CA2256605A1 - Fire-fighting agents containing polysaccharides and fluorochemical oligomeric surfactants - Google Patents
Fire-fighting agents containing polysaccharides and fluorochemical oligomeric surfactants Download PDFInfo
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Abstract
The subject matter of the invention is a fire-fighting concentrate composition comprising: a) a fluorochemical oligomer having a plurality of pendent fluoroaliphatic groups; b) one or more fluorochemical surfactants and one or more non-fluorinated surfactants; c) a polysaccharide; d) water; and e) optionally a polymeric stabilizer and thickener other than a polysaccharide, one or more water-soluble organic solvents, and other usual additives. The fire-fighting concentrate composition of the invention is a stable low viscosity 3x3 fire-fighting composition having excellent fire extinguishing performance against fires of both polar and non-polar solvents.
Description
CA 022~660~ 1998-11-26 FIG~ITING AGENTS CONTAINING POLYSACC~IARIDES AND
FLUOROCHEMICAL OLIGOMERIC SURFACTANTS
The present invention relates to fire-fi~htin~ compositions. More particularly it relates to low viscosity fire-fightine foam compositions, especially 0 "3x3" (three by three) concentrates. The low viscosity compositions of the present invention are found to have excellent fire-extin~ hing properties against both polar and non-polar solvent fires.
Various fire-exting~ hing foams have been developed for use against fires of non-polar solvents or liquids such as gasoline, kerosene, light oils, heavy oils and 5 crude oils. Many ofthese fire-extingl~i.chinf~ concentrates provide film-forming characteristics on the surface of a non-polar hydrophobic liquid. The use of fluorochemical surfactants is taught in U.S. Patent Nos. 3,475,333; 4,472,286;
4,460,480 and 4,717,744. A fire-extingllishing composition which includes them can form a thin aqueous film on the surface of a flammable liquid and inhibit the 20 reignition of the fl~mm~ble liquid once e~ctine~ hed by the foam. The fluorochemical surfactants in the aforementioned patents are incorporated into protein-based fire-fighting compositions in order to impart improved properties such as increased foam mobility, reduced e~ctingllishing times and reduced fuel pick-up. These compositions are useful for fighting fires of burning hydrophobic or non-25 polar hydrocarbon liquids.
However, when such fire-extingllishing foams are applied to fires of polar solvents such as alcohols, ketones, esters, ethers and amines, the foam collapses due to water drainage from foam l~mell~e. Polar solvents penetrate the aqueous foam and speed up water drainage. Certain water-soluble polymers slow down this 30 penetration, and thus slow down the foam collapse. For this reason, fire-fighting foam concentrates for polar solvents generally contain as a key component water-soluble or swellable polymeric materials, e.g., polysaccharides or protein hydrolysates. They cause the aqueous foam to form a gelatinous 'mat' or membranewhen it comes in contact with a polar hydrophilic liquid.
CA 022~660~ 1998-11-26 U.S. Patent Nos. 3,957,657; 4,420,434; 4,424,133; 4,387,032; 4,306,979;
4,060,489; 4,464,267 and 4,060,132 describe the use of thixotropic polysaccharide gums in fire-fightin~ compositions for polar solvent fires. Such foams form a mc~ e on the surface of the polar solvent that protects the rest of the foam from coll~psin~ Protein hydrolysates can be used in col"~inalion with polysaccharide gums to fight polar-solvent fires. The use of non-oligomeric ampholytic sulphonamide fluorochemical surf~ct~nts with hydrolyzed protein and polysaccharide gums to fight polar solvent fires has been described in U. S. Patent No. 4,424,133.
o U.S. Patent Nos. 4,303,534 and 4,563,287 describe the use of aqueous fire-fightinp compositions comprising a water-soluble high molecular weight compound which contains fluoroalkyl groups and water-solubilizable groups, having a molecular weight of not less than 5,000 and a fluorine content of not less than 10%
by weight, and which is soluble in water in an amount of at least 0.1% by weight at 25~C as an additive to a foam fire-extin~.i.ching agent, particularly for fires of polar organic solvents (US '534) and cooking oil (US '287), respectively. The foam fire-extin~ hing agent to which the compound having fluoroalkyl groups is added may be any conventional one such as a fluorine-co..~ il-g surfactant, a synthetic surfactant cont~inin~ no fluorine atom or a partially hydrolyzed protein-cont~ining 20 foam agent.
U.S. Patent No. 5,218,021 teaches perfluoro-terminated-cooligomers derived from perfluoroalkyl radicals and non-ionic hydrophilic and anionic hydrophilic monomers via free radical co-oligomerization. The cooligomers are useful as additives in polar-solvent fire-fighting compositions when used in 25 conjunction with polysaccharides and other adjuvants.
U.S. Patent No. 5,391,721 describes aqueous film-forming foam (AFFF) concentrates for fighting polar and non-polar fuel and solvent fires, comprisinghydrocarbon solvents, hydrocarbon surf~ct~nt~, fluorosurfactants, high molecularweight polysaccharides, ~l~in~tes, salts of aryl or alkylaryl sulfonates and water, and 30 a method for modifying the viscosity of the AFFF concentrates.
CA 022~660~ 1998-11-26 JP-A-2121681 (1990) discloses a protein foam fire-e~ctin~ hing agent, which contains a cationic or amphoteric fluorine-co.~ g oligomer having an average molecular weight of 4000 or lower. The oligomer is ionically reacted with protein to give a fluorinated protein which is suitably soluble in water and easily s foamed without p.~e;~ ;on; the foam is hardly soluble in polar solvents. The agent is particularly suitable for e~tin~ hing fire of polar solvents.
WO 94/18245 describes novel water-soluble polyperfluoroalkylated surf~ct~nt~ derived from polycarboxylic functional polymers and having oil and alcohol repellent properties enabling their use in synthetic or protein-based extin~liching foam compositions for putting out not only burning hydrocarbons but also burning polar liquids (alcohols, ethers, esters, etc.) without requiring thickening agents such as polysaccharides.
Multi-purpose non-polar and polar-solvent fire-fi~hting foam concentrates are typically form~ ted to be diluted (proportioned) to di~~ L concentrations for use on di~ren~ types of fires. For fires involving non-polar fuels such as hydrocarbon liquids, the concentrates are proportioned at the point of application through the foam nozzle to the 3% level (3 parts concentrate with 97 parts fresh or salt water). Fires involving polar solvents require a dilution to 6%. These products are known in the industry as "3x6" ("three by six") products.
Recent advances in polar-solvent fire-fighting forrnulation technology have made it possible to forrnulate concentrates that can be diluted at a single proportioning level of 3% for all uses. These products are known as "3x3 " ("three by three") products. Among the well known advantages of these 3x3 products are savings in storage space, and savings in cost through the reduced usage level of the concentrate. These products can also elimin~1e the need on the part of the fire-fighters to identify the fuel type in emergency situations; because only one, single proportioning setting at 3% is required for either polar solvent or hydrocarbon fires.
With the 3x6 type of products, the fuel type (i.e., whether the burning fuel is a polar, hydrophilic liquid or a hydrocarbon) has to be identified before the fire-fighter can propt;~ly set the foam proportioning device at either 6% or 3%.
CA 022~660~ l998-ll-26 One of the major disadvantages of a 3x3 agent vs. a 3x6 agent is that high amounts of polysaccharide have to be used in the concentrate to get the desired fire-fighting pe. ro~---ance. These high amounts of polysaccharides lead to high viscosities, ranging between 4000 and 5000 cps. These high viscos;ly materials are s hard to transport by pumps, to uniformly dilute with water before use and to remove enll ~pp~d air leading to problems when material is loaded in storage tanks (too much foam is generated, due to air e..l- ~p..,ent, during loading which will result in the fact that storage tank can only partially be filled). High ~mollnt~ of polysaccharide can also lead to met~ct~ble systems with low initial viscosity (e.g., between 600-800 cps) that during aging over time, especially with heat or in contact with even small amounts of water (air humidity, condense water, residual water in storage tanks), show a significant rise in viscosity (up to 3000 cps and more). This dramatic change in viscosity makes these materials unreliable, because viscosities in reality are much higher than expected (e.g., causing pumping problems). The factthat these materials are met~ctable makes them unpredictable and incon~i~t~nt7 which is a very negative point in fire-fighting where surprises in equipment andmaterials must be lowered to the strict minimllm A need thus exists for a stable, low viscosity 3x3 agent corl~h~ g only low amounts of polysaccharide.
Briefly, in one aspect, the present invention provides a fire-fi~hting concenl,~e composition colllp~i~ing a) a fluorochemical oligomer having a plurality of pendent fluoroaliphatic groups, b) one or more fluorochemical surf~ct~nt.~ and one or more non-fluorinated (e.g., hydrocarbon) surf~ct~nt~;
c) a polysaccharide;
d) water; and e) optionally, a polymeric stabilizer and thickener other than a polysaccharide, one or more water-soluble organic solvent, and other usual additives.
In a further aspect, the invention provides a method of e~ting~ hing polar or non-polar liquid fires, which comprises the steps of diluting, aerating and CA 022~660~ 1998-ll-26 applying to the surface of said liquid an effective amount of the fire-fi~hting concentrate composition for e~ctin~ hin~ said fire.
The aqueous fire-fighting composition of the present invention comprising a fluoro~ mical oligomer having a plurality of pendent fluoroaliphatic groups, one or s more fluoroch~m~c~l surfactant, one or more non-fluorinated surfactant and a polysaccharide provides a unique sslutiQn to the problems encountered in the prior art, wherein contradictory il~oll,.alion can be found as regards suitability of dil~lelll types of fluorochemical oligomers for use together with other components of a fire-fighting composition.
lo U.S. Patent No. 4,303,534, for example, describes an aqueous fire-fi~htin~
composition having a water-soluble high molecular weight additive which containspendant fluoroalkyl groups and water-solubilizable groups together with a partially hydrolyzed protein-co..~ ing foaming agent. Use ofthe fluoroalkyl-group-con1~ining high molecular weight additive together with a polysaccharide in a fire-fighting composition is not mentioned in these patents. These patents also teachthat the molecular weight of the high molecular weight additive must not be lessthan 5,000, and preferably not less than 10,000, because otherwise stable foams are not formed on the surface of a polar organic solvent, and foams of good heat resistance are not produced on the surface of a petrolic solvent.
U.S. Patent No. 5,218,021 teaches the use of cooligomers having terminal perfluoroalkyl moieties as additives in polar solvent fire fighting compositions in conjunction with polysaccharides and other additives. This patent states that the perfluoroalkyl, high molecul~r weight polymers according to U.S. Patent Nos. 4,303,534 and 4,563,287 which contain perfluoroalkyl groups interspersed randomly along the polymeric backbone are not as efficient as cooligomers havingterminal perfluoroalkyl groups. It is also said that the cooligomers interact with polysaccharides in a synergistic manner due to strong association of the co-oli~omçrs with the polysaccharides.
- Accordingly, U.S. Patent Nos. 4,303,534, 4,563,287, and 5,218,021 teach away from the instant invention because, while compounds cont~ining pendent fluoroalkyl groups may be useful as additives in certain foam fire-e~ting~ ehin~
CA 022~660~ 1998-11-26 agents for comb~ting polar organic solvents fires (provided that they have a relatively high molecular weight), these perfluoroalkyl-group-cont~ining compounds are said to be less efficient when used in compositions conlpr;s"lg polysaccharides, where cooligomers having only terminal perfluoroalkyl groups are said to be 5 supenor.
It has now surprisingly been found that fluoro~h~mi~ql oligomers having a plurality of pendent fluoroaliphatic groups, when used together with a polysaccharide, have excellent fire fighting plopellies in 3x3 formulations. Also surprisingly the fluorochemical oligomers having a plurality of pendent o fluoroaliphatic groups in the fire-fighting compositions of the present invention are not restricted to compounds having a molecular weight of not less than 5,000 buteven compounds having a molecular weight as low as 2,000 have excellent fire-fighting properties for both polar and non-polar solvent fires when used in combination with a polysaccharide.
1S Also in the present invention a synergism is observed when both fluorochemical oligomer and polysaccharide are used in the fire-fighting concentrate composition. However, it is believed that this synergism is not caused by stronginteraction between the oligomer and the polysaccharide as is taught in U. S. Patent No. 5,218,021, since the same observation was made with the currently pre~,led 20 amphoteric fluorochemical oligomers.
A further surprising advantage of the compositions of the present invention comprising fluorochemical oligomer having a plurality of pendent fluoroaliphaticgroups and polysaccharide is that, whereas the pl~r~lled compositions of U.S.
Patent No. 5,218,021 (3x6 formulations) comprise polysaccharide up to 10% by 25 weight, compositions of the present invention use polysaccharide at concentrations of 3% or less, and preferably 1.5% or less, by weight. The fluorochemical oligomers used in the composition of the present invention boost the polar solvent resistance dr~m~tically, allowing for reduction of polysaccharide levels and leading to advantageously low viscosity of the concentrate composition.
CA 022~660~ l998-ll-26 Fluoroç~l~mi~l oligomers useful in the fire-fightin~ compositions of the present invention have a plurality of pendent fluoroaliphatic groups (Rf) and water solubilizing moieties are usually connçcted togeth~?r by suitable linking groups.
The fluoroaliphatic group (R~) in the oligorn~r can generally be described as 5 a fluorinated, preferably saturated, monovalent, non-aromatic group of at least 3 carbon atoms. The aliphatic chain may be straight, branched, or, if sufficientlylarge, cyclic and may include oxygen, hexavalent sulfur, or trivalent nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is prerel~;d, but hydrogen or chlorine atoms may be present as substituents provided that not more than one0 atom of either is present for every two carbon atoms. While groups col-~A;..;-l~ a large number of carbon atoms will function adequately, compounds cont~inin~ not more than about 20 carbon atoms are prerel I ed since larger groups usually I epl es~lll a less efficient utilization of fluorine than is possible with shorter chains.
Fluoroaliphatic groups co..lAil~;ng about S to 12 carbon atoms are most preferred.
The water-solubilizing polar group or moiety of the fluorochemical oligomer can be an anionic, cationic, non-ionic or amphoteric moiety, or combinations of said groups or moieties which may be the same or di~el enl. Typical anionic groups include COOH, COOM, SO3M, OSO3H, OSO3M, OPO(OH)2 and OPO(OM)2, where M is a metal ion (such as sodium or potassium), an ammonium ion, or other arnine cation. Typical cationic groups include: NH2, NHR, and NR2, where R is a lower alkyl group such as methyl, ethyl or butyl; and R'3NA', where R' is a lower alkyl group or hydrogen, and A' is an anion such as chloride, sulphate, phosphate or hydroxyl. Typical non-ionic groups include poly(oxyalkylene) moieties, e.g., those derived from polyethylene oxide, polypropylene oxide and mixtures thereof.
Typical amphoteric groups would include N~(CH3)2C2H4COO-, and NR2~~ (amine oxide). The water-solubilizable group or moiety is preferably non-ionic or amphoteric. Amine oxides are highly prerelled.
The linking group is a multivalent, generally divalent, linking group such as an alkylene, arylene, sulfon~mido~lkylene, carbonamidoalkylene or other 30 heteroatom-col;.;ing group such as siloxane, inr.hl~ing combinations of such groups.
. ~ .. ..... . . .. _,, CA 022~660~ 1998-11-26 The fluorochemical oligomers are pl ~rel ably non-ionic or amphoteric. They have about S to 45 weight percent, plerel~bly about 20 to 40 weight percent of carbon-bonded fluorine, based on the weight of the oligomer, the fluorine content residing in said plurality of pendent fluoroaliphatic radicals. These materials are 5 relatively low molecular weight linear polymers, or lightly crc,.c l;.~k~d polymers, col-lA~ from 3 to 4 up to about 25 or 30 monomer units, and thus are "oligo~ ic", as contrasted to "high polymers" having a molecular weight of 100,000 or higher.
A particularly useful class of fluorochemical oligomers falling under the o above general description are polyacrylates. Examples of this class of fluorochemical oligomers can be prepared by copolymerizing any of the known fluorochemical (meth)acrylates and optionally (meth)acryl~mi~e~ such as those described in U.S. Patent No. 5,098,446 (table 1, column 6) or those described inU.S. Patent No. 5,453,540 (columns 14 and 15), with fluorine-free (meth)acrylates 15 and optionally (meth)acrylamides such as those described in U.S. Patent No.
5,453,540 (columns 15 and 16).
The ratio of fluorochemical monomer to fluorine-free monomer may vary in order to obtain subs~nlial water solubility of the oligomer and in order to get a maximum foam stabilizing effect. The ratio will vary depending on the specific 20 monomer con.binalion used. Preferably, the fluorochemical oligomer is soluble in water in an amount of at least 0.5% by weight of the oligomer. Fluorochemical oligomers have been described for example, in U.S. Patent Nos. 4,668,406, 3,787,351 and 5,098,446.
The fluorochemical oligomers can be prepared by methods known to those 2s skilled in the art. Pl erel~bly the oligomers will be prepared by free radical polyme.i~alion in the presence of a chain ll ~llsrer agent in order to control the molecular weight. Useful initiators inch.de organic peroxides, such as benzoyl peroxide, lauryl peroxide and various thermal initiators. Plerelled thermal initiators include 2,2'-azobisiosl,u~y-ol il-ile (ABIN), co.ll..,e--;ially available from E.I.
DuPont de Nemours under the trade name VazoTM 64, and 2,2'-azobis(2,4-dimethylvaleronitrile), available from Wako under the trademark V-65. The CA 022~660~ 1998-11-26 initiator is present in an amount of ~om about 0.01 to 2 parts based on 100 parts of total monomer contçnt Useful chain transfer agents include lllel.,al)lalls, alcohols, and carbon tetrabromide. The chain ~ srel agent is present in an amount of from about 0.1 to about 6 parts based on 100 parts per total monomer content.
s The fluoroçllemic~l oligomers of this invention have an average molecular weight between about 2000 and about 50,000, pleielably between about 2000 and about 20,000, most prefe~bly between about 2000 and about 10,000. The fire-fighting composition of the present invention will comprise from about 0.3 to about 5% by weight ofthe fluorochemical oligomer, preferably between about 0.5 and 0 4%.
The concenll ~te composition of the present invention also comprises one or more fluorochemical surf~c~nts (which gives low surface tension) which may be anionic, cationic, nonionic or amphoteric, and one or more nonfluorinated (e.g.,hydrocarbon) surf~ct~nt~ (which makes the foam) which may be anionic, cationic, amphoteric or nonionic as is known in the art and described in, e.g., U.S. Patent No. 5,085,786 (columns 4-8) and U.S. Patent No. 5,359,096 (columns 5-7). In thiscomposition, the fluorochemical surfactant is used in an amount of from about 1 to about 6% by weight, preferably between about 1.5 and about 4% by weight; and thenonfluorinated surfactant is used in an amount of from about 1 to about 10% by weight, preferably in an amount of from about 2 to about 8% by weight.
The concentrate composition of the present invention also comprises a polysaccharide, preferably an anionic heteropolysaccharide having a high molecular weight. Co,.lme.cially available polysaccharides useful in the invention includethose sold under the trademarks, e.g., KelzanTM and KeltrolTM (available from Kelco). The polyrneric structure is not critical for the purposes of this invention.
Only a small amount of polysaccharide is required to confer a noticeable change in properties. The polysaccharide is used in an amount of from about 0.1 to about 3%
by weight ofthe concentrate composition, preferably between about 0.2 and 1.5%.
Optionally, other polymeric stabilizers and thickeners can be incorporated into the conce~ ale compositions of the invention to çnh~nce the foam stability of the foam produced by aeration of the aqueous solution made from the concentrate.
CA 022~660~ 1998-ll-26 WO 97/45167 o PCT/US97/07459 Examples of suitable polymeric stabilizers and thickeners are partially hydrolyzed protein, ~Larclles and modified starches, polyacrylic acid and its salts and complexes, polyethyleneimine and its salts and complexes, polyvinyl resins, e.g., polyvinylalcohol, polyacryl~mides7 carboxyvinyl polymers, and poly(oxyethylene)glycol.
s When used, the optional polymeric stabilizers and thickeners will be added in an amount of from about 0.1 to about 5%, pre~.~bly between about 0.2% and 1.5%
by weight of the collcellllale.
The concentrate compositions of the invention contain water and preferably include water-soluble solvents to f~ it~te solubilization of the fluorochemical 0 oligomer surf~ct~nt~ and the other components. The solvents also may act as foam stabilizers, freeze protection agents and shelf life enhancers. Suitable solvents include ethylene glycol, diethylene glycol, glycerol, ethyleneglycol monoethylether, diethyleneglycol butylether, dipropyleneglycol monopropylether, dipropyleneglycol monomethylether, methoxy propylene glycol and hexylene glycol. A suitable range of cosolvents in the concentrates of the invention is from 1 to 50 parts, preferably from 4 to 30 parts, by weight per 100 parts of concentrate.
Other ingredients, known to those skilled in the art, that are usually employed in fire-fighting compositions may be employed in the concentrate compositions of this invention. Examples of such ingredients are preservatives, 20 buffers to regulate pH (e.g., tris(2-hydroxyethyl)amine or sodium acetate) and corrosion inhibitors (e.g., toluoltriazole or sodium nitrite).
The composition of the invention is employed in the usual way to combat fires of fl~mm~ble liquids or to prevent evaporation of fl~mm~hle vapours. The composition is particularly suitable for application in the form of a foam. Usually it 2~ is stored in the form of an aqueous concentrate only requiring dilution to 3%concentration with either fresh or sea water to form the llplel~ " and aeration of the premix to produce a foam which is applied to the burning liquid surface.
Objects and advantages ofthis invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in 30 these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
CA 022~660~ l998-ll-26 WO 97/45167 ~ PCT/US97/07459 EXAMPLES
Test methods The following tests have been done to evaluate the foam pl ope:l lies of the compositions of the present invention.
Foam Stability Test Foams were produced by making 100 ml of a 3% foam premix by diluting by weight 3 parts foam concentrate with 97 parts fresh or with synthetic sea water 0 (composition according to ASTM D1141-52), and foaming the reslllt~nt premixusing a Kalorik-type 5353 kitchen mixer at highest speed for 1 minute. Then 50 gof each foam was poured over a 30 second time period onto 250 g solvent cont~ined in a 19 cm diameter x 8 cm high glass dish. The foam was poured onto the solvent in such a way that it spread over and across the solvent from one end of the dish to the other and completely covered the surface of the solvent. The time required for 50% of the foam area to collapse from the first moment the foam touched the solvent was recorded as Tl/2 (solvent). Both acetone and isopropanolwere used as representative polar solvents.
Foam Expansion/Drain Time Foam expansion and drain time were measured in accordance with US
Dep~Lmcnl of Defense Military Specification No. MIL-F-24385, Revision F, Section 4.7.5, using the standard National Foam Systems 2 gaVmin nozzle.
2s Surface Tension and Interfacial Tension The surface and interfacial tension were measured with a Du Nouy Tensiometer according to ASTM D-1331.
Brookfield Viscosity The Brookfield Viscosit,v was measured using a Brookfield LVT
vi~cosimeter using a number 3 spindle at a rotational speed of 30 rpm in a waterbath set at 20~C. The viscosity was recorded after 60 seconds.
Fire-Fighting Tests Labscale The conc~ le of the present invention was diluted to a 3% premix with fresh water (i.e., tap water) or with synthetic sea water (composition accordillg to o ASTM Dl 141-52). 150 ml ofthis 3% solution was foamed in a kitchen blender for 30 secondc, after which the foam was immedi~tely transferred to a glass flask.
Using air pressure, the foam was forced from the flask and passed through a plastic tube to 250 ml of burning polar solvent in a circular metal pan of 0.021 m2 area.
The solvent pre-burn time was 40 seconds. The time required for extin~ hin~ the burning liquid was recorded.
Nordtest Type 023 The fire-fighting propel ~ies of the foams made from the concentrates of the present invention have been tested on a large scale according to a modified Nordtest Type 023. Test conditions:
A circular pan with an area of 2.65 m2 was filled with 180 1 of fuel. The nozzle used was a modified National Foam nozzle with flow rate 11.4 1/min. The fuel pre-burn time was 60 seconds and the foam was applied for a total of 4 min~tes A visual observation was done after 50%, 90%, 99% and 100% (complete fire-eYting~ hm~nt) foam coverage. The hold time before running the 'burnback' test, i.e., the time after completion of foam application, was 1 minute. A visual observation of 50% burnback time was done.
Film Spreading Test Cyclohexane was poured in a petri dish having 10 cm diameter and 1 cm height until the cyclohexane reached a depth of 0.5 cm. Twenty drops of a 3%
premix was put gently on the cyclohexane surface using an eyedropper over a period of about 20 seconds. The film formed was allowed to spread during 30 sec.A burning match was passed over the dish. If the cyclohexane did not ignite, thefilm passed the vapor sealing.
Abbreviations The following abbreviations, trade names and trademarks were used in the ~A~ S
EtFOSEMA: N-ethylperfluorooctylsulfonamidoethylmethacrylate, available from Minnesota Mining and ~l~mlf~ctllring Company, St. Paul, Minnesota, U.S.A. (3M) MeFOSEMA: N-methylperfiuorooctylsulfonamidoethylmethacrylate, available from 3M
DMAEMA: N,N-dimethylaminoethylmethacrylate, available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin, U.S.A.
AMPS-EOA: monoethanolamine salt prepared from 2-acrylamido-2-methylpropane sulfonic acid, available from Aldrich P144DA: A diacrylate made from PluronicTM 44, which is available from BASF
Aktienges.oll~çh~, Ludwigshafen, Germany CW750A: An acrylate made from CarbowaxTM750, C8Fl7SO2N(C2Hs)C2H4OCOC(CH3)-CH2, according to the procedure described in U.S. Patent No. 3,787,351, Example 2. CarbowaxTM750 is available from British Petroleum International Limited, London, United Kingdom 2s AA-EOA: acrylic acid - ethanol amine salt HOEMA: hydroxyethylmethacrylate CW400DMA: A diol ~imeth~crylate, made from CarbowaxTM 400, which can be prepared using the procedure described in U.S. Patent No. 3,787,357, Example 1, except substih1ting CarbowaxTM for PluronicTM44.
CarbowaxTM400 is available from British Petroleum International Limited, London, United Kingdom CA 022~660~ 1998-11-26 DMAPMA/chloroethanol: N,N-dimethyl~l~il~oplopyl meth~crylamide (available from Aldrich), qualc;..l.~ed to 100% by chloroethanol SOS: sodium octyl s.llph~te SDS: sodium decyl sulphate s BC: CarbitollM ether, a diethylene glycol butyl ether DPM: dipropylene glycol monomethyl ether DPnP: dipropylene glycol monoplo~yl ether DMF: dimethylfo- ,..~"-: ~e NMP: N-methylpyrrolitlinone EtOAc: ethyl acetate foamer: C8Fl~SO3K+, a fluorochemical surfactant as described in U.S. Patent No.
5,0~5,786, column 5, line 68, and available from 3M Company WitcolateTM 7093 surfactant: a C6 - C,0 alkyl ether sulfate surfactant, available from Witco KelzanTM gum: a polysaccharide (x~nth~m gum), available from Kelco AnsuliteTM 3x3 low viscosity agent (Ansul, USA) FiniflamTM 3x3 fire-fighting agent (Pirna, Germany) TowalexTM 3x3 freeze-protected fire-fighting agent All parts, ratios, percentages, etc., in the following examples are by weight unless otherwise specified.
Ex~lples 1-14 and Col"palali~/e Examples C1-C4 A. Synthesis of the fluorochemical oligomers I . Fluorochemical oligomer oxides FC- 1 to FC-9 The fluorochemical oligomers identified in Table 1 were prepared according to the general procedure as described below for the synthesis of the fluorochemical oligomer EtFOSEMA/DMAEMA-N-oxide with a monomer ratio (wt) of 60/40.
In a 500 ml, three-necked flask fitted with a condenser, stirrer and thermometer were placed 60 g EtFOSEMA, 40 g DMAEMA, 5 g n-octyl lllelGaplan (RSH), 1 g ABIN and 100 g isopropyl alcohol. The flask was deaeratedwith nitrogen under vacuum for 3 times. The mixture was heated and the reaction CA 022~660~ 1998-11-26 was carried out under nitrogen at 75~C for 16 hours. After the reaction was completed, the solvent was ~Itipl)td at a tem~c~alLlre of 60-80~C under asp;ldlor vacuum. The reaction mixture was cooled to about 45~C a~er which 80 g ethylene glycol and 20 g BC were added. 29.7 g of hydrogen peroxide (35% active in water) was added in small increments over a period of one hour. An immerli~te exotherm was noticed. The reaction was contin.~ed for another 3 hours at 45~C, then for 3 hours at 65~C and finally for 1 hour at 90~C. The reaction mixture was diluted to 30% solids using 103 g deionized water. A slightly hazy, yellow solution was obtained, co.ll~inillg an oligomeric fluorochemical amine oxide having a weight l0 average molecular weight of 4400. The pH of the solution was adjusted to 7 using a 10% aqueous solution of sodium hydroxide Following the above described method, di~ en~ fluorochemical amine oxides as given in Table 1 have been synthe~i7ed Table 1: Composition of EtFOSEMA/DMAEMA-N-OXIDE oligomers FC Monomer ratio Weight oligomerEtFOSEMA/DMAEMA %ABIN %RSH Average MW
FC-6 60/40 0.2 0 43000 FC-7 70/30 0.8 5 4500 FC-8 30/70 0.8 5 4400 FC-9 60/40 0.8 5 5100 Note: For each oligomer, the reaction solvent used was isopropanol, except for FC-3 in which N-methylpyrrolidinone was used.
In all examples given above, the fluorochemical oligomer oxide was obtained as 30% solids in a mixture of ethylene glycol (24%), BC (6%) and water (40%), except for FC-3. In the synthesis of FC-3, the solvent was not stripped after the first reaction and the fluoro~.h~mie~l oli~c ln~r FC-3 was obtained as 30% solids in a rnixture of NMP (30%) and water (40%).
2. Fluorcçh~m.c~l oligomers FC-10 to FC-14 Fluoroch~ cal oligo~ FC-10 to FC-14 were made using the general procedure outlined below:
In a 500 ml, three-necked flask fitted with a condenser, stirrer and thermometer were placed the monomers, initiator and chain transfer agents as listed in Table 2. The flask was deaerated with nitrogen under vacuum for 3 times. The mixture was heated and the reaction was carried out under nitrogen at 75~C for 16 hours. After the reaction was completed, the solvent was optionally (as indicated in Table 2) stripped at a tel.,pe. ~ILIre of 60-80~C under aspirator vacuum. The reaction mixture was diluted to 30% solids using solvent mixtures as given in Table 2. The pH ofthe solution was always adjusted to about 7.
Table 2: Composition of fluorochemical oligomers Chain Weight FC- M~ mixture Transfer % Solvent Final average No. (Ratio) (5~/O) ABINreaction solvent MW
FC-10EtFOSEMA/AMPS- Octyl- 1 DMF DMF/ 5,000 EOA/P144DA Illel~,d~ Water (60120/20) 30/40 FC-l lEtFOSEMA/CW750A Octyl- 0.8 EtOAc EG/BC/ 4,700 (60/40) ll~:lCd~ln (l) Water FC-12EtFOSEMA/AA- Thio- 0.~ IPA EG/BC/ 4,200 EOA/HOEMA glycerol (1) Water (70/15/15) 2416140 FC- 13MeFOSEMA/ Mercapto- I IPA EG/BC/ 4,400 CW4000DMA (50/50) ethanol (1) Water FC-14 BuFOSEA/ Mercapto- I NMP NMP/ 4,500 DMAPMA- ethanol Water chlol~l}ldllol (60/40 30/40 Note: (1): solvent stripped CA 022~660~ 1998-11-26 B. Eva1uation of fluoroçh~mi.c~' oligomers in fire-fighting foam agents Foams were made comprising the fluorochemical oligolllG,~ described above. The foams were first p-epaled by mixing water (85.5%) with 0.5% Kelzan gum and 5% BC, whereby a viscous solution was obtained. Then, 2% foamer, 1% C8FI,SO3K+, 4% Witcolate 7093 surfactant and 2% fluorc~.hPtn:c~l oli~,olllel were added (each pel ce~ ge based on solids by weight) and the mixture was stirred for 2 hours at 60~C. A clear brown solution with a Brookfield viscosity (spindle 3) bt;Lween 700-800 cps was obtained. The foams thus plepaled were used in the following e~ les.
lo Examples I to 14 were made by diluting 3 g ofthe concentrates preparedabove to 100 g using tap water to provide a 3% foaming agent premix.
Colllpa~live examples C-l and C-2 were made according to the procedures described in U.S. Patent No. 4,303,534, example 2, and U.S. Patent No. 4,460,480, Example 1, respectively. The foam agents of Comparative Examples C-3 and C-4 were made the same way as the foam agent of Example 2, except that no polysaccharide was added in C-3 and no fluorochemical oligomer was used in C-4.
The 3% foam agents were tested for their foam stability according to the foam stability test described above and using acetone and isopropanol as solvents. The results of the test are provided in Table 3.
Table 3: Foam Stability Test Tln acetone Tln IPA, Ex. No. FC Oligomer min:sec min:sec FC-l 32: 10 38:00 2 FC-2 39:40 45:10 3 FC-3 35:20 --4 FC-4 25:10 --FC-5 12:30 -6 FC-6 6:50 --7 FC-7 43 :50 8 FC-8 7:40 --CA 022~660~ 1998-11-26 Tl'2 ~cetQne T~/2 IPA, Ex No.FC Oligomer min:sec min:sec 9 FC-9 31 :40 --FC-10 32:45 35:40 11 FC-ll 3010 --13 FC-13 26:00 --14 FC-14 30:20 30:50 C-3 FC-2(*) 2 40 3 00 C-4 5:50 --Note * Fluorochemical oligomer of Example 2 was used without polysaccharide in the foam concentrate The data in Table 3 in~lic~te that formulations comprising fluorochemical oligomers according to the invention provide foams which are very resistant to an aggressive polar solvent such as acetone The formulations according to the invention are superior to the state-of-the-art formulations Col-t~ .g fluorochemical oligomers having only terminal fluorinated R-groups (Comparative Example C-2) o or co~ fluorochemical oligomers of high molecular weight and lower fluorine level such as in Comparative Example C-l Co~-.pal~live Example C-3 indicates that foam made using the fluorochemical oligomer of Example 2, but with no addedpolysaccharide, shows poor resi~t~nce against polar solvents Co-~.~a.~ e Example C-4 in~icates that foam made with only polysaccharide and no fluorochemical oligomer also has low foam stability in contact with a polar solvent The fluorochemical oligomer with the polysaccharide improves the foam stability considerably CA 022~660~ 1998-ll-26 E~ les 15 to 19 and Co,.lpa.~ e E~a-.-i)les C-5 to C-10 In E~ ples 15 to 19, foam formulations were ~)re~)ared and tested as fire-fi~htin~ agents using labscale tests. All formulations conlail~ed 2.6% foamer, 1.4%
C8Fl~SO3X+, 4% Witcolate 7093 surfactant, 0.85% Kelzan gum, 2%
fluorochemical oligomer (as in-lic~ted in Table 4), 5% BC and 84.15% water. The Brookfield viscosity of the conce..ll ales ranged between 1600 and 1900 cps.
P-emu~es were made by diluting 30 g of each concentrate to 1000 g using tap water.
150 ml of each 3% premix solution was foamed in a kitchen blender for 30 secondsa~er which the foam was 1. ~nsre. . ed into a glass flask. By air pressure the foam o was added, through a plastic tube, to burning isopropanol (250 ml) after a pre-burn time of 40 seconds.
Comparative Example C-5 was made according to the general procedure described in U.S. Patent No. 4,460,480, Example l.
Co---pa-~Lh~e Example C-6 was made according to the general procedure described for Examples 15 to 19, using fluorochemical oligomer FC-2, but withoutaddition of polysaccharide. Comparative Example C-7 was made according to the procedure described in JP 2121681, Example 6. In Comparative Examples C-8 and C-9, commercially available fire-fi~htin~ agents were tested: AnsuliteTM 3x3 lowviscosity agent (viscosity 700-2000 cps, available from Ansul, USA) in C-8 and TowalexTM 3x3 agent (viscosity 760 cps, available from Total Walther, Germany) in C-9.
Table 4 gives the composition of the fire-fighting agents tested, as well as the results of fire-e~ctin~li.chment time and application rate (liter/min/m2).
2s Table 4: Composition and Pelrolmance of Fire-Fighting Foams FCNo. or Exting~ hment ApplicationRate Ex. No. ProductName time(sec) (liter/min/m2) FC-2 90 1.96 16 FC-7 85 1.98 17 FC-10 100 2.02 18 FC-11 129 2.00 19 FC-12 142 2.04 --. .
CA 022~660~ l998-ll-26 WO 97/45167 20 PCT/US97tO7459 FC No. or Fxtin~ ApplicationRate Ex. No. ProductName time(sec)(liter/min/m2) C-5 -- /** 2.09 C-6 FC-2* /** 2.11 C-7 -- /** 2.08 C-8 AnsuliteTM 3x3 140 2.02 agent C-9 TowalexTM3x3 235 2.08 agent Notes: FC-2*: no polysaccharide used /**: not possible to e~in~lish fire The results in Table 4 indicate that compositions according to the invention have, in almost all cases, superior fire-fi~hting properties compared to the co..-pa-~ e examples.
Examples 20 to 25 In Examples 20 to 25, fire-fighting concentrates were prepared co~ g di~elenl components and combinations as outlined in Table 5.
Table 5: Composition of Foam Components/Ex. No. 20 21 22 23 24 25 Fluoroaliphatic -- -- 2.6 -- -- 2.6 aminocarboxylate(*) Foamer 2.6 2.6 -- 2.6 2.6 --C8FI,SO3K+ 1.3 1.3 1.3 1.3 1.3 1.3 Witcolate7093 5 5 -- 5 5 --Surfactant Kelzan gum 0.9 0.9 0 g0.55 0 35 0.9 FC-2 1.5 1.5 1.5 2 2 1.5 CA 022=,660=, 1998-11-26 Note: (*): fluoroalirh~tic amino carboxylate surfactant as described in U.S. Patent No. 5,144,069, Example 1.
The concentrates were tested as foams delivered from 3% premixes in tap water. The results are given in Table 6.
Table 6: Properties of 3% Foam in Tap Water Characteristic/Ex. No. 20 21 22 23 24 25 Foam expansion 8.4 7.5 7.4 8.6 8.7 7.8 Drain time (min:sec) 10:30 9:4010:00 10:50 10:30 9:50 Surface tension (N/m) 16.7 16.817.1 16.8 16.7 17.2 Interfacial tension (N/m) 2.6 2.4 2.5 2.5 2.5 2.4 Viscosity (cps) 1760 16401880 740 440 1760 o Notes: Interfacial tension: 3% tap water premix/cyclohexane All examples passed the film spreading test on cyclohexane The results in Table 6 indicate that a broad range of formulations can be made having low viscosity, low surface tension, good foamability and good film-forming characteristics. Good film formation is essenti~l for fire-fighting on non-polar liquids. This will be demonstrated in Example 26.
Example 26 In Example 26, a concentrate was prepared from 2.6% foamer, 1.3%
C8FI~SO3K+, 5% Witcolate 7093 surfactant, 1.5% fluorochemical oligomer FC-2, 0.9% Kelzan gum, 0.9% hydroxypropylated corn starch, 10% BC and water (up to 100%). The Brookfield viscosity was 1680 cps. 3% premixes were prepared using tap water and sea water as ~ uents The premixes were tested as nonpolar, fire-fi~hting agents, according to the ISO/DIS 7203-1 test on heptane and according to the specifications for low expansion foam concentrate used to extin~ h fires of water-immiccible liquids. The results are given in Table 7.
CA 022~660~ 1998-11-26 Table 7: Fire-Fighting Pl~p~ ies of Non-Polar Solvent of Example 26 Test Tap Water Sea Water Knockdown (sec) 25 26 90% cover (sec) 38 34 99% cover (sec) 61 54 100% cover (sec) 85 146 The specification requires the fire to be extin~li.shed within 180 seconds.
5 The concentrate passed the test when diluted to 3% with either tap water or sea water. The 3% tap water prernix made from the Example 26 concentrate was further tested on heptane accolding to the Military Specification F 24385 F, on a 4.65 m2 round pan. In Conl~ re Example C-10, a 3% tap water premix made from Ansulite}M 3x3 fire-fighting concentrate was fire-tested. The results are given o in Table 8.
Table 8: Fire-E~in~ hing Properties on Heptane Test Ex. 26 C-10 40 sec s~-mm~tion 354 309 fire-e~c+. in~ hm~nt 34 42 25% burnback 555 390 The data in Tables 7 and 8 indicate that, on nonpolar solvents, a 3x3 foam agent of the present invention is superior in fire performance to a state-of-the-art colll,llelcially available 3x3 agent.
Examples 27 to 31 In Examples 27 to 31 fire-fi~htin~ concentrates were prepared cont~inin~
20 varying amounts of the fluorochemical oligomer FC-2. All concentrates contained 2.6% foamer, 1.4% C8F"SO3K+, 4% Witcolate 7093 surfactant, 0.85% Kelzan gum, 5% BC and the amount of FC-2 inr~ ted in Table 9. Water was added up tolOO%. The solutions had viscosities between 1600 and 1900 cps.
The firc-e,~ hing plope,lies ofthe c~lples were tested in the same way as Ex~mrles 15 to 19. The results are given in Table 9.
Table 9: Fire-Fighting Properties of 3% Foam Application Rate Ex. No. % FC-2 E~in~.isl.. enl time (sec) (liter/min/m2) 27 4 98 1.94 28 2 90 1.96 29 1.5 94 1.98 1 1 10 2.00 3 1 0.5 140 2.08 The results in Table 9 indicate that formulations conl~ini--g even small amounts of fluorochemical oligomer show fast fire-extin~ hm~nt Example 32 and Con.pa~ e Examples C-11 to C-13 In E~lllple 32 and Coll.l.al~live Examples C-l 1 to C-13, fire-fighting tests were done on a large scale. Example 32 comprises fluorochemical oligomer FC-2 in the same composition as Example 15. The fire-fi~hting properties were 5 compared to colr~ lcially available 3x3 fire-fighting agents. Comparative Example C- 1 1 was run with FiniflamTM 3x3 fire-fighting agent, available from Pirna, Germany. Colllpalalive Example C-12 was run with AnsulTM LV 3x3 agent, available from Ansul, USA. C-~lllpal~live Example C-13 was run with Universal GoldTM 3x3 agent, available from Chubb-National, UK. For the test, 3% premixes 20 were made from concentrates using tap water and the agents were foamed through a modified mil spec nozzle. The foams were tested in the modified Nordtest type 023 test, using a 2.65 m2 pan with 180 1 acetone (at a temperature of 3~C) as fuel.
The outside telll~,el ~ re at the time of the test was 5~C. The fuel pre-burn time was one minute. Each foam was applied to the burning fuel under type II
25 application against a backboard. The application rate was 4.4 L/min/m2; the foam CA 022=,660=, l998-ll-26 W O 97/45167 PCTrUS97/07459 application time was four minlltes unless otherwise noted. After colllple~ion offoam application and a one minute holding time, 50% burnback time was measured by reigniting a small pan filled with acetone, and positioning it in the middle of the foam blanket. The time needed for 50% of the fi~el surface to burn again was 5 recorded as 50% burnback time. The results of the fire-fighting test are given in Table 10.
Table 10: Modified Nordtest Type 023 Fire-Fighting Test 50% cover 90% cover 99% cover 100% cover 50%
Ex. No. (sec) (sec) (sec) (sec) burnback 32 46 66 8S 134 pass C-l l 176 202 228 294(2) pass C-12 44 73 114 174 pass C-13 288 336 390 456(3) pass Notes: (1): if the burnback time is more than 300 sec., the sample passes the test (2): total foam application time of 6 min.
0 (3): total foam application time of 8 min.
The data in Table 10 indicates that the fire-fighting agents of the present invention have superior extin~iehm~nt properties compared to the state-of-the-art cGlr",.elcially available products. The e~tin~ hm~nt of the fire is significantly better and the burnback re~ist~nce is high.
Examples 33 to 35 and Comparative E~a,n~ s C-14 to C-15 In Examples 33 to 35, freeze-protected fire-fighting conce~ les were made and evaluated. The agents were p.epal~d by mixing 2.6% foamer, 1.3% C8F~7SO3-K+, 5% Witcolate 7093 surfactant, 10% BC, 1% (Example 33) or 1.5% (Example 34) or 2% (Example 35) of fluorochemical oligomer FC-2, 0.85% Kelzan gum, 0.85% hydroxypropylated corn starch, 22.5% ethylene glycol and water (up to 100% total). In Co.-.~ e Example C-14 AnsuliteTM 3x3 agent (which is not freeze protected) was tested. Comparative Example C- 15 was made with TowalexTM 3x3 freeze-protected fire-fighting agent. The foam agents were tested in the modified Nordtest type 023 test as for Example 32. This time, the outsidetemperature was 29~C, which leplesen~s a highly dem~n/ling test condition (i.e., a relatively high tc~ .alllre)~ The telllpelal~lre ofthe fuel was 19~C. The results of the fire-fighti.~ tests are given in Table 11.
Table 11: Fire-Fighting ~ropel lies of Freeze Protected Agents 50%
50% cover 90% cover 99% cover100% cover burnback Ex. No. (sec) (sec) (sec) (sec) (sec) 33 102 165 168 238 pass 34 65 165 192 225 pass 128 158 215 pass C-14 110 280 365 410(*) C-15 395 445 (*~) I /
s Notes: (*): foam applied for 410 sec (instead of 240 sec) /(**): foam applied for 500 sec (instead of 240 sec), but no fire h, .,f .
/: no fire e?~tin~ .".~;..l lo The data in Table 11 indicate that under high demanding conditions (high temperature), the foam compositions of the present invention are far more efficient than the commercially available state-of-the-art products. The COIllpal a~ e examples did not pass the 50% burnback test.
Examples 36 to 39 E~ ,ples 36 to 39 were run to show that it is possible to make useful foam fire-fightin~ concentrates co~ g dilre-el,l polysaccharides. The concentrates for all examples were made by mixing 2.6% foamer, 1.3% CgF~SO3K+, 1.5%
fluorochemical oligomer FC-2, 5% Witcolate 7093 surfactant, 0.9%
hydroxypropylated corn starch, 10% BC and 0.9% polysaccharide. The polysaccharides used were as follows: in Example 34: polysaccharide K8A13, available from Kelco; in Example 35: x~nth~m gum E 415 food grade, available from Jungbun7~ er~ Austria; in Example 36: KeltrolTM gum, available from Kelco;
and in Example 37: KelzanTM gum, available from Kelco. The concentrate and 3%
~ 25 premix foam properties are given in Table 12.
CA 022~660~ 1998-ll-26 Table 12: Foam Formulations Comprising Di~relel,l Polysaccharides ~-ope,ly\Ex. No. 36 37 38 39 Viscosity (Cps) 1960 1820 1800 1600 Foam eYp~na;on in tap water 13.3 8.8 10.8 10.2 Foam expansion in sea water 11.2 7.5 9.3 8.7 Drain time in tap water (sec) 400 430 490 500 Drain time in sea water (sec) 360 420 455 420 Surface tension (DI-water, N/m) 16.4 16.2 16.3 16.4 Surface tension (sea water, N/m) 17.3 17.4 17.4 17.3 Interfacial tension against cyclohexane:
in DIW (N/m) 3.5 3.9 3.3 3.0 in Sea water (N/m) 2.2 2.2 2.1 2.3 The results indicate that foam formulations cont~ining di~e"
s polysaccharides can be made according to the present invention.
Various modifications and alterations of this invention will become apparenl to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited o to the illustrative embodim~nt~ set forth herein.
FLUOROCHEMICAL OLIGOMERIC SURFACTANTS
The present invention relates to fire-fi~htin~ compositions. More particularly it relates to low viscosity fire-fightine foam compositions, especially 0 "3x3" (three by three) concentrates. The low viscosity compositions of the present invention are found to have excellent fire-extin~ hing properties against both polar and non-polar solvent fires.
Various fire-exting~ hing foams have been developed for use against fires of non-polar solvents or liquids such as gasoline, kerosene, light oils, heavy oils and 5 crude oils. Many ofthese fire-extingl~i.chinf~ concentrates provide film-forming characteristics on the surface of a non-polar hydrophobic liquid. The use of fluorochemical surfactants is taught in U.S. Patent Nos. 3,475,333; 4,472,286;
4,460,480 and 4,717,744. A fire-extingllishing composition which includes them can form a thin aqueous film on the surface of a flammable liquid and inhibit the 20 reignition of the fl~mm~ble liquid once e~ctine~ hed by the foam. The fluorochemical surfactants in the aforementioned patents are incorporated into protein-based fire-fighting compositions in order to impart improved properties such as increased foam mobility, reduced e~ctingllishing times and reduced fuel pick-up. These compositions are useful for fighting fires of burning hydrophobic or non-25 polar hydrocarbon liquids.
However, when such fire-extingllishing foams are applied to fires of polar solvents such as alcohols, ketones, esters, ethers and amines, the foam collapses due to water drainage from foam l~mell~e. Polar solvents penetrate the aqueous foam and speed up water drainage. Certain water-soluble polymers slow down this 30 penetration, and thus slow down the foam collapse. For this reason, fire-fighting foam concentrates for polar solvents generally contain as a key component water-soluble or swellable polymeric materials, e.g., polysaccharides or protein hydrolysates. They cause the aqueous foam to form a gelatinous 'mat' or membranewhen it comes in contact with a polar hydrophilic liquid.
CA 022~660~ 1998-11-26 U.S. Patent Nos. 3,957,657; 4,420,434; 4,424,133; 4,387,032; 4,306,979;
4,060,489; 4,464,267 and 4,060,132 describe the use of thixotropic polysaccharide gums in fire-fightin~ compositions for polar solvent fires. Such foams form a mc~ e on the surface of the polar solvent that protects the rest of the foam from coll~psin~ Protein hydrolysates can be used in col"~inalion with polysaccharide gums to fight polar-solvent fires. The use of non-oligomeric ampholytic sulphonamide fluorochemical surf~ct~nts with hydrolyzed protein and polysaccharide gums to fight polar solvent fires has been described in U. S. Patent No. 4,424,133.
o U.S. Patent Nos. 4,303,534 and 4,563,287 describe the use of aqueous fire-fightinp compositions comprising a water-soluble high molecular weight compound which contains fluoroalkyl groups and water-solubilizable groups, having a molecular weight of not less than 5,000 and a fluorine content of not less than 10%
by weight, and which is soluble in water in an amount of at least 0.1% by weight at 25~C as an additive to a foam fire-extin~.i.ching agent, particularly for fires of polar organic solvents (US '534) and cooking oil (US '287), respectively. The foam fire-extin~ hing agent to which the compound having fluoroalkyl groups is added may be any conventional one such as a fluorine-co..~ il-g surfactant, a synthetic surfactant cont~inin~ no fluorine atom or a partially hydrolyzed protein-cont~ining 20 foam agent.
U.S. Patent No. 5,218,021 teaches perfluoro-terminated-cooligomers derived from perfluoroalkyl radicals and non-ionic hydrophilic and anionic hydrophilic monomers via free radical co-oligomerization. The cooligomers are useful as additives in polar-solvent fire-fighting compositions when used in 25 conjunction with polysaccharides and other adjuvants.
U.S. Patent No. 5,391,721 describes aqueous film-forming foam (AFFF) concentrates for fighting polar and non-polar fuel and solvent fires, comprisinghydrocarbon solvents, hydrocarbon surf~ct~nt~, fluorosurfactants, high molecularweight polysaccharides, ~l~in~tes, salts of aryl or alkylaryl sulfonates and water, and 30 a method for modifying the viscosity of the AFFF concentrates.
CA 022~660~ 1998-11-26 JP-A-2121681 (1990) discloses a protein foam fire-e~ctin~ hing agent, which contains a cationic or amphoteric fluorine-co.~ g oligomer having an average molecular weight of 4000 or lower. The oligomer is ionically reacted with protein to give a fluorinated protein which is suitably soluble in water and easily s foamed without p.~e;~ ;on; the foam is hardly soluble in polar solvents. The agent is particularly suitable for e~tin~ hing fire of polar solvents.
WO 94/18245 describes novel water-soluble polyperfluoroalkylated surf~ct~nt~ derived from polycarboxylic functional polymers and having oil and alcohol repellent properties enabling their use in synthetic or protein-based extin~liching foam compositions for putting out not only burning hydrocarbons but also burning polar liquids (alcohols, ethers, esters, etc.) without requiring thickening agents such as polysaccharides.
Multi-purpose non-polar and polar-solvent fire-fi~hting foam concentrates are typically form~ ted to be diluted (proportioned) to di~~ L concentrations for use on di~ren~ types of fires. For fires involving non-polar fuels such as hydrocarbon liquids, the concentrates are proportioned at the point of application through the foam nozzle to the 3% level (3 parts concentrate with 97 parts fresh or salt water). Fires involving polar solvents require a dilution to 6%. These products are known in the industry as "3x6" ("three by six") products.
Recent advances in polar-solvent fire-fighting forrnulation technology have made it possible to forrnulate concentrates that can be diluted at a single proportioning level of 3% for all uses. These products are known as "3x3 " ("three by three") products. Among the well known advantages of these 3x3 products are savings in storage space, and savings in cost through the reduced usage level of the concentrate. These products can also elimin~1e the need on the part of the fire-fighters to identify the fuel type in emergency situations; because only one, single proportioning setting at 3% is required for either polar solvent or hydrocarbon fires.
With the 3x6 type of products, the fuel type (i.e., whether the burning fuel is a polar, hydrophilic liquid or a hydrocarbon) has to be identified before the fire-fighter can propt;~ly set the foam proportioning device at either 6% or 3%.
CA 022~660~ l998-ll-26 One of the major disadvantages of a 3x3 agent vs. a 3x6 agent is that high amounts of polysaccharide have to be used in the concentrate to get the desired fire-fighting pe. ro~---ance. These high amounts of polysaccharides lead to high viscosities, ranging between 4000 and 5000 cps. These high viscos;ly materials are s hard to transport by pumps, to uniformly dilute with water before use and to remove enll ~pp~d air leading to problems when material is loaded in storage tanks (too much foam is generated, due to air e..l- ~p..,ent, during loading which will result in the fact that storage tank can only partially be filled). High ~mollnt~ of polysaccharide can also lead to met~ct~ble systems with low initial viscosity (e.g., between 600-800 cps) that during aging over time, especially with heat or in contact with even small amounts of water (air humidity, condense water, residual water in storage tanks), show a significant rise in viscosity (up to 3000 cps and more). This dramatic change in viscosity makes these materials unreliable, because viscosities in reality are much higher than expected (e.g., causing pumping problems). The factthat these materials are met~ctable makes them unpredictable and incon~i~t~nt7 which is a very negative point in fire-fighting where surprises in equipment andmaterials must be lowered to the strict minimllm A need thus exists for a stable, low viscosity 3x3 agent corl~h~ g only low amounts of polysaccharide.
Briefly, in one aspect, the present invention provides a fire-fi~hting concenl,~e composition colllp~i~ing a) a fluorochemical oligomer having a plurality of pendent fluoroaliphatic groups, b) one or more fluorochemical surf~ct~nt.~ and one or more non-fluorinated (e.g., hydrocarbon) surf~ct~nt~;
c) a polysaccharide;
d) water; and e) optionally, a polymeric stabilizer and thickener other than a polysaccharide, one or more water-soluble organic solvent, and other usual additives.
In a further aspect, the invention provides a method of e~ting~ hing polar or non-polar liquid fires, which comprises the steps of diluting, aerating and CA 022~660~ 1998-ll-26 applying to the surface of said liquid an effective amount of the fire-fi~hting concentrate composition for e~ctin~ hin~ said fire.
The aqueous fire-fighting composition of the present invention comprising a fluoro~ mical oligomer having a plurality of pendent fluoroaliphatic groups, one or s more fluoroch~m~c~l surfactant, one or more non-fluorinated surfactant and a polysaccharide provides a unique sslutiQn to the problems encountered in the prior art, wherein contradictory il~oll,.alion can be found as regards suitability of dil~lelll types of fluorochemical oligomers for use together with other components of a fire-fighting composition.
lo U.S. Patent No. 4,303,534, for example, describes an aqueous fire-fi~htin~
composition having a water-soluble high molecular weight additive which containspendant fluoroalkyl groups and water-solubilizable groups together with a partially hydrolyzed protein-co..~ ing foaming agent. Use ofthe fluoroalkyl-group-con1~ining high molecular weight additive together with a polysaccharide in a fire-fighting composition is not mentioned in these patents. These patents also teachthat the molecular weight of the high molecular weight additive must not be lessthan 5,000, and preferably not less than 10,000, because otherwise stable foams are not formed on the surface of a polar organic solvent, and foams of good heat resistance are not produced on the surface of a petrolic solvent.
U.S. Patent No. 5,218,021 teaches the use of cooligomers having terminal perfluoroalkyl moieties as additives in polar solvent fire fighting compositions in conjunction with polysaccharides and other additives. This patent states that the perfluoroalkyl, high molecul~r weight polymers according to U.S. Patent Nos. 4,303,534 and 4,563,287 which contain perfluoroalkyl groups interspersed randomly along the polymeric backbone are not as efficient as cooligomers havingterminal perfluoroalkyl groups. It is also said that the cooligomers interact with polysaccharides in a synergistic manner due to strong association of the co-oli~omçrs with the polysaccharides.
- Accordingly, U.S. Patent Nos. 4,303,534, 4,563,287, and 5,218,021 teach away from the instant invention because, while compounds cont~ining pendent fluoroalkyl groups may be useful as additives in certain foam fire-e~ting~ ehin~
CA 022~660~ 1998-11-26 agents for comb~ting polar organic solvents fires (provided that they have a relatively high molecular weight), these perfluoroalkyl-group-cont~ining compounds are said to be less efficient when used in compositions conlpr;s"lg polysaccharides, where cooligomers having only terminal perfluoroalkyl groups are said to be 5 supenor.
It has now surprisingly been found that fluoro~h~mi~ql oligomers having a plurality of pendent fluoroaliphatic groups, when used together with a polysaccharide, have excellent fire fighting plopellies in 3x3 formulations. Also surprisingly the fluorochemical oligomers having a plurality of pendent o fluoroaliphatic groups in the fire-fighting compositions of the present invention are not restricted to compounds having a molecular weight of not less than 5,000 buteven compounds having a molecular weight as low as 2,000 have excellent fire-fighting properties for both polar and non-polar solvent fires when used in combination with a polysaccharide.
1S Also in the present invention a synergism is observed when both fluorochemical oligomer and polysaccharide are used in the fire-fighting concentrate composition. However, it is believed that this synergism is not caused by stronginteraction between the oligomer and the polysaccharide as is taught in U. S. Patent No. 5,218,021, since the same observation was made with the currently pre~,led 20 amphoteric fluorochemical oligomers.
A further surprising advantage of the compositions of the present invention comprising fluorochemical oligomer having a plurality of pendent fluoroaliphaticgroups and polysaccharide is that, whereas the pl~r~lled compositions of U.S.
Patent No. 5,218,021 (3x6 formulations) comprise polysaccharide up to 10% by 25 weight, compositions of the present invention use polysaccharide at concentrations of 3% or less, and preferably 1.5% or less, by weight. The fluorochemical oligomers used in the composition of the present invention boost the polar solvent resistance dr~m~tically, allowing for reduction of polysaccharide levels and leading to advantageously low viscosity of the concentrate composition.
CA 022~660~ l998-ll-26 Fluoroç~l~mi~l oligomers useful in the fire-fightin~ compositions of the present invention have a plurality of pendent fluoroaliphatic groups (Rf) and water solubilizing moieties are usually connçcted togeth~?r by suitable linking groups.
The fluoroaliphatic group (R~) in the oligorn~r can generally be described as 5 a fluorinated, preferably saturated, monovalent, non-aromatic group of at least 3 carbon atoms. The aliphatic chain may be straight, branched, or, if sufficientlylarge, cyclic and may include oxygen, hexavalent sulfur, or trivalent nitrogen atoms bonded only to carbon atoms. A fully fluorinated group is prerel~;d, but hydrogen or chlorine atoms may be present as substituents provided that not more than one0 atom of either is present for every two carbon atoms. While groups col-~A;..;-l~ a large number of carbon atoms will function adequately, compounds cont~inin~ not more than about 20 carbon atoms are prerel I ed since larger groups usually I epl es~lll a less efficient utilization of fluorine than is possible with shorter chains.
Fluoroaliphatic groups co..lAil~;ng about S to 12 carbon atoms are most preferred.
The water-solubilizing polar group or moiety of the fluorochemical oligomer can be an anionic, cationic, non-ionic or amphoteric moiety, or combinations of said groups or moieties which may be the same or di~el enl. Typical anionic groups include COOH, COOM, SO3M, OSO3H, OSO3M, OPO(OH)2 and OPO(OM)2, where M is a metal ion (such as sodium or potassium), an ammonium ion, or other arnine cation. Typical cationic groups include: NH2, NHR, and NR2, where R is a lower alkyl group such as methyl, ethyl or butyl; and R'3NA', where R' is a lower alkyl group or hydrogen, and A' is an anion such as chloride, sulphate, phosphate or hydroxyl. Typical non-ionic groups include poly(oxyalkylene) moieties, e.g., those derived from polyethylene oxide, polypropylene oxide and mixtures thereof.
Typical amphoteric groups would include N~(CH3)2C2H4COO-, and NR2~~ (amine oxide). The water-solubilizable group or moiety is preferably non-ionic or amphoteric. Amine oxides are highly prerelled.
The linking group is a multivalent, generally divalent, linking group such as an alkylene, arylene, sulfon~mido~lkylene, carbonamidoalkylene or other 30 heteroatom-col;.;ing group such as siloxane, inr.hl~ing combinations of such groups.
. ~ .. ..... . . .. _,, CA 022~660~ 1998-11-26 The fluorochemical oligomers are pl ~rel ably non-ionic or amphoteric. They have about S to 45 weight percent, plerel~bly about 20 to 40 weight percent of carbon-bonded fluorine, based on the weight of the oligomer, the fluorine content residing in said plurality of pendent fluoroaliphatic radicals. These materials are 5 relatively low molecular weight linear polymers, or lightly crc,.c l;.~k~d polymers, col-lA~ from 3 to 4 up to about 25 or 30 monomer units, and thus are "oligo~ ic", as contrasted to "high polymers" having a molecular weight of 100,000 or higher.
A particularly useful class of fluorochemical oligomers falling under the o above general description are polyacrylates. Examples of this class of fluorochemical oligomers can be prepared by copolymerizing any of the known fluorochemical (meth)acrylates and optionally (meth)acryl~mi~e~ such as those described in U.S. Patent No. 5,098,446 (table 1, column 6) or those described inU.S. Patent No. 5,453,540 (columns 14 and 15), with fluorine-free (meth)acrylates 15 and optionally (meth)acrylamides such as those described in U.S. Patent No.
5,453,540 (columns 15 and 16).
The ratio of fluorochemical monomer to fluorine-free monomer may vary in order to obtain subs~nlial water solubility of the oligomer and in order to get a maximum foam stabilizing effect. The ratio will vary depending on the specific 20 monomer con.binalion used. Preferably, the fluorochemical oligomer is soluble in water in an amount of at least 0.5% by weight of the oligomer. Fluorochemical oligomers have been described for example, in U.S. Patent Nos. 4,668,406, 3,787,351 and 5,098,446.
The fluorochemical oligomers can be prepared by methods known to those 2s skilled in the art. Pl erel~bly the oligomers will be prepared by free radical polyme.i~alion in the presence of a chain ll ~llsrer agent in order to control the molecular weight. Useful initiators inch.de organic peroxides, such as benzoyl peroxide, lauryl peroxide and various thermal initiators. Plerelled thermal initiators include 2,2'-azobisiosl,u~y-ol il-ile (ABIN), co.ll..,e--;ially available from E.I.
DuPont de Nemours under the trade name VazoTM 64, and 2,2'-azobis(2,4-dimethylvaleronitrile), available from Wako under the trademark V-65. The CA 022~660~ 1998-11-26 initiator is present in an amount of ~om about 0.01 to 2 parts based on 100 parts of total monomer contçnt Useful chain transfer agents include lllel.,al)lalls, alcohols, and carbon tetrabromide. The chain ~ srel agent is present in an amount of from about 0.1 to about 6 parts based on 100 parts per total monomer content.
s The fluoroçllemic~l oligomers of this invention have an average molecular weight between about 2000 and about 50,000, pleielably between about 2000 and about 20,000, most prefe~bly between about 2000 and about 10,000. The fire-fighting composition of the present invention will comprise from about 0.3 to about 5% by weight ofthe fluorochemical oligomer, preferably between about 0.5 and 0 4%.
The concenll ~te composition of the present invention also comprises one or more fluorochemical surf~c~nts (which gives low surface tension) which may be anionic, cationic, nonionic or amphoteric, and one or more nonfluorinated (e.g.,hydrocarbon) surf~ct~nt~ (which makes the foam) which may be anionic, cationic, amphoteric or nonionic as is known in the art and described in, e.g., U.S. Patent No. 5,085,786 (columns 4-8) and U.S. Patent No. 5,359,096 (columns 5-7). In thiscomposition, the fluorochemical surfactant is used in an amount of from about 1 to about 6% by weight, preferably between about 1.5 and about 4% by weight; and thenonfluorinated surfactant is used in an amount of from about 1 to about 10% by weight, preferably in an amount of from about 2 to about 8% by weight.
The concentrate composition of the present invention also comprises a polysaccharide, preferably an anionic heteropolysaccharide having a high molecular weight. Co,.lme.cially available polysaccharides useful in the invention includethose sold under the trademarks, e.g., KelzanTM and KeltrolTM (available from Kelco). The polyrneric structure is not critical for the purposes of this invention.
Only a small amount of polysaccharide is required to confer a noticeable change in properties. The polysaccharide is used in an amount of from about 0.1 to about 3%
by weight ofthe concentrate composition, preferably between about 0.2 and 1.5%.
Optionally, other polymeric stabilizers and thickeners can be incorporated into the conce~ ale compositions of the invention to çnh~nce the foam stability of the foam produced by aeration of the aqueous solution made from the concentrate.
CA 022~660~ 1998-ll-26 WO 97/45167 o PCT/US97/07459 Examples of suitable polymeric stabilizers and thickeners are partially hydrolyzed protein, ~Larclles and modified starches, polyacrylic acid and its salts and complexes, polyethyleneimine and its salts and complexes, polyvinyl resins, e.g., polyvinylalcohol, polyacryl~mides7 carboxyvinyl polymers, and poly(oxyethylene)glycol.
s When used, the optional polymeric stabilizers and thickeners will be added in an amount of from about 0.1 to about 5%, pre~.~bly between about 0.2% and 1.5%
by weight of the collcellllale.
The concentrate compositions of the invention contain water and preferably include water-soluble solvents to f~ it~te solubilization of the fluorochemical 0 oligomer surf~ct~nt~ and the other components. The solvents also may act as foam stabilizers, freeze protection agents and shelf life enhancers. Suitable solvents include ethylene glycol, diethylene glycol, glycerol, ethyleneglycol monoethylether, diethyleneglycol butylether, dipropyleneglycol monopropylether, dipropyleneglycol monomethylether, methoxy propylene glycol and hexylene glycol. A suitable range of cosolvents in the concentrates of the invention is from 1 to 50 parts, preferably from 4 to 30 parts, by weight per 100 parts of concentrate.
Other ingredients, known to those skilled in the art, that are usually employed in fire-fighting compositions may be employed in the concentrate compositions of this invention. Examples of such ingredients are preservatives, 20 buffers to regulate pH (e.g., tris(2-hydroxyethyl)amine or sodium acetate) and corrosion inhibitors (e.g., toluoltriazole or sodium nitrite).
The composition of the invention is employed in the usual way to combat fires of fl~mm~ble liquids or to prevent evaporation of fl~mm~hle vapours. The composition is particularly suitable for application in the form of a foam. Usually it 2~ is stored in the form of an aqueous concentrate only requiring dilution to 3%concentration with either fresh or sea water to form the llplel~ " and aeration of the premix to produce a foam which is applied to the burning liquid surface.
Objects and advantages ofthis invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in 30 these examples, as well as other conditions and details, should not be construed to unduly limit this invention.
CA 022~660~ l998-ll-26 WO 97/45167 ~ PCT/US97/07459 EXAMPLES
Test methods The following tests have been done to evaluate the foam pl ope:l lies of the compositions of the present invention.
Foam Stability Test Foams were produced by making 100 ml of a 3% foam premix by diluting by weight 3 parts foam concentrate with 97 parts fresh or with synthetic sea water 0 (composition according to ASTM D1141-52), and foaming the reslllt~nt premixusing a Kalorik-type 5353 kitchen mixer at highest speed for 1 minute. Then 50 gof each foam was poured over a 30 second time period onto 250 g solvent cont~ined in a 19 cm diameter x 8 cm high glass dish. The foam was poured onto the solvent in such a way that it spread over and across the solvent from one end of the dish to the other and completely covered the surface of the solvent. The time required for 50% of the foam area to collapse from the first moment the foam touched the solvent was recorded as Tl/2 (solvent). Both acetone and isopropanolwere used as representative polar solvents.
Foam Expansion/Drain Time Foam expansion and drain time were measured in accordance with US
Dep~Lmcnl of Defense Military Specification No. MIL-F-24385, Revision F, Section 4.7.5, using the standard National Foam Systems 2 gaVmin nozzle.
2s Surface Tension and Interfacial Tension The surface and interfacial tension were measured with a Du Nouy Tensiometer according to ASTM D-1331.
Brookfield Viscosity The Brookfield Viscosit,v was measured using a Brookfield LVT
vi~cosimeter using a number 3 spindle at a rotational speed of 30 rpm in a waterbath set at 20~C. The viscosity was recorded after 60 seconds.
Fire-Fighting Tests Labscale The conc~ le of the present invention was diluted to a 3% premix with fresh water (i.e., tap water) or with synthetic sea water (composition accordillg to o ASTM Dl 141-52). 150 ml ofthis 3% solution was foamed in a kitchen blender for 30 secondc, after which the foam was immedi~tely transferred to a glass flask.
Using air pressure, the foam was forced from the flask and passed through a plastic tube to 250 ml of burning polar solvent in a circular metal pan of 0.021 m2 area.
The solvent pre-burn time was 40 seconds. The time required for extin~ hin~ the burning liquid was recorded.
Nordtest Type 023 The fire-fighting propel ~ies of the foams made from the concentrates of the present invention have been tested on a large scale according to a modified Nordtest Type 023. Test conditions:
A circular pan with an area of 2.65 m2 was filled with 180 1 of fuel. The nozzle used was a modified National Foam nozzle with flow rate 11.4 1/min. The fuel pre-burn time was 60 seconds and the foam was applied for a total of 4 min~tes A visual observation was done after 50%, 90%, 99% and 100% (complete fire-eYting~ hm~nt) foam coverage. The hold time before running the 'burnback' test, i.e., the time after completion of foam application, was 1 minute. A visual observation of 50% burnback time was done.
Film Spreading Test Cyclohexane was poured in a petri dish having 10 cm diameter and 1 cm height until the cyclohexane reached a depth of 0.5 cm. Twenty drops of a 3%
premix was put gently on the cyclohexane surface using an eyedropper over a period of about 20 seconds. The film formed was allowed to spread during 30 sec.A burning match was passed over the dish. If the cyclohexane did not ignite, thefilm passed the vapor sealing.
Abbreviations The following abbreviations, trade names and trademarks were used in the ~A~ S
EtFOSEMA: N-ethylperfluorooctylsulfonamidoethylmethacrylate, available from Minnesota Mining and ~l~mlf~ctllring Company, St. Paul, Minnesota, U.S.A. (3M) MeFOSEMA: N-methylperfiuorooctylsulfonamidoethylmethacrylate, available from 3M
DMAEMA: N,N-dimethylaminoethylmethacrylate, available from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin, U.S.A.
AMPS-EOA: monoethanolamine salt prepared from 2-acrylamido-2-methylpropane sulfonic acid, available from Aldrich P144DA: A diacrylate made from PluronicTM 44, which is available from BASF
Aktienges.oll~çh~, Ludwigshafen, Germany CW750A: An acrylate made from CarbowaxTM750, C8Fl7SO2N(C2Hs)C2H4OCOC(CH3)-CH2, according to the procedure described in U.S. Patent No. 3,787,351, Example 2. CarbowaxTM750 is available from British Petroleum International Limited, London, United Kingdom 2s AA-EOA: acrylic acid - ethanol amine salt HOEMA: hydroxyethylmethacrylate CW400DMA: A diol ~imeth~crylate, made from CarbowaxTM 400, which can be prepared using the procedure described in U.S. Patent No. 3,787,357, Example 1, except substih1ting CarbowaxTM for PluronicTM44.
CarbowaxTM400 is available from British Petroleum International Limited, London, United Kingdom CA 022~660~ 1998-11-26 DMAPMA/chloroethanol: N,N-dimethyl~l~il~oplopyl meth~crylamide (available from Aldrich), qualc;..l.~ed to 100% by chloroethanol SOS: sodium octyl s.llph~te SDS: sodium decyl sulphate s BC: CarbitollM ether, a diethylene glycol butyl ether DPM: dipropylene glycol monomethyl ether DPnP: dipropylene glycol monoplo~yl ether DMF: dimethylfo- ,..~"-: ~e NMP: N-methylpyrrolitlinone EtOAc: ethyl acetate foamer: C8Fl~SO3K+, a fluorochemical surfactant as described in U.S. Patent No.
5,0~5,786, column 5, line 68, and available from 3M Company WitcolateTM 7093 surfactant: a C6 - C,0 alkyl ether sulfate surfactant, available from Witco KelzanTM gum: a polysaccharide (x~nth~m gum), available from Kelco AnsuliteTM 3x3 low viscosity agent (Ansul, USA) FiniflamTM 3x3 fire-fighting agent (Pirna, Germany) TowalexTM 3x3 freeze-protected fire-fighting agent All parts, ratios, percentages, etc., in the following examples are by weight unless otherwise specified.
Ex~lples 1-14 and Col"palali~/e Examples C1-C4 A. Synthesis of the fluorochemical oligomers I . Fluorochemical oligomer oxides FC- 1 to FC-9 The fluorochemical oligomers identified in Table 1 were prepared according to the general procedure as described below for the synthesis of the fluorochemical oligomer EtFOSEMA/DMAEMA-N-oxide with a monomer ratio (wt) of 60/40.
In a 500 ml, three-necked flask fitted with a condenser, stirrer and thermometer were placed 60 g EtFOSEMA, 40 g DMAEMA, 5 g n-octyl lllelGaplan (RSH), 1 g ABIN and 100 g isopropyl alcohol. The flask was deaeratedwith nitrogen under vacuum for 3 times. The mixture was heated and the reaction CA 022~660~ 1998-11-26 was carried out under nitrogen at 75~C for 16 hours. After the reaction was completed, the solvent was ~Itipl)td at a tem~c~alLlre of 60-80~C under asp;ldlor vacuum. The reaction mixture was cooled to about 45~C a~er which 80 g ethylene glycol and 20 g BC were added. 29.7 g of hydrogen peroxide (35% active in water) was added in small increments over a period of one hour. An immerli~te exotherm was noticed. The reaction was contin.~ed for another 3 hours at 45~C, then for 3 hours at 65~C and finally for 1 hour at 90~C. The reaction mixture was diluted to 30% solids using 103 g deionized water. A slightly hazy, yellow solution was obtained, co.ll~inillg an oligomeric fluorochemical amine oxide having a weight l0 average molecular weight of 4400. The pH of the solution was adjusted to 7 using a 10% aqueous solution of sodium hydroxide Following the above described method, di~ en~ fluorochemical amine oxides as given in Table 1 have been synthe~i7ed Table 1: Composition of EtFOSEMA/DMAEMA-N-OXIDE oligomers FC Monomer ratio Weight oligomerEtFOSEMA/DMAEMA %ABIN %RSH Average MW
FC-6 60/40 0.2 0 43000 FC-7 70/30 0.8 5 4500 FC-8 30/70 0.8 5 4400 FC-9 60/40 0.8 5 5100 Note: For each oligomer, the reaction solvent used was isopropanol, except for FC-3 in which N-methylpyrrolidinone was used.
In all examples given above, the fluorochemical oligomer oxide was obtained as 30% solids in a mixture of ethylene glycol (24%), BC (6%) and water (40%), except for FC-3. In the synthesis of FC-3, the solvent was not stripped after the first reaction and the fluoro~.h~mie~l oli~c ln~r FC-3 was obtained as 30% solids in a rnixture of NMP (30%) and water (40%).
2. Fluorcçh~m.c~l oligomers FC-10 to FC-14 Fluoroch~ cal oligo~ FC-10 to FC-14 were made using the general procedure outlined below:
In a 500 ml, three-necked flask fitted with a condenser, stirrer and thermometer were placed the monomers, initiator and chain transfer agents as listed in Table 2. The flask was deaerated with nitrogen under vacuum for 3 times. The mixture was heated and the reaction was carried out under nitrogen at 75~C for 16 hours. After the reaction was completed, the solvent was optionally (as indicated in Table 2) stripped at a tel.,pe. ~ILIre of 60-80~C under aspirator vacuum. The reaction mixture was diluted to 30% solids using solvent mixtures as given in Table 2. The pH ofthe solution was always adjusted to about 7.
Table 2: Composition of fluorochemical oligomers Chain Weight FC- M~ mixture Transfer % Solvent Final average No. (Ratio) (5~/O) ABINreaction solvent MW
FC-10EtFOSEMA/AMPS- Octyl- 1 DMF DMF/ 5,000 EOA/P144DA Illel~,d~ Water (60120/20) 30/40 FC-l lEtFOSEMA/CW750A Octyl- 0.8 EtOAc EG/BC/ 4,700 (60/40) ll~:lCd~ln (l) Water FC-12EtFOSEMA/AA- Thio- 0.~ IPA EG/BC/ 4,200 EOA/HOEMA glycerol (1) Water (70/15/15) 2416140 FC- 13MeFOSEMA/ Mercapto- I IPA EG/BC/ 4,400 CW4000DMA (50/50) ethanol (1) Water FC-14 BuFOSEA/ Mercapto- I NMP NMP/ 4,500 DMAPMA- ethanol Water chlol~l}ldllol (60/40 30/40 Note: (1): solvent stripped CA 022~660~ 1998-11-26 B. Eva1uation of fluoroçh~mi.c~' oligomers in fire-fighting foam agents Foams were made comprising the fluorochemical oligolllG,~ described above. The foams were first p-epaled by mixing water (85.5%) with 0.5% Kelzan gum and 5% BC, whereby a viscous solution was obtained. Then, 2% foamer, 1% C8FI,SO3K+, 4% Witcolate 7093 surfactant and 2% fluorc~.hPtn:c~l oli~,olllel were added (each pel ce~ ge based on solids by weight) and the mixture was stirred for 2 hours at 60~C. A clear brown solution with a Brookfield viscosity (spindle 3) bt;Lween 700-800 cps was obtained. The foams thus plepaled were used in the following e~ les.
lo Examples I to 14 were made by diluting 3 g ofthe concentrates preparedabove to 100 g using tap water to provide a 3% foaming agent premix.
Colllpa~live examples C-l and C-2 were made according to the procedures described in U.S. Patent No. 4,303,534, example 2, and U.S. Patent No. 4,460,480, Example 1, respectively. The foam agents of Comparative Examples C-3 and C-4 were made the same way as the foam agent of Example 2, except that no polysaccharide was added in C-3 and no fluorochemical oligomer was used in C-4.
The 3% foam agents were tested for their foam stability according to the foam stability test described above and using acetone and isopropanol as solvents. The results of the test are provided in Table 3.
Table 3: Foam Stability Test Tln acetone Tln IPA, Ex. No. FC Oligomer min:sec min:sec FC-l 32: 10 38:00 2 FC-2 39:40 45:10 3 FC-3 35:20 --4 FC-4 25:10 --FC-5 12:30 -6 FC-6 6:50 --7 FC-7 43 :50 8 FC-8 7:40 --CA 022~660~ 1998-11-26 Tl'2 ~cetQne T~/2 IPA, Ex No.FC Oligomer min:sec min:sec 9 FC-9 31 :40 --FC-10 32:45 35:40 11 FC-ll 3010 --13 FC-13 26:00 --14 FC-14 30:20 30:50 C-3 FC-2(*) 2 40 3 00 C-4 5:50 --Note * Fluorochemical oligomer of Example 2 was used without polysaccharide in the foam concentrate The data in Table 3 in~lic~te that formulations comprising fluorochemical oligomers according to the invention provide foams which are very resistant to an aggressive polar solvent such as acetone The formulations according to the invention are superior to the state-of-the-art formulations Col-t~ .g fluorochemical oligomers having only terminal fluorinated R-groups (Comparative Example C-2) o or co~ fluorochemical oligomers of high molecular weight and lower fluorine level such as in Comparative Example C-l Co~-.pal~live Example C-3 indicates that foam made using the fluorochemical oligomer of Example 2, but with no addedpolysaccharide, shows poor resi~t~nce against polar solvents Co-~.~a.~ e Example C-4 in~icates that foam made with only polysaccharide and no fluorochemical oligomer also has low foam stability in contact with a polar solvent The fluorochemical oligomer with the polysaccharide improves the foam stability considerably CA 022~660~ 1998-ll-26 E~ les 15 to 19 and Co,.lpa.~ e E~a-.-i)les C-5 to C-10 In E~ ples 15 to 19, foam formulations were ~)re~)ared and tested as fire-fi~htin~ agents using labscale tests. All formulations conlail~ed 2.6% foamer, 1.4%
C8Fl~SO3X+, 4% Witcolate 7093 surfactant, 0.85% Kelzan gum, 2%
fluorochemical oligomer (as in-lic~ted in Table 4), 5% BC and 84.15% water. The Brookfield viscosity of the conce..ll ales ranged between 1600 and 1900 cps.
P-emu~es were made by diluting 30 g of each concentrate to 1000 g using tap water.
150 ml of each 3% premix solution was foamed in a kitchen blender for 30 secondsa~er which the foam was 1. ~nsre. . ed into a glass flask. By air pressure the foam o was added, through a plastic tube, to burning isopropanol (250 ml) after a pre-burn time of 40 seconds.
Comparative Example C-5 was made according to the general procedure described in U.S. Patent No. 4,460,480, Example l.
Co---pa-~Lh~e Example C-6 was made according to the general procedure described for Examples 15 to 19, using fluorochemical oligomer FC-2, but withoutaddition of polysaccharide. Comparative Example C-7 was made according to the procedure described in JP 2121681, Example 6. In Comparative Examples C-8 and C-9, commercially available fire-fi~htin~ agents were tested: AnsuliteTM 3x3 lowviscosity agent (viscosity 700-2000 cps, available from Ansul, USA) in C-8 and TowalexTM 3x3 agent (viscosity 760 cps, available from Total Walther, Germany) in C-9.
Table 4 gives the composition of the fire-fighting agents tested, as well as the results of fire-e~ctin~li.chment time and application rate (liter/min/m2).
2s Table 4: Composition and Pelrolmance of Fire-Fighting Foams FCNo. or Exting~ hment ApplicationRate Ex. No. ProductName time(sec) (liter/min/m2) FC-2 90 1.96 16 FC-7 85 1.98 17 FC-10 100 2.02 18 FC-11 129 2.00 19 FC-12 142 2.04 --. .
CA 022~660~ l998-ll-26 WO 97/45167 20 PCT/US97tO7459 FC No. or Fxtin~ ApplicationRate Ex. No. ProductName time(sec)(liter/min/m2) C-5 -- /** 2.09 C-6 FC-2* /** 2.11 C-7 -- /** 2.08 C-8 AnsuliteTM 3x3 140 2.02 agent C-9 TowalexTM3x3 235 2.08 agent Notes: FC-2*: no polysaccharide used /**: not possible to e~in~lish fire The results in Table 4 indicate that compositions according to the invention have, in almost all cases, superior fire-fi~hting properties compared to the co..-pa-~ e examples.
Examples 20 to 25 In Examples 20 to 25, fire-fighting concentrates were prepared co~ g di~elenl components and combinations as outlined in Table 5.
Table 5: Composition of Foam Components/Ex. No. 20 21 22 23 24 25 Fluoroaliphatic -- -- 2.6 -- -- 2.6 aminocarboxylate(*) Foamer 2.6 2.6 -- 2.6 2.6 --C8FI,SO3K+ 1.3 1.3 1.3 1.3 1.3 1.3 Witcolate7093 5 5 -- 5 5 --Surfactant Kelzan gum 0.9 0.9 0 g0.55 0 35 0.9 FC-2 1.5 1.5 1.5 2 2 1.5 CA 022=,660=, 1998-11-26 Note: (*): fluoroalirh~tic amino carboxylate surfactant as described in U.S. Patent No. 5,144,069, Example 1.
The concentrates were tested as foams delivered from 3% premixes in tap water. The results are given in Table 6.
Table 6: Properties of 3% Foam in Tap Water Characteristic/Ex. No. 20 21 22 23 24 25 Foam expansion 8.4 7.5 7.4 8.6 8.7 7.8 Drain time (min:sec) 10:30 9:4010:00 10:50 10:30 9:50 Surface tension (N/m) 16.7 16.817.1 16.8 16.7 17.2 Interfacial tension (N/m) 2.6 2.4 2.5 2.5 2.5 2.4 Viscosity (cps) 1760 16401880 740 440 1760 o Notes: Interfacial tension: 3% tap water premix/cyclohexane All examples passed the film spreading test on cyclohexane The results in Table 6 indicate that a broad range of formulations can be made having low viscosity, low surface tension, good foamability and good film-forming characteristics. Good film formation is essenti~l for fire-fighting on non-polar liquids. This will be demonstrated in Example 26.
Example 26 In Example 26, a concentrate was prepared from 2.6% foamer, 1.3%
C8FI~SO3K+, 5% Witcolate 7093 surfactant, 1.5% fluorochemical oligomer FC-2, 0.9% Kelzan gum, 0.9% hydroxypropylated corn starch, 10% BC and water (up to 100%). The Brookfield viscosity was 1680 cps. 3% premixes were prepared using tap water and sea water as ~ uents The premixes were tested as nonpolar, fire-fi~hting agents, according to the ISO/DIS 7203-1 test on heptane and according to the specifications for low expansion foam concentrate used to extin~ h fires of water-immiccible liquids. The results are given in Table 7.
CA 022~660~ 1998-11-26 Table 7: Fire-Fighting Pl~p~ ies of Non-Polar Solvent of Example 26 Test Tap Water Sea Water Knockdown (sec) 25 26 90% cover (sec) 38 34 99% cover (sec) 61 54 100% cover (sec) 85 146 The specification requires the fire to be extin~li.shed within 180 seconds.
5 The concentrate passed the test when diluted to 3% with either tap water or sea water. The 3% tap water prernix made from the Example 26 concentrate was further tested on heptane accolding to the Military Specification F 24385 F, on a 4.65 m2 round pan. In Conl~ re Example C-10, a 3% tap water premix made from Ansulite}M 3x3 fire-fighting concentrate was fire-tested. The results are given o in Table 8.
Table 8: Fire-E~in~ hing Properties on Heptane Test Ex. 26 C-10 40 sec s~-mm~tion 354 309 fire-e~c+. in~ hm~nt 34 42 25% burnback 555 390 The data in Tables 7 and 8 indicate that, on nonpolar solvents, a 3x3 foam agent of the present invention is superior in fire performance to a state-of-the-art colll,llelcially available 3x3 agent.
Examples 27 to 31 In Examples 27 to 31 fire-fi~htin~ concentrates were prepared cont~inin~
20 varying amounts of the fluorochemical oligomer FC-2. All concentrates contained 2.6% foamer, 1.4% C8F"SO3K+, 4% Witcolate 7093 surfactant, 0.85% Kelzan gum, 5% BC and the amount of FC-2 inr~ ted in Table 9. Water was added up tolOO%. The solutions had viscosities between 1600 and 1900 cps.
The firc-e,~ hing plope,lies ofthe c~lples were tested in the same way as Ex~mrles 15 to 19. The results are given in Table 9.
Table 9: Fire-Fighting Properties of 3% Foam Application Rate Ex. No. % FC-2 E~in~.isl.. enl time (sec) (liter/min/m2) 27 4 98 1.94 28 2 90 1.96 29 1.5 94 1.98 1 1 10 2.00 3 1 0.5 140 2.08 The results in Table 9 indicate that formulations conl~ini--g even small amounts of fluorochemical oligomer show fast fire-extin~ hm~nt Example 32 and Con.pa~ e Examples C-11 to C-13 In E~lllple 32 and Coll.l.al~live Examples C-l 1 to C-13, fire-fighting tests were done on a large scale. Example 32 comprises fluorochemical oligomer FC-2 in the same composition as Example 15. The fire-fi~hting properties were 5 compared to colr~ lcially available 3x3 fire-fighting agents. Comparative Example C- 1 1 was run with FiniflamTM 3x3 fire-fighting agent, available from Pirna, Germany. Colllpalalive Example C-12 was run with AnsulTM LV 3x3 agent, available from Ansul, USA. C-~lllpal~live Example C-13 was run with Universal GoldTM 3x3 agent, available from Chubb-National, UK. For the test, 3% premixes 20 were made from concentrates using tap water and the agents were foamed through a modified mil spec nozzle. The foams were tested in the modified Nordtest type 023 test, using a 2.65 m2 pan with 180 1 acetone (at a temperature of 3~C) as fuel.
The outside telll~,el ~ re at the time of the test was 5~C. The fuel pre-burn time was one minute. Each foam was applied to the burning fuel under type II
25 application against a backboard. The application rate was 4.4 L/min/m2; the foam CA 022=,660=, l998-ll-26 W O 97/45167 PCTrUS97/07459 application time was four minlltes unless otherwise noted. After colllple~ion offoam application and a one minute holding time, 50% burnback time was measured by reigniting a small pan filled with acetone, and positioning it in the middle of the foam blanket. The time needed for 50% of the fi~el surface to burn again was 5 recorded as 50% burnback time. The results of the fire-fighting test are given in Table 10.
Table 10: Modified Nordtest Type 023 Fire-Fighting Test 50% cover 90% cover 99% cover 100% cover 50%
Ex. No. (sec) (sec) (sec) (sec) burnback 32 46 66 8S 134 pass C-l l 176 202 228 294(2) pass C-12 44 73 114 174 pass C-13 288 336 390 456(3) pass Notes: (1): if the burnback time is more than 300 sec., the sample passes the test (2): total foam application time of 6 min.
0 (3): total foam application time of 8 min.
The data in Table 10 indicates that the fire-fighting agents of the present invention have superior extin~iehm~nt properties compared to the state-of-the-art cGlr",.elcially available products. The e~tin~ hm~nt of the fire is significantly better and the burnback re~ist~nce is high.
Examples 33 to 35 and Comparative E~a,n~ s C-14 to C-15 In Examples 33 to 35, freeze-protected fire-fighting conce~ les were made and evaluated. The agents were p.epal~d by mixing 2.6% foamer, 1.3% C8F~7SO3-K+, 5% Witcolate 7093 surfactant, 10% BC, 1% (Example 33) or 1.5% (Example 34) or 2% (Example 35) of fluorochemical oligomer FC-2, 0.85% Kelzan gum, 0.85% hydroxypropylated corn starch, 22.5% ethylene glycol and water (up to 100% total). In Co.-.~ e Example C-14 AnsuliteTM 3x3 agent (which is not freeze protected) was tested. Comparative Example C- 15 was made with TowalexTM 3x3 freeze-protected fire-fighting agent. The foam agents were tested in the modified Nordtest type 023 test as for Example 32. This time, the outsidetemperature was 29~C, which leplesen~s a highly dem~n/ling test condition (i.e., a relatively high tc~ .alllre)~ The telllpelal~lre ofthe fuel was 19~C. The results of the fire-fighti.~ tests are given in Table 11.
Table 11: Fire-Fighting ~ropel lies of Freeze Protected Agents 50%
50% cover 90% cover 99% cover100% cover burnback Ex. No. (sec) (sec) (sec) (sec) (sec) 33 102 165 168 238 pass 34 65 165 192 225 pass 128 158 215 pass C-14 110 280 365 410(*) C-15 395 445 (*~) I /
s Notes: (*): foam applied for 410 sec (instead of 240 sec) /(**): foam applied for 500 sec (instead of 240 sec), but no fire h, .,f .
/: no fire e?~tin~ .".~;..l lo The data in Table 11 indicate that under high demanding conditions (high temperature), the foam compositions of the present invention are far more efficient than the commercially available state-of-the-art products. The COIllpal a~ e examples did not pass the 50% burnback test.
Examples 36 to 39 E~ ,ples 36 to 39 were run to show that it is possible to make useful foam fire-fightin~ concentrates co~ g dilre-el,l polysaccharides. The concentrates for all examples were made by mixing 2.6% foamer, 1.3% CgF~SO3K+, 1.5%
fluorochemical oligomer FC-2, 5% Witcolate 7093 surfactant, 0.9%
hydroxypropylated corn starch, 10% BC and 0.9% polysaccharide. The polysaccharides used were as follows: in Example 34: polysaccharide K8A13, available from Kelco; in Example 35: x~nth~m gum E 415 food grade, available from Jungbun7~ er~ Austria; in Example 36: KeltrolTM gum, available from Kelco;
and in Example 37: KelzanTM gum, available from Kelco. The concentrate and 3%
~ 25 premix foam properties are given in Table 12.
CA 022~660~ 1998-ll-26 Table 12: Foam Formulations Comprising Di~relel,l Polysaccharides ~-ope,ly\Ex. No. 36 37 38 39 Viscosity (Cps) 1960 1820 1800 1600 Foam eYp~na;on in tap water 13.3 8.8 10.8 10.2 Foam expansion in sea water 11.2 7.5 9.3 8.7 Drain time in tap water (sec) 400 430 490 500 Drain time in sea water (sec) 360 420 455 420 Surface tension (DI-water, N/m) 16.4 16.2 16.3 16.4 Surface tension (sea water, N/m) 17.3 17.4 17.4 17.3 Interfacial tension against cyclohexane:
in DIW (N/m) 3.5 3.9 3.3 3.0 in Sea water (N/m) 2.2 2.2 2.1 2.3 The results indicate that foam formulations cont~ining di~e"
s polysaccharides can be made according to the present invention.
Various modifications and alterations of this invention will become apparenl to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited o to the illustrative embodim~nt~ set forth herein.
Claims (10)
1. A fire-fighting concentrate composition comprising (a) fluorochemical oligomer having a plurality of pendent fluoroaliphatic groups, (b) one or more fluorochemical surfactants and one or more non-fluorinated surfactants, (c) polysaccharide, and (d) water.
2. The composition according to claim 1 wherein the fluoraliphatic groups are fluorinated, saturated, monovalent, non-aromatic groups of 3 to 20 carbon atoms.
3. The composition according to any one of claims 1 or 2 wherein the fluorochemical oligomer comprises 5 to 45% by weight of carbon-bonded fluorine based on the weight of the oligomer.
4. The composition according to any one of claims 1 to 3 wherein the fluorochemical oligomer is derived from fluorine containing (meth)acrylates and fluorine-free (meth)acrylates.
5. The composition according to any one of claims 1 to 4, wherein the fluorochemical oligomer has an average molecular weight from 2000 to 50,000.
6. The composition according to any one of claims 1 to 5, wherein the fluorochemical oligomer is comprised in an amount from 0.3 to 5% by weight.
7. The composition according to any one of claims 1 to 6 wherein the polysaccharide is comprised in an amount of 0.1 to 3% by weight of the concentrate composition.
8. The composition according to any one of claims 1 to 7 which is a 3x3 fire-fighting composition.
9. A method of extinguishing polar or non-polar liquid fires comprising the steps of diluting, aerating, and applying to the surface of said liquid an effective amount of a composition according to any one of claims 1 to 8.
10. The use of a fluorochemical oligomer having a plurality of pendant fluoroaliphatic groups in combination with a polysaccharide in a 3x3 fire-fighting concentrate composition for extinguishing both polar and non-polar solvent fires.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96108870 | 1996-05-31 | ||
| EP96108870.5 | 1996-05-31 | ||
| PCT/US1997/007459 WO1997045167A1 (en) | 1996-05-31 | 1997-05-05 | Fire-fighting agents containing polysaccharides and fluorochemical oligomeric surfactants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2256605A1 true CA2256605A1 (en) | 1997-12-04 |
Family
ID=29433258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002256605A Abandoned CA2256605A1 (en) | 1996-05-31 | 1997-05-05 | Fire-fighting agents containing polysaccharides and fluorochemical oligomeric surfactants |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2256605A1 (en) |
| ID (1) | ID17724A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904201A (en) * | 2022-04-29 | 2022-08-16 | 国网电力科学研究院有限公司 | Water-based fire extinguishing agent based on double-end-base type fluorosilicone surfactant |
-
1997
- 1997-05-05 CA CA002256605A patent/CA2256605A1/en not_active Abandoned
- 1997-05-26 ID IDP971749A patent/ID17724A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114904201A (en) * | 2022-04-29 | 2022-08-16 | 国网电力科学研究院有限公司 | Water-based fire extinguishing agent based on double-end-base type fluorosilicone surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| ID17724A (en) | 1998-01-22 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |