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EP1362619B1 - Composition extinctrice d'incendie - Google Patents

Composition extinctrice d'incendie Download PDF

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Publication number
EP1362619B1
EP1362619B1 EP03015503A EP03015503A EP1362619B1 EP 1362619 B1 EP1362619 B1 EP 1362619B1 EP 03015503 A EP03015503 A EP 03015503A EP 03015503 A EP03015503 A EP 03015503A EP 1362619 B1 EP1362619 B1 EP 1362619B1
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EP
European Patent Office
Prior art keywords
composition
extinguishing
fire
fluorinated
fluorinated ketone
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
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EP03015503A
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German (de)
English (en)
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EP1362619A2 (fr
EP1362619A3 (fr
Inventor
Paul Rivers
Richard M. Minday
Fred E. Behr
Daniel R. Vitcak
Richard M. Flynn
Michael G. Costello
Michael J. Parent
John G. Owens
Zhongxing Zhang
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority claimed from EP00948791.9A external-priority patent/EP1261398B2/fr
Publication of EP1362619A2 publication Critical patent/EP1362619A2/fr
Publication of EP1362619A3 publication Critical patent/EP1362619A3/fr
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Publication of EP1362619B1 publication Critical patent/EP1362619B1/fr
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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
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes

Definitions

  • This invention relates to fire extinguishing compositions comprising at least one fluorinated ketone compound and at least one to co-extinguishing agent, and to systems for extinguishing, controlling, or preventing fires using such compositions.
  • Halogenated hydrocarbon fire extinguishing agents have traditionally been utilized in flooding applications protecting fixed enclosures (e.g., computer rooms, storage vaults, telecommunications switching gear rooms, libraries, document archives, petroleum pipeline pumping stations, and the like), or in streaming applications requiring rapid extinguishing (e.g., military flight lines, commercial hand-held extinguishers, or fixed system local application).
  • Such extinguishing agents are not only effective but, unlike water, also function as "clean extinguishing agents," causing little, if any, damage to the enclosure or its contents.
  • bromine-containing compounds e.g., bromotrifluoromethane (CF 3 Br, Halon TM 1301) and bromochlorodifluoromethane (CF 2 ClBr, Halon TM 1211).
  • bromine-containing halocarbons are highly effective in extinguishing fires and can be dispensed either from portable streaming equipment or from an automatic room flooding system activated either manually or by some method of fire detection.
  • these compounds have been linked to ozone depletion.
  • the Montreal Protocol and its attendant amendments have mandated that Halon TM 1211 and 1301 production be discontinued (see, e.g., P. S. Zurer, "Looming Ban on Production of CFCs, Halons Spurs Switch to Substitutes," Chemical & Engineering News, page 12, November 15, 1993 ).
  • Such substitutes should have a low ozone depletion potential; should have the ability to extinguish, control, or prevent fires or flames, e.g., Class A (trash, wood, or paper), Class B (flammable liquids or greases), and/or Class C (electrical equipment) fires; and should be "clean extinguishing agents," i.e., be electrically non-conducting, volatile or gaseous, and leave no residue.
  • substitutes will also be low in toxicity, not form flammable mixtures in air, have acceptable thermal and chemical stability for use in extinguishing applications, and have short atmospheric lifetimes and low global warming potentials.
  • the urgency to replace bromofluorocarbon fire extinguishing compositions is especially strong in the U.S. military (see, e.g., S. O. Andersen et al., "Halons, Stratospheric Ozone and the U.S. Air Force," The Military Engineer, Vol. 80, No. 523, pp. 485-492, August, 1988 ).
  • This urgency has continued throughout the 1990s (see US Navy Halon 1211 Replacement Plan Part 1 - Development of Halon 1211 Alternatives, Naval Research Lab, Washington, D.C., November 1, 1999 ).
  • this invention provides a fire extinguishing composition comprising:
  • the invention provides a system comprising the above composition and means for introducing said composition to a fire.
  • this invention provides a process for controlling or extinguishing fires.
  • the process comprises introducing to a fire or flame (e.g., by streaming or by flooding) the above non-flammable extinguishing composition comprising at least one fluorinated ketone compound containing up to two hydrogen atoms.
  • the extinguishing composition is introduced in an amount sufficient to extinguish the fire or flame.
  • the fluorinated ketone compound can optionally contain one or more catenated (i.e., "in-chain”) oxygen, nitrogen or sulfur heteroatoms and has a boiling point in the range of from about 0° C. to about 150° C.
  • the fluorinated ketone compounds used in the process of the invention are surprisingly effective in extinguishing fires or flames while leaving no residue (i.e., function as clean extinguishing agents).
  • the compounds can be low in toxicity and flammability, have no or very low ozone depletion potentials, and have short atmospheric lifetimes and low global warming potentials relative to bromofluorocarbons, bromochlorofluorocarbons, and many substitutes therefor (e.g., hydrochlorofluorocarbons, hydrofluorocarbons, and perfluorocarbons). Since the compounds exhibit good extinguishing capabilities and are also environmentally acceptable, they satisfy the need for substitutes or replacements for the commonly-used bromine-containing fire extinguishing agents which have been linked to the destruction of the earth's ozone layer.
  • this invention also provides a process for preventing fires in enclosed areas.
  • the present invention also uses fluoroketones of the formula (CF 3 ) 2 CFC(O)CF 2 Cl and CF 3 OCF 2 CF 2 C(O)CF(CF 3 ) 2 in fire extinguishing compositions which include such fluoroketones in amounts sufficient to extinguish a fire.
  • Compounds that can be utilized in the processes and composition of the invention are fluorinated ketone compounds.
  • the compounds are utilized alone or in combination with one another, and in combination with at least one other known extinguishing agent selected from hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoropolyethers, hydrofluoroethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, and hydrobromofluorocarbons.
  • the compounds can be solids, liquids, or gases under ambient conditions of temperature and pressure, but are preferably utilized for extinguishing in either the liquid or the vapor state (or both).
  • normally solid compounds are preferably utilized after transformation to liquid and/or vapor through melting, sublimation, or dissolution in a liquid co-extinguishing agent. Such transformation can occur upon exposure of the compound to the heat of a fire or flame.
  • Fluorinated ketones useful in this invention are ketones which are fully fluorinated, i.e., all of the hydrogen atoms in the carbon backbone have been replaced with fluorine; or ketones which are folly fluorinated except for one or two hydrogen, chlorine, bromine and/or iodine atoms remaining on the carbon backbone.
  • Fire performance is compromised when too many hydrogen atoms are present on the carbon backbone.
  • a fluorinated ketone with three or more hydrogen atoms on the carbon backbone performs more poorly than a ketone with the same fluorinated carbon backbone but having two, one or zero hydrogen atoms, so that significantly more extinguishing composition of the former is required to extinguish a given fire.
  • the fluoroketones may also include those that contain one or more catenated heteroatoms interrupting the carbon backbone in the perfluorinated portion of the molecule.
  • a catenated heteroatom is, for example, a nitrogen, oxygen or sulfur atom
  • the majority of halogen atoms attached to the carbon backbone are fluorine; most preferably, all of the halogen atoms are fluorine so that the ketone is a perfluorinated ketone. More preferred fluorinated ketones have a total of 4 to 8 carbon atoms.
  • perfluorinated ketone compounds suitable for use in the processes and compositions of the invention include CF 3 CF 2 C(O)CF(CF 3 ) 2 , (CF 3 ) 2 CFC(O)CF(CF 3 ) 2 , CF 3 (CF 2 ) 2 C(O)CF(CF 3 ) 2 , CF 3 (CF 2 ) 3 C(O)CF(CF 3 ) 2 , CF 3 (CF 2 ) 5 C(O)CF 3 , CF 3 CF 2 C(O)CF 2 CF 2 CF 3 , CF 3 C(O)CF(CF 3 ) 2 and perfluorocyclohexanone.
  • the fluorinated ketones offer important benefits in environmental friendliness and can offer additional important benefits in toxicity.
  • CF 3 CF 2 C(O)CF(CF 3 ) 2 has low acute toxicity, based on short term inhalation tests with mice exposed for four hours at a concentration of 50,000 ppm in air.
  • CF 3 CF 2 C(O)CF(CF 3 ) 2 has an estimated atmospheric lifetime of 3 to 5 days.
  • Other fluorinated ketones show similar absorbances and are expected to have similar atmospheric lifetimes. As a result of their rapid degradation in the lower atmosphere, the perfluorinated ketones have short atmospheric lifetimes and would not be expected to contribute significantly to global warming.
  • Fluorinated ketones can be prepared by known methods, e.g., by dissociation of perfluorinated carboxylic acid esters by reacting the perfluorinated ester with a source of fluoride ion under reacting conditions, as described in U.S. Patent No. 5,466,877 (Moore et al. ), by combining the ester with at least one initiating reagent selected from the group consisting of gaseous, non-hydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acylating agents.
  • initiating reagent selected from the group consisting of gaseous, non-hydroxylic nucleophiles; liquid, non-hydroxylic nucleophiles; and mixtures of at least one non-hydroxylic nucleophile (gaseous, liquid, or solid) and at least one solvent which is inert to acy
  • the fluorinated carboxylic acid ester precursors can be derived from the corresponding fluorine-free or partially fluorinated hydrocarbon esters by direct fluorination with fluorine gas as described in U.S. Patent No. 5,399,718 (Costello et al. ).
  • Fluorinated ketones that are alpha-branched to the carbonyl group can be prepared as described in, for example, U.S. Patent No. 3,185,734 (Fawcett et al. ) and J. Am. Chem. Soc., v. 84, pp. 4285-88, 1962 .
  • These branched fluorinated ketones are most conveniently prepared by hexafluoropropylene addition to acyl halides in an anhydrous environment in the presence of fluoride ion at an elevated temperature, typically at around 50 to 80°C.
  • the diglyme/fluoride ion mixture can be recycled for subsequent fluorinated ketone preparations, e.g., to minimize exposure to moisture.
  • hexafluoropropylene dimer and/or trimer may reside as a by-product in the branched perfluoroketone product.
  • the amount of dimer and/or trimer may be minimized by gradual addition of hexafluoropropylene to the acyl halide over an extended time period, e.g., several hours.
  • dimer and/or trimer impurities can usually be removed by distillation from the perfluoroketone.
  • the dimer and/or trimer impurity may be conveniently removed in an oxidative fashion by treating the reaction product with a mixture of an alkali metal permanganate in a suitable organic solvent such as acetone, acetic acid, or a mixture thereof at ambient or elevated temperatures, preferably in a sealed vessel.
  • a suitable organic solvent such as acetone, acetic acid, or a mixture thereof at ambient or elevated temperatures, preferably in a sealed vessel.
  • Acetic acid is a preferred solvent for this purpose; it has been observed that acetic acid tends not to degrade the ketone whereas in some instances some degradation of the ketone was noted when acetone was used.
  • the oxidation reaction is preferably carried out at an elevated temperature, i.e., above room temperature, preferably from about 40°C or higher, to accelerate the reaction.
  • the reaction can be carried out under pressure, particularly if the ketone is low boiling.
  • the reaction is preferably carried out with agitation to facilitate complete mixing of two phases which may not
  • acyl halides e.g., acyl halides containing from two to about five carbon atoms
  • significant pressure build-up can occur in the reactor at elevated reaction temperatures (e.g., at temperatures ranging from about 50°C to about 80°C).
  • this pressure build-up can be minimized if only a fraction of the acyl halide charge (e.g., about 5 to 30 percent) is initially added to the reactor and the remaining portion of acyl halide is co-charged with the hexafluoropropylene continuously or in small increments (preferably in an equimolar ratio) over an extended time period (e.g., 1 to 24 hours, depending in part upon the size of the reactor).
  • the initial acyl halide charge and the subsequent co-feeding to the reactor also serves to minimize the production of by-product hexafluoropropylene dimers and/or trimers.
  • the acyl halide is preferably an acyl fluoride and may be perfluorinated (e.g., CF 3 COF, C 2 F 5 COF, C 3 F 7 COF), may be partially fluorinated (e.g., HCF 2 CF 2 COF), or may be unfluorinated (e.g., C 2 H 5 COF), with the product ketone formed being perfluorinated or partially fluorinated.
  • the perfluoroketones may also include those that contain one or more catenated heteroatoms interrupting the carbon backbone in the perfluorinated portion of the molecule, such as, for example, a nitrogen, oxygen or sulfur atom.
  • Perfluorinated ketones which may be linear can be prepared according to the teachings of U.S. Pat. No. 4,136,121 (Martini et al. ) by reacting a perfluorocarboxylic acid alkali metal salt with a perfluorinated acid fluoride. Such ketones can also be prepared according to the teachings of U.S. Pat. No. 5,998,671 (Van Der Puy ) by reacting a perfluorocarboxylic acid salt with a perfluorinated acid anhydride in an aprotic solvent at elevated temperatures.
  • the extinguishing process of the invention can be carried out by introducing a non-flammable extinguishing composition comprising at least one fluorinated ketone compound and at least one co-extinguishing agent to a fire or flame.
  • the fluorinated ketone compounds are utilized alone or in a mixture with each other, and with other commonly used clean extinguishing agents, selected from hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, hydrobromocarbons, iodofluorocarbons, and hydrobromofluorocarbons.
  • co-extinguishing agents can be chosen to enhance the extinguishing capabilities or modify the physical properties (e.g., modify the rate of introduction by serving as a propellant) of an extinguishing composition for a particular type (or size or location) of fire and can preferably be utilized in ratios (of co-extinguishing agent to fluorinated ketone compound(s)) such that the resulting composition does not form flammable mixtures in air.
  • the extinguishing mixture contains from about 10-90% by weight of at least one fluorinated ketone and from about 90-10% by weight of at least one co-extinguishing agent.
  • the fluorinated ketone compound(s) used in the composition has a boiling points in the range of from about 0° C to about 150° C, preferably from about 0° C to about 110° C.
  • the extinguishing composition can preferably be used in either the gaseous or the liquid state (or both), and any of the known techniques for introducing the composition to a fire can be utilized.
  • a composition can be introduced by streaming, e.g., using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed space surrounding a fire or hazard.
  • the composition can optionally be combined with inert propellant, e.g., nitrogen, argon, or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized.
  • fluorinated ketone compound(s) having boiling points in the range of from about 20° C to about 110° C can preferably be utilized.
  • fluorinated ketone compound(s) having boiling points in the range of from about 20° C to about 110° C are generally preferred.
  • fluorinated ketone compound(s) having boiling points in the range of from about 0° C to about 75° C are generally preferred.
  • the extinguishing composition is introduced to a fire or flame in an amount sufficient to extinguish the fire or flame.
  • the amount of extinguishing composition needed to extinguish a particular fire will depend upon the nature and extent of the hazard.
  • cup burner test data e.g., of the type described in the Examples, infra
  • cup burner test data can be useful in determining the amount or concentration of extinguishing composition required to extinguish a particular type and size of fire.
  • This invention also provides an extinguishing composition
  • an extinguishing composition comprising (a) at least one fluorinated ketone compound; and (b) at least one co-extinguishing agent selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons, hydrobromofluorocarbons, and hydrobromocarbons.
  • co-extinguishing agents which can be used in the extinguishing composition include CF 3 CH 2 CF 3 , C 5 F 11 H, C 6 F 13 H, C 4 F 9 H, CF 3 CFHCFHCF 2 CF 3 , H(CF 2 ) 4 H, CF 3 H, C 2 F 5 H, CF 3 CFHCF 3 , CF 3 CF 2 CF 2 H, CF 3 CHCl 2 , CF 3 CHClF, CF 3 CHF 2 , C 3 F 7 OCH 3 , C 4 F 9 OCH 3 , F(C 3 F 6 O)CF 2 H, F(C 3 F 6 O) 2 CF 2 H, HCF 2 O(CF 2 CF 2 0)CF 2 H , HCF 2 O(CF 2 CF 2 O) 2 CF 2 H, HCF2O(CF 2 O)(CF 2 CF 2 O)CF 2 H, C 2 F 5 Cl, CF 3 Br, CF 2 ClB r ,
  • the ratio of co-extinguishing agent to fluorinated ketone is preferably such that the resulting composition does not form flammable mixtures in air (as defined by standard test method ASTM E681-85).
  • the weight ratio of co-extinguishing agent to fluorinated ketone may vary from about 9:1 to about 1:9.
  • fluorinated ketone compositions can be utilized in co-application processes with not-in-kind fire-fighting technologies to provide enhanced extinguishing capabilities.
  • the liquid composition CF 3 CF 2 C(O)CF(CF 3 ) 2 can be introduced into an aqueous film forming foam (AFFF) solution stream, for example, utilizing a Hydro-Chem TM nozzle manufactured by Williams Fire & Hazard Control, Inc., Mauriceville, TX to give the AFFF three-dimensional fire-fighting capability.
  • AFFF aqueous film forming foam
  • the AFFF can carry the CF 3 CF 2 C(O)CF(CF 3 ) 2 a much longer distance than it could be delivered by itself to a remote three dimensional fuel fire, allowing the CF 3 CF 2 C(O)CF(CF 3 ) 2 to extinguish the three-dimensional fuel fire where the AFFF stream by itself would not.
  • Another co-application process utilizing fluorinated ketones can be extinguishing a fire using a combination of a gelled halocarbon with dry chemical.
  • a dry chemical can be introduced in suspension in the liquid CF 3 CF 2 C(O)CF(CF 3 ) 2 and discharged from a manual handheld extinguisher or from a fixed system.
  • Yet another co-application process utilizing fluorinated ketones is the process where the fluorinated ketone is super-pressurized upon activation of a manual hand-held extinguisher or a fixed system using an inert off-gas generated by the rapid burning of an energetic material such as glycidyl azide polymer.
  • rapid burning of an energetic material such as glycidyl azide polymer that yields a hot gas can be used to heat and gasify a liquid fluorinated ketone of the invention or other liquid fire extinguishing agent to make it easier to disperse.
  • an unheated inert gas e.g., from rapid burning of an energetic material
  • the above-described fluorinated ketone compounds can be useful not only in controlling and extinguishing fires but also in preventing the combustible material from igniting.
  • the invention thus also provides a process for preventing fires or deflagration in an air-containing, enclosed area which contains combustible materials of the self-sustaining or non-self-sustaining type.
  • the process comprises the step of introducing into an air-containing, enclosed area a non-flammable extinguishing composition which is essentially gaseous, i.e., gaseous or in the form of a mist, under use conditions and which comprises at least one fluorinated ketone compound containing up to two hydrogen atoms, optionally up to two halogen atoms selected from chlorine, bromine, iodine, and a mixture thereof, and optionally containing additional catenated heteroatoms, and the composition being introduced and maintained in an amount sufficient to impart to the air in the enclosed area a heat capacity per mole of total oxygen present that will suppress combustion of combustible materials in the enclosed area.
  • a non-flammable extinguishing composition which is essentially gaseous, i.e., gaseous or in the form of a mist, under use conditions and which comprises at least one fluorinated ketone compound containing up to two hydrogen atoms, optionally up to two halogen atoms selected from chlorine
  • Introduction of the extinguishing composition can generally be carried out by flooding or misting, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed space surrounding a fire.
  • any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals.
  • Inert propellants such as those propellants generated by decomposition of energetic materials such as glycidyl azide polymers, can optionally be used to increase the rate of introduction.
  • fluorinated ketone compound(s) (and any co-extinguishing agent(s) utilized) can be chosen so as to provide an extinguishing composition that is essentially gaseous under use conditions.
  • Preferred compound(s) have boiling points in the range of from about 0° C to about 110° C.
  • the composition is introduced and maintained in an amount sufficient to impart to the air in the enclosed area a heat capacity per mole of total oxygen present that will suppress combustion of combustible materials in the enclosed area.
  • the minimum heat capacity required to suppress combustion varies with the combustibility of the particular flammable materials present in the enclosed area.
  • Combustibility varies according to chemical composition and according to physical properties such as surface area relative to volume, porosity, etc.
  • a minimum heat capacity of about 45 cal/°C per mole of oxygen is adequate to extinguish or protect moderately combustible materials (e.g., wood and plastics), and a minimum of about 50 cal/°C per mole of oxygen is adequate to extinguish or protect highly combustible materials (e.g., paper, cloth, and some volatile flammable liquids).
  • Greater heat capacities can be imparted if desired but may not provide significantly greater fire suppression for the additional cost involved.
  • Methods for calculating heat capacity (per mole of total oxygen present) are well-known (see, e.g., the calculation described in U.S. Patent No. 5,040,609 (Dougherty et al. ).
  • the fire prevention process of the invention can be used to eliminate the combustion-sustaining properties of air and to thereby suppress the combustion of flammable materials (e.g., paper, cloth, wood, flammable liquids, and plastic items).
  • flammable materials e.g., paper, cloth, wood, flammable liquids, and plastic items.
  • the process can be used continuously if a threat of fire always exists or can be used as an emergency measure if a threat of fire or deflagration develops.
  • the reactor contents were allowed to cool and were one-plate distilled to obtain 307.1 g containing 90.6% 1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluoromethyl-pentane-3-one and 0.37% C 6 F 12 (hexafluoropropylene dimer) as determined by gas chromatography.
  • the crude fluorinated ketone was water-washed, distilled, and dried by contacting with silica gel to provide a fractionated fluorinated ketone of 99% purity and containing 0.4% hexafluoropropylene dimers.
  • a fractionated fluorinated ketone made according to the same procedures as in Example 1 was purified of dimers using the following procedure.
  • Into a clean dry 600 mL Parr reactor equipped with stirrer, heater and thermocouple were added 61 g of acetic acid, 1.7 g of potassium permanganate, and 301 g of the above-described fractionated 1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluoromethyl-pentane-3-one.
  • the reactor was sealed and heated to 60°C, while stirring, reaching a pressure of 12 psig (1400 torr). After 75 minutes of stirring at 60°C, a liquid sample was taken using a dip tube, the sample was phase split and the lower phase was washed with water.
  • the sample was analyzed using glc and showed undetectable amounts of hexafluoropropylene dimers and small amounts of hexafluoropropylene trimers.
  • a second sample was taken 60 minutes later and was treated similarly. The glc analysis of the second sample showed no detectable dimers or trimers.
  • the reaction was stopped after 3.5 hours, and the purified ketone was phase split from the acetic acid and the lower phase was washed twice with water. 261 g of the ketone was collected, having a purity greater than 99.6% by glc and containing no detectable hexafluoropropylene dimers or trimers.
  • Example 2 The following example was run to demonstrate the use of KMnO 4 /acetic acid to purify C 2 F 5 COCF(CF 3 ) 2 , made according to the teachings set forth in Example 1, which contained a high concentration (about 5%) of hexafluoropropylene dimers.
  • the fluorinated ketone was distilled from the acetic acid, 255 g was collected, and the distilled ketone was washed twice with water. Ultimately, 242 g of the ketone was collected, having a purity of greater than 99.1% with no detectable hexafluoropropylene dimers or trimers (by glc).
  • Example 2 The following example was run to demonstrate the use of KMnO 4 /acetone to purify C 2 F 5 COCF(CF 3 ) 2 , made according to the teachings set forth in Example 1, which contained a very high concentration (about 20%) of hexafluoropropylene dimers.
  • a two liter three-necked round bottom flask was equipped with an overhead air stirrer, water condenser and addition funnel.
  • 360 g of acetone and 78 g (0.49 mol) of potassium permanganate were placed in the flask and the contents cooled to about 18°C.
  • 357 g (0.90 mol) of C 2 F 5 COCF(CF 3 ) 2 (80% purity and containing about 20% hexafluoropropylene dimers, made according to the general procedure described in Example 1), was added slowly dropwise to the cooled contents. After the addition was complete, the resulting solution was stirred for about two hours at room temperature.
  • the ketone was then distilled from the combined product/sulfuric acid mixture as an azeotrope with the residual acetone.
  • the resulting distillate contained two phases which were separated, and the lower phase was washed again with deionized water to provide 138 g of C 2 F 5 COCF(CF 3 ) 2 in a purity of 99.7% and which contained no hexafluoropropylene dimers nor any acetone as determined by glc.
  • Example 3 65% (CF 3 ) 2 CFC(O)CF(CF 3 ) 2 , 35% CF 3 CF 2 CF 2 C(O)CF(CF 3 ) 2 - a blend of compounds from Examples 2 and 7, respectively
  • a mixture consisting of 421 g of trifluoroacetic anhydride, 319.5 g of anhydrous diglyme, 131 g of anhydrous potassium fluoride and 315 g of hexafluoropropylene was heated in a 3-liter HASTELLOY TM (Haynes, Inc., Kokomo, IN) pressure vessel under autogenous pressure at 50°C for 16 hours.
  • the gaseous product was fractionally distilled to give 319.1 g of 1,1,1,3,4,4,4-heptafluoro-3-trifluoromethyl-butan-2-one having a boiling point of 25°C. Purity was 99.6% as determined by gas chromatography. The structure was verified using nuclear magnetic resonance spectroscopy.
  • the resulting aqueous solution was then separated into two portions, and each portion was extracted twice with about 170 g of diethyl ether. The two aqueous portions were recombined, and a final extraction of the entire aqueous solution was then carried out using 205 g of diethyl ether.
  • the ether solution portions were combined and the combined portions were then neutralized and extracted by vigorous stirring with 100 g of 40% aqueous potassium hydroxide.
  • the ether layer was discarded and the water was removed from the dark blue aqueous layer by heating at 50-60°C under aspirator vacuum until nearly dry. Hexane was added and distilled off to azeotropically remove the last residue of water from the chromium salt.
  • the entire recovered acid product was treated with 264 g (1.35 mol) of benzotrichloride, and the resulting mixture was heated to 70°C for 19 hours.
  • Some of the desired acid chloride product, HC 2 F 4 C(O)Cl, distilled from the reaction mixture during this time and was collected in an ice water-cooled trap. The contents of the trap were combined with the reaction mixture and were distilled to yield 70g of acid chloride having 95% purity as determine by glc, and having a (C O) stretch of 1795 cm -1 as determined by infrared spectroscopy. This product was used without further purification in the next step.
  • the final ketone product 1,1,1,2,4,4,5,5-octafluoro-2-trifluoromethylpentan-3-one, was prepared by fluoride-catalyzed addition of hexafluoropropylene to HC 2 F 4 C(O)F using essentially the same procedure as described by R D. Smith et al. in J. Am. Chem. Soc., 84, 4285 (1962 ).
  • the resulting fluorinated ketone product had a boiling point of 70-71 °C.
  • This diketone is available from Sigma Aldrich Chemical Co .
  • Perfluorodibutyl oxalate was prepared from direct fluorination of dibutyl oxalate using essentially the same procedure as described in U.S. Patent No. 5,488,142 (Fall et al. ).
  • a mixture of 1002 g of perfluorodibutyl oxalate, 1008 g of anhydrous diglyme, 40.4 g of anhydrous potassium fluoride and 806 g of hexafluoropropylene was heated in a 3-liter HASTELLOY TM pressure vessel under autogenous pressure with stirring for 16 hours at 50°C. The resulting reaction .
  • This linear ketone can be prepared using essentially the same procedure as described in U.S. Pat. No 4,136,121 (Martini et al. ), for example, by reacting CF 3 CF 2 CF 2 COO - K + with CF 3 CF 2 CF 2 COF in tetraethylene glycol dimethyl ether for about 60 hours at a temperature of about 100°C.
  • the gaseous ketone product was fractionated to give 435 g. of 1,1,1,3,3,4,4,4-octafluoro-butan-2-one, having a boiling point of 0°C, with purity of 99.7% as determined by gas chromatography and mass spectroscopy.
  • 1686 g of the purified hemiketal was slowly added to 1800 mL of concentrated sulfuric acid and was re-fractionated to give 1054 g decafluorocyclohexanone having a boiling point of 53°C and having a purity of greater than 95% as determined by gas chromatography (55.7% yield). The structure was confirmed by nuclear magnetic resonance spectroscopy.
  • a mixture consisting of 775 g of perfluoropentanoyl fluoride, 800 g of anhydrous diglyme, 13.1 g of potassium fluoride, 17.8 g of anhydrous potassium bifluoride and 775 g of hexafluoropropylene was heated in a 3-liter stainless steel pressure vessel under autogeneous pressure at 50°C for 16 hours.
  • the product was fractionally distilled to give 413 g of 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-trifluoromethyl-heptan-3-one, having a boiling point of 97°C and a 99.0% purity as determined by gas chromatography and mass spectroscopy.
  • HALONTM 1211 fire extinguishing agent This manufacture of this product, commercially known as HALONTM 1211 fire extinguishing agent, was commercially phased out as of January 1, 1994 in countries signatory to Montreal Protocol.
  • TRIODIDETM fire extinguishing agent from Pacific Scientific, Carpinteria, CA.
  • This compound is available as FE-36TM fire extinguishing agent from E. I. duPont de Nemours & Co., Wilmington, DE.
  • This mixture is an 80/20 blend of CF 3 CHCl 2 (HCFC-123 or 2,2-dichloro-1,1,1-trifluoroethane - available from Sigma Aldrich Chemical Co.) and CF 4 (tetrafluoromethane - available from Sigma Aldrich Chemical Co., Milwaukee, WI).
  • This compound is available as FM-200TM fire extinguishing agent from Great Lakes Chemical, West Lafayette, IN.
  • This compound is available as 3MTM CEA-308 fire extinguishing agent from 3M Company, St. Paul, MN.
  • This compound is available as 3MTM CEA-410 fire extinguishing agent from 3M Company.
  • This compound is available as 3MTM CEA-614 fire extinguishing agent from 3M Company.
  • This compound is available from 3M Company, St. Paul, MN as NOVECTM HFE-7100 engineering fluid, which is an isomeric mixture of approximately 60% (CF 3 ) 2 CFCF 2 OCH 3 and approximately 40% CF 3 CF 2 CF 2 CF 2 OCH 3 .
  • a jacketed one liter round bottom flask was equipped with an overhead stirrer, a solid carbon dioxide/acetone condenser, and an addition funnel.
  • the flask was charged with 85 g (1.46 mol) of anhydrous potassium fluoride and 375 g of anhydrous diglyme, and the flask and its contents were then cooled to about -20°C using a recirculating refrigeration system.
  • 196 g (1.18 mol) of C 2 F 5 COF was further added to the flask over a period of about one hour.
  • the flask was then warmed to about 24°C, and 184.3 g (1.46 mol) of dimethyl sulfate was then added dropwise via the addition funnel over a 45 minute period.
  • the Micro-Cup Burner Test is a laboratory test which measures the extinguishing ability of an agent based on the quantity of agent required to extinguish a fire under the following test conditions.
  • the Micro-Cup Burner Test utilizes a quartz concentric-tube laminar-diffusion flame burner (micro-cup burner, of similar design to the above-described cup apparatus) aligned vertically with all flows upward.
  • a fuel typically propane unless otherwise specified, flows at 10.0 sccm (standard cubic centimeters per minute) through a 5-mm I.D. inner quartz tube which is centered in a 15-mm I.D. quartz chimney. The chimney extends 4.5 cm above the inner tube.
  • extinguishing composition Prior to the addition of extinguishing composition, a visually stable flame is supported on top of the inner tube, and the. resulting combustion products flow out through the chimney.
  • An extinguishing composition to be evaluated is introduced into the air stream upstream of the burner.
  • Liquid compositions are introduced by a syringe pump (which is calibrated to within 1%) and are volatilized in a heated trap.
  • Gaseous compositions are introduced via a mass-flow controller to the air stream upstream from the burner. For consistency, the air-gaseous composition mixture then flows through the heated trap prior to its introduction to the flame burner.
  • a gas flows are maintained by electronic mass-flow controllers which are calibrated to within 2%.
  • the fuel is ignited to produce a flame and is allowed to burn for 90 seconds. After 90 seconds, a specific flow rate of composition is introduced, and the time required for the flame to be extinguished is recorded.
  • the reported extinguishing concentrations are the recorded volume % of extinguishing composition in air required to extinguish the flame within an average time of 30 seconds or less.
  • the above-mentioned cup burner test measures the performance of an extinguishing composition by determining the minimum volume percent of composition in air required to extinguish a test fire.
  • an experimental extinguishing composition e.g., a fluorinated ketone
  • a state-of-the-art extinguishing composition such as HALONTM 1211 fire extinguishing agent (CF 2 ClBr, a bromochlorofluorocarbon).
  • HALONTM 1211 fire extinguishing agent CF 2 ClBr, a bromochlorofluorocarbon
  • the mass ratio can be calculated by dividing the experimental composition's extinguishing volume percent by the HALONTM 1211 agent's extinguishing volume percent and multiplying the resulting quotient (which, according to the ideal gas law, also represents the ratio of mole percents) times the weight average molecular weight of the experimental composition divided by the molecular weight of HALONTM 1211 agent (165 g/mole).
  • Comparative Examples C12-C13 two fluorinated ketones, each containing three hydrogen atoms on the carbon backbone, were evaluated for their extinguishing concentration and their mass ratio with respect to HALONTM 1211 agent.
  • the data demonstrate generally superior fire extinguishing performance of the perfluoroketones when compared to partially fluorinated ketones with approximately the same carbon number.
  • CF 3 (CF 2 ) 5 C(O)CF 3 (Ex. 4) and CF 3 C(O)CF(CF 3 ) 2 (Ex. 5) where the ketone has a trifluoromethyl group on one side of the carbonyl group and has a perfluorinated alkyl group of 3 or 6 carbons on the other side, both show a lower "Mass Ratio to HALONTM 1211" value (2.17 and 2.19, respectively) than do either (CF 3 ) 2 CFC(O)CH 3 (Comp. Ex.
  • a standard off-the-shelf Amerex 131b HALON TM 1211 handheld extinguisher was used to introduce the extinguishing composition to the fire.
  • the extinguisher was equipped with a standard 1/2 in (1.3 cm) nominal diameter rubber hose with a clean extinguishing agent nozzle attached to the end.
  • the composition was super-pressurized using dry nitrogen at 130-150 psi (900-1040 kPa).
  • the only modification to the standard extinguisher apparatus was that the nozzle orifice used had a slightly larger diameter (0.277 in, 0.70 cm) than did the standard nozzle orifice (0.234 in, 0.60 cm).
  • a 2B UL-rated extinguisher rating requires a skilled firefighter to be able to extinguish a 5 ft 2 (0.46 m 2 ) fire
  • a 5B UL-rated extinguisher rating requires extinguishing a 12.5 ft 2 (1.16 m 2 ) fire
  • the UL specified pans were 12 in (30 cm) deep, into which was introduced 4.0 in (10 cm) of water, onto which was introduced 2 in (5 cm) of commercial grade heptane for fuel, leaving a 6 in (15 cm) freeboard above the fuel surface.
  • Each fire was allowed to pre-burn 60 seconds before extinguishing commenced, using an agent flow rate of 0.75-0.80 kg/sec.
  • the discharge time for the extinguishing of the fire was recorded as was the amount of agent discharged.
  • This example was run to evaluate the fire performance of a fluorinated ketone, CF 3 CF 2 C(O)CF(CF 3 ) 2 (the fluorinated ketone as prepared in Example 1), in a total flooding evaluation for a clean extinguishing agent.
  • a Swagelok Whitey 2000 mL cylinder was filled with 1000 g of CF 3 CF 2 C(O)CF(CF 3 ) 2 and was super-pressurized with nitrogen to 50 psi (345 kPa).
  • Attached to the bottom of the cylinder was a 0.25 in (0.6 cm) Swagelok Whitey SS1RFA-A stainless steel angle valve, to which was fixed 34 in (86.4 cm) of nominal 0.25 in (6.5 mm) piping arrangement, including a 0.25 in (6.5 mm) Jamesbury Clincher 1/4-turn ball valve.
  • the piping was connected to a Bete NF 0500 square edge orifice nozzle.
  • the Bete nozzle was installed to discharge horizontally from a side wall of the box equidistant from two adjacent walls of the enclosure, at a point 35 cm down from the ceiling of the enclosure.
  • the fire testing procedure followed was essentially the same as that described in the Ohmic Heating Test performed by Hughes Associates, Inc., Baltimore, MD (see section A-3-6 of the 2000 Edition of the National Fire Protection Association NFPA 2001, Standard for Clean Agent Fire Extinguishing Systems).
  • the discharge time was approximately 50 seconds and extinguishing of the obstructed fire using CF 3 CF 2 C(O)CF(CF 3 ) 2 was achieved within 35 seconds from the beginning of agent discharge, indicating good performance as a flooding clean extinguishing agent.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Composition extinctrice d'incendie comprenant :
    (a) au moins une cétone fluorée renfermant jusqu'à deux atomes d'hydrogène et présentant un point d'ébullition d'environ 0 °C à environ 150 °C ; et
    (b) au moins un agent co-extincteur choisi parmi le groupe constitué d'hydrofluorocarbures, d'hydrochlorofluorocarbures, d'hydrofluoroéthers, d'hydrofluoropolyéthers, de chlorofluorocarbures, de bromofluorocarbures, de bromochlorofluorocarbures, d'iodofluorocarbures, d'hydrobromofluorocarbures, d'hydrobromocarbures et de leurs mélanges.
  2. Composition selon la revendication 1, dans laquelle (a) et (b) sont dans un rapport pondéral d'environ 9:1 à environ 1:9.
  3. Composition selon la revendication 1, dans laquelle la cétone fluorée renferme en outre jusqu'à deux atomes d'halogène choisis parmi le groupe constitué du chlore, du brome, de l'iode et d'un mélange de ceux-ci.
  4. Composition selon la revendication 1, dans laquelle la cétone fluorée renferme un total de 4 à 8 atomes de carbone.
  5. Composition selon la revendication 1, dans laquelle la cétone fluorée présente un point d'ébullition d'environ 0 °C à environ 110 °C.
  6. Composition selon la revendication 1, dans laquelle la cétone fluorée présente un point d'ébullition d'environ 0 °C à environ 75 °C.
  7. Composition selon la revendication 1, dans laquelle la cétone fluorée est au moins un composé choisi parmi le groupe constitué du CF3CF2C(O)CF(CF3)2, du (CF3)2CFC(O)CF(CF3)2, du CF3(CF2)2C(O)CF(CF3)2, du CF3(CF2)3C(O)CF(CF3)2, du CF3(CF2)5C(O)CF3, du CF3CF2C(O)CF2CF2CF3, du CF3C(O)CF(CF3)2, de la perfluorocyclohexanone et de leurs mélanges.
  8. Composition selon la revendication 1, dans laquelle la cétone fluorée est le C2F5C(O)CF(CF3)2.
  9. Composition selon la revendication 1, dans laquelle l'agent co-extincteur est choisi parmi le groupe constitué du CF3CH2CF3, du C5F11H, du C6F13H, du C4F9H, du CF3CFHCFHCF2CF3, du H(CF2)4H, du CF3H, du C2F5H, du CF3CFHCF3, du CF3CF2CF2H, du CF3CHCl2, du CF3CHClF, du CF3CHF2, du C3F7OCH3, du C4F9OCH3, du F(C3F6O)CF2H, du F(C3F6O)2CF2H, HCF2O(CF2CF2O)CF2H, du HCF2O(CF2CF2O)2CF2H, du HCF2O(CF2O)(CF2CF2O)CF2H, du C2F5Cl, du CF3Br, du CF2ClBr, du CF3I, CF2HBr, du n-C3H7Br, du CF2BrCF2Br, et de leurs mélanges.
  10. Système comprenant une composition selon l'une quelconque des revendications 1 à 9 et un moyen pour introduire ladite composition dans un incendie.
  11. Système selon la revendication 10, dans lequel ledit moyen comprend au moins l'un parmi un équipement de jet et un équipement de noyage.
  12. Système selon la revendication 10, dans lequel ledit moyen combine ladite composition avec un propulseur inerte.
  13. Procédé pour maîtriser ou éteindre des incendies, où le procédé comprend l'introduction dans un incendie ou une flamme d'une composition extinctrice d'incendie telle que définie dans l'une quelconque des revendications 1 à 9.
  14. Utilisation d'une composition telle que définie dans l'une quelconque des revendications 1 à 9 dans un procédé pour maîtriser ou éteindre des incendies ou un procédé pour la prévention d'incendies dans des endroits fermés.
EP03015503A 1999-07-20 2000-07-19 Composition extinctrice d'incendie Expired - Lifetime EP1362619B1 (fr)

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