(12) United States Patent
`Singh et al.
`
`(10) Patent No.:
`
`(45) Date of Patent:
`
`US 9,157,017 B2
`*Oct. 13, 2015
`
`US009 1 570l7B2
`
`(54) COMPOSITIONS CONTAINING FLUORINE
`SUBSTITUTED OLEFINS AND METHODS
`AND SYSTEMS USING SAME
`
`(71) Applicant: Honeywell International Inc.,
`Morristown, NJ (US)
`
`(72)
`
`Inventors: Rajiv R. Singh, Getzville, NY (US);
`Hang T. Pham, Amherst, NY (US); Ian
`Shankland, Buffalo, NY (US)
`
`(73) Assignee: HONEYWELL INTERNATIONAL
`INC., Morristown, NJ (US)
`
`( * ) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. l54(b) by 0 days.
`
`This patent is subject to a terminal dis-
`claimer.
`
`(21) Appl.No.: 14/225,588
`
`(22)
`
`Filed:
`
`Mar. 26, 2014
`
`(65)
`
`Prior Publication Data
`
`US 2014/0202182 A1
`
`Jul. 24, 2014
`
`Related U.S. Application Data
`
`(66) Division of application No. 13/844,206, filed on Mar.
`15, 2013, which is a division of application No.
`11/847,192, filed onAug. 29, 2007, which is a division
`of application No. 10/837,525, filed on Apr. 29, 2004,
`now Pat. No. 7,279,451, and a continuation-in-part of
`application No. 10/694,272, filed on Oct. 27, 2003,
`now Pat. No. 7,230,146, Substitute for application No.
`60/421,435, filed on Oct. 25, 2002.
`
`(60) Provisional application No. 60/421,263, filed on Oct.
`25, 2002.
`
`(51)
`
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`
`Int. Cl.
`C09K 5/04
`A62D 1/00
`B01137/03
`c07c 21/18
`C08J 9/14
`A01N 29/00
`B01131/02
`(52) U.S. Cl.
`CPC .............. .. C09K 5/045 (2013.01), A01N29/00
`(2013.01); A62D 1/00 (2013.01); A62D 1/0057
`(2013.01); B01131/0231 (2013.01); B01J
`37/03 (2013.01); C07C21/18 (2013.01); C08]
`9/146 (2013.01); C08] 2207/04 (2013.01);
`C09K 2205/I26 (2013.01)
`
`(58) Field of Classification Search
`CPC ........................ .. C09K 5/045; C09K 2205/126
`USPC .......................................................... .. 252/67
`See application file for complete search history.
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`4,755,316 A
`4,842,024 A
`5,611,210 A
`6,013,609 A
`6,176,102 B1
`6,260,380 B1*
`6,374,629 B1
`6,640,841 B2
`6,783,691 B1
`6,991,744 B2
`
`7/1988 Magid et al.
`6/1989 Palinchak
`3/1997 Nimitz et al.
`1/2000 Katafuchi
`1/2001 Novak
`7/2001 Arman et al.
`4/2002 Oberle
`11/2003 Thomas
`8/2004 Bivens
`1/2006 Mahler
`
`................. .. 62/646
`
`FOREIGN PATENT DOCUMENTS
`
`JP
`RU
`WO
`
`04-110388 A
`2073058
`02/46328
`
`*
`
`4/1992
`2/1997
`6/2002
`
`OTHER PUBLICATIONS
`
`ACURA Service Bulletin No. 92-027, pp. 1-8, dated Sep. 29, 1992.
`“Characteristics and Performances of New Refrigerants” D. Clodic,
`Y. S. Chang “New Refrigerants: Does cooling have to cost more?”
`Technical Day Paris-Nord Villepinte, Sep. 23, 1999; 13 pp (With
`English translation).
`Support: Letter From Dupont Haskell Lab to USEPA Regarding
`Results of Bacterial Reverse Mutation Assay Conducted With
`41-Propene, 4 1 , 1 ,3 ,3 ,3 -PENTAFLUOR0-, Dated 04117/00.
`TSCA Non-Confidential Business Information 2001.
`ASHRAE Standard—1992.
`Sae J 1657—1993.
`R-1234YF Material Safety Data Sheet—2014.
`Acute Exposure Guideline Levels (AEGLS) Hexafluoropropylene
`(CAS Reg. No. 116-15-4)—2007.
`OSHA 1910.1200 Appendix A—20 14.
`Excerpt from Hazardous Chemicals Desk Reference, Richard J.
`Lewis, Sr., 6th Ed, 2008.
`
`* cited by examiner
`
`Primary Examiner — John Hardee
`(74) Attorney, Agent, or Firm — Colleen D. Szuch
`
`(57)
`
`ABSTRACT
`
`Disclosed are the use of fluorine substituted olefins, including
`tetra- and penta-fluoropropenes, in a variety of applications,
`including in methods ofdepositing catalyst on a solid support,
`methods of sterilizing articles, cleaning methods and compo-
`sitions, methods of applying medicaments, fire extinguish-
`ing/suppression compositions and methods, flavor formula-
`tions, fragrance formulations and inflating agents.
`
`20 Claims, No Drawings
`
`Page 1 of 11
`
`Arkema Exhibit 1001
`
`Arkema Exhibit 1001
`
`Page 1 of 11
`
`

`
`US 9,157,017 B2
`
`1
`COMPOSITIONS CONTAINING FLUORINE
`SUBSTITUTED OLEFINS AND METHODS
`AND SYSTEMS USING SAME
`
`RELATED APPLICATIONS
`
`The present application is a divisional of U.S. Ser. No.
`13/844,206, filed Mar. 15, 2013 (now pending), which is a
`divisional ofU.S. application Ser. No. 11/847,192, filedAug.
`29, 2007 (now pending), which in turn is a divisional of U.S.
`application Ser. No. 10/837,525, filed Apr. 29, 2004 (now
`U.S. Pat. No. 7,279,451), which in turn is a continuation in
`part of each of U.S. application Ser. No. 10/694,272, filed
`Oct. 27, 2003 (now U.S. Pat. No. 7,230,146) and U.S. patent
`application Ser. No. 10/694,273, filed Oct. 27, 2003 (now
`U.S. Pat. No. 7,534,366), which in turn is related to and
`claims the priority benefit of U.S. Provisional Application
`Nos. 60/421,263 and 60/421,435, each ofwhich was filed on
`Oct. 25, 2002. U.S. patent application Ser. No. 10/837,525,
`filedApr. 29, 2004 is also a continuation-in-part ofU.S. patent
`application Ser. No. 10/694,272, filed Oct. 27, 2003 (now
`U.S. Pat. No. 7,230,146). The disclosure ofeach ofthe afore-
`mentioned patent applications and patents is incorporated
`herein by reference.
`
`FIELD OF THE INVENTION
`
`This invention relates to compositions having utility in
`numerous applications, including particularly refrigeration
`systems, and to methods and systems utilizing such compo-
`sitions. In preferred aspects, the present invention is directed
`to refrigerant compositions comprising 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 com-
`pression cycle usually involves the phase change ofthe refrig-
`erant from the liquid to the vapor phase through heat absorp-
`tion at a relatively low pres sure 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
`elevated pressure, condensing the vapor to the liquid phase
`through heat removal at this relatively elevated pressure and
`temperature, and then reducing the pres sure 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 tempera-
`ture, the primary purpose of a heat pump is to add heat at a
`higher temperature relative to the environment.
`Certain fluorocarbons have been a preferred 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 prop-
`erties. Many of the refrigerants commonly utilized in vapor
`compression systems are either single components fluids or
`azeotropic mixtures.
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`Concern has increased in recent years about potential dam-
`age to the earth’s atmosphere and climate, and certain chlo-
`rine-based compounds have been identified as particularly
`problematic in this regard. The use of chlorine-containing
`compositions (such as chlorofluorocarbons (CFCs), hydro-
`chlorofluorocarbons (HCFCs) and the like) as refrigerants in
`air-conditioning and refrigeration systems has become disfa-
`vored 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 (HFCs).
`It is generally considered important, however, that any
`potential substitute refrigerant must also possess those prop-
`erties present in many of the most widely used fluids, such as
`excellent heat transfer properties, chemical stability, low- or
`no-toxicity, non-flammability and lubricant compatibility,
`among others.
`Applicants have come to appreciate that lubricant compat-
`ibility is of particular importance in many of applications.
`More particularly, it is highly desirably for refrigeration fluids
`to be compatible with the lubricant utilized in the compressor
`unit, used in mo st refrigeration systems. Unfortunately, many
`non-chlorine-containing
`refrigeration
`fluids,
`including
`HFCs, are relatively insoluble and/or immiscible in the types
`oflubricants used traditionally with CFC’s and HFCs, includ-
`ing, for example, mineral oils, alkylbenzenes or poly(alpha-
`olefins). In order for a refrigeration fluid-lubricant combina-
`tion to work at a desirable level of efliciently within a
`compression refrigeration, air-conditioning and/or heat pump
`system, the lubricant should be sufliciently soluble in the
`refrigeration liquid over a wide range of operating tempera-
`tures. Such solubility lowers the viscosity ofthe 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-condi-
`tioning or heat pump system, as well as other parts of the
`system, and thus reduce the system efliciency.
`With regard to efficiency in use, it is important to note that
`a loss in refrigerant thermodynamic performance or energy
`efliciency 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 engineer-
`ing 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 “nonflammable” 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. Unfortu-
`nately, many HFCs, which might otherwise be desirable for
`used in refrigerant compositions are not nonflammable. For
`example, the fluoroalkane difluoroethane (HFC-152a) and
`the fluoroalkene 1,1,1-trifluoropropene (HFO-1243zf) are
`each flammable and therefore not viable for use in many
`applications.
`
`Page 2 of 11
`
`Page 2 of 11
`
`

`
`US 9,157,017 B2
`
`3
`Higher fluoroalkenes, that is fluorine-substituted alkenes
`having at least five carbon atoms, have been suggested for use
`as refrigerants. U.S. Pat. No. 4,788,352—Smutny is directed
`to production of fluorinated C5 to C8 compounds having at
`least some degree of unsaturation. The Smutny patent iden-
`tifies 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 colunm 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 plas-
`tics 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 com-
`pounds may have a boiling point, which is too high to make
`them useful as a refrigerant in certain applications.
`Bromofluoromethane
`and
`bromochlorofluoromethane
`
`(Halon
`derivatives, particularly bromotrifluoromethane
`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 fre-
`quently 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 com-
`positions, 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.
`
`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-
`
`<1)
`
`where X is a C2 or a C3 unsaturated, substituted or unsubsti-
`tuted, alkyl radical, each R is independently Cl, F, Br, I or H,
`and z is 1 to 3. Highly preferred among the compounds of
`Formula I are the cis- and trans-isomers of 1,3,3,3-tetrafluo-
`ropropene (HFO-1234ze)
`The present invention provides also methods and systems
`which utilize the compositions of the present
`invention,
`including methods and systems for heat transfer, foam blow-
`ing, solvating, flavor and fragrance extraction and/or delivery,
`and aerosol generation.
`
`DETAILED DESCRIPTION OF PREFERRED
`EMBODIMENTS
`
`The Compositions
`The present invention is directed to compositions compris-
`ing at least one fluoroalkene containing from 3 to 4 carbon
`atoms, preferably three carbon atoms, and at least one carbon-
`carbon double bond. The fluoroalkene compounds of the
`present invention are sometimes referred to herein for the
`
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`
`purpose of convenience as hydrofluoro-olefins or “HFOs” if
`they contain at least one hydrogen. Although it is contem-
`plated that the HFOs ofthe present invention 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 more compounds in accordance with Formula I. In
`preferred embodiments,
`the compositions include com-
`pounds of Formula II below:
`
`(11)
`
`where each R is independently Cl, F, Br, I or H
`R‘ is (CR2)nY,
`Y is 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 I and II are generally effective and
`exhibit utility in refrigerant compositions, blowing agent
`compositions, compatibilizers, aerosols, propellants,
`fra-
`grances, flavor formulations, and solvent compositions ofthe
`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 otherwise con-
`tain 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 whereinY 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 struc-
`tural, geometric and stereoisomers of such compounds are
`effective and of beneficially low toxicity.
`In highly preferred embodiments, especially embodiments
`comprising the low toxicity compounds described above, n is
`zero in which the unsaturated terminal carbon has not more
`
`than one F substituent. Applicant has discovered that such
`compounds have a very low acute toxicity level, as measured
`by inhalation expoure to mice and rats. In certain highly
`preferred embodiments the compositions of the present
`invention comprise one or more tetrafluoropropenes. The
`term “HFO-1234” is used herein to refer to all tetrafluoropro-
`penes. Among the tetrafluoropropenes, both cis- and trans-1,
`3,3,3-tetrafluoropropene (HFO-1234ze) are particularly pre-
`ferred. The term HFO-1234ze is used herein generically to
`refer to 1,3,3,3-tetrafluoropropene, independent of whether it
`is the cis- or trans-form. The terms “cisHFO-1234ze” and
`“transHFO-1234ze” are used herein to describe the cis- and
`
`trans-forms of 1,3,3,3-tetrafluoropropene respectively. The
`term “HFQ-1234ze” therefore includes within its scope
`cisHFO-1234ze,
`transHFO-1234ze, and all combinations
`and mixtures of these.
`
`Although the properties of cisHFO-1234ze and transHFO-
`1234ze differ in at least some respects, it is contemplated that
`each of these compounds is adaptable for use, either alone or
`together with other compounds including its stereoisomer, in
`
`Page 3 of 11
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`Page 3 of 11
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`

`
`US 9,157,017 B2
`
`5
`connection with each of the applications, methods and sys-
`tems described herein. For example, while transHFO-1234ze
`may be preferred for use in certain refrigeration systems
`because of its relatively low boiling point (—19° C.), it is
`nevertheless contemplated that cisHFO-1234ze, with a boil-
`ing point of +9° C., also has utility in certain refrigeration
`systems of the present invention. Accordingly, it is to be
`understood that the terms “HFO-1234ze” and 1,3,3,3-tet-
`rafluoropropene refer to both stereo isomers, and the use of
`this term is intended to indicate that each of the cis- and
`
`trans-forms applies and/or is useful for the stated purpose
`unless otherwise indicated.
`
`HFO-1234 compounds are known materials and are listed
`in Chemical Abstracts databases. The production of fluoro-
`propenes such as CF3CH:CH by catalytic vapor phase fluo-
`rination of various saturated and unsaturated halogen-con-
`taining C3 compounds is described in U.S. Pat. Nos. 2,889,
`379; 4,798,818 and 4,465,786, each ofwhich is incorporated
`herein by reference. EP 974,571, also incorporated herein by
`reference, discloses the preparation of 1,1,1,3-tetrafluoropro-
`pene 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
`pending U.S. Pat. No. 7,230,146 entitled “Process for Pro-
`ducing Fluoropropenes”, which is also incorporated herein
`by reference.
`The present compositions, particularly those comprising
`HFO-1234ze, are believed to possess properties that are
`advantageous for a number of important
`reasons. For
`example, applicants believe, based at least in part on math-
`ematical modeling, that the fluoroolefins ofthe present inven-
`tion 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 ofthe present invention thus have the advantage
`of not contributing substantially to ozone depletion. The pre-
`ferred compositions also do not contribute substantially to
`global warming compared to many ofthe hydrofluoroalkanes
`presently in use.
`In certain preferred forms, compositions of the present
`invention have a Global Warming Potential (GWP) of not
`greater than about 1000, more preferably not greater than
`about 500, and even more preferably not greater than about
`150. In certain embodiments, the GWP of the present com-
`positions is not greater than about 100 and even more prefer-
`ably not greater than about 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 ofthe World Meteorological
`Association’s Global Ozone Research and Monitoring
`Project,” which is incorporated herein by reference.
`In certain preferred forms, 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.
`The amount of the Formula I compounds, particularly
`HFO-1234, contained in the present compositions can vary
`widely, depending the particular application, and composi-
`tions containing more than trace amounts and less than 100%
`of the compound are within broad the scope of the present
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`invention. Moreover, the compositions of the present inven-
`tion can be azeotropic, azeotrope-like or non-azeotropic. In
`preferred embodiments, the present compositions comprise
`HFO-1234, preferably HFO-1234ze, in amounts from about
`5% by weight to about 99% by weight, and even more pref-
`erably from about 5% to about 95%. Many additional com-
`pounds may be included in the present compositions, and the
`presence of all such compounds is within the broad scope of
`the invention. In certain preferred embodiments, the present
`compositions include, in addition to HFO-1234ze, one or
`more of the following:
`Difluoromethane (HFC-32)
`Pentafluoroethane (HFC-125)
`1,1,2,2-tetrafluoroethane (HFC-134)
`1,1,1,2-Tetrafluoroethane (HFC-134a)
`Difluoroethane (HFC-152a)
`1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)
`1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
`1,1,1,3,3-pentafluoropropane (HFC-245fa)
`1,1,1,3,3-pentafluorobutane (HFC-3 65mfc)
`water
`
`CO2
`The relative amount ofany ofthe above noted components, as
`well as any additional components which may be included in
`present compositions, can vary widely within the general
`broad scope of the present invention according to the particu-
`lar application for the composition, and all such relative
`amounts are considered to be within the scope hereof.
`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 com-
`prise compound(s) in accordance with Formula I, more pref-
`erably in accordance with Formula II, and even more prefer-
`ably HFO-1234ze, in an amount that is at least about 50% by
`weight, and even more preferably at least about 70% by
`weight, of the composition. In many embodiments, it is pre-
`ferred that the heat transfer compositions ofthe present inven-
`tion comprise transHFO-1234ze.
`In certain preferred
`embodiments, the heat transfer compositions of the present
`invention comprise a combination of cisHFO-1234ze and
`transHFO1234ze in a cis:trans weight ratio of from about
`1:99 to about 10:99, more preferably from about 1 :99 to about
`5:95, and even more preferably from about 1 :99 to about 3:97.
`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 compo-
`sitions may also include a compatibilizer, 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 offrom about
`0.5 to about 5 percent by weight of the composition. Combi-
`nations of surfactants and solubilizing agents may also be
`added to the present compositions to aid oil solubility, as
`disclosed by U.S. Pat. No. 6,516,837, the disclosure ofwhich
`is incorporated by reference. Commonly used refrigeration
`lubricants such as Polyol Esters (POEs) and Poly Alkylene
`Glycols (PAGs), silicone oil, mineral oil, alkyl benzenes
`(ABs) and poly(alpha-olefin) (PAO) that are used in refrig-
`
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`
`US 9,157,017 B2
`
`7
`eration machinery with hydrofluorocarbon (HFC) refriger-
`ants may be used with the refrigerant compositions of the
`present invention.
`Many existing refrigeration systems are currently adapted
`for use in connection with existing refrigerants, and the com-
`positions ofthe present invention are believed to be adaptable
`for use in many of such systems, either with or without system
`modification. In many applications the compositions of the
`present invention may provide an advantage as a replacement
`in systems, which are currently based on refrigerants having
`a relatively high capacity. Furthermore,
`in embodiments
`where it is desired to use a lower capacity refrigerant compo-
`sition of the present
`invention,
`for reasons of cost for
`example, to replace a refrigerant of higher capacity, such
`embodiments ofthe present compositions provide a potential
`advantage. Thus, It is preferred in certain embodiments to use
`compositions of the present invention, particularly composi-
`tions comprising a substantial proportion of, and in some
`embodiments consisting essentially of transHFO-1234ze, as
`a replacement for existing refrigerants, such as HFC-134a. In
`certain applications, the refrigerants of the present invention
`potentially permit the beneficial use of larger displacement
`compressors, thereby resulting in better energy efiiciency
`than other refrigerants, such as HFC-134a. Therefore the
`refrigerant compositions ofthe present invention, particularly
`compositions comprising transHFP-1234ze, provide the pos-
`sibility of achieving a competitive advantage on an energy
`basis for refrigerant replacement applications.
`It is contemplated that the compositions of the present,
`including particularly those comprising HFO-1234ze, also
`have advantage (either in original systems or when used as a
`replacement for refrigerants such as R-12 and R-500), in
`chillers typically used in connection with commercial air
`conditioning systems. In certain of such embodiments it is
`preferred to including in the present HFO-1234ze composi-
`tions from about 0.5 to about 5% of a flammability suppres-
`sant, such as CF3I.
`The present methods, systems and compositions are thus
`adaptable for use in connection with automotive air condi-
`tioning systems and devices, commercial refrigeration sys-
`tems and devices, chillers, residential refrigerator and freez-
`ers, general air conditioning systems, heat pumps, and the
`like.
`
`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 com-
`pounds ofthe present invention in widely ranging amounts. It
`is generally preferred, however, that for preferred composi-
`tions 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 certain
`preferred embodiments, the blowing agent compositions of
`the present invention and include, in addition to HFO-1234
`(preferably HFO-1234ze) one or more of the following com-
`ponents as a co-blowing agent, filler, vapor pressure modifier,
`or for any other purpose:
`Difluoromethane (HFC-32)
`Pentafluoroethane (HFC- 125)
`1,1,2,2-tetrafluoroethane (HFC-134)
`1,1,1,2-Tetrafluoroethane (HFC-134a)
`Difluoroethane (HFC-152a)
`1,1,1,2,3,3,3-Heptafiuoropropane (HFC-227ea)
`1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
`1,1,1,3,3-pentafluoropropane (HFC-245fa)
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`8
`1,1,1,3,3-pentafluorobutane (HFC-3 65mfc)
`water
`
`CO2
`it is contemplated that the blowing agent compositions of the
`present
`invention may
`comprise
`cisHFO-1234ze,
`transHFO1234ze or combinations thereof. In certain pre-
`ferred embodiments, the blowing agent composition of the
`present invention comprise his a combination of cisHFO-
`1234ze and transHFO1234ze in a cis:trans weight ratio of
`from about 1:99 to about 10:99, and even more preferably
`from about 1:99 to about 5:95.
`
`In other embodiments, the invention provides foamable
`compositions, and preferably polyurethane, polyisocyanu-
`rate and extruded thermoplastic foam compositions, prepared
`using the compositions ofthe 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 compo-
`sition, 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 struc-
`ture, as is well known in the art. The invention also relates to
`foam, and preferably closed cell foam, prepared from a poly-
`mer foam formulation containing a blowing agent comprising
`the compositions of the invention. In yet other embodiments,
`the invention provides foamable compositions comprising
`thermoplastic or polyolefin foams, such as polystyrene (PS),
`polyethylene (PE), polypropylene (PP) and polyethyl-
`eneterpthalate (PET) foams, preferably low-density foams.
`In certain preferred embodiments, dispersing agents, cell
`stabilizers, surfactants and other additives may also be incor-
`porated into the blowing agent compositions of the present
`invention. Surfactants are optionally but preferably added to
`serve as cell stabilizers. Some representative materials are
`sold under the names ofDC-193, B-8404, and L-5340 which
`are, generally, polysiloxane polyoxyalkylene block co-poly-
`mers such as those disclosed in U.S. Pat. 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)phos-
`phate,
`diamrnonium phosphate,
`various
`halogenated
`aromatic compounds, antimony oxide, aluminum trihydrate,
`polyvinyl chloride, and the like.
`Propellant and Aerosol Compositions
`In another aspect, the present invention provides propellant
`compositions comprising or consisting essentially of a com-
`position of the present invention, such propellant composi-
`tion preferably being a sprayable composition. The propellant
`compositions of the present invention preferably comprise a
`material to be sprayed and a propellant comprising, consist-
`ing essentially of, or consisting of a composition in accor-
`dance 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 components, anti-halitosis components
`and any other medication or the like, including preferably any
`other medicament or agent intended to be inhaled. The medi-
`cament or other therapeutic agent is preferably present in the
`composition in a therapeutic amount, with a substantial por-
`tion of the balance of the composition comprising a com-
`pound of Formula I ofthe present invention, preferably HFO-
`1234, and even more preferably HFO-1234ze.
`
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`

`
`US 9,157,017 B2
`
`9
`Aerosol products for industrial, consumer or medical use
`typically contain one or more propellants along with one or
`more active ingredients, inert ingredients or solvents. The
`propellant provides the force that expels the product in aero-
`solized form. While some aerosol products are propelled with
`compressed gases like carbon dioxide, nitrogen, nitrous oxide
`and