WO2002040102A2 - Fire extinguishing methods utilizing hydrofluoroethers - Google Patents

Fire extinguishing methods utilizing hydrofluoroethers Download PDF

Info

Publication number
WO2002040102A2
WO2002040102A2 PCT/US2001/044256 US0144256W WO0240102A2 WO 2002040102 A2 WO2002040102 A2 WO 2002040102A2 US 0144256 W US0144256 W US 0144256W WO 0240102 A2 WO0240102 A2 WO 0240102A2
Authority
WO
WIPO (PCT)
Prior art keywords
och
chfcf
ocf
chcf
cfoch
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.)
Ceased
Application number
PCT/US2001/044256
Other languages
French (fr)
Other versions
WO2002040102A3 (en
Inventor
Mark L. Robin
Thomas F. Rowland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PCBU Services Inc
Original Assignee
PCBU Services Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to MXPA03004354A priority Critical patent/MXPA03004354A/en
Priority to AU3767902A priority patent/AU3767902A/en
Priority to KR10-2003-7006460A priority patent/KR100536885B1/en
Priority to AU2002237679A priority patent/AU2002237679B2/en
Priority to PL36187601A priority patent/PL361876A1/en
Priority to CA002428820A priority patent/CA2428820A1/en
Priority to SK600-2003A priority patent/SK6002003A3/en
Priority to NZ525864A priority patent/NZ525864A/en
Priority to EP01986486A priority patent/EP1333889B1/en
Priority to HU0303867A priority patent/HUP0303867A2/en
Priority to IL15585401A priority patent/IL155854A0/en
Application filed by PCBU Services Inc filed Critical PCBU Services Inc
Priority to BR0115450-8A priority patent/BR0115450A/en
Priority to HK04100872.9A priority patent/HK1058013B/en
Priority to DE60127160T priority patent/DE60127160T2/en
Priority to JP2002542468A priority patent/JP2004516871A/en
Publication of WO2002040102A2 publication Critical patent/WO2002040102A2/en
Priority to IL155854A priority patent/IL155854A/en
Priority to US10/435,455 priority patent/US6849194B2/en
Priority to NO20032238A priority patent/NO20032238L/en
Anticipated expiration legal-status Critical
Publication of WO2002040102A3 publication Critical patent/WO2002040102A3/en
Ceased legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/12—Saturated ethers containing halogen
    • C07C43/123—Saturated ethers containing halogen both carbon chains are substituted by halogen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention is directed to hydrofluoroether fire extinguishing agents and methods for extinguishing fires using the hydrofluoroethers. More particularly, the present invention is directed to fire extinguishing agents and methods using saturated or unsaturated, fluorinated C 4 and/or C s hydrofuoroethers, and blends of one or more of the hydrofluoroethers with one or more other fire extinguishing agents.
  • iodine-containing compounds as fire extinguishing agents has been avoided primarily due to the expense of their manufacture or due to toxicity considerations.
  • the three fire extinguishing agents presently in common use were all bromine-containing compounds, Halon 1301 (CF 3 Br), Halon 1211 (CF 2 BrCl) and Halon 2402 (BrCF 2 CF 2 Br).
  • the effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in U.S. Pat. No. 4,014,799 to Owens.
  • certain chlorine-containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF 3 CF 2 C1) as described by Larsen in U.S. Pat. No. 3,844,354.
  • bromine or chlorine-containing Halons are effective fire fighting agents, those agents containing bromine or chlorine are asserted by some to be capable of the destruction of the earth's protective ozone layer. Also, because the agents contain no hydrogen atoms which would permit their destruction in the troposphere, the agents may also contribute to the greenhouse warming effect.
  • saturated or unsaturated, higher fluorinated hydrofluoroethers and blends thereof with other agents as fire extinguishants for use in fire extinguishing methods and apparatus More particularly, the method of this invention involves introducing to a fire a saturated or unsaturated, fluorinated C 4 or C 5 hydrofluoroether in a fire extinguishing concentration and maintaining such concentration until the fire is extinguished.
  • Specific saturated, fluorinated C 4 or C 5 hydrofluoroethers of this invention include:
  • CF 3 CF CFOCH 3
  • CF 3 CF CFOCH 2 F
  • CF 3 CF CFOCHF 2
  • CF 2 C(CF 3 )CF 2 OCH 3
  • CF 2 C(CF 3 )CF 2 OCH 2 F
  • CF 2 C(CF 3 )CF 2 OCF 2 H
  • CF 2 C(CF 3 )CF 2 OCF 3 .
  • hydrofluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents.
  • the agents of this invention are employed at concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis .
  • the agents of this invention are suitable for use in both total flooding and portable fire suppression applications.
  • Suitable extinguishing agents ('blends') for admixture with the hydrofluoroethers include CF 3 CHFCF 3 , CF 3 CF 2 CF 2 H, CF 3 CH 2 CF 3 , CF 3 CF 2 H, and CF 3 H.
  • hydrofluoroethers of this invention may be produced via numerous routes.
  • CF 3 CHFCF 2 OCF 2 H may be prepared via a three step process comprising
  • saturated and unsaturated C 4 and C 5 hydrofluoroethers have been found to be effective fire extinguishants at concentrations safe for use.
  • hydrofluoroethers contain no bromine or chlorine , they have an ozone depletion potential of zero.
  • the compounds are characterized by short atmospheric lifetimes they are susceptible to breakdown in the lower atmosphere and hence do not pose a threat as greenhouse warming gasses.
  • hydrofluoroethers useful in accordance with this invention are:
  • CF 2 CFCF 2 OCF 3
  • (CF 3 ) 2 C CFOCH 3
  • (CF 3 ) 2 C CFOCH 2 F
  • (CF 3 ) 2 C CFOCF 2 H
  • (CF 3 ) 2 C CFOCH 3
  • CF 2 C(CF 3 )CF 2 OCH 3
  • CF 2 C(CF 3 )CF 2 OCH 2 F
  • CF 2 C(CF 3 )CF 2 OCF 2
  • Hand CF 2 C(CF 3 )CF 2 OCF 3 .
  • These hydrofluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents.
  • hydrofluoroether of this invention concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis, are used; when employed in admixture, concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis, are used.
  • the hydrofluoroethers of this invention are employed in admixture with other fire extinguishing agents ('blends')
  • the hydrofluoroethers desirably comprise of at least about 10 percent by weight of the blend, and the overall concentration of the blend lies in the range of about 3 to 15 % , preferably 5 to 10 % in air, on a v/v basis.
  • Suitable extinguishing agents for admixture with the hydrofluoroethers include CF 3 CHFCF 3 , CF 3 CF 2 CF 2 H, CF 3 CH 2 CF 3 , CF 3 CF 2 H, and CF 3 H.
  • the C 4 or C s hydrofluoroethers of this invention may be effectively employed at substantially any minimum concentrations at which fire may be extinguished, the exact minimum level being dependent on the particular combustible material, the particular hydrofluoroether and the combustion conditions .
  • the hydrofluoroethers or mixtures and blends thereof are employed at a level of at least about 3 % (v/v).
  • agent levels of at least about 5 % (v/v).
  • the maximum amount to be employed will be governed by matters of economics and potential toxicity to living things.
  • Hydrofluoroethers may be applied using conventional application techniques and methods used for Halons such as Halon 1301 and Halon 1211.
  • these agents may be used in a total flooding fire extinguishing system in which the agent is introduced to an enclosed region (e.g., a room or other enclosure) surrounding a fire at a concentration sufficient to extinguish the fire.
  • equipment or even rooms or enclosures may be provided with a source of agent and appropriate piping, valves, and controls so as automatically and/or manually to be introduced an appropriate concentrations in the event that fire should break out.
  • the fire extinguishant may be pressurized with nitrogen or other inert gas at up to about 600 psig at ambient conditions.
  • hydrofluoroether agents may be applied to a fire through the use of conventional portable fire extinguishing equipment. It is usual to increase the pressure in portable fire extinguishers with nitrogen or other inert gasses in order to insure that the agent is completely expelled from the extinguisher. Hydrofluoroether containing systems in accordance with this invention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions.
  • the compounds of the present invention are nondestructive agents, and are especially useful where cleanup of other media poses a problem.
  • hydrofluoroethers of this invention are the extinguishing of liquid and gaseous fueled fires, the protection of electrical equipment, ordinary combustibles such as wood, paper and textiles, hazardous solids, and the protection of computer facilities, data processing equipment and control rooms.
  • This example demonstrates the desirable "throw” obtainable with the fire suppression agents of the present invention when employed in portable ("streaming") applications.
  • the throw is the distance the stream of agent can be discharged; the longer the throw the better, as this allows extinguishment without approaching the fire at too close a distance, which can lead to exposure of the operator to fire and toxic fumes from the combustion process.
  • a 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder was charged with 50 grams of CF 3 CHFCF 2 OCF 2 H and then pressurized with nitrogen to the desired pressure.
  • the cylinder contents were completely discharged and the throw distance noted (Table 1). TABLE 1
  • a 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder was charged with 30 grams of CF 3 CHFCF 2 OCF 2 H and then pressurized with nitrogen to 120 psig.
  • a 2 inch x 4 inch x 0.5 inch SS pan was filled with 20 mL of methanol.
  • the methanol was ignited and allowed to burn for 30 seconds; the agent was then discharged from a distance of 4 feet onto the fire.
  • the methanol fire was extinguished in 1.5 seconds; a total of 16 grams of agent was discharged.
  • Example 2 The method of Example 2 was employed with acetone, isopropanol and heptane fuels. All fires were rapidly extinguished (see Table 2). TABLE 2
  • a 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder was charged with 30 grams of CF 3 CHFCF 2 OCF 2 H and then pressurized with nitrogen to 120 psig.
  • a wood crib was constructed of six layers of 6 inch x 2 inch by 0.125 inch strips of kiln dried fir, each layer consisting of 4 pieces. The crib was soaked with heptane, ignited, and allowed to burn for five minutes. The agent was then discharged onto the fire, resulting in rapid ( ⁇ 2 seconds) extinguishment; a total of 25 grams of agent was discharged. Immediately after extinguishment the wood crib was cold to the touch, demonstrating the efficient suppression afforded by the agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Highly fluorinated, saturated and unsaturated hydrofluoroethers are efficient, economical, non-ozone-depleting fire extinguishing agents used alone or in blends with other fire extinguishing agents in total flooding and portable systems.

Description

FIRE EXTINGUISHING METHODS UTILIZING HYDROFLUOROETHERS
FIELD OF THE INVENTION
The present invention is directed to hydrofluoroether fire extinguishing agents and methods for extinguishing fires using the hydrofluoroethers. More particularly, the present invention is directed to fire extinguishing agents and methods using saturated or unsaturated, fluorinated C4 and/or Cs hydrofuoroethers, and blends of one or more of the hydrofluoroethers with one or more other fire extinguishing agents.
BACKGROUND OF THE INVENTION AND PRIOR ART
The use of certain bromine, chlorine and iodine-containing halogenated chemical agents for the extinguishment of fires is common. These agents are in general thought to be effective due to their interference with the normal chain reactions responsible for flame propagation. The most widely accepted mechanism for flame suppression is the radical trap mechanism proposed by Fryburg in Review of Literature Pertinent to Fire Extinguishing Agents and to Basic Mechanisms Involved in Their Action, NACA-TN 2102 (1950). The finding that the effectiveness of the halogens are on a molar basis in the order Cl<Br<I supports the radical trap mechanism, as reported by Malcom in Vaporizing Fire Extinguishing Agents, Report 117, Dept. of Army Engineering Research and Development Laboratories, Fort Bevoir, NA, 1950 (Project- 8-76-04-003). It is thus generally accepted that compounds containing the halogens Cl, Br and I act by interfering with free radical or ionic species in the flame and that the effectiveness of these halogens is in the order I > Br > Cl. In addition, it is generally thought that to be effective as a fire extinguishing agent, a compound must contain Cl, Br or I.
The use of iodine-containing compounds as fire extinguishing agents has been avoided primarily due to the expense of their manufacture or due to toxicity considerations. Until very recently, the three fire extinguishing agents presently in common use were all bromine-containing compounds, Halon 1301 (CF3Br), Halon 1211 (CF2BrCl) and Halon 2402 (BrCF2CF2Br). The effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in U.S. Pat. No. 4,014,799 to Owens. Although not employed commercially, certain chlorine-containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF3CF2C1) as described by Larsen in U.S. Pat. No. 3,844,354.
Although the above named bromine or chlorine-containing Halons are effective fire fighting agents, those agents containing bromine or chlorine are asserted by some to be capable of the destruction of the earth's protective ozone layer. Also, because the agents contain no hydrogen atoms which would permit their destruction in the troposphere, the agents may also contribute to the greenhouse warming effect.
More recently, hydrofiuorocarbons have been proposed as fire suppression, for example in U.S. Pat. No. 5,124,053. However, a disadvantage of these compounds is their relatively high global warming potential. It is therefore an object of this invention to provide a method for extinguishing fires that extinguishes fires as rapidly and effectively as the techniques employing Halon agents while avoiding the above-named drawbacks.
It is a further object of this invention to provide an agent for the use in a method of the character described that is efficient, economical to manufacture, and environmentally safe with regard to ozone depletion and greenhouse warming effects.
It is a still further object of this invention to provide blends of the new agents and other fire extinguishing agents that are effective and environmentally safe.
SUMMARY OF THE INVENTION
The foregoing and other objects, advantages and features of the present invention may be achieved by employing saturated or unsaturated, higher fluorinated hydrofluoroethers and blends thereof with other agents as fire extinguishants for use in fire extinguishing methods and apparatus. More particularly, the method of this invention involves introducing to a fire a saturated or unsaturated, fluorinated C4 or C5 hydrofluoroether in a fire extinguishing concentration and maintaining such concentration until the fire is extinguished. Specific saturated, fluorinated C4 or C5 hydrofluoroethers of this invention include:
CF3CHFCF2OCH3 , CF3CHFCF2OCH2F, CF3CHFCF2OCF2H , CF3CHFCF2OCF3, (CF3)2CHCF2OCH3, (CF3)2CHCF2OCH2F, (CF3)2CHCF2OCHF2 and (CF3)2CHCF2OCF3. Specific unsaturated, fluorinated C4 or Cs hydrofluoroethers of the present invention include:
CF3CF = CFOCH3, CF3CF = CFOCH2F, CF3CF = CFOCHF2,
CF3CF = CFOCF3, CF2 = CFCF2OCH3, CF2 = CFCF2OCH2F, CF2 = CFCF2OCF2H , CF2 = CFCF2OCF3, (CF3)2C = CFOCH3 , (CF3)2C = CFOCH2F, (CF3)2C = CFOCF2H, (CF3)2C = CFOCF3,
CF2=C(CF3)CF2OCH3, CF2=C(CF3)CF2OCH2F, CF2=C(CF3)CF2OCF2H and CF2=C(CF3)CF2OCF3.
These hydrofluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents. Generally, the agents of this invention are employed at concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis . The agents of this invention are suitable for use in both total flooding and portable fire suppression applications. Suitable extinguishing agents ('blends') for admixture with the hydrofluoroethers include CF3CHFCF3, CF3CF2CF2H, CF3CH2CF3, CF3CF2H, and CF3H.
The hydrofluoroethers of this invention may be produced via numerous routes. For example, CF3CHFCF2OCF2H may be prepared via a three step process comprising
(i) reaction of methanol with commercially available hexafluoropropene (CF3CF=CF2) in the presence of base to produce CF3CHFCF2OCH3;
(ii) chlorination of CF3CHFCF2OCH3 with Cl2 to produce CF3CHFCF2OCHCl2; and (iii) fluorination of CF3CHFCF2OCHCl2 with HF to produce the final product CF3CHFCF2OCF2H.
By further reacting with a strong base like sodium or potassium hydroxide the corresponding unsatured C4 or Cs hydrofluoroethers may be prepared.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, saturated and unsaturated C4 and C5 hydrofluoroethers have been found to be effective fire extinguishants at concentrations safe for use. However, because such hydrofluoroethers contain no bromine or chlorine , they have an ozone depletion potential of zero. Furthermore, since the compounds are characterized by short atmospheric lifetimes they are susceptible to breakdown in the lower atmosphere and hence do not pose a threat as greenhouse warming gasses.
Specific hydrofluoroethers useful in accordance with this invention are:
CF3CHFCF2OCH3, CF3CHFCF2OCH2F, CF3CHFCF2OCF2H, CF3CHFCF2OCF3, (CF3)2CHCF2OCH3, (CF3)2CHCF2OCH2F, (CF3)2CHCF2OCHF2, (CF3)2CHCF2OCF3, CF3CF = CFOCH3, CF3CF = CFOCH2F, CF3CF = CFOCHF2 , CF3CF = CFOCF3, CF2 = CFCF2OCH3, CF2 = CFCF2OCH2F, CF2 = CFCF2OCF2H,
CF2 = CFCF2OCF3, (CF3)2C = CFOCH3, (CF3)2C = CFOCH2F, (CF3)2C = CFOCF2H, (CF3)2C = CFOCH3, CF2 = C(CF3)CF2OCH3, CF2=C(CF3)CF2OCH2F, CF2=C(CF3)CF2OCF2Hand CF2=C(CF3)CF2OCF3. These hydrofluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents. Generally, when a single hydrofluoroether of this invention is employed, concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis, are used; when employed in admixture, concentrations lying in the range of about 3 to 15%, preferably 5 to 10% in air, on a v/v basis, are used. Where the hydrofluoroethers of this invention are employed in admixture with other fire extinguishing agents ('blends'), the hydrofluoroethers desirably comprise of at least about 10 percent by weight of the blend, and the overall concentration of the blend lies in the range of about 3 to 15 % , preferably 5 to 10 % in air, on a v/v basis. The agents of this invention are suitable for use in both total flooding and portable fire suppression applications. Suitable extinguishing agents for admixture with the hydrofluoroethers include CF3CHFCF3, CF3CF2CF2H, CF3CH2CF3, CF3CF2H, and CF3H.
The C4 or Cs hydrofluoroethers of this invention may be effectively employed at substantially any minimum concentrations at which fire may be extinguished, the exact minimum level being dependent on the particular combustible material, the particular hydrofluoroether and the combustion conditions . In general , however , best results are achieved where the hydrofluoroethers or mixtures and blends thereof are employed at a level of at least about 3 % (v/v). Where hydrofluoroethers alone are employed, best results are achieved with agent levels of at least about 5 % (v/v). Likewise, the maximum amount to be employed will be governed by matters of economics and potential toxicity to living things. About 15 % (v/v) provides a convenient maximum concentration for use of hydrofluoroethers and mixtures and blends thereof in occupied areas. Concentrations above 15% (v/v) may be employed in unoccupied areas, with the exact level being determined by the particular combustible material, the hydrofluoroether (or mixture or blend thereof) chosen and the conditions of combustion. The preferred concentration of the hydrofluoroether agents, mixtures and blends in accordance with this invention lies in the range of about 5 to 10% (v/v).
Hydrofluoroethers may be applied using conventional application techniques and methods used for Halons such as Halon 1301 and Halon 1211. Thus, these agents may be used in a total flooding fire extinguishing system in which the agent is introduced to an enclosed region (e.g., a room or other enclosure) surrounding a fire at a concentration sufficient to extinguish the fire. In accordance with a total flooding system apparatus, equipment or even rooms or enclosures may be provided with a source of agent and appropriate piping, valves, and controls so as automatically and/or manually to be introduced an appropriate concentrations in the event that fire should break out. Thus, as is known to those skilled in the art, the fire extinguishant may be pressurized with nitrogen or other inert gas at up to about 600 psig at ambient conditions.
Alternatively, the hydrofluoroether agents may be applied to a fire through the use of conventional portable fire extinguishing equipment. It is usual to increase the pressure in portable fire extinguishers with nitrogen or other inert gasses in order to insure that the agent is completely expelled from the extinguisher. Hydrofluoroether containing systems in accordance with this invention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions.
The compounds of the present invention are nondestructive agents, and are especially useful where cleanup of other media poses a problem.
Some of the applications of the hydrofluoroethers of this invention are the extinguishing of liquid and gaseous fueled fires, the protection of electrical equipment, ordinary combustibles such as wood, paper and textiles, hazardous solids, and the protection of computer facilities, data processing equipment and control rooms.
The invention will be further described with reference to the following specific Examples. However it will be understood that these Examples are illustrative in nature and not restrictive in nature.
EXAMPLE 1
This example demonstrates the desirable "throw" obtainable with the fire suppression agents of the present invention when employed in portable ("streaming") applications. The throw is the distance the stream of agent can be discharged; the longer the throw the better, as this allows extinguishment without approaching the fire at too close a distance, which can lead to exposure of the operator to fire and toxic fumes from the combustion process.
A 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder was charged with 50 grams of CF3CHFCF2OCF2H and then pressurized with nitrogen to the desired pressure. The cylinder contents were completely discharged and the throw distance noted (Table 1). TABLE 1
Throw vs. Pressure for CF3CHFCF2OCF2H System
Pressure, psig Throw, feet
25 10
80 15
120 17
150 18
EXAMPLE 2
This example demonstrates the extinguishment of Class B fires with the agents of the present invention. A 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder was charged with 30 grams of CF3CHFCF2OCF2H and then pressurized with nitrogen to 120 psig. A 2 inch x 4 inch x 0.5 inch SS pan was filled with 20 mL of methanol. The methanol was ignited and allowed to burn for 30 seconds; the agent was then discharged from a distance of 4 feet onto the fire. The methanol fire was extinguished in 1.5 seconds; a total of 16 grams of agent was discharged.
EXAMPLE 3
The method of Example 2 was employed with acetone, isopropanol and heptane fuels. All fires were rapidly extinguished (see Table 2). TABLE 2
Extinguishment with CF3CHFCF2OCF2H
Fuel Extinguishing Agent discharged,
Time, seconds grams acetone 2.0 25 isopropanol 1.5 21 heptane 1.8 11
EXAMPLE 4
This example demonstrates the extinguishment of deep-seated Class A fires with the agents of the present invention. A 150 mL SS cylinder was equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle. The cylinder was charged with 30 grams of CF3CHFCF2OCF2H and then pressurized with nitrogen to 120 psig. A wood crib was constructed of six layers of 6 inch x 2 inch by 0.125 inch strips of kiln dried fir, each layer consisting of 4 pieces. The crib was soaked with heptane, ignited, and allowed to burn for five minutes. The agent was then discharged onto the fire, resulting in rapid (< 2 seconds) extinguishment; a total of 25 grams of agent was discharged. Immediately after extinguishment the wood crib was cold to the touch, demonstrating the efficient suppression afforded by the agent.

Claims

WHAT IS CLAIMED IS:
1. A method for extinguishing a fire comprising the steps
of introducing to the fire a fire extinguishing concentration of a composition comprising a compound selected from the group consisting of a saturated, fluorinated C4 hydrofluoroether, a saturated, fluorinated C5 hydrofluoroether,
an unsaturated, fluorinated C4 hydrofluoroether and an unsaturated, fluorinated C5 hydrofluoroether and maintaining the concentration of the compound until
the fire is extinguished.
2. The method of claim 1 , wherein the compound is selected
from the group consisting of CF3CHFCF2OCH3, CF3CHFCF2OCH2F,
CF3CHFCF2OCF2H , CF3CHFCF2OCF3, (CF3)2CHCF2OCH3,
(CF3)2CHCF2OCH2F, (CF3)2CHCF2OCHF2, (CF3)2CHCF2OCF3,
CF3CF = CFOCH3, CF3CF = CFOCH2F, CF3CF = CFOCHF2 ;
CF3CF = CFOCF3 , CF2 = CFCF2OCH3, CF2 = CFCF2OCH2F,
CF2 = CFCF2OCF2H , CF2 = CFCF2OCF3, (CF3)2C = CFOCH3,
(CF3)2C = CFOCH2F , (CF3)2C = CFOCF2H , (CF3)2C = CFOCH3 ,
CF2=C(CF3)CF2OCH3, CF2=C(CF3)CF2OCH2F, CF2=C(CF3)CF2OCF2H and
CF2=C(CF3)CF2OCF3.
3. The method of claim 1 , wherein the compound is selected
from the group consisting of CF3CHFCF2OCH3, CF3CHFCF2OCH2F,
CF3CHFCF2OCF2H , CF3CHFCF2OCF3 , (CF3)2CHCF2OCH3 , (CF3)2CHCF2OCH2F, (CF3)2CHCF2OCHF2, (CF3)2CHCF2OCF3.
4. The method of claim 1, wherein the compound is employed at a level of at least about 3 % (v/v).
5. The method of claim 1, wherein the compound is employed in a total flooding system.
6. The method of claim 1, wherein the compound is employed in a portable extinguishing system.
7. The method of claim 1, wherein the composition comprises a blend with other fire extinguishing agents.
8. The method of claim 7, wherein the other fire
extinguishing agents are selected from the group consisting of CF3CHFCF3, CF3CF2CF2H, CF3CH2CF3, CF3CF2H, and CF3H.
9. A fire extinguishing agent comprising a compound
selected from the group consisting of CF3CHFCF2OCH3, CF3CHFCF2OCH2F,
CF3CHFCF2OCF2H , CF3CHFCF2OCF3, (CF3)2CHCF2OCH3,
(CF3)2CHCF2OCH2F, (CF3)2CHCF2OCHF2, (CF3)2CHCF2OCF3, CF3CF = CFOCH3, CF3CF = CFOCH2F, CF3CF = CFOCHF2,
CF3CF = CFOCF3, CF2 = CFCF2OCH3, CF2 = CFCF2OCH2F,
CF2 = CFCF2OCF2H , CF2 = CFCF2OCF3, (CF3)2C = CFOCH3,
(CF3)2C = CFOCH2F, (CF3)2C = CFOCF2H, (CF3)2C = CFOCH3,
CF2=C(CF3)CF2OCH3, CF2=C(CF3)CF2OCH2F, CF2=C(CF3)CF2OCF2Hand CF2=C(CF3)CF2OCF3.
10. A method of making CF3CHFCF2OCF2H comprising the steps of
(i) reacting methanol with hexafluoropropene in the presence of base to produce CF3CHFCF2OCH3;
(ii) chlorinating CF3CHFCF2OCH3 with Cl2 to produce
CF3CHFCF2OCHCl2; and
(iii) fluorinating CF3CHFCF2OCHCl2 with HF to produce CF3CHFCF2OCF2H.
11. A method of making a saturated, fluorinated C4 or Cs hydrofluoroether comprising the steps of
(i) reacting a alcohol with a fluorinated C3 or C4 alkene in the presence of a base to form a first reaction product;
(ii) chlorinating the first reaction product with Cl2 to form a second reaction product; and
(iii) fluorinating the second reaction product with HF to form a saturated, fluorinated C4 or C5 hydrofluoroether.
12. The method of claim 11, wherein the base is selected from the group consisting of sodium and potassium hydroxide.
PCT/US2001/044256 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers Ceased WO2002040102A2 (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
IL15585401A IL155854A0 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
KR10-2003-7006460A KR100536885B1 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
AU2002237679A AU2002237679B2 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
PL36187601A PL361876A1 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
CA002428820A CA2428820A1 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
SK600-2003A SK6002003A3 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
BR0115450-8A BR0115450A (en) 2000-11-17 2001-11-14 Fire extinguishing methods using hydrofluoroethers
AU3767902A AU3767902A (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
HU0303867A HUP0303867A2 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
MXPA03004354A MXPA03004354A (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers.
EP01986486A EP1333889B1 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
NZ525864A NZ525864A (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
HK04100872.9A HK1058013B (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers
DE60127160T DE60127160T2 (en) 2000-11-17 2001-11-14 FIRE EXTINGUISHING PROCEDURE USING HYDROFLUOROETHERS
JP2002542468A JP2004516871A (en) 2000-11-17 2001-11-14 Fire extinguishing method using hydrofluoroether
IL155854A IL155854A (en) 2000-11-17 2003-05-12 Fire extinguishing methods utilizing hydrofluoroethers
US10/435,455 US6849194B2 (en) 2000-11-17 2003-05-12 Methods for preparing ethers, ether compositions, fluoroether fire extinguishing systems, mixtures and methods
NO20032238A NO20032238L (en) 2000-11-17 2003-05-16 Fire extinguishing methods utilizing hydrofluoroethers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24968400P 2000-11-17 2000-11-17
US60/249,684 2000-11-17

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/435,455 Continuation-In-Part US6849194B2 (en) 2000-11-17 2003-05-12 Methods for preparing ethers, ether compositions, fluoroether fire extinguishing systems, mixtures and methods

Publications (2)

Publication Number Publication Date
WO2002040102A2 true WO2002040102A2 (en) 2002-05-23
WO2002040102A3 WO2002040102A3 (en) 2003-05-30

Family

ID=22944548

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/044256 Ceased WO2002040102A2 (en) 2000-11-17 2001-11-14 Fire extinguishing methods utilizing hydrofluoroethers

Country Status (20)

Country Link
EP (1) EP1333889B1 (en)
JP (1) JP2004516871A (en)
KR (1) KR100536885B1 (en)
CN (1) CN1612765A (en)
AT (1) ATE355874T1 (en)
AU (2) AU2002237679B2 (en)
BR (1) BR0115450A (en)
CA (1) CA2428820A1 (en)
CZ (1) CZ20031329A3 (en)
DE (1) DE60127160T2 (en)
HU (1) HUP0303867A2 (en)
IL (2) IL155854A0 (en)
MX (1) MXPA03004354A (en)
NO (1) NO20032238L (en)
NZ (1) NZ525864A (en)
PL (1) PL361876A1 (en)
SK (1) SK6002003A3 (en)
WO (1) WO2002040102A2 (en)
YU (1) YU38203A (en)
ZA (1) ZA200303784B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004094002A3 (en) * 2003-04-17 2006-07-13 Pcbu Services Inc Fire extinguishing mixtures, methods, and systems
US7329786B2 (en) 2001-09-28 2008-02-12 Great Lakes Chemical Corporation Processes for producing CF3CFHCF3
US7368089B2 (en) 2003-08-13 2008-05-06 Great Lakes Chemical Corporation Systems and methods for producing fluorocarbons
WO2015013155A1 (en) * 2013-07-25 2015-01-29 3M Innovative Properties Company Nitrogen containing hydrofluoroethers and methods of making same
US11535579B2 (en) 2017-12-13 2022-12-27 3M Innovative Properties Company Hydrofluoroolefin ethers, compositions, apparatuses and methods for using same
US11551827B2 (en) 2017-12-13 2023-01-10 3M Innovative Properties Company Perfluorinated 1-alkoxypropenes in dielectric fluids and electrical devices
US11673861B2 (en) 2017-12-13 2023-06-13 3M Innovative Properties Company Perfluorinated 1-alkoxypropenes, compositions, and methods and apparatuses for using same

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2730543A (en) * 1950-05-20 1956-01-10 Minnesota Mining & Mfg Fluorinated nitriles
US3557294A (en) * 1967-10-12 1971-01-19 Allied Chem Fluorinated ethers as inhalation convulsants
US3943256A (en) * 1973-06-25 1976-03-09 Baxter Laboratories, Inc. Antipsychotic agents
US5278342A (en) * 1992-03-25 1994-01-11 Hampshire Chemical Corp. Vapor phase chlorination of difluoromethyl methyl ether
US5605882A (en) * 1992-05-28 1997-02-25 E. I. Du Pont De Nemours And Company Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane
JP2589917B2 (en) * 1992-08-11 1997-03-12 工業技術院長 1,1-Difluoroethyl methyl ether, method for producing the same, and working fluid containing the same
US5611210A (en) * 1993-03-05 1997-03-18 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
WO1996040834A1 (en) * 1995-06-07 1996-12-19 E.I. Du Pont De Nemours And Company Refrigerants based on hydrofluoroether of fluoroether
US5730894A (en) * 1996-04-16 1998-03-24 E. I. Du Pont De Nemours And Company 1,1,2,2,3,3,4,4-octafluorobutane azeotropic (like) compositions
US6023002A (en) * 1998-01-26 2000-02-08 3M Innovative Properties Company Process for preparing hydrofluoroethers
US6478979B1 (en) * 1999-07-20 2002-11-12 3M Innovative Properties Company Use of fluorinated ketones in fire extinguishing compositions
US6849194B2 (en) * 2000-11-17 2005-02-01 Pcbu Services, Inc. Methods for preparing ethers, ether compositions, fluoroether fire extinguishing systems, mixtures and methods

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7329786B2 (en) 2001-09-28 2008-02-12 Great Lakes Chemical Corporation Processes for producing CF3CFHCF3
US7348461B2 (en) 2001-09-28 2008-03-25 Great Lakes Chemical Corporation Processes for halogenating compounds
US7332635B2 (en) 2001-09-28 2008-02-19 Great Lakes Chemical Corporation Processes for purifying chlorofluorinated compounds
AU2004231729B2 (en) * 2003-04-17 2007-07-05 Great Lakes Chemical Corporation Fire extinguishing mixtures, methods, and systems
WO2004094002A3 (en) * 2003-04-17 2006-07-13 Pcbu Services Inc Fire extinguishing mixtures, methods, and systems
US7223351B2 (en) 2003-04-17 2007-05-29 Great Lakes Chemical Corporation Fire extinguishing mixtures, methods and systems
US7216722B2 (en) 2003-04-17 2007-05-15 Great Lakes Chemical Corporation Fire extinguishing mixtures, methods and systems
EP1925338A1 (en) * 2003-04-17 2008-05-28 Great Lakes Chemical Corporation Fire extinguishing mixtures, methods and systems
KR100850444B1 (en) * 2003-04-17 2008-08-07 그레이트 레이크스 케미칼 코퍼레이션 Digestive Mixtures, Methods and Devices
US7368089B2 (en) 2003-08-13 2008-05-06 Great Lakes Chemical Corporation Systems and methods for producing fluorocarbons
WO2015013155A1 (en) * 2013-07-25 2015-01-29 3M Innovative Properties Company Nitrogen containing hydrofluoroethers and methods of making same
US9540316B2 (en) 2013-07-25 2017-01-10 3M Innovative Properties Company Nitrogen containing hydrofluoroethers and methods of making same
US11535579B2 (en) 2017-12-13 2022-12-27 3M Innovative Properties Company Hydrofluoroolefin ethers, compositions, apparatuses and methods for using same
US11551827B2 (en) 2017-12-13 2023-01-10 3M Innovative Properties Company Perfluorinated 1-alkoxypropenes in dielectric fluids and electrical devices
US11673861B2 (en) 2017-12-13 2023-06-13 3M Innovative Properties Company Perfluorinated 1-alkoxypropenes, compositions, and methods and apparatuses for using same

Also Published As

Publication number Publication date
IL155854A0 (en) 2003-12-23
BR0115450A (en) 2004-01-06
NO20032238D0 (en) 2003-05-16
EP1333889B1 (en) 2007-03-07
AU3767902A (en) 2002-05-27
WO2002040102A3 (en) 2003-05-30
ATE355874T1 (en) 2007-03-15
ZA200303784B (en) 2004-08-16
CZ20031329A3 (en) 2003-12-17
HK1058013A1 (en) 2004-04-30
EP1333889A2 (en) 2003-08-13
NZ525864A (en) 2005-01-28
CN1612765A (en) 2005-05-04
DE60127160T2 (en) 2007-11-22
NO20032238L (en) 2003-07-10
SK6002003A3 (en) 2003-11-04
KR100536885B1 (en) 2005-12-16
PL361876A1 (en) 2004-10-04
CA2428820A1 (en) 2002-05-23
KR20030065510A (en) 2003-08-06
IL155854A (en) 2007-10-31
AU2002237679B2 (en) 2007-08-16
JP2004516871A (en) 2004-06-10
HUP0303867A2 (en) 2004-03-01
DE60127160D1 (en) 2007-04-19
YU38203A (en) 2005-11-28
MXPA03004354A (en) 2005-01-25

Similar Documents

Publication Publication Date Title
US5124053A (en) Fire extinguishing methods and blends utilizing hydrofluorocarbons
JP2008023350A (en) Extinguishing composition, and method for supplying burning matter with the same to extinguish
WO2017023591A1 (en) Method for the suppression of fire
AU629975B2 (en) Fire extinguishing methods and blends utilizing hydrofluorocarbons
EP1333889B1 (en) Fire extinguishing methods utilizing hydrofluoroethers
AU2002237679A1 (en) Fire extinguishing methods utilizing hydrofluoroethers
AU2103995A (en) Ozone friendly fire extinguishing methods and compositions
HK1058013B (en) Fire extinguishing methods utilizing hydrofluoroethers
AU2007205718A1 (en) Fire extinguishing methods utilizing hydrofluoroethers
WO1992001489A1 (en) Fire extinguishing methods utilizing 1-bromo-1,1,2,2-tetrafluoroethane

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: P-382/03

Country of ref document: YU

AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 155854

Country of ref document: IL

Ref document number: 10435455

Country of ref document: US

Ref document number: 2002237679

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1020037006460

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: PV2003-1329

Country of ref document: CZ

Ref document number: 2003/03784

Country of ref document: ZA

Ref document number: 525864

Country of ref document: NZ

Ref document number: 2428820

Country of ref document: CA

Ref document number: 200303784

Country of ref document: ZA

Ref document number: 740/CHENP/2003

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1-2003-500372

Country of ref document: PH

WWE Wipo information: entry into national phase

Ref document number: 6002003

Country of ref document: SK

Ref document number: PA/a/2003/004354

Country of ref document: MX

Ref document number: 2002542468

Country of ref document: JP

Ref document number: 018190561

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2001986486

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020037006460

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2001986486

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: PV2003-1329

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 525864

Country of ref document: NZ

WWG Wipo information: grant in national office

Ref document number: 525864

Country of ref document: NZ

WWG Wipo information: grant in national office

Ref document number: 1020037006460

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 2001986486

Country of ref document: EP