WO1997020599A1 - Procedes d'extinction d'incendie et melanges a base d'ethers d'hydrocarbure fluores - Google Patents

Procedes d'extinction d'incendie et melanges a base d'ethers d'hydrocarbure fluores Download PDF

Info

Publication number
WO1997020599A1
WO1997020599A1 PCT/US1996/019133 US9619133W WO9720599A1 WO 1997020599 A1 WO1997020599 A1 WO 1997020599A1 US 9619133 W US9619133 W US 9619133W WO 9720599 A1 WO9720599 A1 WO 9720599A1
Authority
WO
WIPO (PCT)
Prior art keywords
fire
ether
fluorinated
equal
fire extinguishing
Prior art date
Application number
PCT/US1996/019133
Other languages
English (en)
Inventor
Lawrence R. Grzyll
Dwight D. Back
Charlie Ramos
Nidal A. Samad
Original Assignee
Mainstream Engineering Corporation
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
Application filed by Mainstream Engineering Corporation filed Critical Mainstream Engineering Corporation
Priority to AU11272/97A priority Critical patent/AU1127297A/en
Publication of WO1997020599A1 publication Critical patent/WO1997020599A1/fr

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
    • A62D1/0028—Liquid extinguishing substances

Definitions

  • Thxs application is a contmuation-in-part of Application Serial No. 08/519 , 809 filed on August 25, 1995 m the name of Lawrence Robert Grzyll et al . for FIRE EXTINGUISHING METHODS AND BLENDS UTILIZING UNSATURATED PERFLUOROCARBONS, the sub ect matter of which is incorporated herein by reference.
  • the present invention relates to fire extinguishing methods and blends utilizing fully or partially fluorinated C 2 to C 8 organic ethers.
  • halogenated chemical agents containing combinations of fluorine, chlorine, bromine, iodine, and hydrogen is well-known.
  • the most common of these agents are Halon 1301 (CF 3 Br) , Halon 1211 (CF 2 ClBr) , and Halon 2402
  • extinguishing agents also possess the volatility that makes them useful for total flooding applications or streaming applications in portable fire extinguishers They are clean agents; this means that they leave no residue upon evaporation or during fire suppression They are also nonreactive to the majority of metals and nonmetals with which they come into contact with during use. They are also safe agents, having toxicity characteristics suitable for occupied spaces during their use .
  • 5,124,053 describes the use of saturated, higher fluorinated hydrofluorocarbons and blends thereof with other agents for use in fire extinguishing methods and apparatus. Specifically, U.S. Patent No. 5,124,053 describes the use of saturated C 2 or C 3 higher fluorinated hydrocarbons of the formula C x H y F z , where x is 2 or 3 , y is 1 or 2 , and z is 5, 6, or 7 : where y is 1 and z is 5 when x is 2 and where z is 6 or 7 when x is 3. Because these compounds contain no chlorine or bromine, they have zero ozone depletion potential. The compounds are also asserted not to pose a threat as greenhouse warming gases and also have toxicity characteristics suitable for use in occupied spaces. However, they must be used at much higher flame extinguishing concentrations than the common halons .
  • Halon presented at the International CFC and Halon Alternatives Conference, Baltimore, Maryland, December 3-5, 1991, briefly discusses fluorinated ethers, such as perfluoro-tetrahydrof ran and trifluorome hyl- difluoromethyl ether, as halon alternatives useful as fire extinguishants .
  • fluorinated ethers such as perfluoro-tetrahydrof ran and trifluorome hyl- difluoromethyl ether
  • they must also be used at higher flame extinguishing concentrations than the common halons. It is an object of the present invention to provide a fire extinguishing method that extinguishes fires as effectively as the common Halons by using a minimum concentration to extinguish a fire, and that has similar volatility, residue levels, materials compatibility characteristics, and safety characteristics, and yet is environmentally acceptable.
  • fluorinated C 2 to C 8 organic ethers are effective fire extinguishing agents at concentrations similar to those of the well-known Halons.
  • these materials also have no chlorine or bromine constituents, and thus, have zero ozone depletion potential.
  • C 2 to C 8 perfluoroethers and fluorinated ethers which are useful include compounds of the formula C x F y H z O w for which x is equal or greater than 2 and less than or equal to 8, and w is greater than zero.
  • y 2x+2-z
  • cyclic compounds y will be greater than or equal to 2x-z, and less than or equal to 2x+2-z.
  • non-cyclic and cyclic fluorinated ethers which are useful include difluoromethyl-2 , 2, 2- trifluoroethyl ether (CF 3 -CH 2 -0-CHF 2 ) , heptafluoropropyl- 1, 2, 2, 2-tetrafluoroethyl ether (CF 3 -CF 2 -CF 2 -0-CHF-CF 3 ) , and perfluoro-2-butyltetrahydrofuran (CF 3 -CF 2 -CF 2 -CF 2 -C 4 F 7 0) .
  • difluoromethyl-2 2, 2- trifluoroethyl ether
  • CF 3 -CH 2 -0-CHF 2 heptafluoropropyl- 1, 2, 2, 2-tetrafluoroethyl ether
  • perfluoro-2-butyltetrahydrofuran CF 3 -CF 2 -CF 2 -CF 2 -C 4 F 7 0
  • These compounds may be used alone, in mixture with one another, or in mixture with other fire extinguishing agents or gases. These agents may be applied using the standard fire extinguishing application techniques and methods used for the standard Halons. These agents may be used in total flooding applications or systems where an entire enclosed region is subjected to the agent, or they may be used in portable fire extinguishing equipment. The agents may be pressurized with nitrogen or another inert gas to ensure adequate flow of the agent through the fire suppression system.
  • agents should be used at a minimum concentration to effectively extinguish a fire. This exact concentration depends on several variables, including the exact agent or blend used, the combustion material, and the combustion of fire conditions and scenario. The best laboratory results have been found where the agent is employed at a concentration of at least 3% (v/v) .
  • the maximum concentration employed is determined, generally speaking, by economics and safety. Of course, in unoccupied areas, where no living things are present, the maximum concentration can be increased.
  • the fire suppression effectiveness of difluoromethyl- 2, 2, 2-trifluoroethyl ether, heptafluoropropyl-1, 2 , 2, 2- tetraf 1uoroethy1 ether, and perfluoro-2- butyltetrahydrofuran were demonstrated in a dynamic test using a glass cup burner apparatus and test procedure with n-heptane and air being supplied to the burner. Vapor of the agent being tested, generated by vaporizing the agent with heat, was mixed with air and introduced to the flame. The concentration of the agent in the air mixture was slowly increased until the flame was extinguished; this is referred to as the flame extinguishing concentration (FEC) .
  • FEC flame extinguishing concentration
  • Table 1 provides a summary of the data for difluoromethyl- 2 , 2, 2-trifluoroethyl ether, heptafluoropropyl-1, 2, 2 , 2- tetraf1uoroethy1 ether, and perfluoro-2- butyltetrahydrofuran and compares this data to published values for the standard Halons and for some of the fire suppression agents described in U.S. Patent No. 5,124,053 and Adcock et al . , Fluorinated Ethers, A New Family of Halons . Table 1 shows that, in terms of flame extinguishing concentration, the compounds of this invention are more effective agents than the compounds described in U.S. Patent No. 5,124,053 and Adcock et al . for n-heptane diffusion flames in the cup burner.
  • Agent Air Flow Agent Flow FEC (cc/min) (cc/min) (% v/v) difluoromethyl-2, 2,2- 8,687 1, 121 11.7 trifluoroethyl ether 1 heptafluoropropyl-1,2,2,2- 6,373 247 3.7 tetrafluoroethyl ether 1 perfluoro-2- 6,373 224 3.5 butyltetrahydrofuran 1
  • the residue level of difluoromethyl-2 , 2 , 2- trifluoroethyl ether, heptafluoropropyl - 1 , 2 , 2 , 2 - t e t raf 1 uoroe t hy1 ether, and perfluoro-2- butyltetrahydrofuran were experimentally measured using a method recommended by NIST (NIST Technical Note 1278) . Namely, the measurements were performed by filling 1 cc of the fluids in a crucible that had previously been cleaned and weighed. The agent was then heated and allowed to evaporate. The weight percent residue of the agent was then calculated from the weight of the crucible before and after the test.
  • Difluoromethyl-2 , 2 , 2-trifluoroethyl ether was found to have a residue of 0.02% (w/w)
  • heptafluoropropyl-1, 2 , 2 , 2-tetrafluoroethyl ether had a measured residue of 0.00% (w/w)
  • perfluoro-2- butyltetrahydrofuran was found to have a residue level of 0.00% (w/w) .
  • these levels are acceptable for fire suppression agents according to NIST (NIST Technical Note 1278) .
  • it is desirable that the residue level of the fluorinated ether be no more than about 1.00% (w/w) .
  • the materials compatibility of difluoromethyl-2, 2, 2- trifluoroethyl ether, heptafluoropropyl-1 , 2 , 2 , 2- tetraf luoroethyl ether, and perfluoro-2- butyltetrahydrofuran with metals and nonmetals were experimentally demonstrated using an ASTM-derived method and found to be acceptable.
  • the test apparatus was a thick-walled glass pressure tube that had a glass thread at the top and a threaded plunger valve that allowed for evacuating the tube and charging the tube with another fluid under pressure.
  • the tube was 17.8 cm in length and had an OD (outside diameter) of 25.4 mm.
  • the metals and nonmetals tested were Nitronic 40, copper CDA 172, aluminum 6061-T6, 1020 alloy steel, Teflon TFE, silicon rubber, Buna-N, and Viton. Circular coupons of these materials had been procured that measure 1/2" OD, 1/16" thick, with a 9/64" OD hole in the center. A Teflon rod passed through this hole and suspended the coupon, small Teflon spacers separated the coupons on the Teflon rod. Two coupons from each material were mounted on the Teflon rod and placed in the test container. The tube with the test samples was then evacuated and charged with the candidate agent so that each of the test coupons was covered with liquid agent. The test time was set for one month, and the test temperature was set at room temperature .
  • the nonmetal samples were cleaned prior to the test in a soap/water solution, dried, and weighed to the nearest 0.1 mg prior to mounting on the Teflon rod. After the test the nonmetal coupons were cleaned, examined under a microscope, and their dimensions were measured with a micrometer to determine if any swelling had occurred.
  • Tables 2 and 3 present the results of these materials compatibility tests.
  • Table 2 which presents the results of the materials compatibility tests for the metals, the corrosion rates listed are average values for the two metal samples of each material. The values with a "less-than" (" ⁇ ") symbol correspond to a mass change less than the sensitivity of the balance ( ⁇ 0.1 mg) .
  • Table 3 presents the results of the materials compatibility tests for the nonmetal samples tested. A compatibility rating was defined based on the percentage change in the thickness of the sample before and after the test . Mass changes and diameter changes of the sample were also measured during the test, and were found to correlate highly with the change in sample thickness.
  • the toxicity characteristics of difluoromethyl-2 , 2, 2- trifluoroethyl ether, heptafluoropropyl-1 , 2 , 2 , 2- tetraf 1uoroethy1 ether, and perfluoro-2- butyltetrahydrofuran were also estimated using structural property relations. Accordingly, the 4-hour lethal concentration (LC 50 ) for difluoromethyl-2, 2, 2-trifluoroethyl ether, heptafluoropropyl-1, 2, 2, 2-tetrafluoroethyl ether, and perfluoro-2-butyltetrahydrofuran was estimated to be 2.7, 2.5, and 12.4% (v/v) , respectively.

Landscapes

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

Abstract

Les éthers fluorés s'avèrent d'efficaces agents d'extinction d'incendie à des concentrations comparables à celles des halons usuels; ils présentent une volatilité, des niveaux de résidus, une compatibilité avec les matériaux et une sécurité d'emploi similaires à ceux des halons usuels, tout en étant acceptables pour l'environnement.
PCT/US1996/019133 1995-12-04 1996-12-04 Procedes d'extinction d'incendie et melanges a base d'ethers d'hydrocarbure fluores WO1997020599A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11272/97A AU1127297A (en) 1995-12-04 1996-12-04 Fire extinguishing methods and blends utilizing fluorinated hydrocarbon ethers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US56669295A 1995-12-04 1995-12-04
US08/566,692 1995-12-04

Publications (1)

Publication Number Publication Date
WO1997020599A1 true WO1997020599A1 (fr) 1997-06-12

Family

ID=24263987

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/019133 WO1997020599A1 (fr) 1995-12-04 1996-12-04 Procedes d'extinction d'incendie et melanges a base d'ethers d'hydrocarbure fluores

Country Status (2)

Country Link
AU (1) AU1127297A (fr)
WO (1) WO1997020599A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3031111A1 (fr) * 2014-12-31 2016-07-01 Arkema France

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500388A (en) * 1948-07-21 1950-03-14 Minnesota Mining & Mfg Fluorocarbon ethers
US5117917A (en) * 1990-07-26 1992-06-02 Great Lakes Chemical Corp. Fire extinguishing methods utilizing perfluorocarbons
US5562854A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company Octafluorobutane compositions
US5562861A (en) * 1993-03-05 1996-10-08 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500388A (en) * 1948-07-21 1950-03-14 Minnesota Mining & Mfg Fluorocarbon ethers
US5117917A (en) * 1990-07-26 1992-06-02 Great Lakes Chemical Corp. Fire extinguishing methods utilizing perfluorocarbons
US5562861A (en) * 1993-03-05 1996-10-08 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
US5562854A (en) * 1994-09-29 1996-10-08 E. I. Du Pont De Nemours And Company Octafluorobutane compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ADCOCK, JAMES L. et al., "Fluorinated Ethers a New Family of Halons", In: INTERNATIONAL CFC AND HALON ALTERNATIVES CONFERENCE, BALTIMORE, MARYLAND, DEPARTMENT OF CHEMISTRY THE UNIVERSITY OF TENNESSEE, December 1991, pages 643-651. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3031111A1 (fr) * 2014-12-31 2016-07-01 Arkema France

Also Published As

Publication number Publication date
AU1127297A (en) 1997-06-27

Similar Documents

Publication Publication Date Title
EP2412410B1 (fr) Compositions d'extinction et suppression de feux comprenant des fluorocarbones insaturés
EP0570367B2 (fr) Procédé pour la prévention d'incendie
US5124053A (en) Fire extinguishing methods and blends utilizing hydrofluorocarbons
CA2008862C (fr) Refrigerant a base de bis(difluoromethyl)ether
MXPA05011174A (es) Mezclas, metodos y sistemas para extinguir incendios.
US20030209685A1 (en) Methods for preparing ethers, ether compositions, fluoroether fire extinguishing systems, mixtures and methods
JPH08507524A (ja) Ｃｆｃ及びハロン代替フルオロヨードカーボン混合物
JPH05500920A (ja) 消火剤組成物及び消火方法
US5117917A (en) Fire extinguishing methods utilizing perfluorocarbons
WO1998009686A2 (fr) Melanges d'hydrobromocarbures destines a la protection contre les incendies et les explosions
WO2001060460A1 (fr) Procede d'extinction de feu
WO2017023591A1 (fr) Procédé pour l'extinction d'incendie
US20010032960A1 (en) Fire extinguishing methods and blends utilizing unsaturated perfluorocarbons
US6146544A (en) Environmentally benign non-toxic fire flooding agents
US3822207A (en) Fire-fighting
WO2015048604A1 (fr) Compositions d'extinction d'incendie et de lutte contre l'incendie comprenant du 3-chloro -1,1,1-trifluoropropène
WO1997020599A1 (fr) Procedes d'extinction d'incendie et melanges a base d'ethers d'hydrocarbure fluores
WO1991005585A1 (fr) Compositions extinctrices de feu, procedes et systemes utilisant du bromodifluoromethane
FI103182B (fi) Menetelmä tulipalon sammuttamiseksi
WO2010001430A2 (fr) Agents extincteurs comprenant des mélanges de fluoroiodocarbones et d’hydrofluorocarbones
MXPA06001565A (es) Compuestos de fluorosulfona.
CA2095640C (fr) Composition servant a eteindre un incendie et methode de production de cette composition
RU2225734C2 (ru) Газовый состав для объемного пожаротушения
US6402975B1 (en) Environmentally benign non-toxic fire flooding agents
RU2286821C2 (ru) Газовый огнетушащий состав

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase