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`
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`ff:
`\ E to
`
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`PTO/SBI16 (8-00)
`Approved for use through10/31/2002. OMB 0651-0032
`U.S. Patent and Trademark Office; U.S. DEPARTMENT OF COMMERCE
`nder the Papenlvork Reduction Act of 1995, no persons are required to respond to a collection of information unless it displays a valid OMB control nuifler. if
`A
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`PROVISIONAL APPLICATION FOR PA TENT COVER SHEET
`.52 _§
`§__ 0
`This is a request for filing a PROVISIONAL APPLICATION FOR PATENT under 37 CFR 1.53(c).
`mg
`K.’
`c\;
`"*1
`
`Given Name (first and middle [if any])
`Rajiv R.
`-
`Hang T.
`David P.
`Raymond H.
`
`Family Name or Surname
`Singh
`Pham
`Wilson
`Thomas
`
`Getzvllle, NY 14068
`Amherst, NY 14228
`East Amherst, NY 14051
`Pendleton, NY 14094
`
`Residence
`
`'
`
`I: Additional inventors are being named on the
`
`separately numbered sheets attached hereto
`
`TITLE OF THE INVENTION (280 characters max)
`USE OF 1,1,3,3,3-PENTAFLUOROPROPENE AND 1.3.3.3-TETRAFLUOROPROPENE IN REFRIGERATION
`
`Direct all correspondence to:
`El Customer Number I
`
`—
`
`CORRESPONDENCE ADDRESS
`
`I :———>
`
`Place CustomerNumber
`Bar Code Label here
`
`OR
`
`F.
`lnfllizgal Name
`
`Type Customer Number here
`
`Peter J. Butch, m
`
`19107-2950
`215-923-2139
`
`Ij Other (specify)
`
`1101 Market Street, Suite 2600
`'’'“'ade'P'“a
`Telephone 215-923-4466
`United States
`ENCLOSED APPLICATION PARTS (check all that agply)
`E Specification NumberofPages E:
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`E The Commissioner is hereby authorized to charge filing
`fees or credit any overpayment to Deposit Account Numbe
`"Payment by credit card. Fonn PTO-2038 is attached.
`
`$1 50-00
`
`The invention was made by an agency of the United States Government or under a contract with an agency of the
`United States Government.
`
`No.
`[3 Yes, the name of the U.S. Government agency and the Government contract number are:
`3
`
`Respectfully su
`
`
`bmit
`. P7
`Z_
`Date
`10/25/2002
`SIGNATURE
`/L/%
`REGISTRATION No.
`(if appropriate)
`Docket N
`ber'
`um -
`
`TYPED or PRINTED NAME Pete’ J- Butch» "I
`215-923-4466
`
`
`TELEPHONE
`
`USE ONLY FOR FILING A PROVISIONAL APPLICATION FOR PA TENT
`This collection of information is required by 37 CFR 1.51. The information is used by the public to file (and by the PTO to process) a provisional
`application. Confidentiality is governed by 35 U.S.C. 122 and 37 CFR 1.14. This collection is estimated to take 8 hours to complete, including
`gathering, preparing, and submitting the complete provisional application to the PTO. Time will vary depending upon the individual case. Any
`comments on the amount of time you require to complete this form and/or suggestions for reducing this burden. should be sent to the Chief
`Information Officer, U.S. Patent and Trademark Office, U.S. Department of Commerce, Washington, D.C. 20231. DO NOT SEND FEES OR
`COMPLETED FORMS TO THIS ADDRESS. SEND TO: Box Provisional Application. Assistant Commissioner for Patents, Washington, D.C_
`P1 QLARGEIREVOS
`
`page 1 of 10
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`Arkema Exhibit 1035
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`Page 1 of 10
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`Page 1 of 10
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`Arkema Exhibit 1035
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`

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`
`
`USE OF 1,1,3,3,3—PENTAFLUOROPROPENE
`
`AND 1,3,3,3— TETRAFLUOROPROPENE IN REFRIGERATION
`
`BACKGROUND OF THE INVENTION
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`10
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`I5
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`20
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`25
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`30
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`This invention relates to the use of 1,1 ,3,8,3—pentafluoropropene (HFO-1225) and
`
`1,3,3,3—trifluoropropene (HFO-1234) in refrigeration equipment. These materials are generally
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`useful as refrigerants for heating and cooling and as blowing agents and as aerosol propellants
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`and as fire extinguishing and suppressing agents.
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`Fluorocarbon based fluids have found widespread use in industry for refrigeration
`
`applications such as air conditioning and heat pump applications. Vapor compression is one
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`form of refrigeration.
`
`In its simplest form, vapor compression involves changing the refrigerant
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`from the liquid to the vapor phase through heat absorption as a low pressure and then from the
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`vapor to the liquid phase through heat removal at an elevated pressure.
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`While the primary purpose of refrigeration is to remove energy at low temperature, the
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`primary purpose of a heat pump is to add energy at higher temperature. Heat pumps are
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`considered reverse cycle systems because for heating, the operation of the condenser is
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`interchanged with that of the refrigeration evaporator.
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`Certain chlorofluoromethane and chlorofluoroethane derivatives have gained
`widespread use as refrigerants in applications including air conditioning and heat pump
`applications owing to theirunique combination of chemical and physical properties. The
`
`majority of refrigerants utilized in vapor compression systems are either single components
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`fluids or azeotropic mixtures.
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`Azeotropic or azeotrope-like compositions are desired as refrigerants because they do
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`not fractionate upon boiling. This behavior is desirable because in the previously described
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`vapor compression equipment with which theses refrigerants are employed, condensed
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`material is generated in preparation for cooling or for heating purposes. Unless the refrigerant
`composition exhibits a constant boiling point, i.e. is azeotrope-like, fractionation and
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`segregation will occur upon evaporation and condensation and undesirable refrigerant
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`Page 2 of 10
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`Page 2 of 10
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`Page 2 of 10
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`

`
`u.;_
`"R
`51
`HI
`-.:JLu
`
`
`Patent
`
`Attomey Docket No. H0OO3965 (4510)
`
`distribution may act to upset the cooling or heating.
`
`If a leak occurs in a refrigeration system
`
`during use or service, the composition of the azeotrope-like mixture does not change and thus,
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`system pressures and system performance remain unaffected.
`
`The art is continually seeking new fluorocarbon and hydrofluorocarbon based pure fluid
`
`and azeotrope-like mixtures that offer alternatives for refrigeration and heat pump applications.
`
`Fluoroolefin based materials are of particular interest because they are considered to be
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`environmentally safer substitutes for the presently used fluoroalkanes (FAs), which are
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`suspected of causing global warming.
`
`Substitute refrigerants must also possess those properties unique to the FA refrigerants
`including similar refrigeration characteristics, chemical stability, low toxicity, non—flammability,
`
`and efficiency in-use. The latter characteristic is important in refrigeration and air—conditioning
`
`especially where 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, the ideal CFC refrigerant substitute
`
`would not require major engineering changes to conventional vapor compression technology
`
`currently used with CFC refrigerants. Mathematical models have substantiated that fluoro-
`
`olefins, such as (HFO—1225), or (HFO—1234) will not adversely affect atmospheric chemistry,
`
`being negligible contributors to ozone depletion in comparison to the some other halogenated
`
`species.
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`HFC-152a might be considered to be a refrigerant substitute for R-134a. However,
`
`HFC—152a is disadvantageous to use as a refrigerant because of its flammabilty, which results
`
`in possible hazards in refrigeration machines. The same is true of 1,1 ,1-trifluoropropene (HFO—
`
`1243). HFO-1225 or HFO-1234 are however found to be nonflammable by ASTM standard E-
`
`681 test, a method often used to test flammability of refrigerant and other gases.
`
`Examples of refrigeration, aerosol and blowing agent use of HFO-1225 and HFO-1234
`
`are not known in the literature. HFO-1234 is available as two geometric isomers (I) cis and (Il)
`
`trans. The trans-1234 isomer has a boilingpoint of approximately -19 °C and the cis isomer
`
`has a boiling point of + 9 °C. The trans-1234 isomer is particularly useful as a refrigerant and as
`
`an aerosol propellent and the cis—1234 isomer as a blowingagent.
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`10
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`15
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`25
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`30
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`Page 3 of 10
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`Page 3 of 10
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`Page 3 of 10
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`

`
` Air mm 2: 4;
`7317.33?
`IL,;i3 ""13" I12‘
`
`Patent
`
`Attorney Docket No. HOOO3965 (4510)
`
`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.
`
`DETAILED DESCRIPTION OF THE INVENTION
`
`10
`
`15
`
`20
`
`The present invention is directed to the use of 1,1,3,3,3—pentaf|uoropropene (HFO-1225)
`
`or 1,3,3,3-tetrafluoropropene (HFO—1234) (cis or trans isomers) as a refrigerant in refrigeration,
`
`air conditioning and heat pump cycles. The use of these compositions as aerosol propellants
`
`and foam blowing agents is also disclosed.
`
`The present compositions are advantageous for the following reasons.
`
`Each fluid is a
`
`negligible contributor to ozone depletion. Each fluid also contributes negligibly to global
`
`warming compared to hydrofluoroalkanes presently used. Because the present compositions
`
`are pure, the liquid mixtures will show no shifts in composition during evaporation.
`
`This is
`
`advantageous in a vapor compression cycle as simple blends of refrigerants can not mimic the
`
`performance of a constant-boiling single component refrigerant and are further are penalized by
`reduced heat transfer.
`
`Other components may be added to the mixture to tailor the properties of the refrigerant
`
`according to the need. For example, in the art, propane has been added to refrigerant
`
`compositions to aid oil solubility and may be added to the compositions of HFO-1225 or HFO-
`
`1243. Similar materials may be added to the present mixture. Commonly used refrigeration
`
`oils 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
`
`30
`
`claimed refrigerant.
`
`Furthermore, HFO-1234 and HFO-1225 have been found to be exceptionally stable and
`
`compatible with the POE and PAG refrigeration lubricants. This level of stability is surprising
`
`Page 4 of 10
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`Page 4 of 10
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`Page 4 of 10
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`

`
`Patent
`
`Attorney Docket No. H0003965 (4510)
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`and makes these compounds very suitable for use with these lubricants in refrigeration
`
`..:«v-,» —u‘"\: u
`151:“ 11.33? "'1
`
`processes.
`
`Uses of the Compositions
`
`The compositions of the present invention may be used in a wide variety of applications
`as substitutes for CFCs and HCFCs.
`
`For example, the present compositions are useful as
`
`solvents, blowing agents, refrigerants, cleaning agents and aerosols.
`
`10
`
`15
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`20
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`25
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`30
`
`35
`
`One embodiment of the present invention relates to a blowing agent comprising one or
`
`more compositions of the invention.
`
`In other embodiments, the invention provides foamable
`
`compositions, and preferably polyurethane and polyisocyanurate foam compositions, and
`
`\
`
`methods of preparing foams.
`
`In such foam embodiments, one or more of the present
`
`compositions are included as a blowing agent in a foamable composition, which composition
`
`preferably includes one or more additional components capable of reacting and foaming under
`the proper conditions to form a foam or cellular structure, as is well known in the art. The
`
`present methods preferably comprise providing such a foamable composition and reacting it
`
`under conditions effective to obtain a foam, and preferably a closed cell foam. 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.
`l
`
`Any of the methods well known in the art, such as those described in “Polyurethanes
`
`Chemistry and Technology,” Volumes I and ll, Saunders and Frisch, 1962, John Wiley and
`
`Sons, New York, NY, which is incorporated herein by reference, may be used or adapted for
`
`use in accordance with the foam embodiments of the present invention.
`
`in general, such
`
`preferred methods comprise preparing polyurethane or polyisocyanurate foams by combining
`
`an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents
`
`comprising one or more of the present compositions, and other materials such as catalysts,
`
`surfactants, and optionally, flame retardants, colorants, or other additives.
`
`It is convenient in
`
`many applications to provide the components for polyurethane or polyisocyanurate foams in
`
`pre—blended formulations. Most typically, the foam formulation is pre—blended into two
`
`components. The isocyanate and optionally certain surfactants and blowing agents comprise
`
`the first component, commonly referred to as the “A” component. The polyol or polyol mixture,
`
`surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive
`
`components comprise the second component, commonly referred to as the “B” component.
`
`Page 5 of 10
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`Page 5 of 10
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`Page 5 of 10
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`

`
`Patent
`
`Attorney Docket No. H0OO3965 (4510)
`
`J1"
`‘|!IZ?il
`
`""12
`"f‘.“‘H -ll‘)!
`3.3.~,,?¥ ""li“ 3131;
`
`
`
`Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together
`
`the A and B side components either by hand mix for small preparations and, preferably,
`
`machine mix techniques to form blocks, slabs, laminates, pour-in—place panels and other items,
`
`spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardants,
`
`colorants, auxiliary blowing agents, and even other polyols can be added as a third stream to
`
`the mix head or reaction site. Most conveniently, however, they are all incorporated into one
`B-component as described above.
`
`10
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`20
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`25
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`30
`
`It is also possible to produce thermoplastic foams using the compositions of the
`
`invention. For example, conventional foam polyurethanes and isocyanurate formulations may
`
`be combined with the compositions in a conventional manner to produce rigid foams.
`
`Dispersing agents, cell stabilizers, and surfactants may also be incorporated into the
`
`blowing agent mixture. Surfactants, better known as silicone oils, are 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. Other optional additives for
`
`the blowing agent mixture may include flame retardants such as tri(2—chloroethy|)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.
`
`In another embodiment, the compositions of this invention may be used as propellants
`
`in sprayable compositions, either alone or in combination with known propellants. The
`
`sprayable composition comprises, consists essentially of, and consists of a material to be
`
`sprayed and a propellant comprising, consisting essentially of, and consisting of the azeotrope
`
`and azeotrope-like compositions of the invention.
`
`Inert ingredients, solvents, and other
`
`materials may also be present in the sprayable mixture. Preferably, the sprayable composition
`
`is an aerosol- Suitable materials to be sprayed include, without limitation, cosmetic materials
`
`such as deodorants, perfumes, hair sprays, cleansers, and polishing agents as well as
`
`medicinal materials such as anti-asthma and anti—halitosis medications.
`
`in one process embodiment of the invention, the compositions of the invention may be
`
`used in a method for producing refrigeration which comprisescondensing a refrigerant
`
`comprising the compositions and thereafter evaporating the refrigerant in the vicinity of a body
`to be cooled.
`
`35
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`Page 6 of 10
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`Page 6 of 10
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`Page 6 of 10
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`

`
`Patent
`
`Allomey Docket No. HOOO3965 (4510)
`
`‘
`u"q< “Wu 1;-3“
`«:1
`‘‘‘‘ill
`
`
`
`limit IL.,..‘rL.ui.2Z‘,ti I;'.,?5 1::
`
`
`
`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 body to be heated and thereafter evaporating
`
`the refrigerant.
`
`The HFO-1225, and HFO—1234 of the present invention are known materials. HFO-1225
`
`is commercially available, from example from Syntex Chemical Co. Preferably, the materials
`
`should be used in sufficiently high purity so as to avoid the introduction of adverse influences
`
`upon the cooling or heating properties’ of the system.
`
`EXAMPLES 1 — 3
`
`These examples show that the constant-boiling blends of the present invention have
`
`certain advantages when compared to other refrigerants that are currently used in certain
`
`refrigeration cycles.
`
`The theoretical performance of a refrigerant at specific operating conditions can be
`estimated from the thermodynamic properties of the refrigerant using standard refrigeration
`
`cycle analysis techniques; see for example, R.C. Downing, FLUOROCARBON
`
`REFRIGERANTS HANDBOOK, Chapter 3, Prentice—Hall, 1988. The coefficient of performance
`
`(COP) is a universally accepted measure, especially useful in representing the relative
`
`thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving
`
`evaporation or condensation of the refrigerant.
`
`In refrigeration engineering, this term expresses
`
`the ratio of useful refrigeration to the energy applied by the compressor in compressing the
`
`vapor. The capacity of a refrigerant represents the volumetric efficiency of the refrigerant. To a
`
`compressor engineer, this value expresses the capability of a compressor to pump quantities of
`
`heat for a given volumetric flow rate of refrigerant.
`
`In other words, given a specific compressor,
`
`a refrigerant with a higher capacity will deliver more cooling or heating power.
`
`We have performed refrigeration /air conditioning cycles where the condenser
`
`temperature is typically 150°F and the evaporator temperature is typically —35°F. We have
`
`further assumed isentropic compression and a compressor inlet temperature of 50°F. Such
`
`calculations were performed for HFO-1225 and HFO-1234 as well as for HFC—134a. Tables I-
`
`10
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`15
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`20
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`25
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`30
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`Page 7 of 10
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`Page 7 of 10
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`Page 7 of 10
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`

`
`H
`~ _.
`.
`
`
` ., L...’U1....;liiimi:5,. 1
`..,.1l
`
`
`
`
`
`
`
`
`
`
`Patent
`
`Attorney Docket No. IIOOO3965 (4510)
`
`Ill below list the COP and capacity of the various blends relative to that of HFC-134a over a
`
`range of condenser and evaporator temperatures.
`
`TABLE I
`
`F“"” Relative cop "
`l
`COMPOSTION
`
`Relative cAl3Acifv DISAGE
`TEMPERATURE
`(°F)
`
`158
`
`K
`
`This example showed that HFO-1225 has a better energy efficiency than HFC-134a and
`
`the compressors run cooler also, leading to reduced maintenance problems.
`
`TABLE I1
`
`Relative cop
`
`Relative CAPACITY
`
`DISCHARGE
`TEMPERATURE
`
`REFRIGERANT
`COMPOSTION
`
`HFO trans-1234
`HFC-134a
`
`This example shows that HFO-trans—1234 has a better energy efficiency than HFC-134a
`
`and the compressors run cooler also, leading to reduced maintenance problems.
`
`_
`
`TABLE III
`
`#REFRlGERANT
`COMPOSTION
`
`Relative cop
`
`Relative CAPACITY
`
`DISCHARGE
`TEMPERATURE
`
`(°F>
`
`HFO cis-1234
`HFC-134a
`
`This example shows that HFO-cis-1234 has a better energy efficiency than HFC-134a
`
`and the compressors run cooler also, leading to reduced maintenance problems.
`
`
`
`5
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`10
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`15
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`20
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`l
`l
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`1
`
`i
`j
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`Page 8 of 10
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`Page 8 of 10
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`Page 8 of 10
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`

`
`Patent
`
`Attorney Docket No. H0003965 (4510)
`
`WHAT IS CLAIMED IS:
`
`25
`ll
`!!‘‘‘\'I
`41“
`—i:::::s 'i!,:,.i:’ """!3‘
`
`,_
`
`1.
`
`A method for producing refrigeration which comprises condensing a refrigerant
`
`composition comprising a fluoro-olefin selected from the group consisting of HFO-1225, HFO
`
`cis-1234 and HFO trans-1234, and thereafter evaporating said refrigerant composition in the
`
`vicinity of a body to be cooled.
`
`2.
`
`A method for producing heating which comprises condensing a refrigerant
`
`composition comprising a fluoro—o|efin selected from the group consisting of HFO-1225, HFO
`
`cis-1234 and HFO trans~1234, in the vicinity of a body to be heated and thereafter evaporating
`
`said refrigerant composition.
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`10
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`15
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`Page 9 of 10
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`Page 9 of 10
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`Page 9 of 10
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`

`
`Patent
`
`Attorney Docket No. H0003965 (4510)
`
`
`
`
`
`ABSTRACT OF THE DISCLOSURE
`
`The use of 1,1,3,3,3-pentafluoropropene (HFO—1225) and 1,3,3,3-trifluoropropene
`
`5
`
`(HFO-1234) in refrigeration equipment is disclosed. These materials are generally useful as
`
`refrigerants for heating and cooling and as blowing agents and as aerosol propellants and as
`
`fire extinguishing and suppressing agents.
`
`10
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`Page 10 of 10
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`Page 10 of 10
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`Page 10 of 10