WO1996022129A1 - Fire extinguishing process and composition - Google Patents
Fire extinguishing process and composition Download PDFInfo
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- WO1996022129A1 WO1996022129A1 PCT/US1996/000425 US9600425W WO9622129A1 WO 1996022129 A1 WO1996022129 A1 WO 1996022129A1 US 9600425 W US9600425 W US 9600425W WO 9622129 A1 WO9622129 A1 WO 9622129A1
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Classifications
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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
- A62D1/0071—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 partially-fluorinated compound and to processes for
- extinguishing agents have traditionally been utilized. Such agents are not only effective but, unlike water, also function as "clean extinguishing agents," causing little, if any, damage to the enclosure or its
- halogenated hydrocarbon extinguishing agents have been bromine-containing compounds, e.g., bromotrifluoromethane
- halocarbons are highly effective in extinguishing fires and can be dispensed either from portable equipment or from an automatic room flooding system activated by a fire detector.
- the compounds have been linked to ozone depletion.
- the Montreal Protocol and its attendant amendments specified that Halon 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).
- 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
- U.S. Patent Nos. 5,040,609 and 5,115,868 describe a process for extinguishing, preventing, and controlling fires using a composition containing CHF 3 .
- U.S. Patent No. 5,084,190 discloses a process for extinguishing, preventing, and controlling fires using a composition containing at least one fluoro-substituted propane.
- U.S. Patent No. 5,124,053 (Iikubo et al.) discloses the use of highly fluorinated, saturated C 2 and C 3 hydrofluorocarbons as fire extinguishing agents.
- U.S. Patent No. 5,250,200 (Sallet) describes an environmentally safe fire fighting technique which comprises directing a fire/flame extinguishing amount of an essentially zero ODP hydrofluoroalkane compound (other than a tetrafluoroethane or pentafluoroethane) onto a burning fire or flame.
- 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) a non-flammable (under use conditions) extinguishment composition comprising at least one mono- or dialkoxy-substituted
- the extinguishment composition is introduced in an amount sufficient to extinguish the fire or flame.
- the compound used in the composition can optionally contain one or more additional catenary (i.e., in-chain) heteroatoms (e.g., oxygen or nitrogen) in its perfluorinated portion and preferably has a boiling point in the range of from about 0°C to about 150°C.
- the alkoxy-substituted perfluorocompounds used in the process of the invention are surprisingly effective in extinguishing fires or flames, yet most of them leave no residue (i.e., function as clean extinguishing agents).
- the compounds exhibit
- the compounds are low in toxicity and flammability, have ozone depletion
- bromofluorocarbons bromochlorofluorocarbons, and many substitutes therefor (e.g., hydrochlorofluorocarbons and hydrofluorocarbons). Since the compounds exhibit good extinguishment capabilities while being
- perfluorocycloalkane perfluorocycloalkyl-containing perfluoroalkane
- perfluorocycloalkylene-containing perfluoroalkane compounds include those which contain additional catenary heteroatom(s) in the perfluorinated portion of the molecule (as well as those which do not) and can be utilized alone, in combination with one another, or in combination with other common extinguishing agents (e.g.,
- hydrofluorocarbons hydrochlorofluorocarbons
- bromofluorocarbons bromochlorofluorocarbons
- the compounds can be solids, liquids, or gases under ambient conditions of temperature and pressure, but are preferably utilized for extinguishment in either the liquid or the vapor state (or both). Thus, normally solid compounds are preferably utilized after
- tranformation to liquid and/or vapor through melting. sublimation, or dissolution in liquid co-extinguishing agent. Such tranformation can occur upon exposure of the compound to the heat of a fire or flame.
- a class of useful alkoxy-substituted perfluorocompounds is that which can be represented by the following general formula (I):
- R f (O-R h ) x (I) wherein x is an integer of 1 or 2; when x is 1, R f is selected from the group consisting of linear or
- R f is selected from the group consisting of linear or branched
- perfluoroalkanediyl groups or perfluoroalkylidene groups having from 4 to about 8 carbon atoms are examples of perfluoroalkanediyl groups or perfluoroalkylidene groups having from 4 to about 8 carbon atoms
- perfluorocycloalkylidene groups having from 4 to about 8 carbon atoms; and each R h is independently selected from the group consisting of alkyl groups having from 1 to about 2 carbon atoms; and wherein R f (but not R h ) can contain (optionally contains) one or more catenary heteroatoms.
- perfluorocycloalkylene groups contained within the perfluoroalkyl, perfluoroalkanediyl, and
- perfluoroalkylidene groups can optionally (and
- x is 1, and the compound is normally liquid or gaseous (i.e., liquid or gaseous under ambient conditions of temperature and pressure).
- x is 1; R f is selected from the group consisting of linear or branched perfluoroalkyl groups having from 3 to about 6 carbon atoms,
- perfluorocycloalkyl-containing perfluoroalkyl groups having from 5 to about 7 carbon atoms
- R h is a methyl group
- R f can contain one or more catenary heteroatoms
- the sum of the number of carbon atoms in R f and the number of carbon atoms in R h is greater than or equal to 4.
- perfluoroalkanediyl, and perfluoroalkylidene groups can optionally (and independently) be substituted with, e.g., one or more perfluoromethyl groups.
- alkoxy-substituted perfluorocompounds suitable for use in the processes and composition of the invention include the following compounds:
- alkoxy-substituted perfluorocompounds suitable for use in the process of the invention can be prepared by alkylation of perfluorinated alkoxides prepared by the reaction of the corresponding
- perfluorinated acyl fluoride or perfluorinated ketone with an anhydrous alkali metal fluoride e.g.,
- a fluorinated tertiary alcohol can be allowed to react with a base, e.g., potassium hydroxide or sodium hydride, to produce a perfluorinated tertiary alkoxide which can then be alkylated by reaction with alkylating agent.
- a base e.g., potassium hydroxide or sodium hydride
- Suitable alkylating agents for use in the preparation include dialkyl sulfates (e.g., dimethyl sulfate), alkyl halides (e.g., methyl iodide), alkyl p-toluenesulfonates (e.g., methyl p-toluenesulfonate), alkyl perfluoroalkanesulfonates (e . g . , methyl
- Suitable polar, aprotic solvents include acyclic ethers such as diethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; carboxylic acid esters such as methyl formate, ethyl formate, methyl acetate, diethyl carbonate, propylene carbonate, and ethylene carbonate; alkyl nitriles such as
- N-methylpyrrolidone alkyl sulfoxides such as dimethyl sulfoxide; alkyl sulfones such as dimethylsulfone, tetramethylene sulfone, and other sulfolanes; oxazolidones such as N-methyl-2-oxazolidone; and mixtures thereof.
- Perfluorinated acyl fluorides for use in preparing the alkoxy-substituted perfluorocompounds
- ECF electrochemical fluorination
- KF.2HF Phillips ECF
- perfluorinated ketones can also be prepared by
- hydrocarbon or partially-fluorinated carboxylic acid esters by direct fluorination with fluorine gas).
- Dissociation can be achieved by contacting the
- perfluorinated ester with a source of fluoride ion under reacting conditions (see the method described in U.S. Patent No. 3,900,372 (Childs)) or 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.
- 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 reagents which can be employed in the dissociation are those gaseous or liquid, non-hydroxylic nucleophiles and mixtures of gaseous, liquid, or solid, non-hydroxylic nucleophile(s) and solvent (hereinafter termed "solvent mixtures") which are capable of nucleophilic reaction with
- Suitable gaseous or liquid, non-hydroxylic nucleophiles include dialkylamines, trialkylamines, carboxamides, alkyl sulfoxides, amine oxides, oxazolidones, pyridines, and the like, and mixtures thereof.
- Suitable non- hydroxylic nucleophiles for use in solvent mixtures include such gaseous or liquid, non-hydroxylic
- nucleophiles as well as solid, non-hydroxylic
- nucleophiles e.g., fluoride, cyanide, cyanate, iodide, chloride, bromide, acetate, mercaptide, alkoxide, thiocyanate, azide, trimethylsilyl difluoride,
- bifluoride anions which can be utilized in the form of alkali metal, ammonium, alkyl-substituted ammonium (mono-, di-, tri-, or tetra-substituted), or quaternary phosphonium salts, and mixtures thereof.
- alkali metal ammonium, alkyl-substituted ammonium (mono-, di-, tri-, or tetra-substituted), or quaternary phosphonium salts, and mixtures thereof.
- Such salts are i-n general
- the extinguishment process of the invention can be carried out by introducing a non-flammable extinguishment composition comprising at least one of the above-described alkoxy-substituted
- chlorofluorocarbons bromofluorocarbons
- co-extinguishing agents can be chosen to enhance the extinguishment capabilities or modify the physical properties (e.g., modify the rate of introduction by serving as a
- propellant of an extinguishment composition for a particular type (or size or location) of fire can preferably be utilized in ratios (of co-extinguishing agent to perfluorocompound(s)) such that the resulting composition does not form flammable mixtures in air.
- the perfluorocompound(s) used in the composition have boiling points in the range of from about 0°C to about 150°C, more preferably from about 0°C to about 110°C.
- the extinguishment composition can preferably be used in either the gaseous or the liquid state (or both), and any of the known techniques for
- 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).
- streaming e.g., using conventional portable (or fixed) fire extinguishing equipment
- flooding e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed space surrounding a fire).
- the 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).
- the 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
- inert propellant e.g., nitrogen, argon, or carbon dioxide
- perfluorocompound(s) having boiling points in the range of from about 20°C to about 110°C (especially normally liquid
- perfluorocompounds can preferably be utilized.
- the composition is to be introduced by misting,
- perfluorocompound(s) having boiling points in the range of from about 20°C to about 110°C are generally
- perfluorocompound (s) having boiling points in the range of from about 0°C to about 70°C especially normally gaseous perfluorocompounds are generally preferred.
- the extinguishment composition is introduced to a fire or flame in an amount sufficient to extinguish the fire or flame.
- the amount of extinguishment 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
- extinguishment composition required to extinguish a particular type and size of fire.
- This invention also provides an
- extinguishment composition comprising (a) at least one mono- or dialkoxy-substituted perfluoroalkane,
- perfluorocycloalkane perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound, the compound optionally containing additional catenary heteroatoms in its perfluorinated portion; and (b) at least one co- extinguishing agent selected from the group consisting of hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, chlorofluorocarbons,
- bromofluorocarbons bromochlorofluorocarbons
- co-extinguishing agent is selected from the group consisting of hydrofluorocarbons,
- chlorofluorocarbons bromofluorocarbons
- bromochlorofluorocarbons and hydrobromofluorocarbons; more preferably, hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons, and
- hydrobromofluorocarbons are utilized.
- Representative examples of co-extinguishing agents which can be used in the extinguishment composition include CF 3 CH 2 CF 3 , C 5 F 11 H, C 6 F 13 H, C 4 F 9 H, HC 4 F 8 H, CF 3 H, C 2 F 5 H, CF 3 CFHCF 3 ,
- the ratio of co-extinguishing agent to perfluorocompound is preferably such that the resulting composition does not form flammable mixtures in air (as defined by standard test method ASTM E681-85).
- the invention thus also provides a process for preventing fires or deflagration in an air-containing, enclosed area which contains combustible materials of the non-self-sustaining type.
- the process comprises the step of introducing into an air-containing, enclosed area a non-flammable
- gaseous i.e., gaseous or in the form of a mist, under use conditions and which comprises at least one mono- or dialkoxy-substituted perfluoroalkane,
- perfluorocycloalkane perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound, the compound optionally containing additional catenary heteroatoms in its perfluorinated portion, 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.
- 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 can optionally be used to increase the rate of introduction.
- alkoxy-substituted perfluorocompound(s) (and any co-extinguishing agent(s) utilized) can be chosen so as to provide an
- extinguishment composition which 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
- 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 for moderately combustible materials (e.g., wood and plastics), and a minimum of about 50 cal/°C per mole of oxygen is adequate for 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
- flammable materials e.g., paper, cloth, wood, flammable liquids, and plastic items
- the process may also be useful in inhabited areas, but toxicity testing is incomplete at this time.
- 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 atmospheric lifetime ( ⁇ sample ) of various sample compounds was calculated by the technique described in Y. Tang, Atmospheric Fate of Various Fluorocarbons, M.S. Thesis, Massachusetts Institute of Technology (1993). According to this technique, an ultraviolet (UV) gas cell was charged with a sample compound, a reference compound (either CH 4 or CH 3 Cl), ozone, and water vapor. Hydroxyl radicals were then generated by photolytic decomposition of the ozone in the presence of the water vapor and an inert buffer gas, i.e., helium. As the sample compounds and reference
- Atmospheric lifetime was also estimated from a correlation developed between the highest occupied molecular orbital (HOMO) energy and the known
- GWP Global warming potential
- GWP is the integrated potential warming due to the release of 1 kilogram of sample compound relative to the warming due to 1 kilogram of CO 2 over a specified integration time horizon (ITH) using the following equation:
- ⁇ T is the calculated change in temperature at the earth's surface due to the presence of a particular compound in the atmosphere [calculated using a
- each of the various alkoxy-substituted perfluorocompounds unexpectedly has a lower atmospheric lifetime than the corresponding hydrofluorocarbon, i.e., the hydrofluorocarbon having the same carbon number.
- compositions of the invention was also evaluated to determine their suitability for use in cleaning and coating applications.
- a compound was contacted with a chemical agent such as aqueous sodium acetate, aqueous KOH, concentrated sulfuric acid, or potassium permanganate in acetone to determine the stability of the compound to base, acid, or oxidant, as described below:
- the tube was heated at 110°C in a forced air convection oven for 16 hours. After cooling to room temperature, a 1 mL sample of the tube contents was diluted with 1 mL of total ionic strength adjustment buffer (TISAB, available from Orion Research, Inc., a mixture of 1,2-cyclohexylene dinitrilotetraacetic acid, deionized water, sodium acetate, sodium chloride, and acetic acid).
- TISAB total ionic strength adjustment buffer
- C 4 F 9 OCH 3 (125 g of 99.8% purity, 0.5 mole) was combined with potassium hydroxide (29.4 g, 0.45 mole, dissolved in 26.1 g water) in a 250 mL flask equipped with an overhead stirrer, a condenser, and a thermometer, and the resulting solution was refluxed at 58°C for 19 hours. Water (50 mL) was added to the solution after refluxing, and the resulting product was distilled.
- C 4 F 9 OCH 3 (15 g, 0.06 mole) was combined with sulfuric acid (10 g of 96% by weight, 0.097 mole) in a 50 mL flask containing a stir bar and fitted with a reflux condenser. The resulting mixture was stirred for 16 hours at room temperature, and then the
- a 20 gallon Hastalloy C reactor equipped with a stirrer and a cooling system, was charged with spray-dried potassium fluoride (7.0 kg, 120.3 mole). The reactor was sealed, and the pressure inside the reactor was reduced to less than 100 torr. Anhydrous dimethyl formamide (22.5 kg) was then added to the reactor, and the reactor was cooled to below 0°C with constant agitation. Heptafluorobutyryl fluoride (22.5 kg of 58% purity, 60.6 mole) was added to the reactor contents. When the temperature of the reactor reached -20°C, diethyl sulfate (18.6 kg, 120.8 mole) was added to the reactor over a period of approximately two hours. The resulting mixture was then held for 16 hours with continued agitation, was raised to 50°C for an
- 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 spray-dried potassium fluoride (85 g, 1.46 mol) and anhydrous diethylene glycol dimethyl ether (375 g) and was then cooled to about -20°C using a recirculating refrigeration system.
- C 2 F 5 COF (196 g, 1.18 mol) was added to the flask over a period of about one hour.
- the flask was then warmed to about 24°C, and dimethyl sulfate (184.3 g, 1.46 mol) was then added dropwise via the addition funnel over a 45 minute period.
- the resulting mixture was then stirred at room temperature overnight. Water (a total of 318 mL) was then added dropwise to the mixture.
- the mixture was transferred to a one liter round bottom flask, and the resulting product ether was
- the title compound was prepared essentially as in Example 3 using anhydrous potassium fluoride (32 g, 0.55 mol), anhydrous diethylene glycol dimethyl ether (diglyme, 375 g), methyltrialkyl (C 8 -C 10 )ammonium chloride (AdogenTM 464, available from Aldrich Chemical Company, 12.5 g), C 4 F 9 COF (218 g of 60.7% purity,
- distillate was separated from the upper phase, was washed with water, was treated with aqueous potassium hydroxide solution (53 g of 50%), and was then refluxed for one hour.
- a second azeotropic distillation and water washing yielded crude product which was further purified by distillation through a ten-plate perforated column to provide the product ether (boiling range 82-84°C; 96.2% purity by GLC).
- the product identity was confirmed by GCMS and by 1 H and 19 F NMR.
- the extinguishment concentration i.e., the
- Extinguishment Concentration [F 1 / (F 1 + F 2 ) ] X 100% where F 1 is the composition flow rate in L/min and F 2 is the air flow rate in L/min.
- the above-referenced NFPA 2001 Standard reports extinguishment data for a number of known clean extinguishment compositions in Table A- 3-4.2.1, and this data (along with data for the same compositions from other sources) is included in Table C below as Comparative Examples A-D.
- micro-cup burner uses a much smaller quantity of composition yet provides extinguishment concentration data in good agreement with that obtained by the cup burner method.
- the micro-cup burner method utilizes a quartz
- a fuel e.g., butane
- the chimney extends 4.5 cm above the inner tube.
- Air flows through the annular region between the inner tube and the chimney at 1000 seem.
- extinguishment composition Prior to the addition of extinguishment composition, a visually stable flame is supported on top of the inner tube, and the resulting combustion products flow out through the chimney.
- An extinguishment 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. All 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 1 minute. After 1 minute, a specific flow rate of composition is introduced, and the time required for the flame to be extinguished is recorded.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96902131A EP0804264B1 (en) | 1995-01-20 | 1996-01-11 | Fire extinguishing process and composition |
DE69601861T DE69601861T2 (en) | 1995-01-20 | 1996-01-11 | FIRE EXTINGUISHING MEDIA AND METHOD |
JP52233096A JP3145408B2 (en) | 1995-01-20 | 1996-01-11 | Fire extinguishing method and fire extinguishing composition |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37581795A | 1995-01-20 | 1995-01-20 | |
US08/375,817 | 1995-01-20 | ||
US08/573,190 | 1995-12-15 | ||
US08/573,190 US5718293A (en) | 1995-01-20 | 1995-12-15 | Fire extinguishing process and composition |
Publications (1)
Publication Number | Publication Date |
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WO1996022129A1 true WO1996022129A1 (en) | 1996-07-25 |
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ID=27007208
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1996/000425 WO1996022129A1 (en) | 1995-01-20 | 1996-01-11 | Fire extinguishing process and composition |
Country Status (8)
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US (2) | US5718293A (en) |
EP (1) | EP0804264B1 (en) |
JP (1) | JP3145408B2 (en) |
KR (1) | KR19980701574A (en) |
CN (1) | CN1176606A (en) |
CA (1) | CA2210994A1 (en) |
DE (1) | DE69601861T2 (en) |
WO (1) | WO1996022129A1 (en) |
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Cited By (17)
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US5827446A (en) * | 1996-01-31 | 1998-10-27 | E. I. Du Pont De Nemours And Company | Nonafluoromethoxybutane compositions |
WO1997028229A1 (en) * | 1996-01-31 | 1997-08-07 | E.I. Du Pont De Nemours And Company | Nonafluoromethoxybutane compositions |
US5851436A (en) * | 1996-06-13 | 1998-12-22 | E. I. Du Pont De Nemours And Company | Nonafluoromethoxybutane compositions |
US6281185B1 (en) | 1997-02-19 | 2001-08-28 | 3M Innovative Properties Company | Azeotropic compositions of methoxy-perfluoropropane and their use |
WO1998037163A1 (en) * | 1997-02-19 | 1998-08-27 | Minnesota Mining And Manufacturing Company | Azeotropic compositions of methoxy-perfluoropropane and their use |
US6030934A (en) * | 1997-02-19 | 2000-02-29 | 3M Innovative Properties Company | Azeotropic compositions of methoxy-perfluoropropane and their use |
AU766844B2 (en) * | 1999-04-28 | 2003-10-23 | Cast Centre Pty Ltd | Cover gases |
WO2000064614A1 (en) * | 1999-04-28 | 2000-11-02 | Cast Centre Pty Ltd | Cover gases |
US6929674B1 (en) * | 1999-04-28 | 2005-08-16 | Cast Centre Pty Ltd | Cover gases |
KR100705885B1 (en) * | 1999-04-28 | 2007-04-09 | 캐스트 센터 피티와이. 엘티디. | Cover gases |
US6537346B2 (en) * | 2000-05-04 | 2003-03-25 | 3M Innovative Properties Company | Molten magnesium cover gas using fluorocarbons |
US6685764B2 (en) | 2000-05-04 | 2004-02-03 | 3M Innovative Properties Company | Processing molten reactive metals and alloys using fluorocarbons as cover gas |
US6780220B2 (en) | 2000-05-04 | 2004-08-24 | 3M Innovative Properties Company | Method for generating pollution credits while processing reactive metals |
US6982173B2 (en) | 2001-06-26 | 2006-01-03 | Solvay Solexis, S.P.A. | PFPEs having at least an alkylether end group and respective preparation process |
EP1690911A1 (en) | 2001-06-26 | 2006-08-16 | Solvay Solexis S.p.A. | Perfluoropolyethers (PFPEs) having at least an alkylether end group |
US7115783B2 (en) | 2001-06-26 | 2006-10-03 | Solvay Solexis, S.P.A. | PFPEs having at least an alkylether end group and respective preparation process |
US7488852B2 (en) | 2001-06-26 | 2009-02-10 | Ausimont S.P.A. | PFPEs having at least an alkylether end group and respective preparation process |
Also Published As
Publication number | Publication date |
---|---|
JPH10512473A (en) | 1998-12-02 |
DE69601861D1 (en) | 1999-04-29 |
JP3145408B2 (en) | 2001-03-12 |
KR19980701574A (en) | 1998-05-15 |
US5718293A (en) | 1998-02-17 |
DE69601861T2 (en) | 1999-08-12 |
CA2210994A1 (en) | 1996-07-25 |
EP0804264B1 (en) | 1999-03-24 |
CN1176606A (en) | 1998-03-18 |
US5919393A (en) | 1999-07-06 |
EP0804264A1 (en) | 1997-11-05 |
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