PATENT APPLICATION TRANSMITTAL LETTER
`(Large Entity)
`
`D°°ket N0-
`H0004412US
`
`TO THE COMMISSIONER FOR PATENTS
`
`Transmitted herewith for filing under 35 U.S.C. 111 and 37 C.F.R. 1.53 is the patent application of:
`
`Rajiv R. Singh and Raymond H. P. Thomas
`
`For: FLUORINATED ALKENE REFRIGERANT COMPOSITIONS
`
`031088U.S.PTO
`
`10/695212
`
`Enclosed are:
`
`Certificate of Mailing with Express Mail Mailing Label No.
`sheets of drawings.
`
`EV262354600US
`
`A certified copy of a
`Declaration
`Cl Signed.
`Power of Attorney
`information Disclosure Statement
`
`application.
`
`Unsigned.
`
`Preliminary Amendment
`Other: Application Data Sheet, Two Acknowedgment Postcards
`
`For
`
`#Filed
`
`#Allowed
`
`#Extra
`
`Rate
`
`to cover the filing fee is enclosed.
`D A check in the amount of
`The Director is hereby authorized to charge and credit Deposit Account No.
`as described below.
`Charge the amount of $// 00 as filing fee.
`Credit any overpayment.
`Charge any additional filing fees required under 37 C.F.R. 1.16 and 1.17.
`CI Charge the issue fee set in 37 C.F.R. 1.18 at the mailing of the Notice of Allowance,
`pursuant to 37 C.F.R. 1.311(b).
`
`19-5425
`
`Dated: October 27, 2003
`
`Signature
`
`Peter J. Butch III, Reg. No. 32,203
`Honeywell International, Inc.
`101 Columbia Road, Building Meyer 5
`Morristown, NJ 07962
`Telephone: 973-455-2857
`
`P01 LARGEIREV06
`
`Page 1 of 38
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`Arkema Exhibit 1040
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`

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`CERTIFICATE OF MAILING BY EXPRESS MAIL UNDER 37 CFR 1.10
`
`EV262354600US
`Express Mail Label Number
`
`Docket No. H00O4412US
`S&L File No. P26,269 USA
`
`I hereby certify that the attached Patent Application Transmittal Letter for Large
`
`Entity Concerning Filing Under 35 U.S.C. 111 and 37 C.F.R. 1.53, including a duplicate
`
`copy of the Transmittal Letter, Patent Application specification, an Abstract, an
`Application Data Sheet, a Declaration and Power of Attorney and an acknowledgment
`postcard are being deposited with the United States Postal Service "Express Mail
`Post Office to Addressee" under 37 C.F.R. § 1.10 in an envelope addressed to the
`Mail Stop Patent Application, Commissioner for Patents, Alexandria, VAI22313-1450
`
`on October 27, 2003.
`
`Peter J. Butc
`
`lll
`
`Synnestvedt & Lechner LLP
`2600 Aramark Tower
`1101 Market Street
`
`Philadelphia, PA 19107-2950
`Telephone: (215) 923-4466
`Facsimile: (215) 923-2189
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`M:\PButch\Honeywell\P26269.USA\PatentOffice\ExpressMai|Certificate.wpd
`
`Page 2 of 38
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`

`
`PATENT APPLICATION TRANSMITTAL LETTER
`(Large Entity)
`
`D°°ket N0-
`H0004412US
`
`TO THE COMMISSIONER FOR PATENTS
`
`Transmitted herewith for filing under 35 U.S.C. 111 and 37 C.F.R. 1.53 is the patent application of:
`
`Rajiv R. Singh and Raymond H. P. Thomas
`
`For: FLUORINATED ALKENE REFRIGERANT COMPOSITIONS
`
`031088U.S.PTO
`
`10/695212
`
`Enclosed are:
`
`Certificate of Mailing with Express Mail Mailing Label No.
`sheets of drawings.
`
`EV262354600US
`
`A certified copy of a
`Declaration
`Cl Signed.
`Power of Attorney
`information Disclosure Statement
`
`application.
`
`Unsigned.
`
`Preliminary Amendment
`Other: Application Data Sheet, Two Acknowedgment Postcards
`
`For
`
`#Filed
`
`#Allowed
`
`#Extra
`
`Rate
`
`to cover the filing fee is enclosed.
`D A check in the amount of
`The Director is hereby authorized to charge and credit Deposit Account No.
`as described below.
`Charge the amount of $// 00 as filing fee.
`Credit any overpayment.
`Charge any additional filing fees required under 37 C.F.R. 1.16 and 1.17.
`CI Charge the issue fee set in 37 C.F.R. 1.18 at the mailing of the Notice of Allowance,
`pursuant to 37 C.F.R. 1.311(b).
`
`19-5425
`
`Dated: October 27, 2003
`
`Signature
`
`Peter J. Butch III, Reg. No. 32,203
`Honeywell International, Inc.
`101 Columbia Road, Building Meyer 5
`Morristown, NJ 07962
`Telephone: 973-455-2857
`
`P01 LARGEIREV06
`
`Page 3 of 38
`
`

`
`CERTIFICATE OF MAILING BY EXPRESS MAIL UNDER 37 CFR 1.10
`
`EV262354600US
`Express Mail Label Number
`
`Docket No. H00O4412US
`S&L File No. P26,269 USA
`
`I hereby certify that the attached Patent Application Transmittal Letter for Large
`
`Entity Concerning Filing Under 35 U.S.C. 111 and 37 C.F.R. 1.53, including a duplicate
`
`copy of the Transmittal Letter, Patent Application specification, an Abstract, an
`Application Data Sheet, a Declaration and Power of Attorney and an acknowledgment
`postcard are being deposited with the United States Postal Service "Express Mail
`Post Office to Addressee" under 37 C.F.R. § 1.10 in an envelope addressed to the
`Mail Stop Patent Application, Commissioner for Patents, Alexandria, VAI22313-1450
`
`on October 27, 2003.
`
`Peter J. Butc
`
`lll
`
`Synnestvedt & Lechner LLP
`2600 Aramark Tower
`1101 Market Street
`
`Philadelphia, PA 19107-2950
`Telephone: (215) 923-4466
`Facsimile: (215) 923-2189
`
`M:\PButch\Honeywell\P26269.USA\PatentOffice\ExpressMai|Certificate.wpd
`
`Page 4 of 38
`
`

`
`EXPRESS MAIL LABEL NO. EV262354600US
`
`Docket No. H0004412US
`
`FLUORINATED ALKENE REFRIGERANT COMPOSITIONS
`
`Invented by:
`
`RAYMOND H. THOMAS
`
`5990 Hopi Court
`Pendelton, NY 14094
`Citizen of USA
`
`RAJIV R. SINGH
`
`18 Foxfire Drive
`
`Getzville, NY 14068
`Citizen of USA
`
`Page 5 of 38
`
`

`
`Patent
`Docket No. H0004412
`
`Express Mail Label No. 262354600US
`S&L File No. P26,269 USA
`
`FLUORINATED ALKENE REFRIGERANT COMPOSITIONS
`
`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 which was filed on
`
`Oct. 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 U.S. Patent Applications: Attorney Docket Number H0004412
`
`(26,269) entitled “COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED
`
`OLEFINS,” by Singh et al. and Attorney Docket Number H0O03789 (26,267) entitled
`
`“PROCESS FOR PRODUCING FLUOROPROPENES,” by Tung et al.
`
`FIELD OF THE INVENTION
`
`The present invention relates to compositions used as refrigeration fluids in
`
`compression refrigeration, air-conditioning and heat pump systems.
`
`BACKGROUND OF THE INVENTION
`
`The use of chlorine-containing refrigerants, 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 such compounds. As a result,
`
`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).
`
`In order for any of the replacement materials to be useful in connection with
`
`refrigeration compositions,
`
`the materials must be compatible with the lubricant
`
`utilized in the compressor. Unfortunately, many non-chlorine-containing refrigeration
`
`fluids,
`
`including HFC’s, are relatively insoluble and/or immiscible in the types of
`
`Page 6 of 38
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`

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`Patent
`Docket No. H0004412
`
`Express Mail Label No. 262354600US
`S&L File No. P26,269 USA
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`lubricants used traditionally with CFC’s and HFC’s, including, for example, mineral
`
`oils, alkylbenzenes or poly(a|pha-olefins).
`
`in order for a refrigeration fluid-lubricant
`
`combination to work efficiently within a compression refrigeration, air-conditioning or
`
`heat pump system, the lubricant must 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 compression
`
`refrigeration, air-conditioning or heat pump system evaporator, as well as other parts
`
`of the system, and thus reduce the system efficiency.
`
`Polyalkylene glycol, esterified polyalkylene glycol, and polyol ester lubricating
`
`oils have been developed as misicible lubricants for HFC refrigeration liquids.
`
`Polyalkylene glycol
`
`refrigeration lubricants are disclosed by U.S. Patent No.
`
`4,755,316; 4,971,712, and 4, 975, 212. Polyalkylene glycol esters are disclosed by
`
`U.S. Patent No. 5,008,028. The polyalkylene glycol and polyalkylene glycol ester
`
`lubricating oils are disclosed as being misicible in fluoroalkanes containing one or
`
`two carbon atoms and no double bonds.
`
`Consequently fluorocarbon-based fluids have found widespread use in
`
`industry for refrigeration system applications, including air-conditioning systems and
`
`heat pump applications as well, all of which involve compression refrigeration.
`
`Compression refrigeration generally involves changing the refrigerant from the liquid
`
`to the vapor phase through heat adsorption at a lower pressure and then from the
`
`vapor to the liquid phase through heat removal at an elevated pressure.
`
`While the primary purpose of refrigeration is to remove energy at low temper-
`
`ature, the primary purpose of a heat pump is to add energy at higher temperature.
`
`Heat pumps are considered reverse cycle systems because for heating,
`
`the
`
`operation of the condenser is interchanged with that of the refrigeration evaporator.
`
`Page 7 of 38
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`

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`Patent
`Docket No. HD004412
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`Express Mail Label No. 262354600US
`S&L File No. P26,269 USA
`
`The art is continually seeking new fluorocarbon and hydrofluorocarbon-based
`
`pure fluids that offer alternatives for refrigeration and heat pump applications.
`
`Applicants have come to appreciate that fluoro-olefin-based materials (fluoroalkenes)
`
`are of particular
`
`interest because they have characteristics that make them
`
`environmentally safer substitutes for the presently used fluoroalkanes (HFC’s), that
`
`despite being safe for the ozone layer are suspected of causing global warming.
`
`Applicant has also come to recognize that
`
`refrigeration composition
`
`substitutes for HFC’s in many cases preferably possess certain performance
`
`properties to be considered acceptable substitutes, including acceptable refrigeration
`
`characteristics,
`
`chemical
`
`stability,
`
`low toxicity,
`
`non-flammability,
`
`lubricant
`
`compatibility and efficiency in use. The latter characteristic is important in many
`
`refrigeration systems,
`
`air-conditioning systems and heat pump applications,
`
`especially when a loss in refrigeration 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 would
`
`be advantageous for HFC refrigeration composition substitutes to not require major
`
`engineering changes to conventional vapor compression technology and lubricant
`
`systems currently used with HFC refrigeration liquids.
`
`Flammability is another important property for many applications. That is, it is
`
`considered either important or essential in many applications, including particularly in
`
`I 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 “nonf|ammable” refers to compounds or
`
`compositions which are determined to be nonflammable in accordance with ASTM
`
`standard E-681, dated 2002, which
`
`is
`
`incorporated
`
`herein
`
`by
`
`reference.
`
`Unfortunately, many HFC’s which might othenNise be desirable for used in
`
`refrigerant compositions are not nonflammable.
`
`For example,
`
`the fluoroalkane
`
`Page 8 of 38
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`

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`Patent
`Docket No. H0004412
`
`Express Mail Label No. 262354600US
`S&L File No. P26,269 USA
`
`difluoroethane (HFC-152a) and the fluoroalkene 1,1,1—trifluoropropene (HFC-
`
`1243zf) are each flammable and therefore not viable for use in many applications.
`
`Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five
`
`carbon atoms, have been suggested for use as refrigerants. Smutry, U.S. Patent
`
`No. 4,788,352 is directed to production of fluorinated C5 to C3 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.
`
`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.
`
`Applicant have thus come to appreciate a need for compositions, and
`
`particularly fluid transfer compositions 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. Moreover,
`
`applicant has also recognized that in many applications there remains a need for
`
`fluorocarbon
`
`and
`
`hydrofluorocarbon-based
`
`refrigeration
`
`liquids
`
`that
`
`are
`
`environmentally safer than HFC's, possess similar or better characteristics with
`
`respect to at least certain refrigerant thermodynamic performance properties, and
`
`are compatible with existing lubricant systems.
`
`Page 9 of 38
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`

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`Patent
`Docket No. H0004412
`
`Express Mail Label No. 262354600US
`S&L File No. P26,269 USA
`
`SUMMARY
`
`Applicants have found that the above-noted needs, 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 (I)
`
`where X is a C2 or a C3 unsaturated, substituted or unsubstituted, alkyl radical, R is
`
`independently Cl, Br,
`
`I or H, and z is 1
`
`to 3. The present compositions also
`
`preferably include one or more lubricants in combination with one or more of the
`
`compounds of the present invention.
`
`The present invention provides also methods and systems which utilize the
`
`heat transfer compositions of the present invention.
`
`Page 10 of 38
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`

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`' Patent
`Docket No. H00O4412
`
`Express Mail Label No. EV26235460OUS
`S&L File No. P26,269 USA
`
`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-olefins or “HFOs."
`
`Although it is contemplated that the HFOs of the 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 compounds
`
`in accordance with Formula I.
`
`In preferred embodiments, the compositions include
`
`compounds of Formula II below:
`
`R
`
`>C==C——R'
`
`R
`
`R
`
`(H)
`
`wherein 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 R's is F.
`
`Applicant believes that,
`
`in general, the compounds of the above identified
`
`Formulas I and ll are generally effective and exhibit utility in heat
`
`transfer
`
`applications in general and in compression refrigerant compositions in particular.
`
`However,
`
`it has been 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 contain relatively toxic compounds satisfying
`
`6
`
`Page 11 of 38
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`

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`' Patent
`Docket No. H00O4412
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`Express Mail Label No. EV262354600US
`S&L File No. P26,269 USA
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`the formulas described above. More particularly,
`
`it is believed 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 R’s is F.
`
`It is believed 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 trifluorpropene (HFC -1243), tetra-
`
`fluoropropenes (HFO-1234), pentafluoropropenes (HFO-1225) and combinations of
`
`these. The trans-1234 isomer has a boiling point of approximately -19° C and the cis
`
`isomer has a boiling point of approximately +9° C. The trans isomer is particularly
`
`useful as a refrigerant and as an aersol propellent.
`
`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.
`
`It has been discovered that such compounds have a very acute low toxicity
`
`level, as measured by inhalation exposure to mice and rats. On the other hand, it
`
`has been found that a relatively high degree of toxicity may be 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,
`
`it has been 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.
`
`Page 12 of 38
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`

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`‘ Flatent
`Docket No. HO004412
`
`Express Mail Label No. EV262354600US
`S&L File No. P26,269 USA
`
`HFO-1225 is commercially available,
`
`for 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 U.S. 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 incorpora-ted herein by reference, discloses a vapor phase
`
`catalytic process for the preparation of fluoroalkene using a chloro- or bromo-
`
`halofluorocarbon and H.
`
`EP 974,571, also incorporated herein by reference,
`
`discloses the preparation of 1,1,1,3-tetrafluoro-propene 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
`
`F|uorpropenes" bearing attorney docket number (H0OO3789 (26,267USA)), 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
`
`compositions also do not contribute substantially to global warming compared to
`
`many of the hydrofluoroalkanes presently in use.
`
`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
`
`Page 13 of 38
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`

`
`‘ Patent
`Docket No. HO004412
`
`Express Mail Label No. EV262354600US
`S&L File No. P26,269 USA
`
`an amount that is at least about 50% by weight, and even more preferably at least
`
`about 70 % by weight, of the composition. 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 °/o 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
`
`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), Poly Alkylene Glycols (PAGs) and esterified Poly Alkylene Glycols
`
`that are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants
`
`may be used with the refrigerant compositions of the present invention.
`
`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.
`
`Page 14 of 38
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`

`
`' Flatent
`Docket No. HO004412
`
`Express Mail Label No. EV262354600US
`S&L File No. P26,269 USA
`
`The preferred heat
`
`transfer methods generally comprise providing a
`
`composition of the present invention and causing heat to be transferred to or from
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`the composition by changing the phase of the composition.
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`For example, the
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`present methods provide cooling by absorbing heat from a fluid or article, preferably
`by condensing a refrigerant comprising the present compositions and thereafter
`evaporating the refrigerant in the vicinity of the body or fluid to be cooled.
`In many of
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`such processes, the step of compressing the refrigerant vapor, usually with a rotary
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`compressor or similar equipment, is also included as part of the refrigeration cycle.
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`Such a step is then sometimes followed by an intermediate cooling step to remove at
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`least a portion of the heat added to the refrigerant composition of the present
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`invention by the compression step. This intermediate cooling step is then preferably
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`followed by a nominally isoenthalpic reduction of the pressure of the cooled, high
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`pressure refrigerant vapor to cause at least a portion of the vapor to condense to a
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`relatively cold liquid phase.
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`In such embodiments,
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`it
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`is this reduced temperature
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`refrigerant liquid which is then vaporized by heat transferred from the body or fluid to
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`be cooled.
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`In another process embodiment of the invention, the compositions of the
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`invention may be used in a method for producing heating which comprises
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`condensing a refrigerant comprising the compositions in the vicinity of a liquid or
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`Such methods, as
`body to be heated and thereafter evaporating the refrigerant.
`mentioned hereinbefore, frequently are reverse cycles to the refrigeration cycle
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`described above.
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`According to one aspect of the present invention, a method for producing
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`refrigeration is provided by condensing a fluoroalkene containing from 2 to 5 carbon
`atoms and at least 1 but no more than 2 double bonds and thereafter evaporating
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`the fluoroalkene in the vicinity of a body to be cooled. Fluoroalkenes containing 3
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`carbon atoms and 1 double bond are preferred.
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`Because heat pump systems are simply the reverse of refrigeration systems,
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`according to another aspect of the present invention, a method is provided for
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`producing heating by condensing a fluoroalkene containing from 2 to 5 carbon atoms
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`and at least 1 but no more than 2 double bonds in the vicinity of a body to be heated
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`and thereby evaporating the fluoroalkene. Again, fluoroalkenes containing 3 carbon
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`atoms and 1 double bond are preferred.
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`It has also been discovered that the fluoroalkenes of the present invention are
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`misicible with existing polyalkylene glycol, polyalkylene glycol ester and polyol ester
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`lubricating oils. Therefore, according to another aspect of the present invention, a
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`liquid composition is provided for use in compression refrigeration, air-conditioning
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`and heat pump systems in which a fluoroalkene containing from 2 to 5 carbon atoms
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`and at least 1 but no more than 2 double bonds is combined with a sufficient amount
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`to provide lubrication of an essentially miscible organic lubricant selected from
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`polyalkylene glycol, polyalkylene glycol ester and polyol ester
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`lubricants
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`for
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`compression refrigeration, air-conditioning and heat pump systems.
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`In certain
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`preferred embodiments,
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`the lubricants of this invention are organic compounds
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`which are comprised of carbon, hydrogen and oxygen with a ratio of oxygen to
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`carbon sufficient to provide a degree of miscibility with the fluoroalkene such the
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`when about 1 to 5 weight percent of the lubricant is added to the refrigerant fluid the
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`mixture has one liquid phase. Preferably, the mixture has one liquid phase when 1 to
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`20 weight percent of the lubricant is present in the mixture. Most preferably, the
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`mixture is one liquid phase in all proportions of the components of mixture. This
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`solubility or miscibility preferably exists at at least one temperature from about —40°C
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`and 70°C, and more preferably over essentially the entire temperature range.
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`As used herein the term "refrigeration system" refers to any system or
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`apparatus, or any part or portion of such a system or apparatus, which employs a
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`refrigeration liquid or refrigerant to provide cooling.
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`Such refrigeration systems
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`include,
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`for example, air-conditioners, electric refrigerators, chillers,
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`transport
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`refrigeration systems, commercial refrigeration systems, and the like.
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`The present invention substitutes HFO’s for HFC’s, which, despite being safe
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`for the ozone layer, are suspected of contributing to global warming. At least certain
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`of
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`the preferred HFO’s
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`according to the present
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`invention have physical
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`characteristics that allow for their substitution for HFC’s with only a minimum of
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`equipment changes.
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`The polyalkylene glycol lubricants suitable for use with the present invention
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`typically containing from about 5 to 50 oxylakylene repeating units that contain from
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`1 to 5 carbon atoms. The polyalkylene glycol can be straight chain or branched and
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`can be a homopolymer or co-polymer of 2, 3 or more oxyethylene, oxypropylene,
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`oxybutylene or oxypentylene groups or combinations thereof in any proportions.
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`Preferred polyalkylene glycols
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`contain at
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`least 50% oxypropylene groups.
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`Compositions according to the present
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`invention may contain one or more
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`polyalkylene glycols as the lubricant, one or more polyalkylene glycol esters as the
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`lubricant, one or more polyol esters as the lubricant, or a mixture of one of more
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`polyalkylene glycols, one or more polyalkylene glycol esters and one or more polyol
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`esters. Vinyl ethers are also useful in this invention.
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`Suitable polyalkylene glycols include the polyalkylene glycols of U.S. Patent
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`No. 4, 971,712 and the polyalkylene glycol having hydroxy groups at each terminus
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`disclosed by U.S. Patent No. 4,755,316. The disclosures of both patents are incor-
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`porated herein by reference.
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`While suitable polyalkylene glycols include glycols terminating at each end
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`with a hydroxyl group, other suitable HFO lubricants include polyalkylene glycols in
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`which either or both terminal hydroxyl group is capped. The hydroxyl group may be
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`capped with alkyl groups containing from 1 to 10 carbon atoms, 1 to 10 carbon atom
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`alkyl groups containing heteroatoms such as nitrogen,
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`the fluoroalkyl groups
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`described by U.S. Patent No. 4,975,212, the disclosure of which is incorporated
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`herein by reference, and the like. When both polyalkylene glycol hydroxyl groups
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`are end capped, the same type or a combination of two different types of terminal
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`capping groups can be used.
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`Either or both hydroxyl groups can also be capped by forming the ester
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`thereof with a carboxylic acid as disclosed by U.S. Patent No. 5,008,028,
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`the
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`disclosure of which is also incorporated herein by reference. The lubricating oils of
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`this patent are referred to as polyol esters and polyalkylene glycol esters. The
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`carboxylic acid can also be fluorinated. When both ends of the polyalkylene glycol
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`are capped, either or both ends may be capped with an ester, or one end may be
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`capped with an ester and the other not capped or capped with one of the
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`aforementioned alkyl, heteroalkyl or fluoroalkyl groups.
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`Commercially available polyalkylene glycol
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`lubricants include Goodwrench
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`Refrigeration Oil for HFC-134a systems from General Motors and MOPAR-56 from
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`Daimler-Chrysler, which is a polyalkylene glycol that is bis—capped by acetyl groups.
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`Commercially available polyalkylene glycol esters include Mobil EAL 22 cc available
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`from Exxon-Mobil and Solest 120 available from CPI Engineering Services, Inc. A
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`wide variety of polyalkylene glycol lubricants are also available from Dow Chemical.
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`In preferred embodiments, the lubricants of this invention have viscosities of
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`from about 1 to 1000 centistokes at about 37°C, more preferably in the range of from
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`about 10 to about 200 centistokes at about 37°C and even more preferably of from
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`about 30 to about 150 centistokes.
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`In addition to the HFO refrigerant and lubricant, compositions according to the
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`present
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`invention can include other additives or materials of the type used in
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`refrigeration,
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`air-conditioning and heat pump compositions
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`to enhance their
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`performance. For example, the compositions can also include extreme pressure and
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`anti-wear additives, oxidation and thermal stability improvers, pour and floc point
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`depressants, anti-foaming agents, other lubricants soluble in HFO’s, and the like.
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`Examples of such additives are disclosed in U.S. Patent No. 5,254,280,
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`the
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`disclosure of which is incorporated herein by reference. Compositions of the present
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`invention can thus further include a quantity of mineral oil lubricant that would not
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`othen/vise be misicible or soluble with the HFO but is at least partially misicible or
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`partially soluble when added to the HFO in combination with a polyalkylene glycol,
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`polyalkylene glycol ester or polyol ester. Typically, this is a quantity up to about 5-20
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`weight %. A surfactant may also be added to compatibilize the mineral oil with the
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`polyalkylene glycol, polyalkylene glycol ester or polyol ester and the HFO, as
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`d