oxides both inside and outside of this invention. Concentrates also contained hydrocarbon surfactants H-1 and H-2. In Example 17, the concentrate contained fluorinated amine oxide F-1, C8Fi7S ⁇ 2NHC3H6N(CH3)2->O, which is within this invention.
  • the concentrate contained fluorinated amine oxide F-8, C6Fi3SO2NHC3H6N(CH3)2 ⁇ >O, which is outside of this invention.
  • the concentrate contained fluorinated amine oxide F-10, C7Fi5CONHC3H6N(CH3)2 ⁇ O, which is also outside of this invention.
  • the pH of the concentrate was adjusted to a pH of approximately 8, using acetic acid or sodium hydroxide as appropriate.
  • Example 34 Hydrocarbon H-13, an unsubstituted sultaine outside of this invention, performed relatively poorly, giving a surface tension greater than 17 dynes/cm and an interfacial tension of less than 2 dynes/cm.
  • Example 35 where no amphoteric hydrocarbon surfactant was used, poorer foam properties and too high an interfacial tension resulted.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)

Abstract

Cette invention porte sur des compositions concentrées de lutte contre l'incendie qui contiennent des tensioactifs d' aminoxyde fluoré ainsi que des tensioactifs dépourvus de fluor. On décrit également des prémélanges de lutte contre le feu ainsi qu'un procédé de lutte contre les incendies dans lequel on utilise les compositions et les prémélanges. Ces compositions forment des mousses qui sont des agents efficaces de lutte contre le feu, et de plus les tensioactifs d'aminoxyde fluoré adsorbent bien la saleté, la boue et d'autres substrats. Cette propriété d'adsorption permet d'éliminer rapidement de l'environnement le tensioactif.
PCT/US1997/022746 1997-12-10 1997-12-10 Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure WO1999029373A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
BR9714908-0A BR9714908A (pt) 1997-12-10 1997-12-10 Composição de combate a incêndio, composição de pré-mistura de formação de espuma, e, processo de extinção de um incêndio com lìquido polar ou não polar
CA002312067A CA2312067A1 (fr) 1997-12-10 1997-12-10 Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure
KR1020007006264A KR20010032921A (ko) 1997-12-10 1997-12-10 흡착성 플루오로카본 계면활성제를 포함하는 소화제
AU55221/98A AU5522198A (en) 1997-12-10 1997-12-10 Fire-fighting agents containing adsorbable fluorocarbon surfactants
EP97951631A EP1037693A1 (fr) 1997-12-10 1997-12-10 Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure
PCT/US1997/022746 WO1999029373A1 (fr) 1997-12-10 1997-12-10 Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure
JP2000524040A JP2001525234A (ja) 1997-12-10 1997-12-10 吸着性フルオロカーボン界面活性剤を含有する消火剤

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/022746 WO1999029373A1 (fr) 1997-12-10 1997-12-10 Agents de lutte contre le feu contenant des tensioactifs adsorbables au fluorocarbure

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KR (1) KR20010032921A (fr)
AU (1) AU5522198A (fr)
CA (1) CA2312067A1 (fr)
WO (1) WO1999029373A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8258341B2 (en) 2009-07-10 2012-09-04 E.I. Du Pont De Nemours And Company Polyfluorosulfonamido amine and intermediate
US8729138B2 (en) 2010-03-25 2014-05-20 E I Du Pont De Nemours And Company Mixture of polyfluoroalkylsulfonamido alkyl amines
US8779196B2 (en) 2010-03-25 2014-07-15 E I Du Pont De Nemours And Company Polyfluoroalkylsulfonamido alkyl halide intermediate
WO2015126854A1 (fr) * 2014-02-18 2015-08-27 Hydrant International Trading Co., Ltd. Compositions d'extinction d'incendie
US9168408B2 (en) 2010-03-25 2015-10-27 The Chemours Company Fc, Llc Surfactant composition from polyfluoroalkylsulfonamido alkyl amines
WO2020121248A1 (fr) * 2018-12-12 2020-06-18 3M Innovative Properties Company Oxydes aminés tensioactifs fluorés
WO2020123546A1 (fr) * 2018-12-10 2020-06-18 Molekule Inc. Système d'extinction d'incendies

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Publication number Priority date Publication date Assignee Title
CN110801596A (zh) * 2019-11-12 2020-02-18 江西圣辉生化科技有限公司 一种灭火剂组合物及其制备方法和应用
CN110787403A (zh) * 2019-11-12 2020-02-14 江西圣辉生化科技有限公司 一种灭火剂组合物及其制备和应用
CN114796964B (zh) * 2022-03-31 2023-07-28 珠海金禹科技有限公司 一种环保型水系灭火剂及其制备方法

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US3772195A (en) * 1969-06-12 1973-11-13 Minnesota Mining & Mfg Fire extinguishing composition comprising a fluoroaliphatic surfactant fluorine-free surfactant
US4983769A (en) * 1980-02-29 1991-01-08 P C U K Produits Chimiques Ugine Kuhlmann Perfluoroalkylamine oxides and use of these products in fire extinguishing compositions
EP0621057A1 (fr) * 1993-04-23 1994-10-26 Elf Atochem S.A. Emulseurs pour extincteurs d'incendie portatifs

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GB1302612A (fr) * 1969-02-19 1973-01-10
US3772195A (en) * 1969-06-12 1973-11-13 Minnesota Mining & Mfg Fire extinguishing composition comprising a fluoroaliphatic surfactant fluorine-free surfactant
US4983769A (en) * 1980-02-29 1991-01-08 P C U K Produits Chimiques Ugine Kuhlmann Perfluoroalkylamine oxides and use of these products in fire extinguishing compositions
EP0621057A1 (fr) * 1993-04-23 1994-10-26 Elf Atochem S.A. Emulseurs pour extincteurs d'incendie portatifs

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8258341B2 (en) 2009-07-10 2012-09-04 E.I. Du Pont De Nemours And Company Polyfluorosulfonamido amine and intermediate
US9168408B2 (en) 2010-03-25 2015-10-27 The Chemours Company Fc, Llc Surfactant composition from polyfluoroalkylsulfonamido alkyl amines
US8729138B2 (en) 2010-03-25 2014-05-20 E I Du Pont De Nemours And Company Mixture of polyfluoroalkylsulfonamido alkyl amines
US8779196B2 (en) 2010-03-25 2014-07-15 E I Du Pont De Nemours And Company Polyfluoroalkylsulfonamido alkyl halide intermediate
TWI671097B (zh) * 2014-02-18 2019-09-11 海浚國際貿易有限公司 滅火組合物
CN106457013A (zh) * 2014-02-18 2017-02-22 消防栓国际贸易有限公司 灭火组合物
WO2015126854A1 (fr) * 2014-02-18 2015-08-27 Hydrant International Trading Co., Ltd. Compositions d'extinction d'incendie
US10518120B2 (en) 2014-02-18 2019-12-31 Hydraᴺᵀ International Trading Co., Ltd. Fire extinguishing compositions
TWI704001B (zh) * 2014-02-18 2020-09-11 海浚國際貿易有限公司 滅火組合物
WO2020123546A1 (fr) * 2018-12-10 2020-06-18 Molekule Inc. Système d'extinction d'incendies
US11291874B2 (en) 2018-12-10 2022-04-05 Molekule, Inc. System for extinguishing fires
AU2019396216B2 (en) * 2018-12-10 2022-09-29 Molekule Inc. System for extinguishing fires
WO2020121248A1 (fr) * 2018-12-12 2020-06-18 3M Innovative Properties Company Oxydes aminés tensioactifs fluorés
CN113166634A (zh) * 2018-12-12 2021-07-23 3M创新有限公司 含氟氧化胺表面活性剂

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CA2312067A1 (fr) 1999-06-17
KR20010032921A (ko) 2001-04-25
EP1037693A1 (fr) 2000-09-27
JP2001525234A (ja) 2001-12-11
AU5522198A (en) 1999-06-28

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