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Title:
STABILIZED FLUOROOLEFIN COMPOSITIONS AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE
Document Type and Number:
WIPO Patent Application WO/2020/222865
Kind Code:
A1
Abstract:
The present invention relates to compositions comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor. The stabilized compositions may be useful in cooling and heating apparatus, such as refrigeration, air-conditioning, chillers, and heat pumps, as well as in applications as foam blowing agents, solvents, aerosol propellants, fire extinguishants, and sterilants.

Inventors:
PENG SHENG (US)
SUN-BLANKS JIAN (US)
KIPP BRIAN (US)
Application Number:
PCT/US2019/058438
Publication Date:
November 05, 2020
Filing Date:
October 29, 2019
Export Citation:
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Assignee:
CHEMOURS CO FC LLC (US)
International Classes:
C09K5/04; C10M171/00
Domestic Patent References:
WO2010002016A12010-01-07
WO2007126760A22007-11-08
WO2008027595A12008-03-06
WO2009042847A12009-04-02
WO2009018117A12009-02-05
Foreign References:
US20170267906A12017-09-21
US20060043330A12006-03-02
US20100301259A12010-12-02
US20110108757A12011-05-12
US20130161554A12013-06-27
US20060022166A12006-02-02
US20170146265A12017-05-25
JP2009298918A2009-12-24
US6969701B22005-11-29
US8133407B22012-03-13
US20060022166A12006-02-02
US20060043330A12006-03-02
US20080157022A12008-07-03
EP2057245A22009-05-13
US8101094B22012-01-24
US8535555B22013-09-17
US8097181B22012-01-17
US8075796B22011-12-13
US6066768A2000-05-23
US8147709B22012-04-03
US8877086B22014-11-04
US20110272624A12011-11-10
US57525605A2005-09-12
US20070290164A12007-12-20
US25021908A2008-10-13
US20060116310A12006-06-01
US5152926A1992-10-06
US4755316A1988-07-05
US5976399A1999-11-02
CA2557873A12005-11-10
Other References:
JEANNEAUX, JOURNAL OF FLUORINE CHEMISTRY, vol. 4, 1974, pages 261 - 270
"Synthetic Lubricants and High-Performance Fluids", 1993, MARCEL DEKKER
Attorney, Agent or Firm:
TUCKER, N. Lynn (US)
Download PDF:
Claims:
CLAIMS

What is claimed is:

1. A composition comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products derived from the fluoroolefin.

2. The composition of Claim 1 wherein the composition comprises less than about 0.03 wt.% of oligomeric, homopolymers or other polymeric products.

3. The composition of Claim 1 further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates.

4. The composition of Claim 3 wherein the inhibitor comprises at least one

member selected from the group consisting of d-limomene, a-terpinene, a- tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1 , 4- diol.

5. The composition of Claim 3 further comprising at least one lubricant.

6. The composition of Claim 5 further comprising a lubricant selected from the group consisting of POE, PAG, and PVE. 7. The composition of Claim 3 wherein the fluoroolefin comprises at least one member of HFO-1234yf and FIFO-1234ze.

8. The composition of Claim 6 further comprising at least one member selected from the group consisting of HFC-125, FIFC-134a, FIFC-152a, 236fa, FIFC- 227ea and carbon dioxide. 9. The composition of Claim 1 comprising FIFO-1234yf, FIFC-32, and at least one inhibitor selected from the group consisting of of d-limonene and a-terpinene.

10. The composition of Claim 7, 8, or 9 further comprising at least one member selected from the group consisting of FIFC-134a, FIFO-1243zf, FIFO-1225ye, HFO-1234ze, 3,3,3-trifluoropropyne, HCFO-1233xf, HFC-244bb and

HFC-245cb.

11. The composition of Claim 7, 8, or 9 further comprising at least one member selected from the group consisting of FICC-40, FICFC-22, CFC-115, FICFC- 124, HCFC-1122, and CFC-1113.

12. The composition of Claim 4 wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm (by weight).

13. The composition of Claim 4 further comprising at least one member selected from the group consisting of butylated hydroxytoluene, butylated

hydroxyanisole, tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1 -

(2,4,5-trihydroxyphenyl)-1 -butaone, phenolics, bisphenol methane

derivatives, and 2,2'-methylene bis (4-methyl-6-t-butyl phenol).

14. The composition of Claim 7 wherein the inhibitor comprises at least one of d- limonene and a-terpinene. 15. The composition of Claim 1 wherein the inhibitor comprises a liquid at a

temperature of about -80 to 180°C.

16. The composition of Claim 1 further comprising at least one antioxidant.

17. The composition of Claim 7 further comprising at least one member selected from the group consisting of FIFO-1225yeZ, FIFO-1243zf, FIFO-1234ze, FIFC-236ea, FIFC-245fa, and 3,3,3-trifluoropropyne.

18. The composition of Claim 1 wherein the composition is substantially free of ammonia and CF3I.

19. The composition of Claim 1 wherein the composition consists essentially of FIFO-1234yf, FIFC-32, and d-limonene and does not contain ammonia or CF3I.

20. The composition of Claim 16 wherein the composition consists essentially of FIFO-1234yf, FIFC-32, 3,3,3-trifluoropropyne and d-limonene.

21. A method for reducing formation of oligomers and homopolymers comprising contacting a composition comprising at least one fluoroolefin and FIFC-32 with an effective amount of at least one member selected from the group consisting of d-limomene, a-terpinene, a-tocopherol, butylated

hydroxytoluene, 4-methoxyphenol, and benzene-1 ,4-diol, that is effective to reduce oligomer or homopolymer formation. 22. The method of claim 21 wherein the composition has been exposed to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates before said contacting. 23. A method for heating or cooling using the composition of Claim 21.

24. A container with a refrigerant comprising the composition of any of Claims 1 through 4.

25. A refrigeration, air-conditioning, heatpump, or chiller system comprising at least one evaporator, at least one compressor, at least one condenser and at least one expansion device and containing the composition of any of Claims 1 through 4.

26. The composition of Claim 1 comprising:

a) a refrigerant consisting of HFO-1234yf and HFC-32; and

b) at least one inhibitor selected from the group consisting of d-limonene and a-terpinene.

Description:
TITLE OF INVENTION

STABILIZED FLUOROOLEFIN COMPOSITIONS AND METHODS FOR THEIR PRODUCTION, STORAGE AND USAGE

BACKGROUND OF THE INVENTION

1. Field of the Invention.

The present invention relates broadly to stabilized compositions comprising at least one fluoroolefin, HFC-32, and at least one inhibitor comprising at least one member selected from the group consisting of limonene, a-terpinene, a- tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1 ,4-diol.

2. Description of Related Art.

New environmental regulations on refrigerants have forced the refrigeration and air-conditioning industry to look for new refrigerants with low global warming potential (GWP).

Replacement refrigerants are being sought that have low GWP, no toxicity, non-flammability, reasonable cost and excellent refrigeration performance.

Fluoroolefins have been proposed as refrigerants, alone or in

mixtures. These products have been extensively tested for chemical stability and compatibility with materials typically used in air conditioning or refrigeration systems (ref.“1234yf - A Low GWP Refrigerant For MAC, Honeywell/DuPont Joint Collaboration” presentation to JAMA/JARIA, October 3, 2007) and shown to be stable under typical operating conditions. However, it has been observed that certain fluoroolefins can exhibit degradation and/or produce unwanted by-products under abnormal conditions such as extreme temperatures or contact with other compounds in a contaminated system (e.g., excessive oxygen, oxidizing chemicals, or radical generating compounds, among various contaminants) that might occur unexpectedly in a particular use and/or application. Such degradation may occur when fluoroolefins are utilized as refrigerants or heat transfer fluids. This degradation may occur by any number of different mechanisms.

Examples of stabilized compositions are disclosed in JP 2009298918; US 6,969,701 ; US 8,133,407; US 2006/0022166; US 2006/0043330;

US 2008/0157022; and WO 2007/126760 as well as EP 2057245; US 8101094; US 8535555; US8097181 ; and US 8075796; the disclosure of which is hereby incorporated by reference.

Under certain abnormal conditions and in the presence of undesired contaminants that can function as an initiator, fluoroolefins may oligomerize or homopolymerize in the presence of certain contaminants that may be present. Accordingly, there is a need in this art for stabilized fluoroolefin containing compositions having reduced, if not eliminated potential to oligomerize or homopolymerize.

SUMMARY OF THE INVENTION

Disclosed herein is a composition comprising at least one fluoroolefin, FIFC- 32, and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products derived from the fluoroolefin.

Also disclosed herein is method for reducing formation of oligomers and homopolymers comprising contacting a composition comprising at least one fluoroolefin and HFC-32 with an effective amount of at least one member selected from the group consisting of d-limomene, a-terpinene, a-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1 , 4-diol, that is effective to reduce oligomer or homopolymer formation.

Also disclosed herein is a method for cooling using a composition comprising at least one fluoroolefin, FIFC-32 and an effective amount of at least one inhibitor.

Also disclosed herein is a container with a refrigerant comprising at least one fluoroolefin, FIFC-32, and an effective amount of at least one inhibitor. DETAILED DESCRIPTION OF THE INVENTION

The present invention can improve the ability of hydrofluoroolefin containing composition to withstand abnormal conditions, and also solves potential problems associated with initiators (e.g., contaminants) causing a fluoroolefin (e.g., tetrafluoropropene) to oligomerize or homopolymerize, by adding at least one inhibitor to a composition comprising a fluoroolefin and HFC-32. By“inhibitor” it is meant to refer to at least one compound in accordance with the present invention that reduces, if not eliminates, conversion of hydrofluoroolefins into oligomers or polymers. While oligomerization or homopolymerization reactions may be accelerated by relatively high temperatures, such reactions may also occur under ambient conditions depending upon the concentration and type of initiator (e.g., contaminant). The inhibitor can function as a radical inhibitor and without affecting the refrigeration performance or compatibility of the composition with refrigerant oil and equipment (e.g., resins used in seals). The stabilized compositions may be useful in cooling/heating systems and as replacements for existing refrigerants with higher global warming potential.

To avoid possible instability of the fluoroolefins, it has been found that adding certain inhibitor compounds, namely hydrocarbons comprising at least one of cyclic monoterpene; lipophilic organic compounds including tocopherols such as a-tocopherol; phenols, aromatic organic compounds having at least one chemical moiety OQH4(OH) including benzene-1 ,4-diol, to fluoroolefin containing

compositions will increase the stability thereof during packaging, storage and usage in refrigeration or air-conditioning system applications. Specific examples of inhibitor compounds comprise at least one member selected from the group consisting of d-limomene, a-terpinene, a-Tocopherol, Butylated hydroxytoluene, 4-Methoxyphenol, Benzene-1 , 4-diol. In one embodiment of the invention, the inventive inhibitor composition comprises a liquid at a temperature from about - 100 to about 220°C, about -90 to about 200°C and in some cases about -80 to about 185°C.

In one particular embodiment, the invention relates to compositions

comprising a fluoroolefin, HFC-32, and an inhibitor that can interact or react with O2 and fluoroolefin polyperoxides and in turn inhibit or preclude reaction of such compounds with a hydrofluoroolefin. Examples of such an inhibitor comprise at least one of d-limonene and a-terpinene. D-Limonene and a-terpinene have the following structures:

Limonene a-Terpinene

In one embodiment of the invention, the inhibitor comprises a-terpinene. Without wishing to be bound by any theory or explanation, it is believed that due to the presence of the conjugated double bond in its structure, a-terpinene can form an aromatic ring upon oxidation. In another embodiment of the invention, the inhibitor comprises d-limonene.

In one embodiment of the invention, d-limonene or a-terpinene, optionally with an antioxidant, has unique fragrance even at a few ppm level. This pleasant odor can be utilized for refrigerant leakage detection with refrigerant and blends based on hydrofluoroolefins (e.g., comprising at least one of 1234yf, 1234ze and combinations thereof). This is especially beneficial for early refrigerant leakage detection in household air conditioners or mobile air conditioners as professional electronic leak detectors often are not available in either location.

One embodiment of the invention relates to a composition comprising:

a. at least one fluoroolefin;

b. HFC-32; and

c. an effective amount of at least one inhibitor comprising: hydrocarbons comprising cyclic monoterpene; lipophilic organic compounds including tocopherol including a-Tocopherol; phenols, aromatic organic compounds having the chemical formula OQH4(OH) including benzene-1 , 4-diol.

One embodiment of the invention relates to any of the foregoing compositions and further comprising at least one anti-oxidant. While any suitable anti-oxidant can be employed, examples of suitable anti-oxidants comprise at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1 -(2,4,5- trihydroxyphenyl)-1 -butaone, bisphenol methane derivatives, 2,2'-methylene bis (4-methyl-6-t-butyl phenol), among other phenolics, and combinations thereof.

One particular embodiment relates to using the foregoing anti-oxidants with an inhibitor comprising at least one of d-limonene and a-terpinene.

Another embodiment of the invention relates to a method for stabilizing a composition comprising at least one fluoroolefin, said method comprising adding an effective amount of at least one inhibitor wherein the inhibitor is a hydrocarbon comprising at least one member selected from the group consisting of cyclic monoterpene; lipophilic organic compounds including tocopherol including a-Tocopherol; phenols, and aromatic organic compounds having the chemical formula OQH4(OH) including benzene-1 ,4-diol, and mixtures thereof, to said composition comprising at least one fluoroolefin and HFC-32.

Another embodiment of the invention relates to a method for reducing oligomerization or homopolymerization of a composition comprising at least one fluoroolefin, which is caused by the presence of an inadvertent or undesired contaminant present in at least one of conduits, transfer lines, including tubing and piping, and other systems used for handling the fluoroolefin containing compositions; packaging (containers), and a refrigeration, air-conditioning, heat pump or chiller system, said method comprising adding an inhibitor comprising at least one hydrocarbons comprising cyclic monoterpene; lipophilic organic compounds including tocopherol including a-Tocopherol;

phenols, aromatic organic compounds having the chemical formula OQH4(OH) including benzene-1 ,4-diol, and mixtures thereof, to at least one of said system, container and composition comprising at least one fluoroolefin and HFC-32.

A further embodiment of the invention relates to a composition containing fluoroolefin and HFC-32 within a container wherein the fluoroolefin has a reduced potential to oligomerize or homopolymerize in comparison to compositions without the inventive inhibitor composition. One embodiment of the invention relates to a composition comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products derived from the fluoroolefin.

Another embodiment of the invention relates to any of the foregoing

compositions wherein the composition comprises less than about 0.03 wt.% of oligomeric, homopolymers or other polymeric products.

Another embodiment of the invention relates to any of the foregoing

compositions and further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and

hydropersulfates.

Another embodiment of the invention relates to any of the foregoing

compositions wherein the inhibitor comprises at least one member selected from the group consisting of d-limomene, a-terpinene, a-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, benzene-1 , 4-diol.

Another embodiment of the invention relates to any of the foregoing further comprising at least one lubricant. In some embodiment, the lubricant is selected from the group consisting ofPOE, PAG, and PVE.

Another embodiment of the invention relates to any of the foregoing

compositions wherein the fluoroolefin comprises at least one member selected from the group consisting of HFO-1234yf and FIFO-1234ze.

Another embodiment of the invention relates to any of the foregoing

compositions and further comprising at least one member selected from the group consisting of HFC-125, HFC-134a, HFC-152a, HFC-227ea and carbon dioxide.

Another embodiment of the invention relates to any of the foregoing

compositions and further comprising at least one member selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3- trifluoropropyne, HCFO-1233xf, HFC-244bb and HFC-245cb. Another embodiment of the invention relates to any of the foregoing compositions and further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and

CFC-1113.

Another embodiment of the invention relates to any of the foregoing compositions wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm (by weight).

Another embodiment of the invention relates to any of the foregoing compositions and further comprising at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary- butylhydroquinone, gallate, 2-phenyl-2-propanol, 1 -(2,4,5-trihydroxyphenyl)-1 - butaone, phenolics, bisphenol methane derivatives, and 2,2'-methylene bis (4- methyl-6-t-butyl phenol).

Another embodiment of the invention relates to any of the foregoing compositions wherein the inhibitor comprises at least one of d-limonene or a- terpinene.

Another embodiment of the invention relates to any of the foregoing compositions wherein the inhibitor comprises a liquid at a temperature of about - 80 to 180°C.

Another embodiment of the invention relates to any of the foregoing compositions and optionally further comprising at least one antioxidant.

Another embodiment of the invention relates to any of the foregoing compositions and further comprising at least one member selected from the group consisting of HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne.

Another embodiment of the invention relates to any of the foregoing compositions wherein the member comprises FIFO-1234ze, FIFO-1225yeZ and 3,3,3-trifluoropropyne. Another embodiment of the invention relates to any of the foregoing compositions wherein the composition is substantially free of at least one of ammonia and CF3I.

Another embodiment of the invention relates to any of the foregoing compositions wherein the composition consists essentially of HFO-1234yf, FIFC- 32, and d-limonene and does not contain ammonia or CF3I.

Another embodiment of the invention relates to any of the foregoing compositions wherein the composition consists essentially of FIFO-1234yf, FIFC- 32, 3,3,3-trifluoropropyne and d-limonene.

One embodiment of the invention relates to a method for reducing formation of oligomers and homopolymers comprising contacting a composition comprising at least one fluroolefin and FIFC-32 with an amount of at least one member selected from the group consisting of d-limonene, a-terpinene, a-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1 , 4-diol, that is effective to reduce oligomer or homopolymer formation.

Another embodiment of the invention relates to any of the foregoing methods wherein the composition has been exposed to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfatees before said contacting.

Another embodiment of the invention relates to any of the foregoing methods that employs any of the foregoing compositions for heating or cooling.

Another embodiment of the invention relates to a container with a refrigerant comprising any of the foregoing compositions.

The embodiments of the invention can be used alone or in combinations with each other, and that different embodiments can be combined and form part of the invention.

The present invention provides a stabilized composition comprising at least one fluoroolefin, FIFC-32, and an effective amount of at least one inhibitor. By “stabilized” it is meant to refer to a composition comprising an effective amount of at least one inhibitor compound that inhibits, if not eliminates, a fluoroolefin from interacting with another compound and forming dimers, oligomers, homopolymers or polymeric products. Examples of such compounds that can cause such interactions include oxidizers such as air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates, hydropersulfates among other initiators. Initiator compounds can be present in an amount from about 10 to about 15,000 ppm by weight, about 1 ,000 to about 10,000 ppm by weight and in some cases about 1 ,000 to about

3,000 ppm by weight and in some embodiments 30 to 2,000 ppm by weight. Such initiator compounds can be present as contaminants in at least one of conduits, transfer lines, tubing, piping, and other systems used for handling the fluoroolefin containing compositions; packaging (containers), storage, and a refrigeration, air- conditioning or heat pump system. Without wishing to be bound by any theory or explanation it is believed that certain contaminants can function as radical initiators thereby causing the fluoroolefin to oligomerization, homopolymerization or form other polymeric products.

In one embodiment of the invention, the inventive compositions are

substantially free of oligomers, homopolymers or other polymeric products derived from a hydrofluoroolefin. By“substantially free” it is meant that the composition contains less than about 1 wt.%, less than about 0.07 wt.%, less than about 0.03 wt.% and and in some cases about 0 ppm by weight of such products when measured by IR or NMR. Polymer that may be present may also be observed visually.

In another embodiment of the invention, the inventive compositions are substantially free of certain conventional inhibitor compounds including

sesquiterpene compounds such as at least one member selected from the group consisting of farnesol, farnesene; ionic liquids such as an ionic liquid comprising an anion selected from the group consisting of [CH3CO2] , [HSO4] , [CH3OSO3] , [C2H5OSO3]-, [AICU]-, [CO3] 2 -, [HCOs]-, [NO2]-, [NOs]-, [SO4] 2 -, [PO4] 3 -, [HPO4] 2 -, [H2PO4] , [HS03],and certain fluorinated anion wherein the fluorinated anion is selected from the group consisting of [BF4] , [PF6] , [SbF6] , [CF3SO3] ,

[HCF2CF2SO3]-, [CF3HFCCF2SO3]-, [HCCIFCF2SO3]-, [(CF 3 S0 2 )2N]-,

[(CF 3 CF 2 S02)2N]-, [(CF 3 S0 2 )3C]-, [CF3CO2]-, [CF3OCFHCF2SO3]-, [CF3CF2OCFHCF2SO3]-, [CF3CFHOCF2CF2SO3]-, [CF2HCF2OCF2CF2SO3]-, [CF2ICF2OCF2CF2SO3]-, [CF3CF2OCF2CF2SO3]-, [(CF 2 HCF 2 S02)2N]-,

[(CF3CFFICF2S02)2N] · , and mixtures thereof. By substantially free it is meant that the inventive compositions contains less than about 500 ppm by weight, typically less than about 250 ppm by weight, in some cases about 100 ppm by weight and in some cases about 0 ppm by weight of such conventional inhibitors

The inventive compositions have a variety of utilities including working fluids, which include blowing agents, aerosol propellants, sterilants or, 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), among others. The inventive compounds are particularly suited for use in mobile air conditioning systems and as a component for making a refrigerant blend for use in stationary heat transfer systems.

A blowing agent is a volatile composition that expands a polymer matrix to form a cellular structure.

An aerosol propellant is a volatile composition of one or more components that exerts a pressure greater than one atmosphere to expel a material from a container.

A sterilant is a volatile biocidal fluid or blend containing a volatile biocidal fluid that destroys a biologically active material or the like.

A heat transfer medium (also referred to herein as a heat transfer fluid, a heat transfer composition or a 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.

As used herein, the terms“comprises,”“comprising,”“includes,”“incl uding,” “has,”“having” or any other variation thereof, are intended to cover a non exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of.

Where applicants have defined an invention or a portion thereof with an open- ended term such as“comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms“consisting essentially of” or“consisting of.”

Also, use of“a” or“an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

The term fluoroolefin, as used herein, describes compounds which comprise carbon atoms, fluorine atoms, and optionally hydrogen atoms. In one

embodiment, the fluoroolefins used in the compositions of the present invention comprise compounds with 2 to 12 carbon atoms. In another embodiment the fluoroolefins comprise compounds with 3 to 10 carbon atoms, and in yet another embodiment the fluoroolefins comprise compounds with 3 to 7 carbon atoms. Representative fluoroolefins include but are not limited to all compounds as listed in Table 1 , Table 2, and Table 3.

One embodiment of the present invention provides fluoroolefins having the formula E- or Z-R 1 CH=CHR 2 (Formula I), wherein R 1 and R 2 are, independently, Ci to C6 perfluoroalkyl groups. Examples of R 1 and R 2 groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3,

CF(CF 3 )CF 2 CF3, CF 2 CF(CF 3 )2, C(CF 3 )3, CF2CF2CF2CF2CF3,

CF 2 CF 2 CF(CF3)2, C(CF 3 )2C2F 5 , CF2CF2CF2CF2CF2CF3, CF(CF 3 )

CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment the fluoroolefins of Formula I have at least about 4 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 5 carbon atoms in the molecule. Exemplary, non-limiting Formula I compounds are presented in Table 1 .

TABLE 1

Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R 1 l with a perfluoroalkyltrihydroolefin of the formula

R 2 CH=CH2 to form a trihydroiodoperfluoroalkane of the formula R 1 CH2CHIR 2 . This trihydroiodoperfluoroalkane can then be dehydroiodinated to form

R 1 CH=CHR 2 . Alternatively, the olefin R 1 CH=CHR 2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R 1 CHICH2R 2 formed in turn by reacting a perfluoroalkyl iodide of the formula R 2 I with a perfluoroalkyltrihydroolefin of the formula R 1 CH=CH2.

Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel ® nickel-copper alloys, Hastelloy ® nickel based alloys and Inconel ® nickel-chromium alloys. Alternatively, the reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1 : 1 to about 4:1 , preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by

Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, pages 261 -270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150°C to 300°C, preferably from about 170°C to about 250°C, and most preferably from about 180°C to about 230°C. Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the

dehydroiodination step or may preferably be recovered and purified by distillation prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting the

trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide. Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.

Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the

trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. Said reaction vessel may be fabricated from glass, ceramic, or metal and is preferably agitated with an impeller or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about 10°C to about 100°C, preferably from about 20°C to about 70°C. The

dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the

trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g.,

tetrabutylammonium bromide, tetrabutylammonium hydrosulfate,

triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides

(e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance. Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion. The compound of Formula I may be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.

In another embodiment of the present invention, fluoroolefins comprise cyclic fluoroolefins (cyclo-[CX=CY(CZW) n -] (Formula II) wherein X, Y, Z, and W are independently selected from FI and F, and n is an integer from 2 to 5). In one embodiment the fluoroolefins of Formula II, have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula II have at least about 4 carbon atoms in the molecule. In yet another embodiment, the

fluoroolefins of Formula II have at least about 5 carbon atoms in the molecule. Representative cyclic fluoroolefins of Formula II are listed in Table 2.

TABLE 2

The compositions of the present invention may comprise a single compound of Formula I or Formula II, for example, one of the compounds in Table 1 or Table 2, or may comprise a combination of compounds of Formula I or Formula II. In another embodiment, fluoroolefins may comprise those compounds listed in Table 3. TABLE 3

The compounds listed in Table 2 and Table 3 are available commercially or may be prepared by processes known in the art or as described herein.

1.1.1.4.4-pentafluoro-2-butene may be prepared from 1 ,1 ,1 ,2,4,4- hexafluorobutane (CHF2CH2CHFCF3) by dehydrofluorination over solid KOFI in the vapor phase at room temperature. The synthesis of 1 ,1 ,1 ,2,4,4- hexafluorobutane is described in US 6,066,768, incorporated herein by reference.

1.1.1.4.4.4-hexafluoro-2-butene may be prepared from 1 ,1 ,1 ,4,4,4-hexafluoro- 2-iodobutane (CF3CFIICFI2CF3) by reaction with KOFI using a phase transfer catalyst at about 60°C. The synthesis of 1 ,1 ,1 ,4,4,4-hexafluoro-2-iodobutane may be carried out by reaction of perfluoromethyl iodide (CF3I) and 3,3,3- trifluoropropene (CF3CH=CH2) at about 200°C under autogenous pressure for about 8 hours.

3.4.4.5.5.5-hexafluoro-2-pentene may be prepared by dehydrofluorination of

1.1.1.2.2.3.3-heptafluoropentane (CF3CF2CF2CH2CH3) using solid KOFI or over a carbon catalyst at 200-300°C. 1 ,1 ,1 ,2,2,3,3-heptafluoropentane may be prepared by hydrogenation of 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CFI=CFl2).

1.1.1.2.3.4-hexafluoro-2-butene may be prepared by dehydrofluorination of

1.1.1.2.3.3.4-heptafluorobutane (CH2FCF2CHFCF3) using solid KOH.

1.1.1.2.4.4-hexafluoro-2-butene may be prepared by dehydrofluorination of

1.1.1.2.2.4.4-heptafluorobutane (CFIF2CFI2CF2CF3) using solid KOFI.

1.1.1.3.4.4-hexafluoro2-butene may be prepared by dehydrofluorination of

1.1.1.3.3.4.4-heptafluorobutane (CF3CFI2CF2CFIF2) using solid KOFI.

1.1.1.2.4-pentafluoro-2-butene may be prepared by dehydrofluorination of

1.1.1.2.2.3-hexafluorobutane (CFI2FCFI2CF2CF3) using solid KOFI.

1.1.1.3.4-pentafluoro-2-butene may be prepared by dehydrofluorination of

1.1.1.3.3.4-hexafluorobutane (CF3CFI2CF2CFI2F) using solid KOFI.

1 ,1 ,1 ,3-tetrafluoro-2-butene may be prepared by reacting 1 ,1 ,1 ,3,3- pentafluorobutane (CF3CFI2CF2CFI3) with aqueous KOFI at 120°C.

1.1.1.4.4.5.5.5-octafluoro-2-pentene may be prepared from

(CF3CFIICFI2CF2CF3) by reaction with KOFI using a phase transfer catalyst at about 60°C. The synthesis of 4-iodo-1 ,1 ,1 ,2,2,5,5,5-octafluoropentane may be carried out by reaction of perfluoroethyliodide (CF3CF2I) and 3,3,3- trifluoropropene at about 200°C under autogenous pressure for about 8 hours.

1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from

1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-iodohexane (CF3CF2CFIICFI2CF2CF3) by reaction with KOFI using a phase transfer catalyst at about 60°C. The synthesis of

1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-iodohexane may be carried out by reaction of perfluoroethyliodide (CF3CF2I) and 3,3,4,4,4-pentafluoro-1 -butene

(CF3CF2CFI=CFl2) at about 200°C under autogenous pressure for about 8 hours. 1 .1 .1 .4.5.5.5-heptafluoro-4-(trifluoromethyl)-2-pentene may be prepared by the dehydrofluorination of 1 , 1 ,1 , 2,5,5, 5-heptafluoro-4-iodo-2-(trifluoromethyl)- pentane (CFsCHICh CFtCFs^) with KOH in isopropanol. CF 3 CHICH2CF(CF3)2 is made from reaction of (CF3)2CFI with CF3CFI=CFl2 at high temperature, such as about 200°C.

1 , 1 ,1 ,4,4,5,5,6,6,6-decafluoro-2-hexene may be prepared by the reaction of 1 , 1 ,1 ,4,4,4-hexafluoro-2-butene (CF3CFI=CFICF3) with tetrafluoroethylene

(CF 2 =CF 2 ) and antimony pentafluoride (SbFs).

2,3,3,4,4-pentafluoro-1 -butene may be prepared by dehydrofluorination of 1 , 1 ,2,2,3, 3-hexafluorobutane over fluorided alumina at elevated temperature.

2.3.3.4.4.5.5.5-ocatafluoro-1 -pentene may be prepared by dehydroflurination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solid KOFI.

1 .2.3.3.4.4.5.5-octafluoro-1 -pentene may be prepared by dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over fluorided alumina at elevated temperature.

2.3.3.3-tetrafluoro-1 -propene may be prepared by converting at least one of HCFC-244bb or HFC-245eb into FIFO-1234yf.

1 .3.3.3-tetrafluoro-1 -propene may be prepared by conversion of FIFC-245fa into FIFO-1234ze by dehydrofluorination.

Many of the compounds of Formula I, Formula II, Table 1 , Table 2, and Table 3 exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the present invention is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, F1 1 E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. As another example, FIFO-1225ye is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

In one particular embodiment, the fluoroolefin component of the inventive composition comprises FIFO-1234yf and/or FIFO-1234ze. In another particular embodiment, the fluoroolefin comprises FIFO-1234yf and/or FIFO-1234ze having a purity of greater than 99 wt%, greater than 99.5 wt% pure and in some cases greater than 99.5 to 99.98 weight percent pure. In another particular embodiment, the fluoroolefin comprises at least 99.5 wt% of HFO-1234yf or HFO-1234ze and less than 0.5 wt% and greater than 0.0001 wt% of the other fluoroolefin, less than 0.3 wt% and in some cases less than 0.2 wt% of the other fluoroolefin.

In another particular embodiment, the fluoroolefin component can comprise the compositions disclosed in U.S. Patent Nos 8,147,709 and 8,877,086; hereby incorporated by reference.

In another particular embodiment, the fluoroolefin component comprises greater than about 99.5 wt% FIFO-1234yf and one or more members selected from the group consisting of FIFO-1225ye, FIFO-1243zf, FIFO-1234ze, FIFC- 236ea, HFC-244bb, HFC-245fa, HFC-245eb, HFC-245cb, 3,3,3-trifluoropropyne, and mixtures thereof. The amount of FIFO-1225ye (E/Z isomers) can range from greater than 0 to about 200 ppm by weight, about 1 to about 150 ppm and in some cases about 5 to about 50 ppm. The amount of FIFO-1243zf can range from about 0.1 to about 250 ppm, about 10 to about 200 ppm and in some cases about 15 to about 150 ppm. The amount of FIFO-1234ze (E isomer) can range from about 1 to about 1 ,500 ppm, about 5 to about 1 ,000 ppm and in some cases about 50 to 500 ppm. The amount of FIFC-236ea can range from about 1 to about 50 ppm, about 5 to about 25 ppm and in some cases about 10 to about 20 ppm. The amount of FIFC-245fa, FIFC-245eb and/or FIFC-245cb can range from about 0 to about 20 ppm, about 1 to about 15 ppm and in some cases about 5 to about 10 ppm. The amount of 3,3,3-trifluoropropyne can range from about 0 to about 500 ppm, about 1 to about 300 ppm and in some cases about 5 to about 100 ppm.

In another embodiment, the fluoroolefin component comprises FIFO-1234yf and at least one additional compound selected from the group consisting of FO- 1114, FIFO-1123, HCFO-1131 a, HFCO-1131 -trans, HCO-1140, HCFO-1214ya, FO-1216, HCFO-1224yd, FIFO-1225ye(E), HCFO-1233zd(E), FIFO-1234ze(E), FIFO-1252, HFC-143a, HCFC-225, HFC-245eb, HFC-254eb, HFC-263fb,

CF3CF2I, HFC-236fa, HCFC-142b, HCFC-244cc, HCFO-1223, FIFO-1132a, FIFO- 2316 (hexafluorobutadiene), FIFO-1327 isomer, FIFO-1336mzzE, FIFO-1336 isomer, FIFO-1234ze(Z) and FICFO-1224 isomer. In one particular embodiment, the fluoroolefin component comprises HFO-1234yf and greater than zero and less than about 1 wt.%, less than about 0.5 wt% and in some cases less than 0.25 wt% of additional compounds.

In a further embodiment, the inventive inhibitor can be used with at least one of HCFO-1233zd and FICFO-1224yd, and compositions of blends comprising at least one of FICFO-1233zd and FICFO-1224yd.

Difluoromethane (FIFC-32 or R-32) is commercially available or may be made by methods known in the art, such as by dechlorofluorination of methylene chloride. In one embodiment, the FIFC-32 component of the inventive

composition comprises FIFC-32 having a purity of greater than 99 wt%, greater than 99.5 wt% pure and in some cases greater than 99.5 to 99.98 weight percent pure. In another particular embodiment, the FIFC-32 component comprises greater than 99.99 wt% pure. In one embodiment, the FIFC-32 component further comprises FIFC-32 and at least one additional compound selected from the group consisting of FIFC-23 (trifluoromethane), FICFC-31 (chlorofluoromethane), FIFC-41 (fluoromethane), FI FC-143a (1 , 1 , 1 -trifluoroethane), FICFC-22

(chlorodifluoromethane), CFC-12 (dichlorodifluoromethane), FICC-40

(chloromethane), and FIFC-134a (1 , 1 , 1 ,2-tetrafluoroethane).

In some embodiments the present compositions comprise FIFO-1234yf and FIFC-32 in particular weight ratios. Of note are compositions comprising from about 20 to about 85 weight percent FIFO-1234yf and from about 80 to about 15 weight percent FIFC-32 relative to the total amount of FIFO-1234yf and FIFC-32 in the composition. In certain embodiments the compositions comprise from about 20 to about 40 weight percent FIFO-1234yf and from about 60 to about 80 weight percent FIFC-32. In other embodiments, the compositions contain from about 30 to about 32 weight percent FIFO-1234yf and from about 68 to about 70 weight percent FIFC-32. In other embodiments, the compositions comprise from about 77 to about 80 weight percent FIFO-1234yf and from about 20 to about 23 weight percent FIFC-32.

In particular embodiments the compositions may contain;

about 31 .1 wt% FIFO-1234yf and about 68.9 wt% FIFC-32; about 31 wt% HFO-1234yf and about 69 wt% HFC-32;

about 65 wt% FIFO-1234yf and about 35 wt% FIFC-32; or

about 78.5 wt% FIFO-1234yf and about 21.5 wt% FIFC-32.

Any suitable effective amount of inhibitor may be used in the foregoing compositions comprising at least one fluoroolefin. As described herein, the phrase“effective amount” refers to an amount of inhibitor of the present invention which, when added to a composition comprising at least one fluoroolefin, results in a composition wherein the fluoroolefin will not interact with an initiator, and/or degrade to produce as great a reduction in performance, for example, when in use in a cooling apparatus as compared to the composition without an inhibitor. For cooling apparatus, such effective amounts of inhibitor may be determined by way of testing under the conditions of standard test ASFIRAE 97-2007 (RA 2017). In a certain embodiment of the present invention, an effective amount may be said to be that amount of inhibitor that when combined with a composition comprising at least one fluoroolefin and FIFC-32 allows a cooling apparatus utilizing said composition comprising at least one fluoroolefin and FIFC-32 to perform at the same level of refrigeration performance and cooling capacity as if a composition comprising 1 ,1 ,1 ,2-tetrafluoroethane (R-134a), or other standard refrigerant (R-12, R-22, R-502, R-507A, R-508, R401A, R401 B, R402A, R402B, R408, R-410A, R- 404A, R407C, R-413A, R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R- 114, R-11 , R-113, R-123, R-124, R236fa, or R-245fa) depending upon what refrigerant may have been used in a similar system in the past, were being utilized as the working fluid.

The instant invention employs effective amounts of at least one of the foregoing inhibitors. While any suitable effective amount can be employed, effective amounts comprise from about 0.001 weight percent to about 10 weight percent, about 0.01 weight percent to about 5 weight percent, about 0.3 weight percent to about 4 weight percent, about 0.3 weight percent to about 1 weight percent based on the total weight of compositions comprising at least one fluoroolefin and FIFC-32 as described herein. In one embodiment, an effective amount comprises about 10 to about 2,000 ppm by weight, about 10 to about 1 ,000 ppm and in some cases about 10 to about 500 ppm of at least one initiator. One embodiment of the invention relates to any of the foregoing compositions and further comprising at least one anti-oxidant. While any suitable anti-oxidant can be employed, examples of suitable anti-oxidants comprise at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1 -(2,4,5- trihydroxyphenyl)-1 -butanone, phenolics, bisphenol methane derivatives, 2,2'- methylene bis (4-methyl-6-t-butyl phenol), and combinations thereof. The amount of anti-oxidant can range from about 0.01 to about 5,000 ppm by weight, about 0.03 to about 2000 ppm and in some cases about 0.05 to about 1000 ppm. An example of one particular embodiment relates to using the foregoing anti-oxidant with at least one inhibitor comprising a-terpinene and limonene. An example of one particular embodiment relates to using the foregoing anti-oxidant with an inhibitor comprising at least one of a-terpinene and d-limonene.

In one embodiment, the foregoing compositions of the present invention may further comprise at least one additional compound selected from the group consisting of fluoroolefins (as described previously herein), hydrofluorocarbons, hydrocarbons, dimethyl ether, ammonia, carbon dioxide (CO2) and mixtures thereof, meaning mixtures of any of the additional compounds listed in this paragraph. The amount of the additional compound can range from about 1 to about 90 % by weight, about 5 to about 75 wt% and in some cases about 10 to about 50 wt%.

In one embodiment, the additional compounds may comprise other

hydrofluorocarbons. The hydrofluorocarbon (HFC) compounds of the present invention comprise saturated compounds containing carbon, hydrogen, and fluorine. Of particular utility are hydrofluorocarbons having 1 -7 carbon atoms and having a normal boiling point of from about -90°C to about 80°C.

Hydrofluorocarbons are commercial products available from a number of sources, or may be prepared by methods known in the art. Representative

hydrofluorocarbon compounds include but are not limited to fluoromethane (CH3F, HFC-41 ), trifluoromethane (CHF3, HFC-23), pentafluoroethane (CF3CHF2, HFC- 125), 1 ,1 ,2,2-tetrafluoroethane (CHF2CHF2, HFC-134), 1 ,1 ,1 ,2-tetrafluoroethane (CF3CH2F, HFC-134a), 1 ,1 ,1 -trifluoroethane (CF3CH3, HFC-143a), 1 ,1 - difluoroethane (CHF2CH3, HFC-152a), fluoroethane (CH3CH2F, HFC-161 ), 1.1.1.2.2.3.3-heptafluoropropane (CF3CF2CHF2, HFC-227ca), 1 ,1 ,1 ,2, 3,3,3- heptafluoropropane (CF3CFIFCF3, FIFC-227ea), 1 ,1 ,2,2,3,3,-hexafluoropropane (CHF2CF2CHF2, HFC-236ca), 1 ,1 ,1 ,2,2,3-hexafluoropropane (CF3CF3CH2F, HFC-236cb), 1 ,1 ,1 ,2,3,3-hexafluoropropane (CF3CHFCHF2, HFC-236ea),

1.1.1.3.3.3-hexafluoropropane (CF3CH2CF3, HFC-236fa), 1 , 1 ,2, 2,3- pentafluoropropane (CFIF2CF2CFI2F, FIFC-245ca), 1 ,1 ,1 ,2,2-pentafluoropropane (CF3CF2CH3, HFC-245cb), 1 ,1 ,2,3,3-pentafluoropropane (CHF2CHFCHF2, HFC- 245ea), 1 ,1 ,1 ,2,3-pentafluoropropane (CF3CHFCH2F, HFC-245eb), 1 ,1 , 1 ,3, 3- pentafluoropropane (CF3CFI2CFIF2, FIFC-245fa), 1 ,2,2,3-tetrafluoropropane (CH2FCF2CH2F, HFC-254ca), 1 ,1 ,2,2-tetrafluoropropane (CHF2CF2CH3, HFC- 254cb), 1 ,1 ,2,3-tetrafluoropropane (CHF2CHFCH2F, HFC-254ea), 1 , 1 ,1 ,2- tetrafluoropropane (CF3CFIFCFI3, FIFC-254eb), 1 ,1 ,3,3-tetrafluoropropane

(CHF2CH2CHF2, HFC-254fa), 1 ,1 ,1 ,3-tetrafluoropropane (CF3CH2CH2F, HFC- 254fb), 1 ,1 ,1 -trifluoropropane (CF3CFI2CFI3, FIFC-263fb), 2,2-difluoropropane (CH3CF2CH3, HFC-272ca), 1 ,2-difluoropropane (CH2FCHFCH3, HFC-272ea),

1.3-difluoropropane (CFI2FCFI2CFI2F, FIFC-272fa), 1 ,1 -difluoropropane

(CHF2CH2CH3, HFC-272fb), 2-fluoropropane (CH3CHFCH3, HFC-281 ea), 1 - fluoropropane (CFI2FCFI2CFI3, FIFC-281fa), 1 ,1 ,2,2,3,3,4,4-octafluorobutane (CHF2CF2CF2CHF2, HFC-338pcc), 1 ,1 ,1 ,2,2,4,4,4-octafluorobutane

(CF3CH2CF2CF3, HFC-338mf), 1 ,1 ,1 ,3,3-pentafluorobutane (CF3CH2CHF2, HFC- 365mfc), 1 ,1 ,1 ,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3, HFC-43- 10mee), and 1 ,1 ,1 ,2,2, 3,4,5, 5,6,6, 7,7, 7-tetradecafluoroheptane

(CF3CF2CFIFCFIFCF2CF2CF3, FIFC-63-14mee). In another embodiment, the additional compounds comprise hydrocarbons. The hydrocarbons of the present invention comprise compounds having only carbon and hydrogen. Of particular utility are compounds having 3-7 carbon atoms. Flydrocarbons are commercially available through numerous chemical suppliers. Representative hydrocarbons include but are not limited to propane, n-butane, isobutane, cyclobutane, n- pentane, 2-methylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, 2- methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n-heptane, and cycloheptane. In another embodiment, additional compounds comprise hydrocarbons containing heteroatoms, such as dimethylether (DME, CH3OCH3). DME is commercially available.

In another embodiment, additional compounds comprise carbon dioxide (CO2), which is commercially available from various sources or may be prepared by methods known in the art.

In some particular embodiments, the compositions comprising additional hydrofluorocarbon compounds are selected from:

about 30 wt% HFO-1234yf, about 11 wt% HFC-32, and about 59 wt% HFC-125;

about 26 wt% FIFO-1234yf, about 67 wt% FIFC-32, and about 7 wt%

HFC-125;

about 31 wt% HFO-1234yf, about 20 wt% HFC-32, about 20 wt% HFC-125, and about 20 wt% HFC-134a;

about 75.5 wt% HFO-1234yf, about 21.5 wt% HFC-32, and about 3 wt% CO2;

about 70 wt% HFO-1234yf, about 18 wt% HFC-32, and about 12 wt% HFC-152a; or

about 14 wt% HFO-1234yf, about 36 wt% HFC-32, about 30 wt% HFC-125, about 14 wt% HFC-134a, and about 6 wt% CO2.

In another embodiment, the foregoing compositions of the present invention are substantially free of additional compounds and, in particular, substantially free of at least one of dimethyl ether, CF3I, ammonia, and carbon dioxide. In one preferred aspect of this embodiment, the foregoing compositions are substantially free of CF3I. By“substantially free of additional compounds” it is meant that the compositions as well as the inhibitor comprise less than about 10 wt%, usually less than about 5 wt% and in some cases 0 wt% of the additional compounds.

Of particular note are fluoroolefin compositions comprising HFO-1234yf and/or HFO-1234ze, HFC-32, and additional compounds comprising : HFO- 1225ye; HFO-1225ye and HFC-134a; HFO-1225ye and HFC-125. Further fluoroolefin compositions comprise a blend of at least one of HFO-1234yf or HFO- 1234ze, and HFC-32, as well as i) HFC-134a and HFC-125; ii) HFC-134a; iii) HFC-227ea; iv) HFC-236fa; and v) HFC-134.

In other embodiments of the invention, the fluoroolefin comprises at least about 99 mass.% FIFO-1234yf and greater than 0 but less than 1 mass% of at least one member selected from the group consisting of FIFC-134a, FIFO-1243zf, FIFO-1225ye, FIFO-1234ze, 3,3,3-trifluoropropyne, HCFO-1233xf, HFC-245cb and combinations thereof.

In other embodiments of the invention, the fluoroolefin comprises at least about 99 mass % FIFO-1234ze and greater than 0 but less than 1 mass% of at least one member selected from the group consisting of FIFO-1234yf, FIFC-245fa, FIFC-236fa, FIFO-1234ye and combinations thereof.

In other embodiments of the invention, the fluoroolefin comprises one or more of the foregoing fluoroolefins that are blended with at least one hydrofluorocarbon. Examples of suitable hydrofluorocarbons comprise at least one member selected from the group consisting of FHFC-125, FIFC-134a, FIFC-152a, 236fa and FIFC- 227ea. The amount of hydrofluorocarbon can range from about 25 to about 75 wt%, about 30 to about 60 wt% and in some cases about 30 to about 50 wt%. In one particular embodiment, the foregoing amounts of hydrofluorocarbon are blended with at least one of FIFO-1234yf and FIFO-1234ze.

If desired, the blended composition can further comprise at least one additional member selected from the group consisting of FICC-40, FICFC-22, CFC-1 15, HCFC-124, HCFC-1 122, and CFC-1 1 13. The amount of the additional member can comprise greater than 0 to about 5 wt.%, about 0 to about 2 wt.% and in some cases about 0 to about 0.5 wt.%. In one particular embodiment, the foregoing amounts of additional members are blended with at least one of FIFO- 1234yf and FIFO-1234ze. In another particular embodiment, the foregoing amounts of additional members are blended with at least one of FIFO-1234yf and FIFO-1234ze, FIFC-32, and at least one additional hydrofluorocarbon selected from the group consisting of FHFC-125, FIFC-134a, FIFC-152a, FIFC-236fa and FIFC-227ea, and in some cases, combined with carbon dioxide.

In another embodiment, the present compositions comprise: a) a refrigerant consisting of HFO-1234yf and HFC-32; and b) at least one inhibitor selected from the group consisting of d-limonene and a-terpinene.

In another embodiment, the present compositions comprise:

a) a refrigerant consisting of FIFO-1234yf, FIFC-32 and FIFC-125; and b) at least one inhibitor selected from the group consisting of d-limonene and a-terpinene.

In one embodiment, the foregoing compositions of the present invention may further comprise at least one lubricant. Lubricants 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 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 or ring structure saturated hydrocarbons, which may be paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention 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, silicones, and poly-alpha-olefins. Representative conventional lubricants of the present invention are the commercially available BVM 100 N (paraffinic mineral oil sold by BVA Oils), naphthenic mineral oil commercially available under the trademark from Suniso ® 3GS and Suniso ® 5GS by Crompton Co., naphthenic mineral oil commercially available from Pennzoil under the trademark Sontex ® 372LT, naphthenic mineral oil commercially available from Calumet Lubricants under the trademark Calumet ® RO-30, linear alkylbenzenes commercially available from Shrieve Chemicals under the trademarks Zerol ® 75, Zerol ® 150 and Zerol ® 500 and branched alkylbenzene, sold by Nippon Oil as HAB 22.

In another embodiment, lubricants of the present invention 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), as well as commercially available POE32-3MAF, and ND-11 ; and polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan) and commercially available ND-12; and polyvinyl ethers (PVEs).

In one embodiment, the compositions comprise lubricants selected from the group consisting of polyol esters (POE), polyalkylene glycols (PAG), and polyvinyl ethers (PVE.

Lubricants of the present invention are selected by considering a given compressor’s requirements and the environment to which the lubricant will be exposed. The amount of lubricant can range from about 1 to about 50 wt%, about 1 to about 20 wt% and in some cases about 1 to about 3 wt%. In one particular embodiment, the foregoing compositions are combined with a PAG lubricant for usage in an automotive air conditioning system having an internal combustion engine. In another particular embodiment, the foregoing compositions are combined with a POE lubricant for usage in an automotive air conditioning or heat pump system having an electric or hybrid electric drive train.

In one embodiment of the invention, in addition to the inventive inhibitor, the composition can comprise at least one additive which can improve the refrigerant and air-conditioning system lifetime and compressor durability are desirable. In one aspect of the invention, the foregoing compositions comprise at least one member selected from the group consisting of acid scavengers, performance enhancers, and flame suppressants. Additives which can improve the refrigerant and A/C lifetime and compressor durability are desirable. In one aspect of the invention, the inventive refrigerant containing composition is used to introduce lubricant into the A/C system as well as other additives, such as a) acid scavengers, b) performance enhancers, and c) flame suppressants.

An acid scavenger may comprise a siloxane, an activated aromatic

compound, or a combination of both. Serrano et al (paragraph 38 of US

2011/0272624 A1 ), which is hereby incorporated by reference, discloses that the siloxane may be any molecule having a siloxyfunctionality. The siloxane may include an alkyl siloxane, an aryl siloxane, or a siloxane containing mixtures of aryl and alkyl substituents. For example, the siloxane may be an alkyl siloxane, including a dialkylsiloxane or a polydialkylsiloxane. Preferred siloxanes include an oxygen atom bonded to two silicon atoms, i.e. , a group having the structure:

SiOSi. For example, the siloxane may be a siloxane of Formula IV:

R 1 [Si(R 2 R 3 )40]nSi(R 2 R 3 )R 4 , Where n is 1 or more. Siloxanes of Formula IV have n that is preferably 2 or more, more preferably 3 or more, (e.g., about 4 or more). Siloxanes of formula IV have n that is preferably about 30 or less, more preferably about 12 or less, and most preferably about 7 or less. Preferably the R 4 group is an aryl group or an alkyl group. Preferably the R 2 groups are aryl groups or alkylgroups or mixtures thereof. Preferably the R 3 groups are aryl groups or alkyl groups or mixtures thereof. Preferably the R 4 group is an aryl group or an alkyl group. Preferably R 1 , R 2 , R 3 , R 4 , or any combination thereof are not hydrogen.

The R 2 groups in a molecule may be the same or different. Preferably the R 2 groups in a molecule are the same. The R 2 groups in a molecule may be the same or different from the R 3 groups. Preferably, the R 2 groups and R 3 groups in a molecule are the same. Preferred siloxanes include siloxanes of Formula IV, wherein R1 , R 2 , R 3 , R 4 , R 5 , or any combination thereof is a methyl, ethyl, propyl, or butyl group, or any combination thereof. Exemplary siloxanes that may be used include hexamethyldisiloxane, polydimethylsiloxane,

polymethylphenylsiloxane, dodecamethylpentasiloxane, decamethylcyclo- pentasiloxane, decamethyltetrasiloxane, octamethyltrisiloxane, or any combination thereof. Incorporated by previous reference from Serrano et al notes that in one aspect of the invention, the siloxane is an alkylsiloxane containing from about 1 to about 12 carbon atoms, such as hexamethyldisiloxane. The siloxane may also be a polymer such as polydialkylsiloxane, Where the alkyl group is a methyl, ethyl, propyl, butyl, or any combination thereof. Suitable polydialkylsiloxanes have a molecular weight from about 100 to about 10,000. Highly preferred siloxanes include hexamethyldisiloxane, polydimethylsiloxane, and combinations thereof. The siloxane may consist essentially of polydimethylsiloxane,

hexamethyldisoloxane, or a combination thereof.

The activated aromatic compound may be any aromatic molecule activated towards a Friedel-Crafts addition reaction, or mixtures thereof. An aromatic molecule activated towards a Friedel-Crafts addition reaction is defined to be any aromatic molecule capable of an addition reaction with mineral acids. Especially aromatic molecules capable of addition reactions with mineral acids either in the application environment (AC system) or during the ASHRAE 97: 2007“Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems” thermal stability test. Such molecules or compounds are typically activated by substitution of a hydrogen atoms of the aromatic ring with one of the following groups: -NH 2 , -NHR, -NR 2 , -OH, -0-, -NHCOCHs, -NHCOR, - OCH3, -OR, -CH3, -C 2 H5, -R, or -C6H5, where R is a hydrocarbon (preferably a hydrocarbon containing from about 1 to about 100 carbon atoms). The activated aromatic molecule may be an alcohol, or an ether, where the oxygen atom (i.e. , the oxygen atom of the alcohol or ether group) is bonded directly to an aromatic group. The activated aromatic molecule may be an amine Where the nitrogen atom (i.e., the nitrogen atom of the amine group) is bonded directly to an aromatic group. By way of example, the activated aromatic molecule may have the formula ArXRn, where X is O (i.e., oxygen) or N (i.e., nitrogen); n=1 when X=0; n=2 when x=N; Ar is an aromatic group (i.e., group, C6H5); R may be H or a carbon containing group; and when n=2, the R groups may be the same or different. For example, R may be H (i.e., hydrogen), Ar, an alkyl group, or any combination thereof. Exemplary activated aromatic molecules that may be employed in a refrigerant composition according to the teachings herein include diphenyl oxide (i.e., diphenyl ether), methyl phenyl ether (e.g., anisole), ethyl phenyl ether, butyl phenyl ether or any combination thereof. One highly preferred aromatic molecule activated towards a Friedel-Crafts addition reaction is diphenyl oxide.

Incorporated by previous reference from Serrano et al. The acid scavenger (e.g., the activated aromatic compound, the siloxane, or both) may be present in any concentration that results in a relatively low total acid number, a relatively low total halides concentration, a relatively low total organic acid concentration, or any combination thereof. Preferably the acid scavenger is present at a concentration greater than about 0.0050 wt%, more preferably greater than about 0.05 wt% and even more preferably greater than about 0.1 wt% (e.g. greater than about

0.5 wt%) based on the total weight of the refrigerant composition. The acid scavenger preferably is present in a concentration less than about 3 wt%, more preferably less than about 2.5 wt% and most preferably greater than about 2 wt% (e. g. less than about 1.8 wt%) based on the total Weight of the refrigerant composition.

Additional examples of acid scavengers which may be included in the refrigerant composition and preferably are excluded from the refrigerant composition include those described by Kaneko (US. patent application Ser.

No. 11/575,256, published as U.S. Patent Publication 2007/0290164, paragraph 42, expressly incorporated herein by reference), such as one or more of: phenyl glycidyl ethers, alkyl glycidyl ethers, alkyleneglycolglycidylethers,

cyclohexeneoxides, otolenoxides, or epoxy compounds such as epoxidized soybean oil, and those described by Singh et al. (US. patent application Ser.

No. 11/250,219, published as US20060116310, paragraphs 34-42, expressly incorporated herein by reference).

Preferred additives include those described in US. Pat. Nos. 5,152,926;

4,755,316, which are hereby incorporated by reference. In particular, the preferred extreme pressure additives include mixtures of (A) tolyltriazole or substituted derivatives thereof, (B) an amine (e.g. Jeffamine M-600) and (C) a third

component which is (i) an ethoxylated phosphate ester (e.g. Antara LP-700 type), or (ii) a phosphate alcohol (e.g. ZELEC 3337 type), or (iii) a Zinc

dialkyldithiophosphate (e.g. Lubrizol 5139, 5604, 5178, or 5186 type), or (iv) a mercaptobenzothiazole, or (v) a 2,5-dimercapto-1 ,3,4-triadiaZole derivative (e. g. Curvan 826) or a mixture thereof. Additional examples of additives which may be used are given in US. Pat. No. 5,976,399 (Schnur, 5:12-6:51 , hereby incorporated by reference).

Acid number is measured according to ASTM D664-01 in units of mg KOH/g. The total halides concentration, the fluorine ion concentration, and the total organic acid concentration is measured by ion chromatography. Chemical stability of the refrigerant system is measured according to ASHRAE 97: 2007 (RA 2017) “Sealed Glass Tube Method to Test the Chemical Stability of Materials for Use within Refrigerant Systems”. The viscosity of the lubricant is tested at 40°C according to ASTM D-7042.

Mouli et al. (WO 2008/027595 and WO 2009/042847) teach the use of alkyl silanes as a stabilizer in refrigerant compositions containing fluoroolefins.

Phosphates, phosphites, epoxides, and phenolic additives also have been employed in certain refrigerant compositions. These are described for example by Kaneko (U.S. patent application Ser. No. 11/575,256, published as U.S.

Publication 2007/0290164) and Singh et al. (U.S. patent application Ser. No.

11/250,219, published as U.S. Publication 2006/0116310). All of these

aforementioned applications are expressly incorporated herein by reference.

Preferred flame suppressants include those described in patent application “Compositions containing fluorine substituted olefins CA 2557873 A1” and incorporated by reference along with fluorinated products such as HFC-125 and/or Krytox ® lubricants, also incorporated by reference and described in patent application“Compositions comprising fluoroolefins and uses thereof

W02009018117A1

The compositions of the present invention may be prepared by any

convenient method to combine the desired amount 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.

The present invention further relates to a process for producing cooling comprising condensing a composition comprising at least one fluoroolefin, HFC- 32, and an effective amount of inhibitor comprising at least one of d-limonene and a-terpinene, and thereafter evaporating said composition in the vicinity of a body to be cooled.

A body to be cooled may be any space, location or object requiring

refrigeration or air-conditioning. In stationary applications the body may be the interior of a structure, i.e. residential or commercial, or a storage location for perishables, such as food or pharmaceuticals. For mobile refrigeration

applications the body may be incorporated into a transportation unit for the road, rail, sea or air. Certain refrigeration systems operate independently with regards to any moving carrier, these are known as“intermodal” systems. Such intermodal systems include“containers” (combined sea/land transport) as well as“swap bodies” (combined road and rail transport).

The present invention further relates to a process for producing heat comprising condensing a composition comprising at least one fluoroolefin, HFC- 32, and an effective amount of an inhibitor comprising at least one of d-limonene and a-terpinene in the vicinity of a body to be heated, and thereafter evaporating said composition.

A body to be heated may be any space, location or object requiring heat. These may be the interior of structures either residential or commercial in a similar manner to the body to be cooled. Additionally, mobile units as described for cooling may be similar to those requiring heating. Certain transport units require heating to prevent the material being transported from solidifying inside the transport container.

Another embodiment of the invention relates to a air-conditioning,

refrigeration, heatpump, or chiller apparatus comprising at least one evaporator, at least one compressor, at least one condenser and at least one expansion device characterized as containing the foregoing compositions.

Another embodiment of the invention relates to storing the foregoing compositions in gaseous and/or liquid phases within a sealed container wherein the oxygen and/or water concentration in the gas and/or liquid phases ranges from about 3 vol ppm to less than about 3,000 vol ppm at a temperature of about 25C, about 5 vol ppm to less than about 1 ,000 vol ppm and in some cases about 5 vol ppm to less than about 500 vol ppm.

The container for storing the foregoing compositions can be constructed of any suitable material and design that is capable of sealing the compositions therein while maintaining gaseous and liquids phases. Examples of suitable containers comprise pressure resistant containers such as a tank, a filling cylinder, and a secondary filling cylinder. The container can be constructed from any suitable material such as carbon steel, manganese steel, chromium- molybdenum steel, among other low-alloy steels, stainless steel and in some cases an aluminum alloy. The container can include a pierce top or valves suitable for dispensing flammable substances.

While any suitable method can be employed for stabilizing fluorocarbon containing compositions, examples of such methods including blending the foregoing inhibitors with the foregoing fluoroolefin composition, purging lines and containers with a material comprising the inhibitor (e.g., an inhibitor with a nitrogen carrier, or the inventive stabilized composition); among other suitable methods.

The following examples are provided to illustrate certain embodiments of the invention and shall not limit the scope of the appended claims.

EXAMPLE 1

A mixture of HFO-1234yf (30 g having at least 99.5 wt.% purity*) and initiator (with and without inhibitor) was heated in a 210 mL shake tube at the temperature and for the period of time given in Table 4. The shake tube was visually inspected for polymer formation as well as by using IR in accordance with conventional methods by detecting yf polymer peaks. Polymer can also be detected by using conventional NMR methods.

*The HFO-1234yf comprised 99.7 wt.% HFO-1234yf, 1 ,000 ppm HFO-1234ze,

150 ppm FIFO-1225yeZ, 3 ppm trifluoropropyne with the remainder comprising compounds that do not affect the refrigerant performance of the mixture. TABLE 4

EXAMPLE 2

A refrigerant blend comprising a mixture of HFO-1234yf (30g having the composition of Example 1 ), at least one additional compound and an initiator (and without inhibitor) was heated in a 210mL shake tube at the temperature and for the period of time given in Table 5. Examples 1 -6 evaluate an inhibitor with Opteon™ XP-10 refrigerant (R513a) and a commercially available lubricant.

Examples 7-12 evaluate an inhibitor with Opteon™ XP-40 refrigerant (R449a) and a commercially available lubricant. Examples 13-18 evaluate an inhibitor with HFO-1234yf and a commercially available lubricant. XP10 refrigerant comprises 56 wt% FIFO-1234yf and 44 wt% FIFC-134a, and XP40 refrigerant comprises 24.3 wt% R32, 24.7wt % R125, 25.3 wt.% 1234yf, and 25.7 wt.% 134a. XP10 and XP40 refrigerants are commercially available from The Chemours Company. The shake tube was visually inspected for polymer formation as well as by using NMR. Data reported below is ppm by weight.

TABLE 5

EXAMPLE 3

A refrigerant blend comprising a mixture of HFO-1234yf and HFC-32 (30 g), and an initiator, with and without inhibitor, are heated in a 210 mL shake tube at the temperature and for the period of time given in Table 6. Control-A and

Examples 1 -7 contain R-454C (a refrigerant blend containing 21.5 wt% FIFC-32 and 78.5 wt% FIFO-1234yf), an inhibitor, and a commercially available POE or PAG lubricant. Note that Example 1 has inhibitor, and no lubricant. Control-B and Examples 8-14 contain R-454-B (a refrigerant blend containing 69 wt% FIFC-32 and 31 wt% FIFO-1234yf), an inhibitor, and a commercially available POE or PAG lubricant. Note that Example 8 has inhibitor and no lubricant. POE32-3MAF and ND-11 are commercially available POE lubricants. ND-12 is a commercially available PAG lubricant. After heating, the shake tubes are visually inspected for polymer formation as well as being analyzed by NMR. N/D indicates that no polymer was found.

TABLE 6

Although certain aspects, embodiments and principals have been described above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Select Embodiments

Embodiment A1 : A composition comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products derived from the fluoroolefin.

Embodiment A2: The composition of Embodiment A1 wherein the composition comprises less than about 0.03 wt.% of oligomeric, homopolymers or other polymeric products.

Embodiment A3: The composition of any of Embodiments A1 -A2 further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides,

hydroperoxides, persulfates, percarbonates, perborates and hydropersulfatees.

Embodiment A4: The composition of any of Embodiments A1 , A2 or A3 wherein the inhibitor comprises at least one member selected from the group consisting of d-limomene, a-terpinene, a-tocopherol, butylated hydroxytoluene, 4- methoxyphenol, and benzene-1 ,4-diol.

Embodiment A5: The composition of any of Embodiments A1 , A2, A3, or A4 further comprising at least one lubricant.

Embodiment A6: The composition of any of Embodiments A1 , A2, A3, A4, or A5 further comprising a lubricant selected from the group consisting of POE, PAG, and PVE.

Embodiment A7: The composition of any of Embodiments A1 , A2, A3, A4, A5, or A6 wherein the fluoroolefin comprises at least one member of HFO-1234yf and FIFO-1234ze.

Embodiment A8: The composition of any of Embodiments A1 , A2, A3, A4, A5,

A6 or A7 further comprising at least one member selected from the group consisting of HFC-125, HFC-134a, HFC-152a, 236fa, HFC-227ea and carbon dioxide.

Embodiment A9: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7 or A8 further comprising at least one member selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3- trifluoropropyne, HCFO-1233xf, HFC-244bb and HFC-245cb.

Embodiment A10: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, or A9 further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC- 1113.

Embodiment A11 : The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, or A10 wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm (by weight).

Embodiment A12: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, or A11 further comprising at least one member selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tertiary-butylhydroquinone, gallate, 2-phenyl-2-propanol, 1 -(2,4,5- trihydroxyphenyl)-1 -butaone, phenolics, bisphenol methane derivatives, and 2,2'- methylene bis (4-methyl-6-t-butyl phenol).

Embodiment A13: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 , or A12 wherein the inhibitor comprises at least one of d-limonene and a-terpinene.

Embodiment A14: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 , A12, or A13 wherein the inhibitor comprises a liquid at a temperature of about -80 to 180C.

Embodiment A15: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 , A12, A13, or A14 further comprising at least one antioxidant.

Embodiment A16: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 , A12, A13, A14, or A15 further comprising at least one member selected from the group consisting of FIFO-1225yeZ, FIFO-1243zf, FIFO- 1234ze, FIFC-236ea, FIFC-245fa, and 3,3,3-trifluoropropyne. Embodiment A17: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, or A16 wherein the member comprises HFO-1234ze, HFO-1225yeZ and 3,3,3-trifluoropropyne.

Embodiment A18: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, or A17 wherein the composition is substantially free of ammonia and CF3I.

Embodiment A19: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, or A18 wherein the composition consists essentially of FIFO-1234yf, FIFC-32, and d-limonene and does not contain ammonia or CF3I.

Embodiment A20: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, or A19 wherein the composition consists essentially of FIFO-1234yf, FIFC-32, 3,3,3- trifluoropropyne and d-limonene.

Embodiment A21 : The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, or A20 comprising FIFO-1234yf, FIFC-32, and at least one inhibitor selected from the group consisting of of d-limonene and a-terpinene.

Embodiment A22: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, A20, or A21 comprising:

about 31 .1 wt% FIFO-1234yf and about 68.9 wt% FIFC-32; about 31 wt% FIFO-1234yf and about 69 wt% FIFC-32; about 65 wt% HFO-1234yf and about 35 wt% FIFC-32; or about 78.5 wt% FIFO-1234yf and about 21 .5 wt% FIFC-32; based on the total weight of FIFO-1234yf and FIFC-32 in the composition. Embodiment A23: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, A20, A21 , or A22 comprising:

a) a refrigerant consisting of HFO-1234yf and HFC-32; and

b) at least one inhibitor selected from the group consisting of d-limonene and a-terpinene.

Embodiment A23: The composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, A20, A21 , or A22 comprising:

a) a refrigerant consisting of FIFO-1234yf, FIFC-32, and FIFC-125; and b) at least one inhibitor selected from the group consisting of d-limonene and a-terpinene.

Embodiment B1 : A method for reducing formation of oligomers and

homopolymers comprising contacting a composition comprising at least one fluoroolefin and FIFC-32 with an effective amount of at least one member selected from the group consisting of d-limomene, a-terpinene, a-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1 ,4-diol, that is effective to reduce oligomer or homopolymer formation.

Embodiment B2: The method of Embodiment B1 wherein the composition has been exposed to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates before said contacting.

Embodiment C1 : A method for heating or cooling using the composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, A20, A21 , A22, or A23.

Embodiment D1 : A container with a refrigerant comprising the composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A1 1 , A12, A13, A14, A15, A16, A17, A18, A19, A20, A21 , A22, or A23. Embodiment E1 : A refrigeration, air-conditioning, heatpump, or chiller apparatus comprising at least one evaporator, at least one compressor, at least one condenser and at least one expansion device characterized as containing the composition of any of Embodiments A1 , A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 , A12, A13, A14, A15, A16, A17, A18, A19, A20, A21 , A22, or A23.