(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) lntemational Publication Date
`6 May 2004 (06.05.2004)
`
`(10) International Publication Number
`
`WO 2004/037913 A2
`
`(51) International Patent Classification7:
`
`C08L
`
`(21) International Application Number:
`PCT/US2003/033874
`
`(74) Agents: SZUCH, Colleen et al.; Honeywell International,
`Inc., 101 Columbia Road, P.O. Box 2245, Morristown, NJ
`07962-2245 (US).
`
`(22) International Filing Date: 27 October 2003 (27.10.2003)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`60/421,263
`60/421,435
`
`25 October 2002 (25.10.2002)
`25 October 2002 (25.10.2002)
`
`US
`US
`
`(71) Applicant (for all designated States except US): HON-
`EYWELL INTERNATIONAL, INC. [US/US]; 101 Co-
`lumbia Road, P.O. Box 2245, Morristown, NJ 07962-2245
`(US).
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): SINGH, Rajiv,
`R.
`[US/US]; 18 Foxfire Drive, Getzville, NY 14068
`(US). PHAM, Hang, T. [US/US]; 136 Larkspur Lane,
`Amherst, NY 14228 (US). WILSON, David, P. [US/US];
`118 Waxwing Court, East Amherst, NY 14051 (US).
`THOIVIAS, Raymond, H. [US/US]; 5990 Hopi Court,
`Pendleton, NY 14094 (US).
`
`Designated States (national): AE, AG, AL, AM, AT, AU,
`AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CO, CR, CU,
`CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI, GB, GD, GE,
`GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR,
`KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK,
`MN, MW, MX, MZ, NI, NO, NZ, OM, PG, PH, PL, PT,
`RO, RU, SC, SD, SE, SG, SK, SL, SY, TJ, TM, TN, TR,
`TT, TZ, UA, UG, US, UZ, VC, VN, YU, ZA, ZM, ZW.
`
`Designated States (regional): ARIPO patent (GH, GM,
`KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZM, ZW),
`Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European patent (AT, BE, BG, CH, CY, CZ, DE, DK, EE,
`ES, FI, FR, GB, GR, HU, IE, IT, LU, MC, NL, PT, RO,
`SE, SI, SK, TR), OAPI patent (BF, BJ, CF, CG, CI, CM,
`GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Published:
`
`without international search report and to be republished
`upon receipt of that report
`
`For two—letter codes and other abbreviations, refer to the "Guid-
`ance Notes on Codes and Abbreviations " appearing at the begin-
`ning of each regular issue of the PCT Gazette.
`
`N <
`
`3
`
`«'2
`V-1
`ax
`l\
`
`(54) Title: COMPOSITIONS CONTAINING FLOURINE SUBSTITUTED OLEFINS
`
`mcR :
`
`1-
`
`ccN
`
`O (57) Abstract: The use of pentafluoropropene (HFO—1225) and tetrafluoropropene (HFO—1234) in refrigeration equipment is dis-
`closed. These materials are generally useful as refrigerants for heating and cooling, as blowing agents, as aerosol propellants, as
`solvent composition, and as fire extinguishing and suppressing agents.
`
`Arkema Exhibit 1030
`
`Arkema Exhibit 1030
`
`1 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`RELATED APPLICATIONS
`
`The present application is related to and claims the priority benefit of U.S.
`
`Provisional Application Nos. 60/421,263, and 60/421,435, each of whichwas filed on
`
`October 25, 2002, and each of which is incorporated herein by reference. The
`
`present application is also related to and incorporates by reference each of the
`
`following concurrently filed United States Patent Applications: Attorney Docket
`
`Number H0004412 (26269) entitled "Fluorinated Alkene Refrigerant Composition,”
`
`by Raymond Thomas and Attorney Docket Number H0O03789 (26267) entitled
`
`“Process For Producing Fluoropropenes,” by Hsueh Sung Tung et al.
`
`FIELD OF THE INVENTION
`
`This invention relates to compositions having utility in numerous applications,
`
`including particularly refrigeration systems, and to methods and systems which
`
`utilize such compositions.
`
`In preferred aspects, the present invention is directed to
`
`refrigerant compositions which comprise at least one multi-fluorinated olefin of the
`
`present invention.
`
`BACKGROUND OF THE INVENTION
`
`Fluorocarbon based fluids have found widespread use in many commercial
`
`and industrial applications. For example, fluorocarbon based fluids are frequently
`
`used as a working fluid in systems such as air conditioning, heat pump and
`
`refrigeration applications. The vapor compression cycle is one of the most
`
`commonly used type methods to accomplish cooling or heating in a refrigeration
`
`system. The vapor compression cycle usually involves the phase change of the
`
`refrigerant from the liquid to the vapor phase through heat absorption at a relatively
`
`low pressure and then from the vapor to the liquid phase through heat removal at a
`
`relatively low pressure and temperature, compressing the vapor to a relatively
`
`2 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`elevated pressure, condensing the vapor to the liquid phase through heat removal at
`
`this relatively elevated pressure and temperature, and then reducing the pressure to
`
`start the cycle over again.
`
`While the primary purpose of refrigeration is to remove heat from an object or
`
`other fluid at a relatively low temperature, the primary purpose of a heat pump is to
`
`add heat at a higher temperature relative to the environment.
`
`Certain fluorocarbons have been a prefen'ed component in many heat
`
`exchange fluids, such as refrigerants, for many years in many applications. For,
`
`example, fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane
`
`derivatives, have gained widespread use as refrigerants in applications including air
`
`conditioning and heat pump applications owing to their unique combination of
`
`chemical and physical properties. Many of the refrigerants commonly utilized in
`
`vapor compression systems are either single components fluids or azeotropic
`
`mixtures.
`
`Concern has increased in recent years about potential damage to the earth’s
`
`atmosphere and climate, and certain chlorine-based compounds have been
`
`identified as particularly problematic in this regard. The use of chlorine-containing
`
`compositions (such as chlorofluorocarbons (CFC’s), hydrochlorofluorocarbons
`
`(HCF's) and the like) as refrigerants in air-conditioning and refrigeration systems has
`
`become disfavored because of the ozone-depleting properties associated with many
`
`of such compounds. There has thus been an increasing need for new fluorocarbon
`
`and hydrofluorocarbon compounds and compositions that offer alternatives for
`
`refrigeration and heat pump applications. For example, it has become desirable to
`
`retrofit chlorine—containing refrigeration systems by replacing chlorine-containing
`
`refrigerants with non-chlorine-containing refrigerant compounds that will not deplete
`
`the ozone layer, such as hydrofluorocarbons (HFC’s).
`
`It is generally considered important, however, that any potential substitute
`
`refrigerant must also possess those properties present in many of the most widely
`
`used fluids, such as excellent heat transfer properties, chemical stability, Iow- or no-
`
`toxicity, non-flammability and lubricant compatibility, among others.
`
`Applicants have come to appreciate that lubricant compatibility is of particular
`
`importance in many of applications. More particularly, it is highly desirably for
`
`3 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`refrigeration fluids to be compatible with the lubricant utilized in the compressor unit,
`
`used in most refrigeration systems. Unfortunately, many non—chlorine-containing
`
`refrigeration fluids, including HFC’s, are relatively insoluble and/or immiscible in the
`
`types of lubricants used traditionally with CFC's and HFC’s, including, for example,
`
`mineral oils, alkylbenzenes or poly(alpha-olefins).
`
`in order for a refrigeration fluid-
`
`lubricant combination to work at a desirable level of efficiently within a compression
`
`refrigeration, air-conditioning and/or heat pump system, the lubricant should be
`
`sufficiently soluble in the refrigeration liquid over a wide range of operating
`
`temperatures. Such solubility lowers the viscosity of the lubricant and allows it to
`
`flow more easily throughout the system.
`
`In the absence of such solubility, lubricants
`
`tend to become lodged in the coils of the evaporator of the refrigeration, air-
`
`conditioning or heat pump system, as well as other parts of the system, and thus
`
`reduce the system efficiency.
`
`With regard to efficiency in use, it is important to note that a loss in refrigerant
`
`thermodynamic performance or energy efficiency may have secondary
`
`environmental impacts through increased fossil fuel usage arising from an increased
`
`demand for electrical energy.
`
`Furthermore, it is generally considered desirably for CFC refrigerant
`
`substitutes to be effective without major engineering changes to conventional vapor
`
`compression technology currently used with CFC refrigerants.
`
`Flammability is another important property for many applications. That is, it is
`
`considered either important or essential in many applications, including particularly in
`
`heat transfer applications, to use compositions which are non-flammable. Thus, it is
`
`frequently beneficial to use in such compositions compounds which are
`
`nonflammable. As used herein, the term “nonflammab|e” refers to compounds or
`
`compositions which are determined to be nonflammable as determined in
`
`accordance with ASTM standard E-681, dated 2002, which is incorporated herein by
`
`reference. Unfortunately, many HFC’s which might othenrvise be desirable for used
`
`in refrigerant compositions are not nonflammable. For example, the fluoroalkane
`
`difluoroethane (HFC-152a) and the fluoroalkene 1,1,1—trifluorpropene (HFO-1243zf)
`
`are each flammable and therefore not viable for use in many applications.
`
`Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five
`
`4 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`carbon atoms, have been suggested for use as refrigerants. U.S. Patent No.
`
`4,788,352 — Smutny is directed to production of fluorinated C5 to Ca compounds
`
`having at least some degree of unsaturation. The Smutny patent identifies such
`
`higher olefins as being known to have utility as refrigerants, pesticides, dielectric
`
`fluids, heat transfer fluids, solvents, and intermediates in various chemical reactions.
`
`(See column 1, lines 11 — 22).
`
`While the fluorinated olefins described in Smutny may have some level of
`
`effectiveness in heat transfer applications, it is believed that such compounds may
`
`also have certain disadvantages. For example, some of these compounds may tend
`
`to attack substrates, particularly general-purpose plastics such as acrylic resins and
`
`ABS resins. Furthermore, the higher olefinic compounds described in Smutny may
`
`also be undesirable in certain applications because of the potential level of toxicity of
`
`such compounds which may arise as a result of pesticide activity noted in Smutny.
`
`Also, such compounds may have a boiling point which is too high to make them
`
`useful as a refrigerant in certain applications.
`
`Bromofluoromethane and bromochlorofluoromethane derivatives, particularly
`
`bromotrifluoromethane (Halon 1301) and bromochlorodifluoromethane (Halon 1211)
`
`have gained widespread use as fire extinguishing agents in enclosed areas such as
`
`airplane cabins and computer rooms. However, the use of various halons is being
`
`phased out due to their high ozone depletion. Moreover, as halons are frequently
`
`used in areas where humans are present, suitable replacements must also be safe
`
`to humans at concentrations necessary to suppress or extinguish fire.
`
`Applicants have thus come to appreciate a need for compositions, and
`
`particularly heat transfer compositions, fire extinguishing/suppression compositions,
`
`blowing agents, solvent compositions, and compatabilizing agents, that are
`
`potentially useful in numerous applications, including vapor compression heating and
`
`cooling systems and methods, while avoiding one or more of the disadvantages
`
`noted above.
`
`5 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`SUMMARY
`
`Applicants have found that the above-noted need, and other needs, can be
`
`satisfied by compositions comprising one or more C3 or C4 fluoroalkenes, preferably
`
`compounds having Formula I as follows:
`
`XCFzR3-z U)
`
`where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl radical,
`
`each R is independently Cl, F, Br, I or H, and z is 1 to 3.
`
`The present invention provides also methods and systems which utilize the
`
`compositions of the present invention, including methods and systems for heat
`
`transfer, foam blowing, solvating, and aerosol generation.
`
`DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
`
`THE COMPOSITIONS
`
`The present invention is directed to compositions comprising at least one
`
`fluoroalkene containing from 3 to 4 carbon atoms and at least one carbon-carbon
`
`double bond. The fluoroalkene compounds of the present invention are sometimes
`
`referred to herein for the purpose of convenience as hydrofluoro—o|efins or “HFOs” if
`
`they contain at least one hydrogen Although it is contemplated that the HFOs of the
`
`president mentioned may contain two carbon -- carbon double bonds, such
`
`compounds at the present time are not considered to be preferred.
`
`As mentioned above, the present compositions comprise one or compounds
`
`in accordance with Formula I.
`
`In preferred embodiments, the compositions include
`
`compounds of Formula II below:
`
`T=c—R'
`
`n\
`R/°
`
`(N)
`
`where each R is independently CI, F, Br, I or H
`
`R’ is (CR2),.Y,
`
`6 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`Yis CRF2
`
`and n is 0 or 1.
`
`in highly preferred embodiments, Y is CF3, n is 0 and at least one of the remaining
`
`Rs is F.
`
`Applicants believe that, in general, the compounds of the above identified
`
`Formulas l and ii are generally effective and exhibit utility in refrigerant compositions,
`
`blowing agent compositions, compatibilzers, and solvent compositions of the present
`
`invention. However, applicants have surprisingly and unexpectedly found that
`
`certain of the compounds having a structure in accordance with the formulas
`
`described above exhibit a highly desirable low level of toxicity compared to other of
`
`such compounds. As can be readily appreciated, this discovery is of potentially
`
`enormous advantage and benefit for the formulation of not only refrigerant
`
`compositions, but also any and all compositions which would othen/vise contain
`
`relatively toxic compounds satisfying the formulas described above. More
`
`particularly, applicants believe that a relatively low toxicity level is associated with
`
`compounds of Formula II, preferably wherein Y is CF3, wherein at least one R on the
`
`unsaturated terminal carbon is H, and at least one of the remaining Rs is F.
`
`Applicants believe also that all structural, geometric and stereoisomers of such
`
`compounds are effective and of beneficially low toxicity.
`
`in highly preferred embodiments, especially embodiments which comprise the
`
`low toxicity compounds described above, n is zero. Thus, in certain preferred
`
`embodiments the compositions of the present invention comprise one or more
`
`compounds selected from the group consisting of tetrafluoropropenes (HFO—1234),
`
`pentafluoropropenes (HFO-1225) and combinations of these.
`
`It is even more preferred that the compounds of the present invention are the
`
`tetrafluoroprpoene and pentafluoropropene compounds in which the unsaturated
`
`terminal carbon has not more than one F substituent, specifically: 1, 3, 3, 3-
`
`tetrafluoropropene (HFO-1234ze); 2, 3, 3, 3—tetrafluoropropene (HFO-1234yf); and
`
`1,2,3,3,3—pentafluoropropene (HFO-1225ye), and any and all stereoisomers of each
`
`of these. Applicant has discovered that such compounds have a very low acute
`
`toxicity level, as measured by inhalation exposure to mice and rats. On the other
`
`hand, applicants have found that a relatively high degree of toxicity may be
`
`7 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`associated with certain compounds adaptable for use with the present compositions,
`
`namely, those compounds which have more than one F on the terminal unsaturated
`
`carbon, or which do not have at least one H on the terminal unsaturated carbon. For
`
`example, applicants have discovered that 1,1,3,3,3-pentafluoropropene (HFO-
`
`1225zc) exhibits an unacceptably high degree of toxicity, as measured by inhalation
`
`exposure to mice and rats.
`
`The preferred compounds of the present invention, namely, HFO-1225 and
`
`HFO—1234 are known materials and are listed in Chemical Abstracts databases.
`
`HFO-1225 is commercially available, from example from Syntex Chemical Co.
`
`Futhermore, methods are described generally in the patent literature for producing
`
`fluoroalkenes. For example, the production of fluoropropenes such as CF3CH=CH2
`
`by catalytic vapor phase fluorination of various saturated and unsaturated halogen-
`
`containing C3 compounds is described in US. Patent Nos. 2,889,379; 4,798,818 and
`
`4,465,786, each of which is incorporated herein by reference. U.S. Patent No.
`
`5,532,419, which is also incorporated herein by reference, discloses a vapor phase
`
`catalytic process for the preparation of fluoroalkene using a ch|oro- or bromo-
`
`halofluorocarbon and HF. EP 974,571, also incorporated herein by reference,
`
`discloses the preparation of 1,1,1,3-tetrafluoropropene by contacting 1,1,1,3,3-
`
`pentafluoropropane (HFC-245fa) in the vapor phase with a chromium-based catalyst
`
`at elevated temperature, or in the liquid phase with an alcoholic solution of KOH,
`
`NaOH, Ca(OH)2 or Mg(OH)2, in addition, methods for producing compounds in
`
`accordance with the present invention are described generally in connection with
`
`concurrently filed United States Patent Application entitled "Process for Producing
`
`Fluorpropenes" bearing attorney docket number (H0003789 (26267)), which is also
`
`incorporated herein by reference.
`
`The present compositions are believed to possess properties that are
`
`advantageous for a number of important reasons. For example, applicants believe,
`
`based at least in part on mathematical modeling, that the fluoroolefins of the present
`
`invention will not have a substantial negative affect on atmospheric chemistry, being
`
`negligible contributors to ozone depletion in comparison to some other halogenated
`
`species. The preferred compositions of the present invention thus have the
`
`advantage of not contributing substantially to ozone depletion. The preferred
`
`8 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`compositions also do not contribute substantially to global warming compared to
`
`many of the hydrofluoroalkanes presently in use.
`
`Preferably, the compositions of the present invention have a Global Warming
`
`Potential (GWP) of not greater than 150, more preferably not greater than 100 and
`
`even more preferably not greater than 75. As used herein, “GWP” is measured
`
`relative to that of carbon dioxide and over a 100 year time horizon, as defined in
`
`“The Scientific Assessment of Ozone Depletion, 2002, a report of the World
`
`Meteorological Association's Global Ozone Research and Monitoring Project,” which
`
`is incorporated herein by reference.
`
`The present compositions also preferably have an Ozone Depletion Potential
`
`(ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more
`
`preferably about zero. As used herein, “ODP” is as defined in “The Scientific
`
`Assessment of Ozone Depletion, 2002, A report of the World Meteorological
`
`Association's Global Ozone Research and Monitoring Project," which is incorporated
`
`herein by reference.
`
`HEAT TRANSFER COMPOSITIONS
`
`Although it is contemplated that the compositions of the present invention may
`
`include the compounds of the present invention in widely ranging amounts, it is
`
`generally preferred that refrigerant compositions of the present invention comprise
`
`compound(s) in accordance with Formula I, and even more preferably Formula II, in
`
`an amount that is at least about 50% by weight, and even more preferably at least
`
`about 70 % by weight, of the composition.
`
`The compositions of the present invention may include other components for
`
`the purpose of enhancing or providing certain functionality to the composition, or in
`
`some cases to reduce the cost of the composition. For example, refrigerant
`
`compositions according to the present invention, especially those used in vapor
`
`compression systems, include a lubricant, generally in amounts of from about 30 to
`
`about 50 percent by weight of the composition. Furthermore, the present
`
`compositions may also include a compatibilzer, such as propane, for the purpose of
`
`aiding compatibility and/or solubility of the lubricant. Such compatibilizers, including
`
`propane, butanes and pentanes, are preferably present in amounts of from about 0.5
`
`9 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`to about 5 percent by weight of the composition. Combinations of surfactants and
`
`solubilizing agents may also be added to the present compositions to aid oil
`
`solubility, as disclosed by U.S. Patent No. 6,516,837, the disclosure of which is
`
`incorporated by reference. Commonly used refrigeration lubricants such as Polyol
`
`Esters (POEs) and Poly Alkylene Glycols (PAGs) that are used in refrigeration
`
`machinery with hydrofluorocarbon (HFC) refrigerants may be used with the
`
`refrigerant compositions of the present invention.
`
`BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS
`
`Blowing agents may also comprise or constitute one or more of the present
`
`compositions. As mentioned above, the compositions of the present invention may
`
`include the compounds of the present invention in widely ranging amounts,.
`
`It is
`
`generally preferred, however, that for preferred compositions for use as blowing
`
`agents in accordance with the present invention, compound(s) in accordance with
`
`Formula I, and even more preferably Formula II, are present in an amount that is at
`
`least about 5 % by weight, and even more preferably at least about 15 % by weight,
`
`of the composition.
`
`in other embodiments, the invention provides foamable compositions, and
`
`preferably polyurethane, polyisocyanurate and extruded thermoplastic foam
`
`compositions, prepared using the compositions of the present invention.
`
`In such
`
`foam embodiments, one or more of the present compositions are included as or part
`
`of a blowing agent in a foamable composition, which composition preferably includes
`
`one or more additional components capable of reacting and/or foaming under the
`
`proper conditions to form a foam or cellular structure, as is well known in the art.
`
`The invention also relates to foam, and preferably closed cell foam, prepared from a
`
`polymer foam formulation containing a blowing agent comprising the compositions of
`
`the invention.
`
`In yet another embodiments, the invention provides a foamable
`
`composition comprising thermoplastic foams, such as polystyrene and polyethylene
`
`(PE), preferably low density PE.
`
`In certain preferred embodiments, dispersing agents, cell stabilizers,
`
`surfactants and other additives may also be incorporated into the blowing agent
`
`compositions of the present invention. Surfactants are optionally but preferably
`
`10 of 29
`
`10 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`added to serve as cell stabilizers. Some representative materials are sold under the
`
`names of DC-193, B-8404, and L-5340 which are, generally, polysiloxane
`
`polyoxyalkylene block co-polymers such as those disclosed in U.S. Patent Nos.
`
`2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by
`
`reference. Other optional additives for the blowing agent mixture may include flame
`
`retardants such as tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate, tri(2,3-
`
`dibromopropyl)-phosphate, tri(1,3-dichloropropyl) phosphate, diammonium
`
`phosphate, various halogenated aromatic compounds, antimony oxide, aluminum
`
`trihydrate, polyvinyl chloride, and the like.
`
`PROPELLANT COMPOSITIONS
`
`In another aspect, the present invention provided propellant compositions
`
`comprising or consisting essentially of a composition of the present invention, such
`
`propellant composition preferably being a sprayable composition. The propellant
`
`compositions of the present invention preferably comprise a material to be sprayed
`
`and a propellant comprising, consisting essentially of, or consisting of a composition
`
`in accordance with the present invention.
`
`inert ingredients, solvents, and other
`
`materials may also be present in the sprayable mixture. Preferably, the sprayable
`
`composition is an aerosol. Suitable materials to be sprayed include, without
`
`limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleansers,
`
`and polishing agents as well as medicinal materials such as anti-asthma and anti-
`
`halitosis medications.
`
`METHODS AND SYSTEMS
`
`The compositions of the present invention are useful in connection with
`
`numerous methods and systems, including as heat transfer fluids in methods and
`
`systems for transferring heat, such as refrigerants used in refrigeration, air
`
`conditioning and heat pump systems. The present compositions are also
`
`advantageous for in use in systems and methods of generating aerosols, preferably
`
`comprising or consisting of the aerosol propellant in such systems and methods.
`
`Methods of forming foams and methods of extinguishing and suppressing fire are
`
`also included in certain aspects of the present invention. The present invention also
`
`11 0f29
`
`11 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`provides in certain aspects methods of removing residue from articles in which the
`
`present compositions are used as solvent compositions in such methods and
`
`systems.
`
`HEAT TRANSFER METHODS
`
`The preferred heat transfer methods generally comprise providing a
`
`composition of the present invention and causing heat to be transferred to or from
`
`the composition changing the phase of the composition. For example, the present
`
`methods provide cooling by absorbing heat from a fluid or article, preferably by
`
`evaporating the present refrigerant composition in the vicinity of the body or fluid to
`
`be cooled to produce vapor comprising the present composition. Preferably the
`
`methods include the further step of compressing the refrigerant vapor, usually with a
`
`compressor or similar equipment to produce vapor of the present composition at a
`
`relatively elevated pressure. Generally, the step of compressing the vapor results in
`
`the addition of heat to the vapor, thus causing an increase in the temperature of the
`
`relatively high pressure vapor. Preferrably, the present methods include removing
`
`from this relatively high temperature, high pressure vapor at least a portion of the
`
`heat added by the evaporation and compression steps. The heat removal step
`
`preferably includes condensing the high temperature, high pressure vapor while the
`
`vapor is in a relatively high pressure condition to produce a relatively high pressure
`
`liquid comprising a composition of the present invention. This relatively high
`
`pressure liquid preferably then undergoes a nominally isoenthalpic reduction in
`
`pressure to produce a relatively low temperature, low pressure liquid.
`
`In such
`
`embodiments, it is this reduced temperature refrigerant liquid which is then vaporized
`
`by heat transferred from the body or fluid to be cooled.
`
`In another process embodiment of the invention, the compositions of the
`
`invention may be used in a method for producing heating which comprises
`
`condensing a refrigerant comprising the compositions in the vicinity of a liquid or
`
`body to be heated.. Such methods, as mentioned hereinbefore, frequently are
`
`reverse cycles to the refrigeration cycle described above.
`
`FOAM BLOWING METHODS
`
`12 of 29
`
`12 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`One embodiment of the present invention relates to methods of forming
`
`foams, and preferably polyurethane and polyisocyanurate foams. The methods
`
`generally comprise providing a blowing agent composition of the present inventions,
`
`adding (directly or indirectly) the blowing agent composition to a foamable
`
`composition, and reacting the foamable composition under the conditions effective to
`
`form a foam or cellular structure, as is well known in the art. Any of the methods well
`
`known in the art, such as those described in “Polyurethanes Chemistry and
`
`Technology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons,
`
`New York, NY, which is incorporated herein by reference, may be used or adapted
`
`for use in accordance with the foam embodiments of the present invention.
`
`In
`
`general, such preferred methods comprise preparing polyurethane or
`
`polyisocyanurate foams by combining an isocyanate, a polyol or mixture of polyols, a
`
`blowing agent or mixture of blowing agents comprising one or more of the present
`
`compositions, and other materials such as catalysts, surfactants, and optionally,
`
`flame retardants, colorants, or other additives.
`
`It is convenient in many applications to provide the components for
`
`polyurethane or polyisocyanurate foams in pre-blended formulations. Most typically,
`
`the foam formulation is pre-blended into two components. The isocyanate and
`
`optionally certain surfactants and blowing agents comprise the first component,
`
`commonly referred to as the "A" component. The polyol or polyol mixture, surfactant,
`
`catalysts, blowing agents, flame retardant, and other isocyanate reactive
`
`components comprise the second component, commonly referred to as the “B”
`
`component. Accordingly, polyurethane or polyisocyanurate foams are readily
`
`prepared by bringing together the A and B side components either by hand mix for
`
`small preparations and, preferably, machine mix techniques to form blocks, slabs,
`
`laminates, pour-in-place panels and other items, spray applied foams, froths, and the
`
`like. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing
`
`agents, and even other polyols can be added as a third stream to the mix head or
`
`reaction site. Most preferably, however, they are all incorporated into one
`
`B-component as described above.
`
`It is also possible to produce thermoplastic foams using the compositions of
`
`the invention. For example, conventional polystyrene and polyethylene formulations
`
`13 of 29
`
`13 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`may be combined with the compositions in a conventional manner to produce rigid
`
`foams.
`
`CLEANING METHODS
`
`The present invention also provides methods of removing containments from
`
`a product, part, component, substrate, or any other article or portion thereof by
`
`applying to the article a composition of the present invention. For the purposes of
`
`convenience, the term "article" is used herein to refer to all such products, parts,
`
`components, substrates, and the like and is further intended to refer to any surface
`
`or portion thereof. Furthermore, the term "contaminant" is intended to refer to any
`
`unwanted material or substance present on the article, even if such substance is
`
`placed on the article intentionally. For example, in the manufacture of
`
`semiconductor devices it is common to deposit a photoresist material onto a
`
`substrate to fonn a mask for the etching operation and to subsequently remove the
`
`photoresist material from the substrate. The term "contaminant" as used herein is
`
`intended to cover and encompass such a photo resist material.
`
`Preferred methods of the present invention comprise applying the present
`
`composition to the article, with vapor degreasing and solvent cleaning methods
`
`being particularly preferred for certain applications, especially those intricate parts
`
`and difficult to remove soils. Preferred vapor degreasing and solvent cleaning
`
`methods consist of exposing an article, preferably at room-temperature, to the
`
`vapors of a boiling solvent. Vapors condensing on the object have the advantage of
`
`providing a relatively clean, distilled solvent to wash away grease or other
`
`contamination. Such processes thus have an additional advantage in that final
`
`evaporation of the present solvent composition from the object leaves behind
`
`relatively little residue as compared to the case where the object is simply washed in
`
`liquid solvent.
`
`For applications in which the article includes contaminants that are difficult to
`
`remove, it is preferred that the present methods involve raising the temperature of
`
`the solvent composition of the present invention above ambient or to any other
`
`temperature that is effective in such application to substantially improve the cleaning
`
`action of the solvent. Such processes are also generally preferred for large volume
`
`14 of 29
`
`14 of 29
`
`

`
`WO 2004/037913
`
`PCT/US2003/033874
`
`assembly line operations where the cleaning of the article, particularly metal parts
`
`and assemblies, must be done efficiently and quickly.
`
`In preferred embodiments, the cleaning methods of the present invention
`
`comprise immersing the article to be cl