AU2017201286B2 - Compositions comprising fluoroolefins and uses thereof - Google Patents

Abstract

The present invention relates to fluoroolefin compositions. The fluoroolefin compositions of the present invention are useful as refrigerants or heat transfer fluids and in processes for producing cooling or heat. Additionally, the fluoroolefin compositions of the present invention may be used to replace currently used refrigerant or heat transfer fluid compositions that have higher global warming potential.

Description

The present invention relates to fluoroolefin compositions. The fluoroolefin compositions of the present invention are useful as refrigerants or heat transfer fluids and in processes for producing cooling or heat. Additionally, the fluoroolefin compositions of the present invention may be used to replace currently used refrigerant or heat transfer fluid compositions that have higher global warming potential.

2017201286 24 Feb 2017

P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990

COMPLETE SPECIFICATION

FOR A DIVISIONAL PATENT

ORIGINAL

Name of Applicant:	E. I. DU PONT DE NEMOURS AND COMPANY
Actual Inventors:	SIEVERT, Allen Capron NAPPA, Mario Joseph MINOR, Barbara Haviland LECK, Thomas J. RAO, Velliyur Nott Mallikarjuna SWEARINGEN, Ekaterina N. SCHMITZ, Corneille MOULI, Nandini PERTI, Deepak
Address for Service:	Houlihan2, Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia
Invention Title:	COMPOSITIONS COMPRISING FLUOROOLEFINS AND USES THEREOF

The following statement is a full description of this invention, including the best method of performing it known to the Applicant:1

2017201286 24 Feb 2017

FIELD OF THE INVENTION

The present Application is a Divisional Application from Australian Patent Application No. 2015202652 which is a Divisional of Application No. 2012229664 and in turn is a Divisional of Application No. 2006308717. The entire disclosures of Australian Patent Application No.’s 2015202652, 2012229664, 2006308717 and their corresponding International Application No. PCT/US2006/042686, are incorporated herein by reference.

The present invention relates to compositions for use in refrigeration, airconditioning or heat pump systems wherein the composition comprises at least one fluoroolefin. The compositions of the present invention are useful in processes for producing refrigeration or heat, as heat transfer fluids and many other uses.

BACKGROUND OF THE INVENTION

The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the mobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a include HFC152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO2. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternative refrigerants are being sought.

An aspect of the present invention is to provide novel refrigerant compositions and heat transfer fluid compositions that provide unique characteristics

2017201286 24 Feb 2017 to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.

Refrigerants and heat transfer fluids comprising a fluorinated terminal olefin are disclosed in: US-A-5 037 573; JP 04 110388; JP 05 085970; WO 2004/037913; US 2005/233932; US 2004/127383; US-A-3 723 318; US-B-6 258 292; and EP-A-1 191 080.

A heat transfer fluid comprising a perfluorinated internal olefin, i.e. octafluoro-2-butene, is disclosed in Proceedings of the 31st Intersociety Energy Conversion Engineering Conference, IEEE, US, vol 2, 11 August 1996, pp 1506-1511.

Refrigerants comprising various fluorinated olefins are disclosed in EP-A1016839.

In EP-A-0 670 295 the olefin 1,1,1,4,4,4-hexafluoro-2-butene is disclosed as an intermediate in the synthesis of 1,1,1,4,4,4-hexafluorobutane.

Any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia.

BRIEF SUMMARY OF THE INVENTION

The present disclosure broadly relates to a refrigerant or heat transfer fluid composition comprising at least one fluoroolefin.

The present invention provides a refrigerant or heat transfer fluid composition comprising 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF₃)₂.

The present invention further provides a process for cooling, the process comprising condensing a composition comprising 1,3,4,4,4-pentafluoro-3(trifluoromethyl)-l -butene (CHF=CHCF(CF₃)₂) and thereafter evaporating the composition in the vicinity of a body to be cooled.

The present invention further provides a process for heating, the process comprising evaporating a composition comprising 1,3,4,4,4-pentafluoro-3(trifluoromethyl)-l -butene (CHF=CHCF(CF₃)₂) and thereafter condensing the composition in the vicinity of a body to be heated.

The present invention further provides a method for producing heating or cooling in a refrigeration, air-conditioning, or heat pump apparatus, the method comprising introducing a refrigerant or heat transfer fluid composition into the apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger; wherein the refrigerant or

2017201286 11 Sep 2018 heat transfer fluid composition comprises 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1butene (CHF=CHCF(CF₃)2).

The present invention further provides a method of using a composition comprising 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2) as a heat transfer fluid composition, the method comprising transporting the composition from a heat source to a heat sink.

The present invention further provides a refrigeration, air-conditioning or heat pump apparatus containing a composition comprising 1,3,4,4,4-pentafluoro-3(trifluoromethyl)-l-butene (CHF=CHCF(CF3)2).

Where the terms “comprise”, “comprises”, “comprised” or “comprising” are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

The present invention further provides a refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.

The present invention further provides a process for cooling, the process comprising condensing the composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, and thereafter evaporating the composition in the vicinity of a body to be cooled.

The present invention further provides a process for heating, the process comprising evaporating the composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,24

2017201286 11 Sep 2018 trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, and thereafter condensing the composition in the vicinity of a body to be heated.

The present invention further provides a method of using the composition comprising at least one compound selected from the group consisting of: 1,1,2,3tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc);

2.3.3- trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, in a compression refrigeration, air-conditioning, or heat pump apparatus, the method comprising providing the composition to the apparatus, and providing a suitable means for detecting the ultra-violet flurescent dye at, or in the vicinity of, a leak point in the apparatus.

The present invention further provides a method for producing heating or cooling in a refrigeration, air-conditioning, or heat pump apparatus, the method comprising introducing a refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1 propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1 propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, into the apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger.

The present invention further provides a method for replacing the use of a high global warming potential refrigerant, the method comprising: providing the composition comprising at least one compound selected from the group consisting of:

1.1.2.3- tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1 -propene (HFC1243yc); 1,1,3-trifluoro-1 -propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a

4a

2017201286 11 Sep 2018 lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, in refrigeration, air conditioning, or heat pump apparatus in place of, or in combination with, a high global warming potential refrigerant in the apparatus.

The present invention further provides a method of using the composition comprising at least one compound selected from the group consisting of: 1,1,2,3tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc);

2.3.3- trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, to lower global warming potential (GWP) of an original refrigerant or heat transfer fluid composition, the method comprising combining the original refrigerant or heat transfer fluid composition with the composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alphaolefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, to produce a second refrigerant or heat transfer fluid composition wherein the second refrigerant or heat transfer fluid composition has a lower GWP than the original refrigerant or heat transfer fluid composition.

The present invention further provides a method for reducing the global warming potential (GWP) of an original refrigerant or heat transfer fluid composition in a refrigeration, air-conditioning or heat pump apparatus, wherein the original refrigerant or heat transfer fluid has a GWP of about 150 or higher; the method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

1.1.2.3- tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes,

4b

2017201286 11 Sep 2018 synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, into the refrigeration, air-conditioning or heat pump apparatus.

The present invention further provides a method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition, the method comprising providing a composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alphaolefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, as the second refrigerant or heat transfer fluid composition.

The present invention further provides method of using the composition comprising at least one compound selected from the group consisting of: 1,1,2,3tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc);

2.3.3- trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3trifluoro-1-propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof, as a heat transfer fluid composition, the method comprising transporting the composition from a heat source to a heat sink.

The present invention further provides a refrigeration, air-conditioning or heat pump apparatus containing a composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc);

1.1.3.3- tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.

The present invention further provides a mobile refrigeration or airconditioning apparatus containing the composition comprising at least one compound selected from the group consisting of: 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc);

1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf);

4c

2017201286 11 Sep 2018

1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1,2,3 trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1-propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure broadly relates to compositions comprising at least one fluoroolefin. By fluoroolefin is meant any compound containing carbon, fluorine and optionally, hydrogen or oxygen that also contains at least one double bond.

These fluoroolefins may be linear, branched or cyclic.

These compositions have a variety of utilities in working fluids, which include use as heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air-conditioning systems, heat pumps, chillers, and the like).

A heat transfer fluid (also referred to herein as a heat transfer composition or heat transfer fluid composition) is a working fluid used to carry heat from a heat source to a heat sink.

A refrigerant is a compound or mixture of compounds that function as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from a liquid to a gas and back.

The present invention provides a fluoroolefin listed in Table 1.

TABLE 1

Name	Structure	Chemical name
HFC-1438ezym	CHF=CHCF(CF3)2	1,3,4,4,4-pentafluoro-3(trifluoromethyl )-1 -butene

4d

2017201286 24 Feb 2017

The compound listed in Table 1 is available commercially or may be prepared by processes known in the art.

Fluoroolefins may be prepared from fluoroalkanes by dehydrofluorination over solid KOH in the vapor phase at room temperature. The synthesis of a fluoroalkane is described in US 6,066,768.

Fluoroolefins may be prepared from fluoroiodoalkanes by reaction with KOH using a phase transfer catalyst at about 60°C. The synthesis of a fluoroiodoalkane may be carried out by reaction of perfluoromethyl iodide (CF₃I) and fluoroalkane at about 200°C under autogenous pressure for about 8 hours.

Fluoroolefins may be prepared by dehydrofluorination of fluoroalkanes using solid KOH or over a carbon catalyst at 200-300°C. Fluoroalkanes may be prepared by hydrogenation of fluoroalkenes.

Fluoroolefins may be prepared by reacting fluoroalkanes with aqueous KOH at 120°C

Fluoroolefins may be prepared by the dehydrofluorination of fluoroiodoalkanes with KOH in isopropanol.

Fluoroolefins may be prepared by dehydrofluorination of fluoroalkanes over fluorided alumina at elevated temperature.

The compositions of the present invention may comprise a single compound or may further comprise other fluoroolefins. Additionally, the compounds of the present invention may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers or any combination thereof in any ratio.

Compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefin of the present invention or mixtures of fluoroolefin of this invention with other refrigerants will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding the fluoroolefin to said mixtures.

The compositions of the present invention that are combinations or mixtures may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

2017201286 24 Feb 2017

An alternative means for making a composition of the present invention comprises (i) reclaiming a volume of one or more components of a refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficiently to enable reuse of said one or more of the reclaimed components, (iii) and optionally, combining all or part of said reclaimed volume of components with at least one additional refrigerant composition or component.

A refrigerant container may be any container in which is stored a refrigerant blend composition that has been used in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Said refrigerant container may be the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus in which the refrigerant blend was used. Additionally, the refrigerant container may be a storage container for collecting reclaimed refrigerant blend components, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend or refrigerant blend component that may be moved out of the refrigerant container by any method known for transferring refrigerant blends or refrigerant blend components.

Impurities may be any component that is in the refrigerant blend or refrigerant blend component due to its use in a refrigeration apparatus, air-conditioning apparatus or heat pump apparatus. Such impurities include but are not limited to refrigeration lubricants, particulates such as metal or elastomer that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits.

The present invention also relates to a composition comprising HFC1438ezym fluoroolefin as defined above and at least one flammable refrigerant or heat transfer fluid.

2017201286 24 Feb 2017

Flammability of a fluoroolefin appears to be related to the numbers of fluorine atoms and the numbers of hydrogen atoms in the molecule. The equation below provides a flammability factor that may be calculated as an indication of predicted flammability:

flammability factor = F_ (F + H) wherein:

F = the number of fluorine atoms; and H = the number of hydrogen atoms in a molecule.

As certain compounds have been experimentally determined to be flammable, the cut-off for non-flammable fluoroolefin flammability factors has been determined. Fluoroolefins may be determined to be flammable or non-flammable by testing under conditions specified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) Standard 34-2001, under ASTM (American Society of Testing and Materials) E681 -01, with an electronic ignition source. Such tests of flammability are conducted with the compound of interest at 101 kPa (14.7 psia) and a specified temperature (often 100 °C (212 °F)) at various concentrations in air in order to determine the lower flammability limit (LFL) and/or upper flammability limit (UFL) of the test compound in air.

Fluoroolefins may be determined to be flammable or non-flammable based upon the value of the flammability factor. If the flammability factor is found to be equal to or greater than 0.70, then the fluoroolefin may be expected to be non-flammable. If the flammability factor is less than 0.70, then the fluoroolefin may be expected to be flammable.

While the flammability factor provides a basis for predicting flammability of certain fluoroolefin compounds, there may be certain variables, such as position of the hydrogen atoms on the molecule that would account for certain isomers with a given molecular formula being flammable while other isomers are non-flammable.

Therefore, the flammability factor may only be used as a tool for predicting flammability characteristics.

Flammable refrigerants comprise any compound, which may be demonstrated to propagate a flame under specified conditions of temperature, pressure and composition when mixed with air. Flammable refrigerants may be identified by testing under conditions specified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) Standard 34-2001, under

2017201286 24 Feb 2017

ASTM (American Society of Testing and Materials) E681 -01, with an electronic ignition source. Such tests of flammability are conducted with the refrigerant at 101 kPa (14.7 psia) and a specified temperature (typically 100 °C (212 °F), or room temperature, that being about 23 ^QC (73 ^QF) at various concentrations in air in order to determine the lower flammability limit (LFL) and upper flammability limit (UFL) of the test compound in air.

In practical terms, a refrigerant may be classified as flammable if upon leaking from a refrigeration apparatus or air-conditioning apparatus, and contacting an ignition source a fire may result. The compositions comprising HFC-1438ezym of the present invention, during such a leak, have a low probability of causing a fire.

Refrigerants comprising HFC-1438ezym of the present invention may further comprise hydrocarbon ethers, such as dimethyl ether (DME, CH₃OCH₃) and methyl t-butyl ether (MTBE, (CH₃)₃COCH₃), both available from multiple commercial sources.

Refrigerants comprising HFC-1438ezym of the present invention may further comprise ammonia (NH₃), a commercially available compound.

Examples of non-flammable refrigerants that may be combined with other refrigerants of the present invention include R-134a, R-134, R-23, R125, R-236fa, R245fa, and mixtures of HCFC-22/HFC-152a/HCFC-124 (known by the ASHRAE designations, R401 or R-401A, R-401B, and R-401C), HFC-125/HFC-143a/HFC-134a (known by the ASHRAE designation, R-404 or R-404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations, R407 or R-407A, R-407B, and R-407C), HCFC22/HFC-143a/HFC-125 (known by the ASHRAE designation, R408 or R-408A), HCFC 22/HCFC-124/HCFC-142b (known by the ASHRAE designation: R-409 or R-409A), HFC-32/HFC-125 (known by the ASHRAE designation R-410A), and HFC-125/HFC143a (known by the ASHRAE designation: R-507 or R507A) and carbon dioxide.

One aspect of the present invention is to provide a non-flammable refrigerant with a global warming potential of less than 150, preferably less than 50. Another aspect of the present invention is to reduce the flammability of flammable refrigeration mixtures by adding non-flammable fluoroolefins to said mixtures.

The composition comprising HFC-1438ezym of the present invention that are useful as refrigerants or heat transfer fluids may contain an effective amount of fluoroolefin to produce a composition that is non-flammable based upon results of ASTM E681-01.

The present inventive compositions comprising at least one flammable refrigerant and HFC-1438ezym fluoroolefin may contain about 1 weight percent to about 99 weight percent fluoroolefin and about 99 weight percent to about 1 weight

2017201286 24 Feb 2017 percent flammable refrigerant.

In another embodiment, the compositions of the present invention may contain about 10 weight percent to about 80 weight percent HFC-1438ezym fluoroolefin and about 90 weight percent to about 20 weight percent flammable refrigerant. In yet another embodiment, the compositions of the present invention may contain about 20 weight percent to about 70 weight percent HFC-1438ezym fluoroolefin and about 80 weight percent to about 30 weight percent flammable refrigerant.

The present invention further relates to a method for reducing the flammability of a flammable refrigerant said method comprising combining the flammable refrigerant with HFC-1438ezym fluoroolefin. The amount of fluoroolefin added must be an effective amount to produce a non-flammable composition as determined by ASTM 681 -01.

Composition comprising HFC-1438ezym of the present invention may be used in combination with a desiccant in a refrigeration, air-conditioning, or heat pump system to aid in removal of moisture. Desiccants may be composed of activated alumina, silica gel, or zeolite based molecular sieves. Representative molecular sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL). For refrigerants with small molecular size such as HFC-32, XH-11 desiccant is preferred.

The composition comprising HFC-1438ezym of the present invention may further comprise at least one lubricant. Lubricants useful with the compositions of the present invention comprise those suitable for use with refrigeration or air-conditioning apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled Lubricants in Refrigeration Systems, pages 8.1 through 8.21, herein incorporated by reference. Lubricants useful with the compositions of the present invention may comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants useful with the compositions of the present invention may further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, and poly(alphaolefins). Representative conventional lubricants useful with the compositions of the present invention are the

2017201286 24 Feb 2017 commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), Suniso® 3GS and Suniso® 5GS (naphthenic mineral oil sold by Crompton Co.), Sontex®

372LT (naphthenic mineral oil sold by Pennzoil), Calumet® RO-30 (naphthenic mineral oil sold by Calumet Lubricants), Zerol® 75, Zerol® 150 and Zerol® 500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).

Lubricants useful with the compositions of the present invention further comprise those, which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air-conditioning apparatus’ operating conditions. Such lubricants and their properties are discussed in “Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs).

Lubricants useful with the compositions of the present invention are selected by considering a given compressor’s requirements and the environment to which the lubricant will be exposed.

Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, foaming and antifoam control agents, leak detectants and the like. In general, these additives are present only in small amounts relative to the overall lubricant composition. They are typically used at concentrations of from less than about 0.1 % to as much as about 3 % of each additive. These additives are selected on the basis of the individual system requirements. Some typical examples of such additives may include, but are not limited to, lubrication enhancing additives, such as alkyl or aryl esters of phosphoric acid and of thiophosphates. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and assymetrical polyhydroxyl lubrication additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as antioxidants, free radical scavengers, and water scavengers (drying compounds) may be employed. Such additives include but are not limited to, nitromethane, hindered phenols (such as butylated hydroxy toluene, or BHT), hydroxylamines, thiols,

2017201286 24 Feb 2017 phosphites, epoxides or lactones. Water scavengers include but are not limited to ortho esters such as trimethyl-, triethyl-, or tripropylortho formate. Single additives or combinations may be used.

In one embodiment, the present invention provides compositions comprising HFC-1438ezym and at least one stabilizer selected from the group consisting of thiophosphates, butylated triphenylphosphorothionates, organo phosphates, dialkylthiophosphate esters, terpenes, terpenoids, fullerenes, functionalized perfluoropolyethers, polyoxyalkylated aromatics, epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thiols, lactones, thioethers, nitromethanes, alkylsilanes, benzophenone derivatives, arylsulfide, divinyl terephthalate, diphenyl terephthalate, alkylamines, hindered amine antioxidants, and phenols, The alkylamines can include triethylamine, tributylamine, diisopropylamine, triisopropylamine, triisobutylamine, and other members of this family of alkylamine compounds.

In another embodiment, the stabilizers useful with the compositions of the present invention may comprise specific combinations of stabilizers. One combination of stabilizers of particular interest comprises at least one terpene or terpenoid. These terpenes or terpenoids may be combined with at least one compound selected from epoxides, fluorinated epoxides, and oxetanes.

Terpenes are hydrocarbon compounds characterized by structures containing more than one repeating isoprene (2-methyl-1,3-butadiene) unit. Terpenes may be acyclic or cyclic. Representative terpenes include but are not limited to myrcene (2-methyl-6-methyl-eneocta-1,7-diene), allo-cimene, beta-ocimene, terebene, limonene (or d-limonene), retinal, pinene (or alpha-pinene), menthol, geraniol, farnesol, phytol, Vitamin A, terpinene, delta-3-carene, terpinolene, phellandrene, fenchene and mixtures thereof. Terpene stabilizers are commercially available or may be prepared by methods known in the art or isolated from natural sources.

Terpenoids are natural products and related compounds characterized by structures containing more than one repeating isoprene unit and optionally contain oxygen. Representative terpenoids include carotenoids, such as lycopene (CAS reg. no. [502-65-8]), betacarotene (CAS reg. no. [7235-40-7]), and xanthophylls, i.e. zeaxanthin (CAS reg. no. [144-68-3]); retinoids, such as hepaxanthin (CAS reg. no. [512-39-0]), and isotretinoin (CAS reg. no. [4759-48-2]); abietane (CAS reg. no. [64043-7]); ambrosane (CAS reg. no. [24749-18-6]); aristolane (CAS reg. no. [29788-496]); atisane (CAS reg. no. [24379-83-7]); beyerane (CAS reg. no. [2359-83-3]), bisabolane (CAS reg. no. [29799-19-7]); bornane (CAS reg. no. [464-15-3]); caryophyllane (CAS reg. no. [20479-00-9]); cedrane (CAS reg. no. [13567-54-9]);

2017201286 24 Feb 2017 dammarane (CAS reg. no. [545-22-2]); drimane (CAS reg. no. [5951-58-6]); eremophilane (CAS reg. no. [3242-05-5]); eudesmane (CAS reg. no. [473-11-0]); fenchane (CAS reg. no. [6248-88-0]); gammacerane (CAS reg. no. [559-65-9]); germacrane (CAS reg. no. [645-10-3]); gibbane (CAS reg. no. [6902-95-0]); grayanotoxane (CAS reg. no. [39907-73-8]); guaiane (CAS reg. no. [489-80-5]); himachalane (CAS reg. no. [20479-45-2]); hopane (CAS reg. no. [471-62-5]); humulane (CAS reg. no. [430-19-3]); kaurane (CAS reg. no. [1573-40-6]); labdane (CAS reg. no. [561-90-0]); lanostane (CAS reg. no. [474-20-4]); lupane (CAS reg. no. [464-99-3]); p-menthane (CAS reg. no. [99-82-1]); oleanane (CAS reg. no. [471-67-0]); ophiobolane (CAS reg. no. [20098-65-1]); picrasane (CAS reg. no. [35732-97-9]); pimarane (CAS reg. no. [30257-03-5]); pinane (CAS reg. no. [473-55-2]); podocarpane (CAS reg. no. [471-78-3]); protostane (CAS reg. no. [70050-78-1]); rosane (CAS reg. no. [6812-82-4]); taxane (CAS reg. no. [1605-68-1]); thujane (CAS reg. no. [471-12-5]); trichothecane (CAS reg. no. [24706-08-9]); and ursane (CAS reg. no. [464-93-7]). The terpenoids of the present invention are commercially available or may be prepared by methods known in the art or may be isolated from the naturally occurring source.

In one embodiment, the terpene or terpenoid stabilizers may be combined with at least one epoxide. Representative epoxides include 1,2-propylene oxide (CAS reg. no. [75-56-9]); 1,2-butylene oxide (CAS reg. no. [106-88-7]); or mixtures thereof.

In another embodiment, the terpene or terpenoid stabilizers useful with the compositions of the present invention may be combined with at least one fluorinated epoxide. The fluorinated epoxides may be depicted by Formula 3, wherein each of R² through R5 is H, alkyl of 1 - 6 carbon atoms or fluoroalkyl of 1 -6 carbon atoms with the proviso that at least one of R² through R⁵ is a fluoroalkyl group.

R³ R⁵

Formula 3

Representative fluorinated epoxide stabilizers include but are not limited to trifluoromethyloxirane and 1,1 -bis(trifluoromethyl)oxirane. Such compounds may be prepared by methods known in the art, for instance by methods described in, Journal of Fluorine Chemistry, volume 24, pages 93-104 (1984), Journal of Organic Chemistry,

2017201286 24 Feb 2017 volume 56, pages 3187 to 3189 (1991), and Journal of Fluorine Chemistry, volume 125, pages 99-105 (2004).

In another embodiment, the terpene or terpenoid stabilizers useful with the compositions of the present invention may be combined with at least one oxetane. The oxetane stabilizers may be compounds with one or more oxetane groups and is represented by Formula 4, wherein Ri-R₆ are the same or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

Formula 4

Representative oxetane stabilizers include but are not limited to 3-ethyl-3hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co., Ltd); and 3-ethyl-3-((2ethyl-hexyloxy)methyl)-oxetane, such as OXT-212 (Toagosei Co., Ltd).

Another embodiment of particular interest is a combination of stabilizers comprising fullerenes. The fullerene stabilizers may be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. The epoxides, fluorinated epoxides, and oxetanes for combination with fullerenes have been previously described herein as for combination with terpenes or terpenoids.

Another embodiment of particular interest is a combination of stabilizers comprising phenols. The fullerene stabilizers may be combined with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes. The epoxides, fluorinated epoxides, and oxetanes for combination with phenols have been previously described herein as for combination with terpenes or terpenoids.

Phenol stabilizers comprise any substituted or unsubstituted phenol compound including phenols comprising one or more substituted or unsubstituted cyclic, straight chain, or branched aliphatic substituent group, such as, alkylated monophenols including 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinone and alkylated hydroquinones including t-butyl hydroquinone, other derivatives of hydroquinone; and the like, hydroxylated thiodiphenyl ethers, including 4,4’-thio-bis(2-methyl-6-tert13

2017201286 24 Feb 2017 butylphenol); 4,4’-thiobis(3-methyl-6-tertbutylphenol); 2,2’-thiobis(4methyl-6-tertbutylphenol); and the like, alkylidene-bisphenols including,: 4,4’-methylenebis(2,6-ditert-butylphenol); 4,4’-bis(2,6-di-tert-butylphenol); derivatives of 2,2’- or 4,4biphenoldiols; 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); 2,2’-methylenebis(4methyl-6-tertbutylphenol); 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4,4isopropylidenebis(2,6-di-tert-butylphenol); 2,2’-methylenebis(4-methyl-6-nonylphenol); 2,2’-isobutylidenebis(4,6-dimethylphenol; 2,2’-methylenebis(4-methyl-6cyclohexylphenol, 2,2- or 4,4- biphenyldiols including 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); butylated hydroxyl toluene (BHT), bisphenols comprising heteroatoms including 2,6-di-tert-alpha-dimethylamino-p-cresol, 4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N’-dimethylaminomethylphenol); sulfides including; bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tertbutyl-4-hydroxybenzyl)sulfide; and the like.

In one embodiment of the present invention, these combinations of stabilizers comprising terpenes or terpenoids, or fullerenes or phenols with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes, may further comprise an additional stabilizer compound selected from the group consisting of:

areoxalyl bis(benzylidene)hydrazide (CAS reg. no. 6629-10-3); N,N’-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS reg. no. 3268778-8);

2,2’-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate) (CAS reg. no. 70331-94-1);

N,N’-(disalicyclidene)-1,2-propanediamine (CAS reg. no. 94-91-1); and ethyenediaminetetraacetic acid (CAS reg. no. 60-00-4) and salts thereof.

In another embodiment of the present invention, these combinations of stabilizers comprising terpenes or terpenoids, or fullerenes or phenols with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes, may further comprise at least one alkylamine selected from the group consisting of triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amine antioxidants.

The compositions of the present invention may further comprise a compound or composition that is a tracer and is selected from the group consisting of hydrofluorocarbon (HFCs), deuterated hydrocarbon, deuterated hydrofluorocarbon, perfluorocarbons, fluoroether, brominated compound, iodated compound, alcohol, aldehyde, ketones, nitrous oxide (N₂O) and combinations thereof. The tracer used in the present invention are different compositions from those used as refrigerant or heat

2017201286 24 Feb 2017 transfer fluids, are added to the refrigerant and heat transfer compositions in previously determined quantities to allow detection of any dilution, contamination or other alteration of the composition, as described in U. S. 2005/0230657.

Typical tracer compounds for use in the present compositions are listed in

Table 2.

TABLE 2

Compound	Structure
Deuterated hydrocarbons and hydrofluorocarbons
Ethane-d6	CD3CD3
Propane-d8	CD3CD2CD3
HFC-32-d2	CD2F2
HFC-134a-d2	CD2FCF3
HFC-143a-d3	CD3CF3
HFC-125-d	CDF2CF3
HFC-227ea-d	CF3CDFCF3
HFC-227ca-d	CF3CF2CDF2
HFC-134-d2	CDF2CDF2
HFC-236fa-d2	CF3CD2CF3
HFC-245cb-d3	CF3CF2CD3
HFC-263fb-d2*	CF3CD2CH3
HFC-263fb-d3	CF2CH2CD3
Fluoroethers
HFOC-125E	CHF2OCF3
HFOC-134aE	CH2FOCF3
HFOC-143aE	CH3OCF3
HFOC-227eaE	CF3OCHF-F3
HFOC-236faE	CF3OCH2CF3
HFOC-245faE3y or HFOC245faEa3	CHF2OCH2CF3 (or CHF2CH2OCF3)
HFOC-245cbE3y or HFOC-245cboc3	CH3OCF2CF3 (or CH3CF2OCF3)
HFE-42-11 mcc (or Freon® E1)	CF3CF2CF2OCHFCF3
Freon® E2	CF3CF2CF2OCF(CF3)CF2OCHFCF3

2017201286 24 Feb 2017

Hydrofluorocarbons
HFC-23	CHFg
HFC-161	CH3CH2F
HFC-152a	CH3CHF2
HFC-134	CHF2CHF2
HFC-227ea	CF3CHFCF3
HFC-227ca	CHF2CF2CF3
HFC-236cb	CH2FCF2CF3
HFC-236ea	CF3CHFCHF2
HFC-236fa	CF3CH2CF3
HFC-245cb	CF3CF2CH3
HFC-245fa	CHF2CH2CF3
HFC-254cb	CHF2CF2CH3
HFC-254eb	CF3CHFCH3
HFC-263fb	CF3CH2CH3
HFC-272ca	CH3CF2CH3
HFC-281ea	CH3CHFCH3
HFC-281fa	CH2FCH2CH3
HFC-329p	CHF2CF2CF2CF3
HFC-329mmz	(CHg) 2CHCF3
HFC-338mf	CF3CH2CF2CF3
HFC-338pcc	CHF2CF2CF2CHF2
HFC-347S	CH3CF2CF2CF3
HFC-43-10mee	CF3CHFCHFCF2CF3
Perfluorocarbons
PFC-116	CF3CF3
PFC-C216	Cyclo(-CF2CF2CF2-)
PFC-218	CF3CF2CF3
PFC-C318	Cyclo(-CF2CF2CF2CF2-)
PFC-31-10mc	CF3CF2CF2CF3
PFC-31-10my	(CF3)2CFCF3
PFC-C51-12mycm	Cyclo(-CF(CF3)CF2CF(CF3)CF2-)
PFC-C51 -12mym, trans	Cyclo(-CF2CF(CF3)CF(CF3CF2-)
PFC-C51-12mym, cis	Cyclo(-CF2CF(CF3)CF(CF3)CF2-)
Perfluoromethylcyclo-pentane	Cyclo(-CF2CF2(CF3)CF2CF2CF2-)

2017201286 24 Feb 2017

Perfluoromethylcyclo-hexane	Cyclo(-CF2CF2(CF3)CF2CF2CF2CF2-)
Perfluorodimethylcyclo-hexane (ortho, meta, or para)	Cyclo(-CF2CF2(CF3)CF2CF2(CF3)CF2-)
Perfluoroethylcyclohexane	Cyclo(-CF2CF2(CF2CF3)CF2CF2CF2CF2- )
Perfluoroindan	C9F10 (see structure below)

c

F

Perfluorotrimethylcyclo-hexane (all possible isomers)	Cyclo(- CF2(CF3)CF2(CF3)CF2CF2(CF3)CF2-)
Perfluoroisopropylcyclo-hexane	Cyclo(- CF2CF2(CF2(CF3)2)CF2CF2CF2CF2-)
Perfluorodecalin (cis or trans, trans	C-ioF18 (see structure below)
shown)
Perfluoromethyldecalin (cis or trans	C11F20 (see structure below)
and all additional possible isomers)	Γ F F F F f
Brominated compounds
Bromomethane	CH3Br
Bromofluoromethane	CH2FBr
Bromodifluoromethane	CHF2Br
Dibromofluoromethane	CHFBr2
Tribromomethane	CHBr3
Bromoethane	CH3CH2Br
Bromoethene	CH2=CHBr
1,2-dibromoethane	CH2BrCH2Br
1 -bromo-1,2-difluoroethene	CFBr=CHF

2017201286 24 Feb 2017

lodated compounds
lodotrifluoromethane	CF3I
Difluoroiodomethane	chf2i
Fluoroiodomethane	ch2fi
1,1,2-trif luoro-1 -iodoethane	cf2ich2f
1,1,2,2-tetrafluoro-1 -iodoethane	cf2ichf2
1,1,2,2-tetrafluoro-1,2-diiodoethane	cf2icf2i
lodopentafluorobenzene	c6f5i
Alcohols
Ethanol	ch3ch2oh
n-propanol	ch3ch2ch2oh
Isopropanol	CH3CH(OH)CH3
Aldehydes and Ketones
Acetone (2-propanone)	CH3C(O)CH3
n-propanal	ch3ch2cho
n-butanal	ch3ch2ch2cho
Methyl ethyl ketone (2-butanone)	CH3C(O)CH2CH3
Other
Nitrous oxide	n2o

The compounds listed in Table 2 are available commercially (from chemical supply houses) or may be prepared by processes known in the art.

Single tracer compounds may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain two or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.

Additionally, some compounds exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a tracer blend.

The tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm.

2017201286 24 Feb 2017

Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.

The compositions of the present invention may further comprise an ultraviolet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant composition or heat transfer fluids by permitting one to observe the fluorescence of the dye in the refrigerant or heat transfer fluid composition at or in the vicinity of a leak point in said apparatus in the refrigeration, airconditioning, heat pump apparatus. One may observe the fluorescence of the dye under an ultra-violet light. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants and heat transfer fluids.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum.

The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if refrigerant or heat transfer fluid containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point, or in the vicinity of the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye or combinations thereof. Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1 -trifluoroalkanes.

Hydrocarbon solubilizing agents useful with the compositions of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 16 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane.

Hydrocarbon ether solubilizing agents useful with the compositions of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Polyoxyalkylene glycol ether solubilizing agents useful with the compositions of the present invention are represented by the formula R¹[(OR²)xOR³]y, wherein: x is an integer from 1 -3; y is an integer from 1 -4; R¹ is selected from

2017201286 24 Feb 2017 hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R² is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R³ is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹ and R³ is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. As used herein, bonding sites mean radical sites available to form covalent bonds with other radicals. Hydrocarbylene radicals mean divalent hydrocarbon radicals. In the present invention, preferred polyoxyalkylene glycol ether solubilizing agents are represented by R¹[(OR²)xOR³]y: x is preferably 1-2; y is preferably 1; R¹ and R³ are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R² is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. The R¹ and R³ hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R¹ and R³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/t-butyl, pentyl, isopentyl, neopentyl, /erf-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar®), R¹ and R³ are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R² aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR²)_X - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R² in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R² oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R¹ is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. Representative R¹ aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R¹ aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.

2017201286 24 Feb 2017

Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃) (propylene glycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropylene glycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃) (tripropylene glycol methyl (or dimethyl) ether), C₂H₅OCH₂CH(CH₃)O(H or C₂H₅) (propylene glycol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₂(H or C₂H₅) (dipropylene glycol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (or diethyl) ether), C₃H₇OCH₂CH(CH₃)O(H orC₃H₇) (propylene glycol n-propyl (or di-n-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₂(H orC₃H₇) (dipropylene glycol n-propyl (or di-n-propyl) ether) , C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇) (tripropylene glycol n-propyl (or di-n-propyl) ether), C₄H₉OCH₂CH(CH₃)OH (propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉) (dipropylene glycol n-butyl (or di-n-butyl) ether), C₄H₉O[CH₂CH(CH₃)O]₃(H or C₄H₉) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH₃)₃COCH₂CH(CH₃)OH (propylene glycol t-butyl ether), (CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol t-butyl (or di-t-butyl) ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropylene glycol t-butyl (or di-t-butyl) ether), C₅H₁₁OCH₂CH(CH₃)OH (propylene glycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH (butylene glycol n-butyl ether),

C₄H₉O[CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether), trimethylolpropane tri-nbutyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) and trimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide solubilizing agents useful with the compositions of the present invention comprise those represented by the formulae R¹C(O)NR²R³ and cyclo[R⁴C(O)N(R⁵)], wherein R¹, R², R³ and R⁵are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R¹, R², R³ and R⁵ may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹, R², R³ and R⁵may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three nonhydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹'³, and the presence of any such nonhydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents

2017201286 24 Feb 2017 consist of carbon, hydrogen, nitrogen and oxygen. Representative R¹, R², R³ and R⁵ aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/t-butyl, pentyl, isopentyl, neopentyl, te/t-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents are those wherein R⁴ in the aforementioned formula cyclo-[R⁴C(0)N(R⁵)-] may be represented by the hydrocarbylene radical (CR⁶R⁷)n, in other words, the formula: cyclo-[(CR⁶R⁷)nC(0)N(R⁵)-] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R⁵ is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R⁶ and R⁷are independently selected (for each n) by the rules previously offered defining R¹'³. In the lactams represented by the formula: cyclo[(CR⁶R⁷)_nC(O)N(R⁵)-], all R⁶ and R⁷ are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R⁵ is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones.

Representative amide solubilizing agents include but are not limited to: 1octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butylpyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1dodecylpyrrolid-2-one, Ν,Ν-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents useful with the compositions of the present invention comprise ketones represented by the formula R¹C(O)R², wherein R¹ and R² are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R¹ and R² in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R¹ and R² may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R² may optionally include substituted hydrocarbon radicals, that is, radicals containing nonhydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms.

2017201286 24 Feb 2017

In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹ and R², and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations.

Representative R¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R¹C(O)R² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, te/t-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone solubilizing agents include but are not limited to: 2butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents useful with the compositions of the present invention comprise nitriles represented by the formula R¹CN, wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R¹ in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units. R¹ may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R¹ aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R¹CN include pentyl, isopentyl, neopentyl, te/t-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

2017201286 24 Feb 2017

Representative nitrile solubilizing agents include but are not limited to: 1 cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents useful with the compositions of the present invention comprise chlorocarbons represented by the formula RCI_X, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RCI_X include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te/t-butyl, pentyl, isopentyl, neopentyl, te/t-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents useful with the compositions of the present invention comprise esters represented by the general formula R¹CO₂R², wherein R¹ and R²are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.

Representative esters include but are not limited to: (CH3)2CHCH2OOC(CH2)2-4OCOCH₂CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a commercial C₇ alkyl acetate), “Exxate 800” (a commercial C₈ alkyl acetate), dibutyl phthalate, and tert-butyl acetate.

Lactone solubilizing agents useful with the compositions of the present invention comprise lactones represented by structures [A], [B], and [C]:

2017201286 24 Feb 2017

These lactones contain the functional group -CO2- in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R1 through R₈ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 through R₈ may be connected forming a ring with another R1 through R₈. The lactone may have an exocyclic alkylidene group as in structure [C], wherein R1 through R₆ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals.

Each R1 though R₆ may be connected forming a ring with another R1 through R₆. The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units.

Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 3.

TABLE 3

Additive	Molecular Structure	Molecular Formula	Molecular Weight (amu)
(E,Z)-3-ethylidene-5- methyl-dihydro-furan-2- one		C7H10O2	126
(E,Z)-3-propylidene-5- methyl-dihydro-furan-2- one		08Ηι202	140
(E,Z)-3-butylidene-5- methyl-dihydro-furan-2- one		C9H14O2	154
(E,Z)-3-pentylidene-5- methyl-dihydro-furan-2- one		C10H16O2	168
(E,Z)-3-Hexylidene-5- methyl-dihydro-furan-2- one		ΟιιΗι8Ο2	182
(E,Z)-3-Heptylidene-5- methyl-dihydro-furan-2- one		C12H20O2	196

2017201286 24 Feb 2017

(E,Z)-3-octylidene-5- methyl-dihydro-furan-2- one		C13H22O2	210
(E,Z)-3-nonylidene-5- methyl-dihydro-furan-2- one	-	C14H24O2	224
(E,Z)-3-decylidene-5- methyl-dihydro-furan-2- one	-	C15H26O2	238
(E,Z)-3-(3,5,5- trimethylhexylidene)-5- methyl-dihydrofuran-2- one		C14H24O2	224
(E,Z)-3- cyclohexylmethylidene- 5-methyl-dihydrofuran- 2-one		C12H18O2	194
gamma-octalactone		CgHuO2	142
gamma-nonalactone		C9H16O2	156
gamma-decal acto n e		C10H18O2	170
gamma-undecalactone	Cr	C11H20O2	184
gamma-dodecalactone	''''''Cm	C12H22O2	198
3-hexyldihydro-furan-2- one	o	C10H18O2	170
3-heptyldihydro-furan-2- one	0	C11H20O2	184
c/s-3-ethyl-5-methyl- dihydro-furan-2-one	0	C7H12O2	128
c/s-(3-propyl-5-methyl)- dihydro-furan-2-one		C8H14O2	142
c/s-(3-butyl-5-methyl)- dihydro-furan-2-one	—	C9H16O2	156
c/s-(3-pentyl-5-methyl)- dihydro-furan-2-one		C10H18O2	170

2017201286 24 Feb 2017

c/s-3-hexyl-5-methyl- dihydro-furan-2-one	0	C11H20O2	184
c/s-3-heptyl-5-methyl- dihydro-furan-2-one	0	C12H22O2	198
c/s-3-octyl-5-methyl- dihydro-furan-2-one	0	C13H24O2	212
c/s-3-(3,5,5- trimethylhexyl)-5- methyl-dihydro-furan-2- one		C14H26O2	226
c/s-3-cyclohexylmethyl- 5-methyl-dihydro-furan- 2-one	σΝ	C12H20O2	196
5-methyl-5-hexyl- dihydro-furan-2-one	0	C11H20O2	184
5-methyl-5-octyl- dihydro-furan-2-one	0	C13H24O2	212
Hexahydroisobenzofuran-1 -one	H	C8H12O2	140
cfe/te-decalactone		Ci0Hi8O2	170
cfe/te-undecalactone		C11H20O2	184
cfe/te-dodecalactone		C12H22O2	198
mixture of 4-hexyldihydrofuran-2-one and 3-hexyl-dihydro-furan-2one			C10H18O2	170

Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40°C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40°C. Lactone solubilizing agents may be available commercially or prepared by methods as described in US 2006/030719.

2017201286 24 Feb 2017

Aryl ether solubilizing agents useful with the compositions of the present invention further comprise aryl ethers represented by the formula R¹OR², wherein: R¹ is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R¹ aryl radicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatic hydrocarbon radicals in the general formula R¹OR² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and te/t-butyl. Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents useful with the compositions of the present invention comprise those represented by the general formula R¹OCF2CF2H, wherein R¹ is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C8H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether.

Fluoroether solubilizing agents may further comprise ethers derived from fluoroolefins and polyols. The fluoroolefins may be of the type CF₂=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃ or ORf, wherein R_f is CF₃, C₂F₅, or C₃F₇. Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. Linear polyols may be of the type

HOCH₂(CHOH)_x(CRR’)yCH₂OH, wherein R and R’ are hydrogen, or CH₃, or C₂H₅ and wherein x is an integer from 0-4, and y is an integer from 0-4. Branched polyols may be of the type C(OH)t(R)_u(CH₂OH)_v[(CH₂)_mCH₂OH]_w, wherein R may be hydrogen, CH₃ or C₂H₅, m may be an integer from 0 to 3, t and u may be 0 or 1, v and w are integers from 0 to 4, and also wherein t + u + v + w = 4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.

1,1,1-Trifluoroalkane solubilizing agents useful with the compositions of the present invention comprise 1,1,1 -trifluoroalkanes represented by the general formula CF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1 -trifluoroalkane solubilizing agents include but are not limited to: 1,1,1 -trifluorohexane and 1,1,1 -trifluorododecane.

2017201286 24 Feb 2017

Solubilizing agents useful with the compositions of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.

In the present compositions comprising HFC-1438ezym refrigerant and UV fluorescent dye, or comprising HFC-1438ezym heat transfer fluid and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

Solubility of these UV fluorescent dyes in refrigerant and heat transfer compositions may be poor. Therefore, methods for introducing these dyes into the refrigeration, air-conditioning, or heat pump apparatus have been awkward, costly and time consuming. US-RE-36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or airconditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air-conditioning apparatus are described in the literature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerant thereby not requiring any specialized method for introduction to the refrigeration, airconditioning, or heat pump apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the HFC-1438ezym refrigerant in combination with a solubilizing agent. The inventive compositions will allow the storage and transport of dye-containing refrigerant or heat transfer fluid even at low temperatures while maintaining the dye in solution.

In the present compositions comprising HFC-1438ezym refrigerant, UV fluorescent dye and solubilizing agent, or comprising HFC-1438ezym heat transfer fluid and UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant or heat transfer fluid. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant or heat transfer fluid, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

2017201286 24 Feb 2017

Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel, all of which are commercially available, as well as d-limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001 % to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.

The present invention further relates to a method of using the HFC1438ezym refrigerant or heat transfer fluid compositions comprising ultraviolet fluorescent dye to detect leaks in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus. The presence of the dye in the compositions allows for detection of leaking refrigerant in the refrigeration, air-conditioning, or heat pump apparatus. Leak detection helps to address, resolve and/or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps to contain chemicals used in the operation of the apparatus.

The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye or comprising heat transfer fluid and UV fluorescent dye, as described herein, and optionally, a solubilizing agent as described herein, to refrigeration, air-conditioning, or heat pump apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamps, often referred to as a “black light” or “blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for detecting UV fluorescent dye. Once the ultra-violet fluorescent dye containing composition has been introduced to the refrigeration, air-conditioning, or heat pump apparatus and has been allowed to circulate throughout the system, a leak point or the vicinity of the leak point can be located by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point.

Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector, and air.

Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle reuses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid

2017201286 24 Feb 2017 refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.

There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified as reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed.

The compositions of the present invention comprising HFC-1438ezym fluoroolefin may be useful in any of the compressor types mentioned above. The choice of refrigerant for any given compressor will depend on many factors including for instance, boiling point and vapor pressure requirements.

Either positive displacement or dynamic compressors may be used in the present inventive processes. A centrifugal type compressor is one preferred type of equipment for certain of the refrigerant compositions comprising HFC-1438ezym fluoroolefin.

A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is a stage of the compressor. Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure. Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities.

Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to

2017201286 24 Feb 2017 zero or nearly zero. A positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure.

Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression.

The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity.

Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine. A centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1,2,2trichlorotrifluoroethane (CFC-113). The refrigerant of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal equipment.

Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors (mini-centrifugal compressors) are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters (about 6 inches).

A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a compression ratio of about 4 to 1; that is, the absolute discharge pressure can be four times the absolute suction pressure. Several examples of twostage centrifugal compressor systems, particularly for automotive applications, are described in US-A-5 065 990 and US-A-5 363 674.

The present disclosure further relates to a method for producing heating or cooling in a refrigeration, air-conditioning, or heat pump apparatus, said method comprising introducing a refrigerant or heat transfer fluid composition into said apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger; wherein said refrigerant or heat transfer fluid composition comprises HFC-1438ezym.

2017201286 24 Feb 2017

The method for producing heating or cooling may be used in stationary airconditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air-conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self-contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

The composition of the present invention may additionally be used in airconditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the HFC1438ezym refrigerant composition of the present invention. A low operating pressure and density, if observed, result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat exchanger arrangement may be used. Therefore, a preferred heat exchanger for the HFC-1438ezym refrigerant or heat transfer fluid compositions of the present invention is a single slab/single pass heat exchanger.

The present invention further relates to a process for producing cooling comprising evaporating the HFC-1438ezym fluoroolefin composition of the present invention in the vicinity of a body to be cooled, and thereafter condensing said composition.

The present invention further relates to a process for producing heat comprising condensing the HFC-1438ezym fluoroolefin composition of the present invention in the vicinity of a body to be heated, and thereafter evaporating said composition.

The present invention further relates to a process to produce cooling comprising compressing a composition comprising HFC-1438ezym fluoroolefin in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be cooled. Additionally, the centrifugal compressor of the inventive method may be a multi-stage centrifugal compressor and preferably a 2-stage centrifugal compressor.

The present invention further relates to a process to produce cooling in a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said apparatus comprises at least one single slab/single pass heat exchanger, said process comprising condensing a composition comprising HFC-1438ezym fluoroolefin

2017201286 24 Feb 2017 of the present invention, and thereafter evaporating said composition in the vicinity of a body to be cooled.

The composition of the present invention are particularly useful in small turbine centrifugal compressors (mini-centrifugal compressors), which can be used in auto and window air-conditioning, heat pumps, or transport refrigeration, as well as other applications. These high efficiency mini-centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R134a automobile air-conditioning system. When the cycling operation of conventional systems at high driving speeds is taken into account, the advantage of these low pressure systems becomes even greater.

Alternatively, rather than use electrical power, the mini-centrifugal compressor may be powered by an engine exhaust gas driven turbine or a ratioed gear drive assembly with ratioed belt drive. The electrical power available in current automobile design is about 14 volts, but the new mini-centrifugal compressor requires electrical power of about 50 volts. Therefore, use of an alternative power source would be advantageous. A refrigeration apparatus or air-conditioning apparatus powered by an engine exhaust gas driven turbine is described in detail in WO 2006/094304. A refrigeration apparatus or air-conditioning apparatus powered by a ratioed gear drive assembly is described in detail in WO 2006/102492.

The present invention further relates to a process to produce cooling comprising compressing a composition comprising HFC-1438ezym of the present invention, in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.

The present invention further relates to a process to produce cooling comprising compressing a composition comprising HFC-1438ezym of the present invention, in a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.

The present invention relates to a process to produce cooling in a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said apparatus comprises at least one single slab/single pass heat exchanger, said process comprising compressing a composition comprising HFC-1438ezym of the

2017201286 24 Feb 2017 present invention, in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be cooled.

The present invention further relates to a method for replacing or substituting for a refrigerant composition having a GWP of about 150 or more, or a high GWP refrigerant, with a composition having a lower GWP. One method comprises providing a composition comprising HFC-1438ezym fluoroolefin of the present invention as the replacement. In another embodiment of the present invention the refrigerant or heat transfer fluid composition comprising HFC-1438ezym of the present invention, having a lower GWP than the composition being replaced or substituted is introduced into the refrigeration, air conditioning or heat pump apparatus In some cases, the high GWP refrigerant present in the apparatus will need to be removed from the apparatus before introduction of the lower GWP compositions. In other cases, the HFC-1438ezym fluoroolefin composition of the present invention may be introduced into the apparatus while the high GWP refrigerant is present.

Global warming potentials (GWPs) are an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100 year time horizon is commonly the value referenced.

A high GWP refrigerant would be any compound capable of functioning as a refrigerant or heat transfer fluid having a GWP at the 100 year time horizon of about 1000 or greater, alternatively 500 or greater, 150 or greater, 100 or greater, or 50 or greater. Refrigerants and heat transfer fluids that are in need of replacement, based upon GWP calculations published by the Intergovernmental Panel on Climate Change (IPCC), include but are not limited to HFC-134a (1,1,1,2-tetrafluoroethane).

It is envisioned that the HFC-1438ezym compositions of the present invention may have zero or low ozone depletion potential and low global warming potential (GWP). The HFC-1438ezym fluoroolefin of the present invention or mixtures of HFC-1438ezym fluoroolefin with other refrigerants may have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. Typically, the HFC-1438ezym fluoroolefin of the present invention are expected to have GWP of less than about 25. One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding HFC-1438ezym fluoroolefin to said mixtures.

2017201286 24 Feb 2017

The present invention further relates to a method for lowering the GWP of a refrigerant or heat transfer fluid, said method comprising combining said refrigerant or heat transfer fluid with HFC-1438ezym fluoroolefin of the present invention. In another embodiment, the method for lowering the global warming potential comprises combining a first composition with a composition comprising HFC-1438ezym fluorolefin, to produce a second composition suitable for use as a refrigerant or heat transfer fluid, and wherein said second composition has a lower global warming potential than said first composition. It may be determined that the GWP of a mixture or combination of compounds may be calculated as a weighted average of the GWP for each of the pure compounds.

The present invention further relates to a method of using the composition of the present invention comprising HFC-1438ezym fluoroolefin to lower global warming potential of an original refrigerant or heat transfer fluid composition, said method comprising combining said original refrigerant or heat transfer fluid composition with the composition of the present invention comprising HFC-1438ezym fluoroolefin, to produce a second refrigerant or heat transfer fluid composition wherein said second refrigerant or heat transfer fluid composition has a lower global warming potential than said original refrigerant or heat transfer fluid composition.

The present invention further relates to a method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, airconditioning or heat pump apparatus, wherein said original refrigerant or heat transfer fluid has a GWP of about 150 or higher; said method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition of the present invention into said refrigeration, air-conditioning or heat pump apparatus.

The present method for reducing the GWP of an original refrigerant may further comprise removing the original refrigerant or heat transfer fluid composition from said refrigeration, air-conditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer fluid is introduced.

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition comprising providing a composition of the present invention as the second refrigerant or heat transfer fluid composition. An original refrigerant may be any refrigerant being used in a refrigeration, air-conditioning or heat pump apparatus in need of replacement.

The original refrigerant or heat transfer fluid needing replacement may be any of hydrofluorocarbon refrigerants, chlorofluorocarbon refrigerants,

2017201286 24 Feb 2017 hydrochlorofluorocarbon, refrigerants, fluoroether refrigerants, or blends of refrigerant compounds.

The hydrofluorocarbon refrigerants which may need replacing include but are not limited to: CHF₃ (HFC-23), CH₂F₂ (HFC-32), CH₃F (HFC-41), CHF₂CF₃ (HFC125), CHF₂CHF₂ (HFC-134), CH₂FCF₃ (HFC-134a), CHF₂CH₂F (HFC143), CF₃CH₃ (HFC-143a), CHF₂CH₃ (HFC-152a), CH₂FCH₃ (HFC-161), CHF₂CF₂CF₃ (HFC-227ca), CF₃CFHCF₃ (HFC-227ea), CHF₂CF₂CHF₂ (HFC-236ca), CH₂FCF₂CF₃ (HFC-236cb), CHF₂CHFCF₃ (HFC-236ea), CF₃CH₂CF₃ (HFC-236fa), CH₂FCF₂CHF₂ (HFC-245ca), CH₃CF₂CF₃ (HFC-245cb), CHF₂CHFCHF₂ (HFC-245ea), CH₂FCHFCF₃ (HFC-245eb), CHF₂CH₂CF₃ (HFC-245fa), CH₂FCF₂CH₂F (HFC-254ca), CH₃CF₂CHF₂ (HFC-254cb), CH₂FCHFCHF₂ (HFC-254ea), CH₃CHFCF₃ (HFC-254eb), CHF₂CH₂CHF₂ (HFC254fa), CH₂FCH₂CF₃ (HFC-254fb), CF₃CH₂CH₃ (HFC-263fb), CH₃CF₂CH₂F (HFC263ca), CH₃CF₂CH₃ (HFC-272ca), CH₃CHFCH₂F (HFC-272ea), CH₂FCH₂CH₂F (HFC272fa), CH₃CH₂CF₂H (HFC-272fb), CH₃CHFCH₃ (HFC-281ea), CH₃CH₂CH₂F (HFC281 fa), CHF₂CF₂CF₂CF₂H (HFC-338pcc), CF₃CH₂CF₂CH₃ (HFC-365mfc), CF₃CHFCHFCF₂CF₃ (HFC-43-10mee). These hydrofluorocarbon refrigerants are available commercially or may be prepared by methods known in the art.

Hydrofluorocarbon refrigerants which may need replacing may further comprise azeotropic, azeotrope-like and non-azeotropic compositions, including HFC125/HFC-143a/HFC-134a (known by the ASHRAE designation, R404 or R404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE designations, R407 or R407A, R407B, or R407C), HFC-32/HFC-125 (R410 or R410A), and HFC-125/HFC-143a (known by the ASHRAE designation: R507 or R507A), R413A (a blend of R134a/R218/isobutane), R423A (a blend of R134a/R227ea), R507A (a blend of R125/R143a), and others.

Chlorofluorocarbon refrigerants which may need replacing include R22 (CHF₂CI), R123 (CHCI₂CF₃), R124 (CHCIFCF₃), R502 (being a blend of CFC-115 (CCIF₂CF₃) and R22), R503 (being a blend of R23/R13 (CCIF₃)), and others.

Hydrochlorofluorocarbons which may need replacing include R12 (CF₂CI₂), R11 (CCI₃F), R113 (CCI₂FCCIF₂), R114 (CF₂CICF₂CI), R401Aor R401B (being blends of R22/R152a/R124), R408A (a blend of R22/R125/R143a), and others.

The fluoroether refrigerants which may need replacing may comprise compounds similar to hydrofluorocarbons, which also contain at least one ether group oxygen atom. The fluoroether refrigerants include but are not limited to C₄F₉OCH₃, and C₄F₉OC₂H₅ (both available commercially).

The original refrigerant or heat transfer fluid compositions which may need replacement may optionally further comprise combinations of refrigerants that contain

2017201286 24 Feb 2017 up to 10 weight percent of dimethyl ether, or at least one C₃ to C₅ hydrocarbon, e.g., propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). Examples of refrigerants containing such C₃ to C₅ hydrocarbons are azeotrope-like compositions of HCFC-22/HFC-125/propane (known by the ASHRAE designation, R402 or R402A and R402B), HCFC22/octafluoropropane/propane (known by the ASHRAE designation, R403 or R403A and R403B), octafluoropropane/HFC-134a/isobutane (known by the ASHRAE designation, R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/isobutane (known by the ASHRAE designation, R414 or R414A and R414B), HFC-134a/HCFC-124/nbutane (known by the ASHRAE designation, R416 or R416A), HFC-125/HFC-134a/nbutane (known by the ASHRAE designation, R417 or R417A), HFC-125/HFC134a/dimethyl ether (known by the ASHRAE designation, R419 or R419A), and HFC125/HFC-134a/isobutane (known by ASHRAE designation, R422 , R422A, R422B, R422C, R422D).

The HFC-1438ezym fluoroolefin may be used to replace refrigerant in existing equipment designed for use of said refrigerant. Additionally, the HFC1438ezym fluoroolefin may be used to replace refrigerant in existing equipment without the need to change or replace the lubricant.

The present invention relates to a method for reducing the fire hazard in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising introducing a composition comprising HFC-1438ezym of the present invention into said refrigerant apparatus or air-conditioning apparatus.

Refrigerant that may leak from a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, is a major concern when considering flammability. Should a leak occur in a refrigeration apparatus or air-conditioning apparatus, refrigerant and potentially a small amount of lubricant may be released from the system. If this leaking material comes in contact with an ignition source, a fire may result. By fire hazard is meant the probability that a fire may occur either within or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus. Reducing the fire hazard in a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus may be accomplished by using a refrigerant or heat transfer fluid that is not considered flammable as determined and defined by the methods and standards described previously herein. Additionally, HFC-1438ezym fluoroolefin of the present invention may be added to a flammable refrigerant or heat transfer fluid, either in the apparatus already or prior to adding to the apparatus. The HFC-1438ezym fluoroolefin of the present invention may reduce the probability of a

2017201286 24 Feb 2017 fire in the event of a leak and/or reduce the degree of fire hazard by reducing the temperature or size of any flame produced.

The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining HFC-1438ezym fluoroolefin with a flammable refrigerant and introducing the combination into a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus.

The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining HFC-1438ezym fluoroolefin with a lubricant and introducing the combination into the refrigeration apparatus, airconditioning apparatus, or heat pump apparatus comprising flammable refrigerant.

The present invention further relates to a method for reducing fire hazard in or in the vicinity of a refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising introducing HFC-1438ezym into said apparatus.

The present invention further relates to a method of using a flammable refrigerant in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, said method comprising combining said flammable refrigerant with HFC1438ezym.

The present invention further relates to a method for reducing flammability of a flammable refrigerant or heat transfer fluid, said method comprising combining the flammable refrigerant with HFC-1438ezym.

The present invention further relates to a process for transfer of heat from a heat source to a heat sink wherein the composition comprising HFC-1438ezym of the present invention serve as heat transfer fluid. Said process for heat transfer comprises transporting the composition of the present invention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well.

A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or

2017201286 24 Feb 2017 freezer cases in a supermarket, building spaces requiring air-conditioning, or the passenger compartment of an automobile requiring air-conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.

2017201286 11 Sep 2018

Claims (22)

1. The Claims defining the invention are as follows:

   1. A refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of:

   1,1,2,3-tetrafluoro-1 -propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1 -propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 1,1,2-trifluoro-1 -propene (HFC-1243yc); 1,1,3-trifluoro-1 -propene (HFC-1243zc); 1,2,3-trifluoro-1propene (HFC-1243ye); and 1,3,3-trifluoro-1 -propene (HFC-1243ze); and further comprising a lubricant selected from the group consisting of mineral oils, paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.
2. 2. The composition of claim 1, further comprising an additive selected from the group consisting of (i) water scavenger; and (ii) odor masking agent.
3. 3. The composition of claim 1 or claim 2, further comprising a tracer compound wherein the tracer compound is detectable and is selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof, and wherein the tracer compound is different from the refrigerant or heat transfer fluid.
4. 4. The composition of any one of claims 1 to 3, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of the dye; and combinations thereof.
5. 5. The composition of claim 4, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and

   1,1,1-trifluoroalkanes; and combinations thereof.

   2017201286 11 Sep 2018
6. 6. The composition of any one of claims 1 to 5, further comprising a stabilizer selected from the group consisting of:

   a. at least one terpene or terpenoid in combination with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes;

   b. at least one fullerene in combination with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes; and

   c. at least one phenol in combination with at least one compound selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes.
7. 7 The composition of claim 6, further comprising at least one additional stabilizer selected from the group consisting of:

   areoxalyl bis(benzylidene)hydrazide; N,N’-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine); 2,2’-oxamidobis-ethyl-(3,5-d-terbutyl-4-hydroxyhydorcinnamate) N,N’-(disalicyclidene)-1,2-propanediamine; and ethyenediaminetetraacetic acid and salts thereof.
8. 8 The composition of any one of claims 8 to 7, further comprising at least one alkylamine selected from the group consisting of triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amine antioxidants.
9. 9. A process for cooling, the process comprising condensing the composition of any one of claims 1 to 8 and thereafter evaporating the composition in the vicinity of a body to be cooled.
10. 10. A process for heating, the process comprising evaporating the composition of any one of claims 1 to 8 and thereafter condensing the composition in the vicinity of a body to be heated.
11. 11. A method of using the composition of claim 4 or claim 5 in a compression refrigeration, air-conditioning, or heat pump apparatus, the method comprising providing the composition to the apparatus, and providing a suitable

    2017201286 11 Sep 2018 means for detecting the ultra-violet fluorescent dye at, or in the vicinity of, a leak point in the apparatus.
12. 12. A method for producing heating or cooling in a refrigeration, airconditioning, or heat pump apparatus, the method comprising introducing a refrigerant or heat transfer fluid composition according to anyone of claims 1 to 8 into the apparatus having (a) a centrifugal compressor; (b) a multi-stage centrifugal compressor, or (c) a single slab/single pass heat exchanger.
13. 13. The method of claim 12, wherein the method comprises compressing th composition in a centrifugal compressor, condensing the composition, and thereafter evaporating the composition in the vicinity of a body to be heated or cooled.
14. 14. The method according to claim 12 or claim 13, wherein the centrifugal compressor is powered by (a) an engine exhaust gas driven turbine; or (b) a ratioed gear drive assembly with a ratioed belt drive.
15. 15. A method for replacing the use of a high global warming potential refrigerant, the method comprising: providing the composition of any one of claims 1 to 8 in refrigeration, air conditioning, or heat pump apparatus in place of, or in combination with, a high global warming potential refrigerant in the apparatus.
16. 16. A method of using the composition of any one of claims 1 to 8 to lower global warming potential (GWP) of an original refrigerant or heat transfer fluid composition, the method comprising combining the original refrigerant or heat transfer fluid composition with the composition of any one of claims 1 to 8, to produce a second refrigerant or heat transfer fluid composition wherein the second refrigerant or heat transfer fluid composition has a lower GWP than the original refrigerant or heat transfer fluid composition.
17. 17. A method for reducing the global warming potential (GWP) of an original refrigerant or heat transfer fluid composition in a refrigeration, airconditioning or heat pump apparatus, wherein the original refrigerant or heat transfer fluid has a GWP of about 150 or higher; the method comprising introducing a second, lower GWP refrigerant or heat transfer fluid composition

    2017201286 11 Sep 2018 of any one of claims 1 to 8 into the refrigeration, air-conditioning or heat pump apparatus.
18. 18. The method of claim 17, further comprising removing the original refrigerant or heat transfer fluid composition from the refrigeration, airconditioning or heat pump apparatus before the second, lower global warming potential refrigerant or heat transfer fluid is introduced.
19. 19. A method for replacing an original refrigerant or heat transfer fluid composition with a second refrigerant or heat transfer fluid composition, the method comprising providing a composition of any one of claims 1 to 8 as the second refrigerant or heat transfer fluid composition.
20. 20. A method of using the composition of any one of claims 1 to 8 as a heat transfer fluid composition, the method comprising transporting the composition from a heat source to a heat sink.
21. 21. A refrigeration, air-conditioning or heat pump apparatus containing a composition as claimed in any one of claims 1 to 8.
22. 22. A mobile refrigeration or air-conditioning apparatus containing the composition as claimed in any one of claims 1 to 8.