EP0212017A1 - Thixotropische feuerunterdrückende Zusammensetzung die ein Karboxypolymer gelbildendes Mittel enthält - Google Patents

Thixotropische feuerunterdrückende Zusammensetzung die ein Karboxypolymer gelbildendes Mittel enthält Download PDF

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Publication number
EP0212017A1
EP0212017A1 EP85305735A EP85305735A EP0212017A1 EP 0212017 A1 EP0212017 A1 EP 0212017A1 EP 85305735 A EP85305735 A EP 85305735A EP 85305735 A EP85305735 A EP 85305735A EP 0212017 A1 EP0212017 A1 EP 0212017A1
Authority
EP
European Patent Office
Prior art keywords
composition according
fire
liquid
gelling agent
ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85305735A
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English (en)
French (fr)
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EP0212017B1 (de
Inventor
William B. Tarpley
Gerald L. Ruscitto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
C. F. VENTURE CORP.
CEASE FIRE CORPORATION
Original Assignee
CEASE FIRE Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CEASE FIRE Corp filed Critical CEASE FIRE Corp
Priority to DE8585305735T priority Critical patent/DE3575378D1/de
Priority to IL7612485A priority patent/IL76124A/xx
Priority claimed from US06/820,927 external-priority patent/US4652383A/en
Publication of EP0212017A1 publication Critical patent/EP0212017A1/de
Application granted granted Critical
Publication of EP0212017B1 publication Critical patent/EP0212017B1/de
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0064—Gels; Film-forming compositions

Definitions

  • the present invention relates to a fire-suppressing composition containing an ammonium salt in powder form in a non-polar liquid which is thixotropically gelled by a carboxy polymer gelling agent.
  • Liquified gases have been used to disseminate fine powders including pesticides, medicinal products, cosmetic products, and fire extinguishing powders.
  • gelling agents such as "CAB-O-SIL” (a trademark of Cabot Corporation) have been used.
  • Gelled liquid fire-suppressing suspensions are taught in U.S. Patent Nos. 4,226,727 and 4,234,432.
  • Ammonium salts are useful fire-suppressing agents in powdered form. It has been found that a suspension of such powders having improved stability results from the addition of a carboxy polymer in small amounts as a gellant.
  • a non-aqueous fire-suppressing composition comprising a non-polar thixotropically gelled liquid, a carboxy polymer gelling agent in an amount effective to gel the liquid, and an ammonium salt.
  • the composition may include as further additives either a viscosity modifier functional at low temperatures, a drying agent, or both.
  • the present invention also pertains to a method of extinguishing fires by applying the aforesaid composition.
  • a suspension of ammonium salts in powder form in a gelled non-polar liquid results from the present invention.
  • a carboxy polymer gelling agent is used to form the suspen­sions, which are thixotropic and exhibit excellent stability.
  • the gelled liquid component of the present invention includes one or more fire-quenching liquids in combination with one or more fire-quenching liquified gases and/or one or more overpressurized gases. If a fire-quenching liquified gas (e.g. trifluorobromomethane) is used, the fire-quenching liquid may be omitted.
  • a fire-quenching liquified gas e.g. trifluorobromomethane
  • the gelled liquid component must be capable of filling the interparticulate spaces in the suspension under pressure, i.e., when the suspension is at rest. Preferably, it is capable of expanding upon release of pressure to a gaseous vapor or droplet cloud carrying the fire-extinguishing particles. Finally, the gelled liquid component must provide some measure of fire quenching capability.
  • Fire-quenching liquids useful in the gelled liquid component include, but are not limited to, the following: methylene bromide, methyl iodide, terafluorodibromoethane, trifluorotrichloroethane, fluorotrichloromethane, chloro­form, bromoform, carbon tetrachloride, and the like.
  • Liquified gases which may be used according to the present invention include, but are not limited to, the following: trifluorobromomethane, difluorochlorobomo­ methane, perfluoropropane, perfluorocylobutane, dichloro­difluoromethane, tetrafluoromethane, methyl bromide, trifluoromethane, trifluorochloromethane, hexafluoro­ethane, and the like.
  • Several of these gases have been designated as Halon materials. "Halon” is the National Fire Protection Association designation for halogenated fire extinguishing materials. Halon products are available from Great Lakes Chemical Company, DuPont Company, and ICI Americas, Inc.
  • Halon 1211 (difluorochlorobromomethane), Halon 1301 (trifluorobromomethane), and mixtures thereof, are useful.
  • a mixture comprising from about 50% to about 60% difluorochlorobromomethane and from about 40% to about 50% trifluorobromomethane is particularly useful at low temperatures.
  • Overpressurizing gases useful in the gelled liquid component include nitrogen, carbon dioxide, helium. argon, and the like.
  • the gelled liquid component comprises from about 70 to about 30 percent by weight of the composition according to the present invention.
  • the solids component comprising from about 30 to 70 weight percent of the present composition contains one or more powdered ammonium salts and one or more carboxy polymer gelling agents.
  • suitable powdered ammonium salts include mono-, di-, and triammonium phosphate, ammonium calcium phosphate, sodium ammonium phosphate, ammonium sulfate, ammonium chloride and ammonium aluminum sulfate.
  • Monoammonium phosphate (MAP) powder is particularly useful. ABC dry chemical fire-extinguish­ing powder, which is 90 to 95 percent MAP, is preferred.
  • fire-supressing powders may be used in conjunction with one or more ammonium salts.
  • Such powders include sodium bicarbonate, potassium bicarbonate, urea adducts of potassium bicarbonate such as are available from ICI under the trademark "MONAX", sodium chloride, potassium chloride, and the like.
  • MONAX sodium bicarbonate
  • sodium chloride potassium chloride
  • potassium chloride sodium chloride
  • auxiliary fire-suppressing powder is necessary.
  • the gelling agent is a polymer containing carboxyl groups in the free acid form. Excluded from the present invention are polymeric materials wherein carboxyl groups are substantially in neutralized or salt form. We have found these agents to be adequate absent conversion to the free acid.
  • polymers which are functional derivatives of free polycarboxylic acids e.g., polyacrylamides, wherein the functional groups have been substantially hydrolyzed to the free acid form.
  • polyacrylamides 40% hydrolized polyacrylamide available from National Starch & Chemical Co. under the trademark "POLYHALL 40-J” will satisfactorily gel the nonpolar liquid component of the present composi­tion, in the presence of an ammonium salt. Forty percent of the nitrile groups in this polyacrylamide are hydrolyzed to the corresponding acid function.
  • POLYHALL 33-J wherein only 33% of the nitrile groups are hydrolyzed, forms a much weaker suspension.
  • those skilled in the art will be able to readily determine by routine experimentation the extent to which such groups must be first converted to the free acid form for gellation of the nonpolar liquid to occur.
  • the carboxy polymer acids useful in the present invention include carboxy vinyl polymers, such as those available from B.F. Goodrich under the "CARBOPOL” trademark; polysaccharides having pendent free carboxyl groups such as alginic acid and guar derivatives; hydrolyzed or partially hydrolyzed polyacrylamides such as "POLYHALL 40-J” (40% hydrolyzed); synthetic resins containing free carboxyl groups, such as the ionic exchange resins which are co­polymers of methacrylic acid and divinyl benzene available from Rohm & Haas Co., Philadelphia, Pa. under the trademark "AMBERLITE IPC-50".
  • Other polymeric materials having free carboxyl groups, or having groups functionally equivalent to carboxyl which are readily convertible to the free acid form, are known to those skilled in the art, and may be employed in the present invention.
  • the suspending power exerted over non-polar liquids by the carboxy polymer gelling agents described is due to a synergistic interaction between the free carboxyl function and the ammonium compound.
  • the gelling agent was mixed with difluorochlorobromomethane, or a blend of difluorochlorobromomethane and trifluor­bromomethane in the absence of ammonium compound, no gel formed. The gelling agent was insoluble in the liquid, and floated to the surface.
  • the preferred gelling agents are carboxy vinyl poly­mers.
  • CARBOPOL 934 and 941 are particularly suitable.
  • CARBOPOL is offered by the manufacturer to thicken and suspend insolubles, and to stabilize emulsions, primarily in aqueous systems. Where “CARBOPOL” is to be used with less polar liquids, the manufacturers recommend the addi­tion of an amount of long chain fatty amine as a gelling adjuvant.
  • CARBOPOL is ineffective as a gelling agent for the liquified halogenated hydrocarbon gases which form the liquid component of the present compo­sition, even in the presence of the recommended gelling adjuvants. What is surprising is that "CARBOPOL” will gel such non-polar liquids in the presence of an ammonium compound.
  • a composition of the present invention was prepared according to Example 1, containing 45% solids and 55% of the liquified gases difluorochlorobromomethane and tri­fluorobromomethane.
  • a typical composition using a further fire extinguish­ing powder (KHCO3) in addition to an ammonium salt is as follows:
  • JGUAR CMG a carboxymethylated guar gum derivative available from the manufacturer as a sodium salt, was converted to the free acid form in a 70% acqueous solution of methanol, followed by a certification with glacial acetic acid and stirring. The solution was allowed to stand overnight, then was filtered and washed with pure methanol until all acetic acid was removed.
  • CA-15 used in Run 16, an amphoteric starch available from National Starch Company, contains carboxylic acid groups, but these groups are neutralized by the presence of amine functions in the same molecule. Hence, no gella­tion occurred.
  • Example 7-13 The effect of the identity of the ammonium compound upon gellation was investigated in Example 7-13 by following the procedure of Example 6 using 4 grams of "CARBOPOL 941", 60 grams of difluorochlorobromomethane and 36 grams of ammonium compound. The results are set forth in Table 2.
  • CARBOPOL 941 did not succeed in forming an acceptable suspension of ammonium alginate in difluoro­chlorobromomethane (Example 13), it is believed that the negative result is due not to the absence of interaction between ammonium alginate and the carboxy vinyl gelling agent, but rather because of the hard, coarse nature of the sodium alginate powder, which was found very difficult to grind to the appropriate fine particle size necessary for suspension.
  • the ammonium salts used according to the present invention are hygroscopic. Monoammonium phosphate, in parti­cular, readily absorbs moisture from the atmosphere, thereby adding water to the composition. The presence of water is undesirable for two reasons. First, water promotes the formation of HBr and HF. At elevated temperatures, Halon materials will break down and react with any free water present to readily form these acids. HF and HBr are highly corrosive, and attack the metal components of the delivery vessel. Second, liquified gases such as the Halon materials have a refrigerating effect. Any free water present in the composition readily freezes to form ice which clogs the delivery system. To protect aganst the formation of acid and ice, it is necessary that free water be kept from the composition.
  • the compo­sition therefore may include a drying agent in an amount sufficient to sequester any moisture in the system.
  • the drying agent is a non-corrosive material which will not harm the metal components of the delivery vessel.
  • Suitable drying agents comprise metal salts and oxides. Molecular seives may also be used for this purpose.
  • Other drying agents are known to those skilled in the art. We have found that sodium sulfate, calcium sulfate, calcium chloride and calcium oxide are effective. Calcium oxide is preferred because of its secondary effect as a neutraliz­ing agent in counteracting acids which may be generated through the breakdown of Halon materials.
  • the fire-suppressing composition of the present invention may also include at least one viscosity modifier in an effective amount.
  • the viscosity modifier acts to prevent separation of the gel at temperatures as low as -40°F, and prevents excessive thinning of the composition at temperatures up to 120°F.
  • Chorides of sodium, magnesium, aluminum and postassium may be used.
  • Other metal salts may be used.
  • the same salt may function as both drying agent and viscosity modifier.
  • the gelled liquid compositions according to the present invention may be prepared by first mixing the various solid components with an intensive mixer, then adding the liquid component, with continued mixing.
  • the solids components may be added to the liquid component, with intensive mixing.
  • Examples 14-24 are set forth to illustrate the present invention wherein the gelled liquid component comprises a mixture of difluorochlorobromomethane and trifluorobromomethane. Amounts of ingredients are expressed in grams.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
EP19850305735 1983-06-21 1985-08-13 Thixotropische feuerunterdrückende Zusammensetzung die ein Karboxypolymer gelbildendes Mittel enthält Expired EP0212017B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8585305735T DE3575378D1 (de) 1985-08-13 1985-08-13 Thixotropische feuerunterdrueckende zusammensetzung die ein karboxypolymer gelbildendes mittel enthaelt.
IL7612485A IL76124A (en) 1985-08-13 1985-08-18 Thixotropic fire suppressant composition containing carboxy polymer gelling agent

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US50648583A 1983-06-21 1983-06-21
US70165085A 1985-02-14 1985-02-14
US06/820,927 US4652383A (en) 1985-02-14 1986-01-21 Vinyl polymer gelling agent for powder dissemination composition

Publications (2)

Publication Number Publication Date
EP0212017A1 true EP0212017A1 (de) 1987-03-04
EP0212017B1 EP0212017B1 (de) 1990-01-17

Family

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Family Applications (1)

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EP19850305735 Expired EP0212017B1 (de) 1983-06-21 1985-08-13 Thixotropische feuerunterdrückende Zusammensetzung die ein Karboxypolymer gelbildendes Mittel enthält

Country Status (3)

Country Link
EP (1) EP0212017B1 (de)
JP (1) JPS6244270A (de)
AU (1) AU559312B2 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU595198B2 (en) * 1985-05-03 1990-03-29 Ernest De Ruiter The use of an aqueous swollen macromolecule-containing system as water for fire fighting
WO1992001491A1 (en) * 1990-07-26 1992-02-06 Great Lakes Chemical Corporation Fire extinguishing methods utilizing perfluorocarbons
US5393437A (en) * 1994-05-31 1995-02-28 Chemguard, Inc. Fire extinguishing material
WO2001030451A1 (en) * 1999-10-26 2001-05-03 Powsus, Inc. Reduction of hf
EP1131136A4 (de) * 1998-09-01 2005-01-05 Powsus Inc Feuerlöschgele und verfahren zur ihrer herstellung und verwendung
US9586070B2 (en) 2013-01-22 2017-03-07 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102861409B (zh) * 2012-09-27 2015-12-09 西安坚瑞安全应急设备有限责任公司 一种金属含氧酸盐类灭火组合物
US9265978B2 (en) 2013-01-22 2016-02-23 Miraculum Applications, Inc. Flame retardant and fire extinguishing product for fires in liquids
US9597538B2 (en) 2013-01-22 2017-03-21 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in liquids

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3229769A (en) * 1963-01-28 1966-01-18 Dow Chemical Co Method for controlling the spread of fire
US3345289A (en) * 1965-11-01 1967-10-03 Gen Aniline & Film Corp Fire retardant composition of diammonium phosphate containing methylvinyl ether-maleic anhydride copolymer as thickener
US3634234A (en) * 1969-12-15 1972-01-11 Monsanto Co Stabilized ammonium phosphate solutions comprising a galactomannan gum and a metal salt
GB2006620A (en) * 1977-10-26 1979-05-10 Energy & Minerals Res Co Powder dissemination composition
US4226727A (en) * 1978-07-21 1980-10-07 Energy & Minerals Research Co. Persistent fire suppressant composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59189869A (ja) * 1983-04-11 1984-10-27 昭和電工株式会社 防災用具

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3229769A (en) * 1963-01-28 1966-01-18 Dow Chemical Co Method for controlling the spread of fire
US3345289A (en) * 1965-11-01 1967-10-03 Gen Aniline & Film Corp Fire retardant composition of diammonium phosphate containing methylvinyl ether-maleic anhydride copolymer as thickener
US3634234A (en) * 1969-12-15 1972-01-11 Monsanto Co Stabilized ammonium phosphate solutions comprising a galactomannan gum and a metal salt
GB2006620A (en) * 1977-10-26 1979-05-10 Energy & Minerals Res Co Powder dissemination composition
US4226727A (en) * 1978-07-21 1980-10-07 Energy & Minerals Research Co. Persistent fire suppressant composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU595198B2 (en) * 1985-05-03 1990-03-29 Ernest De Ruiter The use of an aqueous swollen macromolecule-containing system as water for fire fighting
WO1992001491A1 (en) * 1990-07-26 1992-02-06 Great Lakes Chemical Corporation Fire extinguishing methods utilizing perfluorocarbons
US5393437A (en) * 1994-05-31 1995-02-28 Chemguard, Inc. Fire extinguishing material
EP1131136A4 (de) * 1998-09-01 2005-01-05 Powsus Inc Feuerlöschgele und verfahren zur ihrer herstellung und verwendung
WO2001030451A1 (en) * 1999-10-26 2001-05-03 Powsus, Inc. Reduction of hf
US9586070B2 (en) 2013-01-22 2017-03-07 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials
US9878190B2 (en) 2013-01-22 2018-01-30 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials

Also Published As

Publication number Publication date
JPS6244270A (ja) 1987-02-26
AU559312B2 (en) 1987-03-05
JPH0214857B2 (de) 1990-04-10
EP0212017B1 (de) 1990-01-17

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