EP1275417B1 - Composition extinctrice d'incendie - Google Patents

Composition extinctrice d'incendie Download PDF

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Publication number
EP1275417B1
EP1275417B1 EP20010116661 EP01116661A EP1275417B1 EP 1275417 B1 EP1275417 B1 EP 1275417B1 EP 20010116661 EP20010116661 EP 20010116661 EP 01116661 A EP01116661 A EP 01116661A EP 1275417 B1 EP1275417 B1 EP 1275417B1
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Prior art keywords
ignition
heptane
group
fire extinguishing
seconds
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German (de)
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EP1275417A1 (fr
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Kazunori Tanaka
Kenji Nagao
Yutaka Hashimoto
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to DE60140529T priority patent/DE60140529D1/de
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes
    • 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
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant

Definitions

  • the present invention relates to a fire extinguishing composition comprising polyethyleneimine or a derivative thereof, and more particularly to a fire extinguishing composition which is superior in terms of rapid extinguishing performance, flame resistance, fuel resistance, and reignition prevention performance.
  • fire extinguishing compositions of type (4) above are aqueous film forming foam compositions based on a fluorine based surfactant, to which a water soluble high molecular weight material (such as a polysaccharide) has been added to give thixotropic properties.
  • foams which consist of this type of composition lose water at the combustion interface, and the remaining water soluble high molecular weight material, incorporating air bubbles, forms a gel-like mat across the solvent surface, preventing direct contact between the upper part of foam and the solvent, and covering the entire combustion surface. It is believed that the fire is then extinguished by cooling and smothering effects.
  • compositions of type (4) offer better foam development on the combustion surface, and also offer an improved fire extinguishing effect.
  • fire extinguishing compositions of the type (4) above will display poor fire extinguishing effect on solvents such as alcohols (such as isopropyl alcohol and t-butanol) or propylene oxide which have large heats of combustion or are highly volatile, and so depending on the type of solvent, the dilution ratio of the composition concentrate may need to be increased, which makes handling somewhat troublesome.
  • solvents such as alcohols (such as isopropyl alcohol and t-butanol) or propylene oxide which have large heats of combustion or are highly volatile
  • these fire extinguishing compositions incorporate large amounts of water soluble high molecular weight material, and so the composition concentrate is extremely viscous (at least 1200 mm 2 /s), and moreover the viscosity value varies considerably with temperature. Consequently, considerable care needs to be taken with the fire extinguishing equipment (such as mixers and piping), and there are handling concerns associated with the practical application of these types of compositions to existing equipment. Furthermore, conventionally these type of fire extinguishing compositions have been prone to forming a thin membrane (skin) on the surface of the liquid and on the walls of the tank during storage, and moreover producing sedimentation on the bottom of the tank, and problems have also arisen over the life of the product with concerns that they do not cope with extended storage. In addition, these types of fire extinguishing compositions also have a relatively high freezing point of approximately 0°C, and because they are not reversible in terms of freezing and remelting, use or storage of such compositions in cold regions requires special considerations.
  • a fire extinguishing composition which displays superior fuel resistance, flame resistance (for example, reignition sealing) and heat resistance when compared with conventional compositions was disclosed by the present applicants in Japanese Unexamined Patent Application, First Publication No. Sho-59-230566 , and comprises a surfactant with an anionic hydrophilic group and a cationic water soluble high molecular weight compound, mixed with a third constituent comprising a polybasic acid compound of 3 to 24 carbon atoms.
  • this fire extinguishing composition is able to be used for extinguishing both polar solvent fires and non-polar solvents, the time required to extinguish a fire is relatively long, and the composition could not be claimed to offer rapid fire extinguishing performance.
  • the composition also has problems in terms of flame resistance, and reignition prevention.
  • a fire extinguishing composition which comprises a surfactant and a cationic water-soluble polymeric substance, wherein the surfactant is a fluorine-containing aminosulfonate-type surface-active agent.
  • the composition also contains a polybasic acid compound.
  • WO 96/05889 relates to water-soluble fluorochemical foam stabilizers and film formers derived from polyamines, perfluoroalkyl group containing esters or acid halides and hydrophilic and hydrophobic group-containing compounds which react with primary, secondary and tertiary amino groups.
  • An object of the present invention is to provide a fire extinguishing composition which when compared with conventional fire extinguishing compositions displays superior rapid fire extinguishing performance, flame resistance, fuel resistance and reignition prevention performance, for both non-polar solvent fires and polar solvent fires, as well as displaying superior stability as a diluted solution.
  • the present invention is a fire extinguishing composition which comprises a cationic polyamine based high molecular weight compound (A) which has primary, secondary, and tertiary cationic groups within the molecular structure, a surfactant with an anionic hydrophilic group (B) and a polybasic acid compound (C) characterized in that said primary cationic groups account for no more than 40% by weight of the total cationic groups within the molecule.
  • A cationic polyamine based high molecular weight compound
  • B secondary, and tertiary cationic groups within the molecular structure
  • B anionic hydrophilic group
  • C polybasic acid compound
  • the present invention provides a method for extinguishing fire, comprising the steps of providing a fire extinguishing composition according to the present invention; and applying the composition to a fire.
  • the fire extinguishing composition of the present invention forms a foam which is extremely stable with respect to polar solvents, and yet also forms an aqueous film on the surface of non-polar solvents such as petroleum, and offers flame resistance and fuel resistance properties which display markedly improved rapid fire extinguishing performance and reignition prevention.
  • the cationic polyamine based high molecular weight compound (A) used in the present invention refers to a high molecular weight compound which incorporates cationic groups such as amino groups, ammonium groups, pyridinium groups or quaternary ammonium groups, and is a water soluble high molecular weight compound with a solubility in conventional water of at least 0.1 % by weight.
  • the cationic groups described above comprise primary, secondary and tertiary groups, and the cationic groups can exist on either the main chain or a side chain of the polyamine based high molecular weight compound.
  • primary cationic groups must account for no more than 40% by weight of the total cationic groups.
  • the degree of polymerization of the water soluble high molecular weight compound is regulated by the water solubility of the compound, and from the oligomer region, degrees of polymerization of at least several tens of thousands, namely weight average molecular weights of 1,000 to 1,000,000 are typical, with values of 4,000 to 300,000 being preferred, and degrees of polymerization of 50,000 to 100,000 being the most desirable in terms of producing a composition with the most superior fire extinguishing performance, flame resistance and fuel resistance with respect to polar solvents.
  • cationic polyamine based high molecular weight compound (A) examples include those detailed below, although it should be noted that the present invention is in no way limited by these specific examples.
  • additional cationic polyamine based high molecular weight compounds may be used in conjunction with the cationic polyamine based high molecular weight compound (A) used as the essential constituent.
  • these compatible cationic polyamine based high molecular weight compounds include:
  • a fire extinguishing composition of the present invention must not only display the type of performance required of a foam type fire extinguishing composition with rapid fire extinguishing performance, flame resistance, and an ability to retain a layer of foam on the liquid surface of both non-water soluble hazardous materials and water soluble hazardous materials, namely fuel resistance, but must also satisfy certain basic properties of specific gravity, pour point, viscosity, hydrogen ion concentration, sedimentation, and corrosiveness and the like as stipulated in the national certification regulations, which are based on a ministerial ordinance (Ministry of Home Affairs Ordinance No. 26) brought into effect on December 9, 1975 and defining the technical specifications relating to foam type fire extinguishing compositions.
  • a variety of cationic polyamine based high molecular weight compounds can be used as the main constituent of a fire extinguishing composition which complies with the above requirements, but as mentioned above, it is a requirement that primary cationic groups within the compound account for no more than 40% by weight of the total cationic groups.
  • a cationic polyamine based high molecular weight compound in which the proportion of primary cationic groups exceeds 40% by weight is used, then not only does sedimentation occur in an aqueous solution produced by mixing 3 to 6 parts by weight of the foam fire extinguishing composition concentrate with 97 to 94 parts of fresh water or sea water, which raises a dilution stability problem in that the composition does not satisfy one of the technical specifications of the Ministry of Home Affairs Ordinance No. 26, but furthermore, sedimentation can block the tips of the various types of nozzles used in actual fire fighting activity, resulting in unexpected situations which inhibit effective fire fighting.
  • Cationic polyamine based high molecular weight compounds in which the proportion of primary cationic groups accounts for no more than 40% by weight of the total number of cationic groups, and the secondary cationic groups account for at least 35% by weight of the total cationic groups, display even more superior effects in terms of fire extinguishing performance and dilution stability, and are consequently preferred.
  • polyethyleneimine or partially modified polyethyleneimine being used in preference.
  • a typical method of manufacturing polyethyleneimine comprises synthesizing ethyleneimine by a direct cyclodehydration of gaseous mono ethanolamine in the presence of a solid acid-base catalyst, and then subjecting the ethyleneimine produced by this method to a ring-opening polymerization in the presence of an acid catalyst to form polyethyleneimine.
  • Reaction kinetics mean that polyethyleneimine manufactured in this manner will not be a perfectly linear macromolecule, but will rather be a high molecular weight compound with a branched structure comprising primary, secondary and tertiary amine groups, as shown in the chemical equation below.
  • the acid catalyst used in the ring-opening polymerization of ethyleneimine may utilize any of the mineral acid, inorganic or organometallic based Lewis acids, although the branched structure will vary depending on the catalyst used, as will the ratio of primary, secondary and tertiary amines within the produced molecule.
  • a surfactant (B) with an anionic hydrophilic group is also included in the fire extinguishing composition of the present invention.
  • a surfactant with an anionic hydrophilic group undergoes an electrostatic interaction with the cationic polyamine based high molecular weight compound (A), and the surfactant in the present invention is a compound with at least one anionic hydrophilic group within each molecule.
  • Preferred anionic hydrophilic groups include groups such as -COOH, -SO 3 H, -OSO 3 H, and -OP(OH) 2 , with -SO 3 H being particularly desirable. Furthermore, in terms of counter ions for the cationic groups, compounds with organic or inorganic anionic groups may also be used.
  • the hydrophilic group of the surfactant may incorporate one or more of the same, or different anionic groups, or alternatively, an amphoteric ion type surfactant which incorporates a cationic hydrophilic group and/or a nonionic group in addition to the anionic hydrophilic group, is also possible.
  • amphoteric ion type surfactants are preferred for compatibility reasons.
  • hydrophobic group of the surfactant examples include aliphatic hydrocarbon groups of 6 or more carbon atoms, dihydrocarbyl siloxane chains, or fluorinated aliphatic groups of 3 to 20 carbon atoms and preferably 6 to 16 carbon atoms. Of these hydrophobic groups, fluorinated aliphatic groups are particularly desirable as they offer improved fuel resistance. Furthermore, the surfactant may also comprise a mixture of different surfactants with different hydrophobic groups.
  • the surfactants with an anionic hydrophilic group (B) used in the fire extinguishing composition of the present invention can be broadly classified into: (B-1) fluorine containing amino acid type amphoteric surfactants, (B-2) fluorine containing aminosulfonate type surfactants, (B-3) fluorine containing aminocarboxylate type surfactants, (B-4) fluorine containing trianion type amphoteric surfactants, (B-5) fluorine containing tricarboxylic acid type amphoteric surfactants, (B-6) fluorine containing sulfobetaine type amphoteric surfactants, (B-7) fluorine containing aminosulfate type surfactants, (B-8) fluorine containing sulfatobetaine type surfactants, (B-9) fluorine containing sulfobetaine type surfactants, (B-10) fluorine containing amine oxide type surfactants, and (B-11) other surfactants.
  • the fluorine containing amino acid type amphoteric surfactants B-1 are compounds represented by the general formula (B-1): (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms, Y represents either -SO 2 - or -CO-, and Q 1 and Q 2 represent organic bivalent linking groups such as aliphatic hydrocarbon groups, aliphatic hydrocarbon groups substituted with hydroxyl groups, aromatic hydrocarbon groups, substituted aromatic hydrocarbon groups, or combinations thereof, with preferred groups including straight chain alkylene groups of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl group, the 2-methoxypropan-1,3-diyl group, the 2-ethoxypropan-1,3-diyl group, and the 2-propoxypropan-1,3-diyl group.
  • Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms
  • Y represents either -SO 2 - or -CO-
  • R 1 and R 2 represent hydrogen atoms, aliphatic hydrocarbon groups of 1 to 12 carbon atoms, or aliphatic hydrocarbon groups which have been substituted with hydrophilic groups, or R 1 and R 2 may be linked together forming a ring with the adjacent nitrogen atom.
  • A represents an anionic hydrophilic group such as -COO - , -SO 3 - , -OSO 3 - , or -OP(OH)O - .
  • M represents a hydrogen atom, an alkali metal, an alkali earth metal, an ammonium group, or an organic cationic group.
  • the fluorine containing aminosulfonate type surfactants (B-2) are compounds represented by the general formula (B-2): Rf-Z-Q 1 -N(R)-Q 2 -SO 2 M
  • Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms
  • Z represents a bivalent linking group such as -SO 2 N(R 1 )-, -CON(R 1 )-, -(CH 2 CH 2 ) i SO 2 N(R 1 )-, or compounds covered by the general formula or the general formula (where R 1 is a hydrogen atom or an alkyl group of 1 to 12 carbon atoms, and i is an integer from 1 to 10), and Q 1 represents a straight chain alkylene group of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl group, the 2-ethoxypropan-1,3-diyl group, or the 2-propoxypropan-1,3-diyl group.
  • R represents a hydrogen atom, an alkyl group of 1 to 3 carbon atoms, a hydroxyalkyl group, -Q 2 SO 3 M, or -(CH 2 ) k COOM (where k is an integer of 1 to 4), Q 2 represents a straight chain alkylene group of 1 to 5 carbon atoms, the 2-hydroxypropan-1,3-diyl group, the 2-ethoxypropan-1,3-diyl group, the 2-propoxypropan-1,3-diyl group, or a bivalent linking group represented by the general formula below.
  • M represents a hydrogen atom, an alkali metal, an alkali earth metal, or a cationic atom or group of atoms represented by the formula below.
  • -N(H) m (R 4 ) 4-m In the formula, R 4 represents an alkyl group of 1 to 3 carbon atoms, or a hydroxyalkyl group, and m is an integer of 0 to 4.)
  • the fluorine containing aminocarboxylate type surfactants (B-3) are compounds represented by the general formula (B-3):
  • Rf represents a polyfluoroalkyl group, a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexyl alkyl group or a polyfluorocyclohexyl alkenyl group of 3 to 20 carbon atoms which may also incorporate oxygen atoms
  • Z represents a linking group of one of the formulae below.
  • R 1 represents an alkyl group, an alkenyl group or an aromatic ring containing monovalent group incorporating of 1 to 18 carbon atoms, and i represents an integer of 1 to 3.
  • Q represents a bivalent linking group of one of the formula below. or (In the formulae, l represents an integer of 1 to 6, m and n each represent an integer of 2 to 6, and p and q each represent the number 2 or 3 respectively.)
  • Q 1 and Q 2 each represent a alkylene group of 1 to 3 carbon atoms.
  • M 1 and M 2 each represent a hydrogen atom or an inorganic or an organic cation.
  • the fluorine containing trianion type amphoteric surfactants (B-4) are compounds represented by the general formula (B-4): (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms, Z represents a bivalent linking group, Q represents a straight chain alkylene group of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl group, -(CH 2 ) m -O-(CH 2 ) n - (where m and n are each integers from 2 to 6) or -(CH 2 ) p -O-(CH 2 ) 2 -O-(CH 2 ) q - (where p and q each represent the number 2 or 3 respectively).
  • the fluorine containing tricarboxylic acid type amphoteric surfactants (B-5) are compounds represented by the general formula (B-5) : (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms, and Z represents -SO 2 -, -CO-, -(CH 2 ) l -SO 2 -, -(CH 2 ) l -CO- (where l represents an integer from 1 to 6), or a bivalent group represented by either the formula or the formula R 1 represents the 2-hydroxyethyl group, a group represented by the general formula -(CH 2 ) a -O-(CH 2 ) b -CH 3 (where a represents an integer from 2 to 10, and b represents an integer from 1 to 9), or an alkyl group of 1 to 12 carbon atoms, Q 1 represents a straight chain alkylene group of 2 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl group, or
  • the fluorine containing sulfobetaine type amphoteric surfactants (B-6) are compounds represented by the general formula (B-6):
  • Rf represents a group comprising a fluorinated aliphatic group of 3 to 20 carbon atoms
  • Z represents a bivalent linking group incorporating a sulfonamide group or a carbonamide group
  • Q 1 , Q 2 and Q 3 each represent independently a bivalent aliphatic group of 1 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxyl group, an aromatic hydrocarbon group, or a bivalent group formed through a combination of the above groups.
  • R represents a hydrogen atom, a hydrocarbyl group of 1 to 12 carbon atoms, or a -(CH 2 CH 2 O) i H or a -(CH 2 CH(CH 3 )O) i H group (where i represents an integer of 1 to 20),
  • M 1 and M 2 each represent a hydrogen atom or an inorganic or an organic cation
  • X represents an inorganic or an organic anion.
  • the fluorine containing aminosulfate type surfactants (B-7) are compounds represented by the general formula (B-7): (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms, Z represents -SO 2 -, -CO-, a bivalent group represented by one of the formulae or -(CH 2 ) a -CO- (where a represents an integer of 1 to 10), R 1 represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, a -(CH 2 ) b -OR 3 group or a -(CH 2 CH 2 O) d -R 2 group (where b represents an integer from 1 to 10, d represents an integer of 1 to 20, and R 3 represents a lower alkyl group or alkoxyl group), and Y represents -(CH 2 ) e -, -(CH 2 ) p -O-(CH 2 ) 2 -O-(CH 2 ) q
  • R 2 represents a hydrogen atom, an alkyl group, alkenyl group, or hydroxyl substituted alkyl group of 1 to 18 carbon atoms, a -(CH 2 CH 2 ) m -H group (where m represents an integer of 2 to 20), Q 1 OSO 3 M, Q 1 SO 2 M or (CH 2 ) i COOM (where i represents an integer from 1 to 4).
  • Q 1 represents a straight chain alkyl group of 2 to 12 carbon atoms, the 2-hydroxypropan-1,3-diyl group or -(CH 2 CH 2 O) k -CH 2 CH 2 - (where k represents an integer from 1 to 50).
  • M represents a hydrogen atom or an inorganic or an organic cation.
  • B-7-c C 7 F 15 CON(CH 3 )(CH 2 ) 3 N(CH 3 )CH 2 CH 2 OSO 3 NH 4
  • B-7-d C 7 F 15 CONH(CH 2 ) 6 N(CH 2 CH 2 OSO 3 Na) 2
  • the fluorine containing sulfatobetaine type surfactants (B-8) are compounds represented by the general formula (B-8): (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms, Z represents -SO 2 -, -CO-, or -(CH 2 ) a -CO- (where a represents an integer of 1 to 10), R 1 represents a hydrogen atom, an alkyl group of 1 to 12 carbon atoms, a -(CH 2 ) b -OR 3 group or a -(CH 2 CH 2 O) d -R 2 group (where b represents an integer from 1 to 10, d represents an integer of 1 to 20, and R 2 represents a lower alkyl group or alkoxyl group), and Y represents -(CH 2 ) e -, -(CH 2 ) p -O-(CH 2 ) 2 -O-(CH 2 ) q - or -(CH 2 )
  • R 2 and R 3 each represent independently an alkyl group, alkenyl group, hydroxyl substituted alkyl group, or aromatic substituted alkyl group of 1 to 18 carbon atoms, or a -(CH 2 CH 2 O) i -H group (where i represents an integer of 2 to 20), or alternatively R 2 and R 3 may be linked together to form a heterocyclic ring with the adjacent nitrogen atom, and Q 1 represents a straight chain alkylene chain of 2 to 12 carbon atoms, the 2-hydroxypropan-1,3-diyl group or-(CH 2 CH 2 O) k -CH 2 CH 2 - (where k represents an integer from 1 to 50).)
  • the fluorine containing sulfobetaine type surfactants (B-9) are compounds represented by the general formula (B-9):
  • Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms which may incorporate an oxygen atom, or a fluorinated alicyclic group
  • Z represents a bivalent linking group
  • Q 1 represents a straight chain alkylene chain of 1 to 6 carbon atoms, or -(CH 2 ) m -O-(CH 2 ) n - or -(CH 2 ) p -O-(CH 2 ) 2 -O-(CH 2 ) q - (where m and n each represent an integer of 2 to 6, and p and q each represent independently a value of 2 or 3)
  • Q 2 represents a straight chain alkylene chain of 1 to 6 carbon atoms, the 2-hydroxypropan-1,3-diyl group or -(CH 2 CH 2 O) r -CH 2 CH 2 - (
  • M 1 , M 2 and M 3 each represent independently a hydrogen atom or an inorganic or an organic cation.
  • examples of preferred inorganic or organic cations include Li + , Na + , K + , Ca + , Mg + , [N(H) s (R) 4-s ] + (where R is an alkyl group of 1 to 4 carbon atoms or a hydroxyethyl group, and s represents an integer from 0 to 4), or
  • X represents an inorganic or an organic anion.
  • Examples of preferred inorganic or organic anions include OH - , Cl - , Br - , I - , ClO 4 - , 1/2SO 4 - , CH 3 SO 4 - , NO 3 - , CH 3 COO - or the phosphate ion.
  • the fluorine containing amine oxide type surfactants (B-10) are compounds represented by the general formula (B-10):
  • Rf represents a fluorinated aliphatic group of 8 to 18 carbon atoms, or a fluorinated alicyclic group of 10 to 20 carbon atoms with either an ether oxygen atom or thioether linkage
  • Q represents -SO 2 - or -CO-
  • R 1 represents H, an alkyl group of 1 to 6 carbon atoms, a halogenated alkyl group of 1 to 6 carbon atoms, -OH, -SH, an alkoxyl group of 1 to 6 carbon atoms, a thioalkyl group of 1 to 6 carbon atoms, -NO 2 , -CN, or NRR'- (where R and R' each represent H or an alkyl group of 1 to 6 carbon atoms), R 2 and R 3 each represent H, an alkyl group of 1 to 6 carbon atoms, a halogen
  • this (B-10) compound is the compounds represented by the formulae (B-10-a) to (B-10-o) shown below, although the present invention is not limited to the compounds shown.
  • surfactants (B-11) other than the surfactants (B-1) to (B-10) which are able to be used in the fire extinguishing composition of the present invention include compounds represented by the formulae (B-11-a) to (B-11-g) shown below, although the present invention is not limited to the compounds shown.
  • the mixing proportions of the cationic polyamine based high molecular weight compound (A) and the surfactant (B) should preferably be within a weight ratio range from 5:1 to 1:3, with ratios within a range from 3:1 to 1:1 being even more desirable.
  • a polybasic acid compound (C) By adding a polybasic acid compound (C) to a fire extinguishing composition of the present invention, the polybasic acid compound undergoes an electrostatic interaction with the polyethyleneimine or derivative thereof, thereby improving the flame resistance and fuel resistance of the composition even further.
  • the polybasic acid compound (C) is a compound which incorporates an acid group within the molecule, there are no restrictions on the type or the number of acid groups, nor on the length of the carbon chain or the molecular weight, and any compound can be used. Furthermore, such a polybasic acid compound (C) is a compound with no surfactant properties, and suitable examples include dibasic, tribasic, tetrabasic, pentabasic or hexabasic acids of 3 to 24 carbon atoms with an aromatic group, an aliphatic group or a heterocyclic ring or the like, or the alkali metal salts or ammonium salts of such acids.
  • the acid group in the polybasic acid compound (C) may be a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group or the like. Furthermore, in those cases where polybasic acid compounds are used, either a single compound, or two or more different compounds may be used in combination. Of these various polybasic acid compounds (C), dibasic acid compounds of 4 to 18 carbon atoms are particularly desirable from the viewpoint of compatibility.
  • polybasic acid compound (C) examples include compounds represented by the formulae (C-1) to (C-32) shown below, as well as the alkali metal salts (Na salts, K salts, Li salts and the like) or ammonium salts thereof, although the present invention is not limited to these specific compounds.
  • the mixing proportions of the cationic polyamine based high molecular weight compound (A) and the polybasic acid compound (C) should preferably be within a weight ratio range from 5:1 to 1:3, with ratios within a range from 4:1 to 1:1 being even more desirable.
  • the mixing proportions of the cationic polyamine based high molecular weight compound (A) with the surfactant with an anionic hydrophilic group (B) and the polybasic acid compound (C) will vary depending on the combination of the constituents, although typically weight ratios (B):[(A)+(C)] within a range from 2:1 to 1:50 are preferable, with ratios within a range from 1:1 to 1:10 being even more desirable.
  • the fire extinguishing composition of the present invention displays superior solubility stability in both concentrated and diluted forms, and as such offers excellent extended storage. Furthermore, because of the superior solubility and low viscosity of the composition, a strong concentrate with a high dilution ratio can be easily manufactured. The kinematic viscosity of a concentrate with a 3% dilution ratio can be suppressed to a value of no more than 100 mm 2 /s at 20°C, which results in excellent handling properties.
  • the amount of the cationic polyamine based high molecular weight compound (A) added can be kept to a reasonably small amount, little deleterious effect is observed on the performance of the composition, and the freezing point of the fire extinguishing composition concentrate can be kept below -5°C.
  • a suitable amount of a surfactant (D) with a cationic hydrophilic group may also be included in the composition with the aim of effectively lowering the surface tension and the interfacial tension with petroleum of the aqueous solution of the fire extinguishing composition.
  • the surfactant with a cationic hydrophilic group (D) incorporates a cationic hydrophilic group.
  • the cationic hydrophilic group of the surfactant with a cationic hydrophilic group (D) include pyridinium salts, quaternary ammonium salts, imidazaolinium salts, and benzalkonium salts. Of these cationic hydrophilic groups, pyridinium salts and quaternary ammonium salts are preferred from the viewpoint of compatibility, and quaternary ammonium salts are particularly desirable.
  • suitable counter ions for the cationic group include organic and inorganic anions.
  • hydrophobic group of the surfactant (D) examples include aliphatic hydrocarbon groups of 6 or more carbon atoms, dihydrocarbyl siloxane chains, or fluorinated aliphatic groups of 3 to 20 carbon atoms and preferably 6 to 16 carbon atoms.
  • surfactants with fluorinated aliphatic groups are particularly desirable as they offer improved fire extinguishing performance.
  • Examples of the surfactant with a cationic hydrophilic group (D) include compounds represented by the general formula (D-1): (In the formula, Rf represents a fluorinated aliphatic group of 3 to 20 carbon atoms which may also incorporate oxygen atoms, and Y represents a bivalent group such as -(CH 2 CH 2 ) i -, -CH 2 CH 2 SCH 2 COO-, -(CH 2 CH 2 ) i -SO 2 -, -(CH 2 CH 2 ) i -CO-, or (where i represents an integer from 1 to 6).
  • R represents a hydrogen atom or an aliphatic hydrocarbon group of 1 to 6 carbon atoms
  • Q 1 represents an aliphatic hydrocarbon group, an aliphatic hydrocarbon group substituted with a hydroxyl group, an aromatic hydrocarbon group or a substituted aromatic hydrocarbon group, although a straight chain alkylene group of 1 to 6 carbon atoms is preferred.
  • R 1 to R 3 can represent the same group or different groups, and each represent a hydrogen atom or an aliphatic hydrocarbon group of 1 to 6 carbon atoms, and X - represents an organic or an inorganic anion.
  • additives may also be added to a fire extinguishing composition of the present invention.
  • additives include additional foam stabilizers, freezing point depressants, rust prevention agents, and pH regulators and the like.
  • Additional foam stabilizers are mainly additives used for adjusting the expansion ratio or drainage, and suitable examples include non-ionic surfactants such as glycerin aliphatic esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene ethers, polyethylene glycol fatty acid esters, alkyl alkanol amides and alkyl polyglucosides; amphoteric surfactants such as betaine alkyl dimethylaminoacetate, alkyl dimethylamine oxides, alkyl carboxymethylhydroxyethyl imidazolium betaine, alkylamide propyl betaine, and alkylhydroxy sulfobetaine; as well as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, gum arabic, sodium alginate, polypropylene glycol and polyvin
  • suitable freezing point depressants include ethylene glycol, propylene glycol, the cellosolve compounds (ethyl cellosolve and butyl cellosolve), caribtol compounds (ethyl carbitol, butyl carbitol, hexyl carbitol and octyl carbitol), lower alcohols (isopropyl alcohol, butanol, octanol), and urea.
  • Rust prevention agents and pH regulators can utilize any of the various commonly known compounds, and there are no particular restrictions.
  • the fire extinguishing composition of the present invention can be used as a fire extinguishing agent by using known methods for blowing in, or mixing, air, carbon dioxide, nitrogen, a low boiling point fluorocarbon such as difluorodicholoromethane, or another suitable non-flammable gas with the composition.
  • the viscosity of the fire extinguishing composition concentrate of the present invention is comparatively low, a strong concentrate can be stored in a storage tank, and then at the time of use, normal methods can be used for introducing the composition into a water flow and adjusting the dilution ratio at some point before the mixture reaches a device such as a fire extinguishing apparatus or foam nozzle. Foam is then generated by blowing in, or mixing a non-flammable gas such as air, and the foam is discharged over the flame or sent under the surface of the flame.
  • the composition can be prediluted to a usable concentration, and then used to fill devices such as fire extinguishers, parking lot fire extinguishing equipment, fixed fire extinguishing equipment for hazardous materials, or packaged fire extinguishing equipment.
  • suitable methods for discharging the fire extinguishing composition of the present invention include the use of any of those discharge nozzles commonly used in the industry for delivering fire extinguishing compositions, and desired performance levels are able to be achieved.
  • suitable nozzles include the foam chamber and ISO standard compliant nozzle most widely used for petroleum tanks and the like, UL standard compliant nozzles, MIL standard compliant nozzles, hand nozzles attached to chemical fire engines and the like, air foam hand nozzles, SSI nozzles, the Japan Marine Standards Association specified HK nozzle, as well as foam heads used in driving lot fire extinguishing equipment, and spray heads and the like.
  • fire extinguishing compositions of the present invention can be used in a wide variety of discharge methods. Furthermore, a fire extinguishing composition of the present invention can also be applied to a wider range of fires than conventional fire extinguishing compositions.
  • Specific examples of the use of the compositions of this invention include deployment on chemical fire engines and concentrate carrier vehicles employed by public fire fighting organizations, as well as deployment at petroleum sites or industrial sites with crude oil tanks or other hazardous material facilities, airport facilities, harbor facilities or shipping vessels involved in the loading of hazardous materials, gas stands, underground parking lots, buildings, tunnels and bridges.
  • the compositions can also be used on general fires such as timber fires in housing, or rubber and plastic fires such as tire fires.
  • fire extinguishing compositions of the present invention display superior qualities of fuel resistance, flame resistance, heat resistance and foam forming properties
  • the strong concentrate or diluted aqueous solution can also be used for extinguishing cooking oil or salad oil fires by pouring directly onto the combustion surface to smother or cool the fire.
  • a fire extinguishing composition of the present invention also displays superior stability of the diluted solution, and so the diluted solution can be used for filling spray cans and then used as simple household fire extinguishers.
  • the foam generated from a fire extinguishing composition of the present invention is able to exist in a stable manner on aqueous solutions based on water, sol-gel type materials, sludge and pollutants, as well as various organic solvents and organic materials. Consequently, the volatilization of volatile materials from this wide range of materials can be suppressed, enabling the compositions of the present invention to also be used for preventing the ignition of flammable materials, and preventing the generation of odors.
  • fire extinguishing compositions of the present invention may also be used in combination with powdered fire extinguishing compositions, protein based foam fire extinguishing compositions and synthetic interface foam fire extinguishing compositions comprising materials such as sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, ammonium sulfate, ammonium phosphate, and calcium carbonate.
  • FIG. 1 is an NMR spectrum of a sample of a polyethyleneimine (A-I) representing the cationic polyamine based high molecular weight compound (A), which was measured using an EX-27 FT-NMR device manufactured by NEC Corporation, Ltd. The measurement conditions are listed below.
  • the ratios between the primary amine, secondary amine and tertiary amine groups were calculated from the integral curve for the peaks A to G in FIG. 1 , using the following formulae.
  • Amount of primary amine a F + G
  • Amount of secondary amine b F + D / 2 + E / 2
  • Amount of tertiary amine c A + B + C - F / 2 / 3
  • Primary amine proportion weight % a / a + b + c ⁇ 100
  • Secondary amine proportion weight % b / a + b + c ⁇ 100
  • Tertiary amine proportion weight % c / a + b + c ⁇ 100
  • Table 1 shows the relative proportions of primary amine, secondary amine and tertiary amine groups measured by the above method for polyethyleneimine (A-I) samples representing the cationic polyamine based high molecular weight compound (A), including "EPOMIN P-1050” manufactured by Nippon Shokubai Co. Ltd. (hereafter abbreviated as (A-I-1)), “LUPASOL P” manufactured by BASF Corporation Ltd. of Germany (and hereafter abbreviated as (A-I-2)), N-acylated polyethyleneimine (A-II-1) and (A-II-2) produced by the synthetic example 1 and the synthetic example 2 respectively, as well as derivatives thereof.
  • A-I polyethyleneimine
  • the external appearance, freezing point, kinematic viscosity as measured at -10°C, and the amount of sedimentation in a 3% solution diluted with water from the water supply, for the produced fire extinguishing compositions (3% concentrates), are shown in Table 2 and Table 3 in accordance with the technical specifications listed in the Ministry of Home Affairs Ordinance No. 26. Table 2 Example No.
  • Example 4 A-II-1 B-1-e C-2 totally -17°C 100 cst trace transparent
  • Example 5 A-II-1 B-1-h C-4 totally -17°C 144 cst trace transparent
  • Example 6 A-II-1 B-1-n C-3 totally -18°C 122 cst trace transparent
  • Example 7 A-II-1 B-1-m C-13 totally -16°C 119 cst trace transparent
  • Example 8 A-I-1 B-1-u C-16 totally -19°C 136 cst trace transparent
  • Example 9 A-I-1 B-2-a C-23
  • Example 21 A-I-1 B-4-g C-14 totally -16°C 117 cst trace transparent
  • Example 23 A-I-1 B-5-i C-10 totally -17°C 128 cst trace transparent
  • Example 25 A-I-1 B-6-c C-11 totally -18°C 131 cst trace transparent
  • Example 26 A-I-1 B-6-b C-28 totally -19°C 113 cst trace transparent
  • Example 27 A-II-1 B-6-a C-16 totally -16°C 122 cst trace transparent
  • Example 28 A-II-1 B-6-f C-22 totally -20°C 137 cst trace transparent
  • Example 29 A-II-1 B-6-e C-3 totally -18°
  • Each dilute solution was then used for filling a pressurized tank with 100 liters of solution, and subsequent foam generation was carried out with a standard foam generation nozzle used for testing aqueous film forming foam fire extinguishing compositions (as per national certification), using a nitrogen pressure of 7 kg/cm 2 , a discharge speed of 10 liters/minute, and a total discharge time of 5 minutes.
  • the temperature of the dilute solution was adjusted to a value of 20°C ⁇ 2°C in each case.
  • Experiments were conducted on the time taken for a 90% coverage of the combustion surface area (90% control time) as an indication of the relative superiority of the foam expansion speed, and the time taken for complete fire extinguishing which represents the most salient measure of fire extinguishing speed.
  • fire extinguishing experiments were also conducted on a polar solvent (a solvent for which the solubility in 100 g of water at 20°C is at least 1 g) based on the methods described in the Fire Fighting Hazards No. 71, and the results of these experiments are shown in table 8, table 9, table 10 and table 11.
  • a polar solvent a solvent for which the solubility in 100 g of water at 20°C is at least 1 g
  • Table 8 a polar solvent for which the solubility in 100 g of water at 20°C is at least 1 g
  • Each dilute solution was then used for filling a pressurized tank with 100 liters of solution, and subsequent foam generation was carried out with a standard foam generation nozzle used for testing aqueous film forming foam fire extinguishing compositions (as per national certification), using a nitrogen pressure of 7 kg/cm 2 , a discharge speed of 10 liters/minute, and a total discharge time of 5 minutes.
  • the temperature of the dilute solution was adjusted to a value of 20°C ⁇ 2°C in each case.
  • This value represents the time period from commencement of the foam discharge, until 90% of the combustion surface area of the fire model (combustion surface area 4 m 2 : B-20 scale) was covered with foam.
  • This value represents the time period from commencement of the foam discharge until the flames on the fire model had been completely extinguished.
  • fire extinguishing compositions (3% concentrates) were prepared using the same compositions and mixing methods as the examples described above, but with the exception that a polyethyleneimine or an N-propyl polyethyleneimine in which the amount of primary amine groups exceeds 40% and the amount of secondary amine groups is less than 35%, was used as the cationic polyamine based high molecular weight compound (A) of the present invention.
  • the compounds used for the cationic polyamine based high molecular weight compound (A), the surfactant with an anionic hydrophilic group (B) and the polybasic acid compound (C) are shown in table 12, together with the external appearance, freezing point, kinematic viscosity, and the amount of sedimentation in a 3% solution diluted with water from the water supply, for the produced fire extinguishing compositions (3% concentrates) carried out in accordance with the technical specifications listed in the Ministry of Home Affairs Ordinance No. 26.

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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 (6)

  1. Composition extinctrice d'incendie comprenant un composé de poids moléculaire élevé à base de polyamine cationique (A) qui comporte des groupes cationiques primaires, secondaires et tertiaires à l'intérieur de chaque molécule, un surfactant ayant un groupe anionique hydrophile (B) et un composé d'un acide polybasique (C), caractérisé en ce que les groupes cationiques primaires ne dépassent pas 40 % en poids de tous les groupes cationiques.
  2. Composition extinctrice d'incendie selon la revendication 1, dans laquelle des groupes cationiques secondaires dans le composé de poids moléculaire élevé à base de polyamine cationique (A) constitue au moins 35 % en poids des tous les groupes cationiques.
  3. Composition extinctrice d'incendie selon la revendication 1, dans laquelle le composé de poids moléculaire élevé à base de polyamine cationique (A) est le polyéthylène imine ou un dérivé de celui-ci.
  4. Composition extinctrice d'incendie selon la revendication 1, dans laquelle le composé d'un acide polybasique (C) est un composé d'un acide dibasique ayant de 4 à 18 atomes de carbone.
  5. Composition extinctrice d'incendie selon la revendication 1, dans laquelle le surfactant ayant un groupe anionique hydrophile (B) est un surfactant à base de fluor ayant un groupe aliphatique fluoré de 3 à 20 atomes de carbone en tant qu'un groupe hydrophobe.
  6. Procédé pour éteindre un incendie comprenant les étapes consistant à fournir une composition extinctrice d'incendie selon l'une quelconque des revendications 1 à 5 et appliquer la composition à l'incendie.
EP20010116661 2001-07-13 2001-07-13 Composition extinctrice d'incendie Expired - Lifetime EP1275417B1 (fr)

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DE60140529T DE60140529D1 (de) 2001-07-13 2001-07-13 Feuerlöschende Zusammensetzung

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017179871A3 (fr) * 2016-04-11 2017-11-30 주식회사 라인안전산업 Agent d'extinction d'incendie à flux chargé ayant d'excellentes performances d'extinction d'incendie et son procédé de production

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KR100777764B1 (ko) * 2001-07-11 2007-11-20 다이니혼 잉키 가가쿠 고교 가부시키가이샤 소화약제
CN110124243B (zh) * 2018-02-08 2021-05-11 浙江睦田消防科技开发有限公司 一种耐海水高倍数泡沫灭火剂

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US4536298A (en) * 1983-03-30 1985-08-20 Dainippon Ink And Chemicals, Inc. Aqueous foam fire extinguisher
JPS59230566A (ja) * 1983-05-31 1984-12-25 大日本インキ化学工業株式会社 消火薬剤
US5750043A (en) * 1994-08-25 1998-05-12 Dynax Corporation Fluorochemical foam stabilizers and film formers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017179871A3 (fr) * 2016-04-11 2017-11-30 주식회사 라인안전산업 Agent d'extinction d'incendie à flux chargé ayant d'excellentes performances d'extinction d'incendie et son procédé de production

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DE60140529D1 (de) 2009-12-31

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