CA2157567C - Fluoroiodocarbon blends as cfc and halon replacements - Google Patents
Fluoroiodocarbon blends as cfc and halon replacements Download PDFInfo
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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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
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- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
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- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
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- C08J2207/00—Foams characterised by their intended use
- C08J2207/04—Aerosol, e.g. polyurethane foam spray
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- C09K2205/32—The mixture being azeotropic
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- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/05—Use of one or more blowing agents together
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- Y10S422/00—Chemical apparatus and process disinfecting, deodorizing, preserving, or sterilizing
- Y10S422/90—Decreasing pollution or environmental impact
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- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/909—Blowing-agent moderator, e.g. kickers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S521/91—Plural blowing agents for producing nonpolyurethane cellular products
Abstract
A new set of effective, environmentally safe, nonflammable, low-toxkity refrigerants, solvents, foam blowing agents, propellants, and firefighting agents is disclosed. The agents are clean, electrically nonconductive, and have short atmospheric lifetimes, zero ozone-depletion potential, and low global warming potentials. The agents comprise at least one fluoroiodocarbon agent satisfying the general formula:
C a H b Br c Cl d F e I f N g O h, wherein a is between and including 1 and 8; b is between anal including 0 and 2; c, d, g and h are each between and including 0 and 1; a is between and including 1 and 17 and f is between and including 1 and 2, either neat or mixed with additives selected from the group consisting of: alcohols, esters, ethers, fluoroethers, hydrocarbons, hydrofluorocarbons, and perfluorocarbons.
C a H b Br c Cl d F e I f N g O h, wherein a is between and including 1 and 8; b is between anal including 0 and 2; c, d, g and h are each between and including 0 and 1; a is between and including 1 and 17 and f is between and including 1 and 2, either neat or mixed with additives selected from the group consisting of: alcohols, esters, ethers, fluoroethers, hydrocarbons, hydrofluorocarbons, and perfluorocarbons.
Description
WO 94120588 PCTlUS9410232i FLUOROIODOCARBON BLENDS AS CFC AND HALON REPLACEMENTS
GOVERNMENT RIGH7.'S
The U.S. Government is granted an irrevocable, non exclusive, nontransferable, royalty-free right to use the invention with the authority to grant said right for governmental purposes.
BACKGROUND OF THE INVENTION
Field of the Invention (Technical Field):
The invention disclosed herein generally relates to fluoroiodocarbo:n compositions of matter, and methods of making and using such compositions of matter.
Backc~.~round Art Chlorofluorocarbons (CFCs) such as CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, and blends containing these CFCs such as R-500 and R-502 are currently used as refrigerants , solvents , foam blowing agents, -.and propellants. C'FCs contain only chlorine, fluorine, and carbon, and have the general formula CxClyFz, where X = 1 or 2 and Y + Z = 2X + 2. A related group of chemicals known as halone> (also called bromofluorocarbons, BFCs), SUBSTITUTE SHEET (RULE 26) WO 94!2058 '~~ ~ ~ PCTIUS94/02321 having the general formula CwBrXCl fF, (where W = 1 or 2, Y - 0 or 1., and X+Y+Z=2W+2) are in current use as firefighting agents.
Because of the great chemical stability of CFCs and S halons, when they are released to the atmosphere only minuscule fractions are destroyed by nat~ ,ral processes in the troposphere. As a result, CFCs and.rialons have long atmospheric lifetimes and migrate to -the stratosphere where they undergo photolysis, forming chlorine and bromine radicals that seriously deplete the earth's protective ozone layer. Each chemical is assigned an ozone-depletion potential (ODP) that reflects its quantitativE: ability to destroy stratospheric ozone . The ozone depletion potential is calculated in each case relative to CFC-11 tCFCl3, trichloro-fluoromethane), which has been assigned a value of 1Ø Currently used CFCs have OD~Ps near 1; halons have ODPs between 2 and 14.
Names, formulas, and ODPs of commonly used CFCs and halons are shown in Table 1.
SUBSTITUTE SHEET (RULE 26) WO 94120588 '~ PCT/US94/02321 TABLE 1. TJAMES, FORMULAS, AND ODPs OF CFCS IN CURRENT
USE AS REFRIGERANTS, SOLVENTS, FOAM BLOWING AGENTS, AND
PRnPFT.T.ANTS .
CFC or Name Formula ODP
Halon CFC-11 trichlorofluoromethane CC1,F 1.0 CFC-12 ~ dichlorodifluoromethane CC1,F, 1.0 113 1,1,2-trichloro-1,2,2- CC1~FCCIFz1.1 CFC- trifluoroethane -CFC-114 1,2-dich.loro-1,1,2,2- CCIFzCCIFz0.8 tetraflu.oroethane CFC-115 chloropentafluoroethane CC1F~CF: 0.5 R-500 a -- 0.3 R-502 b 0.7 Halon 1211 bromochlorodifluoromethane CBrCIF- 4.1 Halon 1301 !'~ bromotri.fluoromethane CBrF, 12.5 i Halon 2402 1,2-dibromotetrafluoroethane CBrF.,CBrF~3.9 a. azeotropi.c blend of CCLzFz (CFC-12, 73.8 wt. o) ana eHry~r3 irlrw-125, 26.2 wt.%).
b. azeotropic blend of CC1F2CF3 (CFC-115, 51.2 wt.%) and CHCIFz (HCFC-22, 48.8 wt.%).
CFC- .1~?, for example, comprises approximately 26 o by weight of worldwide CFC production, and about 150 million pounds per year are produced. The vast majority of this CFC-12 is eventual:Ly released to the atmosphere, where it rises to the stratosphere, is struck by ultraviolet radiation, and decomposes to give chlorine radicals that catalytica:Lly destroy the protective ozone layer of the earth. This deplet=ion of stratospheric ozone allows more ultraviole~= light to reach the surface of the earth, resulting =_n increases in human skin cancer and cataracts plus damage. to crops, natural ecosystems, and materials, in addition to other adverse effects. This invention will significantly decrease these adverse effects by providing f~nvironmentall~y safe alternative agents to use in place of CFCs and halons.
SUBSTITUTE SHEET (RULE 26) - a At present, CFCs, in addition to selected hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are used as refrigerants, solvents, foam blowing agents, and propellants. CFCs have been widely used for these applications because of their effectiveness, low toxicity, nonflammability, electrical nonconductivity, cleanliness on evaporation, mis.,cibility with hydrocarbon and mineral oil lubricants, and relative nonreactivity towards copper, aluminum, and ferrous metals. However, CFCs are being phased out of production in the U. S . under the provisions of the Montreal Protocol, the Clean Air Act Amendments of 1990, and the presidential directive of 11 February 1992. Although HCFCs (with ODPs ranging from 0.02 to 0.11) deplete ozone much less than CFCs, HCFCs do cause some ozone depletion and are also scheduled to be phased out of production eventually under the Montreal Protocol.
The broad class of halocarbons consists of all molecules that contain carbon, may contain hydrogen, and contain at least one of the following halogen atoms:
fluorine, chlorine, bromine, or iodine. Iodocarbons are halocarbons that contain iodine; fluoroiodocarbons contain both fluorine and iodine. Haloalkanes are a subset of halocarbons comprising compounds made up cf only carbon, halogens, and possibly hydrogen, and having no oxygen, nitrogen, or multiple bonds. In principle, haloalkanes may be derived from hydrocarbons by substitution of halogen atoms (F, C1, Br, or I) for hydrogen atoms. Hydrocarbons themselves have been used as very effective refrigerants, solvents, foam blowing agents, and propellants but have the major disadvantage of extremely high flammability. Substitution with a high proportion of halogen atoms imparts nonflammability.
CFCs and other highly halogenated halocarbons therefore possess many of the desirable properties of hydrocarbons plus the substantial advantage of nonflammability.
SUBSTITUTE SHEET (RULE 26) 21°75 67 Toxicity is a major issue in the selection of refrigerants, solvents, foam blowing agents, propellants, and firefig~hting agents. For example, the toxic effects of haloalka.nes include stimulation or suppression of the 5 central nervous system, initiation of cardiac arrythmias, and sensitization of the heart to adrenaline. Inhalation of haloalkanes can cause bronchoconstriction, reduce pulmonary compliance, depress respiratory volume, reduce mean arterial blood pressure, and produce tachycardia.
Long term effects - can include hepatotoxicity, mutagenesi~~, teratogenesis, and carcinogenicity.
Environmental effects of halocarbons including ozone-depletion potential (ODP), global warming potential (GWP), anc. terrestrial impacts must be considered.
Chlorine- and bromine-containing haloalkanes are known to deplete stratospheric ozone, with bromine posing a greater problem (per atom) than chlorine. The depletion of ozone in. the stratosphere results in increased levels of ultraviolet radiation at the surface of the earth, causing increased incidences of skin cancer, cataracts, suppression of human immune systems, crop damage, and damage to aquatic organisms. These problems are considered so serious that the Montreal Protocol and other legislation have placed restrictions or. the production and use of volatile halogenated alkanes.
Flame suppression occurs by two mechanisms:
physical and chemical. The physical mechanism involves heat absorption by the molecules sufficient to lower the temperature of the combusting materials below the ignition point and/or displacement of oxygen thereby terminating combustion. The larger the extinguishant . molecule (t: he more atoms and bonds it contains) the more degrees of vibrational freedom it has, the higher the vapor heat capacity, and the greater the heat removal.
The chemical mechanism involves interruption of free radical f:Lame-propagation chain reactions involving SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCT/US94102321 hydrogen, oxygen, and hydroxyl radicals. It has been speculated (but not proven) that bromine atoms disrupt these chain reactions.
Previous firefighting agents utilized either chemical ~or physical action or both to achieve flame extinguishment.. Agents such as carbon dioxide displace oxygen and also absorb thermal energy. Agents such as water function solely by thermal energy absorption.
Previous halogenated agents such as carbon tetrachloride, bromotrifluoromethane, etc. employ bothfunctional means.
U.S. Army studies on halogenated agents in the 1940's resulted in the adoption of the well known Halon family of agents . Other work by New Mexico Engineering Research Institute has identified neat perfluorocarbons and some neat iodinated agents as having future potential as f ireffighting agents.
In this work a few iodine-containing chemicals in neat form were shown to exhibit similar extin~guishment properties to bromine-containing chemicals.
There are many concerns regarding b_rominated, perfluorinated, and neat iodinated agents. Bromina'ted agent s are presently being eliminated from worldwide _ production, pursuant to the adoption of the Montreal Protocol and the. Clean Air Act of 1990, due to their tremendous potential to destroy the stratospheric ozone a 30 layer. Perf7.uorinated agents have high global warming potential and atmospheric lifetimes estimated to be several thouaand years. Their production and use is being restricted by pending legislation and liability concerns of current manufacturers. The costs of perfluorocarbons are high and their firefighting ' performance i.s less than that of the brominated agents.
SUBSTITUTE SHEET (RULE 26~
WO 94120588 PCTlUS94/02321 In weight and volume critical situations such as aircraft, tanks, and ships, the additional quantity required for extinguishment cannot be tolerated. One neat iodinated agent (trifluoroiodomethane, CF,I) has long been known to have firefighting potential (Dictionary of Organic Compounds; Chapman and Hall, New York, 1982, p. 5477) . Concerns about CF3I revolve around toxicity and dispersion effectiveness.
~romotrifluoromethane (CF3Br) was the choice agent for such gaseous flooding applications and has remained so until the present time.
Refrigerants, solvents, foam blowing agents, propellants, and firefighting agents must be chemically stable during storage and use over long periods of time and must be unreactive with the containment systems in which they are housed. Refrigerants normally operate between the' temperature extremes of -98° C to 8° C. The majority o:F residential, commercial, and institutional applications lie in the range of -23° C to 8° C. In extraordinary cases (e. g., motor burnout) higher temperatures may be experienced, but in such cases the formation of other contaminants would make replacement of the fluid necessary anyway. Although solvents, foam blowing agents, and propellants are normally stored and used at room temperature, they may under unusual circumstances experience transient temperatures up to 150°C durir..g storage. Firefighting agents must be stable on storage at temperatures of -20°C to 50°C, and should decompose at flame temperatures to yield radical-trapping species.
A refrigerant operates by absorbing heat as it evaporates in one region of the apparatus, then gives up the heat a.s it recondenses in another portion of the apparatus. The required properties for effectiveness include appropriate vapor pressure curves, enthalpies of vaporization, solubility behavior (including oil SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94/02321 miscibility), toxicity, and flammability. CFCs 12, 114, 500, and 502 have been used as refrigerants for many years because they possess the required physical properties such as appropriate boiling points and operating pressures, enthalpies of vaporization, miscibility with mineral oi.~--based lubricants, low toxicity and nonflammability., In addition, CFCs are relatively noncorrosive to metals and seal materials.
Properties of commonly-used refrigerants (including typical evaporator and condenser temperatures and typical usages) are set forth in Table 2.
TABLE 2. TYPICAL EVAPORATOR AND CONDENSER TEMPERATURES
FOR CFC REFRIGERANTS
CFC Evap Temp Cond Temp Typical Usages (F) (F) 11 35 to 40 95 to 105 Centrifugal chillers, solvent, foam agent 12 -10 to 35 105 to 125 Auto A/C, freezers, window A/C units 13 -50 to -75 100 to 125 Verv Low temp freezers 113 35 to 40 95 to 105 Centrifugal chillers, solvent, cleaner 114 -24 to 35 100 to 125 Marine chillers, low temp freezers 2 0 115 -50 100 to 125 Low temp freezers 500 -30 to -80 100 to 125 Supermarket cases, vending machines, commercial transport 502 -40 to -100 100 to 125 Low temp refrigeration I
503 -100 to -200100 to 125 Cryogenic freezers Hydrocarbons including cyclopropane, propane, butane, and isobutane have also been used as highly effective refrigerants . However, hydrocarbons have found little commercial use as refrigerants because of their high flammability. They possess all of the other SUBSTITUTE SHEET (RULE 26) 15'~~
required properties The ASHRAE Standard 15 limits the use of most hydrocarbons as Class 2 or 3 refrigerants, limiting their use to laboratory equipment with a total charge of a.ess than 3 pounds or to technical/industrial applications wherein the refrigeration equipment is located rE:motely from inhabited buildings. These restrictions severely limit the current utility of refrigerants 'containing hydroca~bans .
Refrigeration equipment requires lubricant constantly circulating in the refrigerant fluid to avoid friction, overheating, and burnout of the compressor or bearings. Therefore miscibility of refrigerants with lubricants is an essential requirement. For example, most lubricants are not very soluble in hydrofluorocarbons (HFCs), ar~d this has presented major problems in. the use of the alternative agent HFC-134a for refrigeration.
Many billions of dollars worth of installed refrigeration and air-conditioning equipment currently exists. :If CFCs become unavailable and no drop-in replacements are available, much of this equipment will be renderecL inoperable and may wind up in landfills. The useful lifetime will be shortened drastically, and a significant: fraction of the energy and resources put into manufacturing and installing the equipment will be wasted.
A solvent must dissolve hydrophobic soils such as oils, greases, and waxes, should be nonflammable and relatively nontoxic, and should evaporate cleanly. For solvents, chemicals with boiling points between 35°C and 120°C are preferred, because this boiling point range allows evaporation in reasonable time (between one minute and two hours). Traditionally, CFC-113 and 1,1,1-trichloroet:hane have been solvents of choice. Recently, because of environmental concerns about halogenated solvents, interest in hydrocarbon solvents such as SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94102321 Stoddard solvent (a petroleum fraction c~ eight- to eleven-carbon hydrocarbons) has revived, despite the flammability of these solvents. when referring to hydrocarbon petroleum fractions, it is commonly 5 understood that the terms ligroin, mineral spirits, naphtha, petroleum ether, "and petroleum spirits may represent fractions with similar compositions and may at times be used interchangeably.
A foam blowing agent must create uniform, 10 controllable cell size in a polymer matrix, and preferably should provide high insulation value and be nonflammable. For foam blowing a wide variety of agents has been used, including CFC-11, HCFC-22, HCFC-123, HFC
134a, HCFC-141b, and pentane. Water is cften added in the foam blowing agent (up to about 25% by moles) to react with the forming polymer, liberating carbon dioxide and aiding cell formation. More recently, some manufacturers have shifted to using water as the exclusive blowing agent, despite slight losses in insulating ability, dimensional stability, and resistance to aging.
An aerosol propellant must have a high vapor pressure, low heat of vaporization, and stability on storage. In the U.S., CFCs were used as propellants until 1978, and in many countries CFCs are still in use for this purpose. The continued use of CFC aerosol propellants overseas contributes substantially to stratospheric ozone depletion. After 1978 in the U.S.
CFCs were replaced by the hydrocarbons butane and isobutane for many propellant applications. These gases are extremely flammable and people have been burned in fires involving these propellants.
Firefighting agents to replace halons must be effective extinguishants, relatively nontoxic, electrically nonconductive, must evaporate cleanly, and must have low environmental impact. Halons SUBSTfTUTE SHEET (RULE 26) 215 75 ~ 7 WO 94120588 PCTlUS94102321 (bromofluorocarbons), although they meet the first four criteria, have long atmospheric lifetimes and high ozone-depletion potentials, and will be phased out of . production. under the terms of the Montreal Protocol and other regulations.
Although it is relatively easy to identify chemicals having one, two, or three selected properties, it is very difficult to identify chemicals that possess simul-taneously all of the following properties: effective performance, nonflammability, low toxicity, cleanliness, electrical nonconductivity, miscibility with common lubricants, short atmospheric and environmental lifetimes, zero ODP, and very low GWP. Furthermore, the unusual and desirable properties of selected members of the obscure class of fluoroiodocarbons are by no means obvious. Fluoroiodocarbons have only rarely been studied, and very few of their properties are reported in the literature. Conventional chemical wisdom indicates that iodine-containing organic compounds are too toxic and unstab:Le to use for these purposes, and iodocarbons have been :rejected on those grounds by the majority of those skil:Ied in the art. Partly as a result of this prejudice, the properties of the class of fluoroiodoc:arbons have been investi-gated only slightly, and fluoroi.odocarbons have remained a little-known class of chemica7.s .
An important part of this invention is recognizing that the unique properties of fluorine (the most electronegative element) strengthen and stabilize a carbon-to-iodine bond sufficiently to render selected fluoroiodoc:arbons relatively nontoxic and stable enough for use in :solvent cleaning, refrigeration, foam blowing, and aerosol propulsion. Painstaking collection and b estimation of properties and screening for expected effectiveness, low toxicity, and low environmental impact have been carried aut to identify them as being suitable SUBSTITUTE SHEET (RULE 26) WO 94!20588 ,~ PCTIUS94/02321 ' 12 for these ne:w uses. Disclosed herein therefore are both new uses and new combinations of chemicals, leading to new and unexpected results.
Both t:he neat and blended fluoroiodocarbons described herein provide new, environmentally safe, nonflammable refrigerants, solvents, foam blowing agents, aerosol propellants, and. firefighting agents. These compounds have the characteristics of excellent performance, cleanliness, electrical nonconductivity, low 10toxicity, nonflammability (self-extinguishment), short atmospheric lifetime, zero ODP, low GWP, and negligible terrestrial ~erivironmental impact.
Althoug:h some fluoroiodocarbons are described briefly in the known chemical literature, their potential for the uses described herein has never been previously recognized. No fluoroiodoearbons have been used before for solvent cleaning, refrigeration, foam blowing, or aerosol propulsion, either in neat form or in blends.
One neat f:Luoroiodocarbon (CF3.I) has been briefly described as a firefighting agent in the open literature (Dictionary of Orcranic Compounds, Chapman and Hall, New York, 1982, p. 5477). A small number of additional neat fluoroiodocarbons has been proposed by one of the current inventors for use in firefighting, He>wever, neither any blenas containing fluoroiodocarbons nor the new. neat fluoroiodocarbon a 30 agents described herein have ever before been proposed for use in firefighting or any of the other uses described herein. These blends and new neat agents offer substantial advantages in terms of lower cost, lower toxicity, improved physical properties, and greater effectiveness.
~,x~ ~ ' SUBSTITUTE SHEET (RULE 26) SUMMARY OF THE INVENTION
A primary object of an aspect of the invention is the provision of relatively nontoxic agents for use in refrigeration, solvent cleaning, foam blowing, aerosol propulsion, and f:irefighting. Another object of an aspect of the invention is the provision of nonflammable and environmentally safe compositions of matter. Yet another object of an aspect of the invention is the provision of fluoroiodocarbon compounds that are clean and electrically nonconductive. Still another object of an aspect of the invention is the provision of neat and blended fluoroiodocarbons having zero ozone-depletion potential, low global warming potential, and negligible atmospheric and terrestrial environmental impacts.
An advantage of the invention is the duplication of existing refriger<~nts, solvents, foam blowing agents, aerosol propellant:, and firefighting agents at lower cost.
Another advantage of the invention is optimization of properties by blending of fluoroiodocarbons with selected 10 additives. Still another advantage of the invention is the provision of effective and, in some cases, superior compositions of :Eluoroiodocarbons as replacements for existing chemical compounds.
According to o:ne embodiment of the invention a composition comprises a blend of from 20 to 75 mol percent of at least one fluoroiodocarbon of the formula CaHbBrCCldFeIfNg, wherein a is between and including 1 and 8; b is between and including 0 and 2, c, d and g are each between and including 0 and 1, a is between and including 1 and 17, and f is between and including 1 and 2, the fluoroiodocarbon being electrically nonconductive and having an ozone ~;, ,~~~~~., 13a depletion potential less than 0.02 and a global warming potential less than that of chlorofluorocarbons, with from 25 to 80 mol percent at least one additive selected from the group consisting of (i) alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and 2-propanol, (ii) esters, (iii) ethers, (iv) miner<~.l spirits, (v) Stoddard's solvent, (vi) hydrocarbons seleci~ed from the group consisting of butane, cyclopropane, decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,.2-dimethylpropane, heptane; isobutane, limonene, 2-methylbutane, 3-methylhexane, 3-methylpentane, nonane, octane, pentane, pinene, propane, turpentine and undecane, (vii) hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-hepta.fluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane, (viii) ketones, and (ix) perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexa:ne, wherein the additive and the fluoroi~odocarbon are nonreactive in the blend, with the provi;~o that when the additive is selected from the group consisting of alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propano~_ and 2-propanol, and ketones, then a is between and including 1 and 3, b is between and including 0 and 2, c, d and g ax-e each between and including 0 and 1, a 13b is between and including 1 and 7, and f is between and including 1 and 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(BEST MODES FOR CARRYING OUT THE INVENTION) Desirable agents must possess all of the following properties: effectiveness, low toxicity, nonflammability, and environmental safety. Although it is relatively to easy find chemicals than meet two or three of these criteria, it is extremely difficult to identify chemicals that meet all desired criteria. The novelty of this invention lies in identifying chemical compounds and blends (and methods of using these) that meet all these criteria. The chemical compounds and blends described herein are effective, relatively nontoxic, nonflammable, and environmentally benign. They have the desired ~ 15 ~ 5 6'~
boiling points, vapor pressures, and heats of vaporization for optimal effectiveness. By mixing a fluoroiodocarbon with another chemical several major advantages are obtained. First, and perhaps most importantly, the mixture is rendered completely nonflammable. Second;, 'by appropriate blending of chemicals, the physical properties (including boiling range, density, viscosity, and lubricant solubility? can be optimized to obtain maximum performance. Third, the already low toxicity can be further reduced. Fourth, the cost of the agent is reduced.
As a general class, iodocarbons are more reactive, less stable, and more toxic than the corresponding chloro or bromocarbons; for this reason they have often been rejected as unsuitable for the applications described here. HowESVer, an important part of this invention is recognizing the tact that the unique properties of fluorine give polyfluorinated iodocarbons exceptionally low reactivity, high stability, and low toxicity.
Because fluorine is the most electronegative element, the presence of two or more fluorine atoms attached to the same carbon atom which is bonded to the iodine atom withdraws e:Lectron density and provides steric hindrance, making the carbon-to-iodine bonds in fiuoroiodocarbons abnormally strong and resistant to chemical reaction.
All of the three common mechanisms of chemical reaction are inhib~_ted in fluoroiodocarbons: unimoiecular nucleophilic substitution (SN1), bimolecular nucleophilic substitution (SN2), and homolytic bond cleavage. Because of this low reactivity, fluoroiodocarbons exhibit unusually high stability and low toxicity. In addition, iodocarbons have never been implicated in ozone depletion, global warming, or long-term terrestrial environmental contamination.
In applying the selection criteria of the invention, with regard to toxicity, each of the preferred compounds SUBSTITUTE SHEET (RULE 26) PCTlUS94102321 is characterized by acute toxicity (either measured or predicted) no greater than that of currently used CFCs.
In this regard, toxicity is measured as LCS~ (lethal concentration at the fifty percent level) for rats over 5 an exposure period of 4 hours. Toxicity data on fluoroiodocarbons is limited at this time but highly encouraging. All of the following fluoroiodocarbons are reported to have mice 1-hour LCSOs of greater than 10,000 ppm: 1-iodoperfluoroethane, 1-iodo-perfluorobutane, and 10 1-iodoperfluorohexane.
If a chemical is to have zero ODP it must either (1) not contain. chlorine nor bromine , or ( 2 ) undergo rapid and complete destruction by natural processes in the troposphere ( and tans never reach the stratosphere ) . The 15 three major mechanisms for destruction of halocarbons in the troposphere are photolysis, attack by hydroxyl radical (O~t) , and attack by oxygen atoms (0) . In the troposphere, because of shielding by stratospheric ozone and other ai.mospheric components, the sunlight present is of longer wavelength (and correspondingly lower energy) than the light present in the stratosphere . If molecules are to be photolyzed in the troposphere they must contain light-absorbing groups (chromophores) and weak bonds.
Such light-absorbing groups with weak bonds include carbon-to-iodine sigma bonds. Carbon-to-iodine bonds are extremely :sensitive to photolysis and cleave easily in the presence of sunlight, even at ground level. Thus, fluoroiodoc:arbons are destroyed rapidly by photolysis in the troposphere and thus do not contribute to ozone depletion or substantially to global warming.
The compounds of the present invention are also selected or.. the basis of their global warming potentials, which are increasingly being considered along with ozone depletion factors. Global warming is caused by absorption by molecules in the atmosphere of infrared radiation ~_eaving the surface of the earth. The longer SUBSTITUTE SHEET (RULE 26) the atmospheric lifetime and the greater the infrared absorption of a molecule, the greater its GWP. It is recognized that some chlorof3uorocarbons have GWPs several thousand times that of carbon dioxide. Because of their rapid photolysis and'resulting short atmospheric lifetimes, fluoroiodocarboris~have greatly reduced GWPs compared to CFCs,.~ halons, HCFCs, HFCs, and perfluorocarbons.
The short atmospheric lifetimes of fluoroiodocarbons are due to the preferential absorption of ultraviolet energy by the carbon-to-iodine bond, causing the agent to decompose in natural sunlight within a short period after it enters the atmosphere. Decomposition byproducts are harmless salts which are cleansed from the environment by natural precipitation. A fluoroiodocarbon may even contain a chlorine or bromine atom without causing measurable stratospheric ozone depletion because the molecule will be destroyed by photolysis of the C-I bond in the troposphere, never reaching the stratosphere.
In addition to undergoing rapid photolysis, iodoalkanes undergo faster hydrolysis than the corresponding chloro- or bromoalkanes; thus they degrade rapidly in natural waterways to form harmless products such as potassium iodide (a common additive to table salt). Because of this rapid degradation, fluoroiodocarbons (in contrast to CFCs) have never been implicated in long-term soil or ground water contamination.
Fluoroiodocarbons are highly effective flame suppression agents, in some cases more effective on a per-mole basis than halons (bromofluorocarbons).
Fluoroiodocarbons not only provide chemical extinguishment, but significant physical extinguishment through heat removal by molecular vibrations. Addition of a sufficient concentration of a fluoroiodocarbon to an otherwise flammable liquid or vapor (such as a SUBSTITUTE SHEET (RULE 26) 21'5 fi'~
1~
hydrocarbon) renders the material self-extinguishing.
The invention described and claimed herein is specifically related to liquid and gaseous chemical agents used to extinguish active and near active fires involving comi~ustible, flammable, and electrically energized mater-ials .
The agents described herein have acceptable stability on storage under normal conditions. To prevent photolysis of the fluoroiodocarbons, they should be protected from sunlight by storage in opaque containers such as metal cylinders or brown glass bottles. If desired, for lc;ng-term storage a small amount of copper metal can be added to enhance the stability of the iodides.
.5 The preferred fluoroiodocarbons meeting the selection criteria are set forth in Table 3 bet ow'. A11 the fluoroiodocarbon agents have boili ng points between -2S°C and +I70°C and satisfy the general chemical formula CaH~Br~Cl~F~ I =N~O;~; wherein a is between and including I and z0 8; b is between and including 0 and 2; c, d, g, and h are each between and including 0 and 1; a is between and including 1 and I7; and f is between and including ~. and 2.
TABLE 3. PREFERRED FLUOROIODOCARBON AGENTS.
5 Name ( s ) rF o rnui a bromodifluoroiodomethane C3rFZI
chlorodifluoroiodomethane CC1F,I
1,1,2,2,3,3,4.4,5,5-decafluoro-1,5-diiodopentane,I(CF~);
1,5-diiodoperfluoropentane 30 difluorodiicdomethane CF,IZ
difluoroiodomethane CAF
I,I,2,2,3,3,4,4,5,5,6,6-dodeCafluoro-1,6-diiodohexane,I(CF2);I
1,6-diiodoperfluorohexane fluoroiodomethane CHZFI
'~.P.., :; , ~. a,F ;~ ;~ , . . ~ n ~r..,~. ".
r..
,.gin, ~E.E~
WO 94120588 ~~ PCTIUS94/02321 1,1,1,2,3,3,3-heptafluoro-2-iodopropane, CF3CFICF3 ~
perfluoroisopropyl iodide 1, 1, 2 , 2 , 3 , 3. , 3-heptafluoro-1-iodopropaneCF3CFZCFzI
, perfluoropropyl iodide 1,1,2,2,3,3.-hexafluoro-1,3-diiodopropane,I(CFz),I
1,3-diiodoperfl.uoropropane 1-iodoheptadecafluorooctane, 1- CF3(CF2),I
iodoperfluorooctane, perfluorooctyl iodide iodoheptafl.uorocyclobutane, ' cyclo- (CFZ) iodoperfluorocyclobutane 1-iodopentadecafluoroheptane, 1- CF3 (CFz) 6I
iodoperfluoroheptane, perfluoroheptyl iodide iodo~entaf l.uorobenzene CSF~I
iodopentafl.uorocyclapropane, CFzCF2CFI
iodoperfluorocyclopropane, , perfluorocyclopropyl iodide 1-iodotride:cafluorohexane, 1- CF3 (CFZ) SI
iodoperfluorohexane, perfluorohexyl iodide 1-iodoundec:afluoropentane, 1- CF,(CFZ)9I
2 0 iodoperfluoropentane, perfluoropentyl iodide N-iodobis-(trifluoromethyl)amine (CF,)ZNI
1,1,2,2,3,.9,4,4,4-nonafluoro-1-iodobutane,l-CF,(CFz)3I
iodoperfluorobutane,perfluorobutvl iodide 1,1,2,2,3,a,4,4-octafluoro-1,4-diiodobutane,I(CFZ)4I
1,4-diiodoperfluorobutane pentafluoroiodoethane, perfluoroethvl CF,CF,I
iodide 1,1,2,2-tet:rafluoro-1,2-diiodoethane, CFZICF2I
1,2-diiodoperf7.uoroethane 1, 1, 2, 2-tet:rafluoro-1-iodoethane CF,ICHF, 3 0 1,1,2-trifa.uoro-1-iodoethane CF2ICH,F
trifluoroiodomethane, trifluoromethyl CF,I
iodide trifluoromethyl-1,1,2,2-tetrafluoro-2- CF30CFzCF2I
iodoethyl ether Preferred additives far blending with 3 5 f luoroiodocarbons are shown in Table 4 . Table 4 includes selected alcohols, esters, ethers, hydrocarbons, hydrofluorocarbons, fluoroethers, ketones, and SUBSTITUTE SHEET (RULE 26) perfluorocarbons with. boiling points between -150°C and +200°C.
Azeotrop ~c blends are particularly preferred because they do not change composition on evaporation and thus do not change properties if part of the mixture evaporates.
We have developed a proprietary computer program for predicting a~:eotrope formation based on the Soave-Redlich-Kwong equation of state and have screened the fluoroiodocarbon blends described herein to identify likely azeotropes. This program also incorporates novel methods we have developed for estimating properties of chemicals and blends: it provides accurate estimates of vapor pressure curves, enthalpies of vaporization, and other properties of interest, allowing selection of optimal blends.
TABLE 4. F~REFERRED ADDITIVES TO BE BLENDED WITH
FLUOROIODOCARBONS
Class Name s Formula alcohol 1-butanol HO ( CHz ) ,CH3 2 -butanol CH, CH ( OH ) CH,CH, ethanol CH,CH,OH
methanol CH,OH
2-methyl-1-propanol HOCH,CH(CH,)CH, 2-methyl-2-propanol (CH,),COH
1-pentanol CH,(CHz),OH
2 -pentanol CH,CHOHCH,CH,CH, 1-propanol HO ( CH2 ) ,CH, 2-propanol ( CH, ) ZCHOH
ester ethyl acetate CH,COOCH,CH, ethyl butanoate, ethylCH;(CHz)=COOCH=CH, butyrate ethyl propanoate, ethyl( CH,CH2COOCH2CH:
pronion.ate ' SUBSTITUTE SHEET (RULE 26) W0 941~~~$~.; PCTIUS94/02321 isobutvl acetate (CH, ) ,CHCH~OCOCH, isoprot~yl acetate CH,COOCH ( CH3 ) , methyl acetate CH,COOCH, methyl butanoate, CFi3(CHz),COOCH3 methyl butyrate methyl propanoate- CH3(CHZ)2COOCH, methyl propionate n-butyl acetate CH, ( CHZ ) ,OCOCH, hexyl acetate CH, ( CHZ ) SOCOCH, n-pentyl acetate, amylCH3(CH2)40COCH, acetate n-propyl acetate CH,(CHz),OCOCH, sec-butyl acetate CH,CH,CH (CH,) OCOCH, ether diethyl ether, ethyl (CHjCH2)20 ether diisopropyl ether, ( (CH3) ZCH) z0 isopropyl ether dimethyl ether, methylCH30CH3 ether di-n-butyl ether, butyl(CH,(CHz),)z0 ether di-n-propyl ether, (CH3CH2CH2) z0 propyl ether 1,4-dioxane cyclo-(CH,CH,O), ethylene oxide, 1,2- CHZOCH~
eDOxvethane propylene oxide, 1,2- CH20CHCH3 er~oxypropane tetrahydrofuran cyclo-(CHZ)qo fluoroether bis-difluoromethyl (CHF2)2o ether hexafluorodimethyl (CF,) zo ether, perfluorodimethvl ether hexafluorooxetane, cyclo-(CFz),O
perfluorooxetane methyl trifluoromethylCH30CF, ether SUBSTITUTE SHEET (RULE 26) WO 94120588 F'CT/US94102321 w ~f octafluorodimethoxymethCF,OCF,OCF3 'i ane octafluoro-l, 3- CF2 (OCFZCFZ) 2 dioxolane, perfluoro-1,3-dioxolane pentaf7.uorodimethyl CHFZOCF3 ether 1, l, 2' ,. 2' , 2' CHFZOCHzCF3 -pentafluoro methyl ethvl ether 1-trifluoromethoxy- CF30CFzCHFz 1,1,2,2-tetrafluoroethane hydrocarbon butane CH, ( CHZ ) ,CH, cvclopropane (CH,), decane CH, ( CH, ) oCH, 2 , 3 -dimethylpentane( CH, ) ZCHCH ( CH, ) CH,CH, 2,4-dimethylpentane ((CH3)ZCH),CH, 2,2-dimethylpropane (CH3),C
heptane CH,(CH,)~CH, hexane CH,(CHZ)qCH, isobutane CH,CH(CH3), ligroin blend cf hydrocarbons 1 imone:ne C, ~H, E
2-methylbutane ( CH3 ) ,CH2CH,CH, 3 -methylhexane CH,CH,CH ( CH, >
CH,CH,CH, 3-methylpentane CH,CH,CH (CH,) CH,CH, naphtha blend of hydrocarbons nonane CH, ( CH, ) ,CH, octane CH,(CHZ)~CH, pentane CH, ( CH, ) , CH, petroleum ether blend of hydrocarbons I
petroleum spirit blend of hydrocarbons SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTIUS94102321 pinene CloHl propane CH,CH,CH3 Stoddard's solvent blend of C8 to C11 hydrocarbons toluene C~H~CH, turpentine blend of hydrocarbons unde cane CH, ( CH, ) 9CH, hydrofluorocardifluoromethane CH2Fz bon 1,1-difluoroethane CHFZCH, 1,1,1,2,3,3,3- CF3CHFCF3 heptafluoropropane pentafluoroethane CF,CHF, 1, 1, 2, 2, 3- CHFZCFZCH2F
pentafluoropropane 1, l, 1, 2- CF3CHzF
tetrafluoroethane 1,1,1-trifluoroethane CH3CF3 trifluoromethane CHF, ketone acetone, propanone, CH3COCH3 2- ' prooanone 2-butanone, butanone, CH3COCHZCH3 methyl ethyl ketone carbon dioxide COz 2-hexanone, methyl CH3COCHZCHzCHzCH3 butyl ketone 3-methyl-2-butanone CH,COCH(CH,), 2-pentanone, methyl CH3COCHZCHZCH3 propyl ketone perfluorocarbodecafluorobutane, CF,(CFz)zCF, n perfluorobutane dodecafluoropentane, CF,(CFz)3CF3 perfluoropentane hexafluorocyclopropane,cyclo-(CFz)a perfluorocyclopropane SUBSTITUTE SHEET (RULE 26) hexaf luoroethane , CF,CF, perf luc>roethane octafluorocyclobutane,cyclo-(CF2)<
perfluorocvclobutane octafluoropropane, CF3CFzCF3 perfluoropropane tetradecafluorohexane,CF3 (CF2) 4CF3 perfluorohexane tetrafluoromethane, CF4 perfluoromethane Ref riQerants This invention discloses that by addition of an appropriate f:Luoroiodocarbon a hydrocarbon is made a more effective heat-transfer fluid and is rendered self-extinguishing. Such mixtures are unique non-flammable hydrocarbon blends.
All the new refrigeration agents described herein including blends are miscible with the four major groups of lubricants: mineral oil, alkylbenzenes, polyol esters (POEs), and polyalkylene glycols (PACs). The presence of higher-atomic-weight halogen atoms tchlorine, bromine, or iodine) in an agent, because of the polarizability of these atoms, allows miscibility with these lubricants.
A further advantage of hydrocarbon-containing refrigerants is that leak detection is greatly simplified compared to C'FCs or HFCs .
As shown. in Table 5, by appropriate chaices of pure agents or blends, drop-in replacements can be formulated to replace c:FCs in existing equipment. The agents described herein allow the replacement of thousands of tons of CFCs in existing equipment with environmentally safe, nonflammable, energy-efficient refrigerants. In new systems redesigned to optimize performance for fiuoroiodocai:bon-containing agents, superior performance will be obtained.
SUBSTITUTE St~EET (RULE 2R) WD 94!20588 ~"PCT/US94102321 Solvents Fluoroiodocarbon agents with boiling points in the desirable range for use as solvents include, for example, 1,1,2,3,3,3-heptafluoro-1-iodopropane, 1,1,1,2,3,3,3 heptafluoro-2-iodopropane, fluoroiodomethane, 1,1,2,2 tetrafluoro-1-iodoethane, 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane, difluorodliodomethane, undecafluoro-1-iodopentane, and tridecafluoro-1-iodohexane. By addition of a fluoroiodocarbon to a flammable solvent such as a hydrocarbon, alcohol, ester, or ketone the solvent is rendered nonflammable. In the case of blends, to prevent loss of the fluoroiodocarbon agent from the blend through evaporation, ideally the fluoroiodocarbon component should either form an azeotrope or have a boiling point equal to or slightly higher than the other component(s).
Foam Blowing Agents By addition of an appropriate quantity of a fluoroiodocarbon to the foam blowing agent, the foam produced is rendered nonflammable and its insulating abilities are improved.
Aerosol Propellants By addition of a sufficient quantity of a volatile fluoroiodocarbon a propellant such as propane, butane, or isobutane is rendered nonflammable.
Firefiahtina A eq nts By blending selected fluoroiodocarbons with hydrofluorocarbons, perfluorocarbons, and fluoroethers, agents are obtained that are highly effective, non-ozone-depleting, and have low toxicity and low cost. In some cases these blended agents provide synergism (better extinguishment than predicted linearly) because of the chemical extinguishment of the fluoroiodocarbon and the physical extinguishment of the additive. The vapor SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94102321 pressure, effectiveness, reactiT,rity with storage vessels and delivery systems, weight, cost, and toxicity may all be optimized by creating blends. Blended azeotropic and near-azeotropic fluo:roiodocarbon firefighting agents 5 allow reductic>n in the cost of the delivered agent by taking advantage of their superior extinguishment capabilities and the lower costs of hydrofluorocarbons, perfluorocarbons, and fluoroethers components compared to fluoroiodocarbons. In addition, they form constant- and 10 near-constant composition agents, simplifying handling and making performance more predicable than that of nonazeotropic blends. Such blends retain their composition at all times, do not fractionate into separate components, remain stable, and provide superior 15 performance. Selected blends act as functional alternatives in existing equipment and delivery systems, minimizing the equipment changes required.
Industrial Applicability:
This invention is further illustrated by the 20 following non-limiting examples.
Refrigerants Table 5 shows preferred examples of drop-in replacement refrigeration agents (including blends).
TABLE 5. EXAMPLES OF PREFERRED DROP-IN REPLACEMENT
Examples of replacements Refrigerant BI? Chemical (s) Approx.
C Proportions (by moles) 11 2'.3.8 CzFsI/n-C3F,I 50:50 n-C,F,I/butane/pentane 5:40:55 CIFSI/pentane 50 : 50 SUBSTITUTE SHEET (RULE 26) WO 94/20588 ~ ~ ~~ PCTIUS94102321 C~FSI/diethyl ether 50:50 n-C3F,I /butane 60:40 12 -29.8 CF,I neat CF3I/propane 60:40 CF,I/CF3CF2CF3 50 : 50 CF3I/CF3CFZCF3 10 : 90 (binary azeotrope) CF3I / CHFZCH3 8 : 92 (binary azeotrope) CF,I/cyclobutane 10:90 (binary azeotrope) CF3I/CF3CFzCF3/CHFZCH3 (ternary azeotrope) CF3I/fluoroethane 55:45 CF3I/cyclopropane 30:70 22 -40.8 CF3I/propane 5:95 or 10:90 CF3I/ (CF3) 20 50: 50 CF, I / CHFZOCF, 5 : 95 CF,I/difluoromethane 40:60 CF3I/pentafluoroethane 30:70 CF,I/1,1,1-trifluoroethane30:70 CF3I/perfluoropropane 30:70 500 -33.5 CF3I/propane 45:55 CF3I/ (CF3) 20 75:25 CF3I/pentafluoroethane 6D:40 CF3I/perfluoroethane 60:40 CF3I/1,1;1-trifluoroethane60:40 CF3I/difluoromethane 70:30 I
CF, I / f luoroethane 3 0 : 7 0 CF3I/perfluoropropane 20:80 502 -45.4 CF,I/difluoromethane 20:80 [ I
SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTlUS94102321 CF'3I/ (CF3) 20 40:60 CF'3I/trifluoromethane 60:40 CF'3I/pentafluoroethane10:90 CF',I/1,1,1-trifluoroethane10:90 CF',I/perfluoroethane 10:90 Solvents The following preferred pure agents and blends meet the requirements of solvent performance, nonflammability, low toxicity, and low environmental impact: neat 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane; neat undecafluoro-1~-iodopentane; neat tridecafluoro-1-iodohexane; 2 to 150 (by moles) 1,1,2,2-tetrafluoro-1-iodoethane with 98 to 85% hexane; 2 to 15 0 (by moles) 1,1,2,3,3,3-he~~tafluoro-1-iodopropane with 98 to 850 pentane; 2 t:o 15% (by moles) 1,1,2,2,3,3,4,4,4-nonafluoro-1-ic~dobutane with 98 to 85o hexane; 2 to 150 (by moles) tr:idecafluoro-1-iodohexane plus 98 to 850 octane, nonane, and/or decane; 2 to 150 (by moles) 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane with 98 to 850 of one or more chemicals selected from the group:
methanol, eth<~nol, 2-butanone, 2-propanol, acetone, methyl acetate, ethyl acetate, tetrahydrofuran, and hexane; and 2 to 150 (by moles) undecafluoro-1-iodopentane with 98 to 85% of at least one chemicals selected from t=he group: heptane, ethanol, 2-propanol, and 2-butanone.
Foam Blowing Ace3 nts The following preferred pure agents and blends meet the requirements for foam blowing agents: neat difluoroiodomethane; neat pentafluoroiodoethane; neat 1,1,2,3,3,3-heptafluoro-1-iodopropane; 2 to 150 (by moles) pentafluoroiodoethane with 98 to 85o butane; 2 to 15 0 (by moles) difluoroiodomethane with 98 to 85 o butane;
SUBSTITUTE SHEET (RULE 26) 2 to 15% (by moles) 1,1,2,3,3,3-heptafluoro-1-iodopropane with 98 to 85% pentane; 2 to 150 (by moles) pentafluoroiodoethane with 98 to 85o pentane; 2 to 15%
(by moles) trifluoroiodomethane with 98 to 85% 1,1-difluoroethane; 2 to 15%,~~..tby moles) trifluoroiodomethane with 98 to 85 o butane; and any of the agents in this list plus up to 40% by weight water.
Aerosol Propellants The following nonflammable preferred blends meet the requirements for aerosol propellants: 2 to 15% (by moles) trifluoroiodomethane with 98 to 85% of one or more of the chemicals selected from the group: propane, butane, isobutane, carbon dioxide.
Firefiahtina Agents The following preferred blends and neat fluoroiodocarbon agents meet the requirements for effective, clean firefighting agents: blends of CF3I
with at least one chemical selected from the group:
trifluoromethane,difluoromethane,pentafluoroethane,and 1,1,1,2-tetrafluoroethane; blends of CF3CFzCF2I with at least one chemical selected from the group CF3CFZI, CHZFI, perfluoropentane, and perfluorohexane; blends of CF3CFzCF2CF2I with perfluorohexane; and neat chlorofluoroiodomethane.
The following examples show the effectiveness of the agents listed as environmentally safe, nonflammable refrigerants, solvents, foam blowing agents, propellants, and f irefighting agents .
Example 1 From a household refrigerator the charge of CFC-12 (about 6 to 8 oz) is removed and collected for recycling, reclamation, or destruction in an environmentally sound manner. The refrigerator is then charged from a SUBSTITUTE SHEET (RULE 26) pressurized bottle through a closed system with an equivalent mas;~ of an azeotropic blend composed of 10%
(by moles) CF3I and 90% cyclobutane. By this process the stratospheric ozone layer has been protected and compliance with international and national environmental regulations has been achieved without harming the performance of the refrigerator, requiring new equipment, or subjecting the service technician or homeowners to flammability or toxicity risks. As additional benefits, if the charge should ever escape accidentally there is no danger from it of flammability, toxicity, or ozone depletion. The stability, low reactivity, and high materials compatibility of the agents allow them to be stored and used for many years. The presence of CF,I
makes it possible to use existing mineral oil lubricants .
No adverse reaction of the new chemicals occurs with residual CFC-1~? left in the system.
Example 2 A large commercial refrigerator is drained of CFC
12, which is collected and recycled, reclaimed, or destroyed in an environmentally sound manner. The refrigerator i:~ charged with a blend of 100 (by moles) trifluoroiodomethane, 20% perfluorodimethyl ether, and 70o butane. Tr.e performance is nearly identical to that with CFC-12, the same mineral oil lubricant can be used, and no materials (e.g., gaskets, O-rings, tubing) must be replaced because of material incompatibilities.
Example 3 A 200-ton centrifugal chiller is drained of CFC-11 (about 700 pourLds) and filled with an equivalent mass of a blend of n-C,,F7I/butane/pentane (5:40:55 by moles).
The chiller is re-energized and resumes normal operation without a lo:~s in capacity or increase in energy consumption and without retrofitting motors or seals.
SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTIUS94/02321 xample 4 A vapor degreaser containing CFC-113 or 1,1,1-trichloroethane is drained and'the chemical is taken for recycling, reclamation, or destruction. The vapor 5 degreaser is filled with ~1,, 1, 2, 2, 3, 3, 4, 4, 4-nonafluoro-1-iodobutane kept at reflux. A printed circuit board having both through-hole and surface-mount components, contaminated during manufacturing with solder flux residue plus other oils and waxes is passed through this 10 vapor degreaser. The board is thoroughly cleaned, no stratospheric ozone is destroyed, and there is no flammability or toxicity risk.
Example 5 Similar to example 4, except that the replacement 15 agent placed in the vapor degreaser is 95% (by moles) octane with 5o tridecafluoro-1-iodohexane.
Example 6 The solvents that have been in use in a manufacturing facility for degreasing of metal parts 20 (CFC-113, 1,1,1-trichloroethane, and Stoddard solvent) are removed and recycled, reclaimed, or destroyed in an environmentally acceptable manner. During manufacturing, a metal component is found to be contaminated on the surface with 350 centistoke machining oil and 250,000 25 centistoke silicone grease. From a squirt bottle in a fume hood the component is rinsed with 1 , 1, 2 , 2 , 3 , 3 , 4 , 4 , 4 -nonafluoro-1-iodobutane, wiped with a clean cloth, and allowed to air dry. Within 15 minutes it is dry and the surface is clean and ready for further processing. This 30 cleaning process did not deplete stratospheric ozone or pose a flammability or toxicity risk to the technician or require excessive investment in engineering controls.
SUBSTITUTE SHEET (RULE 26) Examgle 7 ' A gyroscope contaminated with MIL-H-5606 hydraulic fluid is placed in an ultrasonic cleaning machine filled with tridecafluoro-1-iodohexane. A crossdraft local exhaust removes any escaping vapors and the bath is subj ected to 2 watts/crn2 ultrasonic energy for S minutes .
The gyroscope :is removed, allowed to drain, and hot-air dried. The re:~ulting very clean gyroscope is carefully packaged and sent o:n for further manufacturing or installation.
Example 8 In a dry cleaning operation the perchloroethylene used is removed and recycled or destroyed in an environmentall~~r sound manner. These solvents are replaced with a blend of 50 (by moles) CF3(CFz)SI and 950 petroleum dist:_llate consisting primarily of heptane and octane. The ne:w solvent is effective, nonflammable, and much less toxic than the solvents replaced. Furthermore, it is less dam<~ging to the environment because the risk of ground water contamination by the long-lived species perchloroethylene is eliminated.
Example 9 An alkyd enamel paint is formulated using (instead of pure mineral spirits) a blend of 95% (by moles) mineral spirits and 5% 1-iodoperfluorohexane. The addition of the' fluoroiodocarbon renders the formulation nonflammable a;nd safer to use.
Examgle 10 An adhesive is formulated using (instead of 1,1,1 trichloroethan~~) a blend of 950 (by moles) toluene and 5%
1-iodoperfluorohexane. By this change the adhesive is made nonflammable and less harmful to the environment.
SUBSTITUTE SHEET RULE 26) 'Example 11 A polyurethane foam is blown using as the blowing agent a mixture of 5 o by moles pentafluoroiodoethane with 95% pentane. In contrast to foams blown using CFC-11, during the manufacturing process none of the vapors released cause ozone depletion. In addition, because of the addition of the fluoroiodoalkane, the foam is rendered nonflammable. Finally, at the end of its useful life, when the foam is disposed of, no damage to stratospheric ozone occurs.
Example 12 A can of hair spray is pressurized with a mixture of 4% (by moles) CF3I and 96% butane and/or isobutane.
There is no flammability risk; even if the spray can is accidentally discharged over an open flame no ignition occurs. Discharge of the contents of the can causes no damage to stratospheric ozone.
Example 13 A spray can of household disinfectant is pressurized with a mixture of 4% CF3I and 96o carbon dioxide. Because of the use of the fluoroiodocarbon blend as propellant, any flammability risk is eliminated.
Example 14 A gas mixture consisting of 50 (by moles) CF3I, 12%
ethylene oxide, and 83o nitrogen is used to sterilize bandages, gauze pads, and medical equipment. Because of the addition of the CF3I as a supplemental propellant, the danger of fire or explosion during the process is eliminated.
Example 15 The charge of Halon 1301 is removed from a computer room fire protection system and taken for recycling or SUBSTfTUTE SHEET (RULE 26) WO 94!20588 PCT/US94102321 destruction. In its place, with minor modifications of the system (such as changes in gaskets, O-rings, and nozzles) is placed a gas mixture consisting of 60% (by moles) CF3I and 40% CF3CHzF. In the event of a fire, the new agent rap:Ldly disperses and extinguishes the fire without harming personnel or damaging equipment. No ozone depletion occurs from the emission of the firefighting agent.
Example 16 The Halon 1211 in a 150-lb wheeled flightline extinguisher at an airport is removed and taken for recycling or destruction. In its place, with minor modifications to the extinguisher (such as changes in gaskets, O-rings, and nozzles), is put a mixture of 70%
(by moles) 1,:L,2,2,3,3,3-heptafluoro-1-iodopropane and 30% perflurohe:xane. In case of fire the liquid agent is manually directed as a stream at the base of the flames and rapidly extinguishes the fire without harming personnel or damaging equipment. No ozone depletion occurs from the emission of the firefighting agent.
Example 17 A cylinder containing approximately 1 lb of CF,I
sealed with a lead plug is mounted under the hood of a vehicle. In case of fire, the extinguisher is activated passively as the lead plug melts and the extinguishing agent is automatically discharged, extinguishing the fire and protecting the occupants, vehicle, and contents.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
Although v~he invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results.
Variations and modifications of the present invention SUBSTfTUTE SHEET (RULE 26) will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents.
GOVERNMENT RIGH7.'S
The U.S. Government is granted an irrevocable, non exclusive, nontransferable, royalty-free right to use the invention with the authority to grant said right for governmental purposes.
BACKGROUND OF THE INVENTION
Field of the Invention (Technical Field):
The invention disclosed herein generally relates to fluoroiodocarbo:n compositions of matter, and methods of making and using such compositions of matter.
Backc~.~round Art Chlorofluorocarbons (CFCs) such as CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, and blends containing these CFCs such as R-500 and R-502 are currently used as refrigerants , solvents , foam blowing agents, -.and propellants. C'FCs contain only chlorine, fluorine, and carbon, and have the general formula CxClyFz, where X = 1 or 2 and Y + Z = 2X + 2. A related group of chemicals known as halone> (also called bromofluorocarbons, BFCs), SUBSTITUTE SHEET (RULE 26) WO 94!2058 '~~ ~ ~ PCTIUS94/02321 having the general formula CwBrXCl fF, (where W = 1 or 2, Y - 0 or 1., and X+Y+Z=2W+2) are in current use as firefighting agents.
Because of the great chemical stability of CFCs and S halons, when they are released to the atmosphere only minuscule fractions are destroyed by nat~ ,ral processes in the troposphere. As a result, CFCs and.rialons have long atmospheric lifetimes and migrate to -the stratosphere where they undergo photolysis, forming chlorine and bromine radicals that seriously deplete the earth's protective ozone layer. Each chemical is assigned an ozone-depletion potential (ODP) that reflects its quantitativE: ability to destroy stratospheric ozone . The ozone depletion potential is calculated in each case relative to CFC-11 tCFCl3, trichloro-fluoromethane), which has been assigned a value of 1Ø Currently used CFCs have OD~Ps near 1; halons have ODPs between 2 and 14.
Names, formulas, and ODPs of commonly used CFCs and halons are shown in Table 1.
SUBSTITUTE SHEET (RULE 26) WO 94120588 '~ PCT/US94/02321 TABLE 1. TJAMES, FORMULAS, AND ODPs OF CFCS IN CURRENT
USE AS REFRIGERANTS, SOLVENTS, FOAM BLOWING AGENTS, AND
PRnPFT.T.ANTS .
CFC or Name Formula ODP
Halon CFC-11 trichlorofluoromethane CC1,F 1.0 CFC-12 ~ dichlorodifluoromethane CC1,F, 1.0 113 1,1,2-trichloro-1,2,2- CC1~FCCIFz1.1 CFC- trifluoroethane -CFC-114 1,2-dich.loro-1,1,2,2- CCIFzCCIFz0.8 tetraflu.oroethane CFC-115 chloropentafluoroethane CC1F~CF: 0.5 R-500 a -- 0.3 R-502 b 0.7 Halon 1211 bromochlorodifluoromethane CBrCIF- 4.1 Halon 1301 !'~ bromotri.fluoromethane CBrF, 12.5 i Halon 2402 1,2-dibromotetrafluoroethane CBrF.,CBrF~3.9 a. azeotropi.c blend of CCLzFz (CFC-12, 73.8 wt. o) ana eHry~r3 irlrw-125, 26.2 wt.%).
b. azeotropic blend of CC1F2CF3 (CFC-115, 51.2 wt.%) and CHCIFz (HCFC-22, 48.8 wt.%).
CFC- .1~?, for example, comprises approximately 26 o by weight of worldwide CFC production, and about 150 million pounds per year are produced. The vast majority of this CFC-12 is eventual:Ly released to the atmosphere, where it rises to the stratosphere, is struck by ultraviolet radiation, and decomposes to give chlorine radicals that catalytica:Lly destroy the protective ozone layer of the earth. This deplet=ion of stratospheric ozone allows more ultraviole~= light to reach the surface of the earth, resulting =_n increases in human skin cancer and cataracts plus damage. to crops, natural ecosystems, and materials, in addition to other adverse effects. This invention will significantly decrease these adverse effects by providing f~nvironmentall~y safe alternative agents to use in place of CFCs and halons.
SUBSTITUTE SHEET (RULE 26) - a At present, CFCs, in addition to selected hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are used as refrigerants, solvents, foam blowing agents, and propellants. CFCs have been widely used for these applications because of their effectiveness, low toxicity, nonflammability, electrical nonconductivity, cleanliness on evaporation, mis.,cibility with hydrocarbon and mineral oil lubricants, and relative nonreactivity towards copper, aluminum, and ferrous metals. However, CFCs are being phased out of production in the U. S . under the provisions of the Montreal Protocol, the Clean Air Act Amendments of 1990, and the presidential directive of 11 February 1992. Although HCFCs (with ODPs ranging from 0.02 to 0.11) deplete ozone much less than CFCs, HCFCs do cause some ozone depletion and are also scheduled to be phased out of production eventually under the Montreal Protocol.
The broad class of halocarbons consists of all molecules that contain carbon, may contain hydrogen, and contain at least one of the following halogen atoms:
fluorine, chlorine, bromine, or iodine. Iodocarbons are halocarbons that contain iodine; fluoroiodocarbons contain both fluorine and iodine. Haloalkanes are a subset of halocarbons comprising compounds made up cf only carbon, halogens, and possibly hydrogen, and having no oxygen, nitrogen, or multiple bonds. In principle, haloalkanes may be derived from hydrocarbons by substitution of halogen atoms (F, C1, Br, or I) for hydrogen atoms. Hydrocarbons themselves have been used as very effective refrigerants, solvents, foam blowing agents, and propellants but have the major disadvantage of extremely high flammability. Substitution with a high proportion of halogen atoms imparts nonflammability.
CFCs and other highly halogenated halocarbons therefore possess many of the desirable properties of hydrocarbons plus the substantial advantage of nonflammability.
SUBSTITUTE SHEET (RULE 26) 21°75 67 Toxicity is a major issue in the selection of refrigerants, solvents, foam blowing agents, propellants, and firefig~hting agents. For example, the toxic effects of haloalka.nes include stimulation or suppression of the 5 central nervous system, initiation of cardiac arrythmias, and sensitization of the heart to adrenaline. Inhalation of haloalkanes can cause bronchoconstriction, reduce pulmonary compliance, depress respiratory volume, reduce mean arterial blood pressure, and produce tachycardia.
Long term effects - can include hepatotoxicity, mutagenesi~~, teratogenesis, and carcinogenicity.
Environmental effects of halocarbons including ozone-depletion potential (ODP), global warming potential (GWP), anc. terrestrial impacts must be considered.
Chlorine- and bromine-containing haloalkanes are known to deplete stratospheric ozone, with bromine posing a greater problem (per atom) than chlorine. The depletion of ozone in. the stratosphere results in increased levels of ultraviolet radiation at the surface of the earth, causing increased incidences of skin cancer, cataracts, suppression of human immune systems, crop damage, and damage to aquatic organisms. These problems are considered so serious that the Montreal Protocol and other legislation have placed restrictions or. the production and use of volatile halogenated alkanes.
Flame suppression occurs by two mechanisms:
physical and chemical. The physical mechanism involves heat absorption by the molecules sufficient to lower the temperature of the combusting materials below the ignition point and/or displacement of oxygen thereby terminating combustion. The larger the extinguishant . molecule (t: he more atoms and bonds it contains) the more degrees of vibrational freedom it has, the higher the vapor heat capacity, and the greater the heat removal.
The chemical mechanism involves interruption of free radical f:Lame-propagation chain reactions involving SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCT/US94102321 hydrogen, oxygen, and hydroxyl radicals. It has been speculated (but not proven) that bromine atoms disrupt these chain reactions.
Previous firefighting agents utilized either chemical ~or physical action or both to achieve flame extinguishment.. Agents such as carbon dioxide displace oxygen and also absorb thermal energy. Agents such as water function solely by thermal energy absorption.
Previous halogenated agents such as carbon tetrachloride, bromotrifluoromethane, etc. employ bothfunctional means.
U.S. Army studies on halogenated agents in the 1940's resulted in the adoption of the well known Halon family of agents . Other work by New Mexico Engineering Research Institute has identified neat perfluorocarbons and some neat iodinated agents as having future potential as f ireffighting agents.
In this work a few iodine-containing chemicals in neat form were shown to exhibit similar extin~guishment properties to bromine-containing chemicals.
There are many concerns regarding b_rominated, perfluorinated, and neat iodinated agents. Bromina'ted agent s are presently being eliminated from worldwide _ production, pursuant to the adoption of the Montreal Protocol and the. Clean Air Act of 1990, due to their tremendous potential to destroy the stratospheric ozone a 30 layer. Perf7.uorinated agents have high global warming potential and atmospheric lifetimes estimated to be several thouaand years. Their production and use is being restricted by pending legislation and liability concerns of current manufacturers. The costs of perfluorocarbons are high and their firefighting ' performance i.s less than that of the brominated agents.
SUBSTITUTE SHEET (RULE 26~
WO 94120588 PCTlUS94/02321 In weight and volume critical situations such as aircraft, tanks, and ships, the additional quantity required for extinguishment cannot be tolerated. One neat iodinated agent (trifluoroiodomethane, CF,I) has long been known to have firefighting potential (Dictionary of Organic Compounds; Chapman and Hall, New York, 1982, p. 5477) . Concerns about CF3I revolve around toxicity and dispersion effectiveness.
~romotrifluoromethane (CF3Br) was the choice agent for such gaseous flooding applications and has remained so until the present time.
Refrigerants, solvents, foam blowing agents, propellants, and firefighting agents must be chemically stable during storage and use over long periods of time and must be unreactive with the containment systems in which they are housed. Refrigerants normally operate between the' temperature extremes of -98° C to 8° C. The majority o:F residential, commercial, and institutional applications lie in the range of -23° C to 8° C. In extraordinary cases (e. g., motor burnout) higher temperatures may be experienced, but in such cases the formation of other contaminants would make replacement of the fluid necessary anyway. Although solvents, foam blowing agents, and propellants are normally stored and used at room temperature, they may under unusual circumstances experience transient temperatures up to 150°C durir..g storage. Firefighting agents must be stable on storage at temperatures of -20°C to 50°C, and should decompose at flame temperatures to yield radical-trapping species.
A refrigerant operates by absorbing heat as it evaporates in one region of the apparatus, then gives up the heat a.s it recondenses in another portion of the apparatus. The required properties for effectiveness include appropriate vapor pressure curves, enthalpies of vaporization, solubility behavior (including oil SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94/02321 miscibility), toxicity, and flammability. CFCs 12, 114, 500, and 502 have been used as refrigerants for many years because they possess the required physical properties such as appropriate boiling points and operating pressures, enthalpies of vaporization, miscibility with mineral oi.~--based lubricants, low toxicity and nonflammability., In addition, CFCs are relatively noncorrosive to metals and seal materials.
Properties of commonly-used refrigerants (including typical evaporator and condenser temperatures and typical usages) are set forth in Table 2.
TABLE 2. TYPICAL EVAPORATOR AND CONDENSER TEMPERATURES
FOR CFC REFRIGERANTS
CFC Evap Temp Cond Temp Typical Usages (F) (F) 11 35 to 40 95 to 105 Centrifugal chillers, solvent, foam agent 12 -10 to 35 105 to 125 Auto A/C, freezers, window A/C units 13 -50 to -75 100 to 125 Verv Low temp freezers 113 35 to 40 95 to 105 Centrifugal chillers, solvent, cleaner 114 -24 to 35 100 to 125 Marine chillers, low temp freezers 2 0 115 -50 100 to 125 Low temp freezers 500 -30 to -80 100 to 125 Supermarket cases, vending machines, commercial transport 502 -40 to -100 100 to 125 Low temp refrigeration I
503 -100 to -200100 to 125 Cryogenic freezers Hydrocarbons including cyclopropane, propane, butane, and isobutane have also been used as highly effective refrigerants . However, hydrocarbons have found little commercial use as refrigerants because of their high flammability. They possess all of the other SUBSTITUTE SHEET (RULE 26) 15'~~
required properties The ASHRAE Standard 15 limits the use of most hydrocarbons as Class 2 or 3 refrigerants, limiting their use to laboratory equipment with a total charge of a.ess than 3 pounds or to technical/industrial applications wherein the refrigeration equipment is located rE:motely from inhabited buildings. These restrictions severely limit the current utility of refrigerants 'containing hydroca~bans .
Refrigeration equipment requires lubricant constantly circulating in the refrigerant fluid to avoid friction, overheating, and burnout of the compressor or bearings. Therefore miscibility of refrigerants with lubricants is an essential requirement. For example, most lubricants are not very soluble in hydrofluorocarbons (HFCs), ar~d this has presented major problems in. the use of the alternative agent HFC-134a for refrigeration.
Many billions of dollars worth of installed refrigeration and air-conditioning equipment currently exists. :If CFCs become unavailable and no drop-in replacements are available, much of this equipment will be renderecL inoperable and may wind up in landfills. The useful lifetime will be shortened drastically, and a significant: fraction of the energy and resources put into manufacturing and installing the equipment will be wasted.
A solvent must dissolve hydrophobic soils such as oils, greases, and waxes, should be nonflammable and relatively nontoxic, and should evaporate cleanly. For solvents, chemicals with boiling points between 35°C and 120°C are preferred, because this boiling point range allows evaporation in reasonable time (between one minute and two hours). Traditionally, CFC-113 and 1,1,1-trichloroet:hane have been solvents of choice. Recently, because of environmental concerns about halogenated solvents, interest in hydrocarbon solvents such as SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94102321 Stoddard solvent (a petroleum fraction c~ eight- to eleven-carbon hydrocarbons) has revived, despite the flammability of these solvents. when referring to hydrocarbon petroleum fractions, it is commonly 5 understood that the terms ligroin, mineral spirits, naphtha, petroleum ether, "and petroleum spirits may represent fractions with similar compositions and may at times be used interchangeably.
A foam blowing agent must create uniform, 10 controllable cell size in a polymer matrix, and preferably should provide high insulation value and be nonflammable. For foam blowing a wide variety of agents has been used, including CFC-11, HCFC-22, HCFC-123, HFC
134a, HCFC-141b, and pentane. Water is cften added in the foam blowing agent (up to about 25% by moles) to react with the forming polymer, liberating carbon dioxide and aiding cell formation. More recently, some manufacturers have shifted to using water as the exclusive blowing agent, despite slight losses in insulating ability, dimensional stability, and resistance to aging.
An aerosol propellant must have a high vapor pressure, low heat of vaporization, and stability on storage. In the U.S., CFCs were used as propellants until 1978, and in many countries CFCs are still in use for this purpose. The continued use of CFC aerosol propellants overseas contributes substantially to stratospheric ozone depletion. After 1978 in the U.S.
CFCs were replaced by the hydrocarbons butane and isobutane for many propellant applications. These gases are extremely flammable and people have been burned in fires involving these propellants.
Firefighting agents to replace halons must be effective extinguishants, relatively nontoxic, electrically nonconductive, must evaporate cleanly, and must have low environmental impact. Halons SUBSTfTUTE SHEET (RULE 26) 215 75 ~ 7 WO 94120588 PCTlUS94102321 (bromofluorocarbons), although they meet the first four criteria, have long atmospheric lifetimes and high ozone-depletion potentials, and will be phased out of . production. under the terms of the Montreal Protocol and other regulations.
Although it is relatively easy to identify chemicals having one, two, or three selected properties, it is very difficult to identify chemicals that possess simul-taneously all of the following properties: effective performance, nonflammability, low toxicity, cleanliness, electrical nonconductivity, miscibility with common lubricants, short atmospheric and environmental lifetimes, zero ODP, and very low GWP. Furthermore, the unusual and desirable properties of selected members of the obscure class of fluoroiodocarbons are by no means obvious. Fluoroiodocarbons have only rarely been studied, and very few of their properties are reported in the literature. Conventional chemical wisdom indicates that iodine-containing organic compounds are too toxic and unstab:Le to use for these purposes, and iodocarbons have been :rejected on those grounds by the majority of those skil:Ied in the art. Partly as a result of this prejudice, the properties of the class of fluoroiodoc:arbons have been investi-gated only slightly, and fluoroi.odocarbons have remained a little-known class of chemica7.s .
An important part of this invention is recognizing that the unique properties of fluorine (the most electronegative element) strengthen and stabilize a carbon-to-iodine bond sufficiently to render selected fluoroiodoc:arbons relatively nontoxic and stable enough for use in :solvent cleaning, refrigeration, foam blowing, and aerosol propulsion. Painstaking collection and b estimation of properties and screening for expected effectiveness, low toxicity, and low environmental impact have been carried aut to identify them as being suitable SUBSTITUTE SHEET (RULE 26) WO 94!20588 ,~ PCTIUS94/02321 ' 12 for these ne:w uses. Disclosed herein therefore are both new uses and new combinations of chemicals, leading to new and unexpected results.
Both t:he neat and blended fluoroiodocarbons described herein provide new, environmentally safe, nonflammable refrigerants, solvents, foam blowing agents, aerosol propellants, and. firefighting agents. These compounds have the characteristics of excellent performance, cleanliness, electrical nonconductivity, low 10toxicity, nonflammability (self-extinguishment), short atmospheric lifetime, zero ODP, low GWP, and negligible terrestrial ~erivironmental impact.
Althoug:h some fluoroiodocarbons are described briefly in the known chemical literature, their potential for the uses described herein has never been previously recognized. No fluoroiodoearbons have been used before for solvent cleaning, refrigeration, foam blowing, or aerosol propulsion, either in neat form or in blends.
One neat f:Luoroiodocarbon (CF3.I) has been briefly described as a firefighting agent in the open literature (Dictionary of Orcranic Compounds, Chapman and Hall, New York, 1982, p. 5477). A small number of additional neat fluoroiodocarbons has been proposed by one of the current inventors for use in firefighting, He>wever, neither any blenas containing fluoroiodocarbons nor the new. neat fluoroiodocarbon a 30 agents described herein have ever before been proposed for use in firefighting or any of the other uses described herein. These blends and new neat agents offer substantial advantages in terms of lower cost, lower toxicity, improved physical properties, and greater effectiveness.
~,x~ ~ ' SUBSTITUTE SHEET (RULE 26) SUMMARY OF THE INVENTION
A primary object of an aspect of the invention is the provision of relatively nontoxic agents for use in refrigeration, solvent cleaning, foam blowing, aerosol propulsion, and f:irefighting. Another object of an aspect of the invention is the provision of nonflammable and environmentally safe compositions of matter. Yet another object of an aspect of the invention is the provision of fluoroiodocarbon compounds that are clean and electrically nonconductive. Still another object of an aspect of the invention is the provision of neat and blended fluoroiodocarbons having zero ozone-depletion potential, low global warming potential, and negligible atmospheric and terrestrial environmental impacts.
An advantage of the invention is the duplication of existing refriger<~nts, solvents, foam blowing agents, aerosol propellant:, and firefighting agents at lower cost.
Another advantage of the invention is optimization of properties by blending of fluoroiodocarbons with selected 10 additives. Still another advantage of the invention is the provision of effective and, in some cases, superior compositions of :Eluoroiodocarbons as replacements for existing chemical compounds.
According to o:ne embodiment of the invention a composition comprises a blend of from 20 to 75 mol percent of at least one fluoroiodocarbon of the formula CaHbBrCCldFeIfNg, wherein a is between and including 1 and 8; b is between and including 0 and 2, c, d and g are each between and including 0 and 1, a is between and including 1 and 17, and f is between and including 1 and 2, the fluoroiodocarbon being electrically nonconductive and having an ozone ~;, ,~~~~~., 13a depletion potential less than 0.02 and a global warming potential less than that of chlorofluorocarbons, with from 25 to 80 mol percent at least one additive selected from the group consisting of (i) alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and 2-propanol, (ii) esters, (iii) ethers, (iv) miner<~.l spirits, (v) Stoddard's solvent, (vi) hydrocarbons seleci~ed from the group consisting of butane, cyclopropane, decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,.2-dimethylpropane, heptane; isobutane, limonene, 2-methylbutane, 3-methylhexane, 3-methylpentane, nonane, octane, pentane, pinene, propane, turpentine and undecane, (vii) hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-hepta.fluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane, (viii) ketones, and (ix) perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexa:ne, wherein the additive and the fluoroi~odocarbon are nonreactive in the blend, with the provi;~o that when the additive is selected from the group consisting of alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propano~_ and 2-propanol, and ketones, then a is between and including 1 and 3, b is between and including 0 and 2, c, d and g ax-e each between and including 0 and 1, a 13b is between and including 1 and 7, and f is between and including 1 and 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(BEST MODES FOR CARRYING OUT THE INVENTION) Desirable agents must possess all of the following properties: effectiveness, low toxicity, nonflammability, and environmental safety. Although it is relatively to easy find chemicals than meet two or three of these criteria, it is extremely difficult to identify chemicals that meet all desired criteria. The novelty of this invention lies in identifying chemical compounds and blends (and methods of using these) that meet all these criteria. The chemical compounds and blends described herein are effective, relatively nontoxic, nonflammable, and environmentally benign. They have the desired ~ 15 ~ 5 6'~
boiling points, vapor pressures, and heats of vaporization for optimal effectiveness. By mixing a fluoroiodocarbon with another chemical several major advantages are obtained. First, and perhaps most importantly, the mixture is rendered completely nonflammable. Second;, 'by appropriate blending of chemicals, the physical properties (including boiling range, density, viscosity, and lubricant solubility? can be optimized to obtain maximum performance. Third, the already low toxicity can be further reduced. Fourth, the cost of the agent is reduced.
As a general class, iodocarbons are more reactive, less stable, and more toxic than the corresponding chloro or bromocarbons; for this reason they have often been rejected as unsuitable for the applications described here. HowESVer, an important part of this invention is recognizing the tact that the unique properties of fluorine give polyfluorinated iodocarbons exceptionally low reactivity, high stability, and low toxicity.
Because fluorine is the most electronegative element, the presence of two or more fluorine atoms attached to the same carbon atom which is bonded to the iodine atom withdraws e:Lectron density and provides steric hindrance, making the carbon-to-iodine bonds in fiuoroiodocarbons abnormally strong and resistant to chemical reaction.
All of the three common mechanisms of chemical reaction are inhib~_ted in fluoroiodocarbons: unimoiecular nucleophilic substitution (SN1), bimolecular nucleophilic substitution (SN2), and homolytic bond cleavage. Because of this low reactivity, fluoroiodocarbons exhibit unusually high stability and low toxicity. In addition, iodocarbons have never been implicated in ozone depletion, global warming, or long-term terrestrial environmental contamination.
In applying the selection criteria of the invention, with regard to toxicity, each of the preferred compounds SUBSTITUTE SHEET (RULE 26) PCTlUS94102321 is characterized by acute toxicity (either measured or predicted) no greater than that of currently used CFCs.
In this regard, toxicity is measured as LCS~ (lethal concentration at the fifty percent level) for rats over 5 an exposure period of 4 hours. Toxicity data on fluoroiodocarbons is limited at this time but highly encouraging. All of the following fluoroiodocarbons are reported to have mice 1-hour LCSOs of greater than 10,000 ppm: 1-iodoperfluoroethane, 1-iodo-perfluorobutane, and 10 1-iodoperfluorohexane.
If a chemical is to have zero ODP it must either (1) not contain. chlorine nor bromine , or ( 2 ) undergo rapid and complete destruction by natural processes in the troposphere ( and tans never reach the stratosphere ) . The 15 three major mechanisms for destruction of halocarbons in the troposphere are photolysis, attack by hydroxyl radical (O~t) , and attack by oxygen atoms (0) . In the troposphere, because of shielding by stratospheric ozone and other ai.mospheric components, the sunlight present is of longer wavelength (and correspondingly lower energy) than the light present in the stratosphere . If molecules are to be photolyzed in the troposphere they must contain light-absorbing groups (chromophores) and weak bonds.
Such light-absorbing groups with weak bonds include carbon-to-iodine sigma bonds. Carbon-to-iodine bonds are extremely :sensitive to photolysis and cleave easily in the presence of sunlight, even at ground level. Thus, fluoroiodoc:arbons are destroyed rapidly by photolysis in the troposphere and thus do not contribute to ozone depletion or substantially to global warming.
The compounds of the present invention are also selected or.. the basis of their global warming potentials, which are increasingly being considered along with ozone depletion factors. Global warming is caused by absorption by molecules in the atmosphere of infrared radiation ~_eaving the surface of the earth. The longer SUBSTITUTE SHEET (RULE 26) the atmospheric lifetime and the greater the infrared absorption of a molecule, the greater its GWP. It is recognized that some chlorof3uorocarbons have GWPs several thousand times that of carbon dioxide. Because of their rapid photolysis and'resulting short atmospheric lifetimes, fluoroiodocarboris~have greatly reduced GWPs compared to CFCs,.~ halons, HCFCs, HFCs, and perfluorocarbons.
The short atmospheric lifetimes of fluoroiodocarbons are due to the preferential absorption of ultraviolet energy by the carbon-to-iodine bond, causing the agent to decompose in natural sunlight within a short period after it enters the atmosphere. Decomposition byproducts are harmless salts which are cleansed from the environment by natural precipitation. A fluoroiodocarbon may even contain a chlorine or bromine atom without causing measurable stratospheric ozone depletion because the molecule will be destroyed by photolysis of the C-I bond in the troposphere, never reaching the stratosphere.
In addition to undergoing rapid photolysis, iodoalkanes undergo faster hydrolysis than the corresponding chloro- or bromoalkanes; thus they degrade rapidly in natural waterways to form harmless products such as potassium iodide (a common additive to table salt). Because of this rapid degradation, fluoroiodocarbons (in contrast to CFCs) have never been implicated in long-term soil or ground water contamination.
Fluoroiodocarbons are highly effective flame suppression agents, in some cases more effective on a per-mole basis than halons (bromofluorocarbons).
Fluoroiodocarbons not only provide chemical extinguishment, but significant physical extinguishment through heat removal by molecular vibrations. Addition of a sufficient concentration of a fluoroiodocarbon to an otherwise flammable liquid or vapor (such as a SUBSTITUTE SHEET (RULE 26) 21'5 fi'~
1~
hydrocarbon) renders the material self-extinguishing.
The invention described and claimed herein is specifically related to liquid and gaseous chemical agents used to extinguish active and near active fires involving comi~ustible, flammable, and electrically energized mater-ials .
The agents described herein have acceptable stability on storage under normal conditions. To prevent photolysis of the fluoroiodocarbons, they should be protected from sunlight by storage in opaque containers such as metal cylinders or brown glass bottles. If desired, for lc;ng-term storage a small amount of copper metal can be added to enhance the stability of the iodides.
.5 The preferred fluoroiodocarbons meeting the selection criteria are set forth in Table 3 bet ow'. A11 the fluoroiodocarbon agents have boili ng points between -2S°C and +I70°C and satisfy the general chemical formula CaH~Br~Cl~F~ I =N~O;~; wherein a is between and including I and z0 8; b is between and including 0 and 2; c, d, g, and h are each between and including 0 and 1; a is between and including 1 and I7; and f is between and including ~. and 2.
TABLE 3. PREFERRED FLUOROIODOCARBON AGENTS.
5 Name ( s ) rF o rnui a bromodifluoroiodomethane C3rFZI
chlorodifluoroiodomethane CC1F,I
1,1,2,2,3,3,4.4,5,5-decafluoro-1,5-diiodopentane,I(CF~);
1,5-diiodoperfluoropentane 30 difluorodiicdomethane CF,IZ
difluoroiodomethane CAF
I,I,2,2,3,3,4,4,5,5,6,6-dodeCafluoro-1,6-diiodohexane,I(CF2);I
1,6-diiodoperfluorohexane fluoroiodomethane CHZFI
'~.P.., :; , ~. a,F ;~ ;~ , . . ~ n ~r..,~. ".
r..
,.gin, ~E.E~
WO 94120588 ~~ PCTIUS94/02321 1,1,1,2,3,3,3-heptafluoro-2-iodopropane, CF3CFICF3 ~
perfluoroisopropyl iodide 1, 1, 2 , 2 , 3 , 3. , 3-heptafluoro-1-iodopropaneCF3CFZCFzI
, perfluoropropyl iodide 1,1,2,2,3,3.-hexafluoro-1,3-diiodopropane,I(CFz),I
1,3-diiodoperfl.uoropropane 1-iodoheptadecafluorooctane, 1- CF3(CF2),I
iodoperfluorooctane, perfluorooctyl iodide iodoheptafl.uorocyclobutane, ' cyclo- (CFZ) iodoperfluorocyclobutane 1-iodopentadecafluoroheptane, 1- CF3 (CFz) 6I
iodoperfluoroheptane, perfluoroheptyl iodide iodo~entaf l.uorobenzene CSF~I
iodopentafl.uorocyclapropane, CFzCF2CFI
iodoperfluorocyclopropane, , perfluorocyclopropyl iodide 1-iodotride:cafluorohexane, 1- CF3 (CFZ) SI
iodoperfluorohexane, perfluorohexyl iodide 1-iodoundec:afluoropentane, 1- CF,(CFZ)9I
2 0 iodoperfluoropentane, perfluoropentyl iodide N-iodobis-(trifluoromethyl)amine (CF,)ZNI
1,1,2,2,3,.9,4,4,4-nonafluoro-1-iodobutane,l-CF,(CFz)3I
iodoperfluorobutane,perfluorobutvl iodide 1,1,2,2,3,a,4,4-octafluoro-1,4-diiodobutane,I(CFZ)4I
1,4-diiodoperfluorobutane pentafluoroiodoethane, perfluoroethvl CF,CF,I
iodide 1,1,2,2-tet:rafluoro-1,2-diiodoethane, CFZICF2I
1,2-diiodoperf7.uoroethane 1, 1, 2, 2-tet:rafluoro-1-iodoethane CF,ICHF, 3 0 1,1,2-trifa.uoro-1-iodoethane CF2ICH,F
trifluoroiodomethane, trifluoromethyl CF,I
iodide trifluoromethyl-1,1,2,2-tetrafluoro-2- CF30CFzCF2I
iodoethyl ether Preferred additives far blending with 3 5 f luoroiodocarbons are shown in Table 4 . Table 4 includes selected alcohols, esters, ethers, hydrocarbons, hydrofluorocarbons, fluoroethers, ketones, and SUBSTITUTE SHEET (RULE 26) perfluorocarbons with. boiling points between -150°C and +200°C.
Azeotrop ~c blends are particularly preferred because they do not change composition on evaporation and thus do not change properties if part of the mixture evaporates.
We have developed a proprietary computer program for predicting a~:eotrope formation based on the Soave-Redlich-Kwong equation of state and have screened the fluoroiodocarbon blends described herein to identify likely azeotropes. This program also incorporates novel methods we have developed for estimating properties of chemicals and blends: it provides accurate estimates of vapor pressure curves, enthalpies of vaporization, and other properties of interest, allowing selection of optimal blends.
TABLE 4. F~REFERRED ADDITIVES TO BE BLENDED WITH
FLUOROIODOCARBONS
Class Name s Formula alcohol 1-butanol HO ( CHz ) ,CH3 2 -butanol CH, CH ( OH ) CH,CH, ethanol CH,CH,OH
methanol CH,OH
2-methyl-1-propanol HOCH,CH(CH,)CH, 2-methyl-2-propanol (CH,),COH
1-pentanol CH,(CHz),OH
2 -pentanol CH,CHOHCH,CH,CH, 1-propanol HO ( CH2 ) ,CH, 2-propanol ( CH, ) ZCHOH
ester ethyl acetate CH,COOCH,CH, ethyl butanoate, ethylCH;(CHz)=COOCH=CH, butyrate ethyl propanoate, ethyl( CH,CH2COOCH2CH:
pronion.ate ' SUBSTITUTE SHEET (RULE 26) W0 941~~~$~.; PCTIUS94/02321 isobutvl acetate (CH, ) ,CHCH~OCOCH, isoprot~yl acetate CH,COOCH ( CH3 ) , methyl acetate CH,COOCH, methyl butanoate, CFi3(CHz),COOCH3 methyl butyrate methyl propanoate- CH3(CHZ)2COOCH, methyl propionate n-butyl acetate CH, ( CHZ ) ,OCOCH, hexyl acetate CH, ( CHZ ) SOCOCH, n-pentyl acetate, amylCH3(CH2)40COCH, acetate n-propyl acetate CH,(CHz),OCOCH, sec-butyl acetate CH,CH,CH (CH,) OCOCH, ether diethyl ether, ethyl (CHjCH2)20 ether diisopropyl ether, ( (CH3) ZCH) z0 isopropyl ether dimethyl ether, methylCH30CH3 ether di-n-butyl ether, butyl(CH,(CHz),)z0 ether di-n-propyl ether, (CH3CH2CH2) z0 propyl ether 1,4-dioxane cyclo-(CH,CH,O), ethylene oxide, 1,2- CHZOCH~
eDOxvethane propylene oxide, 1,2- CH20CHCH3 er~oxypropane tetrahydrofuran cyclo-(CHZ)qo fluoroether bis-difluoromethyl (CHF2)2o ether hexafluorodimethyl (CF,) zo ether, perfluorodimethvl ether hexafluorooxetane, cyclo-(CFz),O
perfluorooxetane methyl trifluoromethylCH30CF, ether SUBSTITUTE SHEET (RULE 26) WO 94120588 F'CT/US94102321 w ~f octafluorodimethoxymethCF,OCF,OCF3 'i ane octafluoro-l, 3- CF2 (OCFZCFZ) 2 dioxolane, perfluoro-1,3-dioxolane pentaf7.uorodimethyl CHFZOCF3 ether 1, l, 2' ,. 2' , 2' CHFZOCHzCF3 -pentafluoro methyl ethvl ether 1-trifluoromethoxy- CF30CFzCHFz 1,1,2,2-tetrafluoroethane hydrocarbon butane CH, ( CHZ ) ,CH, cvclopropane (CH,), decane CH, ( CH, ) oCH, 2 , 3 -dimethylpentane( CH, ) ZCHCH ( CH, ) CH,CH, 2,4-dimethylpentane ((CH3)ZCH),CH, 2,2-dimethylpropane (CH3),C
heptane CH,(CH,)~CH, hexane CH,(CHZ)qCH, isobutane CH,CH(CH3), ligroin blend cf hydrocarbons 1 imone:ne C, ~H, E
2-methylbutane ( CH3 ) ,CH2CH,CH, 3 -methylhexane CH,CH,CH ( CH, >
CH,CH,CH, 3-methylpentane CH,CH,CH (CH,) CH,CH, naphtha blend of hydrocarbons nonane CH, ( CH, ) ,CH, octane CH,(CHZ)~CH, pentane CH, ( CH, ) , CH, petroleum ether blend of hydrocarbons I
petroleum spirit blend of hydrocarbons SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTIUS94102321 pinene CloHl propane CH,CH,CH3 Stoddard's solvent blend of C8 to C11 hydrocarbons toluene C~H~CH, turpentine blend of hydrocarbons unde cane CH, ( CH, ) 9CH, hydrofluorocardifluoromethane CH2Fz bon 1,1-difluoroethane CHFZCH, 1,1,1,2,3,3,3- CF3CHFCF3 heptafluoropropane pentafluoroethane CF,CHF, 1, 1, 2, 2, 3- CHFZCFZCH2F
pentafluoropropane 1, l, 1, 2- CF3CHzF
tetrafluoroethane 1,1,1-trifluoroethane CH3CF3 trifluoromethane CHF, ketone acetone, propanone, CH3COCH3 2- ' prooanone 2-butanone, butanone, CH3COCHZCH3 methyl ethyl ketone carbon dioxide COz 2-hexanone, methyl CH3COCHZCHzCHzCH3 butyl ketone 3-methyl-2-butanone CH,COCH(CH,), 2-pentanone, methyl CH3COCHZCHZCH3 propyl ketone perfluorocarbodecafluorobutane, CF,(CFz)zCF, n perfluorobutane dodecafluoropentane, CF,(CFz)3CF3 perfluoropentane hexafluorocyclopropane,cyclo-(CFz)a perfluorocyclopropane SUBSTITUTE SHEET (RULE 26) hexaf luoroethane , CF,CF, perf luc>roethane octafluorocyclobutane,cyclo-(CF2)<
perfluorocvclobutane octafluoropropane, CF3CFzCF3 perfluoropropane tetradecafluorohexane,CF3 (CF2) 4CF3 perfluorohexane tetrafluoromethane, CF4 perfluoromethane Ref riQerants This invention discloses that by addition of an appropriate f:Luoroiodocarbon a hydrocarbon is made a more effective heat-transfer fluid and is rendered self-extinguishing. Such mixtures are unique non-flammable hydrocarbon blends.
All the new refrigeration agents described herein including blends are miscible with the four major groups of lubricants: mineral oil, alkylbenzenes, polyol esters (POEs), and polyalkylene glycols (PACs). The presence of higher-atomic-weight halogen atoms tchlorine, bromine, or iodine) in an agent, because of the polarizability of these atoms, allows miscibility with these lubricants.
A further advantage of hydrocarbon-containing refrigerants is that leak detection is greatly simplified compared to C'FCs or HFCs .
As shown. in Table 5, by appropriate chaices of pure agents or blends, drop-in replacements can be formulated to replace c:FCs in existing equipment. The agents described herein allow the replacement of thousands of tons of CFCs in existing equipment with environmentally safe, nonflammable, energy-efficient refrigerants. In new systems redesigned to optimize performance for fiuoroiodocai:bon-containing agents, superior performance will be obtained.
SUBSTITUTE St~EET (RULE 2R) WD 94!20588 ~"PCT/US94102321 Solvents Fluoroiodocarbon agents with boiling points in the desirable range for use as solvents include, for example, 1,1,2,3,3,3-heptafluoro-1-iodopropane, 1,1,1,2,3,3,3 heptafluoro-2-iodopropane, fluoroiodomethane, 1,1,2,2 tetrafluoro-1-iodoethane, 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane, difluorodliodomethane, undecafluoro-1-iodopentane, and tridecafluoro-1-iodohexane. By addition of a fluoroiodocarbon to a flammable solvent such as a hydrocarbon, alcohol, ester, or ketone the solvent is rendered nonflammable. In the case of blends, to prevent loss of the fluoroiodocarbon agent from the blend through evaporation, ideally the fluoroiodocarbon component should either form an azeotrope or have a boiling point equal to or slightly higher than the other component(s).
Foam Blowing Agents By addition of an appropriate quantity of a fluoroiodocarbon to the foam blowing agent, the foam produced is rendered nonflammable and its insulating abilities are improved.
Aerosol Propellants By addition of a sufficient quantity of a volatile fluoroiodocarbon a propellant such as propane, butane, or isobutane is rendered nonflammable.
Firefiahtina A eq nts By blending selected fluoroiodocarbons with hydrofluorocarbons, perfluorocarbons, and fluoroethers, agents are obtained that are highly effective, non-ozone-depleting, and have low toxicity and low cost. In some cases these blended agents provide synergism (better extinguishment than predicted linearly) because of the chemical extinguishment of the fluoroiodocarbon and the physical extinguishment of the additive. The vapor SUBSTITUTE SHEET (RULE 26) WO 94120588 PCTlUS94102321 pressure, effectiveness, reactiT,rity with storage vessels and delivery systems, weight, cost, and toxicity may all be optimized by creating blends. Blended azeotropic and near-azeotropic fluo:roiodocarbon firefighting agents 5 allow reductic>n in the cost of the delivered agent by taking advantage of their superior extinguishment capabilities and the lower costs of hydrofluorocarbons, perfluorocarbons, and fluoroethers components compared to fluoroiodocarbons. In addition, they form constant- and 10 near-constant composition agents, simplifying handling and making performance more predicable than that of nonazeotropic blends. Such blends retain their composition at all times, do not fractionate into separate components, remain stable, and provide superior 15 performance. Selected blends act as functional alternatives in existing equipment and delivery systems, minimizing the equipment changes required.
Industrial Applicability:
This invention is further illustrated by the 20 following non-limiting examples.
Refrigerants Table 5 shows preferred examples of drop-in replacement refrigeration agents (including blends).
TABLE 5. EXAMPLES OF PREFERRED DROP-IN REPLACEMENT
Examples of replacements Refrigerant BI? Chemical (s) Approx.
C Proportions (by moles) 11 2'.3.8 CzFsI/n-C3F,I 50:50 n-C,F,I/butane/pentane 5:40:55 CIFSI/pentane 50 : 50 SUBSTITUTE SHEET (RULE 26) WO 94/20588 ~ ~ ~~ PCTIUS94102321 C~FSI/diethyl ether 50:50 n-C3F,I /butane 60:40 12 -29.8 CF,I neat CF3I/propane 60:40 CF,I/CF3CF2CF3 50 : 50 CF3I/CF3CFZCF3 10 : 90 (binary azeotrope) CF3I / CHFZCH3 8 : 92 (binary azeotrope) CF,I/cyclobutane 10:90 (binary azeotrope) CF3I/CF3CFzCF3/CHFZCH3 (ternary azeotrope) CF3I/fluoroethane 55:45 CF3I/cyclopropane 30:70 22 -40.8 CF3I/propane 5:95 or 10:90 CF3I/ (CF3) 20 50: 50 CF, I / CHFZOCF, 5 : 95 CF,I/difluoromethane 40:60 CF3I/pentafluoroethane 30:70 CF,I/1,1,1-trifluoroethane30:70 CF3I/perfluoropropane 30:70 500 -33.5 CF3I/propane 45:55 CF3I/ (CF3) 20 75:25 CF3I/pentafluoroethane 6D:40 CF3I/perfluoroethane 60:40 CF3I/1,1;1-trifluoroethane60:40 CF3I/difluoromethane 70:30 I
CF, I / f luoroethane 3 0 : 7 0 CF3I/perfluoropropane 20:80 502 -45.4 CF,I/difluoromethane 20:80 [ I
SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTlUS94102321 CF'3I/ (CF3) 20 40:60 CF'3I/trifluoromethane 60:40 CF'3I/pentafluoroethane10:90 CF',I/1,1,1-trifluoroethane10:90 CF',I/perfluoroethane 10:90 Solvents The following preferred pure agents and blends meet the requirements of solvent performance, nonflammability, low toxicity, and low environmental impact: neat 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane; neat undecafluoro-1~-iodopentane; neat tridecafluoro-1-iodohexane; 2 to 150 (by moles) 1,1,2,2-tetrafluoro-1-iodoethane with 98 to 85% hexane; 2 to 15 0 (by moles) 1,1,2,3,3,3-he~~tafluoro-1-iodopropane with 98 to 850 pentane; 2 t:o 15% (by moles) 1,1,2,2,3,3,4,4,4-nonafluoro-1-ic~dobutane with 98 to 85o hexane; 2 to 150 (by moles) tr:idecafluoro-1-iodohexane plus 98 to 850 octane, nonane, and/or decane; 2 to 150 (by moles) 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane with 98 to 850 of one or more chemicals selected from the group:
methanol, eth<~nol, 2-butanone, 2-propanol, acetone, methyl acetate, ethyl acetate, tetrahydrofuran, and hexane; and 2 to 150 (by moles) undecafluoro-1-iodopentane with 98 to 85% of at least one chemicals selected from t=he group: heptane, ethanol, 2-propanol, and 2-butanone.
Foam Blowing Ace3 nts The following preferred pure agents and blends meet the requirements for foam blowing agents: neat difluoroiodomethane; neat pentafluoroiodoethane; neat 1,1,2,3,3,3-heptafluoro-1-iodopropane; 2 to 150 (by moles) pentafluoroiodoethane with 98 to 85o butane; 2 to 15 0 (by moles) difluoroiodomethane with 98 to 85 o butane;
SUBSTITUTE SHEET (RULE 26) 2 to 15% (by moles) 1,1,2,3,3,3-heptafluoro-1-iodopropane with 98 to 85% pentane; 2 to 150 (by moles) pentafluoroiodoethane with 98 to 85o pentane; 2 to 15%
(by moles) trifluoroiodomethane with 98 to 85% 1,1-difluoroethane; 2 to 15%,~~..tby moles) trifluoroiodomethane with 98 to 85 o butane; and any of the agents in this list plus up to 40% by weight water.
Aerosol Propellants The following nonflammable preferred blends meet the requirements for aerosol propellants: 2 to 15% (by moles) trifluoroiodomethane with 98 to 85% of one or more of the chemicals selected from the group: propane, butane, isobutane, carbon dioxide.
Firefiahtina Agents The following preferred blends and neat fluoroiodocarbon agents meet the requirements for effective, clean firefighting agents: blends of CF3I
with at least one chemical selected from the group:
trifluoromethane,difluoromethane,pentafluoroethane,and 1,1,1,2-tetrafluoroethane; blends of CF3CFzCF2I with at least one chemical selected from the group CF3CFZI, CHZFI, perfluoropentane, and perfluorohexane; blends of CF3CFzCF2CF2I with perfluorohexane; and neat chlorofluoroiodomethane.
The following examples show the effectiveness of the agents listed as environmentally safe, nonflammable refrigerants, solvents, foam blowing agents, propellants, and f irefighting agents .
Example 1 From a household refrigerator the charge of CFC-12 (about 6 to 8 oz) is removed and collected for recycling, reclamation, or destruction in an environmentally sound manner. The refrigerator is then charged from a SUBSTITUTE SHEET (RULE 26) pressurized bottle through a closed system with an equivalent mas;~ of an azeotropic blend composed of 10%
(by moles) CF3I and 90% cyclobutane. By this process the stratospheric ozone layer has been protected and compliance with international and national environmental regulations has been achieved without harming the performance of the refrigerator, requiring new equipment, or subjecting the service technician or homeowners to flammability or toxicity risks. As additional benefits, if the charge should ever escape accidentally there is no danger from it of flammability, toxicity, or ozone depletion. The stability, low reactivity, and high materials compatibility of the agents allow them to be stored and used for many years. The presence of CF,I
makes it possible to use existing mineral oil lubricants .
No adverse reaction of the new chemicals occurs with residual CFC-1~? left in the system.
Example 2 A large commercial refrigerator is drained of CFC
12, which is collected and recycled, reclaimed, or destroyed in an environmentally sound manner. The refrigerator i:~ charged with a blend of 100 (by moles) trifluoroiodomethane, 20% perfluorodimethyl ether, and 70o butane. Tr.e performance is nearly identical to that with CFC-12, the same mineral oil lubricant can be used, and no materials (e.g., gaskets, O-rings, tubing) must be replaced because of material incompatibilities.
Example 3 A 200-ton centrifugal chiller is drained of CFC-11 (about 700 pourLds) and filled with an equivalent mass of a blend of n-C,,F7I/butane/pentane (5:40:55 by moles).
The chiller is re-energized and resumes normal operation without a lo:~s in capacity or increase in energy consumption and without retrofitting motors or seals.
SUBSTITUTE SHEET (RULE 26) WO 94!20588 PCTIUS94/02321 xample 4 A vapor degreaser containing CFC-113 or 1,1,1-trichloroethane is drained and'the chemical is taken for recycling, reclamation, or destruction. The vapor 5 degreaser is filled with ~1,, 1, 2, 2, 3, 3, 4, 4, 4-nonafluoro-1-iodobutane kept at reflux. A printed circuit board having both through-hole and surface-mount components, contaminated during manufacturing with solder flux residue plus other oils and waxes is passed through this 10 vapor degreaser. The board is thoroughly cleaned, no stratospheric ozone is destroyed, and there is no flammability or toxicity risk.
Example 5 Similar to example 4, except that the replacement 15 agent placed in the vapor degreaser is 95% (by moles) octane with 5o tridecafluoro-1-iodohexane.
Example 6 The solvents that have been in use in a manufacturing facility for degreasing of metal parts 20 (CFC-113, 1,1,1-trichloroethane, and Stoddard solvent) are removed and recycled, reclaimed, or destroyed in an environmentally acceptable manner. During manufacturing, a metal component is found to be contaminated on the surface with 350 centistoke machining oil and 250,000 25 centistoke silicone grease. From a squirt bottle in a fume hood the component is rinsed with 1 , 1, 2 , 2 , 3 , 3 , 4 , 4 , 4 -nonafluoro-1-iodobutane, wiped with a clean cloth, and allowed to air dry. Within 15 minutes it is dry and the surface is clean and ready for further processing. This 30 cleaning process did not deplete stratospheric ozone or pose a flammability or toxicity risk to the technician or require excessive investment in engineering controls.
SUBSTITUTE SHEET (RULE 26) Examgle 7 ' A gyroscope contaminated with MIL-H-5606 hydraulic fluid is placed in an ultrasonic cleaning machine filled with tridecafluoro-1-iodohexane. A crossdraft local exhaust removes any escaping vapors and the bath is subj ected to 2 watts/crn2 ultrasonic energy for S minutes .
The gyroscope :is removed, allowed to drain, and hot-air dried. The re:~ulting very clean gyroscope is carefully packaged and sent o:n for further manufacturing or installation.
Example 8 In a dry cleaning operation the perchloroethylene used is removed and recycled or destroyed in an environmentall~~r sound manner. These solvents are replaced with a blend of 50 (by moles) CF3(CFz)SI and 950 petroleum dist:_llate consisting primarily of heptane and octane. The ne:w solvent is effective, nonflammable, and much less toxic than the solvents replaced. Furthermore, it is less dam<~ging to the environment because the risk of ground water contamination by the long-lived species perchloroethylene is eliminated.
Example 9 An alkyd enamel paint is formulated using (instead of pure mineral spirits) a blend of 95% (by moles) mineral spirits and 5% 1-iodoperfluorohexane. The addition of the' fluoroiodocarbon renders the formulation nonflammable a;nd safer to use.
Examgle 10 An adhesive is formulated using (instead of 1,1,1 trichloroethan~~) a blend of 950 (by moles) toluene and 5%
1-iodoperfluorohexane. By this change the adhesive is made nonflammable and less harmful to the environment.
SUBSTITUTE SHEET RULE 26) 'Example 11 A polyurethane foam is blown using as the blowing agent a mixture of 5 o by moles pentafluoroiodoethane with 95% pentane. In contrast to foams blown using CFC-11, during the manufacturing process none of the vapors released cause ozone depletion. In addition, because of the addition of the fluoroiodoalkane, the foam is rendered nonflammable. Finally, at the end of its useful life, when the foam is disposed of, no damage to stratospheric ozone occurs.
Example 12 A can of hair spray is pressurized with a mixture of 4% (by moles) CF3I and 96% butane and/or isobutane.
There is no flammability risk; even if the spray can is accidentally discharged over an open flame no ignition occurs. Discharge of the contents of the can causes no damage to stratospheric ozone.
Example 13 A spray can of household disinfectant is pressurized with a mixture of 4% CF3I and 96o carbon dioxide. Because of the use of the fluoroiodocarbon blend as propellant, any flammability risk is eliminated.
Example 14 A gas mixture consisting of 50 (by moles) CF3I, 12%
ethylene oxide, and 83o nitrogen is used to sterilize bandages, gauze pads, and medical equipment. Because of the addition of the CF3I as a supplemental propellant, the danger of fire or explosion during the process is eliminated.
Example 15 The charge of Halon 1301 is removed from a computer room fire protection system and taken for recycling or SUBSTfTUTE SHEET (RULE 26) WO 94!20588 PCT/US94102321 destruction. In its place, with minor modifications of the system (such as changes in gaskets, O-rings, and nozzles) is placed a gas mixture consisting of 60% (by moles) CF3I and 40% CF3CHzF. In the event of a fire, the new agent rap:Ldly disperses and extinguishes the fire without harming personnel or damaging equipment. No ozone depletion occurs from the emission of the firefighting agent.
Example 16 The Halon 1211 in a 150-lb wheeled flightline extinguisher at an airport is removed and taken for recycling or destruction. In its place, with minor modifications to the extinguisher (such as changes in gaskets, O-rings, and nozzles), is put a mixture of 70%
(by moles) 1,:L,2,2,3,3,3-heptafluoro-1-iodopropane and 30% perflurohe:xane. In case of fire the liquid agent is manually directed as a stream at the base of the flames and rapidly extinguishes the fire without harming personnel or damaging equipment. No ozone depletion occurs from the emission of the firefighting agent.
Example 17 A cylinder containing approximately 1 lb of CF,I
sealed with a lead plug is mounted under the hood of a vehicle. In case of fire, the extinguisher is activated passively as the lead plug melts and the extinguishing agent is automatically discharged, extinguishing the fire and protecting the occupants, vehicle, and contents.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
Although v~he invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results.
Variations and modifications of the present invention SUBSTfTUTE SHEET (RULE 26) will be obvious to those skilled in the art and it is intended to cover in the appended claims all such modifications and equivalents.
Claims (98)
1. A composition, comprising a blend of from 20 to 75 mol percent of at least one fluoroiodocarbon of the formula C a H b Br c Cl d F e I f N f O g, wherein a is between and including 1 and 8, b is between and including 0 and 2, c, d and g are each between and including 0 and 1, a is between and including 1 and 17, and f is between and including 1 and 2, the fluoroiodocarbon being electrically nonconductive and having an ozone depletion potential less than 0.02 and a global warming potential less than that of chlorofluorocarbons, with from 25 to 80 mol percent at least one additive selected from the group consisting of (i) alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and 2-propanol, (ii) esters, (iii) ethers, (iv) mineral spirits, (v) Stoddard's solvent, (vi) hydrocarbons selected from the group consisting of butane, cyclopropane, decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2-dimethylpropane, heptane, isobutane, limonene, 2-methylbutane, 3-methylhexane, 3-methylpentane, nonane, octane, pentane, pinene, propane, turpentine and undecane, (vii) hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane, (viii) ketones, and (ix) perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane, wherein the additive and the fluoroiodocarbon are nonreactive in the blend, with the proviso that when the additive is selected from the group consisting of alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and propanol, and ketones, then a is between and including 1 and 3, b is between and including 0 and 2, c, d and g are each between and including 0 and 1, a is between and including 1 and 7, and f is between and including 1 and 2.
2. The composition of claim 1, wherein the at least one fluoroiodocarbon is selected from the group consisting of bromodifluoroiodomethane, chlorodifluoroiodomethane, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-diiodopentane, difluorodiiodomethane, difluoroiodomethane, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane, fluoroiodomethane, 1,1,1,2,3,3,3-heptafluoro-2-iodopropane, 1,1,2,2,3,3,3-heptafluoro-1-iodopropane, 1,1,2,2,3,3-hexafluoro-1,3-diiodopropane, 1-iodoheptadecafluorooctane, iodoheptafluorocyclobutane, 1-iodopentadecafluoroheptane, iodopentafluorocyclopropane, 1-iodo-tridecafluorohexane, 1-iodo-undecafluoropentane, N-iodobis-(trifluoromethyl)amine, 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane, 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane, pentafluoroiodoethane, 1,1,2,2-tetrafluoro-1,2-diiodoethane, 1,1,2,2-tetrafluoro-1-iodoethane, 1,1,2-trifluoro-1-iodoethane, and trifluoroiodomethane.
3. The composition of claim l, wherein the additive comprises an alcohol selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol, and 2-propanol.
4. The composition of claim l, wherein the additive comprises an ester selected from the group consisting of ethyl acetate, ethyl butanoate, ethyl propanoate, n-butyl acetate, n-pentyl acetate, hexyl acetate, isobutyl acetate, isopropyl acetate, methyl acetate, methyl butanoate, methyl propanoate, n-propyl acetate, and sec-butyl acetate.
5. The composition of claim 1, wherein the additive comprises an ether selected from the group consisting of diethyl ether, diisopropyl ether, dimethyl ether, di-n-butyl ether, di-n-propyl ether, 1,4-dioxane, ethylene oxide, propylene oxide, and tetrahydrofuran.
6. The composition of claim 1, wherein the additive comprises mineral spirits, Stoddard's solvent, or a hydrocarbon selected from the group consisting of butane, cyclopropane, decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2-dimethylpropane, heptane, isobutane, limonene, 2-methylbutane, 3-methylhexane, methylpentane, nonane, octane, pentane, pinene, propane, turpentine, and undecane.
7. The composition of claim 1, wherein the additive comprises a hydrofluorocarbon selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, and 1,1,1-trifluoroethane.
8. The composition of claim 1, wherein the additive comprises a perfluorocarbon selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane.
9. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I and the additive comprises at least one component selected from the group consisting of difluoromethane, pentafluoroethane, 1,1,1-trifluoroethane, propane, 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane and butane.
10. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises 1,1-difluoroethane.
and the additive comprises 1,1-difluoroethane.
11. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises at least one component selected from the group consisting of butane and isobutane.
and the additive comprises at least one component selected from the group consisting of butane and isobutane.
12. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises at least one component selected from the group consisting of butane, diethyl ether, and pentane.
13. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2I and the additive comprises at least one component selected from the group consisting of acetone, methyl acetate, and tetrahydrofuran.
14. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2I and the additive comprises at least one component selected from the group consisting of ethanol, butanone, 2-propanol, and ethyl acetate.
15. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2CF2CF2I and the additive comprises at least one component selected from the group consisting of heptane and mineral spirits.
16. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2CF2CF2CF2I and the additive comprises at least one component selected from the group consisting of nonane, octane, and Stoddard's solvent.
17. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2CF2CF2CF2CF2I and the additive comprises at least one component selected from the group consisting of decane, hexyl acetate, limonene, mineral spirits, pinene, Stoddard's solvent, turpentine, and undecane.
18. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises difluoromethane.
and the additive comprises difluoromethane.
19. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises pentafluoroethane.
and the additive comprises pentafluoroethane.
20. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises 1,1,1-trifluoroethane.
and the additive comprises 1,1,1-trifluoroethane.
21. The composition of claim 1, wherein the fluoroiodocarbon is CF3I and the additive comprises propane.
22. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises 1,1,1,2-tetrafluoroethane.
and the additive comprises 1,1,1,2-tetrafluoroethane.
23. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises butane.
and the additive comprises butane.
24. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2I
and the additive comprises butane or isobutane.
and the additive comprises butane or isobutane.
25. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises butane.
26. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises diethyl ether.
27. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises pentane.
28. The composition of claim 1, wherein the fluoroiodocarbon is included in an amount of from 20 mol percent to 60 mol percent.
29. The composition of claim 1, wherein the fluoroiodocarbon is included in an amount of from 30 mol percent to 75 mol percent.
30. The composition of claim 1, wherein at least 30 mol percent of the fluoroiodocarbon is employed.
31. The composition of claim 1, wherein the fluoroiodocarbon is CF3I.
32. The composition of claim 1, wherein the fluoroiodocarbon is CF3(CF2)2I, CF3(CF2)3I, CF3(CF2)4I or CF3(CF2)5I.
33. The composition of claim 1, wherein the additive comprises a ketone selected from the group consisting of acetone, 2-butanone, and 3-methyl-2-butanone.
34. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and additive .comprises ethanol.
35. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises butanone.
36. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises 2-propanol.
37. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises ethyl acetate.
38. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises isopropyl acetate.
39. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises heptane.
40. The composition of claim 1, wherein the additive comprises pentane and the fluoroiodocarbon comprises CF3I, CF3CF2I, or CF3CF2CF2I.
41. An aerosol propellant comprising the composition of claim 1, wherein the aerosol propellant is non-flammable.
42. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3I
and the additive comprises decafluorobutane.
and the additive comprises decafluorobutane.
43. The composition of claim 1, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises tetradecafluorohexane.
44. A refrigerant composition comprising the composition as defined by claim 1, wherein the additive is selected from the group consisting of alcohols, ethers, hydrocarbons, hydrofluorocarbons, and perfluorocarbons.
45. A solvent comprising the composition as defined by claim 1, wherein when a is 1, the fluoroiodocarbon is selected from the group consisting of fluoroiodomethane, difluoroiodomethane, difluorodiiodomethane, bromodifluoroiodomethane and chlorodifluoroiodomethame.
46. A foam blowing agent comprising the composition as defined by claim 1, wherein the additive is selected from the group consisting of ethers, hydrocarbons, hydrofluorocarbons, ketones and perfluorocarbons.
47. An aerosol propellant comprising the composition as defined by claim 1, wherein the additive is selected from the group consisting of ethers, hydrocarbons, hydrofluorocarbons, and perfluorocarbons.
48. A fire extinguishing agent comprising the composition as defined by claim 1, wherein the additive is selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane.
49. The composition of claim 1, comprising a blend of from 20 to 75 mol percent of at least one fluoroiodocarbon of the formula C a H b Br c Cl d F e I f N g, wherein a is between and including 1 and 8, b is between and including 0 and 2, c, d and g are each between and including 0 and 1, e is between and including 1 and 17, and f is between and including 1 and 2, the fluoroiodocarbon being electrically nonconductive and having an ozone depletion potential less than 0.02 and a global warming potential less than that of chlorofluorocarbons, with from 25 to 80 mol percent at least one additive selected from the group consisting of (i) alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and 2-propanol, (ii) esters selected from the group consisting of ethyl acetate, ethyl butanoate, ethyl propanoate, n-butyl acetate, n-pentyl acetate, hexyl acetate, isobutyl acetate, isopropyl acetate, methyl acetate, methyl butanoate, methyl propanoate, n-propyl acetate, and sec-butyl acetate, (iii) ethers selected from the group consisting of diethyl ether, diisopropyl ether, dimethyl ether, di-n-butyl ether, di-n-propyl ether, 1,4-dioxane, ethylene oxide, propylene oxide, and tetrahydrofuran, (iv) mineral spirits, (v) Stoddard's solvent, (vi) hydrocarbons selected from the group consisting of butane, cyclopropane, decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2-dimethylpropane, heptane, isobutane, limonene, 2-methylbutane, 3-methylhexane, 3-methylpentane, mineral spirits, nonane, octane, pentane, pinene, propane, Stoddard's solvent, turpentine and undecane, (vii) hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane and 1,1,1-trifluoroethane, (viii) ketones selected from the group consisting of acetone, propanone, 2-propanone, butanone, 2-butanone, 2-petanone, 2-hexanone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone and carbon dioxide, and (ix) perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane, wherein the additive and the fluoroiodocarbon are nonreactive in the blend, with the proviso that when the additive is selected from the group consisting of alcohols selected from the group consisting of 1-butanol, 2-butanol, ethanol, methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol and propanol, and ketones, then a is between and including 1 and 3, b is between and including 0 and 2, c, d and g are each between and including 0 and 1, e is between and including 1 and 7, and f is between and including 1 and 2.
50. A method for providing refrigeration, comprising the steps of:
(a) providing a refrigerating amount of a refrigerant composition in a cooling system, and (b) operating the cooling system, wherein the refrigerant composition comprises a composition according to claim 1 in which the additive is selected from the group consisting of alcohols, ethers, hydrocarbons, ketones, hydrofluorocarbons, and perfluorocarbons.
(a) providing a refrigerating amount of a refrigerant composition in a cooling system, and (b) operating the cooling system, wherein the refrigerant composition comprises a composition according to claim 1 in which the additive is selected from the group consisting of alcohols, ethers, hydrocarbons, ketones, hydrofluorocarbons, and perfluorocarbons.
51. A method of using a solvent to clean a surface of an article, comprising the steps of providing a solvent to an applicator, and applying the solvent from the applicator to a surface of an article, the solvent removing a contaminant from the surface of the article, wherein the solvent comprises a composition according to claim 1, with the proviso that when a is 1, the fluoroiodocarbon is selected from the group consisting of fluoroiodomethane, difluoroiodomethane, difluorodiiodomethane, bromodifluoroiodomethane and chlorodifluoroiodomethane.
52. A method of using a foam blowing agent, comprising the steps of:
a) injecting a foam blowing agent into a monomer, where the foam blowing agent comprises a composition according to claim 1 in which the additive is selected from the group consisting of ethers, hydrocarbons, hydrofluorocarbons, ketones, and perfluorocarbons;
b) allowing the monomer to polymerize;
c) allowing the agent to substantially vaporize; and d) allowing resulting cell walls to harden.
a) injecting a foam blowing agent into a monomer, where the foam blowing agent comprises a composition according to claim 1 in which the additive is selected from the group consisting of ethers, hydrocarbons, hydrofluorocarbons, ketones, and perfluorocarbons;
b) allowing the monomer to polymerize;
c) allowing the agent to substantially vaporize; and d) allowing resulting cell walls to harden.
53. A method of discharging a liquid composition from a container in aerosol form, comprising providing in the container a mixture of the liquid composition and an aerosol propellant, said aerosol propellant comprising a composition according to claim 1, wherein the additive is selected from the group consisting of ethers, hydrocarbons, hydrofluorocarbons, and perfluorocarbons, and discharging the mixture from the container, the liquid composition being discharged in aerosol form.
54. A method of using a fire extinguishing agent, comprising the steps of:
(a) providing a fire-extinguishing agent comprising a composition according to claim 1, wherein the additive is selected from the group consisting of hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1-trifluoroethane and 1,1,2-trifluoroethane, and perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane, in a discharge apparatus; and (b) discharging a fire-extinguishing amount of the fire-extinguishing agent from the discharge apparatus into contact with a combustible or flammable material.
(a) providing a fire-extinguishing agent comprising a composition according to claim 1, wherein the additive is selected from the group consisting of hydrofluorocarbons selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1-trifluoroethane and 1,1,2-trifluoroethane, and perfluorocarbons selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane, in a discharge apparatus; and (b) discharging a fire-extinguishing amount of the fire-extinguishing agent from the discharge apparatus into contact with a combustible or flammable material.
55. The method of any one of claims 50, 51, 52, 53 and 54, wherein the fluoroiodocarbon is selected from the group consisting of bromodifluoroiodomethane, chlorodifluoroiodomethane, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-diiodopentane, difluorodiiodomethane, difluoroiodomethane, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane, fluoroiodomethane, 1,1,1,2,3,3,3-heptafluoro-2-iodopropane, 1,1,2,2,3,3,3-heptafluoro-1-iodopropane, 1,1,2,2,3,3-hexafluoro-1,3-diiodopropane, 1-iodoheptadecafluorooctane, iodoheptafluorocyclobutane, 1-iodopentadecafluoroheptane, iodopentafluorocyclopropane, 1-iodo-tridecafluorohexane, 1-iodo-undecafluoropentane, N-iodobis-(trifluoromethyl)amine, 1,1,2,2,3,3,4,4,4-nonafluoro-1-iodobutane, 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane, pentafluoroiodoethane, 1,1,2,2-tetrafluoro-1,2-diiodoethane, 1,1,2,2-tetrafluoro-1-iodoethane, and 1,1,2-trifluoro-1-iodoethane.
56. The method of any one of claims 50, 51, 52, 53 and 54, wherein at least 30 mol percent of the fluoroiodocarbon is employed.
57. The method of any one of claims 50, 52, 53 and 54, wherein the fluoroiodocarbon is CF3I.
58. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises difluoromethane.
59. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises pentafluoroethane.
60. The method of any one of claims 50, 52 and 53, wherein the fluoroiodocarbon comprises CF3I and the additive comprises propane.
61. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises 1,1-difluoroethane.
62. The method of any one of claims 50, 52 and 53, wherein the fluoroiodocarbon comprises CF3I and the additive comprises butane.
63. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises 1,1,1-trifluoroethane.
64. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises 1,1,1,2-tetrafluoroethane.
65. The method of any one of claims 50, 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3CF2I and the additive comprises isobutane.
66. The method of any one of claims 50, 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3CF2I and the additive comprises butane.
67. The method of any one of claims 50, 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3CF2CF2CF2I and the additive comprises acetone.
68. The method of any one of claims 50 and 51, wherein the additive comprises an alcohol selected from the group consisting of 1-butanol, 2-butanol, ethanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 1-propanol, and 2-propanol.
69. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises an ether selected from the group consisting of diethyl ether, diisopropyl ether, dimethyl ether, di-n-butyl ether, di-n-propyl ether, 1,4-dioxane, ethylene oxide, propylene oxide, and tetrahydrofuran.
70. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises a hydrocarbon selected from the group consisting of butane, cyclopropane, 2,2-dimethylpropane, isobutane, 2-methylbutane, 3-methylpentane, pentane, and propane.
71. The method of any one of claims 50, 51, 52, 53 and 54, wherein the additive comprises a hydrofluorocarbon selected from the group consisting of difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, pentafluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,2-tetrafluoroethane, and 1,1,1-trifluoroethane.
72. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises a perfluorocarbon selected from the group consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane.
73. The method of any one of claims 50, 51, 52, 53 and 54, wherein the fluoroiodocarbon is CF3(CF2)2I, CF3(CF2)3I, CF3(CF2)4I or CF3(CF2)5I.
74. The method of claim 51, wherein the contaminant is a hydrophobic soil.
75. The method of claim 51, wherein ultrasonic energy is applied to the surface of the article having the solvent thereon.
76. The method of claim 51, wherein the additive comprises an ester selected from the group consisting of ethyl acetate, hexyl acetate, n-pentyl acetate, isopropyl acetate, and methyl acetate.
77. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises mineral spirits, Stoddard's solvent, or a hydrocarbon selected from the group consisting of decane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2-dimethylpropane, heptane, isobutane, 2-methylbutane, 3-methylhexane, 3-methylpentane, nonane, octane, pentane, pinene, propane, turpentine, and undecane.
78. The method of any one of claims 50, 51 and 52, wherein the additive comprises a ketone selected from the group consisting of acetone, 2-butanone, and 3-methyl-2-butanone.
79. The method of any one of claims 50, 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises diethyl ether.
80. The method of any one of claims 50, 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises pentane.
81. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)3I
and the additive comprises methyl acetate.
and the additive comprises methyl acetate.
82. The method of any one of claims 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3(CF2)3I and the additive comprises tetrahydrofuran.
83. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)4I
and additive comprises ethanol.
and additive comprises ethanol.
84. The method of any one of claims 51 and 52, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises butanone.
85. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)4I
and the additive comprises 2-propanol.
and the additive comprises 2-propanol.
86. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)4I
and the additive comprises ethyl acetate.
and the additive comprises ethyl acetate.
87. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)4I
and the additive comprises isopropyl acetate.
and the additive comprises isopropyl acetate.
88. The method of any one of claims 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3(CF2)4I and the additive comprises heptane.
89. The method of any one of claims 51, 52 and 53, wherein the fluoroiodocarbon comprises CF3(CF2)5I and the additive comprises heptane.
90. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)7I
and the additive comprises limonene.
and the additive comprises limonene.
91. The method of claim 51, wherein the fluoroiodocarbon comprises CF3(CF2)7I
and the additive comprises hexyl acetate.
and the additive comprises hexyl acetate.
92. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises pentane and the fluoroiodocarbon comprises CF3I, CF3CF2I, or CF3CF2CF2I.
93. The method of any one of claims 50, 51, 52 and 53, wherein the additive comprises a hydrocarbon selected from the group consisting of butane, cyclopropane, isobutane, pentane, and propane.
94. The method of claim 53, wherein the additive comprises a perfluorocarbon selected from the group consisting of decafluorobutane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, and octafluoropropane.
95. The method of claim 53, wherein the aerosol propellant is non-flammable.
96. The method of claim 57, wherein the fluoroiodocarbon comprises CF3I and the additive comprises decafluorobutane.
97. The method of any one of claims 50, 51, 52, 53 and 54, wherein the fluoroiodocarbon comprises CF3CF2CF2I and the additive comprises tetradecafluorohexane.
98. The method of claim 54, wherein the additive comprises a perfluorocarbon selected from the group of consisting of decafluorobutane, dodecafluoropentane, hexafluorocyclopropane, hexafluoroethane, octafluorocyclobutane, octafluoropropane, and tetradecafluorohexane.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/027,227 | 1993-03-05 | ||
US08/027,227 US5611210A (en) | 1993-03-05 | 1993-03-05 | Fluoroiodocarbon blends as CFC and halon replacements |
PCT/US1994/002321 WO1994020588A1 (en) | 1993-03-05 | 1994-03-03 | Fluoroiodocarbon blends as cfc and halon replacements |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2157567A1 CA2157567A1 (en) | 1994-09-15 |
CA2157567C true CA2157567C (en) | 2004-11-30 |
Family
ID=21836455
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002157567A Expired - Fee Related CA2157567C (en) | 1993-03-05 | 1994-03-03 | Fluoroiodocarbon blends as cfc and halon replacements |
Country Status (13)
Country | Link |
---|---|
US (9) | US5611210A (en) |
EP (1) | EP0687287B1 (en) |
JP (1) | JPH08507524A (en) |
KR (1) | KR960701169A (en) |
CN (1) | CN1052031C (en) |
AT (1) | ATE193903T1 (en) |
AU (1) | AU681640B2 (en) |
BR (1) | BR9405991A (en) |
CA (1) | CA2157567C (en) |
DE (1) | DE69424935D1 (en) |
RU (1) | RU2140955C1 (en) |
TW (1) | TW357095B (en) |
WO (1) | WO1994020588A1 (en) |
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1994
- 1994-03-03 EP EP94910828A patent/EP0687287B1/en not_active Expired - Lifetime
- 1994-03-03 RU RU95121752/04A patent/RU2140955C1/en not_active IP Right Cessation
- 1994-03-03 DE DE69424935T patent/DE69424935D1/en not_active Expired - Lifetime
- 1994-03-03 CA CA002157567A patent/CA2157567C/en not_active Expired - Fee Related
- 1994-03-03 WO PCT/US1994/002321 patent/WO1994020588A1/en active IP Right Grant
- 1994-03-03 BR BR9405991A patent/BR9405991A/en active Search and Examination
- 1994-03-03 AU AU63587/94A patent/AU681640B2/en not_active Ceased
- 1994-03-03 CN CN94191986A patent/CN1052031C/en not_active Expired - Fee Related
- 1994-03-03 AT AT94910828T patent/ATE193903T1/en not_active IP Right Cessation
- 1994-03-03 JP JP6520174A patent/JPH08507524A/en active Pending
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- 1994-06-30 US US08/269,323 patent/US7083742B1/en not_active Expired - Fee Related
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1995
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- 1995-03-31 US US08/414,566 patent/US5562861A/en not_active Expired - Lifetime
- 1995-09-05 KR KR1019950703755A patent/KR960701169A/en not_active Application Discontinuation
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1996
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- 1996-09-10 US US08/707,960 patent/US5695688A/en not_active Expired - Lifetime
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CA2157567A1 (en) | 1994-09-15 |
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US5674451A (en) | 1997-10-07 |
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US5605647A (en) | 1997-02-25 |
AU6358794A (en) | 1994-09-26 |
US5444102A (en) | 1995-08-22 |
AU681640B2 (en) | 1997-09-04 |
CN1122606A (en) | 1996-05-15 |
EP0687287B1 (en) | 2000-06-14 |
US5685915A (en) | 1997-11-11 |
US5562861A (en) | 1996-10-08 |
KR960701169A (en) | 1996-02-24 |
RU2140955C1 (en) | 1999-11-10 |
JPH08507524A (en) | 1996-08-13 |
CN1052031C (en) | 2000-05-03 |
EP0687287A1 (en) | 1995-12-20 |
US5716549A (en) | 1998-02-10 |
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