# Patent

## Title
Compositions comprising a fluoroolefin

## Abstract

The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.

## Background
CROSS REFERENCE(S) TO RELATED APPLICATION(S)
This application claims the priority benefit of and is a continuation-in-part of U.S. patent application Ser. No. 11/393,109, filed Mar. 30, 2006, now abandoned which is a continuation-in-part of and claims the priority benefit of U.S. patent application Ser. No. 11/369,227, filed Mar. 2, 2006, now abandoned which claims the priority benefit of U.S. Provisional Application 60/658,543, filed Mar. 4, 2005, and U.S. Provisional Application 60/710,439, filed Aug. 23, 2005, and U.S. Provisional Application 60/732,769, filed Nov. 1, 2005.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to compositions for use in refrigeration, air-conditioning, and heat pump systems wherein the composition comprises a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing cooling or heat, as heat transfer fluids, foam blowing agents, aerosol propellants, and fire suppression and fire extinguishing agents.
2. Description of Related Art
The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol.
Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the mobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry.
Currently proposed replacement refrigerants for HFC-134a include 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. 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 refrigerants.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a composition comprising HFC-1225ye and at least one compound selected from the group consisting of: HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3 and CF3I.
The present invention further relates to a composition comprising HFC-1234ze and at least one compound selected from the group consisting of: HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3 and CF3I. The present invention further relates to a composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
The present invention further relates to a composition comprising HFC-1234ye and at least one compound selected from the group consisting of: HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
The present invention further relates to a composition comprising HFC-1243zf and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.


DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to compositions comprising at least one fluoroolefin. The compositions of the present invention further comprise at least one additional component that may be a second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis(trifluoromethyl)sulfide, CF3I, or CO2. The fluoroolefin compounds and other components of the present inventive compositions are listed in Table 1.









TABLE 1





Compound
Chemical name
Chemical formula







HFC-1225ye
1,2,3,3,3-pentafluoropropene
CF3CF═CHF


HFC-1234ze
1,3,3,3-tetrafluoropropene
CF3CH═CHF


HFC-1234yf
2,3,3,3-tetrafluoropropene
CF3CF═CH2


HFC-1234ye
1,2,3,3-tetrafluoropropene
CHF2CF═CHF


HFC-1243zf
3,3,3-trifluoropropene
CF3CH═CH2


HFC-32
difluoromethane
CH2F2


HFC-125
pentafluoroethane
CF3CHF2


HFC-134
1,1,2,2-tetrafluoroethane
CHF2CHF2


HFC-134a
1,1,1,2-tetrafluoroethane
CH2FCF3


HFC-143a
1,1,1-trifluoroethane
CH3CF3


HFC-152a
1,1-difluoroethane
CHF2CH3


HFC-161
fluoroethane
CH3CH2F


HFC-227ea
1,1,1,2,3,3,3-
CF3CHFCF3



heptafluoropropane


HFC-236ea
1,1,1,2,3,3-hexafluoropropane
CF3CHFCHF2


HFC-236fa
1,1,1,3,3,3-hexafluoroethane
CF3CH2CF3


HFC-245fa
1,1,1,3,3-pentafluoropropane
CF3CH2CHF2


HFC-365mfc
1,1,1,3,3-pentafluorobutane
CF3CH2CH2CHF2



Propane
CH3CH2CH3



n-butane
CH3CH2CH2CH3


i-butane
isobutane
CH3CH(CH3)CH3



2-methylbutane
CH3CH(CH3)CH2CH3



n-pentane
CH3CH2CH2CH2CH3



cyclopentane
cyclo-(CH2)5—


DME
dimethylether
CH3OCH3


CO2
carbon dioxide
CO2


CF3SCF3
bis(trifluoromethyl)sulfide
CF3SCF3



iodotrifluoromethane
CF3I


NH3
Ammonia
NH3









The individual components listed in Table 1 may be prepared by methods known in the art.
The fluoroolefin compounds used in the compositions of the present invention, HFC-1225ye, HFC-1234ze, and HFC-1234ye, may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof. For instance, 1,3,3,3-tetra-fluoropropene (HFC-1234ze) is meant to represent the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio. Another example is HFC-1225ye, by which is represented the cis-isomer, trans-isomer, or any combination or mixture of both isomers in any ratio. The compositions of the present invention contain primarily the cis or Z isomer of HFC-1225ye.
The compositions of the present invention include the following:
HFC-1225ye and at least one compound selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I;
HFC-1234ze and at least one compound selected from the group consisting of HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I;
HFC-1234yf and at least one compound selected from the group consisting of HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2, NH3, and CF3I;
HFC-1243zf and at least one compound selected from the group consisting of HFC-1234ye, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I; and
HFC-1234ye and at least one compound selected from the group consisting of HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, CO2 and CF3I.
The compositions of the present invention may be generally useful when the fluoroolefin is present at about 1 weight percent to about 99 weight percent, preferably about 20 weight percent to about 99 weight percent, more preferably about 40 weight percent to about 99 weight percent and still more preferably 50 weight percent to about 99 weight percent.
The present invention further provides compositions as listed in Table 2.









TABLE 2









Concentration ranges (wt %)










Components
Preferred
More preferred
Most preferred





HFC-1225ye/HFC-32
1-99/99-1
30-99/70-1
90-99/10-1;





95/5/97/3


HFC-1225ye/HFC-134a
1-99/99-1
40-99/60-1
90/10


HFC-1225ye/CO2
0.1-99.9/99.9-0.1
70-99.7/30-0.3
99/1


HFC-1225ye/ammonia
0.1-99.9/0.1-99.9
40-99.9/0.1-60
90/10, 85/15, 80/





20, 95/5


HFC-1225ye/HFC-1234yf
1-99/99-1
51-99/49-1 and 60-90/
60/40, 51/49




40-10


HFC-1225ye/HFC-152a/HFC-32
1-98/1-98/1-98
50-98/1-40/1-40
85/10/5





81/15/4





82/15/3


HFC-1225ye/HFC-152a/CO2
1-98/1-98/0.1-98
50-98/1-40/0.3-30
84/15/1





84/15.5/0.5


HFC-1225ye/HFC-152a/propane
1-98/1-98/1-98
50-98/1-40/1-20
85/13/2


HFC-1225ye/HFC-152a/i-butane
1-98/1-98/1-98
50-98/1-40/1-20
85/13/2


HFC-1225ye/HFC-152a/DME
1-98/1-98/1-98
50-98/1-40/1-20
85/13/2


HFC-1225ye/HFC-152a/CF3I
1-98/1-98/1-98
20-90/1-50/1-60


HFC-1225ye/HFC-134a/HFC-
1-98/1-98/1-98
40-98/1-50/1-40
76/9/15


152a


HFC-1225ye/HFC-134a/HFC-32
1-98/1-98/1-98
1-80/1-80/1-80
88/9/3


HFC-1225ye/HFC-134a/HFC-161
1-98/1-98/1-98
40-98/1-50/1-20
86/10/4


HFC-1225ye/HFC-134a/CO2
1-98/1-98/0.1-98
40-98/1-50/0.3-30
88.5/11/0.5


HFC-1225ye/HFC-134a/propane
1-98/1-98/1-98
40-98/1-50/1-20
87/10/3


HFC-1225ye/HFC-134a/i-butane
1-98/1-98/1-98
40-98/1-50/1-20
87/10/3


HFC-1225ye/HFC-134a/DME
1-98/1-98/1-98
40-98/1-50/1-20
87/10/3


HFC-1225ye/HFC-134/HFC-32
1-98/1-98/1-98
40-98/1-50/1-40
88/9/3


trans-HFC-1234ze/HFC-134a
1-99/99-1
30-99/70-1
90/10


trans-HFC-1234ze/HFC-32
1-99/99-1
40-99/60-1
95/5


trans-HFC-1234ze/HFC-32/CF3I
1-98/1-98/1-98
20-90/0.1-60/1-70


trans-HFC-1234ze/HFC-152a
1-99/99-1
40-99/60-1
80/20


trans-HFC-1234ze/HFC-125
1-99/99-1
30-99/70-1


HFC-1234yf/HFC-134a
1-99/99-1
30-99/70-1
90/10


HFC-1234yf/HFC-32
1-99/99-1
40-99/60-1
95/5


HFC-1234yf/HFC-125
0.1-99/99-0.1
40-99/1-60


HFC-1234yf/HFC-152a
1-99/99-1
40-99/60-1
80/20


HFC-1225ye/HFC-134a/HFC-
1-97/1-97/1-97/
20-97/1-80/1-50/
74/8/17/1


152a/HFC-32
0.1-97
0.1-50


HFC-1225ye/HFC-1234yf/HFC-
1-98/1-98/0.1-98
10-90/10-90/0.1-50
70/20/10 and


134a


20/70/10


HFC-1225ye/HFC-1234yf/HFC-32
1-98/1-98/0.1-98
10-90/5-90/0.1-50
25/73/2,





75/23/2,





49/49/2, 85/10/5,





90/5/5


HFC-1225ye/HFC-1234yf/HFC-
1-97/1-97/0.1-97/
10-80/10-80/1-60/1-60


32/CF3I
1-97


HFC-1225ye/HFC-1234yf/HFC-
1-98/1-98/0.1-98
10-90/10-90/0.1-50
70/25/5 and


152a


25/70/5


HFC-1225ye/HFC-1234yf/HFC-
1-98/1-98/0.1-98
10-90/10-90/0.1-50
25/71/4,


125


75/21/4, 75/24/1





and 25/74/1


HFC-1225ye/HFC-1234yf/CF3I
1-98/1-98/1-98
9-90/9-90/1-60
40/40/20 and





45/45/10


HFC-32/HFC-125/HFC-1225ye
0.1-98/0.1-98/
5-70/5-70/5-70
30/30/40 and



0.1-98

23/25/52


HFC-32/HFC-125/trans-HFC-
0.1-98/0.1-98/
5-70/5-70/5-70
30/50/20 and


1234ze
0.1-98

23/25/52


HFC-32/HFC-125/HFC-1234yf
0.1-98/0.1-98/
5-70/5-70/5-70
40/50/10,



0.1-98

23/25/52,





15/45/40, and





10/60/30


HFC-32/HFC-134a/HFC-
1-97/1-97/1-97/
1-60/1-60/1-60/1-60


1225ye/CF3I
1-97


HFC-32/HFC-134a/HFC-
1-96/1-96/1-96/
1-50/1-50/1-50/1-50/


1225ye/HFC-1234yf/CF3I
1-96/1-96
1-50


HFC-32/HFC-125/HFC-
1-96/1-96/1-96/
1-50/1-50/1-50/1-50/


134a/HFC-1225ye/CF3I
1-96/1-96
1-50


HFC-125/HFC-1225ye/n-butane
0.1-98/0.1-98/
5-70/5-70/1-20
65/32/3 and



0.1-98

85.1/11.5/3.4


HFC-32/NH3/HFC-1225ye
1-98/1-98/1-98
1-60/10-60/10-90


HFC-32/NH3/HFC-1225ye/CF3I
1-97/1-97/1-97/
1-60/1-60/10-80/1-60



1-97


HFC-32/NH3/HFC-1234yf/CF3I
1-97/1-97/1-97/
1-60/1-60/10-80/5-80



1-97


HFC-125/trans-HFC-1234ze/n-
0.1-98/0.1-98/
5-70/5-70/1-20
66/32/2 and


butane
0.1-98

86.1/11.5/2.4


HFC-125/HFC-1234yf/n-butane
0.1-98/0.1-98/
5-70/5-70/1-20
67/32/1 and



0.1-98

87.1/11.5/1.4


HFC-125/HFC-1225ye/isobutane
0.1-98/0.1-98/
5-70/5-70/1-20
85.1/11.5/3.4



0.1-98

and 65/32/3


HFC-1225ye/HFC-125/ammonia
0.1-98/0.1-98/
20-98/1-60/0.1-40



0.1-98


HFC-1225ye/HFC-32/HFC-
0.1-97/0.1-97/
20-97/1-60/1-60/


125/ammonia
0.1-97/0.1-97
0.1-40


HFC-125/trans-HFC-
0.1-98/0.1-98/
5-70/5-70/1-20
86.1/11.5/2.4


1234ze/isobutane
0.1-98

and 66/32/2


HFC-125/HFC-1234yf/isobutane
0.1-98/0.1-98/
5-70/5-70/1-20 and
87.1/11.5/1.4



0.1-98
80-98/1-19/1-10
and 67/32/1


HFC-1234yf/HFC-32/HFC-143a
1-50/1-98/1-98
15-50/20-80/5-60


HFC-1234yf/HFC-32/isobutane
1-40/59-98/1-30
10-40/59-90/1-10


HFC-1234yf/HFC-125/HFC-143a
1-60/1-98/1-98
10-60/20-70/20-70


HFC-1234yf/HFC-125/isobutane
1-40/59-98/1-20
10-40/59-90/1-10


HFC-1234yf/HFC-125/CF3I
1-98/0.1-98/1-98
10-80/1-60/1-60


HFC-1234yf/HFC-134/propane
1-80/1-70/19-90
20-80/10-70/19-50


HFC-1234yf/HFC-134/DME
1-70/1-98/29-98
20-70/10-70/29-50


HFC-1234yf/HFC-134a/propane
1-80/1-80/19-98
10-80/10-80/19-50


HFC-1234yf/HFC-134a/n-butane
1-98/1-98/1-30
10-80/10-80/1-20


HFC-1234yf/HFC-134a/isobutane
1-98/1-98/1-30
10-80/10-80/1-20


HFC-1234yf/HFC-134a/DME
1-98/1-98/1-40
10-80/10-80/1-20


HFC-1234yf/HFC-134a/CF3I
1-98/1-98/1-98
10-80/1-60/1-60


HFC-1234yf/HFC-143a/propane
1-80/1-98/1-98
10-80/10-80/1-50


HFC-1234yf/HFC-143a/DME
1-40/59-98/1-20
5-40/59-90/1-10


HFC-1234yf/HFC-152a/n-butane
1-98/1-98/1-30
10-80/10-80/1-20


HFC-1234yf/HFC-152a/isobutane
1-98/1-90/1-40
10-80/10-80/1-20


HFC-1234yf/HFC-152a/DME
1-70/1-98/1-98
10-70/10-80/1-20


HFC-1234yf/HFC-152a/CF3I
1-98/1-98/1-98
10-80/1-60/1-60


HFC-1234yf/HFC-227ea/propane
1-80/1-70/29-98
10-60/10-60/29-50


HFC-1234yf/HFC-227ea/n-butane
40-98/1-59/1-20
50-98/10-49/1-10


HFC-1234yf/HFC-
30-98/1-69/1-30
50-98/10-49/1-10


227ea/isobutane


HFC-1234yf/HFC-227ea/DME
1-98/1-80/1-98
10-80/10-80/1-20


HFC-1234yf/n-butane/DME
1-98/1-40/1-98
10-80/10-40/1-20


HFC-1234yf/isobutane/DME
1-98/1-50/1-98
10-90/1-40/1-20


HFC-1234yf/DME/CF3I
1-98/1-98/1-98
10-80/1-20/10-80


HFC-1234yf/DME/CF3SCF3
1-98/1-40/1-98
10-80/1-20/10-70


HFC-1225ye/trans-HFC-
1-98/1-98/1-98
10-80/10-80/10-80


1234ze/HFC-134


HFC-1225ye/trans-HFC-
1-98/1-98/1-98
10-80/10-80/10-80


1234ze/HFC-227ea


HFC-1225ye/trans-HFC-
1-60/1-60/39-98
10-60/10-60/39-80


1234ze/propane


HFC-1225ye/trans-HFC-
1-98/1-98/1-30
10-80/10-80/1-20


1234ze/n-butane


HFC-1225ye/trans-HFC-
1-98/1-98/1-98
10-80/10-80/1-30


1234ze/DME


HFC-1225ye/trans-HFC-1234ze/
1-98/1-98/1-98
10-80/10-80/10-80


CF3SCF3


HFC-1225ye/HFC-1243zf/HFC-
1-98/1-98/1-98
10-80/10-80/10-80


134


HFC-1225ye/HFC-1243zf/n-
1-98/1-98/1-30
10-80/10-80/1-20


butane


HFC-1225ye/HFC-
1-98/1-98/1-40
10-80/10-80/1-30


1243zf/isobutane


HFC-1225ye/HFC-1243zf/DME
1-98/1-98/1-98
10-80/10-80/1-30


HFC-1225ye/HFC-1243zf/CF3I
1-98/1-98/1-98
10-80/10-80/10-80


HFC-1225ye/HFC-134/HFC-152a
1-98/1-98/1-98
10-80/10-80/1-50


HFC-1225ye/HFC-134/HFC-
1-98/1-98/1-98
10-80/10-80/10-80


227ea


HFC-1225ye/HFC-134/n-butane
1-98/1-90/1-40
10-80/10-80/1-30


HFC-1225ye/HFC-134/isobutane
1-98/1-90/1-40
10-80/10-80/1-30


HFC-1225ye/HFC-134/DME
1-98/1-98/1-40
10-80/10-80/1-30


HFC-1225ye/HFC-227ea/DME
40-98/1-59/1-30
50-98/1-49/1-20


HFC-1225ye/n-butane/DME
1-98/1-30/1-98
60-98/1-20/1-20


HFC-1225ye/n-butane/CF3SCF3
1-98/1-20/1-98
10-80/1-10/10-80


HFC-1225ye/isobutane/DME
1-98/1-60/1-98
40-90/1-30/1-30


HFC-1225ye/isobutane/CF3I
1-98/1-40/1-98
10-80/1-30/10-80


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
10-80/10-80/10-80


1243zf/HFC-227ea


trans-HFC-1234ze/HFC-1243zf/n-
1-98/1-98/1-30
10-80/10-80/1-20


butane


trans-HFC-1234ze/HFC-
1-98/1-98/1-40
10-80/10-80/1-30


1243zf/isobutane


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
10-80/10-80/1-40


1243zf/DME


trans-HFC-1234ze/HFC-32/CF3I
1-98/1-98/1-98
10-80/1-70/1-80


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
10-80/10-80/1-50


134/HFC-152a


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
10-80/10-80/10-80


134/HFC-227ea


trans-HFC-1234ze/HFC-134/DME
1-98/1-98/1-40
10-80/10-80/1-30


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
10-80/10-80/1-50


134a/HFC-152a


trans-HFC-1234ze/HFC-152a/n-
1-98/1-98/1-50
10-80/10-80/1-30


butane


trans-HFC-1234ze/HFC-
1-98/1-98/1-98
20-90/1-50/1-30


152a/DME


trans-HFC-1234ze/HFC-227ea/n-
1-98/1-98/1-40
10-80/10-80/1-30


butane


trans-HFC-1234ze/n-butane/DME
1-98/1-40/1-98
10-90/1-30/1-30


trans-HFC-1234ze/n-butane/CF3I
1-98/1-30/1-98
10-80/1-20/10-80


trans-HFC-
1-98/1-60/1-98
10-90/1-30/1-30


1234ze/isobutane/DME


trans-HFC-1234ze/isobutane/
1-98/1-40/1-98
10-80/1-20/10-80


CF3I


trans-HFC-1234ze/isobutane/
1-98/1-40/1-98
10-80/1-20/10-80


CF3SCF3


HFC-1243zf/HFC-134/HFC-
1-98/1-98/1-98
10-80/10-80/10-80


227ea


HFC-1243zf/HFC-134/n-butane
1-98/1-98/1-40
10-80/10-80/1-30


HFC-1243zf/HFC-134/DME
1-98/1-98/1-98
10-80/10-80/1-30


HFC-1243zf/HFC-134/CF3I
1-98/1-98/1-98
10-80/10-80/10-80


HFC-1243zf/HFC-134a/HFC-
1-98/1-98/1-98
10-80/10-80/1-50


152a


HFC-1243zf/HFC-134a/n-butane
1-98/1-98/1-40
10-80/10-80/1-30


HFC-1243zf/HFC-152a/propane
1-70/1-70/29-98
10-70/1-50/29-40


HFC-1243zf/HFC-152a/n-butane
1-98/1-98/1-30
10-80/1-80/1-20


HFC-1243zf/HFC-152a/isobutane
1-98/1-98/1-40
10-80/1-80/1-30


HFC-1243zf/HFC-152a/DME
1-98/1-98/1-98
10-80/1-80/1-30


HFC-1243zf/HFC-227ea/n-butane
1-98/1-98/1-40
10-80/1-80/1-30


HFC-1243zf/HFC-
1-98/1-90/1-50
10-80/1-80/1-30


227ea/isobutane


HFC-1243zf/HFC-227ea/DME
1-98/1-80/1-90
10-80/1-80/1-30


HFC-1243zf/n-butane/DME
1-98/1-40/1-98
10-90/1-30/1-30


HFC-1243zf/isobutane/DME
1-98/1-60/1-98
10-90/1-30/1-30


HFC-1243zf/isobutane/CF3I
1-98/1-40/1-98
10-80/1-30/10-80


HFC-1243zf/DME/CF3SCF3
1-98/1-40/1-90
10-80/1-30/10-80


HFC-1225ye/HFC-32/CF3I
1-98/1-98/1-98
5-80/1-70/1-80


HFC-1225ye/HFC-1234yf/HFC-
1-97/1-97/1-97/
1-80/1-70/5-70/5-70


32/HFC-125
1-97


HFC-1225ye/HFC-1234yf/HFC-
1-97/1-97/1-97/
5-80/5-70/5-70/5-70


32/HFC-134a
1-97


HFC-1225ye/HFC-1234yf/HFC-
1-96/1-96/1-96/
1-70/1-60/1-70/1-60/


32/HFC-125/CF3I
1-96/1-96
1-60


HFC-1225ye/HFC-32/HFC-
1-97/1-97/1-97/
10-80/5-70/5-70/5-70


125/HFC-152a
1-97


HFC-1225ye/HFC-32/HFC-
1-97/1-97/1-97/
5-70/5-70/5-70/1-30


125/isobutane
1-97


HFC-1225ye/HFC-32/HFC-
1-97/1-97/1-97/
5-70/5-70/5-70/1-30


125/propane
1-50


HFC-1225ye/HFC-32/HFC-
1-97/1-97/1-97/
5-70/5-70/5-70/1-30


125/DME
1-50


HFC-1225ye/HFC-32/CF3I/DME
1-97/1-97/1-97/
5-70/5-70/5-70/1-30



1-50


HFC-1225ye/HFC-32/HFC-
1-97/1-97/1-97/
10-80/5-70/5-70/1-80


125/CF3I
1-97


HFC-1234yf/HFC-32/CF3I
1-98/1-98/1-98
10-80/1-70/1-80


HFC-1234yf/HFC-32/HFC-
1-97/1-97/1-97/
5-70/5-80/1-70/5-70


134a/CF3I
1-97


HFC-1234yf/HFC-32/HFC-125
1-98/1-98/1-98
10-80/5-80/10-80


HFC-1234yf/HFC-32/HFC-
1-97/1-97/1-97/
10-80/5-70/10-80/5-80


125/CF3I
1-97









The most preferred compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present in the concentrations as listed +/−2 weight percent. The compositions containing CO2 would be expected to maintain the desired properties and functionality when the CO2 was present at the listed concentration +/−0.2 weight percent.
The compositions of the present invention may be azeotropic or near-azeotropic compositions. By azeotropic composition is meant a constant-boiling mixture of two or more substances that behave as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture distills/refluxes without compositional change. Constant-boiling compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non-azeotropic mixture of the same compounds. An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation, which may reduce efficiency of the system. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system. In the situation where one component of a mixture is flammable, fractionation during leakage could lead to a flammable composition either within the system or outside of the system.
A near-azeotropic composition (also commonly referred to as an “azeotrope-like composition”) is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance. One way to characterize a near-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change. Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is near-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
Azeotropic compositions of the present invention at a specified temperature are shown in Table 3.













TABLE 3







Wt %
Wt %


T


Component A
Component B
A
B
Psia
kPa
(C.)





















HFC-1234yf
HFC-32
7.4
92.6
49.2
339
−25


HFC-1234yf
HFC-125
10.9
89.1
40.7
281
−25


HFC-1234yf
HFC-134a
70.4
29.6
18.4
127
−25


HFC-1234yf
HFC-152a
91.0
9.0
17.9
123
−25


HFC-1234yf
HFC-143a
17.3
82.7
39.5
272
−25


HFC-1234yf
HFC-227ea
84.6
15.4
18.0
124
−25


HFC-1234yf
propane
51.5
48.5
33.5
231
−25


HFC-1234yf
n-butane
98.1
1.9
17.9
123
−25


HFC-1234yf
isobutane
88.1
11.9
19.0
131
−25


HFC-1234yf
DME
53.5
46.5
13.1
90
−25


HFC-1225ye
trans-HFC-
63.0
37.0
11.7
81
−25



1234ze


HFC-1225ye
HFC-1243zf
40.0
60.0
13.6
94
−25


HFC-1225ye
HFC-134
52.2
47.8
12.8
88
−25


HFC-1225ye
HFC-152a
7.3
92.7
14.5
100
−25


HFC-1225ye
propane
29.7
70.3
30.3
209
−25


HFC-1225ye
n-butane
89.5
10.5
12.3
85
−25


HFC-1225ye
isobutane
79.3
20.7
13.9
96
−25


HFC-1225ye
DME
82.1
17.9
10.8
74
−25


HFC-1225ye
CF3SCF3
37.0
63.0
12.4
85
−25


trans-HFC-1234ze
HFC-1243zf
17.0
83.0
13.0
90
−25


trans-HFC-1234ze
HFC-134
45.7
54.3
12.5
86
−25


trans-HFC-1234ze
HFC-134a
9.5
90.5
15.5
107
−25


trans-HFC-1234ze
HFC-152a
21.6
78.4
14.6
101
−25


trans-HFC-1234ze
HFC-227ea
59.2
40.8
11.7
81
−25


trans-HFC-1234ze
propane
28.5
71.5
30.3
209
−25


trans-HFC-1234ze
n-butane
88.6
11.4
11.9
82
−25


trans-HFC-1234ze
isobutane
77.9
22.1
12.9
89
−25


trans-HFC-1234ze
DME
84.1
15.9
10.8
74
−25


trans-HFC-1234ze
CF3SCF3
34.3
65.7
12.7
88
−25


HFC-1243zf
HFC-134
63.0
37.0
13.5
93
−25


HFC-1243zf
HFC-134A
25.1
74.9
15.9
110
−25


HFC-1243zf
HFC-152A
40.7
59.3
15.2
104
−25


HFC-1243zf
HFC-227ea
78.5
21.5
13.1
90
−25


HFC-1243zf
propane
32.8
67.2
31.0
213
−25


HFC-1243zf
n-butane
90.3
9.7
13.5
93
−25


HFC-1243zf
isobutane
80.7
19.3
14.3
98
−25


HFC-1243zf
DME
72.7
27.3
12.0
83
−25


cis-HFC-1234ze
HFC-236ea
20.9
79.1
30.3
209
25


cis-HFC-1234ze
HFC-245fa
76.2
23.8
26.1
180
25


cis-HFC-1234ze
n-butane
51.4
48.6
6.08
42
−25


cis-HFC-1234ze
isobutane
26.2
73.8
8.74
60
−25


cis-HFC-1234ze
2-methylbutane
86.6
13.4
27.2
188
25


cis-HFC-1234ze
n-pentane
92.9
7.1
26.2
181
25


HFC-1234ye
HFC-236ea
24.0
76.0
3.35
23.1
−25


HFC-1234ye
HFC-245fa
42.5
57.5
22.8
157
25


HFC-1234ye
n-butane
41.2
58.8
38.0
262
25


HFC-1234ye
isobutane
16.4
83.6
50.9
351
25


HFC-1234ye
2-methylbutane
80.3
19.7
23.1
159
25


HFC-1234ye
n-pentane
87.7
12.3
21.8
150
25









Additionally, ternary azeotropes composition have been found as listed in Table 4.















TABLE 4











Pres
Pres
Temp


Component A
Component B
Component C
Wt % A
Wt % B
Wt % C
(psi)
(kPa)
(° C.)























HFC-1234yf
HFC-32
HFC-143A
3.9
74.3
21.8
50.02
345
−25


HFC-1234yf
HFC-32
isobutane
1.1
92.1
6.8
50.05
345
−25


HFC-1234yf
HFC-125
HFC-143A
14.4
43.5
42.1
38.62
266
−25


HFC-1234yf
HFC-125
isobutane
9.7
89.1
1.2
40.81
281
−25


HFC-1234yf
HFC-134
propane
4.3
39.1
56.7
34.30
236
−25


HFC-1234yf
HFC-134
DME
15.2
67.0
17.8
10.38
71.6
−25


HFC-1234yf
HFC-134a
propane
24.5
31.1
44.5
34.01
234
−25


HFC-1234yf
HFC-134a
n-butane
60.3
35.2
4.5
18.58
128
−25


HFC-1234yf
HFC-134a
isobutane
48.6
37.2
14.3
19.86
137
−25


HFC-1234yf
HFC-134a
DME
24.0
67.9
8.1
17.21
119
−25


HFC-1234yf
HFC-143a
propane
17.7
71.0
11.3
40.42
279
−25


HFC-1234yf
HFC-143a
DME
5.7
93.0
1.3
39.08
269
−25


HFC-1234yf
HFC-152a
n-butane
86.6
10.8
2.7
17.97
124
−25


HFC-1234yf
HFC-152a
isobutane
75.3
11.8
12.9
19.12
132
−25


HFC-1234yf
HFC-152a
DME
24.6
43.3
32.1
11.78
81.2
−25


HFC-1234yf
HFC-227ea
propane
35.6
17.8
46.7
33.84
233
−25


HFC-1234yf
HFC-227ea
n-butane
81.9
16.0
2.1
18.07
125
−25


HFC-1234yf
HFC-227ea
isobutane
70.2
18.2
11.6
19.27
133
−25


HFC-1234yf
HFC-227ea
DME
28.3
55.6
16.1
15.02
104
−25


HFC-1234yf
n-butane
DME
48.9
4.6
46.4
13.15
90.7
−25


HFC-1234yf
isobutane
DME
31.2
26.2
42.6
14.19
97.8
−25


HFC-1234yf
DME
CF3I
16.3
10.0
73.7
15.65
108
−25


HFC-1234yf
DME
CF3SCF3
34.3
10.5
55.2
14.57
100
−25


HFC-1225ye
trans-HFC-
HFC-134
47.4
5.6
47.0
12.77
88.0
−25



1234ze


HFC-1225ye
trans-HFC-
HFC-227ea
28.4
52.6
19.0
11.63
80.2
−25



1234ze


HFC-1225ye
trans-HFC-
propane
20.9
9.1
70.0
30.36
209
−25



1234ze


HFC-1225ye
trans-HFC-
n-butane
65.8
24.1
10.1
12.39
85.4
−25



1234ze


HFC-1225ye
trans-HFC-
DME
41.0
40.1
18.9
10.98
75.7
−25



1234ze


HFC-1225ye
trans-HFC-
CF3SCF3
1.0
33.7
65.2
12.66
87.3
−25



1234ze


HFC-1225ye
HFC-1243zf
HFC-134
28.7
47.3
24.1
13.80
95.1
−25


HFC-1225ye
HFC-1243zf
n-butane
37.5
55.0
7.5
13.95
96.2
−25


HFC-1225ye
HFC-1243zf
isobutane
40.5
43.2
16.3
14.83
102
−25


HFC-1225ye
HFC-1243zf
DME
19.1
51.0
29.9
12.15
83.8
−25


HFC-1225ye
HFC-1243zf
CF3I
10.3
27.3
62.3
14.05
96.9
−25


HFC-1225ye
HFC-134
HFC-152a
63.6
26.8
9.6
12.38
85.4
−25


HFC-1225ye
HFC-134
HFC-227ea
1.3
52.3
46.4
12.32
84.9
−25


HFC-1225ye
HFC-134
n-butane
18.1
67.1
14.9
14.54
100
−25


HFC-1225ye
HFC-134
isobutane
0.7
74.0
25.3
16.68
115
−25


HFC-1225ye
HFC-134
DME
29.8
52.5
17.8
9.78
67.4
−25


HFC-1225ye
HFC-227ea
DME
63.1
31.0
5.8
10.93
75.4
−25


HFC-1225ye
n-butane
DME
66.0
13.0
21.1
11.34
78.2
−25


HFC-1225ye
n-butane
CF3SCF3
71.3
5.6
23.0
12.25
84.5
−25


HFC-1225ye
isobutane
DME
49.9
29.7
20.4
12.83
88.5
−25


HFC-1225ye
isobutane
CF3I
27.7
2.2
70.1
13.19
90.9
−25


trans-HFC-
HFC-1243zf
HFC-227ea
7.1
73.7
19.2
13.11
90.4
−25


1234ze


trans-HFC-
HFC-1243zf
n-butane
9.5
81.2
9.3
13.48
92.9
−25


1234ze


trans-HFC-
HFC-1243zf
isobutane
3.3
77.6
19.1
14.26
98.3
−25


1234ze


trans-HFC-
HFC-1243zf
DME
2.6
70.0
27.4
12.03
82.9
−25


1234ze


trans-HFC-
HFC-134
HFC-152a
52.0
42.9
5.1
12.37
85.3
−25


1234ze


trans-HFC-
HFC-134
HFC-227ea
30.0
43.2
26.8
12.61
86.9
−25


1234ze


trans-HFC-
HFC-134
DME
27.7
54.7
17.7
9.76
67.3
−25


1234ze


trans-HFC-
HFC-134a
HFC-152a
14.4
34.7
51.0
14.42
99.4
−25


1234ze


trans-HFC-
HFC-152a
n-butane
5.4
80.5
14.1
15.41
106
−25


1234ze


trans-HFC-
HFC-152a
DME
59.1
16.4
24.5
10.80
74.5
−25


1234ze


trans-HFC-
HFC-227ea
n-butane
40.1
48.5
11.3
12.61
86.9
−25


1234ze


trans-HFC-
n-butane
DME
68.1
13.0
18.9
11.29
77.8
−25


1234ze


trans-HFC-
n-butane
CF3I
81.2
9.7
9.1
11.87
81.8
−25


1234ze


trans-HFC-
isobutane
DME
55.5
28.7
15.8
12.38
85.4
−25


1234ze


trans-HFC-
isobutane
CF3I
34.9
6.1
59.0
12.57
86.7
−25


1234ze


trans-HFC-
isobutane
CF3SCF3
37.7
1.1
61.7
12.66
87.3
−25


1234ze


HFC-1243zf
HFC-134
HFC-227ea
58.6
34.1
7.3
13.54
93.4
−25


HFC-1243zf
HFC-134
n-butane
27.5
58.7
13.9
14.72
101
−25


HFC-1243zf
HFC-134
DME
18.7
63.5
17.8
10.11
69.7
−25


HFC-1243zf
HFC-134
CF3I
11.4
23.9
64.7
14.45
99.6
−25


HFC-1243zf
HFC-134a
HFC-152a
41.5
21.5
37.1
14.95
103
−25


HFC-1243zf
HFC-134A
n-butane
7.0
81.4
11.6
17.03
117
−25


HFC-1243zf
HFC-152a
propane
2.9
34.0
63.0
31.73
219
−25


HFC-1243zf
HFC-152a
n-butane
28.8
60.3
11.0
15.71
108
−25


HFC-1243zf
HFC-152a
isobutane
6.2
68.5
25.3
17.05
118
−25


HFC-1243zf
HFC-152a
DME
33.1
36.8
30.1
11.41
78.7
−25


HFC-1243zf
HFC-227ea
n-butane
62.0
28.4
9.6
13.67
94.3
−25


HFC-1243zf
HFC-227ea
isobutane
27.9
51.0
21.1
15.00
103
−25


HFC-1243zf
HFC-227ea
DME
48.1
44.8
7.2
12.78
88.1
−25


HFC-1243zf
n-butane
DME
60.3
10.1
29.6
12.28
84.7
−25


HFC-1243zf
isobutane
DME
47.1
26.9
25.9
13.16
90.7
−25


HFC-1243zf
isobutane
CF3I
32.8
1.1
66.1
13.97
96.3
−25


HFC-1243zf
DME
CF3SCF3
41.1
2.3
56.6
13.60
93.8
−25









The near-azeotropic compositions of the present invention at a specified temperature are listed in Table 5.










TABLE 5





Component A
Component B
(wt % A/wt % B)
T (C.)


















HFC-1234yf
HFC-32
1-57/99-43
−25


HFC-1234yf
HFC-125
1-51/99-49
−25


HFC-1234yf
HFC-134
1-99/99-1
−25


HFC-1234yf
HFC-134a
1-99/99-1
−25


HFC-1234yf
HFC-152a
1-99/99-1
−25


HFC-1234yf
HFC-161
1-99/99-1
−25


HFC-1234yf
HFC-143a
1-60/99-40
−25


HFC-1234yf
HFC-227ea
29-99/71-1
−25


HFC-1234yf
HFC-236fa
66-99/34-1
−25


HFC-1234yf
HFC-1225ye
1-99/99-1
−25


HFC-1234yf
trans-HFC-1234ze
1-99/99-1
−25


HFC-1234yf
HFC-1243zf
1-99/99-1
−25


HFC-1234yf
propane
1-80/99-20
−25


HFC-1234yf
n-butane
71-99/29-1
−25


HFC-1234yf
isobutane
60-99/40-1
−25


HFC-1234yf
DME
1-99/99-1
−25


HFC-1225ye
trans-HFC-1234ze
1-99/99-1
−25


HFC-1225ye
HFC-1243zf
1-99/99-1
−25


HFC-1225ye
HFC-134
1-99/99-1
−25


HFC-1225ye
HFC-134a
1-99/99-1
−25


HFC-1225ye
HFC-152a
1-99/99-1
−25


HFC-1225ye
HFC-161
1-84/99-16, 90-99/
−25




10-1


HFC-1225ye
HFC-227ea
1-99/99-1
−25


HFC-1225ye
HFC-236ea
57-99/43-1
−25


HFC-1225ye
HFC-236fa
48-99/52-1
−25


HFC-1225ye
HFC-245fa
70-99/30-1
−25


HFC-1225ye
propane
1-72/99-28
−25


HFC-1225ye
n-butane
65-99/35-1
−25


HFC-1225ye
isobutane
50-99/50-1
−25


HFC-1225ye
DME
1-99/99-1
−25


HFC-1225ye
CF3I
1-99/99-1
−25


HFC-1225ye
CF3SCF3
1-99/99-1
−25


trans-HFC-1234ze
cis-HFC-1234ze
73-99/27-1
−25


trans-HFC-1234ze
HFC-1243zf
1-99/99-1
−25


trans-HFC-1234ze
HFC-134
1-99/99-1
−25


trans-HFC-1234ze
HFC-134a
1-99/99-1
−25


trans-HFC-1234ze
HFC-152a
1-99/99-1
−25


trans-HFC-1234ze
HFC-161
1-52/99-48, 87-99/
−25




13-1


trans-HFC-1234ze
HFC-227ea
1-99/99-1
−25


trans-HFC-1234ze
HFC-236ea
54-99/46-1
−25


trans-HFC-1234ze
HFC-236fa
44-99/56-1
−25


trans-HFC-1234ze
HFC-245fa
67-99/33-1
−25


trans-HFC-1234ze
propane
1-71/99-29
−25


trans-HFC-1234ze
n-butane
62-99/38-1
−25


trans-HFC-1234ze
isobutane
39-99/61-1
−25


trans-HFC-1234ze
DME
1-99/99-1
−25


trans-HFC-1234ze
CF3SCF3
1-99/99-1
−25


trans-HFC-1234ze
CF3I
1-99/99-1
−25


HFC-1243zf
HFC-134
1-99/99-1
−25


HFC-1243zf
HFC-134a
1-99/99-1
−25


HFC-1243zf
HFC-152a
1-99/99-1
−25


HFC-1243zf
HFC-161
1-99/99-1
−25


HFC-1243zf
HFC-227ea
1-99/99-1
−25


HFC-1243zf
HFC-236ea
53-99/47-1
−25


HFC-1243zf
HFC-236fa
49-99/51-1
−25


HFC-1243zf
HFC-245fa
66-99/34-1
−25


HFC-1243zf
propane
1-71/99-29
−25


HFC-1243zf
n-butane
62-99/38-1
−25


HFC-1243zf
isobutane
45-99/55-1
−25


HFC-1243zf
DME
1-99/99-1
−25


cis-HFC-1234ze
HFC-236ea
1-99/99-1
25


cis-HFC-1234ze
HFC-236fa
1-99/99-1
25


cis-HFC-1234ze
HFC-245fa
1-99/99-1
25


cis-HFC-1234ze
n-butane
1-80/99-20
−25


cis-HFC-1234ze
isobutane
1-69/99-31
−25


cis-HFC-1234ze
2-methylbutane
60-99/40-1
25


cis-HFC-1234ze
n-pentane
63-99/37-1
25


HFC-1234ye
HFC-134
38-99/62-1
25


HFC-1234ye
HFC-236ea
1-99/99-1
−25


HFC-1234ye
HFC-236fa
1-99/99-1
25


HFC-1234ye
HFC-245fa
1-99/99-1
25


HFC-1234ye
Cis-HFC-1234ze
1-99/99-1
25


HFC-1234ye
n-butane
1-78/99-22
25


HFC-1234ye
cyclopentane
70-99/30-1
25


HFC-1234ye
isobutane
1-68/99-32
25


HFC-1234ye
2-methylbutane
47-99/53-1
25


HFC-1234ye
n-pentane
57-99/43-1
25









Ternary and higher order near-azeotrope compositions comprising fluoroolefin have also been identified as listed in Table 6.









TABLE 6






Near-azeotrope range
Temp


Components
(weight percent)
(° C.)

















HFC-1225ye/HFC-134a/HFC-152a
1-98/1-98/1-98
25


HFC-1225ye/HFC-134a/HFC-161
1-98/1-98/1-98
25


HFC-1225ye/HFC-134a/isobutane
1-98/1-98/1-40
25


HFC-1225ye/HFC-134a/DME
1-98/1-98/1-20
25


HFC-1225ye/HFC-152a/isobutane
1-98/1-98/1-50
25


HFC-1225ye/HFC-152a/DME
1-98/1-98/1-98
25


HFC-1225ye/HFC-1234yf/HFC-134a
1-98/1-98/1-98
25


HFC-1225ye/HFC-1234yf/HFC-152a
1-98/1-98/1-98
25


HFC-1225ye/HFC-1234yf/HFC-125
1-98/1-98/1-20
25


HFC-1225ye/HFC-1234yf/CF3I
1-98/1-98/1-98
25


HFC-1225ye/HFC-134a/HFC-
1-97/1-97/1-97/1-10
25


152a/HFC-32


HFC-125/HFC-1225ye/isobutane
80-98/1-19/1-10
25


HFC-125/trans-HFC-
80-98/1-19/1-10
25


1234ze/isobutane


HFC-125/HFC-1234yf/isobutane
80-98/1-19/1-10
25


HFC-32/HFC-125/HFC-1225ye
1-98/1-98/1-4
25


HFC-32/HFC-125/trans-HFC-1234ze
1-98/1-98/1-50
25


HFC-32/HFC-125/HFC-1234yf
1-98/1-98/1-55
25


HFC-125/trans-HFC-1234ze/n-butane
80-98/1-19/1-10
25


HFC-125/HFC-1234yf/n-butane
80-98/1-19/1-10
25


HFC-1234yf/HFC-32/HFC-143a
1-50/1-98/1-98
−25


HFC-1234yf/HFC-32/isobutane
1-40/59-98/1-30
−25


HFC-1234yf/HFC-125/HFC-143a
1-60/1-98/1-98
−25


HFC-1234yf/HFC-125/isobutane
1-40/59-98/1-20
−25


HFC-1234yf/HFC-134/propane
1-80/1-70/19-90
−25


HFC-1234yf/HFC-134/DME
1-70/1-98/29-98
−25


HFC-1234yf/HFC-134a/propane
1-80/1-80/19-98
−25


HFC-1234yf/HFC-134a/n-butane
1-98/1-98/1-30
−25


HFC-1234yf/HFC-134a/isobutane
1-98/1-98/1-30
−25


HFC-1234yf/HFC-134a/DME
1-98/1-98/1-40
−25


HFC-1234yf/HFC-143a/propane
1-80/1-98/1-98
−25


HFC-1234yf/HFC-143a/DME
1-40/59-98/1-20
−25


HFC-1234yf/HFC-152a/n-butane
1-98/1-98/1-30
−25


HFC-1234yf/HFC-152a/isobutane
1-98/1-90/1-40
−25


HFC-1234yf/HFC-152a/DME
1-70/1-98/1-98
−25


HFC-1234yf/HFC-227ea/propane
1-80/1-70/29-98
−25


HFC-1234yf/HFC-227ea/n-butane
40-98/1-59/1-20
−25


HFC-1234yf/HFC-227ea/isobutane
30-98/1-69/1-30
−25


HFC-1234yf/HFC-227ea/DME
1-98/1-80/1-98
−25


HFC-1234yf/n-butane/DME
1-98/1-40/1-98
−25


HFC-1234yf/isobutane/DME
1-98/1-50/1-98
−25


HFC-1234yf/DME/CF3I
1-98/1-98/1-98
−25


HFC-1234yf/DME/CF3SCF3
1-98/1-40/1-80
−25


HFC-1225ye/trans-HFC-
1-98/1-98/1-98
−25


1234ze/HFC-134


HFC-1225ye/trans-HFC-
1-98/1-98/1-98
−25


1234ze/HFC-227ea


HFC-1225ye/trans-HFC-
1-60/1-60/1-98
−25


1234ze/propane


HFC-1225ye/trans-HFC-1234ze/n-
1-98/1-98/1-30
−25


butane


HFC-1225ye/trans-HFC-1234ze/DME
1-98/1-98/1-98
−25


HFC-1225ye/trans-HFC-1234ze/
1-98/1-98/1-98
−25


CF3SCF3


HFC-1225ye/HFC-1243zf/HFC-134
1-98/1-98/1-98
−25


HFC-1225ye/HFC-1243zf/n-butane
1-98/1-98/1-30
−25


HFC-1225ye/HFC-1243zf/isobutane
1-98/1-98/1-40
−25


HFC-1225ye/HFC-1243zf/DME
1-98/1-98/1-98
−25


HFC-1225ye/HFC-1243zf/CF3I
1-98/1-98/1-98
−25


HFC-1225ye/HFC-134/HFC-152a
1-98/1-98/1-98
−25


HFC-1225ye/HFC-134/HFC-227ea
1-98/1-98/1-98
−25


HFC-1225ye/HFC-134/n-butane
1-98/1-90/1-40
−25


HFC-1225ye/HFC-134/isobutane
1-98/1-90/1-40
−25


HFC-1225ye/HFC-134/DME
1-98/1-98/1-40
−25


HFC-1225ye/HFC-227ea/DME
40-98/1-59/1-30
−25


HFC-1225ye/n-butane/DME
1-98/1-30/1-98
−25


HFC-1225ye/n-butane/CF3SCF3
1-98/1-20/1-98
−25


HFC-1225ye/isobutane/DME
1-98/1-60/1-98
−25


HFC-1225ye/isobutane/CF3I
1-98/1-40/1-98
−25


trans-HFC-1234ze/HFC-1243zf/HFC-
1-98/1-98/1-98
−25


227ea


trans-HFC-1234ze/HFC-1243zf/n-
1-98/1-98/1-30
−25


butane


trans-HFC-1234ze/HFC-
1-98/1-98/1-40
−25


1243zf/isobutane


trans-HFC-1234ze/HFC-1243zf/DME
1-98/1-98/1-98
−25


trans-HFC-1234ze/HFC-134/HFC-
1-98/1-98/1-98
−25


152a


trans-HFC-1234ze/HFC-134/HFC-
1-98/1-98/1-98
−25


227ea


trans-HFC-1234ze/HFC-134/DME
1-98/1-98/1-40
−25


trans-HFC-1234ze/HFC-134a/HFC-
1-98/1-98/1-98
−25


152a


trans-HFC-1234ze/HFC-152a/n-
1-98/1-98/1-50
−25


butane


trans-HFC-1234ze/HFC-152a/DME
1-98/1-98/1-98
−25


trans-HFC-1234ze/HFC-227ea/n-
1-98/1-98/1-40
−25


butane


trans-HFC-1234ze/n-butane/DME
1-98/1-40/1-98
−25


trans-HFC-1234ze/n-butane/CF3I
1-98/1-30/1-98
−25


trans-HFC-1234ze/isobutane/DME
1-98/1-60/1-98
−25


trans-HFC-1234ze/isobutane/CF3I
1-98/1-40/1-98
−25


trans-HFC-1234ze/isobutane/
1-98/1-40/1-98
−25


CF3SCF3


HFC-1243zf/HFC-134/HFC-227ea
1-98/1-98/1-98
−25


HFC-1243zf/HFC-134/n-butane
1-98/1-98/1-40
−25


HFC-1243zf/HFC-134/DME
1-98/1-98/1-98
−25


HFC-1243zf/HFC-134/CF3I
1-98/1-98/1-98
−25


HFC-1243zf/HFC-134a/HFC-152a
1-98/1-98/1-98
−25


HFC-1243zf/HFC-134a/n-butane
1-98/1-98/1-40
−25


HFC-1243zf/HFC-152a/propane
1-70/1-70/29-98
−25


HFC-1243zf/HFC-152a/n-butane
1-98/1-98/1-30
−25


HFC-1243zf/HFC-152a/isobutane
1-98/1-98/1-40
−25


HFC-1243zf/HFC-152a/DME
1-98/1-98/1-98
−25


HFC-1243zf/HFC-227ea/n-butane
1-98/1-98/1-40
−25


HFC-1243zf/HFC-227ea/isobutane
1-98/1-90/1-50
−25


HFC-1243zf/HFC-227ea/DME
1-98/1-80/1-90
−25


HFC-1243zf/n-butane/DME
1-98/1-40/1-98
−25


HFC-1243zf/isobutane/DME
1-98/1-60/1-98
−25


HFC-1243zf/isobutane/CF3I
1-98/1-40/1-98
−25


HFC-1243zf/DME/CF3SCF3
1-98/1-40/1-90
−25









Certain of the compositions of the present invention are non-azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of Table 2, but outside of the near-azeotropic ranges of Table 5 and Table 6 may be considered to be non-azeotropic.
A non-azeotropic composition may have certain advantages over azeotropic or near azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than a single substance. One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change. Another way to characterize a non-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different. Herein, a composition is non-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent.
The compositions of the present invention 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 may be a method for making a refrigerant blend composition, wherein said refrigerant blend composition comprises a composition as disclosed herein, 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.
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 described earlier herein, particulates including but not limited to metal, metal salt or elastomer particles, that may have come out of the refrigeration apparatus, air-conditioning apparatus or heat pump apparatus, and any other contaminants that may adversely effect the performance of the refrigerant blend composition.
Such impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend component without adversely effecting the performance or equipment within which the refrigerant blend or refrigerant blend component will be used.
It may be necessary to provide additional refrigerant blend or refrigerant blend component to the residual refrigerant blend or refrigerant blend component in order to produce a composition that meets the specifications required for a given product. For instance, if a refrigerant blend has 3 components in a particular weight percentage range, it may be necessary to add one or more of the components in a given amount in order to restore the composition to within the specification limits.
Compositions of the present invention have zero or low ozone depletion potential and low global warming potential (GWP). Additionally, the compositions of the present invention will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the present invention is to reduce the net GWP of refrigerant mixtures by adding fluoroolefins to said mixtures.
The compositions of the present invention may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R11 (CFC-11, fluorotrichloromethane), R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), R407C (ASHRAE designation for a blend of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane), R410A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R32), R417A, (ASHRAE designation for a blend of 46.6 weight percent R125, 50.0 weight percent R134a, and 3.4 weight percent n-butane), R422A, R422B, R422C and R422D, (ASHRAE designation for a blend of 85.1 weight percent R125, 11.5 weight percent R134a, and 3.4 weight percent isobutane), R404A, (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1,1,1-trifluoroethane), and 4.0 weight percent R134a) and R507A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R143a). Additionally, the compositions of the present invention may be useful as replacements for R12 (CFC-12, dichlorodifluoromethane) or R502 (ASHRAE designation for a blend of 51.2 weight percent CFC-115 (chloropentafluoroethane) and 48.8 weight percent HCFC-22).
Often replacement refrigerants are most useful if capable of being used in the original refrigeration equipment designed for a different refrigerant. The compositions of the present invention may be useful as replacements for the above-mentioned refrigerants in original equipment. Additionally, the compositions of the present invention may be useful as replacements for the above mentioned refrigerants in equipment designed to use the above-mentioned refrigerants.
The compositions of the present invention may further comprise a lubricant. Lubricants of the present invention comprise refrigeration lubricants, i.e. those lubricants suitable for use with refrigeration, air-conditioning, or heat pump apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems”, pages 8.1 through 8.21. Lubricants of the present invention may comprise those commonly known as “mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). Lubricants of the present invention further comprise those commonly known as “synthetic oils” in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and napthenes, and poly(alphaolefins). Representative conventional lubricants of the present 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 sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
Lubricants of the present invention further comprise those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration, air-conditioning, or heat pump apparatus' operating conditions. Such lubricants and their properties are discussed in “Synthetic Lubricants and High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers (PVEs). These lubricants are readily available from various commercial sources.
Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed. Lubricants of the present invention preferably have a kinematic viscosity of at least about 5 cs (centistokes) at 40° C.
Commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance lubricity and system stability. These additives are generally known within the field of refrigeration compressor lubrication, and include anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, 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 anti oxidants, free radical scavengers, and water scavengers may be employed. Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.
The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of an additive such as, for example, a stabilizer, free radical scavenger and/or antioxidant. Such additives include but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. Single additives or combinations may be used.
The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a water scavenger (drying compound). Such water scavengers may comprise ortho esters such as trimethyl-, triethyl-, or tripropylortho formate.
The compositions of the present invention may further comprise a tracer selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodated compounds, alcohols, aldehydes, ketones, nitrous oxide (N2O) and combinations thereof. The tracer compounds are added to the 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 Ser. No. 11/062,044, filed Feb. 18, 2005.
Typical tracer compounds for use in the present compositions are listed in Table 7.








TABLE 7





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
CF3OCHFCF3


HFOC-236faE
CF3OCH2CF3


HFOC-245faEβγ or HFOC-
CHF2OCH2CF3


245faEαβ
(or CHF2CH2OCF3)


HFOC-245cbEβγ or HFOC-
CH3OCF2CF3


245cbαβ
(or CH3CF2OCF3)


HFE-42-11mcc (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
CHF2CH2CF


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


PFC-C51-12mycm
Cyclo(—CF(CF3)CF2CF(CF3)CF2—)


PFC-C51-12mym,
trans-cyclo(—CF2CF(CF3)CF(CF3)CF2—)


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,
Cyclo(—CF2CF2(CF3)CF2CF2(CF3)CF2—)


meta, or para)


Perfluoroethylcyclohexane
Cyclo(—CF2CF2(CF2CF3)CF2CF2CF2CF2—)


 


Perfluoroindan
C9F10 (see structure below) 





 


Perfluorotrimethylcyclo-hexane (all
Cyclo(—CF2(CF3)CF2(CF3)CF2CF2(CF3)CF2—)


possible isomers)


Perfluoroisopropylcyclo-hexane
Cyclo(—CF2CF2(CF2(CF3)2)CF2CF2CF2CF2—)


 


Perfluorodecalin (cis or trans, trans shown)
C10F18 (see structure below) 





 


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





 







Brominated compounds








Bromomethane
CH3Br


Bromofluoromethane
CH2FBr


Bromodifluoromethane
CHF2Br


Dibromofluoromethane
CHFBr2


Tribromomethane
CHBr3


Bromoethane
CH3CH2Br


Bromoethene
CH2═CHBr


1,2-dibromoethane
CH2BrCH2Br


1-bromo-1,2-difluoroethene
CFBr═CHF







Iodated compounds








Iodotrifluoromethane
CF3I


Difluoroiodomethane
CHF2I


Fluoroiodomethane
CH2FI


1,1,2-trifluoro-1-iodoethane
CF2ICH2F


1,1,2,2-tetrafluoro-1-iodoethane
CF2ICHF2


1,1,2,2-tetrafluoro-1,2-diiodoethane
CF2ICF2I


lodopentafluorobenzene
C6F5I







Alcohols








Ethanol
CH3CH2OH


n-propanol
CH3CH2CH2OH


Isopropanol
CH3CH(OH)CH3







Aldehydes and Ketones








Acetone (2-propanone)
CH3C(O)CH3


n-propanal
CH3CH2CHO


n-butanal
CH3CH2CH2CHO


Methyl ethyl ketone (2-butanone)
CH3C(O)CH2CH3







Other








Nitrous oxide
N2O









The compounds listed in Table 7 are available commercially (from chemical supply houses) or may be prepared by processes known in the art.
Single tracer compounds may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be combined in any proportion to serve as a tracer blend. The tracer blend may contain multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, a tracer blend may contain 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon in combination with one or more perfluorocarbons.
Additionally, some of the compounds in Table 7 exist as multiple isomers, structural or optical. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a tracer blend.
The tracer compound or tracer blend may be present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of about 50 ppm to about 500 ppm and most preferably, the tracer compound or tracer blend is present at a total concentration of about 100 ppm to about 300 ppm.
The compositions of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitrites, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The compatibilizer is used to improve solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants. Refrigeration lubricants are needed to lubricate the compressor of a refrigeration, air-conditioning or heat pump apparatus. The lubricant must move throughout the apparatus with the refrigerant in particular it must return from the non-compressor zones to the compressor to continue to function as lubricant and avoid compressor failure.
Hydrofluorocarbon refrigerants are generally not compatible with convention refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes and poly(alpha)olefins. Many replacement lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers, suggested for use with hydrofluorocarbon refrigerants are expensive and absorb water readily. Water in a refrigeration, air-conditioning system or heat pump can lead to corrosion and the formation of particles that may plug the capillary tubes and other small orifices in the system, ultimately causing system failure. Additionally, in existing equipment, time-consuming and costly flushing procedures are required to change to a new lubricant. Therefore, it is desirable to continue to use the original lubricant if possible.
The compatibilizers of the present invention improve solubility of the hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
Polyoxyalkylene glycol ether compatibilizers 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 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 compatibilizers 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, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether compatibilizers may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar®), R1 and R3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals—(OR2)x—that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R2 in one polyoxyalkylene glycol ether compatibilizer molecule may be the same, or one molecule may contain different R2 oxyalkylene groups. The present polyoxyalkylene glycol ether compatibilizers preferably comprise at least one oxypropylene radical. Where R1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. Representative R1 aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R1 aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.
Representative polyoxyalkylene glycol ether compatibilizers include but are not limited to: CH3OCH2CH(CH3)O(H or CH3) (propylene glycol methyl (or dimethyl)ether), CH3O[CH2CH(CH3)O]2(H or CH3) (dipropylene glycol methyl (or dimethyl)ether), CH3O[CH2CH(CH3)O]3(H or CH3) (tripropylene glycol methyl (or dimethyl)ether), C2H5OCH2CH(CH3)O(H or C2H5) (propylene glycol ethyl (or diethyl)ether), C2H5O[CH2CH(CH3)O]2(H or C2H5) (dipropylene glycol ethyl (or diethyl)ether), C2H5O[CH2CH(CH3)O]3(H or C2H5) (tripropylene glycol ethyl (or diethyl)ether), C3H7OCH2CH(CH3)O(H or C3H7) (propylene glycol n-propyl (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 or C4H9) (tripropylene glycol n-butyl (or di-n-butyl)ether), (CH3)3COCH2CH(CH3)OH (propylene glycol t-butyl ether), (CH3)3CO[CH2CH(CH3)O]2(H or (CH3)3) (dipropylene glycol t-butyl (or di-t-butyl)ether), (CH3)3CO[CH2CH(CH3)O]3(H or (CH3)3) (tripropylene glycol t-butyl (or di-t-butyl)ether), C5H11OCH2CH(CH3)OH (propylene glycol n-pentyl ether), C4H9OCH2CH(C2H5)OH (butylene glycol n-butyl ether), C4H9O[CH2CH(C2H5)O]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C2H5C(CH2O(CH2)3CH3)3) and trimethylolpropane di-n-butyl ether (C2H5C(CH2OC(CH2)3CH3)2CH2OH).
Amide compatibilizers of the present invention comprise those represented by the formulae R1C(O)NR2R3 and cyclo-[R4C(O)N(R5)], wherein R1, R2, R3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R1, R2, R3 and R5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R1, R2, R3 and R5 may 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 compatibilizers 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, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide compatibilizers 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 R7 are independently selected (for each n) by the rules previously offered defining R1-3. In the lactams represented by the formula: cyclo-[(CR6R7)nC(O)N(R5)—], all R6 and R7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones.
Representative amide compatibilizers include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.
Ketone compatibilizers of the present invention comprise ketones represented by the formula R1C(O)R2, wherein R1 and R2 are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R1 and R2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R1 and R2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R1 and R2 may optionally include substituted hydrocarbon radicals, that is, radicals containing 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 non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R1 and R2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R1C(O)R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 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 compatibilizers include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.
Nitrile compatibilizers of the present invention comprise nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R1 in said nitrile compatibilizers is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile compatibilizers 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 phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
Representative nitrile compatibilizers include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
Chlorocarbon compatibilizers of the present invention comprise chlorocarbons represented by the formula RClx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon compatibilizers is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RClx 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.
Representative chlorocarbon compatibilizers include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.
Ester compatibilizers of the present invention comprise esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.
Representative esters include but are not limited to: (CH3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a commercial C7 alkyl acetate), “Exxate 800” (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl acetate.
Lactone compatibilizers of the present invention comprise lactones represented by structures [A], [B], and [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 R8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 though R8 may be connected forming a ring with another R1 through R8. The lactone may have an exocyclic alkylidene group as in structure [C], wherein R1 through R6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 though R6 may be connected forming a ring with another R1 through R6. The lactone compatibilizers have a molecular weight range of from about 100 to about 300 atomic mass units, preferred from about 100 to about 200 atomic mass units.

Representative lactone compatibilizers include but are not limited to the compounds listed in Table 8.










TABLE 8







Molecular
Molecular


Additive
Molecular Structure
Formula
Weight (amu)


















(E,Z)-3-ethylidene-5- methyl-dihydro-furan-2- one




C7H10O2
126


 


(E,Z)-3-propylidene-5- methyl-dihydro-furan-2- one




C8H12O2
140


 


(E,Z)-3-butylidene-5- methyl-dihydro-furan-2- one




C9H14O2
154


 


(E,Z)-3-pentylidene-5- methyl-dihydro-furan-2- one




C10H16O2
168


 


(E,Z)-3-Hexylidene-5- methyl-dihydro-furan-2- one




C11H18O2
182


 


(E,Z)-3-Heptylidene-5- methyl-dihydro-furan-2- one




C12H20O2
196


 


(E,Z)-3-octylidene-5- methyl-dihydro-furan-2- one




C13H22O2
210


 


(E,Z)-3-nonylidene-5- methyl-dihydro-furan-2- one




C14H24O2
224


 


(E,Z)-3-decylidene-5- methyl-dihydro-furan-2- one




C15H26O2
238


 


(E,Z)-3-(3,5,5- trimethylhexylidene)-5- methyl-dihydrofuran-2- one




C14H24O2
224


 


(E,Z)-3- cyclohexylmethylidene- 5-methyl-dihydrofuran- 2-one




C12H18O2
194


 


gamma-octalactone




C8H14O2
142


 


gamma-nonalactone




C9H16O2
156


 


gamma-decalactone




C10H18O2
170


 


gamma-undecalactone




C11H20O2
184


 


gamma-dodecalactone




C12H22O2
198


 


3-hexyldihydro-furan-2- one




C10H18O2
170


 


3-heptyldihydro-furan- 2-one




C11H20O2
184


 


cis-3-ethyl-5-methyl- dihydro-furan-2-one




C7H12O2
128


 


cis-(3-propyl-5-methyl)- dihydro-furan-2-one




C8H14O2
142


 


cis-(3-butyl-5-methyl)- dihydro-furan-2-one




C9H16O2
156


 


cis-(3-pentyl-5-methyl)- dihydro-furan-2-one




C10H18O2
170


 


cis-3-hexyl-5-methyl- dihydro-furan-2-one




C11H20O2
184


 


cis-3-heptyl-5-methyl- dihydro-furan-2-one




C12H22O2
198


 


cis-3-octyl-5-methyl- dihydro-furan-2-one




C13H24O2
212


 


cis-3-(3,5,5- trimethylhexyl)-5- methyl-dihydro-furan-2- one




C14H26O2
226


 


cis-3-cyclohexylmethyl- 5-methyl-dihydro-furan- 2-one




C12H20O2
196


 


5-methyl-5-hexyl- dihydro-furan-2-one




C11H20O2
184


 


5-methyl-5-octyl- dihydro-furan-2-one




C13H24O2
212


 


Hexahydro- isobenzofuran-1-one




C8H12O2
140


 


delta-decalactone




C10H18O2
170


 


delta-undecalactone




C11H20O2
184


 


delta-dodecalactone




C12H22O2
198


 


mixture of 4-hexyl- dihydrofuran-2-one and 3-hexyl-dihydro-furan- 2-one




C10H18O2
170









Lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 40° C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40° C. Lactone compatibilizers may be available commercially or prepared by methods as described in U.S. patent application Ser. No. 10/910,495 filed Aug. 3, 2004, incorporated herein by reference.
Aryl ether compatibilizers of the present invention further comprise aryl ethers represented by the formula R1OR2, wherein: R1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R1 aryl radicals in the general formula R1OR2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R2 aliphatic hydrocarbon radicals in the general formula R1OR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether compatibilizers include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.
Fluoroether compatibilizers 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 compatibilizers include but are not limited to: C8H17OCF2CF2H and C6H13OCF2CF2H. It should be noted that if the refrigerant is a fluoroether, then the compatibilizer may not be the same fluoroether.
Fluoroether compatibilizers may further comprise ethers derived from fluoroolefins and polyols. The fluoroolefins may be of the type CF2═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF3 or ORf, wherein Rf is CF3, C2F5, or C3F7. Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethylvinyl ether. The polyols may be linear or branched. Linear polyols may be of the type HOCH2(CHOH)x(CRR′)yCH2OH, wherein R and R′ are hydrogen, or CH3, or C2H5 and wherein x is an integer from 0-4, and y is an integer from 0-4. Branched polyols may be of the type C(OH)t(R)u(CH2OH)v[(CH2)mCH2OH]w, wherein R may be hydrogen, CH3 or C2H5, m may be an integer from 0 to 3, t and u may be 0 or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4. Representative polyols are trimethylol propane, pentaerythritol, butanediol, and ethylene glycol.
1,1,1-trifluoroalkane compatibilizers of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF3R1, wherein R1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1-trifluoroalkane compatibilizers include but are not limited to: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.
By effective amount of compatibilizer is meant that amount of compatibilizer that leads to efficient solubilizing of the lubricant in the composition and thus provides adequate oil return to optimize operation of the refrigeration, air-conditioning or heat pump apparatus.
The compositions of the present invention will typically contain from about 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent compatibilizer in the compositions of the present invention.
The present invention further relates to a method for improving oil-return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using a composition of the present invention comprising a compatibilizer in said apparatus. The compatibilizer is selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, hydrocarbon ethers and 1,1,11-trifluoroalkanes.
The present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition comprising the compositions of the present invention in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.
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 composition by permitting one to observe the fluorescence of the dye in the composition at a leak point or in the vicinity of refrigeration, air-conditioning, or 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 compositions.
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 a composition containing such a UV fluorescent dye is leaking from a given point in a refrigeration, air-conditioning, or heat pump apparatus, the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or combinations thereof.
In accordance with the present invention, there is provided a method for detecting the composition of the present invention comprising the dye as described in the previous sentence in a compression refrigeration, air conditioning or heat pump apparatus. This method comprises providing the composition to the apparatus and providing a suitable means for detecting this composition at a leak point or in the vicinity of the apparatus.
Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, dimethylether, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes solubilizing agents have been defined previously herein as being compatibilizers for use with conventional refrigeration lubricants.
Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, 2-methylbutane and n-pentane. It should be noted that if the composition contains a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.
Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
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 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, 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.
Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel all commercially available, as well as d-limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.
Solubility of these UV fluorescent dyes in the compositions of the present invention 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. U.S. Pat. No. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration, air-conditioning, or heat pump 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 itself thereby not requiring any specialized method for introduction to the refrigeration, air conditioning apparatus, or heat pump. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system as a solution in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing compositions 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 most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent. 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, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.
The present invention further relates to a method of using the compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration, air-conditioning, or heat pump apparatus. The method comprises introducing the composition into the refrigeration, air-conditioning, or heat pump apparatus. This may be done by dissolving the UV fluorescent dye in the composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and UV fluorescent dye and introducing said combination into refrigeration or air-conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition may be used in the refrigeration, air-conditioning, or heat pump apparatus.
The present invention further relates to a method of using the compositions comprising ultraviolet fluorescent dye to detect leaks. The presence of the dye in the compositions allows for detection of leaking refrigerant in a refrigeration, air-conditioning, or heat pump apparatus. Leak detection helps to address, resolve 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 according to the present invention comprising refrigerant, ultra-violet fluorescent dye, as described herein, and optionally, a solubilizing agent as described herein, to refrigeration, air-conditioning, or heat pump apparatus and employing a suitable means for detecting the UV fluorescent dye-containing refrigerant at a leak point or in the vicinity of the apparatus. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamps, often referred to as a “black light” or “blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. 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 can be found by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point.
The present invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R11, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R422B, R422C and R422D, R507A, and R404A, said method comprising providing a composition of the present invention to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant.
In a particular embodiment of the method as described in the paragraph above the high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R422B, R422C and R422D, R507A, R502, and R404A as described above. The method further comprises providing a composition to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or designed to use said high GWP refrigerant, wherein the composition is selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
Vapor-compression refrigeration, air-conditioning, or heat pump 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.
According to the present invention, there is provided a refrigeration, air-conditioning or heat pump apparatus containing a composition of the present invention. In particular, the refrigeration or air-conditioning apparatus may be a mobile apparatus.
As used herein, mobile refrigeration apparatus or mobile air-conditioning apparatus refers to any refrigeration or air-conditioning apparatus incorporated into a transportation unit for the road, rail, sea or air. In addition, apparatus, which are meant to provide refrigeration or air-conditioning for a system independent of any moving carrier, known as “intermodal” systems, are included in the present invention. Such intermodal systems include “containers” (combined sea/land transport) as well as “swap bodies” (combined road and rail transport). The present invention is particularly useful for road transport refrigerating or air-conditioning apparatus, such as automobile air-conditioning apparatus or refrigerated road transport equipment.
The compositions of the present invention may also be useful in stationary air-conditioning and heat pumps, e.g. chillers, high temperature heat pumps, residential and light commercial and commercial air-conditioning systems. In stationary refrigeration applications, the present compositions may be useful in equipment such as domestic refrigerators, ice machines, walk-in and reach-in coolers and freezers, and supermarket systems.
The present invention further relates to a method of producing cooling comprising evaporating any of the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said composition.
The present invention further relates to a method of producing heat comprising condensing any of the 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 refrigeration, air-conditioning, or heat pump apparatus containing a composition of the present invention wherein said composition comprises at least one fluoroolefin.
The present invention further relates to a mobile air-conditioning apparatus containing a composition of the present invention wherein said composition comprises at least one fluoroolefin.
The present invention further relates to a method for early detection of a refrigerant leak in a refrigeration, air-conditioning or heat pump apparatus. The method comprising using a non-azeotropic composition in said apparatus, and monitoring for a reduction in cooling performance. The non-azeotropic compositions will fractionate upon leakage from a refrigeration, air-conditioning or heat pump apparatus and the lower boiling (higher vapor pressure) component will leak out of the apparatus first. When this occurs, if the lower boiling component in that composition provides the majority of the refrigeration capacity, there will be a marked reduction in the capacity and thus performance of the apparatus. In an automobile air-conditioning system, as an example, the passengers in the automobile will detect a reduction in the cooling capability of the system. This reduction in cooling capability can be interpreted to mean that refrigerant is being leaked and that the system requires repair.
The present invention further relates to a method of using the composition of the present invention as a heat transfer fluid composition. The method comprises transporting said composition from a heat source to a heat sink.
Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well.
A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air-conditioning, or the passenger compartment of an automobile requiring air-conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.
In certain embodiments, particular combinations of the components described above may be used, and in particular weight percentages. The following compositions are meant to be exemplary of such embodiments, without limiting the scope of the compositions of the present invention to the following.
In one embodiment, the present invention relates to a composition comprising: at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycol, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins; and a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
In another embodiment, the present invention relates to a composition comprising: a refrigerant or heat transfer fluid composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I. The composition also comprises a compatibilizer selected from the group consisting of: i) 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; ii) 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; iii) 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; iv) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; v) chlorocarbons represented by the formula RClx, 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; vi) 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; vii) 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; viii) 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 ix) lactones represented by structures [B], [C], and [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 correct atomic mass units; and x) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

According to the present invention, there is provided a refrigeration, air-conditioning or heat pump apparatus containing a composition as described in the paragraph above. In particular, the refrigeration or air-conditioning apparatus may be a mobile apparatus.
Further in accordance with this particular embodiment, the present invention relates to a method for improving oil-return to a compressor in a compression refrigeration, air-conditioning or heat pump apparatus. The method comprises using the composition as described in the paragraph above in the compression refrigeration, air-conditioning or heat pump apparatus.
In another particular embodiment, the present invention relates to a composition comprising (a) at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof; and (b) a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
In accordance with the present invention, there is provided a method for detecting the composition comprising the dye as described in the previous paragraph in a compression refrigeration, air conditioning or heat pump apparatus. This method comprises providing the composition to the apparatus and providing a suitable means for detecting this composition at a leak point or in the vicinity of the apparatus.
According to the present invention, there is provided a refrigeration, air-conditioning or heat pump apparatus containing a composition as described two paragraphs above. In particular, the refrigeration or air-conditioning apparatus may be a mobile apparatus.
Further in accordance with this particular embodiment, the composition including (a) and (b) described three paragraphs above further includes a solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers and 1,1,1-trifluoroalkanes.
In accordance with the present invention, there is provided a method for detecting the composition comprising the dye as described in the previous paragraph in a compression refrigeration, air conditioning or heat pump apparatus. This method comprises providing the composition to the apparatus and providing a suitable means for detecting this composition at a leak point or in the vicinity of the apparatus.
The solubilizing agent of the composition described in the paragraph above is selected from the group consisting of: i) 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; ii) 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; iii) 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; iv) nitriles represented by the formula R1CN, wherein R1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; v) chlorocarbons represented by the formula RClx, 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; vi) 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; vii) 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; viii) 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 ix) lactones represented by structures [B], [C], and [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 x) esters represented by the general formula R1CO2R2, wherein R1 and R2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

The particular composition which includes a compatibilizer as described above, or which includes a dye as described above, or which includes a dye and a solubilizing agent as described above may be used in a method of producing cooling. The method of producing cooling comprises evaporating this composition in the vicinity of a body to be cooled and thereafter condensing said composition. These particular compositions may also be used in a method of producing heat. The method of producing heat comprises condensing this composition in the vicinity of a body to be heated and thereafter evaporating said composition.
In another particular embodiment, the present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition of the present invention in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said refrigerant or heat transfer fluid composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer 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, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RClx, 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 CF3R′, 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 and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins 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 of the type HOCH2CRR′(CH2)z(CHOH)xCH2(CH2OH)y, 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 i) lactones represented by structures [B], [C], and [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, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

In a particular embodiment, the refrigerant or heat transfer fluid composition of the paragraph above is selected from the group consisting of: wherein said refrigerant or heat transfer fluid comprises a composition selected from the group consisting of: about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1234yf; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent trans-HFC-1234ze; about 1 weight percent to about 99 weight percent HFC-1225ye and about 99 weight percent to about 1 weight percent HFC-1243zf; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-134a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-152a; about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent HFC-227ea; and about 1 weight percent to about 99 weight percent trans-HFC-1234ze and about 99 weight percent to about 1 weight percent CF3I.
In another embodiment, the present invention relates to blowing agent compositions comprising the fluoroolefin-containing compositions of the present invention as described herein for use in preparing foams. In other embodiments the invention provides foamable compositions, and preferably polyurethane and polyisocyanate foam compositions, and method of preparing foams. In such foam embodiments, one or more of the present fluoroolefin-containing compositions are included as a blowing agent in foamable compositions, which composition preferably includes one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure. Any of the methods well known in the art, such as those described in “Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention.
The present invention further relates to a method of forming a foam comprising: (a) adding to a foamable composition a fluoroolefin-containing composition of the present invention; and (b) reacting the foamable composition under conditions effective to form a foam.
Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions as described herein for use as propellants in sprayable compositions. Additionally, the present invention relates to a sprayable composition comprising the fluoroolefin-containing compositions as described herein. The active ingredient to be sprayed together with inert ingredients, solvents and other materials may also be present in a sprayable composition. Preferably, the sprayable composition is an aerosol. Suitable active materials to be sprayed include, without limitations, cosmetic materials, such as deodorants, perfumes, hair sprays, cleaners, and polishing agents as well as medicinal materials such as anti-asthma and anti-halitosis medications.
The present invention further relates to a process for producing aerosol products comprising the step of adding a fluoroolefin-containing composition as described herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.
A further aspect provides methods of suppressing a flame, said methods comprising contacting a flame with a fluid comprising a fluoroolefin-containing composition of the present disclosure. Any suitable methods for contacting the flame with the present composition may be used. For example, a fluoroolefin-containing composition of the present disclosure may be sprayed, poured, and the like onto the flame, or at least a portion of the flame may be immersed in the flame suppression composition. In light of the teachings herein, those of skill in the art will be readily able to adapt a variety of conventional apparatus and methods of flame suppression for use in the present disclosure.
A further embodiment provides methods of extinguishing or suppressing a fire in a total-flood application comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into an area to extinguish or suppress fires in that area.
Another embodiment provides methods of inerting an area to prevent a fire or explosion comprising providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the agent in a pressurized discharge system; and discharging the agent into the area to prevent a fire or explosion from occurring.
The term “extinguishment” is usually used to denote complete elimination of a fire; whereas, “suppression” is often used to denote reduction, but not necessarily total elimination, of a fire or explosion. As used herein, terms “extinguishment” and “suppression” will be used interchangeably. There are four general types of halocarbon fire and explosion protection applications. (1) In total-flood fire extinguishment and/or suppression applications, the agent is discharged into a space to achieve a concentration sufficient to extinguish or suppress an existing fire. Total flooding use includes protection of enclosed, potentially occupied spaces such, as computer rooms as well as specialized, often unoccupied spaces such as aircraft engine nacelles and engine compartments in vehicles. (2) In streaming applications, the agent is applied directly onto a fire or into the region of a fire. This is usually accomplished using manually operated wheeled or portable units. A second method, included as a streaming application, uses a “localized” system, which discharges agent toward a fire from one or more fixed nozzles. Localized systems may be activated either manually or automatically. (3) In explosion suppression, a fluoroolefin-containing composition of the present disclosure is discharged to suppress an explosion that has already been initiated. The term “suppression” is normally used in this application because the explosion is usually self-limiting. However, the use of this term does not necessarily imply that the explosion is not extinguished by the agent. In this application, a detector is usually used to detect an expanding fireball from an explosion, and the agent is discharged rapidly to suppress the explosion. Explosion suppression is used primarily, but not solely, in defense applications. (4) In inertion, a fluoroolefin-containing composition of the present disclosure is discharged into a space to prevent an explosion or a fire from being initiated. Often, a system similar or identical to that used for total-flood fire extinguishment or suppression is used. Usually, the presence of a dangerous condition (for example, dangerous concentrations of flammable or explosive gases) is detected, and the fluoroolefin-containing composition of the present disclosure is then discharged to prevent the explosion or fire from occurring until the condition can be remedied.
The extinguishing method can be carried out by introducing the composition into an enclosed area surrounding a fire. Any of the known methods of introduction can be utilized provided that appropriate quantities of the composition are metered into the enclosed area at appropriate intervals. For example, a composition can be introduced by streaming, e.g., using conventional portable (or fixed) fire extinguishing equipment; by misting; or by flooding, e.g., by releasing (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding a fire. The composition can optionally be combined with an inert propellant, e.g., nitrogen, argon, decomposition products of glycidyl azide polymers or carbon dioxide, to increase the rate of discharge of the composition from the streaming or flooding equipment utilized.
Preferably, the extinguishing process involves introducing a fluoroolefin-containing composition of the present disclosure to a fire or flame in an amount sufficient to extinguish the fire or flame. One skilled in this field will recognize that the amount of flame suppressant needed to extinguish a particular fire will depend upon the nature and extent of the hazard. When the flame suppressant is to be introduced by flooding, cup burner test data is useful in determining the amount or concentration of flame suppressant required to extinguish a particular type and size of fire.
Laboratory tests useful for determining effective concentration ranges of fluoroolefin-containing compositions when used in conjunction with extinguishing or suppressing a fire in a total-flood application or fire inertion are described, for example, in U.S. Pat. No. 5,759,430.
EXAMPLES
Example 1
Impact of Vapor Leakage
A vessel is charged with an initial composition at a temperature of either −25° C. or if specified, at 25° C., and the initial vapor pressure of the composition is measured. The composition is allowed to leak from the vessel, while the temperature is held constant, until 50 weight percent of the initial composition is removed, at which time the vapor pressure of the composition remaining in the vessel is measured. Results are shown in Table 9.












TABLE 9








After
After






50%
50%


Composition
Initial P
Initial P
Leak
Leak
Delta P


wt %
(Psia)
(kPa)
(Psia)
(kPa)
(%)















HFC-1234yf/HFC-32












 7.4/92.6
49.2
339
49.2
339
0.0%


 1/99
49.2
339
49.2
339
0.0%


20/80
49.0
338
48.8
337
0.3%


40/60
47.5
327
47.0
324
1.0%


57/43
44.9
309
40.5
280
9.6%


58/42
44.6
308
40.1
276
10.2%







HFC-1234yf/HFC-125












10.9/89.1
40.8
281
40.8
281
0.0%


 1/99
40.3
278
40.2
277
0.0%


20/80
40.5
279
40.3
278
0.4%


40/60
38.7
267
37.0
255
4.4%


50/50
37.4
258
34.0
235
9.0%


51/49
37.3
257
33.7
232
9.6%


52/48
37.1
256
33.3
229
10.3%







HFC-1234yf/HFC-134












 1/99
11.7
81
11.6
80
0.7%


10/90
12.8
88
12.2
84
4.5%


20/80
13.7
95
13.0
89
5.6%


40/60
15.2
105
14.6
101
4.1%


60/40
16.3
113
16.0
110
2.0%


80/20
17.2
119
17.1
118
0.6%


90/10
17.6
121
17.5
121
0.2%


99/1 
17.8
123
17.8
123
0.0%







HFC-1234yf/HFC-134a












70.4/29.6
18.4
127
18.4
127
0.0%


80/20
18.3
126
18.3
126
0.1%


90/10
18.2
125
18.1
125
0.1%


99/1 
17.9
123
17.9
123
0.1%


40/60
17.9
123
17.8
123
0.7%


20/80
17.0
117
16.7
115
1.7%


10/90
16.4
113
16.1
111
1.5%


 1/99
15.6
107
15.6
107
0.3%







HFC-1234yf/HFC-152a












91.0/9.0
17.9
123
17.9
123
0.0%


99/1 
17.9
123
17.8
123
0.1%


60/40
17.4
120
17.2
119
0.7%


40/60
16.6
115
16.4
113
1.6%


20/80
15.7
108
15.4
106
2.0%


10/90
15.1
104
14.9
103
1.5%


 1/99
14.6
100
14.5
100
0.2%







HFC-1234yf/HFC-161












 1/99
25.3
174
25.3
174
0.0%


10/90
25.2
174
25.2
174
0.1%


20/80
24.9
172
24.8
171
0.8%


40/60
23.8
164
23.2
160
2.6%


60/40
22.0
152
21.3
147
3.2%


80/20
19.8
137
19.5
134
1.9%


90/10
18.8
129
18.6
128
0.9%


99/1 
17.9
123
17.9
123
0.1%







HFC-1234yf/FC-143a












17.3/82.7
39.5
272
39.5
272
0.0%


10/90
39.3
271
39.3
271
0.1%


 1/99
38.7
267
38.6
266
0.1%


40/60
38.5
266
37.8
260
1.9%


60/40
36.3
250
32.8
226
9.5%


61/39
36.1
249
32.4
223
10.2%







HFC-1234yf/HFC-227ea












84.6/15.4
18.0
124
18.0
124
0.0%


90/10
18.0
124
18.0
124
0.0%


99/1 
17.9
123
17.9
123
0.0%


60/40
17.6
121
17.4
120
1.2%


40/60
16.7
115
15.8
109
5.4%


29/71
15.8
109
14.2
98
9.7%


28/72
15.7
108
14.1
97
10.2%







HFC-1234yf/HFC-236fa












99/1 
17.8
122
17.7
122
0.2%


90/10
17.0
117
16.6
115
2.4%


80/20
16.2
112
15.4
106
5.1%


70/30
15.3
106
14.0
97
8.5%


66/34
15.0
103
13.5
93
10.0%







HFC-1234yf/HFC-1225ye












 1/99
11.6
80
11.5
79
0.5%


10/90
12.6
87
12.2
84
3.2%


20/80
13.5
93
12.9
89
4.3%


40/60
15.0
103
14.4
99
3.7%


60/40
16.2
111
15.8
109
2.2%


80/20
17.1
118
16.9
117
0.9%


90/10
17.5
120
17.4
120
0.3%


99/1 
17.8
123
17.8
123
0.0%







HFC-1234yf/trans-HFC-1234ze












 1/99
11.3
78
11.3
78
0.4%


10/90
12.2
84
11.8
81
3.3%


20/80
13.1
90
12.5
86
4.6%


40/60
14.6
101
14.0
96
4.3%


60/40
15.8
109
15.4
106
2.7%


80/20
16.9
117
16.7
115
1.1%


90/10
17.4
120
17.3
119
0.5%


99/1 
17.8
123
17.8
123
0.1%







HFC-1234yf/HFC-1243zf












 1/99
13.1
90
13.0
90
0.2%


10/90
13.7
94
13.5
93
1.6%


20/80
14.3
99
14.0
97
2.4%


40/60
15.5
107
15.1
104
2.2%


60/40
16.4
113
16.2
112
1.4%


80/20
17.2
119
17.1
118
0.5%


90/10
17.5
121
17.5
121
0.2%


99/1 
17.8
123
17.8
123
0.0%







HFC-1234yf/propane












51.5/48.5
33.5
231
33.5
231
0.0%


60/40
33.4
230
33.3
229
0.4%


80/20
31.8
220
29.0
200
8.9%


81/19
31.7
218
28.5
196
10.0%


40/60
33.3
230
33.1
228
0.6%


20/80
32.1
221
31.2
215
2.9%


10/90
31.0
214
30.2
208
2.6%


 1/99
29.6
204
29.5
203
0.4%







HFC-1234yf/n-butane












98.1/1.9 
17.9
123
17.9
123
0.0%


99/1 
17.9
123
17.9
123
0.0%


100/0 
17.8
123
17.8
123
0.0%


80/20
16.9
116
16.1
111
4.4%


70/30
16.2
112
14.4
99
10.8%


71/29
16.3
112
14.6
101
9.9%







HFC-1234yf/isobutane












88.1/11.9
19.0
131
19.0
131
0.0%


95/5 
18.7
129
18.6
128
0.7%


99/1 
18.1
125
18.0
124
0.6%


60/40
17.9
123
16.0
110
10.3%


61/39
17.9
123
16.2
112
9.4%







HFC-1234yf/DME












53.5/46.5
13.1
90
13.1
90
0.0%


40/60
13.3
92
13.2
91
0.7%


20/80
14.1
97
13.9
96
1.3%


10/90
14.3
99
14.3
98
0.5%


 1/99
14.5
100
14.5
100
0.0%


80/20
14.5
100
14.0
96
3.3%


90/10
15.8
109
15.3
105
3.5%


99/1 
17.6
121
17.5
121
0.6%







HFC-1234yf/CF3SCF3












 1/99
12.1
83
12.0
83
0.2%


10/90
12.9
89
12.7
87
2.0%


20/80
13.8
95
13.4
92
2.8%


40/60
15.1
104
14.7
101
2.7%


60/40
16.2
112
15.9
110
1.9%


80/20
17.1
118
16.9
117
0.9%


90/10
17.5
120
17.4
120
0.5%


99/1 
17.8
123
17.8
123
0.0%







HFC-1234yf/CF3I












 1/99
12.0
83
12.0
83
0.2%


10/90
12.9
89
12.7
87
1.7%


20/80
13.7
94
13.3
92
2.6%


40/60
15.1
104
14.7
101
2.7%


60/40
16.2
111
15.8
109
2.0%


80/20
17.1
118
16.9
116
1.1%


90/10
17.5
120
17.4
120
0.5%


99/1 
17.8
123
17.8
123
0.1%







HFC-125/HFC-1234yf/isobutane (25° C.)












85.1/11.5/3.4
201.3
1388
201.3
1388
0.0%







HFC-125/HFC-1234yf/n-butane (25° C.)












67/32/1
194.4
1340
190.2
1311
2.2%







HFC-32/HFC-125/HFC-1234yf (25° C.)












40/50/10
240.6
1659
239.3
1650
0.5%


23/25/52
212.6
1466
192.9
1330
9.3%


15/45/40
213.2
1470
201.3
1388
5.6%


10/60/30
213.0
1469
206.0
1420
3.3%







HFC-1225ye/trans-HFC-1234ze












63.0/37.0
11.7
81
11.7
81
0.0%


80/20
11.6
80
11.6
80
0.0%


90/10
11.6
80
11.6
80
0.1%


99/1 
11.5
79
11.5
79
0.0%


60/40
11.7
81
11.7
81
0.0%


40/60
11.6
80
11.6
80
0.1%


20/80
11.5
79
11.4
79
0.2%


10/90
11.3
78
11.3
78
0.1%


 1/99
11.2
77
11.2
77
0.1%







HFC-1225ye/HFC-1243zf












40.0/60.0
13.6
94
13.6
94
0.0%


20/80
13.4
93
13.4
92
0.1%


10/90
13.2
91
13.2
91
0.2%


 1/99
13.0
90
13.0
90
0.0%


60/40
13.4
92
13.4
92
0.4%


80/20
12.8
88
12.6
87
1.4%


90/10
12.3
85
12.1
83
1.5%


99/1 
11.6
80
11.5
79
0.3%







HFC-1225ye/HFC-134












52.2/47.8
12.8
88
12.8
88
0.0%


80/20
12.4
85
12.3
85
0.6%


90/10
12.0
83
11.9
82
0.8%


99/1 
11.5
79
11.5
79
0.2%


40/60
12.7
88
12.7
87
0.2%


20/80
12.3
85
12.2
84
0.8%


10/90
12.0
83
11.9
82
0.9%


 1/99
11.6
80
11.6
80
0.2%







HFC-1225ye/HFC-134a












 1/99
15.5
107
15.5
107
0.0%


10/90
15.2
105
15.2
105
0.3%


20/80
15.0
103
14.9
103
0.5%


40/60
14.4
99
14.2
98
1.0%


60/40
13.6
94
13.4
93
1.4%


80/20
12.7
88
12.5
86
1.6%


90/10
12.2
84
12.0
83
1.3%


99/1 
11.5
80
11.5
79
0.2%







HFC-1225ye/HFC-152a












7.3/92.7
14.5
100
14.5
100
0.0%


 1/99
14.5
100
14.5
100
0.0%


40/60
14.2
98
14.2
98
0.4%


60/40
13.7
95
13.6
93
1.1%


80/20
12.9
89
12.7
87
1.5%


90/10
12.2
84
12.1
83
1.1%


99/1 
11.5
80
11.5
79
0.1%







HFC-1225ye/HFC-161












 1/99
25.2
174
25.2
174
0.0%


10/90
24.9
172
24.8
171
0.6%


20/80
24.5
169
24.0
165
2.0%


40/60
22.9
158
21.4
148
6.5%


56/44
20.9
144
18.8
130
10.0%


99/1 
11.7
81
11.6
80
1.0%


90/10
14.1
97
13.0
90
7.5%


84/16
15.5
107
14.0
96
9.9%


83/17
15.8
109
14.2
98
10.2%







HFC-1225ye/HFC-227ea












 1/99
10.0
69
10.0
69
0.0%


10/90
10.1
70
10.1
70
0.2%


20/80
10.3
71
10.3
71
0.2%


40/60
10.6
73
10.6
73
0.4%


60/40
10.9
75
10.9
75
0.4%


80/20
11.2
77
11.2
77
0.3%


90/10
11.3
78
11.3
78
0.1%


99/1 
11.5
79
11.5
79
0.0%







HFC-1225ye/HFC-236ea












99/1 
11.4
79
11.4
79
0.0%


90/10
11.3
78
11.2
77
0.5%


80/20
11.0
75
10.7
74
2.0%


60/40
10.2
70
9.4
65
8.3%


57/43
10.1
69
9.1
63
9.9%


56/44
10.0
69
9.0
62
10.6%







HFC-1225ye/HFC-236fa












99/1 
11.4
79
11.4
79
0.1%


90/10
11.1
77
11.0
76
1.1%


80/20
10.7
74
10.4
72
2.4%


60/40
9.8
68
9.2
63
6.6%


48/52
9.2
63
8.2
57
10.0%







HFC-1225ye/HFC-245fa












99/1 
11.4
79
11.4
78
0.3%


90/10
10.9
75
10.6
73
2.5%


80/20
10.4
72
9.8
68
5.7%


70/30
9.9
68
8.9
61
9.9%


69/21
9.8
68
8.8
60
10.5%







HFC-1225ye/propane












29.7/70.3
30.4
209
30.4
209
0.0%


20/80
30.3
209
30.2
208
0.2%


10/90
30.0
207
29.9
206
0.4%


 1/99
29.5
203
29.5
203
0.1%


60/40
29.5
203
28.5
197
3.3%


72/28
28.4
195
25.6
176
9.8%


73/27
28.2
195
25.2
174
10.8%







HFC-1225ye/n-butane












89.5/10.5
12.3
85
12.3
85
0.0%


99/1 
11.7
81
11.6
80
0.9%


80/20
12.2
84
12.0
83
1.5%


65/35
11.7
80
10.5
72
9.9%


64/36
11.6
80
10.4
71
10.9%







HFC-1225ye/isobutane












79.3/20.7
13.9
96
13.9
96
0.0%


90/10
13.6
94
13.3
92
2.4%


99/1 
11.9
82
11.6
80
2.8%


60/40
13.5
93
13.0
89
4.1%


50/50
13.1
91
11.9
82
9.6%


49/51
13.1
90
11.8
81
10.2%







HFC-1225ye/DME












82.1/17.9
10.8
74
10.8
74
0.0%


90/10
10.9
75
10.9
75
0.3%


99/1 
11.4
78
11.4
78
0.2%


60/40
11.5
79
11.2
77
2.4%


40/60
12.8
88
12.1
84
4.8%


20/80
13.9
96
13.5
93
3.0%


10/90
14.3
98
14.1
97
1.1%


 1/99
14.5
100
14.4
100
0.1%







HFC-1225ye/CF3I












 1/99
11.9
82
11.9
82
0.0%


10/90
11.9
82
11.8
82
0.1%


20/80
11.8
81
11.8
81
0.0%


40/60
11.7
80
11.7
80
0.0%


60/40
11.6
80
11.6
80
0.0%


80/20
11.5
79
11.5
79
0.0%


90/10
11.5
79
11.5
79
0.0%


99/1 
11.5
79
11.5
79
0.0%







HFC-1225ye/CF3SCF3












37.0/63.0
12.4
86
12.4
86
0.0%


20/80
12.3
85
12.3
85
0.1%


10/90
12.2
84
12.2
84
0.1%


 1/99
12.0
83
12.0
83
0.1%


60/40
12.3
85
12.3
85
0.2%


80/20
12.0
83
11.9
82
0.4%


90/10
11.7
81
11.7
81
0.3%


99/1 
11.5
79
11.5
79
0.1%







HFC-1225ye/HFC-134a/HFC-152a (25° C.)












76/9/15
81.3
561
80.5
555
1.0%







HFC-1225ye/HFC-134a/HFC-161 (25° C.)












86/10/4
82.1
566
80.2
553
2.3%







HFC-1225ye/HFC-134a/isobutane (25° C.)












87/10/3
83.4
575
80.3
554
3.7%







HFC-1225ye/HFC-134a/DME (25° C.)












87/10/3
77.2
532
76.0
524
1.6%







HFC-1225ye/HFC-152a/isobutane (25° C.)












85/13/2
81.2
560
79.3
547
2.3%







HFC-1225ye/HFC-152a/DME (25° C.)












85/13/2
76.6
528
76.0
524
0.8%







HFC-1225ye/HFC-1234yf/HFC-134a (25° C.)












70/20/10
86.0
593
84.0
579
2.3%


20/70/10
98.2
677
97.5
672
0.7%







HFC-1225ye/HFC-1234yf/HFC-152a (25° C.)












70/25/5
85.1
587
83.4
575
2.0%


25/70/5
95.4
658
94.9
654
0.5%







HFC-1225ye/HFC-1234yf/HFC-125 (25° C.)












25/71/4
105.8
729
96.3
664
9.0%


75/21/4
89.5
617
83.0
572
7.3%


75/24/1
85.3
588
82.3
567
3.5%


25/74/1
98.0
676
95.1
656
3.0%







HFC-1225ye/HFC-1234yf/CF3I (25° C.)












40/40/20
87.5
603
86.0
593
1.7%


45/45/10
89.1
614
87.7
605
1.6%







HFC-1225ye/HFC-134a/HFC-152a/HFC-32 (25° C.)












74/8/17/1
86.1
594
81.5
562
5.3%







HFC-125/HFC-1225ye/isobutane (25° C.)












85.1/11.5/3.4
186.2
1284
179.2
1236
3.8%







HFC-32/HFC-125/HFC-1225ye (25° C.)












30/40/30
212.7
1467
194.6
1342
8.5%







trans-HFC-1234ze/cis-HFC-1234ze












99/1 
11.1
77
11.1
76
0.4%


90/10
10.5
72
10.1
70
3.4%


80/20
9.8
68
9.1
63
7.1%


73/27
9.3
64
8.4
58
9.9%


72/28
9.3
64
8.3
57
10.3%







trans-HFC-1234ze/HFC-1243zf












17.0/83.0
13.0
90
13.0
90
0.0%


10/90
13.0
90
13.0
90
0.0%


 1/99
13.0
90
13.0
90
0.0%


40/60
12.9
89
12.9
89
0.1%


60/40
12.6
87
12.5
86
0.6%


80/20
12.1
83
12.0
82
0.8%


90/10
11.7
80
11.6
80
0.7%


99/1 
11.2
77
11.2
77
0.1%







trans-HFC-1234ze/HFC-134












45.7/54.3
12.5
86
12.5
86
0.0%


60/40
12.4
85
12.4
85
0.2%


80/20
12.0
83
11.9
82
0.7%


90/10
11.7
80
11.6
80
0.7%


99/1 
11.2
77
11.2
77
0.1%


20/80
12.2
84
12.2
84
0.4%


10/90
11.9
82
11.9
82
0.6%


 1/99
11.6
80
11.6
80
0.1%







trans-HFC-1234ze/HFC-134a












 9.5/90.5
15.5
107
15.5
107
0.0%


 1/99
15.5
107
15.5
107
0.0%


40/60
15.1
104
15.0
103
0.9%


60/40
14.3
99
14.0
96
2.5%


80/20
13.1
90
12.6
87
4.0%


90/10
12.3
85
11.9
82
3.3%


99/1 
11.3
78
11.3
78
0.5%







trans-HFC-1234ze/HFC-152a












21.6/78.4
14.6
101
14.6
101
0.0%


10/90
14.6
101
14.6
101
0.0%


 1/99
14.5
100
14.5
100
0.0%


40/60
14.5
100
14.5
100
0.1%


60/40
14.1
97
13.9
96
1.1%


80/20
13.2
91
12.8
88
2.5%


90/10
12.4
85
12.0
83
2.6%


99/1 
11.3
78
11.3
78
0.4%







trans-HFC-1234ze/HFC-161












1/99
25.2
174
25.2
174
0.0%


10/90
25.0
172
24.8
171
0.6%


20/80
24.5
169
24.0
165
2.1%


40/60
22.8
157
21.2
146
7.0%


52/48
21.3
147
19.2
132
9.9%


53/47
21.2
146
19.0
131
10.2%


99/1 
11.5
79
11.3
78
1.2%


90/10
13.8
95
12.6
87
8.6%


88/12
14.3
99
12.9
89
9.5%


87/13
14.5
100
13.1
90
10.0%







trans-HFC-1234ze/HFC-227ea












59.2/40.8
11.7
81
11.7
81
0.0%


40/60
11.6
80
11.5
79
0.3%


20/80
11.1
76
10.9
75
1.3%


10/90
10.6
73
10.5
72
1.3%


 1/99
10.0
69
10.0
69
0.2%


80/20
11.6
80
11.5
80
0.2%


90/10
11.4
79
11.4
78
0.3%


99/1 
11.2
77
11.2
77
0.0%







trans-HFC-1234ze/HFC-236ea












99/1 
11.2
77
11.2
77
0.0%


90/10
11.0
76
11.0
76
0.4%


80/20
10.8
75
10.6
73
1.6%


60/40
10.2
70
9.5
66
6.6%


54/46
9.9
69
9.0
62
9.5%


53/47
9.9
68
8.9
61
10.1%







trans-HFC-1234ze/HFC-236fa












99/1 
11.2
77
11.2
77
0.1%


90/10
10.9
75
10.8
75
0.8%


80/20
10.6
73
10.4
71
2.0%


60/40
9.8
67
9.3
64
5.4%


44/56
9.0
62
8.1
56
9.7%


43/57
8.9
62
8.0
55
10.1%







trans-HFC-1234ze/HFC-245fa












99/1 
11.2
77
11.1
77
0.2%


90/10
10.7
74
10.5
73
2.0%


80/20
10.3
71
9.8
68
4.7%


70/30
9.8
68
9.0
62
8.2%


67/33
9.7
67
8.7
60
9.7%


66/34
9.6
66
8.7
60
10.2%







trans-HFC-1234ze/propane












28.5/71.5
30.3
209
30.3
209
0.0%


10/90
30.0
206
29.9
206
0.3%


 1/99
29.5
203
29.5
203
0.1%


40/60
30.2
208
30.1
207
0.4%


60/40
29.3
202
28.3
195
3.4%


71/29
28.4
196
25.7
177
9.3%


72/28
28.3
195
25.4
175
10.2%







trans-HFC-1234ze/n-butane












88.6/11.4
11.9
82
11.9
82
0.0%


95/5 
11.7
81
11.7
80
0.7%


99/1 
11.4
78
11.3
78
0.6%


70/30
11.5
79
11.0
76
4.2%


62/38
11.2
77
10.2
70
9.3%


61/39
11.2
77
10.0
69
10.1%







trans-HFC-1234ze/isobutane












77.9/22.1
12.9
89
12.9
89
0.0%


90/10
12.6
87
12.4
85
1.6%


99/1 
11.4
79
11.3
78
1.1%


60/40
12.6
87
12.3
85
2.4%


39/61
11.7
81
10.6
73
9.8%


38/62
11.7
81
10.5
72
10.1%







trans-HFC-1234ze/DME












84.1/15.9
10.8
74
10.8
74
0.0%


90/10
10.8
75
10.8
75
0.0%


99/1 
11.1
77
11.1
77
0.0%


60/40
11.5
79
11.3
78
2.2%


40/60
12.7
88
12.2
84
4.4%


20/80
13.9
96
13.5
93
2.9%


10/90
14.3
98
14.1
97
1.0%


1/99
14.5
100
14.5
100
0.0%







trans-HFC-1234ze/CF3SCF3












34.3/65.7
12.7
87
12.7
87
0.0%


20/80
12.6
87
12.6
87
0.2%


10/90
12.4
85
12.3
85
0.3%


 1/99
12.0
83
12.0
83
0.1%


60/40
12.4
86
12.4
85
0.5%


80/20
12.0
82
11.8
81
1.1%


90/10
11.6
80
11.5
79
0.9%


99/1 
11.2
77
11.2
77
0.2%







trans-HFC-1234ze/CF3I












 1/99
11.9
82
11.9
82
0.0%


10/90
11.9
82
11.9
82
0.0%


20/80
11.8
81
11.8
81
0.0%


40/60
11.6
80
11.6
80
0.1%


60/40
11.4
79
11.4
79
0.1%


80/20
11.3
78
11.3
78
0.1%


90/10
11.3
78
11.2
77
0.1%


99/1 
11.2
77
11.2
77
0.0%







HFC-32/HFC-125/trans-HFC-1234ze (25° C.)












30/40/30
221.5
1527
209.4
1444
5.5%


30/50/20
227.5
1569
220.2
1518
3.2%







HFC-125/trans-HFC-1234ze/n-butane (25° C.)












66/32/2
180.4
1244
170.3
1174
5.6%







HFC-1243zf/HFC-134












63.0/37.0
13.5
93
13.5
93
0.0%


80/20
13.4
93
13.4
92
0.1%


90/10
13.2
91
13.2
91
0.2%


99/1 
13.0
90
13.0
90
0.0%


40/60
13.3
92
13.3
91
0.5%


20/80
12.7
88
12.6
87
1.3%


10/90
12.3
84
12.1
83
1.5%


 1/99
11.6
80
11.6
80
0.3%







HFC-1243zf/HFC-134a












25.1/74.9
15.9
110
15.9
110
0.0%


10/90
15.8
109
15.8
109
0.1%


 1/99
15.5
107
15.5
107
0.1%


40/60
15.8
109
15.8
109
0.2%


60/40
15.3
106
15.1
104
1.2%


80/20
14.4
99
14.1
97
2.1%


90/10
13.8
95
13.5
93
1.7%


99/1 
13.1
90
13.0
90
0.2%







HFC-1243zf/HFC-152a












40.7/59.3
15.2
104
15.2
104
0.0%


20/80
15.0
103
15.0
103
0.2%


10/90
14.8
102
14.7
102
0.3%


 1/99
14.5
100
14.5
100
0.1%


60/40
15.0
103
14.9
103
0.3%


80/20
14.4
99
14.2
98
1.1%


90/10
13.8
95
13.6
94
1.2%


99/1 
13.1
90
13.1
90
0.2%







HFC-1243zf/HFC-161












 1/99
25.2
174
25.2
174
0.0%


10/90
24.9
172
24.8
171
0.3%


20/80
24.5
169
24.2
167
0.9%


40/60
23.3
160
22.6
156
2.9%


60/40
21.5
148
20.1
139
6.3%


78/22
18.8
130
16.9
117
10.0%


90/10
16.2
111
14.6
101
9.5%


99/1 
13.4
92
13.1
90
1.7%







HFC-1243zf/HFC-227ea












78.5/21.5
13.1
90
13.1
90
0.0%


90/10
13.1
90
13.1
90
0.0%


99/1 
13.0
90
13.0
90
0.0%


60/40
13.0
90
13.0
89
0.2%


40/60
12.6
87
12.5
86
1.1%


20/80
11.8
81
11.5
79
2.7%


10/90
11.1
76
10.7
74
2.8%


 1/99
10.1
69
10.0
69
0.6%







HFC-1243zf/HFC-236ea












99/1 
13.0
89
13.0
89
0.0%


90/10
12.8
88
12.7
87
0.5%


80/20
12.5
86
12.3
84
1.8%


60/40
11.7
81
11.0
76
6.6%


53/47
11.4
79
10.3
71
9.9%


52/48
11.4
78
10.2
70
10.5%







HFC-1243zf/HFC-236fa












99/1 
13.0
89
12.9
89
0.1%


90/10
12.6
87
12.5
86
1.0%


80/20
12.2
84
11.9
82
2.5%


60/40
11.3
78
10.5
73
6.6%


49/51
10.6
73
9.6
66
9.9%


48/52
10.6
73
9.5
65
10.2%







HFC-1243zf/HFC-245fa












99/1 
12.9
89
12.9
89
0.2%


90/10
12.5
86
12.2
84
2.1%


80/20
12.0
83
11.4
79
4.6%


70/30
11.5
79
10.6
73
7.9%


66/34
11.3
78
10.2
70
9.6%


65/35
11.2
77
10.1
69
10.2%







HFC-1243zf/propane












32.8/67.2
31.0
213
31.0
213
0.0%


10/90
30.3
209
30.1
207
0.7%


 1/99
29.5
204
29.5
203
0.1%


60/40
30.1
208
29.2
201
3.2%


72/28
29.0
200
26.1
180
10.2%


71/29
29.2
201
26.5
182
9.3%







HFC-1243zf/n-butane












90.3/9.7 
13.5
93
13.5
93
0.0%


99/1 
13.1
90
13.1
90
0.2%


62/38
12.6
87
11.4
79
9.4%


61/39
12.6
87
11.3
78
10.3%







HFC-1243zf/isobutane












80.7/19.3
14.3
98
14.3
98
0.0%


90/10
14.1
97
14.0
96
0.9%


99/1 
13.2
91
13.1
90
0.7%


60/40
13.8
95
13.4
92
3.2%


45/55
13.1
91
11.9
82
9.5%


44/56
13.1
90
11.8
81
10.1%







HFC-1243zf/DME












72.7/27.3
12.0
83
12.0
83
0.0%


90/10
12.4
85
12.3
85
0.5%


99/1 
12.9
89
12.9
89
0.1%


60/40
12.2
84
12.1
84
0.5%


40/60
13.0
90
12.7
88
2.2%


20/80
14.0
96
13.7
95
2.0%


10/90
14.3
99
14.2
98
0.6%


 1/99
14.5
100
14.5
100
0.0%







cis-HFC-1234ze/HFC-236ea (25° C.)












20.9/79.1
30.3
209
30.3
209
0.0%


10/90
30.2
208
30.2
208
0.0%


 1/99
29.9
206
29.9
206
0.0%


40/60
30.0
207
30.0
207
0.2%


60/40
29.2
201
28.9
199
0.9%


80/20
27.8
191
27.4
189
1.4%


90/10
26.8
185
26.5
183
1.1%


99/1 
25.9
178
25.8
178
0.2%







cis-HFC-1234ze/HFC-236fa (25° C.)












 1/99
39.3
271
39.3
271
0.0%


10/90
38.6
266
38.4
265
0.3%


20/80
37.6
259
37.3
257
0.9%


40/60
35.4
244
34.5
238
2.5%


60/40
32.8
226
31.4
216
4.3%


78/22
29.6
204
28.2
195
4.8%


90/10
27.8
192
26.9
185
3.4%


99/1 
26.0
179
25.8
178
0.5%







cis-HFC-1234ze/HFC-245fa (25° C.)












76.2/23.7
26.2
180
26.2
180
0.0%


90/10
26.0
179
26.0
179
0.0%


99/1 
25.8
178
25.8
178
0.0%


60/40
26.0
179
25.9
179
0.2%


40/60
25.3
174
25.0
173
0.9%


20/80
23.9
164
23.5
162
1.7%


10/90
22.8
157
22.5
155
1.5%


 1/99
21.6
149
21.5
149
0.2%







cis-HFC-1234ze/n-butane












51.4/48.6
6.1
42
6.1
42
0.0%


80/20
5.8
40
5.2
36
9.3%


81/19
5.8
40
5.2
36
10.4%


40/60
6.1
42
6.0
41
0.7%


20/80
5.8
40
5.6
39
3.3%


10/90
5.6
38
5.4
37
3.1%


 1/99
5.3
36
5.2
36
0.6%







cis-HFC-1234ze/isobutane












26.2/73.8
8.7
60
8.7
60
0.0%


10/90
8.7
60
8.6
59
0.3%


 1/99
8.5
59
8.5
59
0.0%


40/60
8.7
60
8.6
60
0.5%


60/40
8.4
58
8.0
55
4.3%


70/30
8.1
56
7.3
50
10.3%


69/31
8.2
56
7.4
51
9.4%







cis-HFC-1234ze/2-methylbutane (25° C.)












86.6/13.4
27.3
188
27.3
188
0.0%


90/10
27.2
187
27.2
187
0.1%


99/1 
26.0
180
25.9
179
0.5%


60/40
25.8
178
24.0
166
6.9%


55/45
25.3
174
22.8
157
10.0%







cis-HFC-1234ze/n-pentane (25° C.)












92.9/9.1
26.2
181
26.2
181
0.0%


99/1
25.9
178
25.9
178
0.1%


80/20
25.6
177
25.2
174
1.8%


70/30
24.8
171
23.5
162
5.6%


64/36
24.3
167
22.0
152
9.2%


63/37
24.2
167
21.8
150
9.9%







HFC-1234ye/HFC-134 (25° C.)












 1/99
75.9
523
75.8
523
0.1%


10/90
73.8
509
73.0
503
1.1%


20/80
71.3
491
69.0
476
3.1%


38/62
66.0
455
59.6
411
9.7%


39/61
65.7
453
58.9
406
10.2%







HFC-1234ye/HFC-236ea (−25° C.)












24.0/76.0
3.4
23
3.4
23
0.0%


10/90
3.3
23
3.3
23
0.3%


 1/99
3.3
23
3.3
23
0.0%


40/60
3.3
23
3.3
23
0.0%


60/40
3.2
22
3.2
22
0.9%


80/20
3.1
21
3.0
21
1.6%


90/10
2.9
20
2.9
20
1.4%


99/1 
2.8
19
2.8
19
0.0%







HFC-1234ye/HFC-236fa (25° C.)












 1/99
39.2
270
39.2
270
0.1%


10/90
37.7
260
37.3
257
1.1%


20/80
36.1
249
35.2
243
2.5%


40/60
32.8
226
31.0
213
5.7%


60/40
29.3
202
26.7
184
8.8%


78/22
25.4
175
23.1
159
9.1%


90/10
23.2
160
21.7
150
6.3%


99/1 
21.0
145
20.8
144
0.8%







HFC-1234ye/HFC-245fa (25° C.)












42.5/57.5
22.8
157
22.8
157
0.0%


20/80
22.5
155
22.4
155
0.3%


10/90
22.1
152
22.0
152
0.3%


 1/99
21.5
148
21.5
148
0.0%


60/40
22.6
156
22.6
156
0.2%


80/20
22.0
152
21.9
151
0.6%


90/10
21.5
148
21.3
147
0.6%


99/1 
20.8
144
20.8
143
0.1%







HFC-1234ye/cis-HFC-1234ze (25° C.)












 1/99
25.7
177
25.7
177
0.0%


10/90
25.6
176
25.6
176
0.0%


20/80
25.3
175
25.3
174
0.1%


40/60
24.7
170
24.5
169
0.5%


60/40
23.7
163
23.5
162
1.0%


78/22
22.4
155
22.2
153
1.2%


90/10
21.7
149
21.5
148
0.9%


99/1 
20.9
144
20.8
144
0.1%







HFC-1234ye/n-butane (25° C.)












41.2/58.8
38.0
262
38.0
262
0.0%


20/80
37.3
257
37.0
255
0.8%


10/90
36.4
251
36.1
249
0.9%


 1/99
35.4
244
35.3
243
0.2%


60/40
37.4
258
36.9
254
1.4%


70/30
36.5
252
34.9
241
4.4%


78/22
35.3
243
31.8
219
9.9%


79/21
35.1
242
31.3
216
10.9%







HFC-1234ye/cyclopentane (25° C.)












99/1 
20.7
143
20.7
143
0.0%


90/10
20.3
140
20.0
138
1.0%


80/20
19.5
134
18.7
129
4.1%


70/30
18.6
128
16.9
116
9.5%


69/31
18.5
128
16.6
115
10.3%







HFC-1234ye/isobutane (25° C.)












16.4/83.6
50.9
351
50.9
351
0.0%


10/90
50.9
351
50.9
351
0.0%


 1/99
50.5
348
50.5
348
0.0%


40/60
50.1
345
49.6
342
1.0%


60/40
47.8
330
45.4
313
5.2%


68/32
46.4
320
42.0
289
9.5%


69/31
46.2
318
41.4
286
10.3%







HFC-1234ye/2-methylbutane (25° C.)












80.3/19.7
23.1
159
23.1
159
0.0%


90/10
22.8
157
22.6
156
1.1%


99/1 
21.2
146
20.9
144
1.0%


60/40
22.5
155
21.7
149
3.6%


47/53
21.5
148
19.4
134
9.6%


46/54
21.4
148
19.2
133
10.1%







HFC-1234ye/n-pentane (25° C.)












87.7/12.3
21.8
150
21.8
150
0.0%


95/5 
21.5
149
21.4
148
0.5%


99/1 
21.0
145
20.9
144
0.4%


60/40
20.5
141
18.9
131
7.7%


57/43
20.3
140
18.3
126
9.7%


56/44
20.2
139
18.1
125
10.4%









The difference in vapor pressure between the original composition and the composition remaining after 50 weight percent is removed is less then about 10 percent for compositions of the present invention. This indicates that the compositions of the present invention would be azeotropic or near-azeotropic.
Example 2
Refrigeration Performance Data
Table 10 shows the performance of various refrigerant compositions of the present invention as compared to HFC-134a. In Table 10, 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
10.0° F.
(5.5° C.)



Return gas temperature
60.0° F.
(15.6° C.)










Compressor efficiency is
100%










Note that the superheat is included in cooling capacity.

















TABLE 10






Evap
Evap
Cond
Cond
Comp
Comp





Composition
Pres
Pres
Pres
Pres
Disch T
Disch T
Cap
Cap


(wt %)
(Psia)
(kPa)
(Psia)
(kPa)
(F.)
(C.)
(Btu/min)
(kW)
COP
























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


HFC-1225ye/HFC-32
46.5
321
197
1358
151
66.1
200
3.50
4.53


(95/5)


HFC-1225ye/HFC-32 (96/4)
44.2
305
189
1303
150
65.6
191
3.35
4.51


HFC-1225ye/HFC-32
43.1
297
184
1269
149
65.0
186
3.26
4.50


(97/3)


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-1225ye/HFC-134a
39.5
272
172
1186
147
63.9
169
2.96
4.40


(90/10)


HFC-1225ye/CO2
43.2
298
179
1234
146
63.3
177
3.10
4.63


(99/1)


HFC-1225ye/HFC-134a/HFC-32
44.5
307
190
1310
150
65.6
191
3.35
4.49


(88/9/3)


HFC-1225ye/HFC-134a/HFC-32
45.5
314
194
1338
151
66.1
195
3.42
4.49


(88/8/4)


HFC-1225ye/HFC-134a/HFC-
41.0
283
178
1227
153
67.2
178
3.12
4.44


152a


(76/9/15)


HFC-1225ye/HFC-134a/HFC-
42.0
290
181
1248
150
65.6
179
3.13
4.42


161


(86/10/4)


HFC-1225ye/HFC-134a/propane
47.0
324
195
1345
148
64.4
197
3.45
4.49


(87/10/3)


HFC-1225ye/HFC-134a/i-butane
41.7
288
178
1227
146
63.3
175
3.06
4.39


(87/10/3)


HFC-1225ye/HFC-134a/DME
38.7
267
169
1165
149
65.0
168
2.94
4.44


(87/10/3)


HFC-1225ye/HFC-134a/CO2
42.4
292
180
1241
147
63.9
182
3.18
4.51


(88.5/11/.5)


HFC-1225ye/HFC-134/HFC-32
43.0
296
185
1276
150
65.6
187
3.27
4.51


(88/9/3)


HFC-1225ye/HFC-152a/HFC-32
46.7
322
198
1365
155
68.3
203
3.55
4.53


(85/10/5)


HFC-1225ye/HFC-152a/HFC-32
45.5
314
193
1331
155
68.3
198
3.47
4.52


(81/15/4)


HFC-1225ye/HFC-152a/HFC-32
44.1
304
188
1296
155
68.3
192
3.36
4.50


(82/15/3)


HFC-1225ye/HFC-152a/propane
44.4
306
185
1276
151
66.1
190
3.33
4.52


(85/13/2)


HFC-1225ye/HFC-152a/i-butane
40.9
282
176
1214
150
65.6
175
3.06
4.44


(85/13/2)


HFC-1225ye/HFC-152a/DME
39.0
269
170
1172
152
66.7
171
3.00
4.46


(85/13/2)


HFC-1225ye/HFC-152a/CO2
44.8
309
185
1276
151
66.1
195
3.42
4.64


(84/15/1)


HFC-1225ye/HFC-152a/CO2
42.3
292
179
1234
151
66.1
184
3.22
4.55


(84/15.5/0.5)


HFC-1225ye/HFC-152a/CF3I
42.0
290
180
1241
155
68.3
181
3.17
4.46


(70/20/10)


HFC-1234yf/HFC-32
58.6
404
230
1586
149
65.0
228
4.00
4.36


(95/5)


HFC-1234yf/HFC-134a
52.7
363
210
1448
145
62.8
206
3.61
4.33


(90/10)


HFC-1234yf/HFC-152a
53.5
369
213
1468
150
65.6
213
3.73
4.38


(80/20)


trans-HFC-1234ze/HFC-32
42.6
294
183
1262
153
67.2
186
3.26
4.51


(95/5)


trans-HFC-1234ze/HFC-32/CF3I
43.5
300
182
1255
154
67.8
184
3.22
4.46


(70/2/28)


trans-HFC-1234ze/HFC-134a
38.1
263
166
1145
149
65.0
165
2.89
4.44


(90/10)


trans-HFC-1234ze/HFC-152a
41.0
284
176
1214
154
67.8
177
3.10
4.48


(80/20)


trans-HFC-1234ze/HFC-125
38.6
266
167
1151
148
64.4
167
2.92
4.45


(96/4)


HFC-1225ye/HFC-1234yf
46.0
317
190
1310
145
62.8
186
3.26
4.35


(51/49)


HFC-1225ye/HFC-1234yf
44.0
303
187
1289
146
63.3
179
3.13
4.30


(60/40)


HFC-1225ye/HFC-1234yf/HFC-
43.0
296
183
1261
147
63.9
179
3.13
4.38


134a (70/20/10)


HFC-1225ye/HFC-1234yf/HFC-
50.7
350
205
1412
145
62.8
200
3.50
4.34


134a (20/70/10)


HFC-1225ye/HFC-1234yf/HFC-
53.0
365
212
1464
146
63.3
210
3.68
4.37


32 (25/73/2)


HFC-1225ye/HFC-1234yf/HFC-
45.3
312
190
1312
148
64.4
189
3.31
4.43


32 (75/23/2)


HFC-1225ye/HFC-1234yf/HFC-
47.6
328
200
1379
151
66.1
203
3.56
4.50


32 (85/10/5)


HFC-1225ye/HFC-1234yf/HFC-
46.7
322
197
1358
151
66.1
200
3.50
4.51


32 (90/5/5)


HFC-1225ye/HFC-1234yf/HFC-
42.8
295
181
1250
147
63.9
179
3.13
4.40


152a (70/25/5)


HFC-1225ye/HFC-1234yf/HFC-
49.9
344
202
1392
146
63.3
199
3.49
4.35


152a (25/70/5)


HFC-1225ye/HFC-1234yf/HFC-
51.6
356
207
1429
145
62.8
202
3.54
4.33


125 (25/71/4)


HFC-1225ye/HFC-1234yf/HFC-
43.4
299
184
1268
146
63.3
180
3.15
4.38


125 (75/21/4)


HFC-1225ye/HFC-1234yf/HFC-
42.4
292
180
1241
145
62.8
176
3.08
4.39


125 (75/24/1)


HFC-1225ye/HFC-1234yf/HFC-
50.2
346
202
1395
144
62.2
198
3.47
4.33


125 (25/74/1)


HFC-1225ye/HFC-1234yf
49.8
343
201
1383
144
62.2
196
3.43
4.34


(25/75)


HFC-1225ye/HFC-1234yf/CF3I
47.9
330
195.0
1344
147.5
64.2
192
3.36
4.34


(40/40/20)


HFC-1225ye/HFC-1234yf/CF3I
47.0
324
192.9
1330
146
63.3
189
3.31
4.35


(45/45/10)


HFC-1225ye/HFC-1234yf/HFC-
49.5
341
202.5
1396
146.9
63.8
201
3.52
4.4


32


(49/49/2)


HFC-1225ye/HFC-134a/HFC-
42.5
293
183
1260
154
67.8
184.3
3.23
4.47


152a/HFC-32 (74/8/17/1)


HFC-1225ye/HFC-134a/HFC-32
47.5
328
201
1386
152
66.7
204
3.57
4.49


(87/8/5)


HFC-1225ye/HFC-1234yf/HFC-
48.1
332
198
1365
145
62.8
193
3.38
4.35


125 (48/48/4)


HFC-1225ye/HFC-1234yf/HFC-
50.5
348
205
1413
148
64.4
204
3.57
4.39


32/CF3I (45/44/2/9)


HFC-1225ye/HFC-1234yf/HFC-
50.1
345
204
1407
148
64.4
202
3.54
4.39


32/CF3I (47/46/2/5)


HFC-1225ye/HFC-32/HFC-125
43.2
298
192
1324
151
66.1
181
3.17
4.28


(94/2/4)


HFC-1234yf/HFC-32/CF3I
58.2
401
224
1544
152
66.7
225
3.94
4.37


(60/2/38)


HFC-1234yf/HFC-32/CF3I
56.2
387
217
1496
151
66.1
217
3.80
4.35


(60/1/39))


HFC-1234yf/CF3I (60/40)
54.1
373
210
1448
149
65.0
209
3.66
4.34


comparative?


HFC-1234yf/HFC-125/CF3I
56.8
392
220
1517
147
63.9
217
3.80
4.31


(70/4/26)


HFC-1234yf/HFC-125/CF3I
56.4
389
219
1510
146
63.3
215
3.77
4.32


(80/4/16)


HFC-1234yf/HFC-125 (96/4)
55.1
380
217
1496
144
62.2
212
3.71
4.31


HFC-1234yf/HFC-134a/CF3I
54.7
377
215
1482
148
64.4
211
3.70
4.32


(70/10/20)


HFC-1234yf/HFC-152a/CF3I
55.1
380
214
1475
154
67.8
216
3.78
4.36


(50/10/40)









Several compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower discharge pressures and temperatures. Capacity for the compositions listed in Table 10 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, HFC-134a, CO2 or HFC-1234yf. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricants.
Example 3
Refrigeration Performance Data
Table 11 shows the performance of various refrigerant compositions of the present invention as compared to R404A and R422A. In Table 11, 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.















TABLE 11








Evap
Cond P
Compr






Press
Press
Disch T
CAP



wt %
(kPa))
(kPa)
(C.)
(kJ/m3)
EER






















Existing Refrigerant








Product


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


HFC-125/HFC-
85.1/11.5/3.4
330
2137
93.3
1699
4.50


1225ye/isobutane


HFC-125/trans-HFC-
86.1/11.5/2.4
319
2096
94.4
1669
4.52


1234ze/isobutane


HFC-125/HFC-
87.1/11.5/1.4
343
2186
93.3
1758
4.52


1234yf/isobutane


HFC-125/HFC-
85.1/11.5/3.4
322
2106
93.5
1674
4.52


1225ye/n-butane


HFC-125/trans-HFC-
86.1/11.5/2.4
314
2083
94.8
1653
4.53


1234ze/n-butane


HFC-125/HFC-
87.1/11.5/1.4
340
2173
93.4
1748
4.53


1234yf/n-butane


HFC-32/HFC-
10/10/′80
173
1435
107
1159
4.97


125/HFC-1225ye


HFC-32/HFC-
25/25/50
276
2041
120
1689
4.73


125/HFC-1225ye


HFC-32/HFC-
25/40/35
314
2217
119
1840
4.66


125/HFC-1225ye


HFC-32/HFC-
30/10/60
265
1990
125
1664
4.78


125/HFC-1225ye


HFC-32/HFC-
30/15/55
276
2046
125
1710
4.76


125/HFC-1225ye


HFC-32/HFC-
30/20/50
287
2102
124
1757
4.73


125/HFC-1225ye


HFC-32/HFC-
30/30/40
311
2218
124
1855
4.68


125/HFC-1225ye


HFC-32/HFC-
30/35/35
324
2271
123
1906
4.66


125/HFC-1225ye


HFC-32/HFC-
35/15/50
296
2157
129
1820
4.72


125/HFC-1225ye


HFC-32/HFC-
35/20/45
308
2212
129
1868
4.70


125/HFC-1225ye


HFC-32/HFC-
35/30/35
332
2321
127
1968
4.66


125/HFC-1225ye


HFC-32/HFC-
35/40/25
357
2424
126
2068
4.64


125/HFC-1225ye


HFC-32/HFC-
50/30/20
390
2584
138
2277
4.54


125/HFC-1225ye


HFC-32/HFC-
40/30/30
353
2418
131
2077
4.66


125/HFC-1225ye


HFC-32/HFC-
40/35/25
364
2465
131
2124
4.64


125/HFC-1225ye


HFC-32/HFC-
45/30/25
372
2505
135
2180
4.66


125/HFC-1225ye


HFC-32/HFC-
10/20/10/60
190
1517
110
1255
4.97


125/HFC-152a/HFC-


1225ye


HFC-32/HFC-
15/25/10/50
221
1709
115
1422
4.90


125/HFC-152a/HFC-


1225ye


HFC-32/HFC-
20/20/15/45
229
1755
121
1485
4.90


125/HFC-152a/HFC-


1225ye


HFC-32/CF3I/HFC-
30/20/50
272
1984
130
1706
4.80


1225ye


HFC-32/CF3I/HFC-
40/10/50
299
2159
137
1860
4.73


1225ye


HFC-32/CF3I/HFC-
30/30/40
286
2030
133
1774
4.80


1225ye


HFC-32/CF3I/HFC-
30/60/10
314
2120
144
1911
4.75


1225ye


HFC-32/CF3I/HFC-
40/20/40
315
2214
139
1936
4.73


1225ye


HFC-32/CF3I//HFC-
30/50/20
309
2101
139
1885
4.78


1225ye


HFC-32/CF3I/HFC-
40/40/20
346
2309
145
2079
4.71


1225ye


HFC-32/CF3I/HFC-
45/45/10
373
2432
152
2217
4.67


1225ye


HFC-32/CF3I/HFC-
45/10/45
319
2260
141
1964
4.71


1225ye


HFC-32/CF3I/HFC-
50/10/40
338
2353
145
2065
4.68


1225ye


HFC-32/CF3I/HFC-
50/20/30
356
2410
147
2150
4.68


1225ye


HFC-32/CF3I/HFC-
25/5/70
230
1781
122
1495
4.90


1225ye


HFC-32/CF3I/HFC-
60/30/10
409
2626
158
2434
4.66


1225ye


HFC-32/CF3I/HFC-
50/25/25
364
2437
149
2192
4.68


1225ye


HFC-32/CF3I/HFC-
50/20/30
356
2410
147
2156
4.68


1225ye


HFC-32/CF3I/HFC-
25/50/25
284
1964
134
1754
4.85


1225ye


HFC-32/CF3I/HFC-
45/30/25
353
2368
146
2124
4.71


1225ye


HFC-32/CF3I/HFC-
5/50/45
199
1377
107
1254
5.11


1234yf


HFC-32/CF3I/HFC-
5/30/65
197
1382
103
1241
5.11


1234yf


HFC-32/CF3I/HFC-
10/25/65
220
1542
107
1374
5.04


1234yf


HFC-32/CF3I/HFC-
20/10/70
255
1786
114
1577
4.95


1234yf


HFC-32/CF3I/HFC-
30/10/60
295
2020
123
1795
4.88


1234yf


HFC-32/CF3I/HFC-
30/20/50
305
2057
125
1843
4.85


1234yf


HFC-32/CF3I/HFC-
30/30/40
314
2091
128
1887
4.85


1234yf


HFC-32/CF3I/HFC-
20/40/40
275
1861
121
1679
4.92


1234yf


HFC-32/CF3I/HFC-
10/40/50
225
1558
111
1404
5.04


1234yf


HFC-32/CF3I/HFC-
50/20/30
378
2447
143
2238
4.73


1234yf


HFC-32/CF3I/HFC-
40/30/30
354
2305
137
2099
4.76


1234yf


HFC-32/CF3I/HFC-
40/40/20
360
2336
142
2136
4.74


1234yf


HFC-32/CF3I/HFC-
35/35/30
338
2217
135
2015
4.78


1234yf


HFC-32/CF3I/HFC-
35/30/35
334
2202
133
1996
4.80


1234yf


HFC-32/CF3I/HFC-
50/25/25
384
2468
145
2267
4.72


1234yf


HFC-32/CF3I/HFC-
40/20/20/20
331
2246
136
1999
4.76


1225ye/HFC-1234yf


HFC-32/CF3I/HFC-
30/20/25/25
290
2029
127
1782
4.83


1225ye/HFC-1234yf


HFC-32/CF3I/HFC-
30/10/30/30
279
1987
125
1728
4.83


1225ye/HFC-1234yf


HFC-32/HFC-
25/25/25/25
297
2089
118
1772
4.76


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
20/30/25/25
286
2025
113
1702
4.64


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
20/30/30/20
290
2033
113
1717
4.76


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
20/30/40/10
297
2048
112
1746
4.78


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/30/20/20
328
2251
122
1925
4.71


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/30/1/39
312
2217
123
1858
4.68


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/30/39/1
342
2275
120
1979
4.73


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/30/10/30
320
2235
123
1891
4.68


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
35/30/5/30
337
2330
127
1986
4.66


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
20/15/10/55
240
1818
115
1513
4.85


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/15/10/45
284
2066
124
1743
4.76


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
40/30/15/15
341
2364
132
2022
4.66


125/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/25/5/35/5
335
2240
121
1954
4.76


125/CF3I/HFC-


1234yf/HFC-1225ye


HFC-32/HFC-
30/25/5/40
338
2245
121
1966
4.76


125/CF3I/HFC-1234yf


HFC-32/HFC-
25/35/35/5
323
2195
115
1837
4.64


125/HFC-


1225ye/isobutane


HFC-32/HFC-
25/38/35/2
318
2214
117
1837
4.64


125/HFC-


1225ye/isobutane


HFC-32/HFC-
25/38/35/2
330
2297
118
1892
4.59


125/HFC-


1225ye/propane


HFC-32/CF3I/HFC-
50/20/25/5
321
2252
150
2010
4.76


1225ye/DME


HFC-32/HFC-
35/30/30/5
293
2135
131
1823
4.76


125/HFC-


1225ye/DME


HFC-32/HFC-
35/33/30/2
320
2268
129
1925
4.68


125/HFC-


1225ye/DME


HFC-32/HFC-
35/35/28/2
324
2288
129
1943
4.68


125/HFC-


1225ye/DME


HFC-32/HFC-
25/50/25
365
2376
115
2040
4.66


125/HFC-1234yf


HFC-32/HFC-
30/30/40
343
2276
120
1982
4.73


125/HFC-1234yf


HFC-32/HFC-
20/30/50
303
2059
112
1770
4.78


125/HFC-1234yf


HFC-32/HFC-
25/25/10/40
323
2154
118
1884
4.78


125/CF3I/HFC-1234yf


HFC-32/HFC-
25/25/10/40
291
2088
121
1757
4.73


125/CF3I/HFC-


1225ye


HFC-32/HFC-
20/30/10/40
279
2017
117
1680
4.73


125/CF3I/HFC-


1225ye


HFC-32/HFC-
20/35/5/40
285
2056
116
1699
4.71


125/CF3I/HFC-


1225ye


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-
40/50/10
299
2159
137
1860
4.74


1225ye/CF3I


HFC-32/HFC-
50/40/10
337
2353
145
2065
4.69


1225ye/CF3I


HFC-32/HFC-
30/20/50
242
1854
128
1578
4.88


134a/HFC-1225ye


FC-32/HFC-
40/10/50
281
2078
135
1783
4.78


134a/HFC-1225ye


FC-32/HFC-
40/20/40
277
2053
136
1775
4.81


134a/HFC-1225ye


FC-32/HFC-
40/30/30
274
2029
137
1762
4.85


134a/HFC-1225ye


FC-32/HFC-
40/40/20
269
2004
138
1747
4.86


134a/HFC-1225ye


FC-32/HFC-
50/30/20
302
2189
145
1929
4.79


134a/HFC-1225ye


HFC-32/HFC-
40/30/20/10
287
2081
139
1828
4.88


134a/HFC-


1225ye/CF3I


HFC-32/HFC-
40/30/15/15
294
2106
140
1862
4.81


134a/HFC-


1225ye/CF3I


HFC-32/HFC-
30/30/30/10
254
1891
130
1637
4.88


134a/HFC-


1225ye/CF3I


HFC-32/HFC-
30/10/30/15/15
280
2016
131
1756
4.83


125/HFC-134a/HFC-


1225ye/CF3I


HFC-32/HFC-
30/10/20/20/20
291
2064
131
1802
4.81


125/HFC-134a/HFC-


1225ye/CF3I


HFC-32/HFC-
30/30/20/20
253
1877
127
1628
4.91


134a/HFC-


1225ye/HFC-1234yf


HFC-32/HFC-
30/30/10/30
259
1892
126
1651
4.90


134a/HFC-


1225ye/HFC-1234yf


HFC-32/HFC-
35/25/5/35
280
2003
129
1762
4.87


134a/HFC-


1225ye/HFC-1234yf


HFC-32/HFC-
35/20/10/30/5
286
2032
130
1790
4.85


134a/HFC-


1225ye/HFC-


1234yf/CF3I


HFC-32/HFC-
35/20/35/10
296
2063
130
1834
4.85


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
35/10/45/10
306
2095
128
1868
4.84


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
25/15/50/10
267
1878
121
1660
4.91


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
30/30/30/10
272
1939
128
1712
4.88


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
30/20/40/10
280
1968
126
1744
4.88


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
30/20/30/20
289
2003
129
1787
4.87


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
30/20/20/30
297
2035
132
1831
4.87


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
25/20/25/30
279
1928
127
1729
4.89


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
40/20/20/20
320
2188
138
1967
4.81


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
50/10/20/20
362
2396
145
2183
4.74


134a/HFC-


1234yf/CF3I


HFC-32/HFC-
50/10/30/10
351
2354
141
2127
4.76


134a/HFC-


1234yf/CF3I


HFC-32/NH3/HFC-
15/15/70
266
2004
152
1831
5.01


1225ye


HFC-32/NH3/HFC-
20/20/60
289
2141
165
2008
5.00


1225ye


HFC-32/NH3/HFC-
20/10/70
265
2002
144
1789
4.96


1225ye


HFC-32/NH3/HFC-
25/25/50
302
2229
178
2118
5.00


1225ye


HFC-32/NH3/HFC-
25/15/60
295
2171
158
2001
4.95


1225ye


HFC-32/NH3/HFC-
30/10/60
297
2182
151
1968
4.89


1225ye


HFC-32/NH3/HFC-
25/25/40/10
305
2246
182
2138
5.00


1225ye/CF3I


HFC-32/NH3/HFC-
20/20/50/10
296
2162
168
2048
5.00


1225ye/CF3I


HFC-32/NH3/HFC-
15/15/55/15
278
2041
156
1899
5.00


1225ye/CF3I


HFC-32/NH3/HFC-
20/10/55/15
280
2052
148
1868
4.95


1225ye/CF3I


HFC-32/NH3/HFC-
20/10/50/20
311
2125
143
2005
4.99


1234yf/CF3I


HFC-32/NH3/HFC-
10/10/20/60
280
1928
152
1857
5.05


1234yf/CF3I


HFC-1225ye/R717
95/5
159
1317
113
1121
5.16


HFC-1225ye/R717
90/10
194
1550
128
1368
5.14


HFC-1225ye/R717
85/15
217
1698
141
1535
5.11


HFC-1225ye/R717
80/20
243
1725
146
1750
5.43


HFC-125/HFC-
5/85/10
205
1613
127
1423
5.11


1225ye/R717


HFC-125/HFC-
10/80/10
212
1651
127
1455
5.09


1225ye/R717


HFC-125/HFC-
15/75/10
220
1687
127
1486
5.04


1225ye/R717


HFC-125/HFC-
20/70/10
227
1723
126
1516
5.02


1225ye/R717


HFC-125/HFC-
25/65/10
235
1757
126
1547
5.00


1225ye/R717


HFC-125/HFC-
20/65/15
248
1845
138
1674
5.04


1225ye/R717


HFC-125/HFC-
20/75/5
195
1525
112
1291
5.02


1225ye/R717


R32/HFC-125/HFC-
25/10/60/5
273
2029
135
1766
4.88


1225ye/R717


R32/HFC-125/HFC-
20/20/55/5
273
2011
130
1740
4.85


1225ye/R717


R32/HFC-125/HFC-
10/20/65/5
235
1787
121
1526
4.92


1225ye/R717


R32/HFC-125/HFC-
25/10/55/10
295
2148
146
1936
4.90


1225ye/R717


R32/HFC-125/HFC-
20/20/50/10
295
2125
142
1911
4.90


1225ye/R717


R32/HFC-125/HFC-
10/20/60/10
262
1938
134
1722
4.95


1225ye/R717


R32/HFC-125/HFC-
10/10/65/15
265
1974
147
1804
5.02


1225ye/R717


R32/HFC-125/HFC-
10/20/55/15
278
2028
146
1859
5.00


1225ye/R717


R32/HFC-125/HFC-
5/25/55/15
270
1967
141
1798
5.00


1225ye/R717


R32/HFC-125/HFC-
10/20/60/10
295
2025
129
1865
5.00


1234yf/R717


R32/HFC-125/HFC-
5/25/60/10
285
1958
125
1797
5.00


1234yf/R717









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 11 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. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricants.
Example 4
Refrigeration Performance Data
Table 12 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22, R410A, R407C, and R417A. In Table 12, 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.



Return gas temperature
15.6° C.



Compressor efficiency is
100%










Note that the superheat is included in cooling capacity.















TABLE 12








Evap
Cond
Compr






Press
Press
Disch T
CAP



wt %
(kPa))
(kPa)
(C.)
(kJ/m3)
EER






















Existing Refrigerant Product








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


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


HFC-32/HFC-125/trans-HFC-
30/50/20
749
2865
81.7
3975
13.10


1234ze


HFC-32/HFC-125/trans-HFC-
23/25/52
546
2252
78.9
3222
13.80


1234ze


HFC-32/HFC-125/HFC-1234yf
40/50/10
868
3185
84.4
4496
13.06


HFC-32/HFC-125/HFC-1234yf
23/25/52
656
2517
76.7
3587
13.62


HFC-32/HFC-125/HFC-1234yf
15/45/40
669
2537
73.3
3494
13.28


HFC-32/HFC-125/HFC-1234yf
10/60/30
689
2586
71.3
3447
12.96


HFC-125/HFC-1225ye/n-butane
65/32/3
563
2213
66.1
2701
12.87


HFC-125/trans-HFC-1234ze/n-
66/32/2
532
2130
67.2
2794
13.08


butane


HFC-125/HFC-1234yf/n-butane
67/32/1
623
2344
66.1
3043
12.85


HFC-125/HFC-1225ye/isobutane
65/32/3
574
2244
66.2
2874
12.79


HFC-125/trans-HFC-
66/32/2
538
2146
67.4
2808
13.04


1234ze/isobutane


HFC-125/HFC-1234yf/isobutane
67/32/1
626
2352
66.3
3051
12.83









Compositions have energy efficiency (EER) comparable to R22, R407C, R417A, and R410A while maintaining low discharge temperatures. Capacity for the compositions listed in Table 12 is also similar to R22, R407C and R417A indicating these compositions could be replacement refrigerants for R22, R407C or R417A in refrigeration and air-conditioning. Those compositions containing hydrocarbon may also improve oil solubility with conventional mineral oil and alkyl benzene lubricant.
Example 5
Refrigeration Performance Data
Table 13 shows the performance of various refrigerant compositions of the present invention as compared to HCFC-22 and R410A. In Table 13, 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° 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 13







Evap
Cond
Compr Disch





Press
Press
Temp
CAP



(kPa)
(kPa)
(C.)
(kJ/m3)
EER





















Existing refrigerant product







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/CF3I (40/30/20)
711
2104
90.6
4605
9.56


HFC-32/HFC-1225ye/CF3I (45/30/25)
737
2176
92.2
4765
9.45


HFC-32/HFC-1225ye/CF3I (45/35/20)
724
2151
91.4
4702
9.45


HFC-32/HFC-134a/HFC-1225ye
607
1880
87.8
4171
9.69


(40/30/30)


HFC-32/HFC-134a/HFC-1225ye
637
1958
89.9
4347
9.66


(45/30/25)


HFC-32/HFC-134a/HFC-1225ye
631
1944
90.2
4326
9.69


(45/35/20)


HFC-32/HFC-134a/HFC-1234yf/CF3I
611
1845
89.6
4107
9.66


(30/20/5/45)


HFC-32/HFC-134a/HFC-1234yf/CF3I
575
1745
86.5
3891
9.76


(25/20/10/45)


HFC-32/HFC-134a/HFC-1234yf/CF3I
646
1939
91.2
4308
9.62


(35/10/5/40)


HFC-32/HFC-134a/HFC-1225ye/HFC-
587
1822
84
4001
9.69


1234yf (34/12/47/7)


HFC-32/HFC-134a/HFC-1225ye/HFC-
561
1752
81.9
3841
9.73


1234yf (30/8/52/10)


HFC-32/HFC-134a/HFC-1225ye/HFC-
597
1852
84.3
4051
9.66


1234yf (35/6/52/7)


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 (55/45)
734
2206
93.0
4825
9.45


HFC-32/HFC-1225ye (60/40)
764
2280
94.9
5001
9.42


HFC-32/HFC-1225ye/CF3I (65/30/5)
808
2376
97.5
5237
9.42


HFC-32/HFC-1225ye/CF3I (65/17.5/17.5)
845
2445
99.4
5408
9.39


HFC-32/HFC-1225ye/CF3I (65/5/30)
879
2508
101.7
5565
9.49


HFC-32/HFC-1225ye/CF3I(60/30/10)
795
2337
96.3
5140
9.42


HFC-32/HFC-1225ye/CF3I (60/20/20)
857
2319
92.5
5565
10.27


HFC-32/HFC-1225ye/CF3I (60/10/30)
852
2442
99.5
5404
9.39


HFC-32/HFC-1225ye/CF3I (55/40/5)
749
2235
93.6
4894
9.42


HFC-32/HFC-1225ye/CF3I (55/25/20)
793
2319
95.7
5098
9.42


HFC-32/HFC-1225ye/CF3I (55/20/25)
808
2345
96.5
5163
9.42


HFC-32/HFC-1225ye/CF3I (55/5/40)
844
2413
99.4
5332
9.39


HFC-32/HFC-1225ye/CF3I (50/45/5)
819
2350
98.3
5176
9.39


HFC-32/HFC-1225ye/CF3I (50/25/25)
774
2264
94.4
4970
9.42


HFC-32/HFC-1225ye/CF3I (50/5/45)
716
2156
91.6
4706
9.45


HFC-32/HFC-1225ye/CF3I (45/50/5)
680
2069
89.5
4509
9.49


HFC-32/HFC-1225ye/CF3I (45/30/25)
737
2176
92.2
4765
9.45


HFC-32/HFC-1225ye/CF3I (45/35/20)
724
2151
91.4
4702
9.45


HFC-32/HFC-1225ye/CF3I (45/25/30)
750
2200
93.0
4825
9.45


HFC-32/HFC-1225ye/CF3I (45/5/50)
789
2276
97.3
4996
9.39


HFC-32/HFC-1225ye/CF3I (40/50/10)
657
2003
87.9
4365
9.52


HFC-32/HFC-1225ye/CF3I (40/30/30)
711
2104
90.6
4605
9.56


HFC-32/HFC-1225ye/CF3I (40/10/50)
749
2178
94.7
4775
9.42


HFC-32/HFC-1234yf/CF3I (60/30/10)
823
2372
93.9
5228
9.45


HFC-32/HFC-1234yf/CF3I (60/20/20)
844
2415
96.0
5335
9.45


HFC-32/HFC-1234yf/CF3I (60/10/30)
862
2459
98.5
5433
9.49


HFC-32/HFC-1234yf/CF3I (55/35/10)
798
2305
91.7
5069
9.49


HFC-32/HFC-1234yf/CF3I (55/5/40)
850
2419
98.9
5347
9.39


HFC-32/HFC-1234yf/CF3I (50/40/10)
769
2232
89.4
4899
9.52


HFC-32/HFC-1234yf/CF3I (50/30/20)
790
2275
91.3
5002
9.49


HFC-32/HFC-1234yf/CF3I (50/20/30)
808
2313
93.4
5095
9.45


HFC-32/HFC-1234yf/CF3I (50/10/40)
821
2345
96.2
5168
9.42


HFC-32/HFC-1234yf/CF3I (50/5/45)
825
2357
97.8
5192
9.39


HFC-32/HFC-1234yf/CF3I (45/10/45)
792
2274
95.0
4999
9.42


HFC-32/HFC-1234yf/CF3I (45/5/50)
794
2283
96.8
5011
9.39


HFC-32/HFC-1234yf/CF3I (40/50/10)
705
2067
85.0
4523
9.59


HFC-32/HFC-1234yf/CF3I (40/40/20)
725
2108
86.5
4622
9.56


HFC-32/HFC-1234yf/CF3I (40/10/50)
759
2192
93.8
4806
9.42


HFC-32/HFC-1234yf/CF3I (40/5/55)
759
2197
95.7
4808
9.39


HFC-32/HFC-134a/HFC-1225ye
713
2156
96.2
4807
9.56


(60/30/10)


HFC-32/HFC-134a/HFC-1225ye
730
2196
95.8
4875
9.52


(60/20/20)


HFC-32/HFC-134a/HFC-1225ye
747
2237
95.3
4941
9.49


(60/10/30)


HFC-32/HFC-134a/HFC-1225ye
727
2187
93.1
4802
9.49


(55/5/40)


HFC-32/HFC-134a/HFC-1225ye
704
2131
93.7
4723
9.56


(55/20/25)


HFC-32/HFC-134a/HFC-1225ye
674
2060
94.7
4605
9.62


(55/40/5)


HFC-32/HFC-134a/HFC-1225ye
695
2110
91.1
4623
9.49


(50/5/45)


HFC-32/HFC-134a/HFC-1225ye
671
2045
91.9
4536
9.62


(50/25/25)


HFC-32/HFC-134a/HFC-1225ye
645
1982
92.8
4433
9.69


(50/45/5)


HFC-32/HFC-134a/HFC-1225ye
662
2027
89.0
4433
9.52


(45/5/50)


HFC-32/HFC-134a/HFC-1225ye
642
1971
89.7
4367
9.66


(45/25/30)


HFC-32/HFC-134a/HFC-1225ye
637
1958
89.9
4347
9.66


(45/30/25)


HFC-32/HFC-134a/HFC-1225ye
631
1944
90.2
4326
9.69


(45/35/20)


HFC-32/HFC-134a/HFC-1225ye
615
1903
90.9
4259
9.73


(45/50/5)


HFC-32/HFC-134a/HFC-1225ye
623
1926
87.0
4224
9.62


(40/10/50)


HFC-32/HFC-134a/HFC-1225ye
607
1880
87.8
4171
9.69


(40/30/30)


HFC-32/HFC-134a/HFC-1225ye
589
1833
88.7
4101
9.76


(40/50/10)


HFC-32/HFC-125/HFC-1225ye (60/5/35)
784
2323
94.6
5087
9.42


HFC-32/HFC-125/HFC-1225ye
803
2365
94.2
5173
9.42


(60/10/30)


HFC-32/HFC-125/HFC-1225ye
822
2407
93.9
5256
9.39


(60/15/25)


HFC-32/HFC-125/HFC-1225ye
742
2220
90.3
4820
9.42


(50/10/40)


HFC-32/HFC-125/HFC-1225ye (50/5/45)
721
2173
90.7
4730
9.45


HFC-32/HFC-125/HFC-1225ye
762
2266
90.0
4911
9.42


(50/15/35)


HFC-32/HFC-125/HFC-1225ye
692
2097
85.9
4518
9.45


(40/15/45)


HFC-32/HFC-125/HFC-1225ye
671
2047
86.2
4425
9.49


(40/10/50)


HFC-32/HFC-125/HFC-1225ye
654
2001
83.8
4304
9.49


(35/15/50)


HFC-32/HFC-134a/HFC-1234yf/CF3I
611
1845
89.6
4107
9.66


(30/20/5/45)


HFC-32/HFC-134a/HFC-1234yf/CF3I
575
1745
86.5
3891
9.76


(25/20/10/45)


HFC-32/HFC-134a/HFC-1234yf/CF3I
646
1939
91.2
4308
9.62


(35/10/5/40)


HFC-32/HFC-134a/HFC-1225ye/HFC-
587
1822
84.0
4001
9.69


1234yf (34/12/47/7)


HFC-32/HFC-134a/HFC-1225ye/HFC-
561
1752
81.9
3841
9.73


1234yf (30/8/52/10)


HFC-32/HFC-134a/HFC-1225ye/HFC-
597
1852
84.3
4051
9.66


1234yf (35/6/52/7)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
862
2470
98.9
5470
9.42


(65/5/10/20)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
818
2389
96.7
5270
9.42


(65/20/10/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
857
2465
99.3
5456
9.39


(65/10/5/20)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
828
2401
95.9
5298
9.45


(65/10/20/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
785
2316
95.2
5090
9.42


(60/30/5/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
809
2345
93.3
5163
9.45


(60/5/30/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
860
2448
99.0
5419
9.39


(60/5/5/30)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
835
2405
96.8
5309
9.42


(60/10/10/20)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
818
2358
95.6
5197
9.42


(55/10/10/25)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
839
2399
97.8
5298
9.42


(55/5/5/35)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
770
2263
92.1
4966
9.45


(55/20/20/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
783
2278
91.1
5005
9.49


(55/5/35/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
755
2243
93.2
4912
9.45


(55/35/5/5)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
816
2339
96.7
5153
9.42


(50/5/5/40)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
798
2303
94.3
5067
9.45


(50/10/10/20)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
752
2213
90.7
4848
9.49


(50/20/20/10)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
744
2161
91.6
4743
9.45


(40/10/10/40)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
728
2127
89.4
4663
9.52


(40/15/15/30)


HFC-32/HFC-1225ye/HFC-1234yf/CF3I
707
2087
87.7
4566
9.52


(40/20/20/20)


HFC-32/HFC-125/HFC-1225ye/CF3I
865
2481
97.0
5453
9.35


(60/10/10/20)


HFC-32/HFC-125/HFC-1225ye/CF3I
873
2488
99.1
5494
9.39


(60/5/5/30)


HFC-32/HFC-125/HFC-1225ye/CF3I
799
2352
95.2
5159
9.42


(60/5/30/5)


HFC-32/HFC-125/HFC-1225ye/CF3I
845
2437
97.4
5367
9.39


(60/5/15/20)


HFC-32/HFC-125/HFC-1225ye/CF3I
847
2414
95.2
5288
9.39


(50/10/5/35)


HFC-32/HFC-125/HFC-1225ye/CF3I
758
2250
90.9
4891
9.42


(50/10/35/5)


HFC-32/HFC-125/HFC-1225ye/CF3I
834
2384
96.7
5238
9.39


(50/5/5/40)


HFC-32/HFC-125/HFC-1225ye/CF3I
797
2315
93.9
5070
9.42


(50/5/20/25)


HFC-32/HFC-125/HFC-1225ye/CF3I
857
2440
93.9
5327
9.39


(50/15/5/30)


HFC-32/HFC-125/HFC-1225ye/CF3I
779
2297
90.5
4983
9.39


(50/15/30/5)


HFC-32/HFC-125/HFC-1234yf/CF3I
875
2494
96.1
5481
9.39


(60/10/10/20)


HFC-32/HFC-125/HFC-1234yf/CF3I
879
2494
98.6
5508
9.39


(60/5/5/30)


HFC-32/HFC-125/HFC-1234yf/CF3I
860
2455
96.0
5410
9.42


(60/5/15/20)


HFC-32/HFC-125/HFC-1234yf/CF3I
852
2421
94.7
5304
9.39


(50/10/5/35)


HFC-32/HFC-125/HFC-1234yf/CF3I
840
2391
96.2
5254
9.39


(50/5/5/40)


HFC-32/HFC-125/HFC-1234yf/CF3I
818
2340
92.3
5134
9.45


(50/5/20/25)


HFC-32/HFC-125/HFC-1234yf/CF3I
862
2447
93.4
5343
9.39


(50/15/5/30)


HFC-32/HFC-125/HFC-1225/HFC-
759
2232
89.8
4873
9.49


1234yf/CF3I (50/5/20/20/5)


HFC-32/HFC-125/HFC-1225/HFC-
829
2370
95.2
5206
9.42


1234yf/CF3I (50/5/5/5/35)


HFC-32/HFC-125/HFC-1225/HFC-
775
2272
89.8
4948
9.45


1234yf/CF3I (50/10/20/15/5)


HFC-32/HFC-125/HFC-1225/HFC-
839
2397
93.8
5248
9.39


1234yf/CF3I (50/10/5/5/30)


HFC1225ye/R717
445
1433
82.2
3306
10.17


HFC1225ye/R717
493
1569
89.0
3666
10.17


HFC1225ye/R717
525
1660
95.0
3921
10.17


HFC1225ye/R717
370
1217
74.1
2767
10.20


HFC-32/HFC-1225ye/R717
594
1855
95.0
4312
10.00


HFC-32/HFC-1225ye/R717
594
1855
91.2
4232
9.90


HFC-32/HFC-1225ye/R717
542
1718
84.7
3846
9.86


HFC-32/HFC-1225ye/R717 (10/85/5)
462
1494
79.9
3361
10.00


HFC-125/HFC-1225ye/R717 (5/80/15)
513
1622
88.7
3778
10.14


HFC-125/HFC-1225ye/R717 (10/75/15)
526
1652
88.4
3834
10.10


HFC-125/HFC-1225ye/R717
533
1666
88.3
3861
10.07


(12.5/72.5/15)


HFC-125/HFC-1225ye/R717 (15/70/15)
539
1680
88.1
3888
10.07


HFC-125/HFC-1225ye/R717 (20/75/5)
444
1411
77.8
3142
10.00


HFC-125/HFC-1225ye/R717 (10/85/5)
410
1327
74.0
2984
10.10


HFC-32/R125/HFC-1225ye/R717
573
1776
90.1
4104
10.03


(5/15/65/15)


HFC-32/R125/HFC-1225ye/R717
591
1822
92.9
4242
10.03


(5/17.5/60/17.5)


HFC-32/R125/HFC-1225ye/R717
604
1861
92.1
4299
9.97


(10/15/60/15)


HFC-32/R125/HFC-1225ye/R717
625
1926
90.5
4370
9.83


(20/10/60/10)


HFC-32/R125/HFC-1225ye/R717
616
1905
86.3
4224
9.73


(25/10/60/5)


HFC-32/R125/HFC-1225ye/R717
579
1806
84.1
4009
9.76


(20/10/65/5)


HFC-32/R125/HFC-1225ye/R717
596
1845
83.9
4079
9.73


(20/15/60/5)









Compositions have energy efficiency (EER) comparable to R22 and R410A while maintaining reasonable discharge temperatures. Capacity for certain compositions listed in Table 13 is also similar to R22 indicating these compositions could be replacement refrigerants for R22 in refrigeration and air-conditioning. Additionally, there are compositions listed in Table 13 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 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 HFC-1234yf, HFC-1225ye and mixtures of the present disclosure at 101 kPa (14.7 psia), 100° C. (212° F.), and 50 percent relative humidity, at various concentrations in air in order to determine the lower flammability limit (LFL) and upper flammability limit (UFL). The results are given in Table 13.











TABLE 14







Composition
LFL (vol % in air)
UFL (vol % in air)









HFC-1225ye
Non-flammable
Non-flammable



(100 wt %)



HFC-1234yf
5.0
14.5



(100 wt %)



HFC-
8.5
12.0



1234yf/1225ye



(50/50 wt %)



HFC-
Non-flammable
Non-flammable



1234yf/1225ye



(40/60 wt %)



HFC-
13.0 
17.0



1225ye/HFC-



32 (60/40 wt %)



HFC-
Non-flammable
Non-flammable



1225ye/HFC-



32 (65/35 wt %)










The results indicate that while HFC-1234yf is flammable, addition of HFC-1225ye reduces the flammability. Therefore, compositions comprising about 1 weight percent to about 49 weight percent HFC-1234yf and about 99 weight percent to about 51 weight percent HFC-1225ye are preferred. Results also show HFC-1225ye reduces the flammability of HFC-32 and results in a non-flammable composition at 65/35 wt % HFC-1225ye/HFC-32.

## Claims

1. An azeotropic or near-azeotropic composition comprising about 1 weight percent to about 99 weight percent HFC-1234yf and about 99 weight percent to about 1 weight percent HFC-134a.

2. The composition of claim 1, comprising from about 30 weight percent to about 99 weight percent HFC-1234yf and from about 70 weight percent to about 1 weight percent HFC-134a.

3. The composition of claim 1, further comprising at least one compound selected from the group consisting of propane, n-butane, isobutane, and dimethyl ether.

4. The composition of claim 3, wherein the azeotropic or near-azeotropic composition is selected from the group consisting of:
about 1 weight percent to about 80 weight percent of HFC-1234yf, about 1 weight percent to about 80 weight percent of HFC-134a, and about 19 weight percent to about 98 weight percent of propane;
about 1 weight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent of HFC-134a, and about 1 weight percent to about 30 weight percent n-butane;
about 1 weight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent HFC-134a, and about 1 weight percent to about 30 weight percent isobutane; and
about 1 eight percent to about 98 weight percent of HFC-1234yf, about 1 weight percent to about 98 weight percent of HFC-134a, and about 1 weight percent to about 40 weight percent of dimethyl ether.

5. The composition of claim 3, wherein the composition is an azeotropic composition selected from the group consisting of:
about 70.4 weight percent HFC-1234yf and about 29.6 weight percent HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about −25° C.;
about 24.5 weight percent HFC-1234yf, about 31.1 weight percent HFC-134a, and about 44.5 weight percent propane having a vapor pressure of about 34.01 psia (234 kPa) at a temperature of about −25° C.;
about 60.3 weight percent HFC-1234yf, about 35.2 weight percent HFC-134a, and about 4.5 weight percent n-butane having a vapor pressure of about 18.58 psia (128 kPa) at about −25° C.;
about 48.6 weight percent HFC-1234yf, about 37.2 weight percent HFC-134a, and about 14.3 weight percent isobutane having a vapor pressure of about 19.86 psia (137 kPa) at about −25° C.; and
about 24.0 weight percent HFC-1234yf, about 67.9 weight percent HFC-134a, and about 8.1 weight percent dimethyl ether having a vapor pressure of about 17.21 psia (110 kPa) at a temperature of about −25° C.

6. The composition of claim 1, further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oil, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins.

7. The composition of claim 6, further comprising a compatibilizer 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, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;
e) chlorocarbons represented by the formula RClx, 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]:




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, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

8. The composition of claim 7, further comprising a stabilizer or odor masking agent.

9. The composition of claim 8, wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones.

10. A method for improving oil-return to the compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using the composition of claim 7 in said apparatus.

11. The composition of claim 1, further comprising a tracer 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.

12. The composition of claim 11, further comprising a tracer selected from the group consisting of CD3CD3, CD3CD2CD3, CD2F2, CF3CD2CF3, CD2FCF3, CD3CF3, CDF2CF3, CF3CDFCF3, CF3CF2CDF2, CDF2CDF2, CF3CF2CD3, CF3CD2CH3, CF2CH2CD3, CF3CF3, cyclo-CF2CF2CF2—, CF3CF2CF3, cyclo-CF2CF2CF2CF2—, CF3CF2CF2CF3, CF3CF(CF3)2, cyclo-CF(CF3)CF2CF(CF3)CF2—, CF3OCHFCF3, CF3OCH2CF3, CF3OCH2CHF2, CF3CH2OCHF2CH3OCF2CF3, CH3CF2OCF3CF3CF2CF2OCHFCF3, 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, trans-perfluorodecalin, 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, n-butanal, methyl ethyl ketone, nitrous oxide, and combinations thereof.

13. The composition of claim 1, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.

14. The composition of claim 13, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, am ides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes.

15. The composition of claim 14, 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, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;
e) chlorocarbons represented by the formula RClx, 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]:




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, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

16. A method for detecting the composition of claim 13 in a compression refrigeration, air conditioning, or heat pump apparatus, said method comprising providing said composition including said ultra-violet fluorescent dye to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus.

17. A method of producing cooling, said method comprising: evaporating said composition of claim 1 in the vicinity of a body to be cooled and thereafter condensing said composition.

18. A method of producing heat, said method comprising: condensing said composition of claim 1 in the vicinity of a body to be heated and thereafter evaporating said composition.

19. A method of solubilizing a refrigerant or heat transfer fluid composition comprising the composition of claim 1 in a refrigeration lubricant selected from the group consisting of mineral oils, alkylbenzenes, synthetic paraffins, synthetic napthenes, and poly(alpha)olefins, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer 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, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;
e) chlorocarbons represented by the formula RClx, 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 and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins 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 of the type HOCH2CRR′(CH2)z(CHOH)xCH2(CH2OH)y, 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
i) lactones represented by structures [B], [C], and [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, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.

20. A method for replacing a high GWP refrigerant in a refrigeration, air-conditioning, or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502, and R404A, said method comprising providing the composition of claim 1 to said refrigeration, air-conditioning, or heat pump apparatus that uses, used or is designed to use said high GWP refrigerant.

21. A method of using the composition of claim 1 as a heat transfer fluid composition, said process comprising comprises transporting said composition from a heat source to a heat sink.

22. A method for making the composition of claim 1, 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.

23. A refrigeration, air-conditioning, or heat pump apparatus containing a composition as claimed in claim 1.

24. The apparatus of claim 23 comprising a stationary air-conditioning system.

25. The apparatus of claim 23 comprising a stationary heat pump system.

26. The apparatus of claim 23 comprising a stationary refrigeration system.

27. A method of forming a foam comprising:
a) adding to a foamable composition the composition of claim 1; and
b) reacting the foamable composition under conditions effective to form a foam.

28. A process for producing aerosol products comprising the step of adding the composition of claim 1 to active ingredients in an aerosol container, wherein said composition functions as a propellant.

29. A method of suppressing a flame comprising contacting the flame with a fluid comprising the composition of claim 1.

30. A method of extinguishing or suppressing a fire in a total-flood application comprising:
a) providing an agent comprising the composition of claim 1,
b) disposing the agent in a pressurized system; and
c) discharging the agent into an area to extinguish or suppress fires in that area.

31. A method of inerting an area to prevent a fire or explosion comprising:
a) providing an agent comprising the composition of claim 1;
b) disposing the agent in a pressurized discharge system; and
c) discharging the agent into the area to prevent a fire or explosion from occurring.

32. The composition of claim 1, wherein the composition is an azeotropic composition comprising about 70.4 weight percent HFC-1234yf and about 29.6 weight percent HFC-134a having a vapor pressure of about 18.4 psia (127 kPa) at a temperature of about −25° C.