Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE OF INVENTION
HALOKETONE REFRIGERANT COMPOSITIONS AND USES THEREOF
CROSS REFERENCES) TO RELATED APPLICATIONS)
This application claims the priority benefit of U.S. Provisional
Application 60/549,978, filed March 4, 2004, and U.S. Provisional
Application 60/575,037, filed May 26, 2004, and U.S. Provisional
Application 60/584,785, filed June 29, 2004.
BAC14GROUND OF THE INVENTION
1. Field of the Invention.
The present invention relates to compositions for use in
refrigeration and air conditioning systems comprising at least one
haloketone or combinations thereof. Further, the present invention relates
to compositions for use in refrigeration and air-conditioning systems
employing a centrifugal compressor comprising at least one haloketone or
combinations thereof. The compositions of the present invention are
useful in processes for producing refrigeration or heat or as heat transfer
fluids.
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
automobile air-conditioning market. Should the regulations be more
broadly applied in the future, an even greater need will be felt for
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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 C02 or ammonia. Many of these suggested
replacements are toxic, flammable, and/or have low energy efficiency.
Therefore, new alternatives are constantly being sought.
The object of the present invention is to provide novel
refrigerant compositions and heat transfer fluids 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 haloketone refrigerant or
heat transfer fluid selected from the group consisting of:
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;
1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone;
1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-
pentanone;
1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone;
1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone;
2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
CF3C(O)CBrFCF2CF3;
CF3C(O)CF2CF2CBrF2;
CBrF2C(O)CF(CF3)2;
CF3C(O)CBr(CF3)2;
CBrF2CF2C(O)CF2CF3;
CF3CBrFC(O)CFZCF3;
CF3CBrFC(O)CF2CF2CF3;
CF3CF2C(O)CBrFCF~CF3;
CF3CF2C(O)CF2CF2CBrF2;
CF3C(O)CBr(CF3)CF2CF3;
CF3C(O)CF(CF3)CBrFCF3;
CF3C(O)CBrFCF2CF2CF2CF3;
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CF3C(O)CF2CF~CF2CF~CBrF2;
CF3CBrFC(O)CF2CF2CF2CF3;
CF3CF2C(O)CBrFCF2CFZCF3;
CF3CF2C(O)CF~CF~CF2CBrF2;
CF3CF2CBrFC(O)CF2CF2CF3;
CBrF2CF2C(O)CF(CF3)CF2CF3;
CF3CBrFC(O)CF(CF3)CF2CF3;
CF3CF2C(O)CBr(CF3)CF2CF3;
CF3CF2C(O)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(O)CF(CF3)2;
CF3CF~CBrFC(O)CF(CF3)2;
CF3CF2CF~C(O)CBr(CF3)2;
(CF3)2CBrC(O)CF(CF3)2;
CF3CBrFCF2C(O)CF(CF3)z;
CHF2CF2C(O)CBr(CF3)2; .
(CF3)2CHC(O)CBr(CF3)2;
CHFZCF2C(O)CBrFCF3;
(CF3)2CHC(O)CBrFCF3;
(CF3)2CHC(O)CBrF~;
CBrF2CF2C(O)CH(CF3)2;
CBrF2C(O)CF(CF3)OCF3;
CBrF2CF2C(O)CF(CF3)OCF3;
CBrF2CF2CF2C(O)CF(CF3)OCF3;
CBrF2C(O)CF(CF3)OC2F5;
CBrF2CF2C(O)CF(CF3)OC~FS;
CBrF2C(O)CF(CF3)OCF2C2F5;
CBrF2CF2C(O)CF(CF3)OCF2C2F5;
CBrF2C(O)CF(CF3)OCF(CF3)2;
CBrF2CF2C(O)CF(CF3)OCF(CF3)2;
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CF3CBrFC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF3;
(CF3)2CBrC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
(CF3)2CBrC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF2C2F5;
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CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CBrF2C(O)CF(OCF2CH F2)CF3;
CBrF2C(O)CH(OCF2CHF2)CF3;
CBrF2C(O)CF(OCH3)CF3;
CBrF2C(O)CF(CF20CH3)CF3;
CCIF2CFBrC(O)CF2CF3;
CBrF2CFCIC(O)CF2CF3;
CCIF2CFBrC(O)CF(CF3)2;
CBrF2CFCIC(O)CF(CF3)2;
CCIF2CFBrC(O)CF(CF3)(C2F5);
CBrF2CFCIC(O)CF(CF3)(C2F5);
CCIF2C(O)CBr(CF3)2;
CCIF~CF2C(O)CBr(CF3)2;
CF3CCIFC(O)CBr(CF3)~;
CCIF2C(O)CBrFCF3;
CCIF~CF2(O)CCBrFCF3;
CF3CCIFC(O)CBrFCF3;
CBrF2C(O)CCI(CF3)2;
CBrF2CF2C(O)CCI(CF3)~;
CBrF~C(O)CCIFCF3;
CBrF2CF2C(O)CCIFCF3; and combinations thereof.
Disclosed herein also are the above listed compounds for
use in refrigeration or air conditioning systems employing a centrifugal
compressor, refrigeration or air conditioning systems employing a multi
stage centrifugal compressor, and/or employing a single slab/single pass
heat exchanger, or refrigeration or air conditioning systems employing a
2-stage centrifugal compressor.
Also disclosed herein are processes for producing refrigeration,
heat, and transfer of heat from a heat source to a heat sink using the
present inventive compositions.
DETAILED DESCRIPTION OF THE INVENTION
The haloketone refrigerant compositions of the present
invention comprise a single compound or a combination comprising more
than one haloketone compound.
Compositions of the present invention have no ozone depletion
potential and low global warming potential . For example, haloketones,
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alone or in mixtures will have global warming potentials lower than many
HFC refrigerants currently in use.
The haloketones of the present invention are compounds
containing fluorine, carbon, at least one ketone group oxygen, and
optionally hydrogen, chlorine or bromine. Haloketones may be
represented by the formula R3COR4, wherein R3 and R4 are independently
selected from straight or branched chain, saturated or unsaturated,
aliphatic or alicyclic fluorinated carbon radicals that may optionally contain
hydrogen, chlorine, or bromine. R3 and Rø may be joined to form a cyclic
haloketone ring. The haloketones may contain from about 2 to 10 carbon
atoms. Preferred haloketones contain 4 to 8 carbon atoms. The
haloketones of the present invention may further contain heteroatoms,
such as oxygen thus forming additional ketone groups, ether groups,
aldehyde groups, or ester groups. Representative haloketones are listed
in Table 1.
The bromofluoroketones of the present invention comprise at
least one selected from the group consisting of:
monobromoperfluoroketones, monohydromonobromoperfluoroketones,
(perfluoroalkoxy)monobromoperfluoroketones,
(fluoroalkoxy)monobromoperfluoroketones, and
monochloromonobromoperfluoroketones. The following compounds are
representative of the monobromoperfluoroketones,
monohydromonobromoperfluoroketones,
(perfluoroalkoxy)monobromoperfluoroketones,
(fluoroalkoxy)monobromoperfluoroketones, and
monochloromonobromoperfluoroketones of the present invention:
CF3C(O)CBrFCF2CF3, CF3C(O)CF2CF2CBrF2, CBrF2C(O)CF(CF3)2,
CF3C(O)CBr(CF3)2, CBrF2CF2C(O)CF2CF3, CF3CBrFC(O)CF2CF3,
CF3CBrFC(O)CF2CF2CF3, CF3CF2C(O)CBrFCF2CF3,
CF3CF2C(O)CF~CF2CBrF2, CF3C(O)CBr(CF3)CF2CF3,
CF3C(O)CF(CF3)CBrFCF3, CF3C(O)CBrFCF2CF2CF2CF3,
CF3C(O)CF2CFZCF2CF2CBrF2, CF3CBrFC(O)CF2CF2CF2CF3,
CF3CF2C(O)CBrFCF2CF2CF3, CF3CF2C(O)CF2CF2CF2CBrF2,
CF3CF2CBrFC(O)CF2CF2CF3, CBrF2CF2C(O)CF(CF3)CF2CF3,
CF3CBrFC(O)CF(CF3)CF2CF3, CF3CF2C(O)CBr(CF3)CF2CF3,
CF3CF2C(O)CF(CBrF2)CF2CF3, CBrF2CF2CF2C(O)CF(CF3)2,
CF3CF2CBrFC(O)CF(CF3)2, CF3CF2CF2C(O)CBr(CF3)2,
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(CF3)2CBrC(O)CF(CF3)2, CF3CBrFCF2C(O)CF(CF3)~,
CHF2CF~C(O)CBr(CF3)2, (CF3)2CHC(O)CBr(CF3)2,
CHF2CF2C(O)CBrFCF3, (CF3)2CHC(O)CBrFCF3, (CF3)2CHC(O)CBrF2,
CBrF~CF2C(O)CH(CF3)~, CBrF2C(O)CF(CF3)OCF3,
CBrF2CF2C(O)CF(CF3)OCF3, CBrF2CF2CF2C(O)CF(CF3)OCF3,
CBrF2C(O)CF(CF3)OC2F5, CBrF2CF2C(O)CF(CF3)OC2F5,
CBrF2C(O)CF(CF3)OCF2C2F5, CBrF2CF2C(O)CF(CF3)OCF2C2F5,
CBrF2C(O)CF(CF3)OCF(CF3)2, CBrF2CF~C(O)CF(CF3)OCF(CF3)2,
CF3CBrFC(O)CF(CF3)OCF(CF3)2, CF3CBrFC(O)CF(CF3)OCF3,
CF3CBrFC(O)CF(CF3)OC2F5, CF3CBrFC(O)CF(CF3)OCF3,
(CF3)2CBrC(O)CF(CF3)OCF3, CF3CBrFC(O)CF(CF3)OC~F5,
(CF3)2CBrC(O)CF(CF3)OC2F5, CF3CBrFC(O)CF(CF3)OCF2C2F5,
CF3CBrFC(O)CF(CF3)OCF(CF3)2, CBrF2C(O)CF(OCF2CHF2)CF3,
CBrF2C(O)CH(OCF2CHF2)CF3, CBrF2C(O)CF(OCH3)CF3,
CBrF2C(O)CF(CF20CH3)CF3, CCIFZCFBrC(O)CF2CF3,
CBrF2CFCIC(O)CF~CF3, CCIF~CFBrC(O)CF(CF3)2,
CBrF2CFCIC(O)CF(CF3)2, CCIF2CFBrC(O)CF(CF3)(C2F5) ,
CBrF2CFCIC(O)CF(CF3)(C2F5) , CCIF2C(O)CBr(CF3)2,
CCIF2CF2C(O)CBr(CF3)~, CF3CCIFC(O)CBr(CF3)2, CCIF2C(O)CBrFCF3,
CCIF2CF~(O)CCBrFCF3, CF3CCIFC(O)CBrFCF3, CBrF2C(O)CCI(CF3)2,
CBrF2CF2C(O)CCI(CF3)2, CBrF2C(O)CCIFCF3 and
CBrF2CF2C(O)CCIFCF3.
TABLE 1
Compound Chemical FormulaChemical Name CAS Rect.
No.
Haloketones
PEIK CFsCF2C(O)CF(CFs)z1,1,1,2,2,4,5,5,5-nonafluoro-4-756-13-8
(trifluoromethyl)-3-pentanone
(or
erfluoroeth liso ro
I ketone
PMIK CFsC(O)CF(CFs)z1,1,1,3,4,4,4-heptafluoro-3-756-12-7
(trifluoromethyl)-2-butanone
(or
erfluorometh liso ro
I ketone
(CFs)zCFC(O)CF(CFs)z1,1,1,2,4,5,5,5-octafluoro-2,4-
bis trifluorometh I
-3- entanone
CHFzCFzC(O)CF(CFs)z1,1,1,2,4,4,5,5-octafluoro-2-
trifluorometh I -3-
entanone
CFsCF2CFzCOCF(CFs)z1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-
trifluorometh I -3-hexanone
CFsOCFz- 1,1,2,2,4,5,5,5-octafluoro-1-
CFzC(O)CF(CFs)z(trifluoromethoxy)-4-(trifluoromethyl)-3-
entanone
CFsCFzC(O)CH(CFs)z1,1,1,2,2,5,5,5-octafluoro-4-61637-91-0
trifluorometh I -3-
entanone
CFsCFzC(O)CCI(CFs)z2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-83714-48-1
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(trifluoromethyl)-3-pentanone
CFsC(O)CBrFCFzCFs3-bromo-1,1,1,3,4,4,5,5,5-nonafluoro-2-
erfluoro entanone
CHFzCFzC(O)CBrFCFs2-bromo-1,1,1,2,4,4,5,5-octafluoro-3-
entanone
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone
(PEIK) is commercially available from 3MT"" (St. Paul, Minnesota).
1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone (PMIK);
1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;
1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone;
1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-
pentanone; and 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone
may be prepared as described in US 6,478,979 incorporated herein by
reference. 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone may
be prepared from "HFP dimer" as described by England in Journal of
Organic Chemistry, volume 49(no. 21 ), pages 4007 to 4008 (1984). 2-
chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone may be
prepared as described by Saloutina, et al, in Izvestiya Adademii Nauk
SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982).
The bromofluoroketones of the present invention described
previously including monobromoperfluoroketones,
monohydromonobromoperfluoroketones,
(perfluoroalkoxy)monobromoperfluoroketones,
(fluoroalkoxy)monobromoperfluoroketones, and
monochloromonobromoperfluoroketones can be prepared as described in
the following.
Monobromoperfluoroketones CF3C(O)CF2CF2CBrF2,
CF3CF2C(O)CF2CF2CBrF2 and CF3C(O)CF2CF2CF2CFaCBrF2 of the
present invention may be prepared by bromination of the corresponding
monohydroperfluoroketones by the technique of Kolenko and Plashkin in
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1648 to
1650 (1977), and by Zapevalov, et al. in Zhurnal Organicheskoi Khimii,
Vol. 26, pages 265 to 272 (1990). CF3C(O)CF2CFZCBrF2 may be
prepared by bromination of monohydroperFluoroketone
CF3C(O)CF2CFZCHF~, which may be prepared by isomerization of an
epoxide as described by Zapelov et al. in Zhurnal Vsesoyuznogo
Khimicheskogo Obshchestva im. D. 1. Mendeleeva, Vol. 18, pages 591 to
593 (1973). CF3CF2C(O)CF2CF2CBrF2 and CF3C(O)CF2CF2CF2CF2CBrF2
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may be prepared by bromination of monohydroperfluoroketones "
CF3CF2C(O)CF2CF2CHF2 and CF3C(O)CF2CF2CF2CFZCHF2, respectively,
by the technique of Saloutina, et al. in Zhurnal Organicheskoi dChimii, Vol.
29, pages 1325 to 1336 (1993).
Preparation of monobromoperfluoroketones
CF3C(O)CF2CF2CBrF2, CF3CF~C(O)CF2CF2CBrF2 and
CF3C(O)CF2CF2CF2CF2CBrF~ of the present invention by conversion of
the monohydroperfluoroketone terminal C-H bond to a terminal C-Br may
be carried out using brominating agents such as elemental bromine,
phosphorous pentabromide, or a mixture of bromine and phosphorous
tribromide. The preferred brominating agent is a mixture of bromine and
phosphorous tribromide.
Reaction of a monohydroperfluoroketone and a brominating
agent may be carried out under substantially anhydrous conditions in the
vapor phase or liquid phase in a container fabricated from materials of
construction suitable for contact with bromine and hydrogen bromide at
temperatures of about 300°C to 600°C. Examples of such materials
of
construction include metallic alloys containing a nickel such as, for
example, HasteIloyT"" C and HasteIloyT"" B. The reaction takes place
under the autogenous pressures of the reactants at the reaction
temperature.
The ratio of the brominating agent to the
monohydroperfluoroketones is at least about 1 mole of brominating agent
per mole of monohydroperfluoroketone and preferably about 1.3 moles of
brominating agent per mole of monohydroperfluoroketone. More than 1.7
moles of brominating agent per mole of monohydroperfluoroketone
provides little benefit.
Brominating the monohydroperfluoroketone may be conducted
at temperatures of from about 300°C to about 600°C. Using the
preferred
brominating agent, the temperature is preferably conducted from about
300°C to 350°C. Contact times between the brominating agent and
the
monohydroperfluoroketone may be from about one hour to about twenty
hours.
At the end of the contact period the reaction mixture is cooled
and then treated with a reagent to decompose the brominating agent such
as sodium sulfite. The monobromoperfluoroketone may be isolated by
collecting the organic phase followed by distillation.
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Monobromoperfluoroketones CF3CF2C(O)CBrFCF2CF3,
CF3CFZCBrFC(O)CF(CF3)2, (CF3)2CBrC(O)CF(CF3)2,
CF3CF2C(O)CBr(CF3)CF2CF3 and CF3CBrFC(O)CF(CF3)CF2CF3, as well
as mixtures of monobromoperfluoroketones of the present invention
CF3C(O)CBrFCF2CF3 and CF3CBrFC(O)CF2CF3, or
CF3C(O)CBrFCF2CF2CF2CF3 and CF3CBrFC(O)CF2CF2CF2CF3, or
CF3CF2C(O)CBrFCF2CF2CF3 and CF3CF2CBrFC(O)CF2CF2CF3, may be
prepared by contacting perfluoroolefin epoxides, such as the epoxide of
perfluoro-2-pentene, perfluoro-2-heptene, or perfluoro-3-heptene, with an
alkali metal bromide as described by Saloutina et al. in Izvestiya Akademii
Nauk SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The
perFluoroolefin epoxides may be prepared by contacting perfluoroolefin
with an alkali metal hypohalite as described by Kolenko, et al. in Izvestiya
Akademii Nauk SSSR, Seriya Khimicheskaya, pages 2509-2512 (1979).
The contact of perfluoroolefin epoxides with alkali metal
bromides may be carried out in a polar non-protic solvent such as glycol
ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl
ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl
ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl
sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and alkane nitrites
such as acetonitrile, propionitrile, and butyronitrile. Preferred solvents for
contacting perfluoroolefin epoxides with alkali metal bromides are glycol
ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl
ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl
ether, and alkane nitrites such as acetonitrile, propionitrile, and
butyronitrile.
Alkali metal bromides suitable for opening the perFluoroolefin
epoxide ring and formation of a C-Br bond include lithium bromide, sodium
bromide, potassium bromide, and cesium bromide; sodium and lithium
bromide are preferred.
The mole ratio of the alkali metal bromide to the perfluoroolefin
epoxide is at least about 2:1, preferably about 10:1.
Reaction of alkali metal bromides and perfluoolefin epoxide
may be conducted in the liquid phase under substantially anhydrous
conditions at temperatures of from about 10°C to about 150°C,
with
contact times of from about 0.5 hour to about thirty-six hours. Specific
pressure conditions are not critical.
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At the end of the contact period the reaction mixture may be
distilled to isolate the monobromoperfluoroketone.
Monobromoperfluoroketones of the present invention
CBrF2C(O)CF(CF3)2, CBrF2CF2C(O)CF2CF3, CF3CBrFCF~C(O)CF(CFs)2,
CF3CF2C(O)CF~CF2CF2CBrF2, CBrF2CF2CF2C(O)CF(CF3)2, and
CBrF2CF2C(O)CF(CF3)CF2CF3 may be prepared by reacting a
monobromoperfluoroacyl fluoride with a perfluoroolefin.
CBrF2C(O)CF(CF3)2 may be prepared by reacting CBrF2C(O)F
with CF3CF=CF2; CBrF2CF2C(O)CF2CF3 may be prepared by reacting
CBrF2CF2C(O)F with CF2=CF2; CF3CF2C(O)CF2CF2CF2CBrF2 may be
prepared by reacting CBrF2CF~CF2CF2C(O)F with CF2=CF2;
CBrF2CF2CF2C(O)CF(CF3)2 may be prepared by reacting
CBrF2CF~CF2C(O)F with CF3CF=CF2; CBrF2CF2C(O)CF(CF3)CF2CF3 may
be prepared by reacting CBrF2CF2C(O)F with CF3CF=CFCF3; and
CF3CBrFCF2C(O)CF(CF3)~ may be prepared by reacting
CF3CBrFCF2C(O)F with CF3CF=CF2.
Monobromoperfluoroketones of the present invention
CF3C(O)CBr(CF3)2, CF3CBrFC(O)CF~CF2CF3, CF3C(O)CBr(CF3)CF2CF3,
CF3C(O)CF(CF3)CBrFCF3, CF3CF2CF2C(O)CBr(CF3)~, may be prepared
by reacting a perfluoroacyl fluoride with a monobromoperfluoroolefin.
CF3C(O)CBr(CF3)2 may be prepared by reacting CF3C(O)F with
CF3CBr=CF2; CF3CBrFC(O)CF~CF2CF3 may be prepared by reacting
CBrF=CF2 with CF3CF2CF2C(O)F; a mixture of CF3C(O)CBr(CF3)CF2CF3
and CF3C(O)CF(CF3)CBrFCF3 may be prepared by reacting
CF3CBr=CFCF3 with CF3C(O)F; and CF3CF2CF2C(O)CBr(CF3)2 may be
prepared by reacting CF3CF2CF2C(O)F with CF3CBr=CF2_
(Perfluoroalkoxy)monobromoperfluoroketones of the present
invention are of the formula R~C(O)CF(CF3)ORF, wherein R~ is a C~ to C3
monobromoperfluoroalkyl radical, and RF is a C~ to C3 perfluoroalkyl
radical, may be obtained by reacting monobromoperfluoroacyl fluorides of
the formula R~C(O)F with perfluorovinyl ethers of the formula
CFA=CFORF. Representative
(perfluoroalkoxy)monobromoperfluoroketones of the present invention
include CBrF2C(O)CF(CF3)OCF3, CBrF2CF2C(O)CF(CF3)OCF3,
CBrF2CF2CF2C(O)CF(CF3)OCF3, CBrF2C(O)CF(CF3)OC2F5,
CBrF2CF2C(O)CF(CF3)OC2F5, CBrF2C(O)CF(CF3)OCF2C2F5,
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CBrF2CF2C(O)CF(CF3)OCF2C2F5, CBrF2C(O)CF(CF3)OCF(CF3)2,
CBrF2CF2C(O)CF(CF3)OCF(CF3)2, CF3CBrFC(O)CF(CF3)OCF(CF3)2,
CF3CBrFC(O)CF(CF3)OCF3, and CF3CBrFC(O)CF(CF3)OC2F5.
CBrF2C(O)CF(CF3)OCF3 may be prepared by reacting
CBrF2C(O)F with CF2=CFOCF3; CBrF2CF2C(O)CF(CF3)OCF3 may be
prepared by reacting CBrF2CF2C(O)F with CFa=CFOCF3;
CBrF2CF2CF2C(O)CF(CF3)OCF3 may be prepared by reacting
CBrF2CF2CF2C(O)F with CF2=CFOCF3; CBrF2C(O)CF(CF3)OC2F5 may be
prepared by reacting CBrF2C(O)F with CFA=CFOC2F5;
CBrF2CF2C(O)CF(CF3)OC~F5 may be prepared by reacting
CBrF2CF2C(O)F with CF2=CFOC2F5; CBrF2C(O)CF(CF3)OCF2C2F5 may
be prepared by reacting CBrF2C(O)F with CF2=CFOCF2C2F5;
CBrF2CF2C(O)CF(CF3)OCF2C2F5 may be prepared by reacting
CBrF2CF2C(O)F with CF2=CFOCF2C2F5; CBrF2C(O)CF(CF3)OCF(CF3)2
may be prepared by reacting CBrF2C(O)F with CF2=CFOCF(CF3)2;
CBrF~CF2C(O)CF(CF3)OCF(CF3)2 may be prepared by reacting
CBrF2CF2C(O)F with CFA=CFOCF(CF3)2; CF3CBrFC(O)CF(CF3)OCF3 may
be prepared by reacting CF3CBrFC(O)F with CF2=CFOCF3; and
CF3CBrFC(O)CF(CF3)OC2F5 may be prepared by reacting CF3CBrFC(O)F
with CF2=CFOC2F5.
(Perfluoroalkoxy)monobromoperfluoroketones of the formula
R'C(O)CF(CF3)ORF may also be obtained by reacting
perfluoroalkoxyperfluoroacyl fluorides of the formula RFOCF(CF3)C(O)F
with a monobromoperfluoroolefin. Representative
(perfluoroalkoxy)monobromoperfluoroketones of the present invention
include CF3CBrFC(O)CF(CF3)OCF3, (CF3)~CBrC(O)CF(CF3)OCF3,
CF3CBrFC(O)CF(CF3)OC2F5, (CF3)2CBrC(O)CF(CF3)OC2F5,
CF3CBrFC(O)CF(CF3)OCF2C2F5, and CF3CBrFC(O)CF(CF3)OCF(CF3)2.
CF3CBrFC(O)CF(CF3)OCF3 may be prepared by reacting
CF30C(CF3)FC(O)F with CF2=CBrF; (CF3)2CBrC(O)CF(CF3)OCF3
may be prepared by reacting CF30C(CF3)FC(O)F with CF3CBr=CF2;
CF3CBrFC(O)CF(CF3)OC2F5 may be prepared by reacting
C2F50C(CF3)FC(O)F with CF2=CBrF; (CF3)2CBrC(O)CF(CF3)OCZFS may
be prepared by reacting C2F50C(CF3)FC(O)F with CFsCBr=CF2;
CF3CBrFC(O)CF(CF3)OCF2C2F5 may be prepared by reacting
C2F5CF20C(CF3)FC(O)F with CF2=CBrF; and
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CF3CBrFC(O)CF(CF3)OCF(CF3)2 may be prepared by reacting
(CF3)2CFOC(CF3)FC(O)F with CF2=CBrF.
(Fluoroalkoxy)monobromoperfluoroketones of the present
invention are of the formula R~C(O)CX(CF3)OR2, wherein X is H or F, R' is
a C~, C2, or C3 bromoperfluoroalkyl radical, and R2 is a C~ to C3 alkyl or
fluoroalkyl radical, may be prepared by reacting monobromoperfluoroacyl
fluorides of the formula R'C(O)F with hydrofluorovinyl ethers of the
formula CF2=CXOR2. Representative
(fluoroalkoxy)monobromoperfluoroketones include
CBrF2C(O)CF(OCF2CHF2)CF3, CBrF2C(O)CH(OCF2CHF2)CF3,
CBrF2C(O)CF(OCH3)CF3, and CBrF2C(O)CF(CF~OCH3)CF3.
CBrF2C(O)CF(OCF2CHF2)CF3 may be prepared by reacting
CBrF2C(O)F with CF2=CFOCF2CHF2; CBrF2C(O)CH(OCF2CHF2)CF3 may
be prepared by reacting CBrF~C(O)F with CF2=CHOCF2CHF2; and
CBrF2C(O)CF(OCH3)CF3 may be prepared by reacting CBrF2C(O)F with
CF2=CFOCH3.
Another (fluoroalkoxy)monobromoperFluoroketone of the
present invention includes CBrF~C(O)CF(CF20CH3)CF3, prepared by
reacting CBrF2C(O)F with CF3CF=CFOCH3.
The reaction of fluoroacyl fluorides with fluoroolefins is
described by Fawcett, et al. in U. S. Patent No. 3,185,734 and Journal of
the American Chemical Society, Vol. 84, pages 4285 to 4288 (1962). The
teachings of these references may be applied to the aforementioned
preparation of monobromoperfluoroketones by the reaction of
monobromoperfluoroacyl fluorides with perfluoroolefins as well as the
aforementioned preparation of monobromoperfluoroketones by the
reaction of perfluoroacyl fluorides with monobromoperFluoroolefins. These
references may also be applied to the preparation of
(perfluoroalkoxy)monobromoperfluoroketones by the reaction of
monobromoperfluoroacyl fluorides with perfluorovinyl ethers, or by the
reaction of perfluoroalkoxyperfluoroacyl fluorides with
monobromoperfluoroolefins. These references may also be applied to the
preparation of (fluoroalkoxy)monobromoperFluoroketones by the reaction
of monobromoperfluoroacyl fluorides with hydrofluorovinyl ethers.
Though not essential for preparing the ketones of the present
invention, reaction of a fluoroacyl fluoride (such as a perfluoroacyl fluoride
or monobromoperfluoroacyl fluoride) with a fluoroolefin (such as a
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perfluoroolefin, monobromoperfluoroolefin, perfluorovinyl ether or
hydrofluorovinyl ether) may be performed in a polar non-protic solvent
such as N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl
sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and glycol ethers such
as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Preferred solvents for reacting fluoroacyl fluorides with fluoroolefin are
glycol ethers. The reaction may be run under substantially anhydrous
conditions.
The mole ratio of the fluoroolefin to fluoroacyl fluoride during
the reaction may be at least about 1:1 to about 2:1, and preferably is about
1.1.
The reaction of fluoroacyl fluoride with fluoroolefin is preferably
conducted in the presence of a fluoride ion source such as an alkali metal
fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth
metal fluoride, tetraalkylammonium fluoride, tetraalkylammonium hydrogen
fluoride, trialkylammonium fluoride, or non-oxidizing transition metal
fluorides. Preferred fluoride ion sources are potassium fluoride, cesium
fluoride, and potassium bifluoride. The fluoride ion source may be present
at a level of 5 mole percent to 20 mole percent, preferably about 10 mole
percent, based on the quantity of fluoroolefin present.
Temperatures of from about 50°C to about 250°C, preferably
from about 100°C to about 150°C are effective to produce any of
the
fluorinated ketones of the present invention by reaction of a fluoroacyl
fluoride with a fluoroolefin.
The reaction of fluoroacyl fluoride with fluoroolefin may take
place in batch mode or in semi-batch mode with the fluoroacyl fluoride
added gradually to the mixture of the fluoroolefin, solvent,~and fluoride ion
source. Contact times suitable for the reaction may be from about 0.5
hour to about 24 hours. The reaction typically takes place under
autogenous pressure provided by the reactants at the reaction
temperature.
Though not added intentionally to the reactions, hydrogen
fluoride may be present in small amounts during the reactions of fluoroacyl
fluorides due to the presence of traces of water. Reaction of fluoroacyl
fluorides with fluoroolefins may be conducted in a vessel formed of
materials compatible with hydrogen fluoride at elevated temperatures and
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pressures. Examples of such materials include stainless steels, in
particular of the austenitic type, the well-known high nickel alloys, such as
MoneITM nickel-copper alloys, HasteIloyTM nickel-based alloys and,
InconeITM nickel-chromium alloys, and copper-clad steel.
The haloketone products may be isolated from the reaction
mixture as a lower liquid layer or by distillation. After removing traces of
fluoride salts by washing with water, such products may be purified by
distillation.
The present invention further includes
monohydromonobromoperfluoroketones in which one of the C-F bonds in
a perfluoroketone has been replaced by a C-Br bond, and in addition,
another of the C-F bonds in said perfluoroketone has been replaced by a
C-H bond. Monohydromonobromoperfluoroketones of the present
invention comprise CHF2CF2C(O)CBrFCF3, (CF3)2CHC(O)CBrFCF3,
CHF2CF2C(O)CBr(CF3)2, (CF3)2CHC(O)CBr(CF3)2, (CF3)2CHC(O)CBrF2
and CBrF2CF2C(O)CH(CF3)2.
CHF2CF~C(O)CBrFCF3 may be prepared by reacting
CHF2CF2C(O)F with CBrF=CF2; (CF3)2CHC(O)CBrFCF3 may be prepared
by reacting (CF3)2CHC(O)F with CBrF=CF2; CHF2CF2C(O)CBr(CF3)2 may
be prepared by reacting CHF2CF2C(O)F with CF3CBr=CF2;
(CF3)2CHC(O)CBr(CF3)2 may be prepared by reacting (CF3)2CHC(O)F
with CF3CBr=CF2; and CBrF2CF2C(O)CH(CF3)2 may be prepared by
reacting CBrF2CF2C(O)F with CF3CH=CF2. The
monohydromonobromoperfluoroketone (CF3)2CHC(O)CBrF2 may be
prepared by the reaction of the bromofluoroacyl fluoride CBrF2C(O)F with
the monohydroperfluoroolefin CF3CH=CFA.
The production of monohydromonobromoperfluoroketones by the
reaction of monohydroperfluoroacyl fluorides with
monobromoperfluoroolefins, as well as by the reaction of
monobromoperfluoroacyl fluorides with monohydroperfluoroolefins, may
use reaction conditions and procedure similar to those discussed
hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin.
The present invention further comprises
monochloromonobromoperfluoroketones in which one of the C-F bonds in
a perfluoroketone has been replaced by a C-Br bond, and in addition,
another one of the C-F bonds in said perfluoroketone has been replaced
by a C-CI bond. Monochloromonobromoperfluoroketones of the present
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invention comprise compounds of the formula CXF2CFYC(O)CFRCF3,
wherein X is CI and Y is Br, or wherein X is Br and Y is CI, and wherein R
is F, a CF3 radical, or a C2F5 radical. These compounds may be prepared
by contacting an acid fluoride of the formula CXF2CFYC(O)F, prepared as
disclosed by Darst, et al. in U. S. Patent No. 5,557,010, with a
perfluoroolefin of the formula CFR=CFR. Representative
monochloromonobromoperfluoroketones include CCIF2CFBrC(O)CF2CF3,
prepared by reacting CCIF2CFBrC(O)F with CF2=CF2;
CBrF2CCIFC(O)CF2CF3, prepared by reacting CBrF2CCIFC(O)F with
CF2=CF2; CCIF2CFBrC(O)CF(CF3)2, prepared by reacting
CCIF2CFBrC(O)F with CF2=CFCF3; and CBrF2CCIFC(O)CF(CF3)2,
prepared by reacting CBrF2CCIFC(O)F with CF2=CFCF3.
Monochloromonobromoperfluoroketones of the present invention
further comprise CCIF2C(O)CBr(CF3)2, CCIF2CF2C(O)CBr(CF3)2,
CF3CCIFC(O)CBr(CF3)2, CCIF2C(O)CBrFCF3, CCIF2CF2C(O)CBrFCF3,
and CF3CCIFC(O)CBrFCF3 which may be prepared by reacting a
monochloroperfluoroacyl fluoride with a monobromoperfluoroolefin.
CCIF~C(O)CBr(CF3)2 may be prepared by reacting CCIF2C(O)F with
CF3CBr=CF2; CCIF~CF2C(O)CBr(CF3)2 may be prepared by reacting
CCIF2CF2C(O)F with CF3CBr=CF2; CF3CCIFC(~)CBr(CF3)2 may be
prepared by reacting CF3CCIFC(O)F with CF3CBr=CF2;
CCIF~C(O)CBrFCF3 may be prepared by reacting CCIF2C(O)F with
CF2=CBrF; CCIF2CF2C(O)CBrFCF3 may be prepared by reacting
CCIF2CF2(O)F with CF2=CBrF; CF3CCIFC(O)CBrFCF3 may be prepared
by reacting CF3CCIFC(O)F with CF2=CBrF.
Monochloromonobromoperfluoroketones of the present invention
further include CBrF2C(O)CCI(CF3)2, CBrF2CF2C(O)CCI(CF3)2,
CBrF2C(O)CCIFCF3, and CBrF2CF2C(O)CCIFCF3 which may be prepared
by reacting a monobromoperfluoroacyl fluoride with a
monochloroperfluoroolefin.
CBrF2C(O)CCI(CF3)2 may be prepared by reacting CBrF2C(O)F
with CF3CC1=CF2; CBrF2CF2C(O)CCI(CF3)2 may be prepared by reacting
CBrF~CF2C(O)F with CF3CCI=CF2; CBrF2C(O)CCIFCF3 may be prepared
by reacting CBrF2C(O)F with CFZ=CCIF; and CBrF2CF2C(O)CCIFCF3 may
be prepared by reacting CBrF2CF2C(O)F with CF2=COIF.
The formation of monohydromonobromoperfluoroketones by
the reaction of fluoroacyl fluorides of the formula CXF2CFYC(O)F with
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perfluoroolefins, or by the reaction of monochloroperfluoroacyl fluorides
with monobromoperfluoroolefins, or by the reaction of
monobromoperfluoroacyl fluorides with monochloroperFluoroolefins, may
use reaction conditions and procedure similar to those discussed
hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin.
The compositions 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.
The refrigerant or heat transfer compositions of the present
invention include:
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone;
1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone;
1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;
1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone;
1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-
pentanone;
1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone;
2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
CF3C(O)CBrFCF2CF3;
CF3C(O)CF2CF2CBrF2;
CBrF2C(O)CF(CF3)2;
CF3C(O)CBr(CF3)2;
CBrF2CF2C(O)CF2CF3;
CF3CBrFC(O)CF2CF3;
CF3CBrFC(O)CF2CF2CF3;
CF3CF2C(O)CBrFCF2CF3;
CF3CF2C(O)CF2CF2CBrF2;
CF3C(O)CBr(CF3)CF2CF3;
CF3C(O)CF(CF3)CBrFCF3;
CF3C(O)CBrFCF2CF2CF2CF3;
CF3C(O)CF2CF2CF2CF2CBrF2;
CF3CBrFC(O)CFZCF2CF~CF3;
CF3CF2C(O)CBrFCF2CF2CF3;
CF3CFZC(O)CF2CF2CF2CBrF2;
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CF3CF2CBrFC(O)CF2CF2CF3;
CBrF2CF2C(O)CF(CF3)CF2CF3;
CF3CBrFC(O)CF(CF3)CF2CF3;
CF3CF2C(O)CBr(CF3)CF2CF3;
CF3CF2C(O)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(O)CF(CF3)2;
CF3CF2CBrFC(O)CF(CF3)2;
CF3CF2CF2C(O)CBr(CF3)2;
(CF3)2CBrC(O)CF(CF3)2;
CF3CBrFCF2C(O)CF(CF3)2;
CHF~CF2C(O)CBr(CF3)~;
(CF3)2CHC(O)CBr(CF3)2;
CHFZCF2C(O)CBrFCF3;
(CF3)2CHC(O)CBrFCF3;
(CF3)2CHC(O)CBrF2;
CBrF2CF2C(O)CH(CF3)2;
CBrF2C(O)CF(CF3)OCF3;
CBrF2CF2C(O)CF(CF3)OCF3;
CBrF2CF2CF2C(O)CF(CF3)OCF3;
CBrF2C(O)CF(CF3)OC2F5;
CBrF2CF2C(O)CF(CF3)OC2F5;
CBrF2C(O)CF(CF~)OCFZC2F5;
CBrF2CF~C(O)CF(CF3)OCF2C2F5;
CBrF2C(O)CF(CF3)OCF(CF3)2;
CBrF2CF2C(O)CF(CF3)OCF(CF3)2;
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CF3CBrFC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF3;
(CF3)2CBrC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC~F5;
(CF3)2CBrC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF2C2F5;
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CBrF2C(O)CF(OCF2CHF2)CF3;
CBrF2C(O)CH(OCF2CHF2)CF3;
CBrF2C(O)CF(OCH3)CF3;
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CBrF2C(O)CF(CF20CH3)CF3;
CCIF2CFBrC(O)CF2CF3;
CBrF2CFCIC(O)CF2CF3;
CCIF2CFBrC(O)CF(CF3)2;
CBrF2CFCIC(O)CF(CF3)2;
CCIF2CFBrC(O)CF(CF3)(C2F5);
CBrF2CFCIC(O)CF(CF3)(C2F5);
CCIF2C(O)CBr(CF3)z;
CCIF2CF2C(O)CBr(CF3)2;
CF3CCIFC(O)CBr(CF3)2;
CCIF2C(O)CBrFCF3;
CCIF2CF2(O)CCBrFCF3;
CF3CCIFC(O)CBrFCF3;
CBrF2C(O)CCI(CF3)2;
CBrF2CF2C(O)CCI(CF3)2;
CBrF2C(O)CCIFCF3;
CBrF2CF2C(O)CCIFCF3; and combinations thereof.
The compositions of the present invention may further
comprise about 0.01 weight percent to about 5 weight percent of a thermal
stabilizer such as nitromethane.
The compositions of the present invention may further
comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The
UV dye is a useful component for detecting leaks of the refrigerant
composition by permitting one to observe the fluorescence of the dye
under an ultra-violet light at the point of a leak within a refrigeration or
air-
conditioning system. Solubilizing agents may be needed due to poor
solubility of such UV dyes in some refrigerants.
By "ultra-violet" dye is meant a UV fluorescent composition that
absorbs light in the ultra-violet or "near" ultra-violet region of the
electromagnetic spectrum. The fluorescence produced by the UV
fluorescent dye under illumination by a UV light that emits radiation with
wavelength anywhere from 10 nanometer to 750 nanometer may be
detected. Therefore, if refrigerant containing such a UV fluorescent dye is
leaking from a given point in a refrigeration or air conditioning 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,
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naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof.
Solubilizing agents of the present invention comprise at least
one compound selected from the group consisting of hydrocarbons,
hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitrites,
ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and
1,1,1-trifluoroalkanes.
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, and n-pentane. It should be noted that if the refrigerant is a
hydrocarbon, then the solubilizing agent may not be the same
hydrocarbon.
Hydrocarbon ether solubilizing agents of the present invention
comprise ethers containing only carbon, hydrogen and oxygen, such as
dimethyl ether (DME).
Polyoxyalkylene glycol ether solubilizing agents of the present
invention are represented by the formula R~[(OR2)XOR3]y, wherein: x is an
integer from 1-3; y is an integer from 1-4; R~ 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 R~ 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. In the present polyoxyalkylene glycol
ether solubilizing agents represented by R~[(OR2)XOR3]Y: x is preferably 1-
2; y is preferably 1; R~ 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 R~ and R3 hydrocarbon radicals having 1 to 6
carbon atoms may be linear, branched or cyclic. Representative R~ and
R3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl,
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isobutyl, sec-butyl, tent-butyl, pentyl, isopentyl, neopentyl, tent-pentyl,
cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present
polyoxyalkylene glycol ether solubilizing agents may be incompatible with
certain compression refrigeration apparatus materials of construction (e.g.
Mylar~), R~ 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 RZ in one polyoxyalkylene glycol ether solubilizing agent
molecule may be the same, or one molecule may contain different RZ
oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing
agents preferably comprise at least one oxypropylene radical. Where R~
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 R~ 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 R~ 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 solubilizing agents
include but are not limited to: CH30CH~CH(CH3)O(H or CH3) (propylene
glycol methyl (or dimethyl) ether), CH30[CH2CH(CH3)O]2(H or CH3)
(dipropylene glycol methyl (or dimethyl) ether), CH30[CH2CH(CH3)O]3(H
or CH3) (tripropylene glycol methyl (or dimethyl) ether),
C~H50CH2CH(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), C2H50[CHZCH(CH3)O]3(H or C2H5) (tripropylene glycol ethyl (or
diethyl) ether), C3H70CH2CH(CH3)O(H or C3H~) (propylene glycol n-propyl
(or di-n-propyl) ether), C3H7O[CH2CH(CH3)O]2(H or C3H~) (dipropylene
glycol n-propyl (or di-n-propyl) ether) , C3H70[CH2CH(CH3)O]3(H or C3H~)
(tripropylene glycol n-propyl (or di-n-propyl) ether), C4H90CH2CH(CH3)OH
(propylene glycol n-butyl ether), C4H90[CH2CH(CH3)O]2(H or C4H9)
(dipropylene glycol n-butyl (or di-n-butyl) ether), C4H90[CH2CH(CH3)O]3(H
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or C4H9) (tripropylene glycol n-butyl (or di-n-butyl) ether),
(CH3)3COCH2CH(CH3)OH (propylene glycol t-butyl ether),
(CH3)3C0[CH2CH(CH3)O]~(H or (CHs)a) (dipropylene glycol t-butyl (or di-t-
butyl) ether), (CHs)sC0[CH2CH(CH3)O]3(H or (CH3)3) (tripropylene glycol t-
butyl (or di-t-butyl) ether), CSH~~OCH2CH(CH3)OH (propylene glycol n-
pentyl ether), C4H90CH2CH(C2H5)OH (butylene glycol n-butyl ether),
C4H90[CH2CH(C2H5)O]2H (dibutylene glycol n-butyl ether),
trimethylolpropane tri-n-butyl ether (C2H5C(CH20(CH2)3CH3)3) and
trimethylolpropane di-n-butyl ether (C2H5C(CH20C(CH2)3CH3)2CH20H).
Amide solubilizing agents of the present invention comprise
those represented by the formulae R~CONR2R3 and cyclo-[R4CON(R5)-],
wherein R~, 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. R~, 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). R~, R2, R3 and R5
may optionally include heteroatom-substituted hydrocarbon radicals, that
is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or
sulfur (this-) 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 R~-3, and the presence of any such non-hydrocarbon
substituents and heteroatoms must be considered in applying the
aforementioned molecular weight limitations. Preferred amide solubilizing
agents consist of carbon, hydrogen, nitrogen and oxygen. Representative
R~, R2, R3 and R5 aliphatic and alicyclic hydrocarbon radicals include
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tart-butyl,
pentyl,
isopentyl, neopentyl, tart-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl,
nonyl, decyl, undecyl, dodecyl and their configurational isomers. A
preferred embodiment of amide solubilizing agents are those wherein R4
in the aforementioned formula cyclo-[R4CON(R5)-] may be represented by
the hydrocarbylene radical (CR6R')n, in other words, the formula: cyclo-
[(CR6R')nCON(R5)-] wherein: the previously-stated values for molecular
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weight apply; n is an integer from 3 to 5; R5 is a saturated hydrocarbon
radical containing 1 to 12 carbon atoms; R6 and R' are independently
selected (for each n) by the rules previously offered defining R~-3. In the
lactams represented by the formula: cyclo-[(CR6R')"CON(R5)-], all R6 and
R' are preferably hydrogen, or contain a single saturated hydrocarbon
radical among the n methylene units, and R5 is a saturated hydrocarbon
radical containing 3 to 12 carbon atoms. For example, 1-(saturated
hydrocarbon radical)-5-methylpyrrolidin-2-ones.
Representative amide solubilizing agents include but are not
limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-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 solubilizing agents of the present invention comprise
ketones represented by the formula R~COR2, wherein R~ 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. R~
and RZ 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. R' and R~ may together form a hydrocarbylene radical
connected and forming a five, six, or seven-membered ring cyclic ketone,
for example, cyclopentanone, cyclohexanone, and cycloheptanone. R~
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). R~ and R2 may
optionally include heteroatom-substituted hydrocarbon radicals, that is,
radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or
sulfur (this-) 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 R' and R2, and the presence of any such non-
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hydrocarbon substituents and heteroatoms must be considered in applying
the aforementioned molecular weight limitations. Representative R' and
R2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula
R~COR2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
tent butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl,
cyclohexyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational
isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and
phenethyl.
Representative ketone solubilizing agents include but are not
limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone,
hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 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.
Nitrite solubilizing agents of the present invention comprise
nitrites represented by the formula RCN, wherein R~ is selected from
aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon
atoms, and wherein said nitrites have a molecular weight of from about 90
to about 200 atomic mass units. R' in said nitrite solubilizing agents is
preferably selected from aliphatic and alicyclic hydrocarbon radicals
having 8 to 10 carbon atoms. The molecular weight of said nitrite
solubilizing agents is preferably from about 120 to about 140 atomic mass
units. R~ 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). R~ 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
R~, and the presence of any such non-hydrocarbon substituents and
heteroatoms must be considered in applying the aforementioned
molecular weight limitations. Representative R~ aliphatic, alicyclic and aryl
hydrocarbon radicals in the general formula RCN include pentyl,
isopentyl, neopentyl, tent-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl,
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nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as
phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.
Representative nitrite solubilizing agents 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 solubilizing agents of the present invention
comprise chlorocarbons represented by the formula RCI,~, wherein; x is
selected from the integers 1 or 2; R is selected from aliphatic and alicyclic
hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said
chlorocarbons have a molecular weight of from about 100 to about 200
atomic mass units. The molecular weight of said chlorocarbon solubilizing
agents is preferably from about 120 to 150 atomic mass units.
Representative R aliphatic and alicyclic hydrocarbon radicals in the
general formula RCIX include methyl, ethyl, propyl, isopropyl, butyl,
isobutyl, sec-butyl, tent-butyl, pentyl, isopentyl, neopentyl, tent-pentyl,
cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and
their configurational isomers.
Representative chlorocarbon solubilizing agents include but are
not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-
chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-
chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.
Ester solubilizing agents of the present invention comprise
esters represented by the general formula R~CO2R2, wherein R~ 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)2CHCH200C(CHZ)2_40COCH2CH(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 C~ alkyl acetate), "Exxate
800" (a commercial C$ alkyl acetate), dibutyl phthalate, and tert-butyl
acetate.
Lactone solubilizing agents of the present invention comprise
lactones represented by structures [A], [B], and [C]:
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O O R
R2 O R2 0, w
.,iiRB R1 I. O R2 O
R3 5R6 R7 R3 R4 R~ 5 R3 R4 R~ s
[A] [B] [C]
These lactones contain the functional group -C02- in a ring of six (A), or
preferably five atoms (B), wherein for structures [A] and [B], R1 through R$
are independently selected from hydrogen or linear, branched, cyclic,
bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R1 though
R$ may be connected forming a ring with another R1 through R8. The
lactone may have an exocyclic alkylidene group as in structure [C],
wherein R1 through R6 are independently selected from hydrogen or linear,
branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals.
Each R1 though R6 may be connected forming a ring with another R1
through R6. The lactone solubilizing agents have a molecular weight
range of from about 80 to about 300 atomic mass units, preferred from
about 80 to about 200 atomic mass units.
Representative lactone solubilizing agents include but are not limited to
the compounds listed in Table 2.
TABLE 2
Additive Molecular StructureMolecular Molecular
Formula Weight
(amu)
(E Z)-3-ethylidene-5-methyl-O
dihydro-furan-2-one C~H~oOz 126
(E Z)-3-propylidene-5-methyl-O
O
dihydro-furan-2-one CeH~zOz 140
(E Z)-3-butylidene-5-methyl-O O
dihydro-furan-2-one C9H~QOz 154
(E Z)-3-pentylidene-5-methyl-O O
dihydro-furan-2-one C~oH~sOz 168
(E Z)-3-Hexylidene-5-methyl-O O
dihydro-furan-2-one Ci~HiaOz 182
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(E Z)-3-Heptylidene-5-methyl-O
O
dihydro-furan-2-one C,zHzoOz 196
(E Z)-3-octylidene-5-methyl-o 0
dihydro-furan-2-one C,3HzzOz 210
\ ~
(E Z)-3-nonylidene-5-methyl-o 0
dihydro-furan-2-one C,QHz40z 224
(E Z)-3-decylidene-5-methyl-o
dihydro-furan-2-one C,SHzsOz 238
(E,Z)-3-(3 5 5-trimethylhexylidene)-o 0
5-methyl-dihydrofuran-2-one__~~ C,4Hz4Oz 224
\
(E,Z)-3-cyclohexylmethylidene-5-o
O
methyl-dihydrofuran-2-one C,zH,eOz 194
gamma-octalactone o
CeH,4Oz 142
gamma-nonalactone o
C9H,sOz 156
gamma-decalactone o 0
C~oH~aOz 170
gamma-undecalactoneo 0
C"HzoOz 184
gamma-dodecalactoneo 0
CtzHzzOa 198
3-hexyldihydro-furan-2-oneo
o C,oH,eOz 170
3-heptyldihydro-furan-2-oneo
C"HzoOz 184
o
cis-3-ethyl-5-methyl-dihydro-furan-o
2-one C,HizOz 128
0
cis-(3-propyl-5-methyl)-dihydro-O
furan-2-one CBH,QOz 142
O
cis-(3-butyl-5-methyl)-dihydro-
furan-2-one CoH,sOz 156
'
cis-(3-pentyl-5-methyl)-dihydro-o
furan-2-one C,oH,eOz 170
0
cis-3-hexyl-5-methyl-dihydro-furan-o
2-one C"HzoOz 184
0
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cis-3-heptyl-5-methyl-dihydro-o
furan-2-one C~zHzzOz 198
0
cis-3-octyl-5-methyl-dihydro-furan-o
2-one C13Hz4~2 212
0
cis-3-(3,5,5-trimethylhexyl)-5-o
methyl-dihydro-furan-2-one C~4HzsOz 226
0
cis-3-cyclohexylmethyl-5-methyl-o
dihydro-furan-2-one C~zHzoOz 196
5-methyl-5-hexyl-dihydro-furan-2-O
one CHzooz 184
O
5-methyl-5-octyl-dihydro-furan-2-O
one CtsHza~z 212
O
Hexahydro-isobenzofuran-1-oneH O
CBH~zOz 140
O
H
delta-decalactone
C~oH~eOz 170
0 0
delta-undecalactone
C, i HzoOz184
0 0
delta-dodecalactone
CtzHzzOz 198
0 0
mixture of 4-hexyl-dihydrofuran-2-
one and 3-hexyl-dihydro-furan-2- C~oH~sOz 170
one o
0
0
Lactone solubilizing agents generally have a kinematic
viscosity of less than about 7 centistokes at 40°C. For instance, gamma-
undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-
5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at
40°C.
Lactone solubilizing agents may be available commercially or prepared by
methods as described in U. S. patent application 10/910,495 (inventors
being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004,
incorporated herein by reference.
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Aryl ether solubilizing agents of the present invention further
comprise aryl ethers represented by the formula R~OR2, wherein: R~ 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 R~ aryl
radicals in the general formula R~OR2 include phenyl, biphenyl, cumenyl,
mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R2 aliphatic
hydrocarbon radicals in the general formula R~OR2 include methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, sec-butyl and tent-butyl. Representative
aromatic ether solubilizing agents include but are not limited to: methyl
phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and
butyl phenyl ether.
Fluoroether solubilizing agents of the present invention
comprise those represented by the general formula R~OCF2CF~H, wherein
R~ is selected from aliphatic and alicyclic hydrocarbon radicals having from
about 5 to about 15 carbon atoms, preferably primary, linear, saturated,
alkyl radicals. Representative fluoroether solubilizing agents include but
are not limited to: C$H~70CF2CF2H and C6H~30CF2CF~H. It should be
noted that if the refrigerant is a fluoroether, then the solubilizing agent
may
not be the same fluoroether.
1,1,1-Trifluoroalkane solubilizing agents of the present
invention comprise 1,1,1-trifluoroalkanes represented by the general
formula CF3R~, wherein R' is selected from aliphatic and alicyclic
hydrocarbon radicals having from about 5 to about 15 carbon atoms,
preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1-
trifluoroalkane solubilizing agents include but are not limited to: 1,1,1-
trifluorohexane and 1,1,1-trifluorododecane.
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, from about 0.001 weight percent to about 1.0 weight
percent of the composition is UV dye, preferably from about 0.005 weight
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percent to about 0.5 weight percent, and most preferably from 0.01 weight
percent to about 0.25 weight percent.
Solubility of these UV fluorescent dyes in refrigerants may be
poor,. Therefore, methods for introducing these dyes into the refrigeration
or air conditioning apparatus have been awkward, costly and time
consuming. US patent 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 or air conditioning apparatus. As refrigerant
and lubricant are circulated through the apparatus, the dye is dissolved or
dispersed and carried throughout the apparatus. Numerous other methods
for introducing dye into a refrigeration or air conditioning apparatus are
described in the literature.
Ideally, the UV fluorescent dye could be dissolved in the
refrigerant itself thereby not requiring any specialized method for
introduction to the refrigeration or air conditioning apparatus. The present
invention relates to compositions including UV fluorescent dye, which may
be introduced into the system dissolved in the refrigerant. The inventive
compositions will allow the storage and transport of dye-containing
refrigerant even at low temperatures while maintaining the dye in solution.
In the present compositions comprising refrigerant, UV
fluorescent dye and solubilizing agent, from about 1 to about 50 weight
percent, preferably from about 2 to about 25 weight percent, and most
preferably from about 5 to about 15 weight percent of the combined
composition is solubilizing agent in the refrigerant. In the compositions of
the present invention the UV fluorescent dye is present in a concentration
from about 0.001 weight percent to about 1.0 weight percent in the
refrigerant, 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.
Optionally, commonly used refrigeration system additives may
optionally be added, as desired, to compositions of the present invention
in order to enhance performance and system stability. These additives
are known within the field of refrigeration, and include, but are not limited
to, anti wear agents, extreme pressure lubricants, corrosion and oxidation
inhibitors, metal surface deactivators, free radical scavengers, and foam
control agents,. In general, these additives are present in the inventive
compositions in small amounts relative to the overall composition.
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Typically concentrations of from less than about 0.1 weight percent to as
much as about 3 weight percent of each additive are used. These
additives are selected on the basis of the individual system requirements.
These additives include members of the triaryl phosphate family of EP
(extreme pressure) lubricity additives, such as butylated triphenyl
phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn-
0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related
compounds. 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
asymmetrical 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.
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 or sold by Intercontinental Fragrance, as well as d-
limonene and pinene. Such odor masking agents may be used at
concentrations of from about 0.001 % to as much as about 15% by weight
based on the combined weight of odor masking agent and solubilizing
agent.
The present invention further relates to a method of using the
refrigerant or heat transfer fluid compositions further comprising ultraviolet
fluorescent dye, and optionally, solubilizing agent, in refrigeration or air
conditioning apparatus. The method comprises introducing the refrigerant
or heat transfer fluid composition into the refrigeration or air conditioning
apparatus. This may be done by dissolving the UV fluorescent dye in the
refrigerant or heat transfer fluid 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 and
UV fluorescent dye and introducing said combination into refrigeration or
air conditioning apparatus containing refrigerant and/or heat transfer fluid.
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The resulting composition is may be used in the refrigeration or air
conditioning apparatus.
The present invention further relates to a method of using the
refrigerant or heat transfer fluid compositions comprising ultraviolet
fluorescent dye to detect leaks. The presence of the dye in the
compostions allows for detection of leaking refrigerant in the refrigeration
or air conditioning 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 comprising
refrigerant, ultra-violet fluorescent dye as described herein, and optionally,
a solubilizing agent as described herein, to refrigeration and air
conditioning apparatus and employing a sutiable means for detecting the
UV fluorescent dye-containing refrigerant. Suitable means for detecting
the dye include, but are not limited to, ultra-violet lamp, 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 or air conditioning 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 of using the
compositions of the present invention for producing refrigeration or heat,
wherein the method comprises producing refrigeration by evaporating said
composition in the vicinity of a body to be cooled and thereafter
condensing said composition; or producing heat by condensing the said
composition in the vicinity of the body to be heated and thereafter
evaporating said composition.
Mechanical refrigeration is primarily an application of
thermodynamics wherein a cooling medium, such as a refrigerant, goes
through a cycle so that it can be recovered for reuse. Commonly used
cycles include vapor-compression, absorption, steam jet or steam-ejector,
and air.
Vapor-compression refrigeration systems include an
evaporator, a compressor, a condenser, and an expansion device. A
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vapor-compression cycle re-uses refrigerant in multiple steps producing a
cooling effect in one step and a heating effect in a different step. The
cycle can be described simply as follows. Liquid refrigerant enters an
evaporator through an expansion device, and the liquid refrigerant boils in
the evaporator at a low temperature to form a gas and produce cooling.
The low-pressure gas enters a compressor where the gas is compressed
to raise its pressure and temperature. The higher-pressure (compressed)
gaseous refrigerant then enters the condenser in which the refrigerant
condenses and discharges its heat to the environment. The refrigerant
returns to the expansion device through which the liquid expands from the
higher-pressure level in the condenser to the low-pressure level in the
evaporator, thus repeating the cycle.
There are various types of compressors that may be used in
refrigeration applications. Compressors can be generally classified as
reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow,
depending
on the mechanical means to compress the fluid, or as positive-
displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g.,
centrifugal or jet), depending on how the mechanical elements act on the
fluid to be compressed.
Either positive displacement or dynamic compressors may be
used in the present inventive process. A centrifugal type compressor is
the preferred equipment for the present refrigerant compositions.
A centrifugal compressor uses rotating elements to accelerate
the refrigerant radially, and typically includes an impeller and diffuser
housed in a casing. Centrifugal compressors usually take fluid in at an
impeller eye, or central inlet of a circulating impeller, and accelerate it
radially outward. Some static pressure rise occurs in the impeller, but
most of the pressure rise occurs in the diffuser section of the casing,
where velocity is converted to static pressure. Each impeller-diffuser set is
a stage of the compressor. Centrifugal compressors are built with from 1
to 12 or more stages, depending on the final pressure desired and the
volume of refrigerant to be handled.
The pressure ratio, or compression ratio, of a compressor is the
ratio of absolute discharge pressure to the absolute inlet pressure.
Pressure delivered by a centrifugal compressor is practically constant over
a relatively wide range of capacities.
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Positive displacement compressors draw vapor into a chamber,
and the chamber decreases in volume to compress the vapor. After being
compressed, the vapor is forced from the chamber by further decreasing
the volume of the chamber to zero or nearly zero. A positive displacement
compressor can build up a pressure, which is limited only by the
volumetric efficiency and the strength of the parts to withstand the
pressure.
Unlike a positive displacement compressor, a centrifugal
compressor depends entirely on the centrifugal force of the high-speed
impeller to compress the vapor passing through the impeller. There is no
positive displacement, but rather what is called dynamic-compression.
The pressure a centrifugal compressor can develop depends
on the tip speed of the impeller. Tip speed is the speed of the impeller
measured at its tip and is related to the diameter of the impeller and its
revolutions per minute. The capacity of the centrifugal compressor is
determined by the size of the passages through the impeller. This makes
the size of the compressor more dependent on the pressure required than
the capacity.
Because of its high-speed operation, a centrifugal compressor
is fundamentally a high volume, low-pressure machine. A centrifugal
compressor works best with a low-pressure refrigerant, such as
trichlorofluoromethane (CFC-11 ) or 1,2,2-trichlorotrifluoroethane (CFC-
113).
Large centrifugal compressors typically operate at 3000 to
7000 revolutions per minute (rpm). Small turbine centrifugal compressors
are designed for high speeds, from about 40,000 to about 70,000 (rpm),
and have small impeller sizes, typically less than 0.15 meters.
A multi-stage impeller may be used in a centrifugal compressor
to improve compressor efficiency thus requiring less power in use. For a
two-stage system, in operation, the discharge of the first stage impeller
goes to the suction intake of a second impeller. Both impellers may
operate by use of a single shaft (or axle). Each stage can build up a
compression ratio of about 4 to 1; that is, the absolute discharge pressure
can be four times the absolute suction pressure. An example of a two-
stage centrifugal compressor system, in this case for automotive
applications, is described in US 5,065,990, incorporated herein by
reference.
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The compositions of the present invention suitable for use in a
refrigeration or air conditioning systems employing a centrifugal
compressor comprise at least one of:
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone;
1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone;
1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;
1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone;
1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-
pentanone;
1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone;
2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
CF3C(O)CBrFCF2CF3;
CF3C(O)CF2CF~CBrF2;
CBrF2C(~)CF(CF3)2;
CF3C(O)CBr(CF3)2;
CBrF2CF2C(O)CF2CF3;
CF3CBrFC(O)CF2CF3;
CF3CBrFC(~)CF2CF2CF3;
CF3CF2C(O)CBrFCF2CF3;
CF3CF2C(O)CF2CF2CBrF2;
CF3C(~)CBr(CF3)CF2CF3;
CF3C(O)CF(CF3)CBrFCF3;
CF3C(O)CBrFCF2CF2CF2CF3;
CF3C(O)CF2CF2CF2CF2CBrF2;
CF3CBrFC(O)CF2CF2CF2CF3;
CF3CF2C(O)CBrFCF2CF2CF3;
CF3CF2C(O)CF2CF2CF2CBrF2;
CF3CF2CBrFC(O)CF2CF2CF3;
CBrF2CF2C(O)CF(CF3)CF2CF3;
CF3CBrFC(O)CF(CF3)CF2CF3;
CF3CF2C(O)CBr(CF3)CF2CF3;
CF3CF2C(O)CF(CBrF2)CF2CF3;
CBrF2CF2CF2C(O)CF(CF3)2;
CF3CF2CBrFC(O)CF(CF3)2;
CF3CF2CF2C(O)CBr(CF3)2;
(CF3)2CBrC(O)CF(CF3)2;
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CF3CBrFCF2C(O)CF(CF3)z;
CHF2CF2C(O)CBr(CF3)2;
(CF3)2CHC(O)CBr(CF3)2;
CHF2CF2C(O)CBrFCF3;
(CF3)2CHC(O)CBrFCF3;
(CF3)2CHC(O)CBrF2;
CBrF~CF~C(O)CH(CF3)~;
CBrF~C(O)CF(CF3)OCF3;
CBrF2CF2C(O)CF(CF3)OCF3;
CBrF2CF2CF2C(O)CF(CF3)OCF3;
CBrF2C(O)CF(CF3)OC2F5;
CBrF2CF2C(O)CF(CF3)OC2F5;
CBrF2C(O)CF(CF3)OCF2C2F5;
CBrF2CF2C(O)CF(CF3)OCF2C2F5;
CBrF2C(O)CF(CF3)OCF(CF3)2s
CBrF2CF2C(O)CF(CF3)OCF(CF3)~;
CF3CBrFC(O)CF(CF3)OCF(CF3)~;
CF3CBrFC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF3;
(CF3)2CBrC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
(CF3)2CBrC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF2C2F5;
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CBrF2C(O)CF(OCFZCHF2)CF3;
CBrF2C(O)CH(OCF2CHF2)CF3;
CBrF2C(O)CF(OCH3)CF3;
CBrF2C(O)CF(CFZOCH3)CF3;
CCIF2CFBrC(O)CF2CF3;
CBrF2CFCIC(O)CF2CF3;
CCIF2CFBrC(O)CF(CF3)~;
CBrF2CFCIC(O)CF(CF3)2;
CCIF2CFBrC(O)CF(CF3)(C2F5);
CBrF2CFCIC(O)CF(CF3)(C2F5);
CCIF~C(O)CBr(CF3)2;
CCIF2CF2C(O)CBr(CF3)2;
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CF3CCIFC(O)CBr(CF3)2;
CCIF2C(O)CBrFCF3;
CCIF2CF2(O)CCBrFCF3;
CF3CCIFC(O)CBrFCF3;
CBrF2C(O)CCI(CF3)2;
CBrF2CF2C(O)CCI(CF3)2;
CBrF2C(O)CCIFCF3;
CBrF2CF2C(O)CCIFCF3; or combinations thereof.
These above-listed compositions are also suitable for use in two-
stage centrifugal compressor systems.
The compositions of the present invention may be used in
stationary air-conditioning, heat pumps or mobile air-conditioning and
refrigeration systems. Stationary air conditioning and heat pump
applications include window, ductless, ducted, packaged terminal, chillers
and commercial, including packaged rooftop. Refrigeration applications
include domestic or home refrigerators and freezers, ice machines, self-
contained coolers and freezers, walk-in coolers and freezers and transport
refrigeration systems.
The compositions of the present invention may additionally be
used in air-conditioning, heating and refrigeration systems that employ fin
and tube heat exchangers, microchannel heat exchangers and vertical or
horizontal single pass tube or plate type heat exchangers.
Conventional microchannel heat exchangers may not be ideal
for the low pressure refrigerant compositions of the present invention. The
low operating pressure and density result in high flow velocities and high
frictional losses in all components. In these cases, the evaporator design
may be modified. Rather than several microchannel slabs connected in
series (with respect to the refrigerant path) a single slab/single pass heat
exchanger arrangement may be used. Therefore, a preferred heat
exchanger for the low pressure refrigerants of the present invention is a
single slab/single pass heat exchanger.
The following compositions of the present invention are suitable for
use in refrigeration or air conditioning systems employing a single
slab/single pass heat exchanger:
1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone;
1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone
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1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone;
1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone;
1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-
pentanone;
1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone;
2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;
CF3C(O)CBrFCF2CF3;
CF3C(O)CF2CF2CBrF2;
CBrF2C(O)CF(CF3)2;
CF3C(O)CBr(CF3)2;
CBrF2CF2C(O)CF2CF3;
CF3CBrFC(O)CF2CF3;
CF3CBrFC(O)CF~CF2CF3;
CF3CF2C(O)CBrFCF2CF3;
CF3CF2C(O)CF2CF2CBrF2;
CF3C(O)CBr(CF3)CF2CF3;
CF3C(O)CF(CF3)CBrFCF3;
CF3C(O)CBrFCF2CF2CF2CF3;
CF3C(O)CFZCF2CF2CFZCBrF2;
CF3CBrFC(O)CF2CF2CF2CF3;
CF3CFaC(O)CBrFCF2CF2CF3;
CF3CF2C(O)CF2CF2CF2CBrF2;
CF3CF2CBrFC(O)CF2CF2CF3;
CBrF2CF2C(O)CF(CF3)CF2CF3;
CF3CBrFC(O)CF(CF3)CF2CF3;
CF3CF2C(O)CBr(CF3)CF2CF3;
CF3CF2C(O)CF(CBrF2)CF2CF3;
CBrF~CF2CF2C(O)CF(CF3)2;
CF3CFZCBrFC(O)CF(CF3)2;
CF3CF2CF2C(O)CBr(CF3)2;
(CF3)2CBrC(O)CF(CF3)2;
CF3CBrFCF2C(O)CF(CF3)2;
CHF2CF2C(O)CBr(CF3)2;
(CF3)2CHC(O)CBr(CF3)2;
CHF2CF2C(O)CBrFCF3;
(CF3)2CHC(O)CBrFCF3;
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(CF3)2CHC(O)CBrF2;
CBrF2CF2C(O)CH(CF3)2;
CBrF~C(O)CF(CF3)OCF3;
CBrF2CF2C(O)CF(CF3)OCF3;
CBrF2CF2CF2C(O)CF(CF3)OCF3;
CBrF2C(O)CF(CF3)OC2F5;
CBrF2CF2C(O)CF(CF3)OC2F5;
CBrF2C(O)CF(CF3)OCF2C2F5;
CBrF2CF2C(O)CF(CF3)OCF2C2F5;
CBrF2C(O)CF(CF3)OCF(CF3)2;
CBrF2CF2C(O)CF(CF3)OCF(CF3)2s
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CF3CBrFC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
CF3CBrFC(O)CF(CF3)OCF3;
(CF3)2CBrC(O)CF(CF3)OCF3;
CF3CBrFC(O)CF(CF3)OC2F5;
(CF3)2CBrC(O)CF(CF3)OC~F5;
CF3CBrFC(O)CF(CF3)OCF~C~F5;
CF3CBrFC(O)CF(CF3)OCF(CF3)2;
CBrF2C(O)CF(OCF2CHF2)CF3;
CBrF2C(O)CH(OCF2CHF2)CF3;
CBrF2C(O)CF(OCH3)CF3;
CBrF2C(O)CF(CF20CH3)CF3;
CCIF2CFBrC(O)CF2CF3;
CBrF2CFCIC(O)CF2CF3;
CCIF2CFBrC(O)CF(CF3)2;
CBrF2CFCIC(O)CF(CF3)2;
CCIFZCFBrC(O)CF(CF3)(C~F5);
CBrF2CFCIC(O)CF(CF3)(C2F5);
CCIF~C(O)CBr(CF3)2;
CCIF2CF2C(O)CBr(CF3)z;
CF3CCIFC(O)CBr(CF3)2;
CCIF2C(O)CBrFCF3;
CCIF2CF2(O)CCBrFCF3;
CF3CCIFC(O)CBrFCF3;
CBrF2C(O)CCI(CF3)2;
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CBrF2CF2C(O)CCI(CF3)2;
CBrF2C(O)CCIFCF3;
CBrFaCF2C(~)CCIFCF3; or combinations thereof.
The compositions of the present invention are particularly
useful in small turbine centrifugal compressors, which can be used in auto
and window air conditioning or heat pumps as well as other applications.
These high efficiency miniature centrifugal compressors may be driven by
an electric motor and can therefore be operated independently of the
engine speed. A constant compressor speed allows the system to provide
a relatively constant cooling capacity at all engine speeds. This provides
an opportunity for efficiency improvements especially at higher engine
speeds as compared to a conventional R-134a automobile air-conditioning
system. When the cycling operation of conventional systems at high
driving speeds is taken into account, the advantage of these low pressure
systems becomes even greater.
Some of the low pressure refrigerant fluids of the present
invention may be suitable as drop-in replacements for CFC-113 in existing
centrifugal equipment.
The present invention relates to a process for producing
refrigeration comprising evaporating the compositions of the present
invention in the vicinity of a body to be cooled, and thereafter condensing
said compositions.
The present invention further relates to a process for producing
heat comprising condensing 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 process for transfer of
heat from a heat source to a heat sink via a heat transfer fluid, wherein the
compositions of the present invention serve as heat transfer fluids. Said
process for heat transfer comprises transferring the compositions of the
present invention from a heat source to a heat sink.
Heat transfer fluids are utilized to transfer, move or remove
heat from one space, location, object or body to a different space, location,
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
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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.
EXAMPLES
EXAMPLE 1
Tip Speed to Develop Pressure
Tip speed can be estimated by making some fundamental
relationships for refrigeration equipment that use centrifugal compressors.
The torque an impeller ideally imparts to a gas is defined as
T = m*(v2*r2-v1 *r1 ) Equation 1
where
T = torque, N*m
m = mass rate of flow, kg/s
v2 = tangential velocity of refrigerant leaving impeller (tip
speed), m/s
r2 = radius of exit impeller, m
v1 = tangential velocity of refrigerant entering impeller, m/s
r1 = radius of inlet of impeller, m
Assuming the refrigerant enters the impeller in an essentially
radial direction, the tangential component of the velocity v1 = 0, therefore
T = m*v2*r2 Equation 2
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The power required at the shaft is the product of the torque and
the rotative speed
P = T*w Equation 3
where
P = power, W
w = rotative speed, rez/s
therefore,
P = T*w = m*v2*r2*w Equation 4
At low refrigerant flow rates, the tip speed of the impeller and
the tangential velocity of the refrigerant are nearly identical; therefore
r2*w = v2 Equation 5
and
P = m*v2*v2 Equation 6
Another expression for ideal power is the product of the
mass rate of flow and the isentropic work of compression,
P = m*Hi*(1000J/kJ) Equation 7
where
Hi = Difference in enthalpy of the refrigerant from a saturated
vapor at the evaporating conditions to saturated condensing conditions,
kJ/kg.
Combining the two expressions Equation 6 and 7
produces,
v2*v2 = 1000*Hi Equation 8
Although Equation 8 is based on some fundamental
assumptions, it provides a good estimate of the tip speed of the impeller
and provides an important way to compare tip speeds of refrigerants.
Table 3 below shows theoretical tip speeds that are calculated
for 1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the
present invention. The conditions assumed for this comparison are:
Evaporator temperature 40.0°F (4.4°C)
Condenser temperature 110.0°F (43.3°C)
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Liquid subcool temperature 10.0°F (5.5°C)
Return gas temperature 75.0°F (23.8°C)
Compressor efficiency is 70%
These are typical conditions under which small turbine centrifugal
compressors perform.
TABLE 3
Hi Hi*0.7 Hi*0.7 V2 V2 rel
Refri erant Btu/lb Btu/lb KJ/K m/s to CFC-113
CFC-113 10.92 7.6 17.8 133.3 n/a
PEIK 11.55 8.1 18.8 137.1 103%
PMIK 10.94 7.7 17.8 133.5 100%
CF3C O CBrFCF2CF39.9 6.9 16.1 127.0 95%
The data shows that compounds of the present invention have
tip speeds within about +/- 5 percent of CFC-113 and would be effective
replacements for CFC-113 with minimal compressor design changes.
EXAMPLE 2
Performance Data
Table 4 shows the performance of various refrigerants
compared to CFC-113. The data are based on the following conditions.
Evaporator temperature 40.0°F (4.4°C)
Condenser temperature 110.0°F (43.3°C)
Subcool temperature 10.0°F (5.5°C)
Return gas temperature 75.0°F (23.8°C)
Compressor efficiency is 70%
TABLE 4
Evap EvapCond Cond ComprCompr CapacityCapacity
RefrigerantPressPressP P DischDischCOP Btu/minkW
PressPress T T
Psia kPa Psia kPa F C
CFC-113 2.7 19 12.8 88 156.369.1 4.1814.8 0.26
PEIK 2.2 15 12.5 86 124.651.4 3.7313.4 0.24
PMIK 7.3 50 33.0 227 127.953.3 3.6837.6 0.66
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CFsC(O)CBrFCFz 0.6 4 4.9 33 I 142.3 I 61.3 I4.08I 4.9 I 0.09
Data show the compositions of the present invention have evaporator and
condenser pressures similar to CFC-113. Some compositions also have
higher capacity or energy efficiency (COP) than CFC-113.
43
