Express Mail Label No.
`
`UTILITY PATENT APPLICATION TRANSMITTAL
`
`(Large Entity)
`(Only for new nonprovisional applications under 37 CFR 1.53(b))
`
`TO THE COMMISSIONER FOR PATENTS
`Mail Stop Patent Application
`P.O. Box 1450
`Alexandria, VA 22313-1450
`
`[ Total Pages in this Submission
`
`Transmitted herewith for filing under 35 U.S.C. 111(a) and 37 C.F.R. 1.53(b) is a new utility patent application for an
`invention entitled:
`
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`and invented by:
`
`R. Singh, H. Pham, D. Wilson, R. Thomas
`
`0694273
`
`03108U.S.PT
`
`If a CONTINUATION APPLICATION, check appropriate box and supply the requisite information:
`
`Cl Continuation
`Which is a:
`
`Cl Divisional
`
`Cl Continuation-in-part (CIP)
`
`of prior application No.:
`
`D Continuation
`
`Cl Divisional
`
`Cl Continuation-in-part (CIP)
`
`of prior application No.:
`
`Which is a:
`
`Cl Continuation D Divisional
`
`Cl Continuation-in-part (CIP)
`
`of prior application No.:
`
`Enclosed are:
`
`Filing fee as calculated and transmitted as described below
`
`Application Elements
`
`Specification having
`
`29
`
`pages and including the following:
`
`.
`
`Descriptive Title of the Invention
`
`. 8 Cross References to Related Applications (if applicable)
`
`Statement Regarding Federally-sponsored Research/Development (if applicable)
`
`DD Reference to Sequence Listing, a Table, or a Computer Program Listing Appendix
`
`B
`
`Background of the Invention
`
`E Brief Summary of the Invention
`
`U Brief Description of the Drawings (if filed)
`
`E Detailed Description
`
`E Claim(s) as Classified Below
`E Abstract of the Disclosure
`
`Page 1 of 4
`
`P01ULRGIREVlJ6
`
`Page 1 of 48
`
`Arkema Exhibit 1038
`
`

`
`UTILITY PATENT APPLICATION TRANSMITTAL
`(Only fornew nonprovisional applications under37 CFR 1.53(b))
`
`(Larg Entity)
`
`Application Elements (C ntinued)
`
`Drawing(s) (when necessary as prescribed by 35 USC 1 13)
`
`T t
`
`I P
`
`'
`
`th' 8 b '
`
`'
`
`
`
`Ci.<1.r>s7svl3.<7svU
`
`CI
`
`C]
`
`Formal
`
`Informal
`
`Number of Sheets
`
`Number of Sheets
`
`Oath or Declaration
`
`Newly executed (original or copy)
`
`Unexecuted
`
`Copy from a prior application (37 CFR 1.63(d)) (for continuation/divisional application only)
`
`With Power of Attorney
`
`Cl Without Power of Attorney
`
`DELETION OF lNVENTOR(S)
`Signed statement attached deleting inventor(s) named in the prior application,
`see 37 C.F.R. 1.63(d)(2) and 1.33(b).
`
`Incorporation By Reference (usable if Box 4b is checked)
`The entire disclosure of the prior application, from which a copy of the oath or declaration is supplied under
`Box 4b,
`is considered as being part of the disclosure of the accompanying application and is hereby
`incorporated by reference therein.
`
`CD ROM or CD-R In duplicate, large table or Computer Program (Appendix)
`
`Application Data Sheet (See 37 CFR 1.76)
`
`Nucleotide and/or Amino Acid Sequence Submission (if applicable, all must be included)
`
`. C] Computer Readable Form (CRF)
`
`. D Specification Sequence Listing on:
`
`i.
`
`CI CD-ROM or CD-R (2 copies); or
`
`ii. CI
`
`Paper
`
`. Ci
`
`Statement(s) Verifying Identical Paper and Computer Readable Copy
`
`Accompanying Application Parts
`
`BDEEIEDDD
`
`Assignment Papers (cover sheet & document(s))
`
`37 CFR 3.73(B) Statement (when there is an assignee)
`
`English Translation Document (if applicable)
`
`Information Disclosure Statement/PTO-1449
`
`Copies of IDS Citations
`
`Preliminary Amendment
`
`Return Receipt Postcard (MPEP 503) (Should be specifically itemized)
`
`Certified Copy of Priority Document(s) (if foreign priority is claimed)
`
`Certificate of Mailing
`
`CI
`
`First Class
`
`Express Mail (Specify Label No.): EV 399607675 US
`
`Page 2 of4
`
`Page 2 of 48
`
`

`
`UTILITY PATENT APPLICATION TRANSMITTAL
`(Large
`ty)
`(Only for new nonprowslonal applications under 37 CFR 1.53(b))
`
`i
`
`Total Pages in this Submission
`
`Acc mpanying Application Parts (Continued)
`
`17.
`
`Additional Enclosures (please identify below):
`
`Application Data Sheet
`
`Request That Application Not Be Published Pursuant To 35 U.S.C. 122(b)(2)
`
`18. CI Pursuant to 35 U.S.C. 122(b)(2), Applicant hereby requests that this patent application not be
`published pursuant to 35 U.S.C. 122(b)(1). Applicant hereby certifies that the invention disclosed in
`this application has not and will not be the subject of an application filed in another country, or under
`a multilateral international agreement, that requires publication of applications 18 months after filing
`of the application.
`
`Warning
`
`An applicant who makes a request not to publish, but who subsequently files in a foreign
`country or under a multilateral international agreement specified in 35 U.S.C. 122(b)(2)(B)(i),
`must notify the Director of such filing not later than 45 days after the date of the filing of
`such foreign or international application. A failure of the applicant to provide such notice
`within the prescribed period shall result in the application being regarded as abandoned,
`unless it is shown to the satisfaction of the Director that the delay in submitting the notice
`was unintentional.
`
`Page 3 of4
`
`Page 3 of 48
`
`

`
`UTILITY PATENT APPLICATION TRANSMITTAL
`
`(Only for new nonprovisional applications under 37 CFR 1.53(b))
`
`Fee Calculation and Transmittal
`
`CLAIMS AS FILED
`
`For
`
`#FiIed
`
`#Extra
`#Al|owed
`EH x
`
`Rate N
`I
`
`Multiple Dependent Claims (check if applicable)
`
`[3
`
`OTHER FEE (specify purpose)
`
`|
`BASIC FEE |
`|
`TOTAL FILING FEE I
`
`$0.00
`$770.00
`$0.00
`$2,558.00
`
`to cover the filing fee is enclosed.
`$2,558.00
`8] A check in the amount of
`The Director is hereby authorized to charge and credit Deposit Account No.
`as described below.
`
`19-5425
`
`Cl Charge the amount of
`Credit any overpayment.
`Charge any additional filing fees required under 37 C.F.R.
`
`as filing fee.
`
`.
`
`.
`
`.
`
`Cl Charge the issue fee set in 37 C.F.R. 1.18 at the maili
`pursuant to 37 C.F.R. 1.311(b).
`
`of the Notice of Allowance,
`
`Signature
`
`Dated: October 27, 2003
`
`oseph F. Posillico, Reg. No. 32,290
`
`Send Correspondence To:
`Colleen D. Szuch, Esquire
`Honeywell International, Inc.
`101 Columbia Road, Building Meyer 5
`Morristown, NJ 07962-2245
`
`Page 4 of 4
`
`P01ULRGIREVD6
`
`Page 4 of 48
`
`

`
`CERTIFICATE OF MAILING BY "EXPRESS MAIL" (37 CFR 1.10)
`
`Docket No-
`
`Applicant(s): R. Singh, H. Pham, D. Wilson, R. Thomas
`
`[-1ooo3965(26446.A)
`
`Serial No.
`
`Examiner
`
`Group Art Unit
`
`Invention: COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`I hereby certify that the following correspondence:
`
`atent Application and accompanying documents
`
`(Identify type ofcorrespondence)
`
`is being deposited with the United States Postal Service "Express Mail Post Office to Addressee" service under
`
`37 CFR 1.10 in an envelope addressed to: The Assistant Commissioner for Patents, Washington, D.C. 20231 on
`
`October 27, 2003
`(Date)
`
`Cl_1’i:is K. Ricco
`mu&%
`(Typed or Printed Name ofPerson Mailing Currespandence)
`
`(Signature nfPersnn Mailin Correspnndence)
`
`EV3 99607675US
`
`(”Express Mail” Mailing Label Number)
`
`Note: Each paper must have its own certificate of mailing.
`
`Page 5 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. HO003965 (26446-A)
`
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`Invented by: Rajiv R. Singh
`18 Foxfire Drive
`
`Getzville, NY 14068
`Citizen of the United States
`
`Hang T. Pham
`136 Larkspur Lane
`Amherst, NY 14228
`Citizen of the United States
`
`David P. Wilson
`
`118 Waxwing Court
`East Amherst, NY 14051
`Citizen of the United States
`
`Raymond H. Thomas
`5990 Hopi Court
`Pendleton, NY 14094
`Citizen of the United States
`
`Page 6 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446-A)
`
`COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
`
`RELATED APPLICATIONS
`
`V
`
`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
`
`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
`
`HO004412 (26269) entitled “Fluorinated Alkene Refrigerant Composition,” by Raymond
`
`Thomas and Attorney Docket Number H0003789 (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
`
`1
`
`Page 7 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. HO0O3965 (26446-A)
`
`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 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 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
`
`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, low- 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
`
`2
`
`Page 8 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446-A)
`
`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).
`
`ln 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 tenn “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. Unfortunately, many
`
`HFC’s 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—-trifluorpropene (HFO-1243zf) are each flammable and therefore not
`
`viable for use in many applications.
`
`Page 9 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446—A)
`
`Higher fluoroalkenes, that is fluorine-substituted alkenes having at least five
`
`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 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.
`
`(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.
`
`Page 10 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0OO3965 (26446-A)
`
`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:
`
`XCFZRS-z (I)
`
`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-olefins 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 Fonnula I.
`
`In preferred embodiments, the compositions include
`
`compounds of Formula II below:
`
`T=c——R'
`
`R\
`R/°
`
`(II)
`
`where each R is independently Cl, F, Br, I or H
`
`5
`
`Page 11 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446-A)
`
`Ft’ is (CR2),,Y,
`
`Y is CRF2
`
`and n is 0 or 1.
`
`In highly preferred embodiments, Y is CF3, n is O 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 Fls 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,
`
`6
`
`Page 12 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446-A)
`
`applicants have 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, applicants
`
`have discovered that 1,1,3,3,3-pentafluoropropene (HFO-122520) 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 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
`
`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)g 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 attomey docket number (HO003789 (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
`
`7
`
`Page 13 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. HO003965 (26446-A)
`
`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.
`
`Preferably, the compositions of the present invention have a Global Wanning
`
`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 ll, 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 oompatibilzer, such as propane, for the purpose of aiding compatibility and/or
`
`8
`
`Page 14 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0O03965 (26446-A)
`
`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) 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
`
`9
`
`Page 15 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. HOOO3965 (26446-A)
`
`and other additives may also be incorporated 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 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.
`
`lnert 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
`
`10
`
`Page 16 of 48
`
`

`
`PATENT
`
`Express Mail Mailing Label No. EV39907675US
`Attorney Docket No. H0003965 (26446-A)
`
`methods of extinguishing and suppressing fire are also included in certain aspects of
`
`the present invention. The present invention also 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