AU2018282475A1

AU2018282475A1 - Compositions comprising fluoroolefins and uses thereof

Info

Publication number: AU2018282475A1
Application number: AU2018282475A
Authority: AU
Inventors: Thomas J. Leck; Barbara Haviland Minor; Nandini Mouli; Mario Joseph Nappa; Deepak Perti; Velliyur Nott Mallikarjuna Rao; Corneille Schmitz; Allen Capron Sievert; Ekaterina N. Swearingen
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2005-11-01
Filing date: 2018-12-21
Publication date: 2019-01-24
Also published as: AU2015202652B2; AU2017201286A1; AU2020220053A1; AU2017201286B2; AU2020213451B2; AU2015202652A1; AU2020213451A1

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

FIELD OF THE INVENTION

The present Application is a Divisional Application from Australian Patent Application No. 2017201286, which is a Divisional of

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 2017201286, 2015202652, 2012229664, 2006308717 and their corresponding International Application No. PCT/US2006/042686, are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to compositions for use in refrigeration, air-conditioning 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, HFC134a 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.

2018282475 21 Dec 2018

	Currently proposed replacement refrigerants for HFC-134a include HFC-152a, 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.
5	Therefore, new alternative refrigerants are being sought. The object of the present invention is to provide novel refrigerant compositions and heat transfer fluid compositions that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current
10	refrigerants. BRIEF SUMMARY OF THE INVENTION The present invention relates to a refrigerant or heat transfer fluid composition comprising at least one compound selected from
15	the group consisting of: (i) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹ and R² are, independently, Ci to C6 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5;
20	(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 2,3,3-trifluoro-1-propene (CHF2CF=CH2); 1,1,2-trifluoro-
25	1-propene (CH3CF=CF2); 1,2,3-trifluoro-1 -propene (CH2FCF=CF2); 1,1,3-trifluoro-1 -propene (CH2FCH=CF2); 1,3,3-trifluoro-1-propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4octafluoro-1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-
30	heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro2-(trifluoromethyl)-1-propene ((CF3)2C=CHF); 1,1,3,3,4,4,4heptafluoro-1-butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-
35	heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4heptafluoro-1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4hexafluoro-1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-

2018282475 21 Dec 2018

	hexafluoro-1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4hexafluoro-1-butene (CHF=CFCHFCF3); 1,2,3,3,4,4hexafluoro-1-butene (CHF=CFCF₂CHF₂); 1,1,2,3,4,4hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4-
5	hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4- hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4- hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-
10	(trifluoromethyl)-l-propene (CH2=C(CF3)2); 1,1,1,2,4pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4pentafluoro-1-butene (CF3CF2CH=CH2); 1,1,1,4,4pentafluoro-2-butene (CHF2CH=CHCF3); 1,1,1,2,3-
15	pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4pentafluoro-1-butene (CH2=CFCF2CHF2); 1,1,2,4,4pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4pentafluoro-2-butene (CH2FCF=CFCHF2); 1,1,3,3,3-
20	pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2- (difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1-butene (CH2=CFCHFCF3); 1,2,4,4,4-pentafluoro-1 -butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1 -butene
25	(CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1 -butene (CHF=CHCF2CHF2); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF₂); 3,3,4,4-tetrafluoro-1 -butene (CH2=CHCF₂CHF₂); 1,1-difluoro-2-(difluoromethyl)-1propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1-
30	propene (CHF=C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)1-propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-
35	pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3);

2018282475 21 Dec 2018

	1.1.1.3.4.4.5.5.5- nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1.2.3.3.4.4.5.5.5- nonafluoro-1 -pentene (CHF=CFCF₂CF₂CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-
5	1-pentene (CF2=CFCF₂CF2CHF₂); 1,1,2,3,4,4,5,5,5nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5-nonafluoro-2pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-
10	(trifluoromethyl)-l-butene (CHF=CFCF(CF₃)₂); 1,1,2,4,4,4hexafluoro-3-(trifluoromethyl)-1 -butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)- 1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1-
15	pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2(trifluoromethyl)-l-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene
20	(CHF=CHCF(CF₃)₂); 1,1,4,4,4-pentafluoro-2(trifluoromethyl)-l-butene (CF2=C(CF3)CH2CF3); 3,4,4,4tetrafluoro-3-(trifluoromethyl)-1 -butene ((CF3)2CFCH=CH2); 3.3.4.4.5.5.5- heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2.3.3.4.4.5.5- heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2);
25	1,1,3,3,5,5,5-heptafluoro-1 -butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3- (trifluoromethyl)-l-butene (CHF=CHCH(CF₃)2); 1,1,1,4-
30	tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF₂CF=CHCH3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-
35	butene (CF3C(CH3)=CHCF3); 3,3,4,5,5,5-hexafluoro-1pentene (CH2=CHCF2CHFCF3); 4,4,4-trifluoro-3(trifluoromethyl)-l -butene (CH2=C(CF3)CH2CF3);

2018282475 21 Dec 2018

	1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2);
5	1.1.1.2.3.4.5.5.5- nonafluoro-4-(trifluoromethyl)-2-pentene ((CF₃)2CFCF=CFCF₃); 1,1,1,4,4,5,5,5-octafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CHC2Fs); 1.1.1.3.4.5.5.5- octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -
10	hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF₃)); 2,3,3,5,5,5-hexafluoro-4(trifluoromethyl)-l -pentene (CH2=CFCF2CH(CF3)2);
15	1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF=C(CH3)CF₂CF3); 1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluorol -hexene
20	(CH2=CHCF2CF2CF₂CHF2); 1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5pentafluoro-2-(trifluoromethyl)-1-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6-heptafluoro-
25	2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6heptafluoro-1-hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4heptafluoro-3-hexene (CF3CF2CF=CFC2Hs); 4,5,5,5tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-
30	2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CFC2Hs); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF₂CF₂C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2Fs);
35	1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF₃CH=CFCF2CF₂C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5);

2018282475 21 Dec 2018

1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF₂CH=CFCF₂C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7tridecafluoro-3-heptene (CF3CF₂CF=CHCF₂C₂F5);

CF₂=CFOCF₂CF₃ (PEVE) and CF₂=CFOCF₃ (PMVE).

The present invention further relates to a composition comprising: (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; wherein said fluoroolefin is selected from the group consisting of:

(a) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹ and R² are, independently, Ci to C6 perfluoroalkyl groups;

(b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (c) fluoroolefins selected from the group consisting of:

1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3pentafluoro-1-propene (CF3CH=CF₂); 1,1,2,3,3-pentafluoro-1propene (CHF₂CF=CF₂); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF₂CF=CF₂); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF₂CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF₂CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1 -propene ((CF3)₂C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF₂=CHCF₂CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂=CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF₂=CFCF₂CHF₂); 2,3,3,4,4,4-hexafluoro-1 -butene (CF3CF₂CF=CH₂); 1,3,3,4,4,4-hexafluoro-1 -butene (CHF=CHCF₂CF3); 1,2,3,4,4,4-hexafluoro-1 -butene (CHF=CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1 -butene (CHF=CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH₂FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF₂CH=CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH=CFCHF₂); 1,1,2,3,3,4-hexafluoro-1-butene (CF₂=CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF₂=CFCHFCHF₂); 3,3,3-trifluoro-2-(trifluoromethyl)-1 -propene

2018282475 21 Dec 2018 (CH2=C(CF3)2); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3(trifluoromethyl)-l-butene (CF2=CFCH(CF3)2); 1,1,1,4,4,415 hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2);

1.1.3.4.4.4- hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-120 butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3(trifluoromethyl)-l-butene (CF2=CHCH(CF3)2); 1,3,4,4,4pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2);

1.1.4.4.4- pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 - butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-130 butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)2-butene (CH3CF=C(CF3)2); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-335 hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3);

2018282475 21 Dec 2018

1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,35 bis(trifluoromethyl)-1 -butene (CH2=CHC(CF3)3); 1,1,1,4,4,4hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro10 4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2);

1.1.1.2.3.4.4.5.5.6.6.7.7.7- tetradecafluoro-2-heptene (CF3CF=CFCF₂CF₂C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2Fs);

1.1.1.3.4.4.5.5.6.6.7.7.7- tridecafluoro-2-heptene (CF3CH=CFCF₂CF₂C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2heptene (CF3CF=CHCF₂CF₂C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5); and

1.1.1.2.2.3.5.5.6.6.7.7.7- tridecafluoro-3-heptene (CF₃CF2CF=CHCF2C2F₅).

The present invention further relates to a method of using a refrigerant or heat transfer fluid composition in refrigeration, airconditioning, or heat pump apparatus, said method comprising introducing said composition into said apparatus having (a) centrifugal compressor;

(b) multi-stage centrifugal compressor, or (c) single slab/single pass heat exchanger; wherein said refrigerant or heat transfer composition is employed in said apparatus to result in heating or cooling; and wherein said refrigerant or heat transfer composition comprises at least one fluoroolefin selected from the group consisting of:

(i) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹ and R² are, independently, Ci to C6 perfluoroalkyl groups,;

(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X,

Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; or (iii) fluoroolefins selected from the group consisting of:

1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3-pentafluoro-1propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1-propene (CHF2CF=CF2);

2018282475 21 Dec 2018

1.2.3.3- tetrafluoro-1 -propene (CHF2CF=CHF); 2,3,3,3-tetrafluoro-1 propene (CF3CF=CH2); 1,3,3,3-tetrafluoro-1-propene (CF3CH=CHF);

1.1.2.3- tetrafluoro-1 -propene (CH2FCF=CF2); 1,1,3,3-tetrafluoro-1 propene (CHF2CH=CF2); 2,3,3-trifluoro-1-propene (CHF2CF=CH2); 3,3,3- trifluoro-1 -propene (CF3CH=CH2); 1,1,2-trifIuoro-1 -propene (CH3CF=CF2);

1.1.3- trifluoro-1 -propene (CH2FCH=CF2); 1,2,3-trifluoro-1 -propene (CH₂FCF=CHF); 1,3,3-trifluoro-1-propene (CHF₂CH=CHF);

1.1.1.2.3.4.4.4- octafluoro-2-butene(CF3CF=CFCF3); 1,1,2,3,3,4,4,4octafluoro-1 -butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF=CHCF₃); 1,2,3,3,4,4,4-heptafluoro-1 -butene (CHF=CFCF₂CF₃);

1.1.1.2.3.4.4- heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-

2-(trifluoromethyl)-1 -propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1 butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂=CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1 -butene (CF2=CFCF₂CHF₂);

2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1 -butene (CHF=CFCF₂CHF₂);

1.1.2.3.4.4- hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF₂CH=CFCF₃); 1,1,1,3,4,4-hexafluoro-2-butene (CF₃CH=CFCHF₂);

1.1.2.3.3.4- hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4hexafluoro-1 -butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-

1-propene (CH2=C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH₂FCH=CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF₃CH=CFCH₂F);

3,3,4,4,4-pentafluoro-1 -butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2butene (CHF2CH=CHCF3); 1,1,1,2,3-pentafluoro-2-butene (CH₃CF=CFCF₃); 2,3,3,4,4-pentafluoro-1-butene (CH2=CFCF₂CHF₂);

1.1.2.4.4- pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3-pentafluoro-

1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2-butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH₂=CFCHFCF₃);

1.2.4.4.4- pentafluoro-1 -butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1 butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF₂);

3.3.4.4- tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-difluoro-2(difluoromethyl)-l-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-210

2018282475 21 Dec 2018 methyl-1 -propene (CHF=C(CF3)(CH3)); 2-difluoromethyl-3,3-difluoro-1 propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3);

1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro5 1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1 -butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3);

3,3,4,5,5,5-hexafluoro-1-pentene (CH2=CHCF2CHFCF3); 3(trifluoromethyl)-4,4,4-trifluoro-1 -butene (CH2=C(CF3)CH2CF3);

2018282475 21 Dec 2018

1.1.2.3.3.4.4.5.5.6.6.6- dodecafluoro-1-hexene (CF3(CF2)3CF=CF2);

1.1.1.2.2.3.4.5.5.6.6.6- dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3);

1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2);

1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CHC2Fs); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-210 butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)1 -pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluoro-1 15 hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2(trifluoromethyl)-l-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5heptafluoro-2-methyl-1 -pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro20 1 -hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-trifluoromethyl-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3heptene (CF3CF2CF=CFCF2C2Fs); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro2-heptene (CF3CH=CFCF₂CF₂C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5);

1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5);

1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5);

CF₂=CFOCF₂CF3 (PEVE); CF₂=CFOCF₃ (PMVE) and combinations thereof.

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

2018282475 21 Dec 2018 components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention 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 foaming agents, blowing agents, fire extinguishing agents, 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), to name a few.

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 20 phase change from a liquid to a gas and back.

The present invention provides fluoroolefins having the formula E- or Z-R¹CH=CHR² (Formula I), wherein R¹ and R² are, independently, Ci to C6 perfluoroalkyl groups. Examples of R¹ and R² groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3,

CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF₃)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF₃) CF2CF2C2F5, and C(CF3)2CF2C2F5. In one embodiment the fluoroolefins of Formula I, have at least about 3 carbon atoms in the molecule. In another embodiment, the fluoroolefins of Formula I have at least about 4 carbon atoms in the molecule. In yet 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

2018282475 21 Dec 2018

Code	Structure	Chemical Name
F11E	CF₃CH=CHCF₃	1,1,1,4,4,4-hexafluoro-2-butene
F12E	cf₃ch=chc₂f₅	1,1,1,4,4,5,5,5-octafluoro-2-pentene
F13E	cf₃ch=chcf₂c₂f₅	1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene
F13iE	CF₃CH=CHCF(CF₃)₂	1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene
F22E	c₂f₅ch=chc₂f₅	1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene
F14E	CF₃CH=CH(CF₂)₃CF₃	1,1,1,4,4,5,5,6,6,7,7,7-dodecafluoro-2-heptene
F14iE	CF₃CH=CHCF₂CF(CF₃)₂	1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)-2hexene
F14sE	CF₃CH=CHCF(CF₃)C₂F₅	1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)-2-hexene
F14tE	CF₃CH=CHC(CF₃)₃	1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)-2pentene
F23E	c₂f₅ch=chcf₂c₂f₅	1,1,1,2,2,5,5,6,6,7,7,7-dodecafluoro-3-heptene
F23iE	C₂F₅CH=CHCF(CF₃)₂	1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)-3hexene
F15E	CF₃CH=CH(CF₂)₄CF₃	1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluoro-2-octene
F15iE	CF₃CH=CH-CF₂CF₂CF(CF₃)₂	1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-2heptene
F15tE	CF₃CH=CH-C(CF₃)₂C₂F₅	1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl )-2hexene
F24E	C₂F₅CH=CH(CF₂)₃CF₃	1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene
F24iE	C₂F₅CH=CHCF₂CF(CF₃)₂	1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-3heptene
F24sE	C₂F₅CH=CHCF(CF₃)C₂F₅	1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)-3heptene
F24tE	C₂F₅CH=CHC(CF₃)₃	1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl )-3hexene
F33E	C₂F₅CF₂CH=CHCF₂C₂F₅	1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene
F3i3iE	(CF₃)₂CFCH=CHCF(CF₃)₂	1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl )-3hexene
F33iE	C₂F₅CF₂CH=CHCF(CF₃)₂	1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)-3heptene
F16E	CF₃CH=CH(CF₂)₅CF₃	1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoro-2nonene
F16sE	CF₃CH=CHCF(CF₃)(CF₂)₂C₂F₅	1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4- (trifluoromethyl)-2-heptene
F16tE	CF₃CH=CHC(CF₃)₂CF₂C₂F₅	1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)-2-heptene
F25E	C₂F₅CH=CH(CF₂)₄CF₃	1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoro-3nonene
F25iE	C₂F₅CH=CH-CF₂CF₂CF(CF₃)₂	1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7- (trif I uorom ethyl )-3-octe ne

2018282475 21 Dec 2018

F25tE	C₂F₅CH=CH-C(CF3)2C2F5	1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)-3heptene
F34E	C2F₅CF₂CH=CH-(CF2)3CF3	1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoro-4nonene
F34iE	C₂F₅CF₂CH=CH- CF₂CF(CF₃)2	1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7- (trifluoromethyl)-4-octene
F34sE	C₂F₅CF2CH=CHCF(CF3)C2F5	1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6- (trifluoromethyl)-4-octene
F34tE	C2F₅CF₂CH=CHC(CF3)3	1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)-3heptene
F3i4E	(CF₃)2CFCH=CH(CF₂)3CF3	1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)- 3-octene
F3i4iE	(CF3)2CFCH=CHCF₂CF(CF₃)2	1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)-3heptene
F3i4sE	(CF3)2CFCH=CHCF(CF3)C₂F₅	1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)-3heptene
F3i4tE	(CF₃)2CFCH=CHC(CF₃)3	1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl )-3hexene
F26E	C₂F₅CH=CH(CF2)5CF3	1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-3decene
F26sE	C₂F₅CH=CHCF(CF3)(CF2)2C2F5	1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5- (trifluoromethyl)-3-nonene
F26tE	C₂F₅CH=CHC(CF3)2- CF2C2F5	1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5- bis(trifluoromethyl)-3-octene
F35E	C2F₅CF₂CH=CH-(CF2)4CF3	1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-4decene
F35iE	C2F₅CF2CH=CHCF₂CF2- CF(CF₃)₂	1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8- (trifluoromethyl)-4-nonene
F35tE	C₂F₅CF2CH=CH-C(CF3)2C2F5	1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6- bis(trifluoromethyl)-4-octene
F3i5E	(CF₃)2CFCH=CH-(CF₂)4CF3	1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2- (trifluoromethyl)-3-nonene
F3i5iE	(CF₃)2CFCH=CHCF₂CF2- CF(CF₃)₂	1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7bis(trifluoromethyl -3-octene
F3i5tE	(CF3)2CFCH=CHC(CF3)2C₂F₅	1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)- 3-heptene
F44E	CF₃(CF2)3CH=CH(CF₂)3CF3	1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5decene
F44iE	CF₃(CF2)3CH=CH-CF₂CF(CF3)2	1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2- (trifluoromethyl)-4-nonene
F44sE	CF3(CF2)3CH=CHCF(CF3)C₂F₅	1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3- (trifluoromethyl)-4-nonene
F44tE	CF3(CF₂)3CH=CHC(CF₃)3	1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,- bis(trifluoromethyl)-3-octene

2018282475 21 Dec 2018

F4i4iE	(CF₃)₂CFCF₂CH=CHCF₂CF- (CF₃)₂	1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7- bis(trifluoromethyl)-4-octene
F4i4sE	(CF₃)₂CFCF₂CH=CHCF(CF₃)- c₂f₅	1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6- bis(trifluoromethyl)-4-octene
F4i4tE	(CF₃)₂CFCF₂CH=CHC(CF₃)₃	1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)- 3-heptene
F4s4sE	C₂F₅CF(CF₃)CH=CH- CF(CF₃)C₂F₅	1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6- bis(trifluoromethyl)-4-octene
F4s4tE	C₂F₅CF(CF₃)CH=CH- C(CF₃)₃	1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)- 3-heptene
F4t4tE	(CF₃)₃CCH=CH- C(CF₃)₃	1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)- 3-hexene

Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R¹I with a perfluoroalkyltrihydroolefin of the formula R²CH=CH2 to form a trihydroiodoperfluoroalkane of the formula R’CFLCHIR². This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R¹CH=CHR². Alternatively, the olefin R¹CH=CHR² may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R’CHICFLR² formed in turn by reacting a perfluoroalkyl iodide of the formula R²I with a perfluoroalkyltrihydroolefin of the formula R¹CH=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).

2018282475 21 Dec 2018

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 10 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 15 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 20 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 25 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, Ν,Ν-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product 30 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 may be fabricated from glass, ceramic, or metal and is preferably agitated with an impeller or stirring mechanism.

2018282475 21 Dec 2018

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 10 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 15 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 25 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 35 X, Y, Z, and W are independently selected from H and F, and n is an integer from 2 to 5). Representative cyclic fluoroolefins of Formula II are listed in Table 2.

2018282475 21 Dec 2018

TABLE 2

Cyclic fluoroolefins	Structure	Chemical name
FC-C1316cc	cyclo-CF2CF2CF=CF-	1,2,3,3,4,4-hexafluorocyclobutene
HFC-C1334cc	cyclo-CF₂CF₂CH=CH-	3,3,4,4-tetrafluorocyclobutene
HFC-C1436	cyclo-CF2CF₂CF₂CH=CH-	3,3,4,4,5,5,- hexafluorocyclopentene
FC-C1418y	cyclo-CF₂CF=CFCF₂CF2-	1,2,3,3,4,4,5,5- octafluorocyclopentene
FC-C151-10y	cyclo-CF₂CF=CFCF2CF₂CF2-	1,2,3,3,4,4,5,5,6,6decafluorocyclohexene

In another embodiment, fluoroolefins may comprise those compounds listed in Table 3.

TABLE 3

Name	Structure	Chemical name
HFC-1225ye	cf₃cf=chf	1,2,3,3,3-pentafluoro-1-propene
HFC-1225zc	cf₃ch=cf₂	1,1,3,3,3-pentafluoro-1-propene
HFC-1225yc	chf₂cf=cf₂	1,1,2,3,3-pentafluoro-1-propene
HFC-1234ye	chf₂cf=chf	1,2,3,3-tetrafluoro-1-propene
HFC-1234yf	cf₃cf=ch₂	2,3,3,3-tetrafluoro-1 -propene
HFC-1234ze	cf₃ch=chf	1,3,3,3-tetrafluoro-1-propene
HFC-1234yc	ch₂fcf=cf₂	1,1,2,3-tetrafluoro-1-propene
HFC-1234zc	chf₂ch=cf₂	1,1,3,3-tetrafluoro-1-propene
HFC-1243yf	chf₂cf=ch₂	2,3,3-trifluoro-1 -propene
HFC-1243zf	cf₃ch=ch₂	3,3,3-trifluoro-1 -propene
HFC-1243yc	ch₃cf=cf₂	1,1,2-trifluoro-1-propene
HFC-1243zc	ch₂fch=cf₂	1,1,3-trifluoro-1-propene
HFC-1243ye	ch₂fcf=chf	1,2,3-trifluoro-1-propene
HFC-1243ze	chf₂ch=chf	1,3,3-trifluoro-1-propene
FC-1318my	cf₃cf=cfcf₃	1,1,1,2,3,4,4,4-octafluoro-2-butene
FC-1318cy	cf₃cf₂cf=cf₂	1,1,2,3,3,4,4,4-octafluoro-1-butene
HFC-1327my	cf₃cf=chcf₃	1,1,1,2,4,4,4-heptafluoro-2-butene
HFC-1327ye	chf=cfcf₂cf₃	1,2,3,3,4,4,4-heptafluoro-1-butene
HFC-1327py	chf₂cf=cfcf₃	1,1,1,2,3,4,4-heptafluoro-2-butene
HFC-1327et	(CF₃)₂C=CHF	1,3,3,3-tetrafluoro-2(trifluoromethyl )-1 -propene
HFC-1327cz	cf₂=chcf₂cf₃	1,1,3,3,4,4,4-heptafluoro-1-butene
HFC-1327cye	cf₂=cfchfcf₃	1,1,2,3,4,4,4-heptafluoro-1-butene
HFC-1327cyc	CF2=CFCF₂CHF₂	1,1,2,3,3,4,4-heptafluoro-1-butene
HFC-1336yf	cf₃cf₂cf=ch₂	2,3,3,4,4,4-hexafluoro-1-butene
HFC-1336ze	chf=chcf₂cf₃	1,3,3,4,4,4-hexafluoro-1-butene
HFC-1336eye	chf=cfchfcf₃	1,2,3,4,4,4-hexafluoro-1-butene
HFC-1336eyc	chf=cfcf₂chf₂	1,2,3,3,4,4-hexafluoro-1-butene
HFC-1336pyy	chf₂cf=cfchf₂	1,1,2,3,4,4-hexafluoro-2-butene
HFC-1336qy	ch₂fcf=cfcf₃	1,1,1,2,3,4-hexafluoro-2-butene
HFC-1336pz	chf₂ch=cfcf₃	1,1,1,2,4,4-hexafluoro-2-butene
HFC-1336mzy	cf₃ch=cfchf₂	1,1,1,3,4,4-hexafluoro-2-butene
HFC-1336qc	CF2=CFCF₂CH₂F	1,1,2,3,3,4-hexafluoro-1-butene
HFC-1336pe	cf₂=cfchfchf₂	1,1,2,3,4,4-hexafluoro-1-butene

2018282475 21 Dec 2018

HFC-1336ft	CH₂=C(CF₃)2	3,3,3-trifluoro-2-(trifluoromethyl)-1- propene
HFC-1345qz	ch₂fch=cfcf₃	1,1,1,2,4-pentafluoro-2-butene
HFC-1345mzy	cf₃ch=cfch₂f	1,1,1,3,4-pentafluoro-2-butene
HFC-1345fz	cf₃cf₂ch=ch₂	3,3,4,4,4-pentafluoro-1 -butene
HFC-1345mzz	chf₂ch=chcf₃	1,1,1,4,4-pentafluoro-2-butene
HFC-1345sy	ch₃cf=cfcf₃	1,1,1,2,3-pentafluoro-2-butene
HFC-1345fyc	ch₂=cfcf₂chf₂	2,3,3,4,4-pentafluoro-1 -butene
HFC-1345pyz	chf₂cf=chchf₂	1,1,2,4,4-pentafluoro-2-butene
HFC-1345cyc	ch₃cf₂cf=cf₂	1,1,2,3,3-pentafluoro-1-butene
HFC-1345pyy	ch₂fcf=cfchf₂	1,1,2,3,4-pentafluoro-2-butene
HFC-1345eyc	ch₂fcf₂cf=cf₂	1,2,3,3,4-pentafluoro-1-butene
HFC-1345ctm	CF₂=C(CF₃)(CH₃)	1,1,3,3,3-pentafluoro-2-methyl-1propene
HFC-1345ftp	CH₂=C(CHF₂)(CF₃)	2-(difluoromethyl)-3,3,3-trifluoro-1propene
HFC1345fye	ch₂=cfchfcf₃	2,3,4,4,4-pentafluoro-1 -butene
HFC-1345eyf	chf=cfch₂cf₃	1,2,4,4,4-pentafluoro-1-butene
HFC-1345eze	chf=chchfcf₃	1,3,4,4,4-pentafluoro-1-butene
HFC-1345ezc	chf=chcf₂chf₂	1,3,3,4,4-pentafluoro-1-butene
HFC-1345eye	chf=cfchfchf₂	1,2,3,4,4-pentafluoro-1-butene
HFC-1354fzc	ch₂=chcf₂chf₂	3,3,4,4-tetrafluoro-1 -butene
HFC-1354ctp	CF₂=C(CHF₂)(CH₃)	1,1,3,3-tetrafluoro-2-methyl-1propene
HFC-1354etm	CHF=C(CF₃)(CH₃)	1,3,3,3-tetrafluoro-2-methyl-1propene
HFC-1354tfp	CH₂=C(CHF₂)₂	2-(difluoromethyl )-3,3-d ifluoro-1propene
HFC-1354my	cf₃cf=chch₃	1,1,1,2-tetrafluoro-2-butene
HFC-1354mzy	ch₃cf=chcf₃	1,1,1,3-tetrafluoro-2-butene
FC-141-10myy	cf₃cf=cfcf₂cf₃	1,1,1,2,3,4,4,5,5,5-decafluoro-2pentene
FC-141-10cy	cf₂=cfcf₂cf₂cf₃	1,1,2,3,3,4,4,5,5,5-decafluoro-lpentene
HFC-1429mzt	(CF₃)₂C=CHCF₃	1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene
HFC-1429myz	cf₃cf=chcf₂cf₃	1,1,1,2,4,4,5,5,5-nonafluoro-2pentene
HFC-1429mzy	cf₃ch=cfcf₂cf₃	1,1,1,3,4,4,5,5,5-nonafluoro-2pentene
HFC-1429eyc	chf=cfcf₂cf₂cf₃	1,2,3,3,4,4,5,5,5-nonafluoro-1pentene
HFC-1429czc	cf₂=chcf₂cf₂cf₃	1,1,3,3,4,4,5,5,5-nonafluoro-lpentene
HFC-1429cycc	cf₂=cfcf₂cf₂chf₂	1,1,2,3,3,4,4,5,5-nonafluoro-lpentene
HFC-1429pyy	chf₂cf=cfcf₂cf₃	1,1,2,3,4,4,5,5,5-nonafluoro-2pentene
HFC-1429myyc	cf₃cf=cfcf₂chf₂	1,1,1,2,3,4,4,5,5-nonafluoro-2pentene
HFC-1429myye	cf₃cf=cfchfcf₃	1,1,1,2,3,4,5,5,5-nonafluoro-2pentene
HFC-1429eyym	CHF=CFCF(CF₃)₂	1,2,3,4,4,4-hexafluoro-3(trifluoromethyl )-1 -butene
HFC-1429cyzm	CF₂=CFCH(CF₃)₂	1,1,2,4,4,4-hexafluoro-3(trifluoromethyl )-1 -butene

2018282475 21 Dec 2018

HFC-1429mzt	CF₃CH= C(CF₃)₂	1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2-butene
HFC-1429czym	CF₂=CHCF(CF₃)₂	1,1,3,4,4,4-hexafluoro-3(trifluoromethyl )-1 -butene
HFC-1438fy	CH2=CFCF₂CF₂CF₃	2,3,3,4,4,5,5,5-octafluoro-1- pentene
HFC-1438eycc	CHF=CFCF₂CF₂CHF2	1,2,3,3,4,4,5,5-octafluoro-1pentene
HFC-1438ftmc	CH₂=C(CF₃)CF₂CF₃	3,3,4,4,4-pentafluoro-2- (trifluoromethyl )-1 -butene
HFC-1438czzm	CF₂=CHCH(CF₃)2	1,1,4,4,4-pentafluoro-3(trifluoromethyl )-1 -butene
HFC-1438ezym	CHF=CHCF(CF₃)₂	1,3,4,4,4-pentafluoro-3(trifluoromethyl )-1 -butene
HFC-1438ctmf	CF₂=C(CF₃)CH₂CF₃	1,1,4,4,4-pentafluoro-2(trifluoromethyl )-1 -butene
HFC-1447fzy	(CF₃)₂CFCH=CH₂	3,4,4,4-tetraf I uoro-3(trifluoromethyl )-1 -butene
HFC-1447fz	CF₃CF₂CF₂CH=CH2	3,3,4,4,5,5,5-heptafluoro-1-pentene
HFC-1447fycc	CH2=CFCF₂CF₂CHF2	2,3,3,4,4,5,5-heptafluoro-1-pentene
HFC-1447czcf	CF2=CHCF₂CH₂CF₃	1,1,3,3,5,5,5-heptafluoro-1-pentene
HFC-1447mytm	CF₃CF=C(CF₃)(CH₃)	1,1,1,2,4,4,4-heptafluoro-3-methyl- 2-butene
HFC-1447fyz	CH₂=CFCH(CF₃)2	2,4,4,4-tetraf I uoro-3(trifluoromethyl )-1 -butene
HFC-1447ezz	CHF=CHCH(CF₃)₂	1,4,4,4-tetrafluoro-3(trifluoromethyl )-1 -butene
HFC-1447qzt	CH₂FCH=C(CF₃)₂	1,4,4,4-tetrafluoro-2- (trifluoromethyl)-2-butene
HFC-1447syt	CH₃CF=C(CF₃)₂	2,4,4,4-tetraf I uoro-2- (trifluoromethyl)-2-butene
HFC-1456szt	(CF₃)₂C=CHCH₃	3-(trifluoromethyl)-4,4,4-trifluoro-2butene
HFC-1456szy	cf₃cf₂cf=chch₃	3,4,4,5,5,5-hexafluoro-2-pentene
HFC-1456mstz	CF₃C(CH₃)=CHCF₃	1,1,1,4,4,4-hexafluoro-2-methyl-2butene
HFC-1456fzce	ch₂=chcf₂chfcf₃	3,3,4,5,5,5-hexafluoro-1-pentene
HFC-1456ftmf	CH₂=C(CF₃)CH₂CF₃	4,4,4-trifluoro-2-(trifluoromethyl)-1butene
FC-151-12C	CF₃(CF₂)₃CF=CF₂	1,1,2,3,3,4,4,5,5,6,6,6dodecafluoro-1-hexene (or perfluoro-1 -hexene)
FC-151-12mcy	cf₃cf₂cf=cfcf₂cf₃	1,1,1,2,2,3,4,5,5,6,6,6dodecafluoro-3-hexene (or perfluoro-3-hexene)
FC-151-12mmtt	(CF₃)₂C=C(CF₃)₂	1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene
FC-151-12mmzz	(CF₃)₂CFCF=CFCF₃	1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-pentene
HFC-152-11mmtz	(CF₃)₂C=CHC₂F₅	1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl)-2-pentene
HFC-152-1 Immyyz	(CF₃)₂CFCF=CHCF₃	1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene
PFBE (or HFC-1549fz)	CF₃CF2CF₂CF₂CH=CH2	3,3,4,4,5,5,6,6,6-nonafluoro-1hexene (or perfluorobutylethylene)
HFC-1549fztmm	CH₂=CHC(CF₃)₃	4,4,4-trifluoro-3,3-

2018282475 21 Dec 2018

		bis(trifluoromethyl)-1-butene
HFC-1549mmtts	(CF3)2C=C(CH₃)(CF₃)	1,1,1,4,4,4-hexafluoro-3-methyl-2(trifluoromethyl)-2-butene
HFC-1549fycz	CH₂=CFCF₂CH(CF₃)2	2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl )-1-pentene
HFC-1549myts	CF₃CF=C(CH₃)CF₂CF₃	1,1,1,2,4,4,5,5,5-nonafluoro-3- methyl-2-pentene
HFC-1549mzzz	CF₃CH=CHCH(CF₃)₂	1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl)-2-pentene
HFC-1558szy	cf₃cf₂cf₂cf=chch₃	3,4,4,5,5,6,6,6-octafluoro-2-hexene
HFC-1558fzccc	ch₂=chcf₂cf₂cf₂chf₂	3,3,4,4,5,5,6,6-octafluoro-2-hexene
HFC-1558mmtzc	(CF₃)₂C=CHCF₂CH₃	1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-pentene
HFC-1558ftmf	CH₂=C(CF₃)CH₂C₂F₅	4,4,5,5,5-pentafluoro-2- (trifluoromethyl )-1-pentene
HFC-1567fts	CF₃CF₂CF₂C(CH₃)=CH₂	3,3,4,4,5,5,5-heptafluoro-2-methyl- 1-pentene
HFC-1567szz	cf₃cf₂cf₂ch=chch₃	4,4,5,5,6,6,6-heptafluoro-2-hexene
HFC-1567fzfc	ch₂=chch₂cf₂c₂f₅	4,4,5,5,6,6,6-heptafluoro-1-hexene
HFC-1567sfyy	cf₃cf₂cf=cfc₂h₅	1,1,1,2,2,3,4-heptafluoro-3-hexene
HFC-1567fzfy	CH₂=CHCH₂CF(CF₃)₂	4,5,5,5-tetraf I uoro-4(trifluoromethyl )-1-pentene
HFC-1567myzzm	CF₃CF=CHCH(CF₃)(CH₃)	1,1,1,2,5,5,5-heptafluoro-4-methyl- 2-pentene
HFC-1567mmtyf	(CF₃)₂C=CFC₂H₅	1,1,1,3-tetrafluoro-2- (trifluoromethyl)-2-pentene
FC-161-14myy	cf₃cf=cfcf₂cf₂c₂f₅	1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene
FC-161-14mcyy	cf₃cf₂cf=cfcf₂c₂f₅	1,1,1,2,2,3,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene
HFC-162-13mzy	cf₃ch=cfcf₂cf₂c₂f₅	1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene
HFC162-13myz	cf₃cf=chcf₂cf₂c₂f₅	1,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene
HFC-162-13mczy	cf₃cf₂ch=cfcf₂c₂f₅	1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene
HFC-162-13mcyz	cf₃cf₂cf=chcf₂c₂f₅	1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene
PEVE	cf₂=cfocf₂cf₃	pentafluoroethyl trifluorovinyl ether
PMVE	cf₂=cfocf₃	trifluoromethyl trifluorovinyl ether

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 KOH 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.

2018282475 21 Dec 2018

1.1.1.4.4.4- hexafluoro-2-butene may be prepared from

1,1,1,4,4,4-hexafluoro-2-iodobutane (CF3CHICH2CF3) by reaction with KOH 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 KOH or over a carbon catalyst at 20010 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 (CF3CF2CF₂CH=CH2).

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 (CHF2CH2CF2CF3) using solid KOH.

1.1.1.3.4.4- hexafluoro2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4,4-heptafluorobutane (CF3CH2CF2CHF2) using solid KOH.

1.1.1.2.4- pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,2,3-hexafluorobutane (CH2FCH2CF2CF3) using solid KOH.

1,1,1,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,3,3,4-hexafluorobutane (CF3CH2CF2CH2F) using solid KOH.

1,1,1,3-tetrafluoro-2-butene may be prepared by reacting 1,1,1,3,3-pentafluorobutane ( CF3CH2CF2CH3) with aqueous KOH at 120 30 °C.

1.1.1.4.4.5.5.5- octafluoro-2-pentene may be prepared from (CF3CHICH2CF2CF3) by reaction with KOH 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 3,3,335 trifluoropropene at about 200°C under autogenous pressure for about 8 hours.

2018282475 21 Dec 2018

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 (CF3CF2CHICH2CF2CF3) by reaction with KOH 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 3,3,4,4,4pentafluoro-1-butene (CF3CF2CH=CH2) 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 (CF3CHICH2CF(CF3)2) with KOH in isopropanol. CF3CHICH2CF(CF3)2 is made from reaction of (CF3)2CFI with CF3CH=CH2 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 (CF3CH=CHCF3) with tetrafluoroethylene (CF2=CF2) 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 dehydrofluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentane over solid KOH.

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.

The compositions of the present invention may comprise a single compound of Formula I, Formula II, or Table 3 or may comprise a combination of said compounds. Additionally, many of the compounds of Formula I, Formula II, and Table 3 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. For instance, 1,3,3,3-tetrafluoropropene (HFC-1234ze) is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is F12E, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). The

2018282475 21 Dec 2018 fluoroolefins of the present invention or mixtures of fluoroolefins 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 5 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 fluoroolefins 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.

An alternative means for making compositions 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, being those

2018282475 21 Dec 2018

	described earlier herein, 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.
5	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
10	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
15	order to restore the composition to within the specification limits. The compositions of the present invention that are useful as refrigerants or heat transfer fluids comprise at least one fluoroolefin selected from the group consisting of: (i) fluoroolefins of the formula E- or Z-R¹CH=CHR²,
20	wherein R¹ and R² are, independently, Ci to Οθ perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5; (ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and
25	n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of: 1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF);1,1,3,3,3pentafluoro-1-propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1propene (CHF2CF=CF2); 1,2,3,3-tetrafluoro-1-propene
30	(CHF2CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF3CF=CH2); 1.1.2.3- tetrafluoro-1 -propene (CH2FCF=CF2); 1,1,3,3-tetrafluoro-1 propene (CHF2CH=CF2); 2,3,3-trifluoro-1-propene (CHF2CF=CH2); 3.3.3- trifIuoro-1 -propene (CF3CH=CH2); 1,1,2-trifIuoro-1 -propene (CH3CF=CF2); 1,2,3-trifluoro-1-propene (CH2FCF=CF2); 1,1,3-
35	trifluoro-1-propene (CH2FCH=CF2); 1,3,3-trifluoro-1-propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene

2018282475 21 Dec 2018 (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-heptafluoro-1 -butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1 -propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1 -butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1 -butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1 -butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1 -butene (CHF=CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1 -propene (CH₂=C(CF₃)2); 1,1,1,2,4-pentafluoro-2-butene (CH₂FCH=CFCF₃);

1,1,1,3,4-pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4pentafluoro-1-butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2butene (CHF2CH=CHCF3); 1,1,1,2,3-pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1 -butene (CH2=CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3-pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2-butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1-butene (CH2=CFCHFCF3); 1,2,4,4,4-pentafluoro-1-butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1 -butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1 -butene (CHF=CHCF2CHF2); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF₂); 3,3,4,4-tetrafluoro-1 -butene (CH2=CHCF2CHF2); 1,1-difluoro-2-(difluoromethyl)-1-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1 -propene (CHF=C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1 -propene

2018282475 21 Dec 2018 (CH₂=C(CHF₂)2); 1,1,1,2-tetrafluoro-2-butene (CF₃CF=CHCH₃);

1,1,1,3-tetrafluoro-2-butene (CH₃CF=CHCF₃); 1,1,1,2,3,4,4,5,5,5decafluoro-2-pentene (CF₃CF=CFCF₂CF₃); 1,1,2,3,3,4,4,5,5,5decafluoro-1-pentene (CF2=CFCF₂CF₂CF₃); 1,1,1,4,4,4-hexafluoro5 2-(trifluoromethyl)-2-butene ((CF₃)₂C=CHCF₃); 1,1,1,2,4,4,5,5,5nonafluoro-2-pentene (CF₃CF=CHCF₂CF₃); 1,1,1,3,4,4,5,5,5nonafluoro-2-pentene (CF₃CH=CFCF₂CF₃); 1,2,3,3,4,4,5,5,5nonafluoro-1-pentene (CHF=CFCF₂CF₂CF₃); 1,1,3,3,4,4,5,5,5nonafluoro-1-pentene (CF2=CHCF₂CF₂CF₃); 1,1,2,3,3,4,4,5,510 nonafluoro-1-pentene (CF2=CFCF₂CF₂CHF2); 1,1,2,3,4,4,5,5,5nonafluoro-2-pentene (CHF₂CF=CFCF₂CF₃); 1,1,1,2,3,4,4,5,5nonafluoro-2-pentene (CF₃CF=CFCF₂CHF₂); 1,1,1,2,3,4,5,5,5nonafluoro-2-pentene (CF₃CF=CFCHFCF₃); 1,2,3,4,4,4-hexafluoro3-(trifluoromethyl)-1-butene (CHF=CFCF(CF₃)₂); 1,1,2,4,4,415 hexafluoro-3-(trifluoromethyl)-1-butene (CF₂=CFCH(CF₃)₂);

1.1.1.4.4.4- hexafluoro-2-(trifluoromethyl)-2-butene (CF₃CH=C(CF₃)₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1butene (CF₂=CHCF(CF₃)₂); 2,3,3,4,4,5,5,5-octafluoro-1-pentene (CH2=CFCF₂CF₂CF₃); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF₂CF₂CHF₂); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1 butene (CH₂=C(CF₃)CF₂CF₃); 1,1,4,4,4-pentafluoro-3(trifluoromethyl)-l-butene (CF₂=CHCH(CF₃)₂); 1,3,4,4,4pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF₃)₂);

1.1.4.4.4- pentafluoro-2-(trifluoromethyl)-1-butene (CF₂=C(CF₃)CH₂CF₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene ((CF₃)₂CFCH=CH₂); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF₃CF₂CF₂CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF₂CF₂CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF₂CH₂CF₃); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF₃CF=C(CF₃)(CH₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CH₂=CFCH(CF₃)₂); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 butene (CHF=CHCH(CF₃)₂); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)2-butene (CH₂FCH=C(CF₃)₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)2-butene (CH₃CF=C(CF₃)₂); 1,1,1 -trifluoro-2-(trifluoromethyl)-235 butene ((CF₃)₂C=CHCH₃); 3,4,4,5,5,5-hexafluoro-2-pentene (CF₃CF₂CF=CHCH₃); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF₃C(CH₃)=CHCF₃); 3,3,4,5,5,5-hexafluoro-1 -pentene

2018282475 21 Dec 2018 (CH2=CHCF2CHFCF3); 4,4,4-trifluoro-3-(trifluoromethyl)-1-butene (CH₂=C(CF3)CH₂CF3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,35 bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3);

1.1.1.4.4.5.5.5- octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1- hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-315 methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2);

3.4.4.5.5.6.6.6- octafluoro-2-hexene (CF3CF2CF2CF=CHCH3);

3.3.4.4.5.5.6.6- octafluorol-hexene (CH2=CHCF2CF2CF2CHF2);

1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1 pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl1-pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6-heptafluoro-2hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro-1hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1 pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CFC2Hs);

1.1.1.3.4.4.5.5.6.6.7.7.7- tridecafluoro-2-heptene (CF3CH=CFCF₂CF₂C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2heptene (CF3CF=CHCF₂CF₂C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5);

1.1.1.2.2.3.5.5.6.6.7.7.7- tridecafluoro-3-heptene

2018282475 21 Dec 2018 (CF₃CF2CF=CHCF₂C2F5); CF₂=CFOCF₂CF3 (PEVE) and CF₂=CFOCF₃ (PMVE).

The present invention further relates to compositions comprising at least one fluoroolefin and at least one flammable refrigerant or heat transfer fluid, wherein the fluoroolefin is selected from the group consisting of:

(i) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹ and R² are, independently, Ci to C6 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least

5;

(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of:

1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF);1,1,3,3,3pentafluoro-1 -propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1 -propene (CHF₂CF=CF₂); 1,2,3,3-tetrafluoro-1-propene (CHF₂CF=CHF); 2,3,3,3tetrafluoro-1 -propene (CF3CF=CH2); 1,1,2,3-tetrafluoro-1 -propene (CH2FCF=CF2); 1,1,3,3-tetrafluoro-1-propene (CHF2CH=CF2); 2,3,320 trifluoro-1-propene (CHF2CF=CH2); 3,3,3-trifluoro-1-propene (CF3CH=CH2); 1,1,2-trifluoro-1 -propene (CH3CF=CF2); 1,2,3-trifluoro-1 propene (CH2FCF=CF2); 1,1,3-trifluoro-1 -propene (CH2FCH=CF2); 1,3,3trifluoro-1-propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF2CF=CF2);

1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1 -propene ((CF₃)₂C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF₂CF₃);

1.1.2.3.4.4.4- heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4- heptafluoro-1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1-butene (CF₃CF₂CF=CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF₂CF₃);

1.2.3.4.4.4- hexafluoro-1-butene (CHF=CFCHFCF₃); 1,2,3,3,4,4hexafluoro-1-butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH₂FCF=CFCF₃);

1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-hexafluoro2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF₂CH₂F); 1,1,2,3,4,4-hexafluoro-1-butene (CF₂=CFCHFCHF₂);

2018282475 21 Dec 2018

3.3.3- trifluoro-2-(trifluoromethyl)-1 -propene (CH2=C(CF3)2); 1,1,1,2,4pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4-pentafluoro-2-butene (CF₃CH=CFCH₂F); 3,3,4,4,4-pentafluoro-1-butene (CF₃CF₂CH=CH2);

1,1,1,4,4-pentafluoro-2-butene (CHF2CH=CHCF3); 1,1,1,2,3-pentafluoro-

2-butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1-butene (CH2=CFCF₂CHF₂); 1,1,2,4,4-pentafluoro-2-butene (CHF₂CF=CHCHF₂);

1.1.2.3.3- pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH₂=CFCHFCF₃);

3.3.4.4- tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1 -difluoro-2- (difluoromethyl)-l-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2methyl-1 -propene (CHF=C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1 propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3);

1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-

1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1 -butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene

2018282475 21 Dec 2018 (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

1.1.1.4.4.4- hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3);

3.3.4.5.5.5- hexafluoro-1 -pentene (CH2=CHCF2CHFCF3); 4,4,4-trifluoro-3- (trifluoromethyl)-l-butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6dodecafluoro-1-hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-

2,3-bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3);

1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2Fs);

1.1.1.3.4.5.5.5- octafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2- butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)1 -pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluorol 30 hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2(trifluoromethyl)-l-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5heptafluoro-2-methyl-1 -pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro35 1 -hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene

2018282475 21 Dec 2018 (CF₃CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CFC2Hs); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2heptene (CF3CF=CFCF₂CF₂C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2Fs);

1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5);

1.1.1.2.4.4.5.5.6.6.7.7.7- tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5);

1.1.1.2.2.4.5.5.6.6.7.7.7- tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5);

1.1.1.2.2.3.5.5.6.6.7.7.7- tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5); CF₂=CFOCF₂CF3 (PEVE) and CF₂=CFOCF3 (PMVE).

Of particular utility in compositions comprising at least one flammable refrigerant and at least one fluoroolefin are those fluoroolefins that themselves are non-flammable. 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.

The flammability factors for several fluoroolefins are listed in Table 4 along with the experimental determination of flammable or non33

2018282475 21 Dec 2018 flammable. Therefore, it can be predicted for the other fluoroolefins of the present disclosure, which will be most useful in combination with the flammable refrigerants of the present disclosure as being in fact nonflammable fluoroolefins.

TABLE 4

Compound	Formula	#F	#H	F/(F+H)	Experimental Flammability (LFL, vol% in air)	Prediction from flammability factor
HFC- 1225ye	C3HF5	5	1	0.83	non-flammable	non-flammable
HFC- 1234yf	C3H2F4	4	2	0.67	6.0	flammable
E-HFC- 1234ze	C3H2F4	4	2	0.67	5.0	flammable
HFC- 1429myz/ mzy (mixture of isomers)	C5HF9	9	1	0.90	non-flammable	non-flammable
F12E	C₆H₂F8	8	2	0.75	non-flammable	non-flammable
Other fluoroolefins
HFC-1243	C3H3F3	3	3	0.15	na	Flammable
FC-1318	C4F8	8	0	1.0	na	non-flammable
HFC-1327	C4HF7	7	1	0.88	na	non-flammable
HFC-1336	C4H2F6	6	2	0.75	na	non-flammable
HFC-1345	C4H3F5	5	3	0.63	na	flammable
HFC-1354	C4H4F4	4	4	0.50	na	flammable
FC-141-10	C5F10	10	0	1.0	na	non-flammable
HFC-1429	C5HF9	9	1	0.90	na	non-flammable
HFC-1438	C5H2F8	8	2	0.80	na	non-flammable
HFC-1447	C5H3F7	7	3	0.70	na	non-flammable
HFC-1456	C5H4F6	6	4	0.6	na	flammable
FC-151-12	C6F12	12	0	1.0	na	non-flammable

2018282475 21 Dec 2018

HFC-152- 11	CeHFn	11	1	0.92	na	non-flammable
HFC-153- 10	C6H2F10	10	2	0.83	na	non-flammable
HFC-1549	CeHsFg	9	3	0.75	na	non-flammable
HFC-1558	C6H4F8	8	4	0.67	na	flammable
HFC-1567	C6H5F7	7	5	0.58	na	flammable
FC-161-14	C7F14	14	0	1.0	na	non-flammable
HFC-162- 13	C7HF13	13	1	0.93	na	non-flammable
HFC-163- 12	C7H2F12	12	2	0.86	na	non-flammable
HFC-164- 11	C7H3F11	11	3	0.79	na	non-flammable
HFC-165- 10	C7H4F10	10	4	0.71	na	non-flammable
HFC-1669	C7H5F9	9	5	0.64	na	flammable
HFC- C1316	C4F6	6	0	1.0	na	non-flammable
HFC- C1418	CsFs	8	0	1.0	na	non-flammable
HFC- C151-10	CeFio	10	0	1.0	na	non-flammable
HFC- C1334	C4H2F4	4	2	0.67	na	flammable
HFC- C1436	C5H2F6	6	2	0.75	na	non-flammable

The fluoroolefins as listed in Table 4 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 5 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.

2018282475 21 Dec 2018

In another embodiment of the present invention, the fluoroolefins for use in compositions with flammable refrigerants are those fluoroolefins selected from the group consisting of:

(b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5, and wherein the flammability factor is greater than or equal to 0.70; and (c) fluoroolefins selected from the group consisting of:

1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3pentafluoro-1-propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1propene (CHF2CF=CF2); 1,1,1,2,3,4,4,4-octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-heptafluoro-1 -butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1 -propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1 -butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1 -butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1 -butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1 -butene (CHF=CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1-butene (CHF=CFCF₂CHF₂); 1,1,2,3,4,4-hexafluoro-2-butene (CHF₂CF=CFCHF₂); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1 -propene (CH2=C(CF3)2); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene

2018282475 21 Dec 2018 (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3(trifluoromethyl)-l-butene (CF2=CFCH(CF3)2); 1,1,1,4,4,410 hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2);

1.1.3.4.4.4- hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-115 butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3(trifluoromethyl)-l-butene (CF2=CHCH(CF3)2); 1,3,4,4,4pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2);

1.1.4.4.4- pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 - butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-125 butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)2-butene (CH3CF=C(CF3)2); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-330 hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3);

1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-235 pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,437

2018282475 21 Dec 2018 hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro5 4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2);

1.1.1.2.2.3.5.5.6.6.7.7.7- tridecafluoro-3-heptene (CF₃CF2CF=CHCF2C2F₅).

In yet another embodiment, the fluoroolefins of the present disclosure that may be particularly useful in combination with flammable refrigerants, may be at least one fluoroolefin selected from the group consisting of:

(a) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹and R² are, independently, Ci to C6 perfluoroalkyl groups, and wherein the flammability factor is greater than or equal to 0.70;

and (b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5, and wherein the flammability factor is greater than or equal to 0.70.

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 of the present invention comprise any compound, which may be demonstrated to propagate a flame under specified conditions of temperature, pressure and composition when

2018282475 21 Dec 2018 mixed with air. Flammable refrigerants may be identified by testing under conditions specified byASHRAE (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 refrigerant at 101 kPa (14.7 psia) and a specified temperature (typically 100 °C (212 °F), or room temperature, that being about 23 °C (73 °F) 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 of the present invention, during such a leak, have a low probability of causing a fire.

Flammable refrigerants of the present invention include hydrofluorocarbons (HFCs), fluoroolefins, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia (NH3), and combinations thereof.

Flammable HFC refrigerants include but are not limited to:

difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1-difluoroethane (HFC152a), fluoroethane (HFC-161), 1,1,1-trifluoropropane (HFC-263fb),

1.1.1.3.3- pentafluoropropane (HFC-365mfc), and combinations thereof. These flammable HFC refrigerants are commercial products available from a number of sources such as chemical synthesis companies or may be prepared by synthetic processes disclosed in the art.

Flammable refrigerants of the present invention further comprise fluoroolefins including but not limited to: 1,2,3,3-tetrafluoro-1propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze);

2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC-1243zf); 1,1,2trifluoro-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).

Flammable refrigerants of the present invention further comprise fluoroethers, compounds similar to hydrofluorocarbons, which

2018282475 21 Dec 2018 also contain at least one ether group oxygen atom. Representative fluoroether refrigerants include but are not limited to C4F9OC2H5, available commercially.

Flammable refrigerants of the present invention further comprise hydrocarbon refrigerants. Representative hydrocarbon refrigerants include but are not limited to propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane (isopentane), cyclobutane, cyclopentane, 2,2-dimethylpropane, 2,2dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 210 methylhexane, 3-methylhexane, 2-methylpentane, 3-ethylpentane, 3methylpentane, cyclohexane, n-heptane, methylcyclopentane, and nhexane. Flammable hydrocarbon refrigerants are readily available from multiple commercial sources.

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

Flammable refrigerants of the present invention further comprise ammonia (NH3), a commercially available compound.

Flammable refrigerants of the present invention may further comprise mixtures of more than one refrigerant such as a mixture of two or more flammable refrigerants (eg. two HFCs or an HFC and a hydrocarbon) or a mixture comprising a flammable refrigerant and a non-flammable refrigerant, such that the overall mixture is still considered to be a flammable refrigerant, identified under the ASTM conditions described herein, or in practical terms.

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, R-245fa, and mixtures of HCFC-22/HFC-152a/HCFC-124 30 (known by the ASHRAE designations, R401 or R-401A, R-401B, and R401C), 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 R35 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

2018282475 21 Dec 2018 designation R-410A), and HFC-125/HFC-143a (known by the ASHRAE designation: R-507 or R507A) and carbon dioxide.

Examples of mixtures of more than one flammable refrigerant include propane/isobutane; HFC-152a/isobutane, R32/propane;

R32/isobutane; and HFC/carbon dioxide mixtures such as HFC-152a/CC>2.

One aspect of the present invention is to provide a nonflammable 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 non10 flammable fluoroolefins to said mixtures.

It may be demonstrated that while certain refrigerants are flammable, it is possible to produce a non-flammable refrigerant composition by adding to the flammable refrigerant another compound that is not flammable. Examples of such nonflammable refrigerant blends 15 include R-410A (HFC-32 is a flammable refrigerant, while HFC-125 is non-flammable), and R-407C (HFC-32 is a flammable refrigerant, while HFC-125 and HFC-134a are not flammable).

The compositions of the present invention that are useful as refrigerants or heat transfer fluids comprising at least one fluoroolefin and 20 at least one flammable refrigerant may contain an effective amount of fluoroolefin to produce a composition that is non-flammable based upon results ofASTM E681-01.

The present inventive compositions comprising at least one flammable refrigerant and at least one fluoroolefin may contain about 1 25 weight percent to about 99 weight percent fluoroolefin and about 99 weight percent to about 1 weight percent flammable refrigerant.

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

Of particular interest is an embodiment of the present disclosure wherein the fluoroolefin comprises HFC-1225ye and the flammable refrigerant comprises HFC-32 (difluoromethane). It has been determined that compositions comprising up to 37 weight percent HFC-32

2018282475 21 Dec 2018 are non-flammable, while compositions comprising 38 weight percent

HFC-32 or greater are flammable as determined by ASTM 681 -01. The present disclosure provides non-flammable compositions comprising about 1.0 weight percent to about 37.0 weight percent HFC-32 and about

99.0 weight percent to about 63 weight percent HFC-1225ye.

Also, of particular interest is an embodiment of the present disclosure wherein the composition comprises HFC-1225ye, HFC-32 and HFC-125. This composition of the present invention comprises about 20 weight percent to about 95 weight percent HFC-1225ye, about 1.0 weight 10 percent to about 65 weight percent HFC-32, and about 1.0 weight percent to about 40 weight percent HFC-125. In another embodiment, the composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC15 125. In yet another embodiment, the composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125. Those compositions containing less than about 40 weight percent HFC-32 are expected to be non-flammable 20 compositions. This flammability limit will vary from less than about 45 weight percent HFC-32 to less than about 37 weight percent HFC-32 depending on the relative ratios of HFC-1225ye and HFC-125 present in the composition.

In another embodiment of particular interest, the flammable 25 refrigerant comprises HFC-1243zf and a non-flammable fluoroolefin intended to reduce the flammability of the overall composition. The composition may comprise about 1.0 weight percent to about 99 weight percent HFC-1243zf and about 99 weight percent to about 1.0 weight percent HFC-1225ye. Alternatively, the composition may comprise 30 about 40 weight percent to about 70 weight percent HFC-1243zf and about 60 weight percent to about 30 weight percent HFC-1225ye.

In another embodiment of particular interest, the composition comprises about 1.0 weight percent to about 98 weight percent HFC1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; 35 and about 1.0 weight percent to about 50 weight percent HFC-125.

Alternatively, the composition comprises about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60

2018282475 21 Dec 2018 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-125.

In another embodiment of particular interest the composition comprises about 1.0 weight percent to about 98 weight percent HFC5 1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye;

and about 1.0 weight percent to about 50 weight percent HFC-32.

Alternatively, the composition comprises about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-32.

In yet another embodiment of particular interest, the composition comprises about 1.0 weight percent to about 97 weight percent HFC-1243zf; about 1.0 weight percent to about 97 weight percent HFC-1225ye; about 1.0 weight percent to about 50 weight percent HFC15 125; and about 1.0 weight percent to about 50 weight percent HFC-32.

Alternatively, the composition comprises about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-125; and about 1.0 weight percent to about 10 weight 20 percent HFC-32.

The present invention further relates to a method for reducing the flammability of a flammable refrigerant said method comprising combining the flammable refrigerant with at least one fluoroolefin. The amount of fluoroolefin added must be an effective amount to produce a 25 non-flammable compositions as determined by ASTM 681 -01.

Compositions 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 acitivated 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 compositions of the present invention may further comprise at least one lubricant. Lubricants of the present invention comprise those 35 suitable for use with refrigeration or air-conditioning apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such

2018282475 21 Dec 2018 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 5 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 10 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, and poly(alphaolefins). Representative conventional lubricants of the present 15 invention are the 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 20 sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).

Lubricants 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 25 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) 30 such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs).

Lubricants 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

2018282475 21 Dec 2018 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, 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 at least one fluoroolefin 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 of the present invention may comprise specific combinations of stabilizers. One combination of

2018282475 21 Dec 2018 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-1,3butadiene) unit. Terpenes may be acyclic or cyclic. Representative terpenes include but are not limited to myrcene (2-methyl-6-methyleneocta-1,7-diene), allo-cimene, beta-ocimene, terebene, limonene (ord10 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. [29788-49-6]); 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]); dammarane (CAS reg. no. [545-22-2]); drimane (CAS reg. no. [5951-58-6]); eremophilane (CAS reg. no. [324205-5]); 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. [471-625]); humulane (CAS reg. no. [430-19-3]); kaurane (CAS reg. no. [1573-406]); labdane (CAS reg. no. [561-90-0]); lanostane (CAS reg. no. [474-2035 4]); lupane (CAS reg. no. [464-99-3]); p-menthane (CAS reg. no. [99-821]); oleanane (CAS reg. no. [471-67-0]); ophiobolane (CAS reg. no. [20098-65-1]); picrasane (CAS reg. no. [35732-97-9]); pimarane (CAS reg.

2018282475 21 Dec 2018 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 1,210 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 of the present invention may be combined with at least one fluorinated epoxide. The fluorinated epoxides of the present invention may be 15 depicted by Formula 3, wherein each of r2 through R$ 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 R$ 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, volume 56, pages 3187 to 3189 (1991), and Journal of Fluorine Chemistry, volume 125, pages 99105 (2004).

In another embodiment, the terpene or terpenoid stabilizers of the present invention may be combined with at least one oxetane. The oxetane stabilizers of the present invention may be compounds with one or more oxetane groups and is represented by Formula 4, wherein R1-R6

2018282475 21 Dec 2018 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 3ethyl-3-((2-ethyl-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-4methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6tertbutylphenol; 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-tert-butylphenol); 4,4’-thiobis(3-methyl-648

2018282475 21 Dec 2018 tertbutylphenol); 2,2’-thiobis(4methyl-6-tert-butylphenol); and the like, alkylidene-bisphenols including,: 4,4’-methylenebis(2,6-di-tertbutylphenol); 4,4’-bis(2,6-di-tert-butylphenol); derivatives of 2,2’- or 4,4biphenoldiols; 2,2’-methylenebis(4-ethyl-6-tertbutylphenol); 2,2’5 methylenebis(4-methyl-6-tertbutylphenol); 4,4-butylidenebis(3-methyl-6tert-butylphenol); 4,4-isopropylidenebis(2,6-di-tert-butylphenol); 2,2’methylenebis(4-methyl-6-nonylphenol); 2,2’-isobutylidenebis(4,6dimethylphenol; 2,2’-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4- biphenyldiols including 2,2’-methylenebis(4-ethyl-6-tert-butylphenol);

butylated hydroxyl toluene (BHT), bisphenols comprising heteroatoms including 2,6-di-tert-alpha-dimethylamino-p-cresol, 4,4-thiobis(6-tert-butylm-cresol); and the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N’dimethylaminomethylphenol); sulfides including; bis(3-methyl-4-hydroxy-5tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl-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. 32687-78-8);

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.

2018282475 21 Dec 2018

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 5 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 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. Patent application serial no. 11/062,044, filed February 18, 2005.

Typical tracer compounds for use in the present compositions are listed in Table 5.

TABLE 5

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-245faEpy or HFOC-	CHF2OCH2CF3

2018282475 21 Dec 2018

245faEap	(or CHF2CH2OCF3)
HFOC-245cbEpy or HFOC-245cbap	CH3OCF2CF3 (or CH3CF2OCF3)
HFE-42-11 mcc (or Freon® E1)	CF3CF2CF2OCHFCF3
Freon® E2	CF₃CF2CF2OCF(CF3)CF₂OCHFCF3
Hydrofluorocarbons
HFC-23	CHF3
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	(CH₃)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

2018282475 21 Dec 2018

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

Perfluorotrimethylcyclo-hexane (all	Cyclo(-
possible isomers)	CF₂(CF3)CF2(CF3)CF2CF2(CF3)CF₂-)
Perfluoroisopropylcyclo-hexane	Cyclo(-
	CF2CF2(CF2(CF3)2)CF2CF2CF₂CF2-)
Perfluorodecalin (cis or trans, trans	C10F18 (see structure below)
shown)

Perfluoromethyldecalin (cis or trans	C11F20 (see structure below)
and all additional possible isomers)


	F F f f
Brominated compounds
Bromomethane	CHsBr
Bromofluoromethane	CH₂FBr
Bromodifluoromethane	CHF₂Br
Dibromofluoromethane	CHFBr₂
Tribromomethane	CHBrs
Bromoethane	CH₃CH₂Br

2018282475 21 Dec 2018

Bromoethene	CH₂=CHBr
1,2-dibromoethane	CH2BrCH₂Br
1 -bromo-1,2-difluoroethene	CFBr=CHF
lodated compounds
lodotrifluoromethane	CFsl
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	CeFsl
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)	ΟΗ₃Ο(Ο)ΟΗ₂ΟΗ₃
Other
Nitrous oxide	N2O

The compounds listed in Table 5 are available commercially (from chemical supply houses) or may be prepared by processes known in 5 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 10 from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.

Additionally, some of the compounds in Table 4 exist as multiple isomers, structural or optical. Single isomers or multiple isomers

2018282475 21 Dec 2018 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. 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 10 present at a total concentration of about 100 ppm to about 300 ppm.

The compositions of the present invention may further comprise an ultra-violet (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 15 dye in the refrigerant or heat transfer fluid composition at or in the vicinity of a leak point in said apparatus in the refrigeration, air-conditioning, 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, airconditioning, 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, 35 nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.

2018282475 21 Dec 2018

Hydrocarbon solubilizing agents 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 5 solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, octane, decane, and hexadecane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention 10 comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Polyoxyalkylene glycol ether solubilizing agents 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 hydrogen 15 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, feri-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with

2018282475 21 Dec 2018 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 R²oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing 10 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 15 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, 1,2,3trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their 20 hydroxyl radicals.

Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH3OCH2CH(CH3)O(H or CH3) (propylene glycol methyl (or dimethyl) ether), ΟΗ₃Ο[ΟΗ₂ΟΗ(ΟΗ3)Ο]2(Η or CH3) (dipropylene glycol methyl (or dimethyl) ether), CH3O[CH2CH(CH3)O]3(H 25 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 or C3H7) (propylene glycol n-propyl 30 (or di-n-propyl) ether), C3H7O[CH2CH(CH3)O]2(H or C3H7) (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 35 or C4H9) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH3)3COCH2CH(CH3)OH (propylene glycol t-butyl ether), (ΟΗ₃)3ΟΟ[ΟΗ₂ΟΗ(ΟΗ3)Ο]2(Η or (CH₃)₃) (dipropylene glycol t-butyl (or di-t56

2018282475 21 Dec 2018 butyl) ether), (CH3)3CO[CH2CH(CH3)O]3(H or (CH3)3) (tripropylene glycol tbutyl (or di-t-butyl) ether), C5HnOCH2CH(CH3)OH (propylene glycol npentyl ether), C4H9OCH2CH(C2H5)OH (butylene glycol n-butyl ether), C4H9O[CH₂CH(C2H5)O]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C2H5C(CH2O(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether (C2H5C(CH2OC(CH2)3CH3)2CH2OH).

Amide solubilizing agents 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, R³and 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 non-hydrocarbon 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 non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents 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, feri-butyl, pentyl, isopentyl, neopentyl, tert-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(O)N(R⁵)-] may be represented by the hydrocarbylene radical (CR⁶R⁷)n, in other words, the formula: cyclo[(CR⁶R⁷)nC(O)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 R^1-3. In the

2018282475 21 Dec 2018 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: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5methylpyrrolidin-2-one, 1 -butylcaprolactam, 1 -cyclohexylpyrrolidin-2-one, 1 -butyl-5-methylpiperid-2-one, 1 -pentyl-5-methylpiperid-2-one, 1 10 hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents 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. R¹and R² 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 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. 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 non35 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

2018282475 21 Dec 2018

R¹C(O)R² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-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: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl 10 ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R¹CN, wherein R¹ is selected from 15 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, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as 35 phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative nitrile solubilizing agents include but are not limited to: 1cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 159

2018282475 21 Dec 2018 cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCIx, wherein; x is 5 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 RCIx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, feri-butyl, pentyl, isopentyl, neopentyl, tert-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, 1chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents 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 Cz alkyl acetate), “Exxate

800” (a commercial Cs alkyl acetate), dibutyl phthalate, and tert-butyl acetate.

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

2018282475 21 Dec 2018

[A] [Β] [C]

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 Rs are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 through Rs may be connected forming a ring with another R1 through Rs. 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 6.

TABLE 6

Additive	Molecular Structure	Molecular Formula	Molecular Weight (amu)
(E,Z)-3-ethylidene-5methyl-dihydro-furan-2one	A:	C7H10O2	126
(E,Z)-3-propylidene-5methyl-dihydro-furan-2one		C8H12O2	140
(E,Z)-3-butylidene-5methyl-dihydro-furan-2one		C9H14O2	154
(E,Z)-3-pentylidene-5methyl-dihydro-furan-2one		C10H16O2	168
(E,Z)-3-Hexylidene-5methyl-dihydro-furan-2one		C11H18O2	182

2018282475 21 Dec 2018

(E,Z)-3-Heptylidene-5methyl-dihydro-furan-2one		C12H20O2	196
(E,Z)-3-octylidene-5methyl-dihydro-furan-2one		C13H22O2	210
(E,Z)-3-nonylidene-5methyl-dihydro-furan-2one		C14H24O2	224
(E,Z)-3-decylidene-5methyl-dihydro-furan-2one		C15H26O2	238
(E,Z)-3-(3,5,5- trimethylhexylidene)-5methyl-dihydrofuran-2one	AC-Y	C14H24O2	224
(E,Z)-3cyclohexylmethylidene5-methyl-dihydrofuran2-one	Yo	C12H18O2	194
gamma-octalactone	—Yr	C8H14O2	142
gamma-nonalactone	--—Yr	C9H16O2	156
gamma-decalactone	—Yr°	C10H18O2	170
gamma-undecalactone	-—--Yr	C11H20O2	184
gamma-dodecalactone	———Yr	C12H22O2	198
3-h exyl d i h yd ro-fu ra n -2one	0	C10H18O2	170
3-heptyldihydro-furan- 2-one	0	C11H20O2	184
c/s-3-ethyl-5-methyldihydro-furan-2-one	0 Y	C7H12O2	128
c/s-(3-propyl-5-methyl)- dihydro-furan-2-one	—	C8H14O2	142
c/s-(3-butyl-5-methyl)- dihydro-furan-2-one	—ήο	C9H16O2	156

2018282475 21 Dec 2018

c/s-(3-pentyl-5-methyl)- dihydro-furan-2-one		C10H18O2	170
c/s-3-hexyl-5-methyldihydro-furan-2-one		C11H20O2	184
c/s-3-heptyl-5-methyldihydro-furan-2-one		C12H22O2	198
c/s-3-octyl-5-methyldihydro-furan-2-one		C13H24O2	212
c/s-3-(3,5,5trimethylhexyl)-5methyl-dihydro-furan-2one	τυ-Α	C14H26O2	226
c/s-3-cyclohexylmethyl- 5-methyl-dihydro-furan2-one	c~4	C12H20O2	196
5-methyl-5-hexyldihydro-furan-2-one	o	C11H20O2	184
5-methyl-5-octyldihydro-furan-2-one	0	C13H24O2	212
Hexahydroisobenzofuran-1 -one	Civ H	C8H12O2	140
de/fa-decalactone		C10H18O2	170
de/fa-undecalactone		C11H20O2	184
de/fa-dodecalactone		C12H22O2	198
mixture of 4-hexyldihydrofuran-2-one and 3-hexyl-dihydro-furan2-one			C10H18O2	170

Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40°C. For instance, gamma63

2018282475 21 Dec 2018 undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl5-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 U. S. patent application 10/910,495, filed August

3, 2004, incorporated herein by reference.

Aryl ether solubilizing agents 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 10 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, 15 propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-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 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 30 chlorine, fluorine, CF3 or ORt, wherein Rt 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, 35 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

2018282475 21 Dec 2018 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 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 1,1,110 trifluoroalkane solubilizing agents include but are not limited to: 1,1,1trifluorohexane and 1,1,1-trifluorododecane.

Solubilizing agents 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 15 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 refrigerant and UV fluorescent dye, or comprising heat transfer fluid and UV fluorescent dye, 20 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 25 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 patent no. RE 36,951, incorporated herein by reference, describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into 30 a component of the refrigeration or air-conditioning 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, air-conditioning, or heat pump apparatus. The present

2018282475 21 Dec 2018 invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant in combination with a solubilizing agent. The inventive compositions will allow the storage and transport of dye-containing refrigerant and heat transfer fluid even at low temperatures while maintaining the dye in solution.

In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, or comprising 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 10 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 15 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

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 20 include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel, all of which are commercially available, as well as dlimonene 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 25 agent.

The present invention further relates to a method of using the 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 30 compositions allows for detection of leaking refrigerant in the refrigeration, air-conditioning, or heat pump apparatus. Leak detection helps to one to address, resolve and/or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one 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

2018282475 21 Dec 2018 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 5 “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 15 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 re-uses 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 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 positivedisplacement (e.g., reciprocating, scroll or screw) or dynamic (e.g.,

2018282475 21 Dec 2018 centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed.

The compositions of the present invention comprising fluoroolefins may be useful in any of the compressor types mentioned 5 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 10 one preferred type of equipment for certain of the refrigerant compositions comprising at least one 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 15 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 20 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 25 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 zero or nearly zero. A positive displacement 30 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 35 impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression.

2018282475 21 Dec 2018

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 5 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 1,2,2-trichlorotrifluoroethane (CFC113). Some of the low pressure refrigerant fluids 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 (minicentrifugal 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 two-stage centrifugal compressor systems, particularly for automotive applications, are described in US 5,065,990 and US 5,363,674, both incorporated herein by reference.

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 at least one fluoroolefin selected from the group consisting of:

2018282475 21 Dec 2018 (i) fluoroolefins of the formula E- or Z-R¹CH=CHR², wherein R¹ and R²are, independently, Ci to C6 perfluoroalkyl groups,;

(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)_n-], wherein X,

Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5 5; or (iii) fluoroolefins selected from the group consisting of:

1.2.3.3.3- pentafluoro-1 -propene (CF3CF=CHF); 1,1,3,3,3-pentafluoro-1 propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1-propene (CHF2CF=CF2);

1.2.3.3- tetrafluoro-1 -propene (CHF2CF=CHF); 2,3,3,3-tetrafluoro-1 - propene (CF3CF=CH2); 1,3,3,3-tetrafluoro-1-propene (CF3CH=CHF);

1.1.2.3- tetrafluoro-1 -propene (CH2FCF=CF2); 1,1,3,3-tetrafluoro-1 propene (CHF2CH=CF2); 2,3,3-trifluoro-1-propene (CHF2CF=CH2); 3,3,3trifluoro-1-propene (CF3CH=CH2); 1,1,2-trifluoro-1 -propene (CH3CF=CF2);

1.1.3- trifluoro-1 -propene (CH2FCH=CF2); 1,2,3-trifluoro-1 -propene (CH₂FCF=CHF); 1,3,3-trifluoro-1 -propene (CHF₂CH=CHF);

1.1.1.2.3.4.4- heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-

2-(trifluoromethyl)-1-propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF₂=CFCHFCF₃); 1,1,2,3,3,4,4-heptafluoro-1 -butene (CF2=CFCF₂CHF₂);

2.3.3.4.4.4- hexafluoro-1 -butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-

1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1 -butene (CHF=CFCF₂CHF₂);

1.1.2.3.3.4- hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4- hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)1-propene (CH2=C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH₂FCH=CFCF₃); 1,1,1,3,4-pentafluoro-2-butene (CF₃CH=CFCH₂F);

3.3.4.4.4- pentafluoro-1 -butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2butene (CHF2CH=CHCF3); 1,1,1,2,3-pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1-butene (CH2=CFCF2CHF2);

1.1.2.4.4- pentafluoro-2-butene (CHF2CF=CHCHF2); 1,1,2,3,3-pentafluoro-

1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2-butene

2018282475 21 Dec 2018 (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF₂)(CF₃)); 2,3,4,4,4-pentafluoro-1-butene (CH₂=CFCHFCF₃);

1.2.4.4.4- pentafluoro-1 -butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1 - butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF₂CHF₂); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF₂);

3.3.4.4- tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-difluoro-2(difluoromethyl)-l-propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2methyl-1 -propene (CHF=C(CF3)(CH3)); 2-difluoromethyl-3,3-difluoro-1 - propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3);

1- pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-

2- butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene

2018282475 21 Dec 2018 (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

1.1.1.4.4.4- hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3);

3.3.4.5.5.5- hexafluoro-1-pentene (CH2=CHCF2CHFCF3); 3(trifluoromethyl)-4,4,4-trifluoro-1 -butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF3(CF2)3CF=CF2);

1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3);

1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene ((CF3)2C=C(CF3)2);

1.1.1.2.3.4.5.5.5- nonafluoro-4-(trifluoromethyl)-2-pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CHC2Fs); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-

2-pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)1 -pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl20 2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluoro-1 hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-225 (trifluoromethyl)-l-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5heptafluoro-2-methyl-1 -pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro1-hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-trifluoromethyl-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3heptene (CF3CF2CF=CFCF2C2Fs); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro35 2-heptene (CF3CH=CFCF₂CF₂C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5);

1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5);

2018282475 21 Dec 2018

1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5); CF₂=CFOCF₂CF3 (PEVE); CF₂=CFOCF3 (PMVE) and combinations thereof.

The method for producing heating or cooling may be used in stationary air-conditioning, 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, self10 contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

The compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or 15 horizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. The low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design 20 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 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 fluoroolefin compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions.

The present invention further relates to a process for producing 30 heat comprising condensing the fluoroolefin compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.

The present invention further relates to a process to produce cooling comprising compressing a composition comprising at least one 35 fluoroolefin in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be

2018282475 21 Dec 2018 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 of the present invention, and thereafter evaporating said composition in the vicinity of a body to be cooled.

The compositions 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 15 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 R-134a 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 minicentrifugal compressor may be powered by an engine exhaust gas driven 25 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 30 powered by an engine exhaust gas driven turbine is described in detail in U.S. Patent Application serial no. 11/367,517, filed March 3, 2006,. A refrigeration apparatus or air-conditioning apparatus powered by a ratioed gear drive assembly is described in detail in U.S. Patent Application serial no. 11/378,832, filed March 17, 2006.

The present invention further relates to a process to produce cooling comprising compressing a composition of the present invention, in a mini-centrifugal compressor powered by an engine exhaust gas driven

2018282475 21 Dec 2018 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 of the present invention, in 5 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 of the 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 at least one fluoroolefin of the present invention as the replacement. In another embodiment of the present invention the refrigerant or heat transfer fluid composition 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 fluoroolefin compositions 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 30 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

2018282475 21 Dec 2018 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 (1,1,1,2tetrafluoroethane).

The present invention will provide compositions that have zero or low ozone depletion potential and low global warming potential (GWP). The fluoroolefins of the present invention or mixtures of fluoroolefins of this invention with other refrigerants will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use.

Typically, the fluoroolefins 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 fluoroolefins to said mixtures.

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 at least one fluoroolefin of the present invention. In another embodiment, the method 20 for lowering the global warming potential comprises combining said first composition with a composition comprising at least one 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 25 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 at least one fluoroolefin to lower global warming potential of an original refrigerant or heat transfer 30 fluid composition, said method comprising combining said original refrigerant or heat transfer fluid composition with the composition of the present invention comprising at least one 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 35 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

2018282475 21 Dec 2018 refrigeration, air-conditioning 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 10 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 15 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, 20 chlorofluorocarbon refrigerants, hydrochlorofluorocarbon, refrigerants, fluoroether refrigerants, or blends of refrigerant compounds.

The hydrofluorocarbon refrigerants of the present invention which may need replacing include but are not limited to: CHF3 (HFC-23), CH2F2 (HFC-32), CH3F (HFC-41), CHF2CF3 (HFC-125), CHF2CHF2 (HFC25 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 30 (HFC-245ea), CH2FCHFCF3 (HFC-245eb), CHF2CH2CF3 (HFC-245fa),

CH2FCF2CH2F (HFC-254ca), CH3CF2CHF2 (HFC-254cb), CH2FCHFCHF2 (HFC-254ea), CH3CHFCF3 (HFC-254eb), CHF2CH2CHF2 (HFC-254fa), CH2FCH2CF3 (HFC-254fb), CF3CH2CH3 (HFC-263fb), CH3CF2CH2F (HFC263ca), CH3CF2CH3 (HFC-272ca), CH3CHFCH2F (HFC-272ea), 35 CH2FCH2CH2F (HFC-272fa), CH3CH2CF2H (HFC-272fb), CH3CHFCH3 (HFC-281ea), CH3CH2CH2F (HFC-281fa), CHF2CF2CF2CF2H (HFC338pcc), CF3CH2CF2CH3 (HFC-365mfc), CF3CHFCHFCF2CF3 (HFC-4377

2018282475 21 Dec 2018

10mee). These hydrofluorocarbon refrigerants are available commercially or may be prepared by methods known in the art.

Hydrofluorocarbon refrigerants of the present invention may further comprise the azeotropic, azeotrope-like and non-azeotropic compositions, including HFC-125/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 of the present invention which may need replacing include R22 (CHF2CI), R123 (CHCI2CF3), R124 (CHCIFCF3), R502 (being a blend of CFC-115 (CCIF2CF3) and R22), R503 15 (being a blend of R23/R13 (CCIF3)), and others.

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

The fluoroether refrigerants of the present invention 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 of the present invention which may need replacement may optionally further comprise combinations of refrigerants that contain up to 10 weight percent of dimethyl ether, or at least one C3 to Cs hydrocarbon, e.g., propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, cyclopentane and neopentane (2,2-dimethylpropane). Examples of refrigerants containing such C3 to Cs hydrocarbons are azeotrope-like compositions of HCFC-22/HFC-125/propane (known by the ASHRAE designation, R402 or R402A and R402B), HCFC-22/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), HFC78

2018282475 21 Dec 2018

134a/HCFC-124/n-butane (known by the ASHRAE designation, R416 or R416A), HFC-125/HFC-134a/n-butane (known by the ASHRAE designation, R417 or R417A), HFC-125/HFC-134a/dimethyl ether (known by the ASHRAE designation, R419 or R419A), and HFC-125/HFC5 134a/isobutane (known by ASHRAE designation, R422 , R422A, R422B, R422C, R422D).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R134a (HFC-134a, 1,1,1,2-tetrafluoroethane,

CF3CH2F) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting R134a with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of trifluoromethyl trifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R152a (HFC-152a, 1,1-difluoroethane, CHF2CH3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting R152a with a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing

R227ea (HFC-227ea, 1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises providing as a substitute a composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R113 (CFC-113, 1,1,2-trichloro-1,2,2-trifluoroethane, CFCI2CF2CI) in refrigeration apparatus, air-conditioning apparatus, or heat

2018282475 21 Dec 2018 pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5-octafluoro4-(trifluoromethyl)-2-butene (HFC-152-1 Immyyz); 1,1,1,4,4,5,5,55 octafluoro-2-(trifluoromethyl)-2-pentene (HFC-152-11 mmtz);

1.1.1.2.2.3.4.5.5.6.6.6- dodecafluoro-3-hexene (HFC-151 -12mcy); 1,1,1,3tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt); 1,2,3,3,4,4,5,5,6,6decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5-heptafluoro-2- methyl-1-pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz);

1.1.1.4.4.5.5.6.6.6- decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-151-12mmzz); and

1.1.1.2.2.5.5.6.6.6- decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R43-10mee (HFC-43-10mee), 1,1,1,2,3,4,4,5,5,5decafluoropentane, CF3CHFCHFCF2CF3) in refrigeration apparatus, airconditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene (HFC152-11 mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene (HFC-152-11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC25 151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4hexafluoro-2,3-bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt);

1.2.3.3.4.4.5.5.6.6- decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5heptafluoro-2-methyl-1 -pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-

1567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);

1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-15112mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being C4F9OCH3 (perfluorobutyl methyl ether) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer

2018282475 21 Dec 2018 fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene (HFC-152-1 Immyyz); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene (HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-35 hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy);

1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene (HFC-15112mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151 -1 Oy);

3.3.4.4.5.5.5- heptafluoro-2-methyl-1 -pentene (HFC-1567fts);

3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-210 hexene (HFC-1567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);

1.1.1.2.3.4.5.5.5- nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-15112mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original 15 composition being R365mfc (HFC-365mfc, 1,1,1,3,3-pentafluorobutane, CF3CH2CF2CH3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,520 octafluoro-4-(trifluoromethyl)-2-butene (HFC-152-11 mmyyz);

1.1.1.4.4.5.5.5- octafluoro-2-(trifluoromethyl)-2-pentene (HFC-15211mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-15112mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4hexafluoro-2,3-bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt);

1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5heptafluoro-2-methyl-1 -pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC1567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E);

1.1.1.2.3.4.5.5.5- nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-151-

12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R11 (CFC-11, trichlorofluoromethane, CFCh) in refrigeration apparatus, air-conditioning apparatus, or heat pump 35 apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,4,4,5,581

2018282475 21 Dec 2018 octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4,5,5,5-decafluoro-2pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC1429myz); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy);

3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz),;1,1,1,4,4,4-hexafluoro5 2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R123 (HCFC-123, 2,2-dichloro-1,1,1-trifluoroethane, 10 CF3CHCI2) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,4,4,5,5octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4,5,5,5-decafluoro-215 pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC1429myz); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429mzy);

3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz),;1,1,1,4,4,4-hexafluoro2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC1429mzt); and 1,1,1,4,4,5,5,5-octafluoro-2-pentene (F12E).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R245fa (HFC-245fa, 1,1,1,3,3-pentafluoropropane, CF3CH2CHF2) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 2,3,3trifluoropropene (HFC-1243yf); 1,1,1,4,4,4-hexafluoro-2-butene (F11E);

1,3,3,3-tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2butene (HFC-1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R114 (CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane, CFCI2CF2CI) in refrigeration apparatus, air-conditioning apparatus, or heat 35 pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,2,3,4,4,4-octafluoro82

2018282475 21 Dec 2018

2-butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc);

2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and 3,3,4,4,4-pentafluoro-

1- butene (HFC-1345fz).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R236fa (HFC-236fa, 1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,2,3,4,4,4-octafluoro-

2- butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FC-C1316cc);

2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and 3,3,4,4,4-pentafluoro1-butene (HFC-1345fz).

The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R401A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 20 E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R401A is the ASHRAE designation for a refrigerant blend containing about 53 weight percent HCFC-22 (chlorodifluoromethane, CHF2CI), about 13 weight percent HFC-152a (1,1-difluoroethane, CHF2CH3), and about 34 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original 30 composition being R401B in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,335 pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R401B is the ASHRAE designation for a

2018282475 21 Dec 2018 refrigerant blend containing about 61 weight percent HCFC-22 (chlorodifluoromethane, CHF2CI), about 11 weight percent HFC-152a (1,1-difluoroethane, CHF2CH3), and about 28 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R409A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R409A is the ASHRAE designation for a refrigerant blend containing about 60 weight percent HCFC-22 (chlorodifluoromethane, CHF2CI), about 25 weight percent HCFC-124 (2chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF), and about 15 weight percent HCFC-142b (1-chloro-1,1 -difluoroethane, CF2CICH3).

The present invention further relates to a method for replacing 20 an original refrigerant or heat transfer fluid composition, said original composition being R409B in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 25 E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R409B is the ASHRAE designation for a refrigerant blend containing about 65 weight percent HCFC-22 (chlorodifluoromethane, CHF2CI), about 25 weight percent HCFC-124 (2chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF), and about 10 weight percent HCFC-142b (1-chloro-1,1 -difluoroethane, CF2CICH3).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original 35 composition being R414B in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition

2018282475 21 Dec 2018 comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropropene (HFC1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE).. R414B is the ASHRAE designation for a refrigerant blend containing about 50 weight percent HCFC-22 (chlorodifluoromethane, CHF2CI), about 39 weight percent HCFC-124 (2chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF), about 1.5 weight percent isobutane (R600a, CH3CH(CH3)CH3) and about 9.5 weight percent HCFC10 142b (1 -chloro-1,1 -difluoroethane, CF2CICH3).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R416A in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises 15 substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R416A is the ASHRAE designation for a refrigerant blend containing about 59 weight percent HFC-134a (1,1,1,2tetrafluoroethane, CF3CH2F)), about 39.5 weight percent HCFC-124 (2chloro-1,1,1,2-tetrafluoroethane, CF3CHCIF), and about 1.5 weight percent n-butane (CH3CH2CH2CH3).

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R12 (CFC-12, dichlorodifluoromethane, CF2CI2) in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE)..

The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid composition, said original composition being R500 in refrigeration apparatus, air-conditioning

2018282475 21 Dec 2018 apparatus, or heat pump apparatus, wherein said method comprises substituting a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE).. R500 is the ASHRAE designation for an azeotropic refrigerant blend containing about 73.8 weight percent R12 ((CFC-12, dichlorodifluoromethane, CF2CI2) and about 26.2 weight percent R152a (HFC-152a, 1,1-difluoroethane, CHF2CH3).

The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In another embodiment, the second refrigerant or heat transfer fluid composition may comprise about 1.0 weight percent to about 10 weight percent HFC-32 and about 99 weight percent to about 90 weight percent HFC-1225ye.

The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition R22, R404A, or R410A and wherein said R22, R404A or R410A is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye. In another embodiment, the second refrigerant or heat transfer fluid composition may comprise about 20 weight percent to about 37 weight percent HFC-32 and about 80 weight percent to about 63 weight percent HFC-1225ye.

The present invention! further relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R410A and wherein said R22, R404A or R410A is substituted by a second refrigerant or heat transfer fluid composition comprising about 20 weight percent to about 95 weight percent HFC-1225ye, about 1.0 weight percent to about 65 weight percent HFC-32, and about 1.0 weight percent to about 40 weight percent HFC-125. In another embodiment, the second

2018282475 21 Dec 2018 refrigerant or heat transfer fluid composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125. In yet another embodiment, the second refrigerant or heat transfer fluid composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125.

The present invention relates to a method for replacing an original refrigerant or heat transfer fluid composition wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising:

HFC-1243zf and HFC-1225ye;

HFC-1243zf, HFC-1225ye, and HFC-125;

HFC-1243zf, HFC-1225ye, and HFC-32; or HFC-1243zf, HFC-1225ye, HFC-125, and HFC-32.

In all the previously described methods for replacing refrigerants, the fluoroolefins may be used to replace refrigerant in existing equipment. Additionally, the fluoroolefins may be used to replace refrigerant in existing equipment designed for use of said refrigerant. Additionally, the fluoroolefins 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 of the present invention into said refrigerant apparatus or air-conditioning apparatus.

Refrigerant that may leak from a refrigeration apparatus, air30 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, air87

2018282475 21 Dec 2018 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, the non-flammable fluoroolefins 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 non-flammable fluoroolefins of the present invention reduce the probability of a 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 at least one non-flammable fluoroolefin with a flammable refrigerant and introducing the combination into a refrigeration apparatus, air-conditioning 15 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 at least one non-flammable fluoroolefin with a lubricant and introducing the 20 combination into the refrigeration apparatus, air-conditioning 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 at 25 least one fluoroolefin 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 at least one fluoroolefin.

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 at least one fluoroolefin.

The present invention further relates to a process for transfer of heat from a heat source to a heat sink wherein the compositions of the present invention serve as heat transfer fluids. Said process for heat

2018282475 21 Dec 2018 transfer comprises transporting the compositions 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, 5 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 15 refrigeration or cooling, such as refrigerator or 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 20 heat sink.

EXAMPLES

EXAMPLE 1

Performance Data

Table 7 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-113, HFC-43-10mee, C4F9OCH3, 30 and HFC-365mfc. The data are based on the following conditions.

Evaporator temperature Condenser temperature Subcool temperature Return gas temperature

40.0°F (4.4°C)

110.0°F (43.3°C)

10.0°F (5.5°C)

75.0°F (23.8°C)

Compressor efficiency is 70%

2018282475 21 Dec 2018

TABLE 7

Compound	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T (F)	Comp Disch T (C)	COP	Cap (Btu/min)	Cap (kW)

CFC-113	2.7	18.6	12.8	88.3	156.3	69.1	4.18	14.8	0.26
HFC-43-10mee	2.0	13.4	10.4	71.9	132.8	56.0	3.94	12.2	0.21
C4F9OCH3	1.5	10.1	8.3	57.0	131.3	55.2	3.93	9.5	0.17
HFC-365mfc	3.6	25.1	16.3	112.1	146.3	63.5	4.11	21.4	0.38

1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-butene ((HFC-152-1 Immyyz)	2.1	14.4	10.7	71.9	127.1	52.8	3.83	12.3	0.24
1,1,1,4,4,5,5,5-octafluoro-2- (trifluoromethyl)-2-pentene (HFC-152-11mmtz)	2.0	13.4	10.4	71.9	127.3	52.9	3.83	11.8	0.23
1,1,1,2,2,3,4,5,5,6,6,6dodecafluoro-3-hexene (FC-151-12mcy)	2.5	17.3	12.3	85.1	121.8	49.9	3.69	13.8	0.24
1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy)	2.5	17.4	11.6	80.1	162.0	72.2	4.25	15.9	0.28
1,1,1,4,4,4-hexafluoro-2,3- bis(trifluoromethyl)-2-butene (FC-151-12mmtt)	2.0	13.5	10.0	69.2	122.7	50.4	3.73	11.2	0.20
1,2,3,3,4,4,5,5,6,6- decafluorocyclohexene (FC-C151-10y)	2.1	14.4	10.6	72.9	126.7	52.6	3.84	12.3	0.22
3,3,4,4,5,5,5-heptafluoro-2methyl-1-pentene (HFC-1567fts)	2.0	14.1	9.9	68.5	130.0	54.4	3.92	12.0	0.21
3,3,4,4,5,5,6,6,6-nonafluoro-1- hexene (PFBE)	1.6	11.0	8.6	59.4	130.7	54.8	3.92	10.0	0.18
4,4,5,5,6,6,6-heptafluoro-2- hexene (HFC-1567szz)	1.3	9.2	7.4	51.3	137.8	58.8	4.04	8.9	0.16
1,1,1,4,4,5,5,6,6,6-decafluoro- 2-hexene (F13E)	2.0	13.7	10.7	73.8	131.1	55.1	3.90	12.4	0.22
1,1,1,2,3,4,5,5,5-nonafluoro- 4-(trifluoromethyl)-2- pentene (FC-151-12mmzz)	2.5	17.3	12.3	85.1	121.8	49.9	3.69	13.8	0.24
1,1,1,2,2,5,5,6,6,6- decafluoro-3-hexene (F22E)	2.4	16.6	12.6	86.7	128.0	53.3	3.83	14.4	0.25

EXAMPLE 2

Performance Data

Table 8 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-11 and HCFC-123. The data are based on the following conditions.

Evaporator temperature 40.0°F (4.4°C)

Condenser temperature 110.0°F (43.3°C)

2018282475 21 Dec 2018

Subcool temperature Return gas temperature Compressor efficiency is

10.0°F (5.5°C)

75.0°F (23.8°C)

70%

TABLE 8

Compound	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T (F)	Comp Disch T (C)	COP	Cap (Btu/min)	Cap (kW)

CFC-11	7.1	49.0	28.0	192.8	190.5	88.1	4.29	41.1	0.72
HCFC-123	5.8	40.3	25.0	172.4	174.2	79.0	4.25	35.2	0.62

1,2,3,3,4,4,5,5- octafluorocyclopentene (FC-C1418y)	6.0	41.6	25.3	174.6	131.7	55.4	3.87	31.6	0.55
1,1,1,2,3,4,4,5,5,5- decafluoro-2-pentene (FC-141-10myy)	7.5	51.8	30.0	206.6	124.9	51.6	3.66	35.3	0.62
1,1,1,2,4,4,5,5,5- nonafluoro-2-pentene (HFC-1429myz)	5.5	37.9	23.7	163.1	132.0	55.6	3.85	29.0	0.51
1,1,1,3,4,4,5,5,5- nonafluoro-2-pentene (HFC-1429mzy)	5.5	37.9	23.7	163.1	132.0	55.6	3.85	29.0	0.51
3,3,4,4,5,5,5heptafluoro-1 -pentene (HFC-1447fz)	5.4	37.0	23.1	159.3	135.3	57.4	3.92	29.0	0.51
1,1,1,4,4,4-hexafluoro-2butene (F11E)	4.7	32.3	20.8	143.4	150.1	65.6	4.11	27.5	0.48
1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl)-2butene (HFC-1429mzt)	4.8	33.0	21.0	144.9	132.6	55.9	3.88	25.9	0.45
1,1,1,4,4,5,5,5- octafluoro-2-pentene (F12E)	5.5	37.9	24.4	168.0	137.0	58.3	3.93	30.6	0.54

EXAMPLE 3

Performance Data

Table 9 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to HFC-245fa. The data are based on the following conditions.

Evaporator temperature

Condenser temperature

Subcool temperature

40.0°F (4.4°C)

110.0°F (43.3°C)

10.0°F (5.5°C)

2018282475 21 Dec 2018

Return gas temperature 75.0°F (23.8°C)

Compressor efficiency is 70%

TABLE 9

Compound	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T (F)	Comp Disch T (C)	COP	Cap (Btu/min)	Cap (kW)

HFC- 245fa	10.0	68.8	38.9	268.5	156.7	69.3	4.10	53.3	0.93

2,3,3-trifluoropropene (HFC-1243yf)	12.6	87.1	45.4	313.0	172.8	78.2	4.19	65.6	1.15
1,1,1,4,4,4-hexafluoro-2- butene (F11E)	12.5	85.9	47.5	327.4	148.8	64.9	3.99	62.8	1.10
1,3,3,3-tetrafluoropropene (HFC-1234ze)	12.1	83.4	45.8	315.6	178.8	81.6	4.19	65.6	1.15
1,1,1,2,4,4,4-heptafluoro- 2-butene (HFC-1327my)	10.5	72.5	39.9	275.0	142.3	61.3	3.94	52.0	0.91
1,2,3,3-tetrafluoropropene (HFC-1234ye)	9.6	66.3	36.9	254.6	176.9	80.5	4.21	53.0	0.93
pentafluoroethyl trifluorovinyl ether (PEVE)	13.1	90.4	49.3	339.8	130.7	54.8	3.69	59.3	1.04

EXAMPLE 4

Performance Data

Table 10 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to CFC-114 and HFC-236fa. The data are based on the following conditions.

Evaporator temperature Condenser temperature Subcool temperature Return gas temperature Compressor efficiency is

40.0°F (4.4°C)

110.0°F (43.3°C)

10.0°F (5.5°C)

75.0°F (23.8°C)

70%

TABLE 10

Compound	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T (F)	Comp Disch T (C)	COP	Cap (Btu/min)	Cap (kW)

CFC-114	15.4	106.5	54.3	374.2	147.2	64.0	3.97	72.9	1.28
HFC-236fa	18.2	125.8	64.2	442.6	142.8	61.6	3.86	82.9	1.45

2018282475 21 Dec 2018

1,1,1,2,3,4,4,4-octafluoro-2butene (FC-1318my)	17.2	118.8	59.1	407.4	131.8	55.4	3.68	72.1	1.26
1,2,3,3,4,4- hexafluorocyclobutene (FC- C1316cc)	16.5	113.5	58.8	405.4	141.1	60.6	3.90	76.6	1.34
2,3,3,4,4,4-hexafluoro-1 - butene (HFC-1336yf)	14.2	98.2	50.2	346.3	139.4	59.7	3.88	65.3	1.14
3,3,4,4,4-pentafluoro-1- butene (HFC-1345fz)	14.8	101.8	53.5	368.5	145.5	63.1	3.95	70.7	1.24

EXAMPLE 5

Performance Data

Table 11 shows refrigeration performance, as pressure in the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), energy efficiency (COP), and capacity (Cap), for compounds of the present invention as compared to HFC-134a, HFC-152a, and HFC-227ea. The data are based on the following conditions.

40.0°F (4.4°C)

110.0°F (43.3°C)

10.0°F (5.5°C)

75.0°F (23.8°C)

70%

TABLE 11

Compound	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T (F)	Comp Disch T (C)	COP	Cap (Btu/min)	Cap (kW)

HFC-134a	49.6	341.6	161.2	1111.4	168.9	76.1	3.86	213.3	3.73
HFC-152a	46.2	318.8	146.5	1009.9	200.1	93.4	4.02	209.4	3.67
HFC-227ea	32.3	222.7	105.5	727.4	142.9	61.6	3.67	129.3	2.26

2,3,3,3-tetrafluoropropene (HFC-1234yf)	47.4	326.7	139.6	962.2	154.8	68.2	3.79	180.5	3.16
3,3,3-trifluoropropene (HFC1243zf)	39.0	268.8	122.0	841.0	166.2	74.6	3.95	166.3	2.91
1,2,3,3,3-pentafluoropropene (HFC-1225ye)	36.1	248.9	112.9	778.4	157.8	69.9	3.86	148.9	2.61
E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze)	35.5	245.0	115.1	793.9	162.4	72.4	3.90	153.8	2.69
trifluoromethyl trifluorovinyl ether (PMVE)	39.3	271.1	124.0	855.2	140.9	60.5	3.57	147.6	2.58

2018282475 21 Dec 2018

EXAMPLE 6

Flammability

Flammable compounds may be identified by testing under ASTM (American Society of Testing and Materials) E681-01, with an electronic ignition source. Such tests of flammability were conducted on compositions of the present disclosure at 101 kPa (14.7 psia), 50 percent relative humidity, and the temperature indicated, at various concentrations in air in order to determine if flammable and if so, find the lower flammability limit (LFL). The results are given in Table 12.

TABLE 12

Composition	Temperature (°C)	LFL (vol % in air)
HFC-1225ye	100	Non-flammable
HFC-1234yf	100	5.0
E-HFC-1234ze	100	6.0
HFC-1429myz/mzy	23	Non-flammable
F12E	23	Non-flammable
HFC-1225ye/HFC- 32 (65/35 wt%)	60	Non-flammable
HFC-1225ye/HFC- 32 (63/37 wt%)	60	Non-flammable
HFC-1225ye/HFC- 32 (62/38wt%)	60	13.0
HFC-1225ye/HFC- 32 (60/40 wt%)	60	13.0

The results indicate that HFC-1234yf and E-HFC-1234ze are flammable, while HFC-1225ye, HFC-1429myz/mzy, and F12E are nonflammable. For mixtures of HFC-1225ye and HFC-32 (which is known to 15 be flammable in the pure state) it has been determined that 37 weight

2018282475 21 Dec 2018 percent HFC-32 is the highest amount that can be present to maintain the non-flammable characteristic. Those compositions comprising fluoroolefins that are non-flammable are more acceptable candidates as refrigerant or heat transfer fluid compositions.

2018282475 21 Dec 2018

EXAMPLE 7

Tip Speed to Develop Pressure

Tip speed can be estimated by making some fundamental relationships for refrigeration equipment that use centrifugal compressors.

The torque an impeller ideally imparts to a gas is defined as

T = m*(v2*r2-vi*n) Equation 1 where

T = torque, Newton-meters m = mass rate of flow, kg/sec

V2 = tangential velocity of refrigerant leaving impeller (tip speed), meters/sec

Γ2 = radius of exit impeller, meters vi = tangential velocity of refrigerant entering impeller, meters/sec n = radius of inlet of impeller, meters

Assuming the refrigerant enters the impeller in an essentially axial direction, the tangential component of the velocity vi = 0, therefore

T = m*V2*r2 Equation 2

The power required at the shaft is the product of the torque and the rotative speed

P = T* ω Equation 3 where

P = power, W ω = angular velocity, radians/s therefore,

P = T*w = m*V2*r2* ω Equation 4

At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore

Γ2*ω = V2 Equation 5 and

P = m*V2*V2 Equation 6

2018282475 21 Dec 2018

Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression,

P = m*Hj*(1 OOOJ/kJ) Equation 7 where

Hj = Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg.

Combining the two expressions Equation 6 and 7 produces,

V2*V2 = 1000*Hj Equation8

Although Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants.

Table 13 below shows theoretical tip speeds that are calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are:

Evaporator temperature

Condenser temperature

40.0°F (4.4°C)

110.0°F (43.3°C)

Liquid subcool temperature

10.0°F (5.5°C)

Return gas temperature

75.0°F (23.8°C)

Compressor efficiency is 70%

These are typical conditions under which small turbine centrifugal compressors perform.

TABLE 13

Compound	Hi Btu/lb	Hi*0.7 Btu/lb	Hi*0.7 KJ/Kg	Tip speed (V2) m/s	Tip speed relative to CFC-113
CFC-113	10.92	7.6	17.8	133.3	n/a

HFC-152-1 Immyyz	11.56	8.1	18.8	137.2	103%
FC-151-12mcy	11.86	8.3	19.3	139.0	104%
HFC-1354mzy	13.96	9.8	22.7	150.8	113%
FC-151-12mmtt	11.93	8.4	19.4	139.4	105%
FC-C151-10y	12.48	8.7	20.3	142.5	107%
HFC-1567fm	14.21	9.9	23.1	152.1	114%

2018282475 21 Dec 2018

PFBE	12.8	9.0	20.8	144.4	108%
HFC-1567szz	13.42	9.4	21.9	147.8	111%
HFC-1438mzz	11.73	8.2	19.1	138.2	104%
FC-151-12mmzz	11.86	8.3	19.3	139.0	104%
HFC-153-1 Omczz	12.23	8.6	19.9	141.1	106%

The example shows that compounds of the present invention have tip speeds within about 15 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design 5 changes. Most preferred compositions have tip speeds within about 10 percent of CFC-113.

EXAMPLE 8

Refrigeration Performance Data

Table 14 shows the performance of various refrigerant compositions of the present invention as compared to HFC-134a. In Table 14, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, COP is energy efficiency, and CAP is capacity. The data are based on the following conditions.

Evaporator temperature

40.0°F (4.4°C)

Condenser temperature

130.0°F (54.4°C)

Subcool amount

Return gas temperature

Compressor efficiency is

10.0°F (5.5°C)

60.0°F (15.6°C)

100%

Note that the superheat is included in cooling capacity.

TABLE 14

Composition (wt%)	Evap Pres (Psia)	Evap Pres (kPa)	Cond Pres (Psia)	Cond Pres (kPa)	Comp Disch T	Comp Disch T	Cap (Btu/	Cap (kW)	COP
			(El		min)
HFC-134a	50.3	346	214	1476	156	68.9	213	3.73	4.41
HFC-1225ye	37.6	259	165	1138	146	63.3	162	2.84	4.41
HFC-1225ye/HFC-152a (85/15)	39.8	274	173	1193	151	66.1	173	3.03	4.45

2018282475 21 Dec 2018


HFC-1225ye/HFC-32 (97/3)	43.1	297	184	1269	149	65.0	186	3.26	4.50
HFC-1225ye/HFC-32 (96/4)	44.2	305	189	1303	150	65.6	191	3.35	4.51
HFC-1225ye/HFC-32 (95/5)	46.5	321	197	1358	151	66.1	200	3.50	4.53
HFC-1225ye/HFC-32 (94/6)	47.3	326	200	1379	153	67.2	203	3.56	4.52
HFC-1225ye/HFC-32 (93/7)	48.8	336	205	1413	154	67.8	210	3.68	4.53
HFC-1225ye/HFC-32 (90/10)	53.0	365	222	1531	157	69.4	227	3.98	4.52
HFC-1243zf/HFC-1225ye (40/60)	40.8	281	172	1186	148	64.4	170	2.97	4.39
HFC-1243zf/HFC-1225ye (50/50)	41.8	288	174	1200	149	65.0	172	3.02	4.37
HFC-1243zf/HFC-1225ye (60/40)	42.9	296	177	1220	149	65.0	175	3.07	4.36
HFC-1243zf/HFC-1225ye (70/30)	44.1	304	180	1241	150	65.6	178	3.12	4.35
HFC-1243zf/HFC-1225ye/HFC- 125 (40/56/4)	42.7	294	179	1234	148	64.4	176	3.09	4.38
HFC-1243zf/HFC-1225ye/HFC- 125 (50/46/4)	43.7	301	181	1248	149	65.0	179	3.13	4.37
HFC-1243zf/HFC-1225ye/HFC- 125 (60/36/4)	44.8	309	184	1269	149	65.0	182	3.18	4.36
HFC-1243zf/HFC-1225ye/HFC- 125 (70/26/4)	49.9	344	201	1386	153	67.2	202	3.54	4.40
HFC-1243zf/HFC-1225ye/HFC- 32 (40/55/5)	48.4	334	199	1372	153	67.2	202	3.54	4.47
HFC-1243zf/HFC-1225ye/HFC- 32 (42/55/3)	45.6	314	189	1303	151	66.1	190	3.33	4.44
HFC-1243zf/HFC-1225ye/HFC- 32 (60/35/5)	50.3	347	203	1400	154	67.8	206	3.60	4.43
HFC-1243zf/HFC-1225ye/HFC- 32 (62/35/3)	47.7	329	194	1338	152	66.7	195	3.41	4.41
HFC-1243zf/HFC-1225ye/HFC- 125/HFC-32 (40/55/4/1)	44.2	305	184	1269	149	65.0	183	3.21	4.41
HFC-1243zf/HFC-1225ye/HFC- 125/HFC-32 (40/55/3/2)	45.3	312	188	1296	150	65.6	188	3.29	4.42

2018282475 21 Dec 2018

HFC-1243zf/HFC-1225ye/HFC- 125/HFC-32 (60/35/4/1)	46.3	319	189	1303	150	65.6	188	3.29	4.37
HFC-1243zf/HFC-1225ye/HFC- 125/HFC-32 (60/35/3/2)	47.3	326	193	1331	151	66.1	192	3.37	4.39

Several compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower or equivalent discharge pressures and temperatures. Capacity for the compositions listed in Table 14 is also similar to R134a indicating these compositions could be replacement refrigerants for R134a in refrigeration and air-conditioning, and in mobile air-conditioning applications in particular. Results also show cooling capacity of HFC-1225ye can be improved with addition of other compounds such as HFC-32.

EXAMPLE 9

Refrigeration Performance Data

Table 15 shows the performance of various refrigerant compositions of the present invention as compared to R404A and R422A.

In Table 15, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.

Evaporator temperature	-17.8°C
Condenser temperature	46.1°C
Subcool amount	5.5°C
Return gas temperature	15.6°C
Compressor efficiency is	70%

Note that the superheat is included in cooling capacity.

100

2018282475 21 Dec 2018

TABLE 15

Existing Refrigerant Product		Evap Press (kPa))	Cond P Press (kPa)	Compr Disch T iC]	CAP (kJ/m3)	EER

R22		267	1774	144	1697	4.99
R404A		330	2103	101.1	1769	4.64
R507A		342	2151	100.3	1801	4.61
R422A		324	2124	95.0	1699	4.54

Candidate Replacement	wt%
HFC-32/HFC-1225ye	20/80	200	1620	117	1331	4.91
HFC-32/HFC-1225ye	30/70	246	1879	126	1587	4.85
HFC-32/HFC-1225ye	40/60	284	2101	134	1788	4.74
HFC-32/HFC-1225ye	35/65	256	1948	130.5	1652	4.85
HFC-32/HFC-1225ye	37/63	264	1991	132.2	1694	4.81
HFC-32/HFC-125/HFC- 1225ye	10/10/'80	173	1435	107.0	1159	4.97
HFC-32/HFC-125/HFC- 1225ye	15/5.5/79.5	184	1509	111.9	1235	4.97
HFC-32/HFC-125/HFC- 1225ye	24/13.7/62.3	242	1851	119.7	1544	4.85
HFC-32/HFC-125/HFC- 1225ye	25/25/50	276	2041	120.0	1689	4.73
HFC-32/HFC-125/HFC- 1225ye	25/40/35	314	2217	119.0	1840	4.66
HFC-32/HFC-125/HFC- 1225ye	27.5/17.5/55	264	1980	122.8	1653	4.78
HFC-32/HFC-125/HFC- 1225ye	30/10/60	265	1990	125.0	1664	4.78
HFC-32/HFC-125/HFC- 1225ye	30/15/55	276	2046	125.0	1710	4.76
HFC-32/HFC-125/HFC- 1225ye	30/19/51	278	2056	124.8	1724	4.75
HFC-32/HFC-125/HFC- 1225ye	30/20/50	287	2102	124.0	1757	4.73

101

2018282475 21 Dec 2018

HFC-32/HFC-125/HFC- 1225ye	30/30/40	311	2218	124.0	1855	4.68
HFC-32/HFC-125/HFC- 1225ye	30/35/35	324	2271	123.0	1906	4.66
HFC-32/HFC-125/HFC- 1225ye	31/20/49	285	2090	125.5	1756	4.74
HFC-32/HFC-125/HFC- 1225ye	33/22/45	298	2157	127.0	1820	4.72
HFC-32/HFC-125/HFC- 1225ye	35/15/50	296	2157	129.0	1820	4.72
HFC-32/HFC-125/HFC- 1225ye	35/20/45	308	2212	129.0	1868	4.70
HFC-32/HFC-125/HFC- 1225ye	35/30/35	332	2321	127.0	1968	4.66
HFC-32/HFC-125/HFC- 1225ye	35/40/25	357	2424	126.0	2068	4.64
HFC-32/HFC-125/HFC- 1225ye	50/30/20	390	2584	138.0	2277	4.54
HFC-32/HFC-125/HFC- 1225ye	40/30/30	353	2418	131.0	2077	4.66
HFC-32/HFC-125/HFC- 1225ye	40/35/25	364	2465	131.0	2124	4.64
HFC-32/HFC-125/HFC- 1225ye	45/30/25	372	2505	135.0	2180	4.66

Several compositions have energy efficiency (EER) comparable top R404A and R422A. Discharge temperatures are also lower than R404A and R507A. Capacity for the compositions listed in Table 15 is also similar to R404A, R507A, and R422A indicating these compositions could be replacement refrigerants for R404A, R507A, or R422A in refrigeration and air-conditioning.

EXAMPLE 10

Refrigeration Performance Data

Table 16 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22 and

102

2018282475 21 Dec 2018

R410A. In Table 16, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.

5	Evaporator temperature	4°C
	Condenser temperature	43° C
	Subcool amount	6°C
	Return gas temperature	18°C
	Compressor efficiency is	70%

Note that the superheat is included in cooling capacity.

TABLE 16

Existing refrigerant product	Evap Press (kPa)	Cond Press (kPa)	Compr Disch Temp (C)	CAP (kJ/m3)	EER
R22	565	1648	90.9	3808	9.97
R410A	900	2571	88.1	5488	9.27

Candidate replacement product (Composition wt%)
HFC-32/HFC-1225ye (40/60)	630	1948	86.7	4242	9.56
HFC-32/HFC-1225ye (45/55)	666	2041	88.9	4445	9.49
HFC-32/HFC-1225ye (50/50)	701	2127	91.0	4640	9.45
HFC-32/HFC-1225ye (30/70)	536	1700	82.1	3729	9.73
HFC-32/HFC-1225ye (35/65)	575	1805	84.5	3956	9.66
HFC-32/HFC-1225ye (37/63)	590	1845	85.5	4043	9.64
HFC-32/HFC-125/HFC-1225ye (60/5/35)	784	2323	94.6	5087	9.42
HFC-32/HFC-125/HFC-1225ye (60/10/30)	803	2365	94.2	5173	9.42
HFC-32/HFC-125/HFC-1225ye (60/15/25)	822	2407	93.9	5256	9.39
HFC-32/HFC-125/HFC-1225ye (50/10/40)	742	2220	90.3	4820	9.42

103

2018282475 21 Dec 2018

HFC-32/HFC-125/HFC-1225ye (50/5/45)	721	2173	90.7	4730	9.45
HFC-32/HFC-125/HFC-1225ye (50/15/35)	762	2266	90.0	4911	9.42
HFC-32/HFC-125/HFC-1225ye (40/15/45)	692	2097	85.9	4518	9.45
HFC-32/HFC-125/HFC-1225ye (40/10/50)	671	2047	86.2	4425	9.49
HFC-32/HFC-125/HFC-1225ye (35/15/50)	654	2001	83.8	4304	9.49
HFC-32/HFC-125/HFC-1225ye (37.5/11.5/51)	643	1976	85.2	4287	9.54
HFC-32/HFC-125/HFC-1225ye (34/6/60)	593	1848	83.8	4028	9.62
HFC-32/HFC-125/HFC-1225ye (30/3/67)	548	1732	82.0	3788	9.70
HFC-32/HFC-125/HFC-1225ye (30/12.7/57.3)	590	1837	81.7	3980	9.60
HFC-32/HFC-125/HFC-1225ye (24/13.7/62.3)	544	1715	78.7	3713	9.66
HFC-32/HFC-125/HFC-1225ye (20/5/75)	471	1522	76.9	3329	9.82
HFC-32/HFC-125/HFC-1225ye (15/5.5/79.5)	427	1398	74.1	3061	9.89

Compositions have energy efficiency (EER) comparable to R22 and R410A while maintaining reasonable discharge temperatures. Capacity for certain compositions listed in Table 16 is also similar to R22 indicating 5 these compositions could be replacement refrigerants for R22 in refrigeration and air-conditioning. Additionally, there are compositions listed in Table 16 with capacity approaching or equivalent to that for R410A indicating that those compositions could be replacement refrigerants for R410A in refrigeration and air-conditioning.

EXAMPLE 11

Refrigeration Performance Data

104

2018282475 21 Dec 2018

Table 17 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22, R410A, R407C, and R417A. In Table 17, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor discharge temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.

	Evaporator temperature	4.4°C
	Condenser temperature	54.4°C
	Subcool amount	5.5°C
10	Return gas temperature	15.6°C
	Compressor efficiency is	100%

Note that the superheat is included in cooling capacity.

TABLE 17

Existing Refrigerant Product		Evap Press (kPa))	Cond Press (kPa)	Compr Disch T £C1	CAP (kJ/m³)	EER

R22		573	2149	88.6	3494	14.73
R410A		911	3343	89.1	4787	13.07
R407C		567	2309	80.0	3397	14.06
R417A		494	1979	67.8	2768	13.78

Candidate Replacement	wt%
HFC-32/HFC-125/HFC- 1225ye	30/40/30	732	2823	81.1	3937	13.20
HFC-32/HFC-125/HFC- 1225ye	23/25/52	598	2429	78.0	3409	13.54

Compositions have energy efficiency (EER) comparable to R22,

R407C, R417A, and R410A while maintaining low discharge temperatures. Capacity for the compositions listed in Table 17 is also similar to R22, R407C and R417A indicating these compositions could be replacement refrigerants for R22, R407C or R417A in refrigeration and air20 conditioning.

Claims

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:

(i) fluoroolefins of the formula E- or Z-R1CH=CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups, and wherein the total number of carbons in the compound is at least 5;

(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of:
2.3.3- trifluoro-1 -propene (CHF2CF=CH2); 1,1,2-trifluoro-1 -propene (CH3CF=CF2); 1,2,3-trifluoro-1 -propene (CH2FCF=CF2); 1,1,3-trifluoro-1 propene (CH2FCH=CF2); 1,3,3-trifluoro-1 -propene (CHF2CH=CHF);

1.1.1.2.3.4.4.4- octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-

1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-heptafluoro-1 -butene (CHF=CFCF2CF3);

1.1.1.2.3.4.4- heptafluoro-2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2(trifluoromethyl)-l -propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1 -butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1-butene (CF2=CFCHFCF3);

1.1.2.3.3.4.4- heptafluoro-1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-

1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF3);

1.2.3.3.4.4- hexafluoro-1 -butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2butene (CHF2CF=CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3);

1.1.1.3.4.4- hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-lbutene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1 -propene (CH2=C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4-pentafluoro-1 -butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2-butene (CHF2CH=CHCF3);

1.1.1.2.3- pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1 -butene (CH2=CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF=CHCHF2);

1.1.2.3.3- pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1 -propene (CH2=C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1 -butene (CH2=CFCHFCF3);

106

2018282475 21 Dec 2018

1.2.4.4.4- pentafluoro-1-butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF2CHF2); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF2);
3.3.4.4- tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-difluoro-2-(difluoromethyl)1 -propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1 -propene (CHF=C(CF3)(CH3)); 3,3-difluoro-2-(difluoromethyl)-1 -propene (CH2=C(CHF2)2); 1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene

107

2018282475 21 Dec 2018 (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3); 3,3,4,5,5,5hexafluoro-1 -pentene (CH2=CHCF2CHFCF3); 4,4,4-trifluoro-3-(trifluoromethyl)1 -butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1 -hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluorol -hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro-1 -hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5); CF2=CFOCF2CF3 (PEVE) and CF2=CFOCF3 (PMVE).

108

2018282475 21 Dec 2018

2. A composition comprising: (i) at least one fluoroolefin compound; and (ii) at least one flammable refrigerant; wherein said fluoroolefin is selected from the group consisting of:

(a) fluoroolefins of the formula E- or Z-R1CH=CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups;

(b) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; and (c) fluoroolefins selected from the group consisting of:

1.2.3.3.3- pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3-pentafluoro-1-propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1-propene (CHF2CF=CF2); 1,1,1,2,3,4,4,4octafluoro-2-butene (CF3CF=CFCF3); 1,1,2,3,3,4,4,4-octafluoro-1 -butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3);

1.2.3.3.4.4.4- heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro2-butene (CHF2CF=CFCF3); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1 -propene ((CF3)2C=CHF); 1,1,3,3,4,4,4-heptafluoro-1-butene (CF2=CHCF2CF3);

1.1.2.3.4.4.4- heptafluoro-1-butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro1-butene (CF2=CFCF2CHF2); 2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1-butene (CHF=CHCF2CF3);

1.2.3.4.4.4- hexafluoro-1 -butene (CHF=CFCHFCF3); 1,2,3,3,4,4-hexafluoro-1 butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2-butene (CHF2CF=CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3);

1.1.1.2.4.4- hexafluoro-2-butene (CHF2CH=CFCF3); 1,1,1,3,4,4-hexafluoro-2butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-1-butene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2);

3.3.3- trifluoro-2-(trifluoromethyl)-1 -propene (CH2=C(CF3)2); 1,1,1,2,3,4,4,5,5,5decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene

109

2018282475 21 Dec 2018 (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5); and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5).

110

2018282475 21 Dec 2018

3. The composition of claim 2 wherein the flammable refrigerant is selected from the group consisting of hydrofluorocarbons, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia, and combinations thereof.
4. The composition of claim 3 wherein said flammable refrigerant is selected from the group consisting of:

difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1-trifluoroethane (HFC143a); 1,1,2-trifluoroethane (HFC-143); 1,1-difluoroethane (HFC-152a); fluoroethane (HFC-161); 1,1,1 -trifluoropropane (HFC-263fb); 1,1, 1,3,3pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye);

1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1 propene (HFC-1243zf); 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 1,3,3trifluoro-1-propene (HFC-1243ze) C4F9OC2H5; propane; propylene; cyclopropane; n-butane; isobutane; n-pentane; 2-methylbutane; 2,2dimethylpropane; cyclopentane, cyclobutane; 2,2-dimethylbutane; 2,3dimethylbutane; 2,3-dimethylpentane; 2-methylhexane; 3-methylhexane; 2methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane; n-heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
5. The composition of claim 4 comprising:

about 63 weight percent to about 99 weight percent HFC-1225ye and about 37 weight percent to about 1.0 weight percent HFC-32;

about 20 weight percent to about 95 weight percent HFC-1225ye, about 1.0 weight percent to about 65 weight percent HFC-32, and about 1.0 weight percent to about 40 weight percent HFC-125;

about 1.0 weight percent to about 99 weight percent HFC-1243zf and about 99 weight percent to about 1.0 weight percent HFC-1225ye;

about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-125;

about 1.0 weight percent to about 98 weight percent HFC-1243zf; about 1.0 weight percent to about 98 weight percent HFC-1225ye; and about 1.0 weight percent to about 50 weight percent HFC-32; or

111

2018282475 21 Dec 2018 about 1.0 weight percent to about 97 weight percent HFC-1243zf; about 1.0 weight percent to about 97 weight percent HFC-1225ye; about 1.0 weight percent to about 50 weight percent HFC-125; and about 1.0 weight percent to about 50 weight percent HFC-32.
6. The composition of claim 5 comprising:

about 90 weight percent to about 99 weight percent HFC-1225ye and about 10 weight percent to about 1.0 weight percent HFC-32;

about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC-32, and about 1.0 weight percent to about 35 weight percent HFC-125;

about 40 weight percent to about 70 weight percent HFC-1243zf and about 60 weight percent to about 30 weight percent HFC-1225ye;

about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-125;

about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-32; or about 40 weight percent to about 70 weight percent HFC-1243zf; about 20 weight percent to about 60 weight percent HFC-1225ye; and about 1.0 weight percent to about 10 weight percent HFC-125; and about 1.0 weight percent to about 10 weight percent HFC-32..
7. The composition of claim 5 comprising:

about 63 weight percent to about 80 weight percent HFC-1225ye and about 37 weight percent to about 20 weight percent HFC-32; or about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC-32 and about 1.0 weight percent to about 28 weight percent HFC-125.
8. The composition of claim 1 or 2 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.

112

2018282475 21 Dec 2018
9. The composition of claim 1 or 2 further comprising an additive selected from the group consisting of (i), water scavenger; and (ii) odor masking agent.
10. The composition of claim 1 or 2 further comprising a tracer compound wherein said tracer is capable of detection and is selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof, and wherein said tracer compound is different from said refrigerant or heat transfer fluid.
11. The composition of claim 10 wherein said tracer is selected from the group consisting of CD3-CD3, CD3-CD2-CD3, CD2F2, CF3-CD2CF3, CD2FCF3, CD3-CF3, CDF2-CF3, CF3-CDF-CF3, CF3-CF2CDF2, CDF2CDF2, CF3CF2-CD3, CF3CD2-CH3, CF2-CH2-CD3, CF3CF3, cyclo-CF2CF2CF2-, CF3CF2CF3, cyclo-CF2CF2CF2CF2-, CF3CF2CF2CF3, CF3CF(CF3)2, cycloCF(CF3)CF2CF(CF3)CF2-, trans-cyclo-CF2CF(CF3)CF(CF3)CF2-, cis-cycloCF2CF(CF3)CF(CF3)CF2-, CF3OCHF2, CF3OCH2F, CF3OCH3, CF3OCHFCF3, CF3OCH2CF3, CF3OCH2CHF2, CF3CH2OCHF2D CH3OCF2CF3, CH3CF20CF30 □CF3CF2CF2OCHFCF3, CF3CF2CF2OCF(CF3)CF2OCHFCF3, CHF3, CH2FCH3, CHF2CH3, CHF2CHF2, CF3CHFCF3, CF3CF2CHF2, CF3CF2CH2F, CHF2CHFCF3, CF3CH2CF3, CF3CF2CH3, CF3CH2CHF2, CHF2CF2CH3, CF3CHFCH3, CF3CH2CH3, CH3CF2CH3, CH3CHFCH3, CH2FCH2CH3, CHF2CF2CF2CF3, (CF3)2CHCF3, CF3CH2CF2CF3, CHF2CF2CF2CHF2, CH3CF2CF2CF3, CF3CHFCHFCF2CF3, perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho, meta, or para), perfluoroethylcyclohexane, perfluoroindan, perfluorotrimethylcyclohexane and isomers thereof, perfluoroisopropylcyclohexane, cis-perfluorodecalin, transperfluorodecalin, cis- or trans-perfluoromethyldecalin and isomers thereof, CH3Br, CH2FBr, CHF2Br, CHFBr2, CHBr3, CH2BrCH3, CHBr=CH2, CH2BrCH2Br, CFBr=CHF, CF3I, CHF2I, CH2FI, CF2ICH2F, CF2ICHF2, CF2ICF2I, C6F5I, ethanol, n-propanol, isopropanol, acetone, n-propanal, nbutanal, methyl ethyl ketone, nitrous oxide, and combinations thereof.

113

2018282475 21 Dec 2018
12. The composition of claim 1 or 2, further comprising at least one ultraviolet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye and combinations thereof.
13. The composition of claim 12, 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 1,1,1trifluoroalkanes.
14. The composition of claim 13, wherein said solubilizing agent is selected from the group consisting of:

a) polyoxyalkylene glycol ethers represented by the formula R1[(OR2)xOR3]y, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R1 is selected from 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 selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units;

b) amides represented by the formulae R1C(O)NR2R3 and cyclo[R4CON(R5)-], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 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;

c) 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;

d) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms,

114

2018282475 21 Dec 2018 and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;

e) chlorocarbons represented by the formula RCIx, wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units;

f) 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;

g) 1,1,1-trifluoroalkanes represented by the formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;

h) fluoroethers represented by the formula R1OCF2CF2H, wherein R1 is selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoroolefins and polyols, wherein said fluoroolefins are of the type CF2=CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH2 (CHOH)x(CRR’ )yCH2OH, wherein R and R’ are hydrogen, CH3 or C2H5, x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1, and said branched polyols are of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2H5, m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also wherein t+u + v + w = 4; and

i) lactones represented by structures [B], [C], and [D]:

[B] [C] [D] wherein, R1 through R8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and

j) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated,

115

2018282475 21 Dec 2018 alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
15. A process for cooling, said process comprising condensing the composition of claim 1 or 2 and thereafter evaporating said composition in the vicinity of a body to be cooled.
16. A process for heating said process comprising evaporating the composition of claim 1 or 2 and thereafter condensing said composition in the vicinity of a body to be heated.
17. A method of using the composition of claim 12 in a compression refrigeration, air-conditioning, or heat pump apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting the ultra-violet flurescent dye at, or in the vicinity of, a leak point in said apparatus.
18. A method for producing heating or cooling in a refrigeration, airconditioning, 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 at least one fluoroolefin selected from the group consisting of:

(i) fluoroolefins of the formula E- or Z-R1CH=CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups,;

(ii) cyclic fluoroolefins of the formula cyclo-[CX=CY(CZW)n-], wherein X, Y, Z, and W, independently, are H or F, and n is an integer from 2 to 5; or (iii) fluoroolefins selected from the group consisting of:

1,2,3,3,3-pentafluoro-1-propene (CF3CF=CHF); 1,1,3,3,3-pentafluoro-1-propene (CF3CH=CF2); 1,1,2,3,3-pentafluoro-1-propene (CHF2CF=CF2); 1,2,3,3tetrafluoro-1 -propene (CHF2CF=CHF); 2,3,3,3-tetrafluoro-1 -propene (CF3CF=CH2); 1,3,3,3-tetrafluoro-1-propene (CF3CH=CHF); 1,1,2,3-tetrafluoro1-propene (CH2FCF=CF2); 1,1,3,3-tetrafluoro-1-propene (CHF2CH=CF2); 2,3,3trifluoro-1-propene (CHF2CF=CH2); 3,3,3-trifluoro-1-propene (CF3CH=CH2);

1,1,2-trifluoro-1 -propene (CH3CF=CF2); 1,1,3-trifIuoro-1 -propene (CH2FCH=CF2); 1,2,3-trifluoro-1-propene (CH2FCF=CHF); 1,3,3-trifluoro-1116

2018282475 21 Dec 2018 propene (CHF2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butene(CF3CF=CFCF3);

1.1.2.3.3.4.4.4- octafluoro-1-butene (CF3CF2CF=CF2); 1,1,1,2,4,4,4-heptafluoro2-butene (CF3CF=CHCF3); 1,2,3,3,4,4,4-heptafluoro-1-butene (CHF=CFCF2CF3); 1,1,1,2,3,4,4-heptafluoro-2-butene (CHF2CF=CFCF3);

1.3.3.3- tetrafluoro-2-(trifluoromethyl)-1-propene ((CF3)2C=CHF); 1,1,3,3,4,4,4heptafluoro-1 -butene (CF2=CHCF2CF3); 1,1,2,3,4,4,4-heptafluoro-1 -butene (CF2=CFCHFCF3); 1,1,2,3,3,4,4-heptafluoro-1-butene (CF2=CFCF2CHF2);

2.3.3.4.4.4- hexafluoro-1 -butene (CF3CF2CF=CH2); 1,3,3,4,4,4-hexafluoro-1 butene (CHF=CHCF2CF3); 1,2,3,4,4,4-hexafluoro-1-butene (CHF=CFCHFCF3);

1.2.3.3.4.4- hexafluoro-1 -butene (CHF=CFCF2CHF2); 1,1,2,3,4,4-hexafluoro-2butene (CHF2CF=CFCHF2); 1,1,1,2,3,4-hexafluoro-2-butene (CH2FCF=CFCF3); 1,1,1,2,4,4-hexafluoro-2-butene (CHF2CH=CFCF3);

1.1.1.3.4.4- hexafluoro-2-butene (CF3CH=CFCHF2); 1,1,2,3,3,4-hexafluoro-lbutene (CF2=CFCF2CH2F); 1,1,2,3,4,4-hexafluoro-1-butene (CF2=CFCHFCHF2); 3,3,3-trifluoro-2-(trifluoromethyl)-1 -propene (CH2=C(CF3)2); 1,1,1,2,4-pentafluoro-2-butene (CH2FCH=CFCF3); 1,1,1,3,4pentafluoro-2-butene (CF3CH=CFCH2F); 3,3,4,4,4-pentafluoro-1 -butene (CF3CF2CH=CH2); 1,1,1,4,4-pentafluoro-2-butene (CHF2CH=CHCF3);

1.1.1.2.3- pentafluoro-2-butene (CH3CF=CFCF3); 2,3,3,4,4-pentafluoro-1 -butene (CH2=CFCF2CHF2); 1,1,2,4,4-pentafluoro-2-butene (CHF2CF=CHCHF2);

1.1.2.3.3- pentafluoro-1-butene (CH3CF2CF=CF2); 1,1,2,3,4-pentafluoro-2butene (CH2FCF=CFCHF2); 1,1,3,3,3-pentafluoro-2-methyl-1-propene (CF2=C(CF3)(CH3)); 2-(difluoromethyl)-3,3,3-trifluoro-1-propene (CH2=C(CHF2)(CF3)); 2,3,4,4,4-pentafluoro-1 -butene (CH2=CFCHFCF3);

1.2.4.4.4- pentafluoro-1-butene (CHF=CFCH2CF3); 1,3,4,4,4-pentafluoro-1butene (CHF=CHCHFCF3); 1,3,3,4,4-pentafluoro-1-butene (CHF=CHCF2CHF2); 1,2,3,4,4-pentafluoro-1 -butene (CHF=CFCHFCHF2);

3.3.4.4- tetrafluoro-1-butene (CH2=CHCF2CHF2); 1,1-difluoro-2-(difluoromethyl)-

1 -propene (CF2=C(CHF2)(CH3)); 1,3,3,3-tetrafluoro-2-methyl-1 -propene (CHF=C(CF3)(CH3)); 2-difluoromethyl-3,3-difluoro-1-propene (CH2=C(CHF2)2);

1,1,1,2-tetrafluoro-2-butene (CF3CF=CHCH3); 1,1,1,3-tetrafluoro-2-butene (CH3CF=CHCF3); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (CF3CF=CFCF2CF3); 1,1,2,3,3,4,4,5,5,5-decafluoro-1-pentene (CF2=CFCF2CF2CF3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCF3); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (CF3CF=CHCF2CF3); 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (CF3CH=CFCF2CF3); 1,2,3,3,4,4,5,5,5-nonafluoro-1 -pentene

117

2018282475 21 Dec 2018 (CHF=CFCF2CF2CF3); 1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (CF2=CHCF2CF2CF3); 1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene (CF2=CFCF2CF2CHF2); 1,1,2,3,4,4,5,5,5-nonafluoro-2-pentene (CHF2CF=CFCF2CF3); 1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene (CF3CF=CFCF2CHF2); 1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene (CF3CF=CFCHFCF3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CHF=CFCF(CF3)2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butene (CF2=CFCH(CF3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (CF3CH=C(CF3)2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCF(CF3)2); 2,3,3,4,4,5,5,5-octafluoro-1 -pentene (CH2=CFCF2CF2CF3); 1,2,3,3,4,4,5,5-octafluoro-1 -pentene (CHF=CFCF2CF2CHF2); 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CH2=C(CF3)CF2CF3); 1,1,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CF2=CHCH(CF3)2); 1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCF(CF3)2); 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene (CF2=C(CF3)CH2CF3); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene ((CF3)2CFCH=CH2); 3,3,4,4,5,5,5-heptafluoro-1 -pentene (CF3CF2CF2CH=CH2); 2,3,3,4,4,5,5-heptafluoro-1 -pentene (CH2=CFCF2CF2CHF2); 1,1,3,3,5,5,5-heptafluoro-1-butene (CF2=CHCF2CH2CF3); 1,1,1,2,4,4,4-heptafluoro-3-methyl-2-butene (CF3CF=C(CF3)(CH3)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene (CH2=CFCH(CF3)2); 1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1 -butene (CHF=CHCH(CF3)2); 1,1,1,4-tetrafluoro-2-(trifluoromethyl)-2-butene (CH2FCH=C(CF3)2); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butene (CH3CF=C(CF3)2); 1,1,1 -trifluoro-2-(trifluoromethyl)-2-butene ((CF3)2C=CHCH3); 3,4,4,5,5,5-hexafluoro-2-pentene (CF3CF2CF=CHCH3);

1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF3C(CH3)=CHCF3); 3,3,4,5,5,5hexafluoro-1 -pentene (CH2=CHCF2CHFCF3); 3-(trifluoromethyl)-4,4,4-trifluoro1 -butene (CH2=C(CF3)CH2CF3); 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1 -hexene (CF3(CF2)3CF=CF2); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (CF3CF2CF=CFCF2CF3); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2butene ((CF3)2C=C(CF3)2); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CFCF3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2pentene ((CF3)2C=CHC2F5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2pentene ((CF3)2CFCF=CHCF3); 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene (CF3CF2CF2CF2CH=CH2); 4,4,4-trifluoro-3,3-bis(trifluoromethyl)-1-butene (CH2=CHC(CF3)3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene

118

2018282475 21 Dec 2018 ((CF3)2C=C(CH3)(CF3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene (CH2=CFCF2CH(CF3)2); 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2-pentene (CF3CF=C(CH3)CF2CF3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene (CF3CH=CHCH(CF3)2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF3CF2CF2CF=CHCH3); 3,3,4,4,5,5,6,6-octafluoro-1 -hexene (CH2=CHCF2CF2CF2CHF2); 1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene ((CF3)2C=CHCF2CH3); 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene (CH2=C(CF3)CH2C2F5); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene (CF3CF2CF2C(CH3)=CH2); 4,4,5,5,6,6,6-heptafluoro-2-hexene (CF3CF2CF2CH=CHCH3); 4,4,5,5,6,6,6-heptafluoro-1 -hexene (CH2=CHCH2CF2C2F5); 1,1,1,2,2,3,4-heptafluoro-3-hexene (CF3CF2CF=CFC2H5); 4,5,5,5-tetrafluoro-4-trifluoromethyl-1-pentene (CH2=CHCH2CF(CF3)2); 1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene (CF3CF=CHCH(CF3)(CH3)); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-pentene ((CF3)2C=CFC2H5); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (CF3CF=CFCF2CF2C2F5); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CF3CF2CF=CFCF2C2F5); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CH=CFCF2CF2C2F5); 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene (CF3CF=CHCF2CF2C2F5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CH=CFCF2C2F5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF3CF2CF=CHCF2C2F5); CF2=CFOCF2CF3 (PEVE); CF2=CFOCF3 (PMVE) and combinations thereof.
19. The method of claim 18 wherein said method comprises compressing said composition in a centrifugal compressor, condensing said composition, and thereafter evaporating said composition in the vicinity of a body to be heated or cooled.
20. The method of claim 18, wherein said centrifugal compressor is a multi-stage centrifugal compressor.
21. The method of claim 18, wherein said centrifugal compressor is a twostage centrifugal compressor.
22. The method according to claim 18, wherein said centrifugal compressor is powered by (a) an engine exhaust gas driven turbine; or (b) a ratioed gear drive assembly with a ratioed belt drive.

119

2018282475 21 Dec 2018
23. A method of using the composition of claim 1, or 2, to reduce fire hazard in refrigeration apparatus, air-conditioning apparatus, or heat pump apparatus wherein said apparatus comprises a flammable refrigerant, said method comprises introducing said composition into said apparatus, and optionally adding a lubricant to said composition added.
24 . The method of claim 23, wherein said flammable refrigerant is selected from the group consisting of:

difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1-trifluoroethane (HFC143a);1,1,2-trifluoroethane (HFC-143); 1,1-difluoroethane (HFC-152a);

fluoroethane (HFC-161); 1,1,1-trifluoropropane (HFC-263fb); 1,1,1,3,3pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye);

1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1 propene (HFC-1243zf); 1,1,2-trifluoro-1 -propene (HFC-1243yc); 1,1,3-trifluoro-1propene (HFC-1243zc); 1,2,3-trifluoro-1-propene (HFC-1243ye); and 1,3,3trifluoro-1-propene (HFC-1243ze); C4F9OC2H5; propane; propylene;

cyclopropane; n-butane; isobutane; n-pentane; 2-methylbutane; 2,2dimethylpropane;cyclopentane, cyclobutane; 2,2-dimethylbutane; 2,3dimethylbutane; 2,3-dimethylpentane; 2-methylhexane; 3-methylhexane; 2methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane; n-heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
25. A method of using the refrigerant or heat transfer fluid composition of claim 1 for reducing the flammability of a flammable refrigerant, said method comprising: combining said flammable refrigerant with said composition.
26. The method of claim 25, wherein said flammable refrigerant is selected from the group consisting of hydrofluorocarbons, fluoroethers, hydrocarbon ethers, hydrocarbons, ammonia, and combinations thereof.
27. The method of claim 26, wherein said flammable refrigerant is selected from the group consisting of:

120

2018282475 21 Dec 2018

Difluoromethane (HFC-32); fluoromethane (HFC-41); 1,1,1trifluoroethane (HFC-143a); 1,1,2-trifluoroethane (HFC-143); 1,1-difluoroethane (HFC-152a); fluoroethane (HFC-161); 1,1,1-trifluoropropane (HFC-263fb);

1.1.1.3.3- pentafluorobutane (HFC-365mfc); 1,2,3,3-tetrafluoro-1-propene (HFC1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1propene (HFC-1234yf); 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);

3.3.3- trifluoro-1-propene (HFC-1243zf); 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); C4F9OC2H5; propane; propylene; cyclopropane; n-butane; isobutane; n-pentane; 2-methylpentane; 2,2dimethylpropane; cyclopentane, cyclobutane; 2,2-dimethylbutane; 2,3dimethylbutane; 2,3-dimethylpentane; 2-methylhexane; 3-methylhexane; 2methylpentane; 3-ethylpentane; 3-methylpentane; cyclohexane; n-heptane; methylcyclopentane; n-hexane; dimethylether; methyl t-butyl ether; ammonia, and combinations thereof.
28. A method for replacing the use of a high global warming potential refrigerant, said method comprising: providing the composition of claim 1 or 2 in refrigeration, air conditioning, or heat pump apparatus in place of, or in combination with, a high global warming potential refrigerant in said apparatus.
29. A method of using the composition of claim 1 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 claim 1, 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.
30. A method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air-conditioning 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 claim 1 or 2 into said refrigeration, air-conditioning or heat pump apparatus. .

121

2018282475 21 Dec 2018
31. The method of claim 30 further comprising removing the original refrigerant or heat transfer fluid composition from said refrigeration, airconditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer fluid is introduced.
32. 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 claim 1 or 2 as the second refrigerant or heat transfer fluid composition.
33. The method of claim 30 said original refrigerant or heat transfer fluid composition is selected from the group consisting of:

(i) 1,1,1,2-tetrafluoroethane (R134a) and said R134a is substituted by a second refrigerant or heat transfer fluid composition comprising trifluoromethyl trifluorovinyl ether (PMVE);

(ii) 1,1-difluoroethane (R152a) and wherein said R152a is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (EHFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), and trifluoromethyl trifluorovinyl ether (PMVE);

(iii) 1,1,1,2,3,3,3-heptafluoropropane (R227ea) and wherein said R227ea is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-

1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3-pentafluoropropene (HFC1225ye), 2,3,3,3-tetrafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene (HFC1243zf), and trifluoromethyl trifluorovinyl ether (PMVE);

(iv) 1,1,2-trichloro-1,2,2-trifluoroethane (R113) and wherein said R113 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting 1,1,1,3,4,5,5,5octafluoro-4-(trifluoromethyl)-2-butene (HFC-152-1 Immyyz); 1,1,1,4,4,5,5,5octafluoro-2-(trifluoromethyl)-2-pentene (HFC-152-11mmtz);

1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151 -12mcy); 1,1,1,3tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3122

2018282475 21 Dec 2018 bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt); 1,2,3,3,4,4,5,5,6,6decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);

4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5,6,6,6decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E);

(v) 1,1,1,2,3,4,4,5,5,5 -decafluoropentane (R43-10mee) and wherein said R43-10mee is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene (HFC-152-

11 mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene (HFC-15211mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy);

1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt); 1,2,3,3,4,4,5,5,6,6decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);

4.4.5.5.6.6.6- heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5,6,6,6decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E);

(vi) C4F9OCH3 and wherein said C4F9OCH3 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5-octafluoro-4(trifluoromethyl)-2-butene (HFC-152-11 mmyyz); 1,1,1,4,4,5,5,5-octafluoro-2(trifluoromethyl)-2-pentene (HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butene (HFC-

1354mzy); 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene (HFC-151 12mmtt); 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151 -1 Oy);

3,3,4,4,5,5,5-heptafluoro-2-methyl-1 -pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC1567szz); 1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-151-12mmzz); and

1.1.1.2.2.5.5.6.6.6- decafluoro-3-hexene (F22E);

123

2018282475 21 Dec 2018 (vii) 1,1,1,3,3-pentafluorobutane (R365mfc) and wherein said R365mfc is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,3,4,5,5,5octafluoro-4-(trifluoromethyl)-2-butene (HFC-152-1 Immyyz); 1,1,1,4,4,5,5,5octafluoro-2-(trifluoromethyl)-2-pentene (HFC-152-11mmtz);

1.1.1.2.2.3.4.5.5.6.6.6- dodecafluoro-3-hexene (HFC-151 -12mcy); 1,1,1,3tetrafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro-2,3bis(trifluoromethyl)-2-butene (HFC-151 -12mmtt); 1,2,3,3,4,4,5,5,6,6decafluorocyclohexene (FC-C151 -1 Oy); 3,3,4,4,5,5,5-heptafluoro-2-methyl-1 pentene (HFC-1567fts); 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE);

4.4.5.5.6.6.6- heptafluoro-2-hexene (HFC-1567szz); 1,1,1,4,4,5,5,6,6,6decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)-2pentene (HFC-151-12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene (F22E);

(viii) fluorotrichloromethane (R11) and wherein said R11 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,4,4,5,5octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz);

1.1.1.3.4.4.5.5.5- nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4,5,5,5heptafluoro-1-pentene (HFC-1447fz),;1,1,1,4,4,4-hexafluoro-2-butene (F11E);

1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC-1429mzt); and

1.1.1.4.4.5.5.5- octafluoro-2-pentene (F12E);

(ix) 2,2,-dichloro-1,1,1 -trifluoroethane (R123) and wherein said R123 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,4,4,5,5octafluorocyclopentene (FC-C1418y); 1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene (FC-141-10myy); 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (HFC-1429myz);

1.1.1.3.4.4.5.5.5- nonafluoro-2-pentene (HFC-1429mzy); 3,3,4,4,5,5,5heptafluoro-1-pentene (HFC-1447fz),;1,1,1,4,4,4-hexafluoro-2-butene (F11E);

1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene (HFC-1429mzt); and

1.1.1.4.4.5.5.5- octafluoro-2-pentene (F12E);

(x) 1,1,1,3,3-pentafluoropropane (R245fa) and wherein said R245fa is substituted by a second refrigerant or heat transfer fluid composition comprising

124

2018282475 21 Dec 2018 at least one compound selected from the group consisting of 2,3,3trifluoropropene (HFC-1243yf); 1,1,1,4,4,4-hexafluoro-2-butene (F11E); 1,3,3,3tetrafluoropropene (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2-butene (HFC1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and pentafluoroethyl trifluorovinyl ether (PEVE);

(xi) 1,2-dichloro-1,1,2,2-tetrafluoroethane (R124) and wherein said R124 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of

1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my); 1,2,3,3,4,4hexafluorocyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-

1336yf); and 3,3,4,4,4-pentafluoro-1-butene (HFC-1345fz);

(xii) 1,1,1,3,3,3-hexafluoropropane (R236fa) and wherein said R236fa is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,1,1,2,3,4,4,4octafluoro-2-butene (FC-1318my); 1,2,3,3,4,4-hexafluorocyclobutene (FCC1316cc); 2,3,3,4,4,4-hexafluoro-1-butene (HFC-1336yf); and 3,3,4,4,4pentafluoro-1 -butene (HFC-1345fz);

(xiii) R401A and wherein said R401A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xiv) R401B and wherein said R401B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-

1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xv) R409A and wherein said R409A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

125

2018282475 21 Dec 2018

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xvi) R409B and wherein said R409B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xvii) R414B and wherein said R414B is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xviii) R416A and wherein said R416A is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze);

1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE);

(xix) dichlorodifluoromethane (R12) and wherein said R12 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3-tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE); and (xx) R500 and wherein said R500 is substituted by a second refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2,3,3,3tetrafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE)-trifluoropropene, 3,3,3trifluoropropene, and trifluoromethyl trifluorovinyl ether.

126

2018282475 21 Dec 2018
34. The method of claim 32 wherein the original refrigerant or heat transfer fluid composition is R134a or R12 and wherein said R134a or R12 is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye.
35. The method of claim 34 wherein the second refrigerant or heat transfer fluid composition comprises about 1.0 weight percent to about 10 weight percent HFC-32 and about 99 weight percent to about 90 weight percent HFC1225ye.
36. The method of claim 32 wherein the original refrigerant or heat transfer fluid composition is R22, R404A, or R410A and wherein said R22, R404A or R410A is substituted by a second refrigerant or heat transfer fluid composition comprising about 1.0 weight percent to about 37 weight percent HFC-32 and about 99 weight percent to about 63 weight percent HFC-1225ye.
37. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 20 weight percent to about 37 weight percent HFC-32 and about 80 weight percent to about 63 weight percent HFC1225ye.
38. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 20 weight percent to about 95 weight percent HFC-1225ye, about 1.0 weight percent to about 65 weight percent HFC32, and about 1.0 weight percent to about 40 weight percent HFC-125.
39. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 30 weight percent to about 90 weight percent HFC-1225ye, about 5.0 weight percent to about 55 weight percent HFC32, and about 1.0 weight percent to about 35 weight percent HFC-125.
40. The method of claim 36 wherein the second refrigerant or heat transfer fluid composition comprises about 40 weight percent to about 85 weight percent HFC-1225ye, about 10 weight percent to about 45 weight percent HFC32 and about 1.0 weight percent to about 28 weight percent HFC-125.

127

2018282475 21 Dec 2018
41. A method of using the composition of claim 1 or 2 as a heat transfer fluid composition, said process comprising comprises transporting said composition from a heat source to a heat sink.
42. A method for making the composition of claim 1 or 2, said method comprising: (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.
43. A refrigeration, air-conditioning or heat pump apparatus containing a composition as claimed in any one of claims 1 or 2.
44. A mobile refrigeration or air-conditioning apparatus containing the composition as claimed in any one of claims 1 or 2.
45. The composition of claims 1 or 2 further comprising a stabilizer selected from the group consisting of:

a. at least one terpenes or terpenoids in combination with at least one selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes.

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

c. at least one phenol in combination with at least one selected from the group consisting of epoxides, fluorinated epoxides, and oxetanes.
46. The composition of claim 45 wherein said stabilizer is selected from the group consisting of:

a. d-limonene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane;

b. alpha-pinene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane;

c. a fullerene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane;

128

2018282475 21 Dec 2018

d. tocopherol and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane;

e. hydroquinone and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane; and

f. butylated hydroxyl toluene and at least one selected from the group consisting of trifluoromethyloxirane and 3-ethyl-3-hydroxymethyloxetane.
47. The composition of claim 45 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.
48. The composition of claim 45 further comprising at least one alkylamine selected from the group consisting of triethylamine; tributylamine; triisopropylamine; diisobutylamine; triisopropylamine; triisobutylamine; and hindered amine antioxidants.
49. A refrigerant or heat transfer fluid composition comprising 2,3,3,3tetrafluoropropene and at least one compound selected from the group consisting of HFC-254eb, HFC-263fb, and mixtures thereof.
50. The composition of claim 49, further comprising at least one lubricant selected from the group consisting of mineral oils, paraffins, naphthalenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyalkylene glycols, polyvinyl ethers, polyol esters and mixtures thereof.
51. The composition of claim 49 or claim 50, further comprising an additive selected from the group consisting of anti-wear agents, extreme pressure lubricants, stabilizers, free-radical scavengers, water scavengers, corrosion and oxidation inhibitors, metal surface deactivators, foaming and antifoam control agents, and leak detectants.
52. The composition of any one of claims 49 to 51, further comprising at least one ultraviolet fluorescent dye selected from the group consisting

129

2018282475 21 Dec 2018 of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives of said dye and combinations thereof.
53. The compositions of claim 52, 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 1,1,1trifluoroalkanes.
54. A process for cooling, said process comprising condensing the composition of any one of claims 49 to 53, and thereafter evaporating said composition in the vicinity of a body to be cooled.
55. A process for heating, said process comprising evaporating the composition of any one of claims 49 to 53, and thereafter condensing said composition in the vicinity of a body to be heated.
56. A method for producing heating or cooling in a refrigeration, airconditioning, 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 the composition of any one of claims 49 to 53.
57. A method for reducing the GWP of an original refrigerant or heat transfer fluid composition in a refrigeration, air-conditioning 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 any one of claims 49 to 53 into said refrigeration, air-conditioning or heat pump apparatus.
58. The method of claim 57, further comprising removing the original refrigerant or heat transfer fluid composition from said refrigeration, air130

2018282475 21 Dec 2018 conditioning or heat pump apparatus before the second, lower GWP refrigerant or heat transfer fluid is introduced.
59. A method of using the composition of any one of claims 49 to 53, as a heat transfer fluid composition, said method comprising transporting said composition from a heat source to a heat sink.
60. A refrigeration, air-conditioning or heat pump apparatus containing a composition of any one of claims 49 to 53.
61. A mobile refrigeration or air-conditioning apparatus containing the composition of any one of claims 49 to 53.
62. A stationary refrigeration, air-conditioning or heat pump apparatus containing the composition of any one of claims 49 to 53.