EP0212017B1 - Composition thixotropique contenant un agent de gélification comportant un polymère de groupements carboxyles pour la suppression des feux - Google Patents

Composition thixotropique contenant un agent de gélification comportant un polymère de groupements carboxyles pour la suppression des feux Download PDF

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Publication number
EP0212017B1
EP0212017B1 EP19850305735 EP85305735A EP0212017B1 EP 0212017 B1 EP0212017 B1 EP 0212017B1 EP 19850305735 EP19850305735 EP 19850305735 EP 85305735 A EP85305735 A EP 85305735A EP 0212017 B1 EP0212017 B1 EP 0212017B1
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EP
European Patent Office
Prior art keywords
composition according
fire
gelling agent
liquid
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.)
Expired - Lifetime
Application number
EP19850305735
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German (de)
English (en)
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EP0212017A1 (fr
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
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CEASE FIRE Corp
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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/fr
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Publication of EP0212017B1 publication Critical patent/EP0212017B1/fr
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Expired - Lifetime 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.
  • Liquefied 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” (Regd. Trademark of Cabot Corporation) have been used.
  • Gelled liquid fire-suppressing suspensions which may include ammonium salts, are disclosed in US-A 4 226 727 and US-A 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 thixotropically-gelled fire-suppressing composition which comprises a non-polar liquid, a carboxy polymer gelling agent in an amount effective to gel the liquid thixotropically 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 suspension, which is thixotropic and exhibits excellent stability.
  • a preferred feature of the invention resides in the provision of the composition in a form which contains by weight 0.5%-8.0% of the gelling agent, the balance being gelled liquid and ammonium salt.
  • the gelled liquid composition of the present invention preferably includes one or more fire-quenching liquids in combination with one or more fire-quenching liquefied gases and/or one or more overpressur- ized gases. If a fire-quenching liquefied gas (e.g. trifluorobromomethane) is used, the fire-quenching liquid may be omitted.
  • a fire-quenching liquefied gas e.g. trifluorobromomethane
  • the gelled liquid composition 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 vapour or droplet cloud carrying the fire-extinguishing particles. Finally, the gelled liquid composition must provide some measure of fire-quenching capability.
  • Fire-quenching liquids useful in the gelled liquid composition include, but are not limited to, the following: methylene bromide, methyl iodide, tetrafluorodibromoethane, trifluorotrichloroethane, fluorotrichloromethane, chloroform, bromoform, carbon tetrachloride and the like.
  • Liquefied gases which may be used according to the present invention include, but are not limited to, the following: trifluorobromomethane, difluorochlorobromomethane, perfluoropropane, perfluorocyclobutane, dichlorodifluoromethane, tetrafluoromethane, methyl bromide, trifluoromethane, trifluorochloromethane, hexafluoroethane and the like.
  • 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 50% to 60% difluorochlorobromomethane and 40% to 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.
  • this contains 70%-30% by weight of gelled liquid and 30% to 70% by weight of solids component containing the ammonium salt and the carboxy polymer gelling agent, the gelling agent itself constituting 0.5% to 8.0% by weight of the composition.
  • the liquefied gases preferably comprise a blend of 50 % ⁇ 60% difluorochloro-bro- momethane and 40%-50% trifluorobromomethane, while the gelling agent is a carboxy vinyl polymer and 35%-50% monoammonium phosphate is present.
  • the solids component contains one or more powdered ammonium salts and one or more carboxy polymer gelling agents.
  • concentration of the gelling agent in the composition is preferably from 0.5% to 8.0% by weight.
  • suitable powdered ammonium salts include mono-, di-, and triammonium phosphate, ammonium calcium phosphate sodium ammonium phosphate, ammonium sulphate, ammonium chloride and ammonium aluminium sulphate.
  • Monoammonium phosphate (MAP) powder is particularly useful. ABC dry chemical fire-extinguishing powder, which is 90 to 95 percent MAP, is preferred.
  • fire-suppressing 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 Regd. Trademark "MONAX", sodium chloride, potassium chloride, and the like.
  • MONAX sodium chloride, potassium chloride, and the like.
  • 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 inadequate unless they undergo 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 e.g., polyacrylamides
  • POLYHALL 40-J 40% hydrolyzed polyacrylamide available from National Starch & Chemical Co. under the Regd. 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.
  • polymers having groups which are functional derivatives of carboxyl 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.
  • 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 pendant 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 co-polymers or methacrylic acid and divinyl benzene available from Rohm & Haas Co., Philadelphia, Pa. under Regd. Trademark "AMBERLITE IPC-50".
  • CARBOPOL The "CARBOPOL” polymers used in the invention have an average equivalent weight of about 76 ⁇ 4, a molecular weight of from about 450,000 to about 4,000,000, and have the general structure: (sold by B.F. Goodrich under the trademark "CARBOPOL” for water soluble resins). These polycarboxylated vinyl resins have Brookfield viscosities (cP) as measured on a Brookfield viscometer (model RVF or RVT) at approximately 25 ° C in a range of from about 4,000 to 60,000 as measured on a 0.5% solution, and from about 3,000 to 7,000 as measured on a 1% solution.
  • cP Brookfield viscosities
  • CARBOPOL particularly "CARBOPOL” polymers have viscosities of from about 30,500 to 39,400 (average molecular weight about 3,000,000); 40,000 to 60,000 (average molecular weight about 4,000,000); and 4,000 to 11,000 (average molecular weight about 1,250,000) measured on a 0.5% solution; and 3,000 to 7,000 (average molecular weight about 750,000) measured on a 1% solution.
  • CARBOPOL 941 has a Brookfield viscosity (cP) at 25 ° C, 0.5% solution, of 4,000-11,000 (average molecular weight about 1,250,000).
  • CARBOPOL” 934 has a Brookfield viscosity at 25 ° C, 0.5% solution, of 30,500-39,400 (average molecular weight about 3,000,000).
  • CARBOPOL 941 and “CARBOPOL” 934 are particularly suitable.
  • 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. We have found that many excellent thickening and/or suspending agents which lack the free carboxyl function do not gel non-polar liquids in the presence of ammonium compound.
  • the suspending powder 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 trifluorobro-. momethane 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 fatty amine as a gelling adjuvant.
  • CARBOPOL is ineffective as a gelling agent for the liquefied 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 liquefied gases difluorochlorobromomethane and trifluorobromomethane.
  • a typical composition using a further fire extinguishing powder (KHC0 3 ) in addition to an ammonium salt is as follows:
  • CARBOPOL 942 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 carboxyl 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 present of water is undesirable for two reasons.
  • Halon materials will break down and react with any free water present to from these acids readily.
  • HF and HBr are highly corrosive, and attack the metal components of the delivery vessel.
  • Second, liquefied 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 against 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 sieves may also be used for this purpose.
  • Other drying agents are known to those skilled in the art. We have found that sodium sulphate, calcium sulphate, 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 ° C (-40 ° F), and prevents excessive thinning of the composition at temperatures up to 48 ° C (120 ° F).
  • Chlorides of sodium, magnesium, aluminium and potassium 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 solid component 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)

Claims (19)

1. Composition non aqueuse à gélification thixotrope utilisable pour l'extinction d'un feu, caractérisée en ce qu'elle comporte:
(a) un liquide non polaire;
(b) un agent gélifiant constitué par un polymère formé à partir de groupements carboxyle, présent en une quantité entraînant la gélification thixotrope du liquide; et
(c) un sel d'ammonium.
2. Composition selon la revendication 1, dans laquelle le sel d'ammonium est choisi parmi le phosphate de monoammonium, le phosphate de diammonium, le phosphate de triammonium, le phosphate d'ammonium- calcium, le phosphate de sodium-ammonium, le sulfate d'ammonium, le chlorure d'ammonium et le sulfate d'ammonium-aluminium.
3. Composition selon la revendication 1 ou 2, dans laquelle l'agent gélifiant est choisi parmi des polymères de vinyle carboxylique, des polysaccharides, des polyacrylamides et des résines synthétiques comportant des groupes carboxyle libres pendants ou des équivalents fonctionnels de tels groupes, qui ont été convertis en l'acide libre, au degré nécessaire pour déclencher la gélification du liquide non polaire:
4. Composition selon l'une quelconque des revendications précédentes, contenant 70% à 30% en poids du liquide gélifié et 30% à 70% en poids d'un composant solide contenant le sel d'ammonium et l'agent gélifiant constitué par un polymère formé à partir de groupements carboxyle, l'agent gélifiant lui- même constituant 0,5% à 8,0% en poids de la composition.
5. Composition selon l'une quelconque des revendications précédentes, contenant un additif supplémentaire, choisi parmi des agents déshydratants, des agents modifiant la viscosité, aptes à agir à basse température, et des combinaisons de tels produits.
6. Composition selon l'une quelconque des revendications précédentes, contenant une poudre d'extinction du feu, choisie parmi le bicarbonate de sodium, le bicarbonate de potassium, des produits d'addition de l'urée avec le bicarbonate de potassium, le chlorure de sodium et le chlorure de potassium.
7. Composition selon l'une quelconque des revendications précédentes, contenant au moins un liquide étouffant le feu et au moins un gaz créant une surpression et choisi parmi l'azote, le gaz carbonique, l'hélium et l'argon.
8. Composition selon l'une quelconque des revendications 1 à 6, contenant au moins un gaz liquéfié d'étouffement du feu en tant que liquide gélifié.
9. Composition selon la revendication 8, contenant au moins un liquide d'étouffement du feu et au moins un gaz liquéfié d'étouffement du feu en tant que liquide gélifié.
10. Composition selon la revendication 7 ou 8, dans laquelle le liquide d'étouffement du feu est choisi parmi le bromure de méthylène, le iodure de méthyle, le tétrafluorodibromoéthane, le trifluorotrichloro- éthane, le fluorotrichlorométhane, le chloroforme, le bromoforme et le tétrachlorure de carbone.
11. Composition selon la revendication 8 ou 9, dans laquelle le gaz liquéfié d'étouffement du feu est choisi parmi le trifluorobromométhane, le difluorochlorobromométhane, le perfluoropropane, le perfluorocyclobutane, le dichlorodifluorométhane, le tétrafluorométhane, le bromure de méthyle, le trifluoromé- thane, le trifluorochlorométhane et l'hexafluoroéthane.
12. Composition selon la revendication 11, dans laquelle le liquide gélifié est un mélange de difluorochlorobromométhane et de trifluorobromométhane.
13. Composition selon la revendication 12, dans laquelle un mélange de 50% à 60% de difluorochlorobromométhane et 40% à 50% de trifluorobromométhane est présent.
14. Composition selon la revendication 12 ou 13, dans laquelle un polymère de vinyle carboxylique est présente en tant qu'agent gélifiant.
15. Composition selon la revendication 14, comprenant 70%-30% d'un gaz liquéfié, qui est un mélange de 50%-60% de difluorochlorobromométhane et de 40%-50% de trifluorobromométhane, de 0,5%-8,0% d'un agent gélifiant formé d'un polymère de vinyle carboxylique et 35%-50% de phosphate de monoammonium.
16. Composition selon la revendication 3 ou 14, dans laquelle l'agent gélifiant est un polymère de vinyle polycarboxylaté possédant un poids équivalent moyen égal à 76±4, un poids moléculaire compris entre 450 000 et 4 000 000, une viscosité Brookfield (cP) se situant dans la gamme de 4000 à 60 000, mesurée sur la base d'une solution à 0,5%, et une viscosité Brookfield (cP) se situant dans la gamme de 3000 à 7000, mesurée sur une solution à 1%, le polymère de vinyle polycarboxylaté possédant la structure générale
Figure imgb0007
et étant présent en une quantité suffisante pour gélifier le liquide.
17. Composition selon la revendication 16, dans laquelle le polymère de vinyle polycarboxylaté possède une viscosité de Brookfield à 25°C, mesurée sur une solution à 0,5%, égale à 4000-11 000 centipoises pour un poids moléculaire moyen égal à environ 1 250 000.
18. Composition selon la revendication 16, dans laquelle le polymère de vinyle polycarboxylaté possède une viscosité Brookfield à 25°C, mesurée sur une solution à 0,5%, égale à 30 500-39 400 centipoises pour un poids moléculaire moyen égal à environ 3 000 000.
19. Procédé pour éteindre un feu, caractérisé par l'application d'une composition selon l'une quelconque des revendications précédentes.
EP19850305735 1983-06-21 1985-08-13 Composition thixotropique contenant un agent de gélification comportant un polymère de groupements carboxyles pour la suppression des feux Expired - Lifetime EP0212017B1 (fr)

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)

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EP0212017A1 EP0212017A1 (fr) 1987-03-04
EP0212017B1 true EP0212017B1 (fr) 1990-01-17

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JP (1) JPS6244270A (fr)
AU (1) AU559312B2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
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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

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DE3515865A1 (de) * 1985-05-03 1986-11-06 Hasso von 4000 Düsseldorf Blücher Verwendung eines waessrigen, gequollene makromolekuele enthaltenden systems als loeschwasser
US5117917A (en) * 1990-07-26 1992-06-02 Great Lakes Chemical Corp. Fire extinguishing methods utilizing perfluorocarbons
US5393437A (en) * 1994-05-31 1995-02-28 Chemguard, Inc. Fire extinguishing material
EP1131136A4 (fr) * 1998-09-01 2005-01-05 Powsus Inc Gels d'extinction d'incendie et procede de preparation et d'utilisation
WO2001030451A1 (fr) * 1999-10-26 2001-05-03 Powsus, Inc. Reduction de fluorure d'hydrogene
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
US9586070B2 (en) 2013-01-22 2017-03-07 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials

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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
US4234432A (en) * 1977-10-26 1980-11-18 Energy And Minerals Research Co. Powder dissemination composition
US4226727A (en) * 1978-07-21 1980-10-07 Energy & Minerals Research Co. Persistent fire suppressant composition
JPS59189869A (ja) * 1983-04-11 1984-10-27 昭和電工株式会社 防災用具

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

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AU559312B2 (en) 1987-03-05
JPS6244270A (ja) 1987-02-26
EP0212017A1 (fr) 1987-03-04
JPH0214857B2 (fr) 1990-04-10

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