WO2006020666A2 - Procedes de preparation d'ethers, de compositions d'ether, systemes, melanges et procedes d'extinction d'incendie au fluoroether - Google Patents

Procedes de preparation d'ethers, de compositions d'ether, systemes, melanges et procedes d'extinction d'incendie au fluoroether Download PDF

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WO2006020666A2
WO2006020666A2 PCT/US2005/028312 US2005028312W WO2006020666A2 WO 2006020666 A2 WO2006020666 A2 WO 2006020666A2 US 2005028312 W US2005028312 W US 2005028312W WO 2006020666 A2 WO2006020666 A2 WO 2006020666A2
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ocf
chfcf
extinguishing
present disclosure
fire
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PCT/US2005/028312
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WO2006020666A3 (fr
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Mark L. Robin
Thomas F. Rowland
John Chien
Janet Boggs
Mitchel Cohn
Vicki Hedrick
Stephan Brandstadter
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Great Lakes Chemical Corporation
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Publication of WO2006020666A3 publication Critical patent/WO2006020666A3/fr

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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes

Definitions

  • the present disclosure is directed to novel ether compounds and in particular aspects halogenated ether compounds and in other embodiments fluorinated ether compounds. Other aspects of the present disclosure are also directed to the production of these ether compounds and their uses. Certain aspects of the present disclosure are directed to hydrofluoroether fire extinguishing agents and methods for extinguishing fires using the hydrofluoroethers. Aspects of the present disclosure are directed to fire extinguishing agents and methods using saturated or unsaturated, fluorinated C 4 and/or C 5 hydrofluoroethers, and blends of one or more of the hydrofluoroethers with one or more other fire extinguishing agents.
  • 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.
  • hydrofluorocarbons have been proposed for fire suppression, for example in U.S. Pat. No. 5,124,053.
  • ethers particularly fluoroethers, have been identified as compounds that may be useful as halon replacements. Typically, these compounds are synthesized with all of the necessary fluorine content in place.
  • An embodiment of the present disclosure provides ethers used as extinguishants (including streaming and total flooding agents), solvents, refrigerants, blowing agents, etchants, anesthetics, and propellants.
  • hydrofluoroethers saturated or unsaturated, higher fluorinated hydrofluoroethers and blends thereof with other agents as fire extinguishants for use in fire extinguishing methods and apparatus.
  • hydrofluoroethers may be used alone, in admixture with each other or as blends with other fire extinguishing agents.
  • Fig. 1. is a diagram of one embodiment of ether production in accordance with an aspect of the present disclosure.
  • Fig. 2 is an illustration of an application of extinguishing mixtures in accordance with an aspect of the present disclosure.
  • Figs. 3A and 3B are kinetic data for reactions in accordance with an aspect of the present disclosure.
  • Fig.4 is IR spectra obtained in accordance with an aspect of the present disclosure.
  • Figs. 5A and 5B are kinetic data for reactions in accordance with an aspect of the present disclosure.
  • Figs. 6A-6C are kinetic data for reactions in accordance with an aspect of the present disclosure.
  • Figs. 7A and 7B are IR spectra of compositions according to an aspect of the present disclosure.
  • fluoroethers are produced and utilized to extinguish combustion.
  • fluoroethers includes all compounds having an ether group and a fluorine atom. Examples of these compounds include, but are not limited to perfluoroethers, hydrofluoroethers, fluorohalogenated ethers, and/or hydrofluorohalogenated ethers. Exemplary aspects of the present disclosure are described with reference to Figures 1 -7. Referring now to Fig. 1 , a reaction apparatus 10 including a source of olefin 1 , a source of alcohol 2, and basic aqueous solution 4 (with the olefin, alcohol, and basic aqueous solution being reagents 7) is shown.
  • the apparatus further includes a reaction vessel 3.
  • olefin 1 , alcohol 2, and a basic aqueous solution 4 are combined to form an ether containing reaction product 5.
  • Reagents can be combined in a batch, semi- continuous, or continuous fashion.
  • Reaction product 5 can remain in reaction vessel 3 and/or be transferred to a separation vessel 6, as shown, where a crude ether product 8 is separated from reagents 7.
  • Reagents 7 can then be returned to reaction vessel 3 to react in the presence of additional or remaining basic aqueous solution 4.
  • G. C. area % corresponds to percentage area of peak in comparison to all peaks generated when the respective sample is analyzed by a gas chromatograph equipped with a flame ionization detector and a silica-plot column.
  • the ether containing reaction product may be removed from reaction vessel 3 in a number of forms including as a gas or as a top, middle or bottom liquid layer.
  • the separation of crude ether 8 from reagents 7 may involve removal of crude ether product 8 as a gas or as a top, middle, or bottom liquid layer and otherwise removal of reagents 7 as a gas or a top, middle, or bottom layer. Consequently, the return of reagents 7 to reaction vessel 3 may take the form of the return of a gas and/or liquid composition.
  • R 1 can include lone halogens, lone hydrogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups either alone or in combination.
  • the halogenated alkyl groups includes all alkyl groups having at least one halogen, regardless of what the remaining elements of the alkyl might be.
  • halogenated alkyl groups include but are not limited to -CHFCI, -CF 3 , or -CF 2 CI.
  • R 2 can include lone halogens, lone hydrogens, halogenated alkyl groups, hydrogenated alkyl groups or perhalogenated alkyl groups either alone or in combination.
  • R 1 and R 2 can be the same or different groups.
  • R 1 includes CF 3 - or F.
  • R 2 can be H or F.
  • R 1 can be F and R 2 can be F.
  • R 1 can be F and R 2 can be H.
  • X and Y can generally represent hydrogen and/or the halogens I, Br, Cl, and/or F.
  • X and Y can be the same element, for example, X can be F and Y can be F.
  • X and Y can be different elements, for example, X can be F and Y can be H.
  • Alcohol 2 includes hydrogenated and halogenated alcohols. According to an aspect of the present disclosure, alcohol 2 can include methanol (CH 3 OH), ethanol (CH 3 CH 2 OH), and/or isopropanol ((CH 3 ) 2 CHOH).
  • Basic aqueous solution 4 can include sufficient base to ensure the formation of an alkoxide upon combination with an alcohol.
  • Bases that can be used to form the alkoxide include those of sodium and potassium such as sodium hydroxide (NaOH) or potassium hydroxide (KOH).
  • basic aqueous solution includes KOH.
  • basic aqueous solution 4 includes an aqueous solution having a KOH concentration of 10-45% (wt./wt.).
  • This KOH solution can be combined with alcohol 2 in reaction vessel 3 to form a first reactant mixture having an alcohol concentration of 50-60% (wt./wt.) and a KOH concentration of 5-20% (wt./wt.).
  • Olefin 1 can then be combined with the first reactant mixture in reaction vessel 3.
  • Reaction vessel 3 can have a temperature from about -10 0 C to about 50°C.
  • the bottom organic phase containing crude ether 8 can be separated from the top mixture that can include reagents 7.
  • reagents 7 can be returned to reaction vessel 3.
  • the crude ether 8 of the present disclosure can generally be referred to as an ether or halogenated ether and have the general formula R 3 CXY-O-R 4 .
  • the R 3 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups.
  • R 3 can include CF 3 CHF-, CF 3 CH 2 -, and/or CHF 2 -.
  • the R 4 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups.
  • R 4 can include - CH 3 , -CH 2 CH 3 , and/or -CH(CH 3 ) 2 .
  • the halogenated ether includes CF 3 CHFCF 2 OCH 3 .
  • the halogenated ether includes CF 3 CH 2 CF 2 OCH 3 .
  • the halogenated ether includes CHF 2 CF 2 OCH 3 .
  • Non-limiting examples 1 -3 demonstrate aspects of ether preparation according to the present disclosure.
  • aqueous 45% (wt./wt.) KOH solution is added to methanol to produce a mixture containing 60% (wt./wt.) methanol and 18% (wt./wt.) KOH.
  • This mixture is placed in a three- neck glass flask equipped with a dry ice condenser, a dip tube, and a thermometer.
  • HFP is fed through the dip tube into the solution at -3°C to 0 0 C.
  • the condenser. is kept at -30 to - 40 0 C in order to condense unreacted HFP back into the reactor.
  • a water bath is used to control the exothermic reaction.. When the solution becomes a milky suspension, the mixture is drawn out of the reactor and allowed to phase separate.
  • the bottom organic phase containing crude CF 3 CHFCF 2 OCH 3 is separated out, and the top mixture with additional methanol is fed back to the reactor.
  • Four aliquots of the crude CF 3 CHFCF 2 OCH 3 are collected at time intervals and analyzed by gas chromatography for lights, unreacted olefin, ether, and heavies. The results are shown below in Table 1.
  • CF 3 CF CF 2 + CH 3 OH -SF 3 CHFCF 2 OCH 3
  • Example 2 is performed as Example 1 with the modification that the reaction is performed using an aqueous mixture having 13% (wt./wt.) KOH and 57% (wt./wt.) methanol at 15°C to 25°C, and two collection aliquots are taken and analyzed by gas chromatography. The gas chromatography results are reported below in Table 2.
  • CF 2 CF 2 + CH 3 OH -QHF 2 CF 2 OCH 3
  • a halogenated ether intermediate can be formed by reacting an ether with a halogen in the presence of actinic energy.
  • This reaction can be carried out in a photochemical reactor.
  • the reactor may be configured to provide actinic energy to its content from an internal and/or an external source.
  • a medium pressure mercury lamp 100 watt, 11.49 watt total radiant energy
  • Other configurations may include the use of 90% 3500 angstrom range of photon black light providing 24 watts of total radiant energy.
  • the reactor may be cooled, for example, from a municipal water source.
  • the halogen can include chlorine (Cl 2 ).
  • halogens such as bromine or iodine may be utilized as well.
  • the reaction can be performed at a temperature from about 1 O 0 C to about 70 0 C.
  • methods include providing a photochemical reactor containing an ether.
  • the ether can have the general formula R 3 CXY-O-R 4 , as described above.
  • the halogenated either intermediate can have the general formula R 5 CXY-O-R 6 .
  • the R 5 group can include hydrogenated alkyl groups, halogenated alkyl groups, and/or perhalogenated alkyl groups.
  • R 5 can include CF 3 CHF-, CF 3 CCIF-, CF 3 CH 2 -, CF 3 CHCI-, CF 3 CCI 2 -, CHF 2 -, and/or CCIF 2 -.
  • the R 6 group can include halogenated alkyl groups or perhalogenated alkyl groups.
  • R 6 can include -CH 2 CI, -CHCI 2 , and/or -CCI 3 .
  • the halogenated ether intermediate can include CF 3 CHFCF 2 OCCI 3 .
  • the halogenated ether intermediate can include CF 3 CHFCF 2 OCHCI 2 .
  • the halogenated ether intermediate can include CF 3 CHFCF 2 OCH 2 CI.
  • the halogenated ether intermediate can include CF 3 CCIFCF 2 OCCI 3 .
  • two halogenated ether intermediates useful in the production of fluoroethers can be produced according to the present disclosure.
  • the ether CF 3 CHFCF 2 OCH 3 can be chlorinated according to the present disclosure to produce a mixture of halogenated ether intermediates such as CF 3 CHFCF 2 OCHCI 2 and CF 3 CHFCF 2 OCCI 3 .
  • Non-limiting Example 4 demonstrates an aspect of the halogenated ether intermediate production methods according to the present disclosure.
  • This reaction is carried out in a jacketed glass photochemical reactor cooled with tap water.
  • a medium pressure mercury lamp (1 OO watt, 1 1.49 watt total radiant energy) is used for the reaction.
  • Chlorine gas is bubbled into 40Og of liquid CF 3 CHFCF 2 OCH 3 at 2O 0 C - 30 0 C and by-product HCI is vented to a water scrubber.
  • the reaction is stopped, the crude reaction mixture is sampled, analyzed by gas chromatography, and then distilled.
  • Two major products are generated in the reaction, CF 3 CHFCF 2 OCHCI 2 [37% (G.C. Area %), b.p. 75°C@42 cmHg] and CF 3 CHFCF 2 OCCI 3 [61 % (G.C. Area %), b.p. 82°C@32 cmHg] for a total of 482g of recovered crude material.
  • halogenated ether intermediates can have the general formula R 5 CXY-O-R 6 , as described above.
  • the halogenated ether intermediate can be selectively fluorinated in the presence of HF and a catalyst to produce a fluoroether.
  • the catalyst can include a chromium/carbon catalyst that has been pre-fluorinated.
  • the catalyst utilized may take pure or supported forms.
  • Supports include but are not limited to those of activated carbon.
  • the catalysts themselves include but are not limited to such catalysts as those of chromium, nickel, iron, vanadium, manganese, cobalt, and/or zinc.
  • the preparation can occur from about 100 °C to about 300 0 C. In certain aspects, the temperature of the reaction is about 200 0 C.
  • the fluoroether produced can have the general formula R 7 -O-R 8 .
  • the R 7 group can include hydrogenated alkyl groups, hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups.
  • R 7 can include CF 3 CHFCF 2 -, CF 3 CCIFCF 2 -, CF 3 CF 2 CF 2 -, CF 3 CH 2 CF 2 -, CF 3 CHCICF 2 -, CF 3 CCI 2 CF 2 -, CHF 2 CF 2 -, CF 3 CF 2 -, and/or CCIF 2 CF 2 -.
  • the R 8 group can include hydrofluorohalogenated alkyl groups, hydrofluorinated alkyl groups, fluorohalogenated alkyl groups, and/or perfluorinated alkyl groups.
  • R 8 can include -CFCI 2 , -CF 2 CI, -CF 3 , - CHFCI, -CF 2 H, and/or CFH 2 .
  • the fluoroether includes the hydrofluoroether CF 3 CHFCF 2 OCF 3 .
  • the fluoroether includes the hydrofluoroether CF 3 CHFCF 2 OCHF 2 .
  • the fluoroether includes the perfluorinated ether CF 3 CF 2 CF 2 OCF 3 .
  • an ether can be fluorinated in the presence of liquid hydrogen fluoride (HF).
  • HF liquid hydrogen fluoride
  • an ether having at least one of the halogens I, Br, or Cl can be fluorinated in the presence of liquid HF to produce a fluoroether.
  • the fluoroether produced according to this aspect of the present disclosure can be characterized as having at least one more fluorine atom than the ether.
  • the ether CF 3 CHFCF 2 OCCI 3 can be fluorinated in the presence of liquid HF to produce the fluoroether CF 3 CHFCF 2 OCFCI 2 .
  • this f luorination can occur from about 40 0 C to about 120 0 C. In one aspect of the present disclosure, this fluorination can occur at approximately 70 0 C.
  • the fluoroether produced according to this aspect of the present disclosure may be utilized as starting materials for other aspects of the present disclosure. Accordingly, the ether can be fluorinated at about 70 0 C and subsequently fluorinated at about 200 0 C. The ether may also be fluorinated at about 70 0 C and subsequently fluorinated at about 230 0 C or 280 0 C.
  • the ether CF 3 CHFCF 2 OCCI 3 can be fluorinated in the presence of liquid HF to produce the fluoroether CF 3 CHFCF 2 OCFCI 2 , which can be fluorinated in the presence of HF and a catalyst as described above to produce the hydrofluoroether CF 3 CHFCF 2 OCF 3 .
  • Non-limiting Examples 5-8 demonstrate aspects of the present disclosure.
  • R 1 CF 3 CHFCF 2
  • Chromium (III) oxide catalyst 1 (38 grams) is charged to a 0.5 inch x 14.125 inch long Inconel® tubing reactor which is heated by a ceramic fiber heater. The catalyst is dried under nitrogen at 250-300 0 C. After drying, the catalyst is prefluorinated at 250-300 0 C using a HFiN 2 mixture (using a 1 :20 dilution). This prefluorination is continued until HF is detected exiting the reactor. At this point, the nitrogen is turned off, and the temperature is increased to 350 0 C. The catalyst is held under these conditions for 16 hours. After pre-fluorinating the catalyst, HF and CF 3 CHFCF 2 OCCI 3 were fed into the reactor at predetermined rates and temperature under atmospheric pressure.
  • R f CF 3 CHFCF 2 , Synetix® CP200A catalyst, PO Box 1 , Billingham, TS23 1 LB, UK
  • An embodiment of the present disclosure also provides multi-step synthetic processes for the production of fluoroethers.
  • methods are provided for manufacturing fluoroethers that include combining an alcohol with an olefin to produce an ether. Subsequently, reacting the ether with a halogenating agent to produce a halogenated ether intermediate and then fluorinating the halogenated ether intermediate with HF to from a fluoroether.
  • the halogenated ether intermediate can be fluorinated with HF at a first temperature to from a fluoroether intermediate. The fluoroether intermediate can then be fluorinated with HF at a second temperature to form a fluoroether.
  • halogenated ether compounds have the formula R 9 OR 10 .
  • R 9 can be partially or fully halogenated, saturated or unsaturated, organic groups
  • R 10 can be partially or fully halogenated, saturated or unsaturated organic groups.
  • these halogenated ether compounds include CF 3 CHFCF 2 OCF 3 .
  • the structure of CF 3 CHFCF 2 OCF 3 was confirmed by gas chromatography mass spectrometry (GC-MS) and fluorine ( 19 F), proton ( 1 H), and carbon ( 13 C) nuclear magnetic resonance (NMR). The boiling point of this compound was also determined.
  • GC-MS gas chromatography mass spectrometry
  • m/e 69 (CF 3 ), 82 (CF 3 CH), 101 (CF 3 CHF), 129 (CHFCF 2 OCF or
  • the present disclosure also provides fire extinguishing mixtures which comprise fluoroether extinguishing agents that can extinguish fires through inertion, and/or dilution, as well as, chemical, physical, and/or thermal extinguishment methods.
  • Thermal extinguishment includes "cooling" a combustion.
  • the present disclosure also provides methods of extinguishing, preventing, and/or suppressing a fire using such fire extinguishing mixtures.
  • the present disclosure further provides fire extinguishing, preventing, and/or suppressing systems for delivering such fire extinguishing mixtures.
  • Fire extinguishing system 11 includes an extinguishing agent storage vessel 13 contiguous coupled to an extinguishing agent control device 14.
  • Control device 14 is coupled to a combustion detector 15 and an extinguishing agent dispersing nozzle 17.
  • Combustion detector 15 can a be a smoke detector and can be configured to provide a signal to control device 14 indicating that combustion has been detected in space 27.
  • Control device 14 can include process circuitry configured to receive the signal from detector 15 and release extinguishing agent from vessel 13 to nozzle 17.
  • Control device 14 can include valves (not shown) coupled to the process circuitry with the valves being configured to be opened by the process circuitry.
  • a combustion 21 occurs within a pan 23 on a pedestal 25.
  • An extinguishing mixture 19 exists within space 27 and is applied to combustion 21 to substantially extinguish the flame.
  • FIG. 2 illustrates a system configured for extinguishing fires within a space that, as illustrated, appears to be enclosed, the application of the mixtures, systems, and methods of the present disclosure are not so limited. In some aspects, the present disclosure may be used to extinguish fires in open spaces, as well as, confined spaces.
  • All combustion suitable for extinguishment, suppression or prevention using the mixtures of the present disclosure or utilizing the methods and systems according to the present disclosure are at least partially surrounded by a space.
  • the available volume of this space can be filled with the compositions of the present disclosure to extinguish, suppress, and/or prevent combustion.
  • the available volume is that volume which can be occupied by a liquid or a gas [i.e. that volume within which fluids (gases and liquids) can exchange].
  • Solid constructions typically are not part of the available volume.
  • Fig. 2 illustrates a single extinguishing agent storage vessel 13. It should be understood that extinguishing mixture 19 can be provided to room 27 from multiple extinguishing agent storage vessels 13 and the present disclosure should not be limited to mixtures, methods, and/or systems that can be provided from a single vessel nor methods or systems that utilize a single vessel. Generally, combustion 21 is extinguished when extinguishing mixture 19 is introduced from vessel 13 through nozzle 17 to space 27. It should also be understood, that while Fig. 2 illustrates a single nozzle 17, multiple nozzles may be utilized, and the present disclosure should not be limited to mixtures, methods, and/or systems utilizing a single nozzle.
  • extinguishing mixture 19 can comprise, consist essentially of, and/or consist of a fluoroether extinguishing agent. In another aspect, extinguishing mixture 19 can comprise, consist essentially of, and/or consist of a fluoroether extinguishing agent and a suppressing additive and/or other fire extinguishing agents.
  • the suppressing additive employed can include diluent gases, water, and/or mixtures thereof.
  • diluent gases can include nitrogen, argon, helium, carbon dioxide, and/or mixtures thereof.
  • these gases can deprive fires of necessary ingredients, such as oxygen and/or fuel.
  • these diluent gases resist decomposition when exposed to combustion.
  • these gases are referred to as inert gases.
  • An exemplary diluent gas can comprise, consist essentially of, and/or consist of nitrogen.
  • the saturated and unsaturated C 4 and C 5 hydrofluoroethers of the present disclosure have been found to be effective fire extinguishants at concentrations safe for use.
  • these ether compounds have the formula R 9 OR 10 .
  • R 9 can be partially or fully halogenated, saturated or unsaturated, organic groups
  • R 10 can be partially or fully halogenated, saturated or unsaturated organic groups. More specifically the extinguishing compounds of the present disclosure can have the general formula Z 1 -O-Z 2 .
  • the Z 2 group can include -CHF 2 , -CF 3 , -CH 2 F, -CH 2 Br, -CFBr 2 , -CHFBr or - CF 2 Br.
  • the extinguishing compound includes CF 3 CHFCF 2 OCF 3 and/or CF 3 CHFCF 2 OCHF 2 .
  • hydrofluoroethers can include at least about 10% by weight of the blends, and the overall concentration of the blend lies in the range from about 3 to about 15%, preferably from about 5 to about 10% in air, on a v/v basis.
  • the agents of this disclosure are suitable for use in both total flooding and portable fire suppression applications.
  • Suitable extinguishing agents for blends with the compounds include CF 3 CHFCF 3 , CF 3 CF 2 CF 2 H, CF 3 CH 2 CF 3 , CF 3 CHFCF 2 H, CF 3 CF 2 H, and
  • the compounds according to the present disclosure may be used in conjunction with difluoromethane (HFC-32), chlorodifluoromethane (HCFC-22), 2,2-dichloro-1 ,1 ,1 - trifluoroethane (HCFC-123), 1 ,2-dichloro-1 ,1 ,2-trifluoroethane (HCFC-123a), 2-chloro- 1 ,1 ,1 ,2-tetrafluoroethane (HCFC-124), 1 -chloro-1 ,1 ,2,2-tetrafluoroethane (HCFC-124a), pentafluoroethane (HFC-125), 1 ,1 ,2,2-tetrafluoroethane (HFC-134), 1 ,1 ,1 ,2- tetrafluoroethane (HFC-134a), 3,3-dichloro-1 ,1 ,1 ,2,2-pentafluoropropane (HCFC-225ca
  • the C 4 or C 5 hydrofluoroethers of this disclosure 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, acceptable 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, acceptable 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.
  • 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.
  • a concentration of the hydrofluoroether agents, mixtures, and blends in accordance with an aspect of this disclosure lies in the range of about 5 to 10% (v/v).
  • an extinguishing mixture comprising, consisting essentially of, and/or consisting of CF 3 CHFCF 2 OCF 3 may be employed. CF 3 CHFCF 2 OCF 3 can be employed at concentrations of about 5 % (v/v).
  • Fluoroethers 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.
  • 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 to automatically and/or manually introduce an appropriate concentration 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 gases in order to insure that the agent is completely expelled from the extinguisher. Hydrofluoroether containing systems in accordance with this disclosure may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions. Non-limiting Examples 9-13 demonstrate aspects of the present disclosure.
  • This example demonstrates the desirable "throw” obtainable with the fire suppression agents of the present disclosure 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 is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder is charged with 50 grams of CF 3 CHFCF 2 OCF 2 H and then pressurized with nitrogen to the desired pressure.
  • the cylinder contents are completely discharged and the throw distance noted (Table 6). Table 6
  • a 150 mL SS cylinder is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder is 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 is filled with 20 mL of methanol.
  • the methanol is ignited and allowed to burn for 30 seconds; the agent is then discharged from a distance of 4 feet onto the fire.
  • the methanol fire can be extinguished in 1.5 seconds; a total of 16 grams of agent was discharged.
  • Example 10 The method of Example 10 is employed with acetone, isopropanol, and heptane fuels. All fires are rapidly extinguished (see Table 7).
  • a 150 ml_ SS cylinder is equipped with an inlet tube and a dip tube connected via an on/off valve to a delivery nozzle.
  • the cylinder is charged with 30 grams of CF 3 CHFCF 2 OCF 2 H and then pressurized with nitrogen to 120 psig.
  • a wood crib can be 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 is soaked with heptane, ignited, and allowed to burn for five minutes.
  • the agent is then discharged onto the fire, rapid ( ⁇ 2 seconds) extinguishment can be achieved; a total of 25 grams of agent is discharged. Immediately after extinguishment, the wood crib is cold to the touch, demonstrating the efficient suppression afforded by the agent.
  • Extinguishing concentrations of the hydrofluoroether CF 3 CHFCF 2 OCF 3 can be determined using a cup burner apparatus, as described in M. Robin and Thomas F. Rowland, "Development of a Standard Cup Burner Apparatus: NFPA and ISO Standard Methods, 1999 Halon Options Technical Working Conference, Apr. 27-29, 1999, Albuquerque, N.Mex.” and incorporated herein by reference.
  • the cup burner method is a standard method for determining extinguishing mixtures and has been adopted in both national and international fire suppression standards. For example, NFPA 2001 Standard on Clean Agent Fire Extinguishing Systems and ISO 14520-1 : Gaseous Fire-Extinguishing Systems, both utilize the cup burner method.
  • a mixture of air and CF 3 CHFCF 2 OCF 3 is flowed through an 85 mm (ID) Pyrex chimney around a 28 mm (OD) fuel cup.
  • a wire mesh screen and a 76 mm (3 inch) layer of 3 mm (OD) glass beads are employed in the diffuser unit to provide thorough mixing of air and CF 3 CHFCF 2 OCF 3 .
  • n-Heptane is gravity fed to a cup from a liquid fuel reservoir consisting of a 250 ml_ separatory funnel mounted on a laboratory jack, which can allow for an adjustable and constant liquid fuel level in the cup.
  • the fuel is ignited with a propane mini-torch and the chimney is placed on the apparatus.
  • the fuel level is then adjusted such that fuel is 1 -2 mm from the ground inner edge of the cup.
  • a 90 second preburn period is allowed, and a primary flow of air is initiated via a calibrated flow meter @ 20-40 L/min.
  • Primary and secondary air flows are monitored by calibrated flow meters (210, 225, 230 and 240 tubes). The flows are maintained until the flames are extinguished. A constant primary flow (240 tube) between 20 to 40 LJmin is maintained in all the tests.
  • the secondary flow of air is passed through CF 3 CHFCF 2 OCF 3 contained in a 1150 ml steel mixing chamber equipped with a dip-tube. The secondary flow, containing air saturated with CF 3 CHFCF 2 OCF 3 , exits the mixing chamber and is mixed with the primary air flow before entering the cup burner's diffuser unit.
  • G. C gas chromatographic analysis
  • the compounds of the present disclosure can be useful where cleanup of other media poses a problem.
  • Some of the applications of the hydrofluoroethers of this disclosure 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.
  • Non-self-sustaining combustible materials include materials which do not contain an oxidizer component capable of supporting combustion.
  • novel ethers according to the present disclosure can also be introduced to a fire for suppression purposes as a liquid or gas or combination of both. This is sometimes referred to as utilizing the composition as a streaming agent.
  • novel ethers according to the present disclosure can be introduced to fires in combination with other compounds as blends.
  • the disclosure provides a process for preventing and controlling fire in an enclosed air-containing mammalian-habitable compartment which contains combustible materials of the non-self-containing type which comprises (a) introducing the novel ether of the present disclosure into the air in the enclosed compartment in an amount sufficient to suppress combustion of the combustible materials in the enclosed compartment; and/or (b) introducing oxygen in an amount from zero to the amount required to provide, together with the oxygen present in the air, sufficient total oxygen to sustain mammalian life.
  • ethers of the present disclosure are used either alone or as blends as extinguishants, including streaming and total flooding agents, solvents, refrigerants, blowing or expansion agents, etchants, anesthetics, propellants, and as power cycle working fluids.
  • novel ethers of the present disclosure may be used to produce refrigeration by condensing the ether either alone or as a blend and thereafter evaporating the condensate in the vicinity of a body to be cooled.
  • the novel ether of the present disclosure may also be used to produce heat by condensing the refrigerant in the vicinity of the body to be heated and thereafter evaporating the refrigerant.
  • One aspect of the present disclosure is based on the finding that an effective amount of a composition consisting essentially of the novel ether according to the present disclosure will prevent and/or extinguish fire based on the combustion of combustible materials, particularly in an enclosed space, without adversely affecting the atmosphere from the standpoint of toxicity to humans, ozone depletion, or "greenhouse effect.”
  • Smog chamber/FTIR techniques can be used to determine: (i) kinetics of reactions with chlorine atoms; (ii) kinetics of reactions with hydroxyl radicals; (iii) infrared spectra; (iv) atmospheric lifetimes; and (v) global warming potentials.
  • the reactor can be surrounded by 22 fluorescent blacklamps (GE F40BLB) which can be used to photochemically initiate the experiments.
  • GE F40BLB 22 fluorescent blacklamps
  • Cl atoms can be generated by photolysis of Cl 2 in accordance with equation (1 ):
  • Reactant and product concentrations can be monitored using in situ Fourier transform infrared spectroscopy.
  • IR spectra can be derived from 32 co-added interferograms with a spectral resolution of 0.25 cm "1 and an analytical path length of 27.1 m.
  • Reference spectra can be acquired by expanding known volumes of reference compounds into the chamber.
  • CH 3 ONO can be obtained from commercial sources at purities >99%. Ultrahigh purity nitrogen, oxygen, and synthetic air diluent gases can be used as received.
  • CH 3 ONO can be prepared by the dropwise addition of concentrated H 2 SO 4 to a saturated solution of NaNO 2 in methanol and can be devoid of any detectable impurities using FTIR analysis.
  • the reactant and reference compounds used in the present work typically do not absorb at wavelengths above the Pyrex cut-off (> 300 nm). Control experiments can be performed in which reactant and product mixtures obtained after UV irradiation are allowed to stand in the dark in the chamber for 30 minutes.
  • the relative rate method is a well established and widely used procedure for measuring the reactivity of Cl atoms and OH radicals with organic compounds (see, e.g., Atkinson, R., J. Phys. Chem. Ref. Data, 1989, Monograph 1 , herein incorporated by reference).
  • Kinetic data can be derived by monitoring the loss of a reactant compound (CF 3 CFHCF 2 OCF 3 or CF 3 CFHCF 2 OCF 2 H in the present work) relative to one or more reference compounds. The decays of the reactant and reference can then plotted using equation (5):
  • CH 3 ONO itself can react with OH at a moderate rate (approximately 3 x 10 "13 cm 3 molecule "1 s "1 ), scavenges OH radicals, and can make loss of a less reactive compound (e.g.,
  • CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H (0.74 - 2.18 Torr) can be used to facilitate monitoring the CF 3 C(O)F product resulting from small ( ⁇ 0.2%) consumptions of
  • Relative rate experiments can be performed to measure the rates of reaction of Cl atoms with CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H. The results are shown in Fig. 3.
  • k 5 (4.09 ⁇ 0.33) x 10 "17 measured in the present work is consistent with the upper limit of k 5 ⁇ 7 x 10 16 cm 3 molecule '1 s "1 (see, e.g., Oyaro, N.; Sellevag, S. R.; Nielsen, CJ. , J. Phys. Chem. A, 2004, submitted, herein incorporated by reference).
  • k(OH+ CF 3 CFHCF 2 OCF 3 ) and k(OH+ CF 3 CFHCF 2 OCF 2 H) can be used to provide estimates of the atmospheric lifetimes of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H. Assuming an atmospheric lifetime for CH 3 CCI 3 with respect to reaction with OH radicals of 5.7 years (see, e.g., Prinn R. G.; Weiss R. F.; Miller B. R. Huang, J.; Alyea, F. N.; Cunnold, D. M.; Fraser, P. J.; Hartley, D.
  • the IR spectra of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H recorded in 700 Torr of air diluent at 296 K are shown in Figure 7.
  • the integrated cross sections (650-1500 cm-1 ) are (4.28 ⁇ 0.22) x 10-16 and (3.64 ⁇ 0.19)x 10-16 cm2 molecule-1 cm-1 for CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H, respectively.
  • Values of the GWP global warming potential for CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H (relative to CFC-11 ) can then be estimated using the expression (see, e.g. Sulbaek Andersen, M. P.; Hurley, M. D.; Wallington, T. J.; Blandini, F.; Jensen, N.
  • GWPHFE IF H FE, IF C FC-H . M H FE, MCFC-H . THPE, and ⁇ C Fc-n are the instantaneous forcings, molecular weights, and atmospheric lifetimes of the HFE and CFC-1 1 and t is the time horizon over which the forcing is integrated.
  • the GWPs of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H (relative to CFC-11 ) are 1.05 and 1.14 for a 20 year horizon and 0.98 and 0.94 for a 100 year time horizon, respectively.
  • the GWPs of CFC-1 1 on 20 and 100 year time horizon are 6300 and 4600 (Wallington, T. J.; Nielsen, O.
  • the GWPs of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H are 6600 and 7180 for a 20 year horizon and 4530 and 4340 for a 100 year time horizon, respectively.
  • the atmospheric lifetimes of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H can be determined to be approximately 40 and 32 years, respectively; and the 100 year time horizon global warming potentials of CF 3 CFHCF 2 OCF 3 and CF 3 CFHCF 2 OCF 2 H relative to CO 2 can be determined to be 4530 and 4340 respectively. All experiments can be performed at 700 Torr of N 2 AD 2 diluent at 296 K.

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Abstract

L'invention concerne des fluoroéthers fluorés, saturés et insaturés, agents d'extinction d'incendie efficaces, économiques, ne détruisant pas l'ozone, utilisés seuls ou en mélange avec d'autres agents d'extinction d'incendie dans des systèmes de saturation totale ou portatif. Elle concerne aussi des procédés de production d'éthers, d'intermédiaires éthers halogénés, et de fluoroéthers, ainsi que des compositions de fluoroéthers. Elle concerne enfin des mélanges, des procédés et des systèmes d'extinction d'incendie au fluoroéther.
PCT/US2005/028312 2004-08-09 2005-08-09 Procedes de preparation d'ethers, de compositions d'ether, systemes, melanges et procedes d'extinction d'incendie au fluoroether WO2006020666A2 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5562861A (en) * 1993-03-05 1996-10-08 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
US5718293A (en) * 1995-01-20 1998-02-17 Minnesota Mining And Manufacturing Company Fire extinguishing process and composition
US5993682A (en) * 1996-09-09 1999-11-30 University Of New Mexico Hydrobromocarbon blends to protect against fires and explosions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5562861A (en) * 1993-03-05 1996-10-08 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
US5695688A (en) * 1993-03-05 1997-12-09 Ikon Corporation Fluoroiodocarbon blends as CFC and halon replacements
US5718293A (en) * 1995-01-20 1998-02-17 Minnesota Mining And Manufacturing Company Fire extinguishing process and composition
US5993682A (en) * 1996-09-09 1999-11-30 University Of New Mexico Hydrobromocarbon blends to protect against fires and explosions

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