U.S. patent application number 14/929916 was filed with the patent office on 2016-07-28 for stabilized iodocarbon compositions.
The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to Lawrence A. Ford, Haridasan K. Nair, Rajiv R. Singh, Raymond H. Thomas, David P. Wilson.
Application Number | 20160215191 14/929916 |
Document ID | / |
Family ID | 46543496 |
Filed Date | 2016-07-28 |
United States Patent
Application |
20160215191 |
Kind Code |
A1 |
Singh; Rajiv R. ; et
al. |
July 28, 2016 |
STABILIZED IODOCARBON COMPOSITIONS
Abstract
Disclosed are compositions comprising at least one iodocarbon
compound and preferably at least one stabilization agent. These
compositions are generally useful as refrigerants for heating and
cooling, as blowing agents, as aerosol propellants, as solvent
composition, and as fire extinguishing and suppressing agents.
Inventors: |
Singh; Rajiv R.; (Getzville,
NY) ; Nair; Haridasan K.; (Williamsville, NY)
; Thomas; Raymond H.; (Pendleton, NY) ; Ford;
Lawrence A.; (Hamburg, NY) ; Wilson; David P.;
(East Amherst, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
MORRIS PLAINS |
NJ |
US |
|
|
Family ID: |
46543496 |
Appl. No.: |
14/929916 |
Filed: |
November 2, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13419071 |
Mar 13, 2012 |
9175201 |
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14929916 |
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11795779 |
Mar 10, 2008 |
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PCT/US05/46982 |
Dec 21, 2005 |
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13419071 |
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12467061 |
May 15, 2009 |
8133407 |
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13419071 |
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13022902 |
Feb 8, 2011 |
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13419071 |
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11937267 |
Nov 8, 2007 |
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13022902 |
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60638003 |
Dec 21, 2004 |
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61051663 |
May 8, 2008 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10M 2205/026 20130101;
C10M 2209/1033 20130101; C10M 2207/042 20130101; C10M 2205/08
20130101; C10M 2207/026 20130101; C09K 5/045 20130101; C10M 171/008
20130101; C10M 2223/049 20130101; C09K 2205/122 20130101; C09K
5/044 20130101; C10M 2211/022 20130101; C09K 2205/126 20130101;
C10N 2020/101 20200501; C10M 2207/023 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; C10M 171/00 20060101 C10M171/00 |
Claims
1. A heat transfer composition comprising: (a) at least one
iodocarbon; (b) at least one refrigerant compound other than said
iodocarbon; and (c) at least one stabilizing compound selected from
the group consisting of: (1) diene-based compounds have at least
two carbon-carbon double bonds and at least four carbon atoms; (2)
epoxy compounds selected from compounds according to Formulas (E1)
and (E2): ##STR00012## where R.sup.1 is an aliphatic radical having
at least 3 carbon atoms; R.sup.2 is an aliphatic radical having 4
or 5 carbon atoms or a polycyclic aromatic radical; (3) phosphites
according to formula P1 below: ##STR00013## where each R is
independently a phenyl radical or a carboxylate radical having at
least 6 but less than 15 carbon atoms; (4) unhindered or mildly
hindered phenols; and (5) combinations of any two or more of these,
said stabilizer compound(s) being present in an amount effective to
stabilize said at least one iodocarbon against degradation.
2. The heat transfer composition of claim 1 wherein R.sup.1
comprises at least 4 carbon atoms.
3. The heat transfer composition of claim 1 wherein R.sup.1 is an
unsaturated aliphatic radical having from 4 to 6 carbon atoms.
4. The heat transfer composition of claim 1 wherein R.sup.1 is a 4
carbon unsaturated aliphatic radical.
5. The heat transfer composition of claim 1 wherein R.sup.2 is a
naphthyl radical.
6. The composition of claim 1 wherein said at least one iodocarbon
comprises CF.sub.3I.
7. The composition of claim 1 wherein said stabilizing compound is
selected from the group consisting of (1) diene-based compounds
have at least two carbon-carbon double bonds and at least four
carbon atoms; (2) epoxy compounds selected from compounds according
to Formulas (E1) and (E2): ##STR00014## where R.sup.1 is an
aliphatic radical having at least 3 carbon atoms; R.sup.2 is an
aliphatic radical having 4 or 5 carbon atoms or a polycyclic
aromatic radical; (3) phosphites according to formula P1 below:
##STR00015## where each R is independently a phenyl radical or a
carboxylate radical having at least 6 but less than 15 carbon
atoms, and combinations of any two or more of (1) through (3).
8. The composition of claim 1 wherein said stabilizing compound is
selected from the group consisting of Myrcene, Geraniol, Farnesol,
Limonene, Diphenyl Phosphite, 1,2-epoxyhexene, Dilauryl hydrogen
phosphate, and combinations of two or more of these.
9. The composition of claim 1 wherein said stabilizing compound is
selected from the group consisting of Myrcene, Geraniol, Farnesol,
Limonene, Diphenyl Phosphite, 1,2-epoxyhexene, Dilauryl hydrogen
phosphate, 2,4-dimethyl-6-tert-butylphenol, Tocopherol and
combinations of two or more of these.
10. A heat transfer composition comprising: (a) at least one
iodocarbon; (b) at least one refrigerant compound other than said
iodocarbon; (c) at least one lubricant comprising
polyalkyleneglycol (PAG); and (d) at least one stabilizing compound
selected from the group consisting of diene-based compounds,
epoxides, phosphates, phosphites, and combinations of these.
11. The composition of claim 10 wherein said at least one
stabilizing compound is present in the composition in an amount
effective to stabilize said at least one iodocarbon against
degradation under the conditions of use for said heat transfer
composition.
12. The composition of claim 10 wherein said diene-based compound
comprises butadiene.
13. The composition of claim 12 wherein said diene-based compound
comprises at least one terpene-based compound.
14. The composition of claim 13 wherein said terpene-based compound
is selected from the group consisting of myrcene, geraniol,
farnesol, limonene, and combinations of these.
15. The composition of claim 10 wherein said stabilizing compound
comprises an epoxide.
16. The composition of claim 15 wherein said epoxide is selected
from the group consisting of 1,2-epoxyhexane, naphthyl glycidyl
ether, and combinations of these.
17. The composition of claim 10 where said stabilizing compound
comprises a phosphate or phosphite.
18. A lubricating oil composition for use in a heat transfer system
comprising: (a) at least one lubricant; and (b) at least one
stabilizing compound selected from the group consisting of : (1)
diene-based compounds have at least two carbon-carbon double bonds
and at least four carbon atoms; (2) epoxy compounds selected from
compounds according to Formulas (E1) and (E2): ##STR00016## where
R.sup.1 is an aliphatic radical having at least 3 carbon atoms;
R.sup.2 is an aliphatic radical having 4 or 5 carbon atoms or a
polycyclic aromatic radical; (3) phosphites according to formula P1
below ##STR00017## where each R is independently a phenyl radical
or a carboxylate radical having at least 6 but less than 15 carbon
atoms; (4) unhindered or mildly hindered phenols; and (5)
combinations of any two or more of these.
19. The lubricant composition of claim 18 wherein said lubricant
comprises in major proportion polyalkyleneglycol (PAG)
lubricant.
20. The lubricant composition of claim 18 wherein said stabilizing
compound is selected from the group consisting of (1) diene-based
compounds have at least two carbon-carbon double bonds and at least
four carbon atoms; (2) epoxy compounds selected from compounds
according to Formulas (E1) and (E2): ##STR00018## where R.sup.1 is
an aliphatic radical having at least 3 carbon atoms; R.sup.2 is an
aliphatic radical having 4 or 5 carbon atoms or a polycyclic
aromatic radical; (3) phosphites according to formula P1 below
##STR00019## where each R is independently a phenyl radical or a
carboxylate radical having at least 6 but less than 15 carbon
atoms, and combinations of any two or more of (1) through (3).
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation of Ser. No.
13/419,071, filed Mar. 13, 2012, which application is a
continuation-in-part of each of U.S. application Ser. No.
11/795,779, filed on Mar. 10, 2008, as a U.S. national stage
application of PCT Application No. PCT/US05/46982, filed on Dec.
21, 2005, which claims priority benefit of U.S. Provisional
Application No. 60/638,003, filed on Dec. 21, 2004, all of which
are incorporated herein by reference. The present application is
also a continuation-in-part of U.S. application Ser. No.
12/467,061, filed on May 15, 2009, which claims priority benefit of
U.S. Provisional Application No. 61/053,663, filed on May 15, 2008,
all of which are incorporated herein by reference. The present
application is also a continuation-in-part of U.S. application Ser.
No. 13/022,902, filed on Feb. 8, 2011, which is a continuation of
U.S. application Ser. No. 11/937,267, filed on Nov. 8, 2007.
BACKGROUND
[0002] Halogenated hydrocarbons have found widespread use in a
variety of industrial applications, including as refrigerants,
aerosol propellants, blowing agents, heat transfer media and gas
dielectrics. Many of these applications have heretofore utilized
compositions comprising major amounts of chlorofluorocarbons
("CFCs") and hydrochlorofluorocarbons ("HCFCs"). However, suspected
environmental problems have become associated with the use of some
of these halogenated hydrocarbons. For example, both CFCs and HCFCs
tend to exhibit relatively high global warming potentials.
Accordingly, it has become desirable in many applications to use
compositions which are otherwise acceptable for the intended use
but which at the same time have lower global warming potentials
than CFCs and other disfavored halogenated compounds.
[0003] Applicants have recognized that certain compositions
comprising iodinated compounds, and in particular, compositions
comprising trifluoroiodomethane, may be used advantageously to
replace various chlorinated compounds, many of which have high
global warming potentials, in refrigeration (and other)
applications to reduce potential environmental damage caused
thereby. Applicants have further recognized, however, that
iodinated compounds, such as trifluoroiodomethane, tend to be
relatively unstable, and often significantly less stable than CFCs,
HCFCs and hydrofluorocarbons (HFCs), especially under certain
conventional refrigeration conditions.
[0004] To be useful as refrigerants and replacements for other CFC,
HCFC and HFC fluids, suitable compositions comprising iodinated
compounds must be stabilized. Applicants have recognized one
possible way to produce suitable stable iodo-compositions is to use
stabilizing compounds therein.
[0005] A variety of stabilizers for use with HCFC and CFC
compositions are known. HFCs, due to their exceptional stability,
may or may not use stabilizers incorporated in their compositions
as known in the art. For example, U.S. Pat. No. 5,380,449 discloses
compositions comprising dichlorotrifluoroethane and stabilizing
amounts of at least one phenol and at least one aromatic or
fluorinated alkyl epoxide. However, because iodo-compounds tend to
be significantly less stable that CFCs and HCFCs, it cannot be
predicted from teachings of stabilizers for CFCs and HCFCs (e.g.
the '449 disclosure) whether the same or similar compounds are
capable of stabilizing iodo-compounds to a sufficient degree for
use as CFC/HCFC replacements. That is, as will be recognized by
those of skill in the art, C--CI and C--F bonds tend to be at least
about 1.5-2 times stronger than C--I bonds. Accordingly, it is
neither inherent nor necessarily reasonable to expect that a
compound that stabilizes an HCFC or CFC will be suitable for an
iodo-compound which requires about twice the amount of added
stability to be useful in refrigerant applications.
[0006] Applicants have thus recognized the need to produce
compositions comprising iodo-compounds, such as
trifluoroiodomethane, that are sufficiently stable for a variety of
uses including as replacements for CFC, HCFC and HFC
refrigerants.
[0007] It has been proposed to utilize certain iodocarbon compounds
in refrigeration applications as replacements for certain of the
CFCs and HCFCs that have heretofore been used. For example,
Japanese Kokai 09-059612 (Application No. 07-220964) discloses
refrigerant compositions comprising trifluoroiodomethane and one or
more phenolic compounds. This patent document indicates that the
phenolic compositions act to stabilize the trifluoroiodomethane
against degradation.
[0008] While the compositions containing phenolic compounds as
stabilizers for trifluoroiodomethane may enjoy a certain degree of
success, in certain applications it may be desirable to not use
phenolic compounds or to use such compounds in a lower
concentration. For example, phenols are generally acidic due to the
dissociability of the hydroxyl group and are relatively reactive.
These characteristics may be undesirable in certain applications
and/or in certain situations.
SUMMARY OF THE INVENTION
[0009] The present invention provides a variety of compositions
comprising iodocarbon compounds, such as trifluoroiodomethane
(CF.sub.3I), that are surprisingly stable and can be used
advantageously in a variety of applications, including as
refrigerants in various cooling systems. In particular, applicants
have discovered unexpectedly that iodocarbon compounds in general,
and C1-C5 iodocarbons, and even more preferably C1-C2 iodocarbons,
particularly (such as the preferred C1 iodocarbon
trifluoroiodomethane) can be combined with one or more stabilizer
compounds selected from a specific set of compounds to produce an
exceptionally well stabilized iodocarbon-containing composition,
preferably a trifluoroiodomethane-containing composition suitable
for commercial, industrial or personal use, and particularly as
heat transfer fluids for use in refrigeration systems, air
conditioning systems (including automotive air conditioning
systems) and the like. In addition, not only are the present
compositions sufficiently stable for a variety of uses, but also,
they tend to exhibit a unique combination of non-flammability and
low combined ozone-depletion and global warming properties, making
them particularly useful candidates as CFC, HCFC, and HFC
refrigerant replacements.
[0010] As used herein, the term "iodocarbon" refers to any compound
containing at least one carbon-iodine bond, and is intended to
cover iodofluorocarbons (compounds which have at least one
carbon-iodine bond and at least one carbon-fluorine bond, but no
other bonds except carbon-carbon bonds) and hydroiodofluorocarbons
(compounds which have at least one carbon-iodine bond, at least one
carbon-fluorine bond, at least on carbon-hydrogen bond, but no
other bonds except carbon-carbon bonds).
[0011] The present invention is therefore directed, in one
embodiment, to compositions comprising at least one iodocarbon
compound, preferably a C1-C5 iodocarbon and even more preferably a
C1 iodocarbon, and at least one stabilizing compound. It is
contemplated that in certain cases the composition may include any
one or more of a class of stabilizers based on free-radical
scavenging functionality, but in many preferred embodiments the
stabilizer comprises, and preferably in at least major proportion,
diene-based compound(s), certain phenol compounds, certain
epoxides, certain phosphites, and certain phosphates.
[0012] In certain preferred embodiments, the diene-based compounds
are isoprene-based compound(s). As the term is used herein,
"diene-based compound" refers to both substituted and unsubstituted
C3-C5 compounds with two or more double bonds in the molecular
structure and to compounds that can be formed by reaction(s)
involving such C3-C5 compounds, provided that at least one
double-bonds is present in such reaction product compound. In
preferred embodiments, the diene-based compound of the present
invention comprises substituted and unsubstituted C3-C20 compounds
with two or more double bonds in the molecular structure. As the
term is used herein, "isoprene-based compound" refers to ispropene,
compounds having an isoprene moiety, and to compounds capable of
being formed by reaction(s) involving isoprene. For example, as
used herein determined diene-based compounds include myrcene and
farsenol, each of which has three carbon-carbon double bonds. Thus,
the term "diene-based" is not limited to compounds having only two
double bonds, but includes compounds having fewer or more than two
carbon--carbon double bonds. In the case of diene-based compounds
which are formed by a combination of C3-C5 dienes, the molecules
which are combined can be the same or different.
[0013] Applicants have come to appreciate that, under certain
conditions of use, iodocarbon compounds tend to be generally less
stable than compounds, which have C--CI and C--F bonds in place of
the C--I bond, and particularly when in the presence of lubricant
compounds and even more particularly when in the presence of
lubricant compounds under temperature conditions that are
experienced by refrigerants in vapor compression cycle operation.
Applicants have thus recognized the desirability of providing
compositions comprising iodocarbon compounds, such as
trifluoroiodomethane, that are sufficiently stable for a variety of
uses, including in heat transfer applications, including as
refrigerants and even more preferably as replacements for CFC and
HCFC refrigerants. Such compositions provide the potential to
reduce environmental damage that would be caused if CFC and
HCFC-based compositions were used instead of the compositions of
the present invention. Applicants have further recognized, however,
that iodinated compounds generally tend to be relatively unstable,
and often significantly less stable than CFCs and HCFCs under
certain conditions of use, such as under conditions existing in
conventional refrigeration systems. For example, while performing
standard, recommended ASHRAE and SAE testing on various
refrigerants, the present inventors discovered that compounds
comprising iodofluorocarbon produced the brown/black color of
iodine, which is believed to have been formed from the degradation
of the iodofluorocarbon during the testing conditions.
[0014] The present inventors have discovered unexpectedly that
iodocarbon compounds, preferably C1-C2 iodocarbons, more preferably
C1 iodocarbons, and even more preferably trifluoroiodomethane, can
be combined with at least one stabilizing compound, preferably a
compound having free radical scavenging functionality, and even
more preferably at least one compound selected from the group
consisting of: (1) diene-based compounds, preferably diene-based
compounds have at least two carbon-carbon double bonds and at least
four carbon atoms; (2) epoxy compounds, including preferably epoxy
compounds selected from substituted or unsubstituted compounds
according to Formulas (E1) and (E2) below:
##STR00001##
[0015] where
[0016] R.sup.1 is an aliphatic radical having at least 3 carbon
atoms, preferably at least 4 carbon atoms, and more preferably in
certain embodiments R.sup.1 is an unsaturated aliphatic radical
having from 4 to 6 carbon atoms, with R.sup.1 being a 4 carbon
unsaturated aliphatic radical in certain highly preferred
embodiments;
[0017] R.sup.2 is an alphiatic radical having 4 or 5 carbon atoms
or a polycyclic aromatic radical, preferably a naphthyl radical,
and combinations of these; [0018] (3) phosphites according to
formula P1 below
[0018] ##STR00002## [0019] where each R is independently a phenyl
radical or [0020] a carboxylate radical having at least 6 but less
than 15 carbon atoms; [0021] (4) unhindered or mildly hindered
phenols, as that term is defined hereinafter, [0022] and
combinations of any two or more of these.
[0023] As used herein, the term mildly hindered phenol means a
substituted phenol in which there are aliphatic substituents at the
2 and 6 positions on the phenol ring and wherein the total number
of substituent carbon atoms at these positions is greater than four
but less than eight. IN preferred embodiments, the total number of
substituent carbon atoms at positions 2 and 6 is five or six, and
even more preferably five. As used herein, the term unhindered
phenol means a phenol in which there are a total of not greater
than a total of two carbon atoms in the combination of any
substituents present at either the 2 or 6 positions on the phenol
ring.
[0024] In certain highly preferred embodiments, the stabilizing
compound used in accordance with the various aspects of the present
invention comprises, and preferably comprises in major proportion,
and more preferably in certain embodiments consists essentially of
at least one compound selected from the group consisting of: (1)
diene-based compounds, preferably diene-based compounds have at
least two carbon-carbon double bonds and at least four carbon
atoms; (2) epoxy compounds, including preferably epoxy compounds
selected from substituted or unsubstituted compounds according to
Formulas (E1) and (E2) below:
##STR00003##
[0025] where
[0026] R.sup.1 is an alphiatic radical having at least 3 carbon
atoms, preferably at least 4 carbon atoms, and more preferably in
certain embodiments R.sup.1 is an unsaturated aliphatic radical
having from 4 to 6 carbon atoms, with R.sup.1 being a 4 carbon
unsaturated aliphatic radical in certain highly preferred
embodiments;
[0027] R.sup.2 is an alphiatic radical having 4 or 5 carbon atoms
or a polycyclic aromatic radical, preferably a naphthyl radical,
and combinations of these; [0028] (3) phosphites according to
formula P1 below:
[0028] ##STR00004## [0029] where each R is independently a phenyl
radical or [0030] a carboxylate radical having at least 6 but less
than 15 carbon atoms; and [0031] combinations of any two or more of
these.
[0032] In addition, not only are the present compositions
sufficiently stable for a variety of uses, but they tend also to
exhibit a unique combination of non-flammability and low
ozone-depletion properties, making them particularly useful as heat
transfer fluids, particularly as replacement candidates for
currently used refrigerants, such as CFC and HCFC refrigerant
replacements. Furthermore, applicants have discovered that many
advantages in accordance with the present invention can be achieved
for compositions comprising, in addition to the iodocarbon, and
preferably also the stabilizing agent, one or more other compounds,
including especially HFCs, preferably C1-C4 HFCs, and halogenated
olefins, preferably C2-C5 halogenated olefins.
[0033] Applicants have further recognized that the preferred
compositions of the present invention are stable and suitable for
use in many systems, apparatus and methods. For example, one aspect
of the present invention provides systems, apparatus and methods
that comprise the compositions of the present invention being
included as a heating or cooling fluid (based on latent heat
transfer and/or sensible heat transfer), such as in refrigeration
applications, including particularly automotive air conditioning
applications. Other systems, apparatus and methods are also within
the scope of the present invention, as explained more fully
hereinafter.
[0034] In yet another aspect, the present invention provides
methods, systems and apparatus for stabilizing a composition
comprising at least one iodocarbon compound by use of a stabilizing
agent which preferably, comprises one or more of the preferred
stabilizing compounds mentioned herein, preferably in many
preferred embodiments comprising a diene-based compound, in
accordance with the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
I. The Compositions--Generally
[0035] The preferred compositions comprise at least one iodocarbon,
preferably a C1 iodofluorocarbon (such as trifluoroiodomethane
(CF.sub.3I)), and preferably also at least one stabilizing agent,
preferably one or more of the preferred stabilizing compounds
mentioned herein, including diene-based compounds, preferably in an
amount effective under conditions of use to stabilize the
iodocarbon against degradation.
[0036] Certain preferred compositions of the present invention
comprise iodocarbon and at least one saturated HFC and/or at least
one haloalkene, preferably one or more C1-C4 HFCs and/or one or
more, C2-C5 haloalkenes.
[0037] When haloalkenes are present, the haloalkene preferably
comprises C2-C4 haloalkene, and even more preferably C2-C4
haloalkene with at least two, and preferably at least three
fluorine substituents. Highly preferred among such haloalkenes,
especially for use in connection with heat transfer applications
such as automotive air conditioning, are tetrafluoropropenes,
particularly 2,3,3,3-tetrafluoropropene (HFO-1234yf). In certain of
such preferred embodiments, the composition comprises from about 5%
to about 50% by weight of iodocarbon, more preferably from about
20% to about 40% by weight of iodocarbon, and even more preferably
from about 25% to about 35% of iodocarbon, and from about 50% to
about 95% by weight of HFCs, preferably C1-C4 HFCs, and/or
halogenated olefins, preferably C2-C5 halogenated olefins, and even
more preferably C2-C4 haloalkene, more preferably from about 60% to
about 80% by weight of HFCs, preferably C1-C4 HFCs, and/or
halogenated olefins, preferably C2-C5 halogenated olefins, and even
more preferably C2-C4 haloalkene, and even more preferably from
about 65% to about 75% of HFCs, preferably C1-C4 HFCs, and/or
halogenated olefins, preferably C2-C5 halogenated olefins, and even
more preferably haloalkene, based on the total weight of the
iodocarbon and the haloalkene.
[0038] Certain preferred compositions of the present invention
comprise iodocarbon and at least one C1-C4 HFC, preferably C1-C3
HFC, and even more preferably C1-C2 HFC. In certain of such
preferred embodiments, the composition comprises from about 50% to
about 95% by weight of iodocarbon, more preferably form about 65%
to about 85% of iodocarbon, and from about 5% to about 50% by
weight of HFC, and even more preferably from about 15% to about 35%
of HFC, based on the total weight of the iodocarbon and the
HFC.
[0039] In preferred embodiments, the present compositions have a
Global Warming Potential (GWP) of not greater than about 1000, more
preferably not greater than about 500, and even more preferably not
greater than about 150, and in certain cases of not greater than
about 100. In certain embodiments, the GWP of the present
compositions is not greater than about 75. As used herein, "GWP" is
measured relative to that of carbon dioxide and over a 100-year
time horizon, as defined in "The Scientific Assessment of Ozone
Depletion, 2002, a report of the World Meteorological Association's
Global Ozone Research and Monitoring Project," which is
incorporated herein by reference.
[0040] The compositions preferably also having an Ozone
Depleting
[0041] Potential (ODP) of not greater than about 0.05, more
preferably not greater than about 0.02 and even more preferably
about zero. As used herein, "ODP" is as defined in "The Scientific
Assessment of Ozone Depletion, 2002, A report of the World
Meteorological Association's Global Ozone Research and Monitoring
Project," which is incorporated herein by reference.
[0042] A. The Iodocarbon
[0043] In view of the teachings contained herein, it is
contemplated that the iodocarbon compound in accordance with the
present invention may comprise one or more of a wide variety of
such compounds. For example, it is contemplated that in certain
preferred embodiments the iodocarbon compound is a C1-C6
iodocarbon, and even more preferably a C1-C3 iodofluorocarbon. The
iodocarbon can be comprised of carbon, hydrogen, fluorine and
iodine.
[0044] In certain preferred compositions of the present invention,
the iodocarbon comprises a C1-C3 iodocarbon, more preferably a C1
iodocarbon, and even more preferably a C1 iodofluorocarbon. In
certain highly preferred embodiments, the at least one iodocarbon
compound comprises, and preferably comprises in major proportion on
the basis of the total iodocarbon compounds, trifluoroiodomethane
(CF.sub.3I). Thus, in certain highly preferred embodiments, the
present compositions comprise at least one C1 compound containing
only carbon-fluorine bonds and carbon-iodine bonds, with C1
compounds containing at least two carbon-fluorine bonds and at
least one carbon-iodine bond being even more preferred.
[0045] Trifluoroiodomethane is readily available from a variety of
commercial sources, including Matheson TriGas, Inc. In addition,
trifluoroiodomethane prepared via any of a variety of conventional
methods may be used. An example of one such conventional method of
preparing trifluoroiodomethane is disclosed in JACS 72, 3806
(1950), "The Degradation of Silver Trifluoroacetate to
Trifluoroiodomethane" by Albert L. Henne and William G. Finnegan,
which is incorporated herein by reference.
[0046] In general, the iodocarbon compounds may be present in the
compositions in widely ranging amounts, depending on numerous
factors, including for example the particular intended conditions
of use of the compound. In certain preferred embodiments,
iodocarbon compound(s) are present in the present composition in
amounts, based on weight, of from about 5% to less than about 100%,
more preferably from about 20% to less than about 100%. In certain
preferred embodiments, particularly those in which the composition
contains HFC(s), the iodocarbon compound(s) are present in the
present composition in amounts, based on weight, of from about 5%
to about 35%, more preferably from about 45% to about 95%, and even
more preferably from about 65% to about 95%. In certain preferred
embodiments, particularly those in which the composition contains
halogenated alkene(s), the iodocarbon compound(s) are present in
the present composition in amounts, based on weight, of from about
15% to about 50%, more preferably from about 20% to about 40%, and
even more preferably from about 25% to about 35%.
[0047] With respect to the relative weight of the iodocarbon
compound(s) and the stabilizing agent, in certain embodiments the
iodocarbon is present in an amount of from about 90% to about
99.999% by weight, more preferably from about 95 wt. % to about
99.99 wt. %, and even more preferably from about 96 wt. % to about
99.7 wt. %, based on the total weight of iodocarbon and stabilizing
agent, preferably diene-based compounds in the composition.
[0048] B. The Stabilizer(s)
[0049] In certain preferred embodiments, the stabilizer compounds
are present in the composition in amounts of from about 0.001% to
about 15% by weight, more preferably from about 0.01 wt. % to about
10 wt. %, and even more preferably from about 0.3 wt. % to about 5
wt. %, and even more preferably from about 1 to about 2 wt. % based
on the total weight of the composition, preferably composition that
is comprised of the iodocarbon, and more preferably the refrigerant
composition that is comprised of the iodocarbon. In some cases, the
stabilizer compounds are present in the composition in amounts of
from about 0.001% to about 15% by weight, more preferably from
about 0.01 wt. % to about 10 wt. %, and even more preferably from
about 0.3 wt. % to about 5 wt. %, and even more preferably from
about 1 to about 2 wt. % based on the total weight of a lubricant
and stabilizer. In certain preferred embodiments, the stabilizer
compound is present in amounts of from about 0.5 wt. % to about 2
wt. %, based on the total weight of composition, preferably the
composition that is comprised of the iodocarbon.
1--Diene-Based Compound(s)
[0050] It is contemplated that any one or more of the available
diene-based compounds are adaptable for use in accordance with the
present invention and that those skilled in the art will be able,
in view of the teachings contained herein, to select the number and
type of such compound(s) appropriate for any particular application
without undue experimentation. The type and nature of the
diene-based compound(s) to be used may depend, to at least some
degree, upon the particular iodocarbon compound(s) being used in
the composition, the expected conditions of use of the
compositions, and related factors.
[0051] It is generally contemplated that the amount of the
diene-based stabilizer used in the compositions of the present
invention can vary widely, depending upon factors such as the type
of iodocarbon in the composition, the expected conditions of use of
the composition, among other factors. In general, it is preferred
to use diene-based stabilizer in an effective amount relative to
the iodocarbon being used. As used herein, the term "effective
amount" refers to an amount of diene-based compound(s) which, when
added to a composition comprising the relevant iodocarbon compound,
such as trifluoroiodomethane, results in a stabilized composition
wherein the iodocarbon degrades more slowly and/or to lesser degree
relative to the same composition, under the same, or similar,
conditions, but in the absence of the diene-based compounds. In the
particular example of trifluoroiodomethane, one of the important
breakdown products is trifluoromethane, which is formed by the
substitution of hydrogen for iodine in the CF.sub.3I molecule.
Similarly, hydrogen can be substituted for iodine in other
iodocarbons, thereby forming compounds that can have relatively
high GWP values, for example greater than 150. These breakdown
products have the effect of raising the GWP of the refrigerant
blends that use iodocarbons. The goal of having a low global
warming potential is therefore defeated. An effective amount of
stabilizer preferably will reduce the amount of decomposition of
the iodocarbon such that the GWP of the refrigerant composition is
below 1000, and even more preferably less than 150. Even without
the consideration of GWP values, breakdown of a component of a
refrigerant composition is undesirable. Thus it is preferred that
the level of the breakdown product described above be less than 2.0
wt %, more preferably less than about 1.0 wt. %, and even more
preferably less than about 0.5 wt % of the total refrigerant
composition. In certain preferred embodiments, the amount of the
diene-based compound(s) is sufficient to result in a stabilized
composition wherein at least one of the iodocarbon compound(s)
therein degrades more slowly and/or to a lesser degree relative to
the same composition but in the absence of the diene-base compound,
when tested according to SAE J1662 (issued June 1993) and/or ASHRAE
97-1983R (issued 1997) standard tests. For example, in certain
preferred embodiments, the amount of breakdown product, that is
product formed by the substitution of hydrogen for iodine in the
iodocarbon, is less than about 0.9 wt. %, and even more preferably
less than about 0.7 wt % after the composition is maintained at
about 300.degree. F. for about two weeks.
[0052] The diene-based compounds of the present invention may be
cyclic or acyclic, with acyclic compounds being generally preferred
in many embodiments. The acyclic diene-based compounds for use in
the present invention are preferably C5-C30 diene-based compounds,
more preferably C5-C20 diene-based compounds and even more
preferably C5-C15 diene based compounds. For cyclic diene-based
compounds, the compound may be aromatic or non-aromatic, with
non-aromatic diene-based cyclic compounds being preferred in
certain embodiments.
[0053] In preferred embodiments the diene-based compounds are
selected from the group consisting of allyl ethers, propadiene,
butadiene, isoprene-based compounds (including terpenes (such as
myrcene, farnesene, and limonene),and terpene derivatives (such as
farnesol, and geraniol)) and combinations of any two or more of
these. As used herein, each of the compounds identified in the
immediately preceding list is intended to include both substituted
and unsubstituted forms of the identified compounds. In certain
preferred embodiments, the diene-based compounds comprise in major
proportion, and even more preferably consist essentially of,
propadiene.
[0054] In certain other preferred embodiments, the diene-based
compounds comprise in major proportion, and even more preferably
consist essentially of, terpenes, terpene derivatives or
combinations of these. As used herein, the term "terpene" means a
compound, which is comprised of at least ten carbon atoms and
contains at least one, and preferably at least two isoprene
moieties. In many preferred embodiments, the terpene compound of
the present invention is formed from the reaction of at least two
isoprene C5 units (CH2=C(CH3)-CH=CH2) (each unit being substituted
or unsubstituted), and thus many of the terpene compounds of the
present invention preferably have as at least 10 carbon atoms and
include at least one isoprene moiety. As used herein, the term
"isoprene moiety" refers to any portion of a molecule, which
includes a radical, which can be formed from substituted or
unsubstituted isoprene. In certain preferred embodiments,
unsubstituted terpenes are preferred.
[0055] In many preferred embodiments, the terpene compound of the
present invention comprises at least one head-to-tail condensation
product of modified or unmodified isoprene molecules. It is
contemplated that any one or more terpene compounds are adaptable
for use in accordance with the present invention and that those
skilled in the art will be able, in view of the teachings contained
herein, to select the number and type of terpene compound(s) for
any particular application without undue experimentation. The
preferred terpenes of the present invention are hydrocarbons having
molecular formula (C.sub.5H.sub.8).sub.n in a cyclic or acyclic,
saturated or unsaturated, substituted or unsubstituted structure,
with n preferably being from 2 to about 6, and even more preferably
2 to 4. Terpenes according to the present invention having the
formula C.sub.10H.sub.16 (including substituted forms) are
sometimes referred to herein as monoterpenes, while terpenes having
the formula C.sub.15H.sub.24 (including substituted forms) are
sometimes referred to herein as sesquiterpenes. Terpenes according
to the present invention having the formula C.sub.20H.sub.32
(including substituted forms) are sometimes referred to herein as
diterpenes, while terpenes having the formula C.sub.30H.sub.24
(including substituted forms) are sometimes referred to as
triterpenes, and so on. Terpenes containing 30 or more carbons are
usually formed by the fusion of two terpene precursors in a regular
pattern. While it is contemplated that all such terpenes are
adaptable for use in accordance with the present invention, the use
of monoterpenes is generally preferred.
[0056] In certain preferred embodiments, the terpene compound(s) of
present compositions comprise, preferably in major proportion, and
even more preferably consist essentially of, one or more acyclic
terpene compounds. Among the acyclic terpenes, it is contemplated
that such compounds may be within the class of compounds identified
as head-to-tail linked isoprenoids or within the class of compounds
that are not joined in that manner. Acyclic terpenes which are
preferred for use in accordance with certain aspects of the present
invention include myrcene (2-methyl-6-methyleneocta-1,7-diene),
allo-cimene, beta-ocimene.
[0057] In certain embodiments, the terpene compounds of the present
invention may comprise cyclic terpene compounds. Among the cyclic
terpenes, mono-, bi-, tri-, or tetracyclic compounds having varying
degrees of unsaturation are contemplated for use in accordance with
the present invention.
[0058] Examples of terpene compounds adaptable for use in
connection with the various aspects of the present invention
include terebene, myrcene, limonene, retinal, pinene, menthol,
geraniol, farnesol, phytol, Vitamin A.sub.1, terpinene, delta-3
carene, terpinolene, phellandrene, fenchene, and the like, as well
as blends thereof, including all their isomers.
[0059] In certain preferred embodiments, the terpene compounds of
the present composition comprise one or more sequiterpenes,
preferably farnesol and/or farnesene. The term "farnesol" is the
compound 3,7,11-trimethyl-2,6,10-dodecatrien-1-ol, including any
and all stereoisomers thereof. Farnesol is a natural organic
compound which is a sesquiterpene alcohol found as a colorless
liquid and is insoluble in water, but miscible with oils. It has
the chemical structure:
##STR00005##
The term "farnesene" includes a-farnesene (i.e.,
3,7,11-trimethyldocecadodeca-1,3,6,19-tetraene) and
.beta.-farnesene (i.e.,
7,11-dimethyl-3-methylene-1,6,10-dodecatriene), including any and
all stereoisomers thereof.
[0060] Examples of terpene derivatives in accordance with the
present invention include oxygen-containing derivatives of terpenes
such as alcohols, aldehydes or ketones containing hydroxyl groups
or carbonyl groups, as well as hydrogenated derivates.
Oxygen-containing derivatives of terpenes are sometimes referred to
herein as terpenoids. In certain embodiments, the diene-based
compounds of the present invention comprise the terpenoid Carnosic
acid. Carnosic acid is a phenolic diterpene that corresponds to the
empirical formula C2028O4. It occurs naturally in plants of the
Libiatae family. For instance, carnosic acid is a constituent of
the species Salvia officinalis (sage) and Rosmarinus officinalis
(rosemary) where it is mainly found in the leaves. Carnosic acid is
also found in thyme and marjoram (see Linde in Salvia
officinalis[Helv. Chim Acta 47, 1234 (1962)] and Wenkert et al. in
Rosmarinus officinalis[J. Org. Chem. 30, 2931 (1965)], and in
various other species of sage, (see Salvia canariensis[Savona and
Bruno, J. Nat. Prod. 46, 594 (1983)] and Salvia willeana[de la
Torre et al., Phytochemistry 29, 668 (1990)]). It is also present
in Salvia triloba and Salvia sclarea. Other potential terpenoids
are illustrated below:
##STR00006## ##STR00007##
[0061] According to certain preferred embodiments, the present
compositions comprise a combination of at least one diene-based
compound (such as isoprene, propadiene and myrcene) and one
additional stabilizing compound chosen from epoxides, such as
aromatic epoxides and fluorinated alkyl epoxides, hindered phenols
such as DL-alpha-tocopherol and 2-tert-butyl-4,6-dimethylphenol,
phosphites such as diphenyl phosphate (e.g., Doverphos 213) and
triphenyl phosphite alone and in mixtures such as Doverphos 9E11,
esters of phosphorous acid such as Doverphos 613 and mixtures of
the above mentioned materials.
[0062] Any suitable relative amount of the at least one diene-based
compound and supplemental optional stabilizer compound(s) may be
used. For example, in certain preferred embodiments the weight
ratio of the diene-based compound(s) to other stabilizer
compound(s) is in the range of from about 1:99 to about 100:0. In
more preferred embodiments, the weight ratio of diene-based
compound(s) to the optional stabilizers is from about 10:1 to about
1:1, more preferably from about 2:1 to about 1:1, and even more
preferably about 1:1.
2--The Phenols
[0063] It is contemplated that any of a variety of phenol compounds
are suitable for use as stabilizer in the present compositions.
While applicants do not wish to be bound by or to any theory of
operation, it is believed that the present phenols act as radical
scavengers in the present compositions and thereby tend to increase
the stability of such compositions. As used herein the term "phenol
compound" refers generally to any substituted or unsubstituted
phenol. Examples of suitable phenol compounds include
4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-bis(2,6-di-tert-butylphenol); 2,2- or 4,4-biphenyldiols
including 4,4'-bis(2-methyl-6-tert-butylphenol); derivatives of
2,2- or 4,4-biphenyldiols;
2,2'-methylenebis(4-ethyl-6-tertbutylpheol);
2,2'-methylenebis(4-methyl-6-tert-butylphenol);
4,4,-butylidenebis(3-methyl-6-tert-butylphenol);
4,4,-isopropylidenebis(2,6-di-tert-butylphenol);
2,2'-methylenebis(4-methyl-6-nonylphenol);
2,2'-isobutylidenebis(4,6-dimethylphenol);
2,2'-methylenebis(4-methyl-6-cyclohexylphenol);
2,6-di-tert-butyl-4-methylphenol (BHT);
2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tert-butylphenol;
2,6-di-tert-.alpha.-dimethylamino-p-cresol;
2,6-di-tert-butyl-4(N,N'-dimethylaminomethylphenol); 4,4'-thiobis
(2-methyl-6-tert-butylphenol); 4,4'-thiobis
(3-methyl-6-tert-butylphenol); 2,2'-thiobis
(4-methyl-6-tert-butylphenol);
bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide; and
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; and the like. Other
suitable phenols include tocopherol, hydroquinone; t-butyl
hydroquinone; and other derivatives of hydroquinone; and the like.
Certain preferred phenols include tocopherol, BHT, hydroquinone and
the like. Certain particularly preferred phenols include tocopherol
and the like. Most phenols are commercially available such as the
Irganox compounds from Ciba. A single phenol compound and/or
mixtures of two or more phenols may be used in the present
compositions.
3--The Epdixides
[0064] It is also contemplated that any of a variety of epoxides
are suitable for use in the compositions of the present invention.
Among the epoxides, aromatic epoxides and fluorinated alkyl
epoxides are preferred additional stabilizers in certain
embodiments. While applicants do not wish to be bound by or to any
theory of operation, it is believed that the epoxides of the
present invention act as acid scavengers in the CF.sub.3I
compositions and thereby tend to increase the stability of such
compositions. Examples of suitable aromatic epoxides include those
defined by the formula I below:
##STR00008##
wherein: R is hydrogen, alkyl, fluoroalkyl, aryl, fluoroaryl,
or
##STR00009##
and Ar is a substituted or unsubstituted phenylene or napthylene
moiety. Certain preferred aromatic epoxides of Formula I include:
butylphenylglycidyl ether; pentylphenylglycidyl ether;
hexylphenylglycidyl ether; heptylphenylglycidyl ether;
octylphenylglycidyl ether; nonylphenylglycidyl ether;
decylphenylglycidyl ether; glycidyl methyl phenyl ether;
1,4-diglycidyl phenyl diether and derivatives thereof;
1,4-diglycidyl naphthyl diether and derivatives thereof; and
2,2'[[[5-heptadecafluorooctyl]1,3phenylene]bis[[2,2,2trifluorome
thyl]ethylidene]oxymethylene]bisoxirane; and the like. Other
preferred aromatic epoxides include naphthyl glycidyl ether,
4-methoxyphenyl glycidyl ether, and derivatives of naphthyl
glycidyl ether; and the like. Certain more preferred aromatic
epoxides include butylphenyl glycidyl ether, and the like. A single
aromatic epoxide and/or mixtures of two or more aromatic epoxides
may be used in the present compositions.
[0065] Any of a variety of alkyl and/or alkenyl epoxides is
suitable for use in the present compositions. Examples of suitable
alkyl and alkenyl epoxides include those of Formula II:
##STR00010##
wherein R.sub.alk is a substituted or unsubstituted alkyl or
alkenyl group. Preferably, R.sub.alk is a substituted or
unsubstituted alkyl or alkenyl group having from about 1 to about
10 carbon atoms, more preferably from about 1 to about 6 carbon
atoms. Certain preferred alkyl epoxides of Formula II include
n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol
diglycidyl ether, and the like, as well as, fluorinated and
perfluorinated alkyl epoxides. More preferred alkyl epoxides
include hexanediol diglycidyl ether and 1,2-epoxyhexane. Certain
preferred alkenyl epoxides of Formula II include allyl glycidyl
ether, fluorinated and perfluorinated alkenyl epoxides, and the
like. More preferred alkenyl epoxides include allyl glycidyl ether
and the like.
[0066] D. Other Components
[0067] The present compositions may optionally incorporate other
components depending upon the particular contemplated use and the
specific iodocarbon and stabilization compounds being used.
1--Co-Refrigerants, Co-Blowing Agents, Etc.
[0068] According to certain embodiments, as explained more fully
hereinafter, the compositions of the present invention may further
comprise one or more components in addition to the iodocarbon and
the stabilizing agent when present, depending upon the expected use
of the composition. For example, the present compositions are
generally adaptable for use in connection with the following
applications, and various co-components may be associated with the
compositions in connection with these and other applications: heat
transfer (including refrigeration, chiller applications, closed
Rankine cycle operations (CRC)); organic Rankine cycle operations
(ORC); foam and/or foam forming operations (including as or part of
a premix and/or blowing agent and/or foam (including thermosetting
foams (such as polyurethane, polyisocyanurate, and phenolic),
thermoplastic foams (such as polystyrene and polyolefin), integral
skin foams, one or two component pressurized froth foam, and the
like; solvent (including solvent cleaning and extraction); aerosol;
oligomer and/or polymer production (such as monomer for
polymerization reactions); propellants; fire extinguishing aids;
surfactants; flushing applications; metered dose inhalers (MDI);
lubricating agents; flame suppressants; therapeutic compositions;
pesticide compositions; herbicide compositions; solvent
applications (including cleaning, extraction and deposition
applications) and the like.
[0069] While it is contemplated that many co-components may be use
with advantage in the present compositions, it is preferred in
several embodiments that the present compositions have as a
co-component one or more of the following components: [0070]
CO.sub.2: [0071] Hydrocarbons (substituted and un-substituted,
particularly C2-C6 hydrocarbons); [0072] Alcohols (substituted and
un-substituted, particularly C2-C6 alcohols); [0073] Ketones
(substituted and un-substituted, particularly C2-05 ketones);
[0074] Aldehydes (substituted and un-substituted, particularly
C2-05 aldehydes); [0075] Ethers/Diethers (substituted and
un-substituted, particularly C2-05 ethers); [0076] Fluoroethers
(substituted and un-substituted, particularly C2-05 fluoroethers);
[0077] Fluoroalkenes (substituted and un-substituted, particularly
C2-C6 fluoroalkenes); [0078] CFC (particularly C2-C5 CFCs) [0079]
HFC (particularly C2-05 HFCs); [0080] HCC (particularly C2-05
HCCs); [0081] HCFC (particularly C2-05 HCFCs); [0082] Haloalkenes,
including preferably fluoroalkenes (substituted and un-substituted,
particularly C2-C6 fluoroalkenes); [0083] HFO (particularly C2-5
HFOs); [0084] HCIFO (particularly C2-05 HCIFOs); [0085] HBrFO
(particularly C2-05 HBrFOs); [0086] Carbonates/dicarbonates; [0087]
Carboxylic acid and derivatives thereof (e.g. carboxylic acid
esters, such as methyl formate); and [0088] Water.
[0089] As used herein, the term "HFO" means compounds that consist
of atoms of carbon, fluorine and hydrogen, and no other atoms, and
in which there is at least one carbon-carbon double bond.
[0090] As used herein, the term "HCIFO" means compounds that
consist of atoms of carbon, chlorine, fluorine and hydrogen, and no
other atoms, and in which there is at least one carbon-carbon
double bond.
[0091] As used herein, the term "HBrFO" means compounds that
consist of atoms of carbon, bromine, fluorine and hydrogen, and no
other atoms, and in which there is at least one carbon-carbon
double bond.
[0092] As used throughout the specification and claims, the
designations C1-C5 and like usages, refer to compounds having at
least one carbon atom and up to about five carbon atoms, etc.
[0093] While it is contemplated that a wide variety of HFCs may be
used in the present compositions and methods, in certain preferred
embodiments it is preferred to use in the compositions one or more
of the following (including any and all isomers of each):
[0094] Difluoromethane (HFC-32);
[0095] Pentafluoroethane (HFC-125);
[0096] 1,1,2,2-tetrafluoroethane (HFC-134);
[0097] 1,1,1,2-Tetrafluoroethane (HFC-134a);
[0098] Trifluorethane (HFC-143a);
[0099] Difluoroethane (HFC-152a);
[0100] 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea);
[0101] 1,1,1,3,3,3-hexafluoropropane (HFC-236fa);
[0102] 1,1,1,3,3-pentafluoropropane (HFC-245fa); and
[0103] 1,1,1,3,3-pentafluorobutane (HFC-365mfc).
[0104] While it is contemplated that a wide variety of HCFCs may be
used in the present compositions and methods, in certain preferred
embodiments it is preferred to use separately or in any
combination: dichlorotrifluoroethanes (such as 2,2-dichloro-1,1,1
trifluoroethane (HCFC-123)); and chlorotetrafluoroethane
(HCFC-124), including any and all isomers of each.
[0105] While it is contemplated that a wide variety of HCCs may be
used in the present compositions and methods, in certain preferred
embodiments it is preferred to use separately or in any
combination: dichloroethenes (such as 1,2-dichloroethane, including
trans-1,2-dichloroethyene); ethylchloride; and 2-chloropropane.
[0106] While it is contemplated that a wide variety of CFCs may be
used in the present compositions and methods, in certain preferred
embodiments it is preferred to use trichlorotrifluoroethanes (such
as 1,1,2-trichlorotrifluoroethane (CFC-113)), especially for use as
a monomer for the production of oligomers and/or polymers.
[0107] While it is contemplated that a wide variety of
fluoroalkenes may be used in the present compositions and methods,
it is particularly preferred in many embodiments that the
compositions comprise one or more C3 or C4 fluoroalkenes,
preferably compounds having Formula I as follows:
XCF.sub.zR.sub.3-z (I)
where X is a C.sub.2 or a C.sub.3 unsaturated, substituted or
unsubstituted, alkyl radical, each R is independently CI, F, Br, I
or H, and z is 1 to 3. Highly preferred among the compounds of
Formula I are the following compounds:
[0108] fluoroethenes
[0109] fluorpropenes;
[0110] fluorobutenes;
[0111] chlorofluorethenes;
[0112] chlorofluoropropenes; and
[0113] chlorofluorobutenes.
[0114] Among the fluroethenes, preferred for use in certain
embodiments of the present invention are: C.sub.2H.sub.3F
(monofluoroethylene or Vinyl Fluoride or VF); C.sub.2H.sub.2F.sub.2
(such as 1,1-Difluoroethylene (Vinylidene Fluoride or VDF);
C.sub.2HF.sub.3 (trifluoroethylene or THFE); and C.sub.2F.sub.4
(tetrafluoroethylene or TFE).
[0115] Among the fluoropropenes, preferred for use in certain
embodiments of the present invention are: C.sub.3H.sub.3F.sub.3
(including all isomers, such as 3,3,3-trifluoropropene
(HFO-1243zf); C.sub.3H.sub.2F.sub.4 (such as cis- and trans-
isomers of 1,3,3,3-etrafluoropro3pene (HFO-1234ze), and
2,3,3,3-tetrafluoropropene (HFO-1234yf)); and C.sub.3HF.sub.5 (such
as isomers of HFO-1225). The term "HFO-1234" is used herein to
refer to all tetrafluoropropenes. Among the tetrafluoropropenes is
included HFO-1234 yf and any and all stero- or geometric isomers
thereof. The terms HFO-1234yf and HFO-1234ze are used herein
generically to refer to 1,1,1,2-tetrafluoropropene and
1,1,1,3-tetrafluoropropene, respectively, independent of its stero
isometry.
[0116] HFO-1234 compounds are known materials and are listed in
Chemical Abstracts databases. The production of fluoropropenes such
as CF.sub.3CH=CH.sub.2 by catalytic vapor phase fluorination of
various saturated and unsaturated halogen-containing C.sub.3
compounds is described in U.S. Pat. Nos. 2,889,379; 4,798,818 and
4,465,786, each of which is incorporated herein by reference. EP
974,571, also incorporated herein by reference, discloses the
preparation of 1,1,1,3-tetrafluoropropene by contacting
1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a
chromium-based catalyst at elevated temperature, or in the liquid
phase with an alcoholic solution of KOH, NaOH, Ca(OH).sub.2 or
Mg(OH).sub.2.
[0117] Among the fluorobutenes, preferred for use in certain
embodiments of the present invention are: C.sub.4H.sub.4F.sub.4
(including all isomers thereof); C.sub.4H.sub.3F.sub.5 (such as all
isomers of HFO-1345); and C.sub.4H.sub.2F.sub.6 (such as all
isomers of HFO-1336).
[0118] Among the chlorofluroethenes, preferred for use in certain
embodiments of the present invention are: C.sub.2F.sub.3CI
(CTFE).
[0119] Among the chlorofluoropropenes, preferred for use in certain
embodiments of the present invention are mono- or di-chlorinated
compounds, including for example: C.sub.3H.sub.2F.sub.4CI (such as
2-chloro-3,3,3-trifluoro-1-propene (including HCFO-1233xf) and
1-chloro-3,3,3-trifluoro-1-propene (including all isomers of
HCFO-1233zd).
[0120] In certain preferred embodiments of the present invention,
the compositions include at least one fluoroalkenes of Formula II
below:
##STR00011## [0121] where each R is independently CI, F, Br, I or H
[0122] R' is (CRAY, [0123] Y is CRF.sub.2 [0124] and n is 0 or
1.
[0125] In highly preferred embodiments, Y is CF.sub.3, n is 0 and
at least one of the remaining Rs is F.
[0126] Applicants believe that, in general, the compounds of the
above identified Formulas I and II, when included in the present
compositions, are generally effective and exhibit utility all of
the uses identified above, including particularly in refrigerant
compositions, blowing agent compositions, compatibilizers,
aerosols, propellants, fragrances, flavor formulations, and solvent
compositions of the present invention. However, applicants have
surprisingly and unexpectedly found that certain of the compounds
having a structure in accordance with the formulas described above
exhibit a highly desirable low level of toxicity compared to other
of such compounds. As can be readily appreciated, this discovery is
of potentially enormous advantage and benefit for the formulation
of not only refrigerant compositions, but also any and all
compositions, which would otherwise contain relatively toxic
compounds satisfying the formulas described above. More
particularly, applicants believe that a relatively low toxicity
level is associated with compounds of Formula II, preferably
wherein Y is CF.sub.3, wherein at least one R on the unsaturated
terminal carbon is H, and at least one of the remaining Rs is F.
Applicants believe also that all structural, geometric and
stereoisomers of such compounds are effective and of beneficially
low toxicity.
[0127] In highly preferred embodiments, especially embodiments
comprising the low toxicity compounds described above, n is zero.
In certain highly preferred embodiments the compositions of the
present invention comprise one or more tetrafluoropropenes. The
term "HFO-1234" is used herein to refer to all tetrafluoropropenes.
Among the tetrafluoropropenes, HFO-1234yf is highly preferred for
use in connection with heat transfer compositions, methods and
systems.
[0128] In other embodiments, it may be preferred to use either or
both cis- and trans-1, 3, 3, 3-tetrafluoropropene (HFO-1234ze). The
term HFO-1234ze is used herein generically to refer to 1, 3, 3,
3-tetrafluoropropene, independent of whether it is the cis- or
trans- form. The terms "cisHFO-1234ze" and "transHFO-1234ze" are
used herein to describe the cis- and trans- forms of 1, 3, 3,
3-tetrafluoropropene respectively. The term "HFO-1234ze" therefore
includes within its scope cisHFO-1234ze, trans HF0-1234ze, and all
combinations and mixtures of these.
[0129] Although the properties of cisHFO-1234ze and transHFO-1234ze
differ in at least some respects, it is contemplated that each of
these compounds is adaptable for use, either alone or together with
other compounds including its stereoisomer, in connection with each
of the applications, methods and systems described herein. For
example, while transHFO-1234ze may be preferred for use in certain
refrigeration systems because of its relatively low boiling point
(-19.degree. C.), it is nevertheless contemplated that
cisHFO-1234ze, with a boiling point of +9.degree. C., also has
utility in certain refrigeration systems of the present invention.
Accordingly, it is to be understood that the terms "HFO-1234ze" and
1, 3, 3, 3-tetrafluoropropene refer to both stereo isomers, and the
use of this term is intended to indicate that each of the cis-and
trans- forms applies and/or is useful for the stated purpose unless
otherwise indicated.
[0130] HFO-1234 compounds are known materials and are listed in
Chemical Abstracts databases. The production of fluoropropenes such
as CF3CH=CH2 by catalytic vapor phase fluorination of various
saturated and unsaturated halogen-containing C3 compounds is
described in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786,
each of which is incorporated herein by reference. EP 974,571, also
incorporated herein by reference, discloses the preparation of
1,1,1,3-tetrafluoropropene by contacting
1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a
chromium-based catalyst at elevated temperature, or in the liquid
phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2.
In addition, methods for producing compounds in accordance with the
present invention are described, by way of nonlimiting example, in
connection with pending U.S. patent application Ser. No. 10/694,272
"Process for Producing Fluoropropenes" and in U.S. Provisional
Application 60/733355, filed Nov. 3, 2005, each of which is
incorporated herein by reference.
[0131] The present compositions, particularly those comprising
HFO-1234, and HFO-1234yf, are believed to possess properties that
are advantageous for a number of important reasons. For example,
applicants believe, based at least in part on mathematical
modeling, that the fluoroolefins of the present invention will not
have a substantial negative affect on atmospheric chemistry, being
negligible contributors to ozone depletion in comparison to some
other halogenated species. The preferred compositions of the
present invention thus have the advantage of not contributing
substantially to ozone depletion. The preferred compositions also
do not contribute substantially to global warming compared to many
of the hydrofluoroalkanes presently in use.
[0132] The amount of the Formula I compounds, particularly
HFO-1234, contained in the present compositions can vary widely,
depending the particular application, and compositions containing
more than about 1% by weight and less than 100% of the compound are
within broad the scope of the present invention. In preferred
embodiments, the present compositions comprise HFO-1234, preferably
HFO-1234yf, in amounts from about 5% by weight to about 99% by
weight, and even more preferably from about 5% to about 95%.
[0133] By way of illustration, but not necessarily by way of
limitation, certain preferred embodiments of the present
compositions may comprise, in addition to the iodocarbon compounds
of the present invention (and in addition to the stabilizer
compound when present), fluoroalkene compounds of the present
invention and/or HFCs in accordance with broad, intermediate and
more specific composition ranges (all amounts understood to be
preceded by "about") are indicated in the table below, with the
percentages being based on the total weight of the three components
indicated in the Table 1 below.
TABLE-US-00001 TABLE 1 BROAD, INTERMEDIATE, MORE SPECIFIC wt % wt %
wt % Fluoralkene(s) 0-95 5-85 5-80 or 0 .sup. Iodocarbon(s)
>0-99 10-90 15-90 or 60-80 HFC(s) 0-95 5-85 5-80 or 20-40
[0134] Certain preferred embodiments of the present compositions
may comprise, in addition to the stabilizer which is preferably
present and any oil or lubricant that is also preferably present in
the heat transfer fluids in accordance with the present invention,
CF.sub.3I and one or more fluoroalkene compounds. In certain
preferred forms the fluoroalkene consists essentially of
tetrafluoropropene, more preferably HFO-1234yf. Broad, intermediate
and more specific composition ranges (all amounts understood to be
preceded by "about") are indicated in the table below, with the
percentages being based on the total of the components is indicated
in the Table 2 below.
TABLE-US-00002 TABLE 2 BROAD, INTERMEDIATE, MORE SPECIFIC, wt % wt
% wt % Fluoralkene(s) 10-95 50-90 60-80 (pref. HFO- 1234yf)
CF.sub.3I >0-<90 10-50 20-40
[0135] Certain highly preferred embodiments of the present
invention comprise heat transfer fluids, particularly for use in
automotive air conditioning systems, comprising from about 65 to
about 75 wt % of HFO-1234yf and from about 25 to about 35 wt %
CF3I, and even more preferably about 70 wt % of HFO-1234yf and
about 30 wt % CF.sub.3I, said percentages being based on the total
combined weight of HFO and CF.sub.3I.
[0136] Certain preferred embodiments of the present compositions
may comprise, in addition to any stabilizer that is present in
accordance with the present invention, CF.sub.3I, certain
fluoroalkene compounds (preferably HFO-1234ze) of the present
invention, and/or certain HFCs (preferably HFC-152a) in accordance
with broad, intermediate and more specific composition ranges (all
amounts understood to be preceded by "about") as indicated in the
table below, with the percentages being based on the total of the
three components indicated in the Table 3.
TABLE-US-00003 TABLE 3 BROAD, INTERMEDIATE, MORE SPECIFIC, wt % wt
% wt % Fluoralkene(s) 0-85 0-85 0 (pref. HFO- 1234ze) CF.sub.3I
>0-<100 10-<100 60-80 HFC(s) (pref. 0-95 25-90 20-40
HFC-152a)
[0137] Certain preferred embodiments of the present compositions
may comprise, in addition to the stabilizer of the present
invention, CF.sub.3I, certain fluoroalkene compounds of the present
invention, and/or certain HFCs (preferably HFC-32) in accordance
with broad, intermediate and more specific composition ranges (all
amounts understood to be preceded by "about") as indicated in the
table below, with the percentages being based on the total of the
three components indicated in the Table 4.
TABLE-US-00004 TABLE 4 BROAD, INTERMEDIATE, MORE SPECIFIC, wt % wt
% wt % Fluoralkene(s) 0-75 0-75 0-75 CF.sub.3I >0-40 >1-33
>1-15 HFC(s) (pref. 50-<100 65-<95 85-99 HFC-32)
2--Lubricants
[0138] According to certain aspects of the present invention, the
composition comprises, in addition to the iodocarbon compound(s), a
lubricant or oil. Any of a variety of conventional lubricants may
be used in the compositions of the present invention. Such
compositions are especially well adapted for use as refrigerants in
heating or cooling cycle equipment, as explained more fully
hereinafter.The composition then contains a at least one lubricant
having hydrogen atoms and carbon atoms, wherein no more than 17% of
the total number of hydrogen atoms which are attached to a carbon
atom are tertiary hydrogen atoms. Preferably the lubricant has less
than 1% of the total number of hydrogen atoms which are attached to
a carbon atom are tertiary hydrogen atoms, and more preferably has
no tertiary hydrogen atoms, that is wherein about 0% of the total
number of hydrogen atoms which are attached to a carbon atom are
tertiary hydrogen atoms.
[0139] It preferably also has a relatively low percentage of
oxygen, and preferably no oxygen in the molecule. It is also
generally preferred to use a lubricant or oil having little
inherent concentration of polar solvent, particularly water. An
important requirement for the lubricant is that there must be
enough lubricant returning to the compressor of the system such
that the compressor is lubricated. Thus suitability of the
lubricant is determined partly by the refrigerant/lubricant
characteristics and partly by the system characteristics. Examples
of suitable lubricants include mineral oil, alkyl benzenes,
including a synthetic lubricant, specifically polyalkyleneglycol
(PAG) lubricant, and preferably a PAG consisting essentially of 2
or more oxypropylene groups and having a viscosity of from about 10
to about 200 centistokes at about 37.degree. C. (sold under the
trade designation ND-8 by Idemitsu Kosan), and PAG sold under the
trade designation RL-897 by DOW, polyvinyl ethers (PVEs), and the
like. Preferred lubricants include a naphthenic mineral oil, a
paraffinic mineral oil, an ester oil, a polyalkylene glycol, a
polyvinyl ether, an alkyl benzene, a polyalphaolefin, a polyester,
a polyol ester, or combinations thereof. Mineral oil, which
comprises paraffin oil or naphthenic oil, is commercially
available. Commercially available mineral oils include Witco LP 250
(registered trademark) from Witco, Zerol 300 (registered trademark)
from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015
from Calumet. Commercially available alkyl benzene lubricants
include Zerol 150 (registered trademark). Commercially available
esters include neopentyl glycol dipelargonate, which is available
as Emery 2917 (registered trademark) and Hatcol 2370 (registered
trademark). Other useful esters include phosphate esters, dibasic
acid esters, and fluoroesters. In some cases, hydrocarbon based
oils are have sufficient solubility with the refrigerant that is
comprised of an iodocarbon, the combination of the iodocarbon and
the hydrocarbon oil might more stable than other types of
lubricant. Such combination may therefore be advantageous.
Preferred lubricants include polyalkylene glycols and esters.
Polyalkylene glycols are highly preferred in certain embodiments
because they are currently in use in particular applications such
as mobile air-conditioning. Mixtures of different lubricants may be
used.
[0140] In one aspect of the present invention involves a selection
of a lubricant comprising in major proportion by weight, and even
more preferably at least about 75% by weight of alkyl benzene-based
compounds, mineral oil compounds, and combinations of these. With
respect to alkyl benzene, applicants have found that such compounds
are preferred from among the numerous other lubricant compounds
which have heretofore been available due to the relatively high
level of miscibility in the preferred refrigerant compositions and
the relatively high level of stability that such molecules exhibit
in the heat transfer compositions and the heat transfer systems of
the present invention. Another preferred molecule for use in
connection with the present invention is referred to herein, by way
of convenience but not by way of limitation, as ethylene
oxide/propylene oxide (EO/PO) molecules. Such molecules in
preferred embodiments have the structure indicated below:
H.sub.3C[--O--CHCH.sub.3-CH.sub.2].sub.n-[O--CH.sub.2CH.sub.2].sub.m-OCH-
.sub.3
[0141] Applicants have found that such EO/PO molecules, which are
also referred to herein as "dual capped EO/PO molecules" due to the
presence of the methyl radical on each end of the molecule, or
alternatively other relatively low chain length alkyl group" can
provide the ability to adjust, to suit each particular application,
the n and the m values. In this way, a lubricant molecule can be
selected to achieve a highly advantageous combination of
miscibility and stability. An advantage that dual capped molecules
perform substantially better in many respects and similar molecules
which are only capped at one end, as illustrated in the examples
below. U.S. Pat. No. 4,975,212, which is incorporated herein by
reference, discloses techniques for capping molecules of this type.
Although it is not generally preferred, is also possible to combine
the preferred lubricants of the present invention with one or more
conventional lubricants.
[0142] Suitable polyol ester lubricants suitable for air
conditioning or refrigeration use are typically prepared by the
condensation of a poly alcohol or polyol compound such as
pentaerythritol, dipentaerythritol, neopentyl glycol or
trimethylpropanol with either pure or mixed, linear or branched
aliphatic carboxylic acids such as a linear or branched
monocarboxylic acid having from about 4 to about 10 carbon atoms.
Polyol ester base stocks polyols are available from Hatco
Corporation. For example Hatcol 3307 is a pure polyol ester
basestock based on neopentyl glycol. Hatcol 3329 and Hatcol 3504
are a pure polyol ester refrigeration base stocks based on
pentaerythritol mixed fatty acids esters. Hatcol 3316 is a polyol
ester of dipentaerythritol and short chain fatty acids. Other
examples of such polyol ester lubricant formulations include the
Cognis ProEco.TM. line of Polyol ester refrigeration lubricants,
ICI's EMKARATE RL line of polyol esters, as well as polyol ester
lubricants provided by Lubrizol subsidiary CPI Engineering
Services, Inc. such as Solest. Preferred compositions according to
the invention, include a lubricant in amounts of from about 20 wt.
% to about 50 wt. %, preferably from about 20 wt. %to about 30 wt.
% by weight of the composition.
3--Other Components
[0143] Any of a variety of other additives may be used in the
compositions of the present invention. Examples of suitable
additives include metal passivators such as nitromethane, extreme
pressure (EP) additives that improve the lubricity and load bearing
characteristics of the lubricant. Examples of EP additives are
described in U.S. Pat. Ser. No. 4,755,316 (Table D) and
incorporated here. Examples of EP additives are organophosphates
including Lubrizol.RTM. 8478 manufactured by the Lubrizol
Corporation. Corrosion inhibitors are also useful and disclosed in
Ser. No. 4,755,316, Table D.
II. Heat Transfer Compositions
[0144] Although it is contemplated that the compositions of the
present invention may include each of the compounds mentioned
herein in widely ranging amounts, it is generally preferred that
heat transfer compositions, and particularly refrigerant
compositions of the present invention comprise iodocarbon
compound(s), and even more preferably C1-C3 iodofluorocarbon
compounds, in an amount that is at least about 25% by weight of the
composition. In certain preferred embodiments in which the
composition comprises HFC and particularly HFC-152a, the
compositions comprise at least about 40% by weight, and even more
preferably at least about 50% by weight of HFC-152a.
[0145] Preferred refrigerant or heat transfer compositions
according to the present invention, especially those used in vapor
compression systems, include a lubricant, generally in amounts of
from about 30 to about 50% by weight of the composition. An
important requirement for the lubricant is that there must be
enough lubricant returning to the compressor of the system such
that the compressor is lubricated. Thus suitability of the
lubricant is determined partly by the refrigerant/lubricant
characteristics and partly by the system characteristics. Examples
of suitable lubricants include mineral oil, alkyl benzenes, polyol
esters, including polyalkylene glycols, polyvinyl ethers (PVEs),
and the like. Mineral oil, which comprises paraffin oil or
naphthenic oil, is commercially available. Commercially available
mineral oils include Witco LP 250 (registered trademark) from
Witco, Zerol 300 (registered trademark) from Shrieve Chemical,
Sunisco 3GS from Witco, and Calumet R015 from Calumet. Commercially
available alkyl benzene lubricants include Zerol 150 (registered
trademark). Commercially available esters include neopentyl glycol
dipelargonate, which is available as Emery 2917 (registered
trademark) and Hatcol 2370 (registered trademark). Other useful
esters include phosphate esters, dibasic acid esters, and
fluoroesters. In some cases, hydrocarbon based oils are have
sufficient solubility with the refrigerant that is comprised of an
iodocarbon, the combination of the iodocarbon and the hydrocarbon
oil might more stable than other types of lubricant. Such
combination may therefore be advantageous. Preferred lubricants
include polyalkylene glycols and esters. Polyalkylene glycols are
highly preferred in certain embodiments because they are currently
in use in particular applications such as mobile air-conditioning.
Of course, different mixtures of different types of lubricants may
be used.
[0146] Preferred forms of the present compositions may also include
a compatibilizer, such as propane, for the purpose of aiding
compatibility and/or solubility of the lubricant. Such
compatibilizers, including propane, butanes and pentanes, are
preferably present in amounts of from about 0.5 to about 5 percent
by weight of the composition. Combinations of surfactants and
solubilizing agents may also be added to the present compositions
to aid oil solubility, as disclosed by U.S. Pat. Ser. No.
6,516,837, the disclosure of which is incorporated by
reference.
[0147] Many existing refrigeration systems are currently adapted
for use in connection with existing refrigerants, and certain
compositions of the present invention are believed to be adaptable
for use in many of such systems, either with or without system
modification. In many applications the compositions of the present
invention may provide an advantage as a replacement in systems,
which are currently based on refrigerants having a relatively high
capacity. Furthermore, in embodiments where it is desired to use a
lower capacity refrigerant composition of the present invention,
for reasons of cost for example, to replace a refrigerant of higher
capacity, such embodiments of the present compositions provide a
potential advantage. Thus, it is preferred in certain embodiments
to use compositions of the present invention, particularly
compositions comprising a substantial proportion of, and in some
embodiments comprising a major proportion of transHFO-1234yf, as a
replacement for existing refrigerants, such as HFC-134a. In certain
applications, the refrigerants of the present invention potentially
permit the beneficial use of larger displacement compressors,
thereby resulting in better energy efficiency than other
refrigerants, such as HFC-134a. Therefore the refrigerant
compositions of the present invention, particularly compositions
comprising transHFP-1234ze, provide the possibility of achieving a
competitive advantage on an energy basis for refrigerant
replacement applications.
[0148] It is contemplated that the compositions of the present,
including particularly those comprising HFO-1234 (and particularly
HFO-1234yf), also have advantage (either in original systems or
when used as a replacement for refrigerants such as R-12 and
R-500), in chillers typically used in connection with commercial
air conditioning systems. In certain of such embodiments it is
preferred to include in the present HFO-1234 compositions from
about 0.5 to about 60% of a flammability suppressant, more
preferably from about 20 to about 50 wt %, preferably an iodocarbon
such as CF.sub.3I in accordance with the present invention.
[0149] The present methods, systems and compositions are thus
adaptable for use in connection with automotive air conditioning
systems and devices, commercial refrigeration systems and devices,
chillers, residential refrigerator and freezers, general air
conditioning systems, heat pumps, ORCs, CRCs and the like.
III. Blowing Agents, Foams and Foamable Compositions
[0150] Blowing agents may also comprise or constitute one or more
of the present compositions. As mentioned above, the compositions
of the present invention may include the iodocarbon compound(s) and
the diene-based compound(s) of the present invention in widely
ranging amounts. It is generally preferred, however, that for
preferred compositions for use as blowing agents in accordance with
the present invention the iodocarbon compound(s) are present in an
amount that is at least about 1% by weight, and even more
preferably at least about 50% by weight, of the composition.
[0151] In certain preferred embodiments, the blowing agent
compositions of the present invention and include, in addition to
HFO-1234 (preferably HFO-1234ze) one or more of the following
components as a co-blowing agent, filler, vapor pressure modifier,
or for any other purpose: [0152] Difluoromethane (HFC-32); [0153]
Pentafluoroethane (HFC-125); [0154] 1,1,2,2-tetrafluoroethane
(HFC-134); [0155] 1,1,1,2-Tetrafluoroethane (HFC-134a); [0156]
Difluoroethane (HFC-152a); [0157] 1,1,1,2,3,3,3-Heptafluoropropane
(HFC-227ea); [0158] 1,1,1,3,3,3-hexafluoropropane (HFC-236fa);
[0159] 1,1,1,3,3-pentafluoropropane (HFC-245fa); [0160]
1,1,1,3,3-pentafluorobutane (HFC-365mfc); [0161] Water; [0162]
CO.sub.2; [0163] methyl formate and its derivatives; [0164]
alcohols (C1-C4) and derivatives thereof; [0165] ketones and
derivatives thereof; [0166] aldehydes and derivatives thereof;
[0167] ethers/diethers and derivatives thereof; [0168] carbonates
and derivatives thereof; [0169] dicarbonates and derivatives
thereof; [0170] and carboxylic acids and their derivatives.
[0171] It is contemplated that the blowing agent compositions of
the present invention may comprise cisHFO-1234ze, transHFO1234ze or
combinations thereof. In certain preferred embodiments, the blowing
agent composition of the present invention comprise a combination
of cisHFO-1234ze and transHFO1234ze in a cis:trans weight ratio of
from about 1:99 to about 30:70, and even more preferably from about
1:99 to about 5:95.
[0172] In other embodiments, the invention provides foamable
compositions, and preferably polyurethane, polyisocyanurate,
phenolic foams, extruded thermoplastic foam compositions, integral
skin foams and one or two component pressurized froth foams
prepared using the compositions of the present invention. In such
foam embodiments, one or more of the present compositions are
included as or part of a blowing agent in a foamable composition,
which composition preferably includes one or more additional
components capable of reacting and/or foaming under the proper
conditions to form a foam or cellular structure, as is well known
in the art. The invention also relates to foam, and preferably
closed cell foam, prepared from a polymer foam formulation
containing a blowing agent comprising the compositions of the
invention. In yet other embodiments, the invention provides
foamable compositions comprising thermoplastic foams, such as such
as polystyrene (PS), polyethylene (PE), polypropylene (PP) and
polyethyleneterpthalate (PET) foams, preferably low-density
foams.
[0173] In certain preferred embodiments, dispersing agents, cell
stabilizers, surfactants and other additives may also be
incorporated into the blowing agent compositions of the present
invention. Surfactants are optionally but preferably added to serve
as cell stabilizers. Some representative materials are sold under
the names of DC-193, B-8404, and L-5340 which are, generally,
polysiloxane polyoxyalkylene block co-polymers such as those
disclosed in U.S. Pat. Ser. Nos. 2,834,748; 2,917,480; and
2,846,458, each of which is incorporated herein by reference. Other
optional additives for the blowing agent mixture may include flame
retardants such as tri(2-chloroethyl)phosphate,
tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,
tri(1,3-dichloropropyl) phosphate, diammonium phosphate, various
halogenated aromatic compounds, antimony oxide, aluminum
trihydrate, polyvinyl chloride, and the like.
IV. Propellant Compositions
[0174] In another aspect, the present invention provides propellant
compositions comprising or consisting essentially of a composition
of the present invention, such propellant compositions preferably
being sprayable compositions. The propellant compositions of the
present invention preferably comprise a material to be sprayed and
a propellant comprising, consisting essentially of, or consisting
of a composition in accordance with the present invention. Inert
ingredients, solvents, and other materials may also be present in
the sprayable mixture. Preferably, the sprayable composition is an
aerosol. Suitable materials to be sprayed include, without
limitation, cosmetic materials such as deodorants, perfumes, hair
sprays, cleansers, and polishing agents as well as medicinal
materials such as anti-asthma and anti-halitosis medications, and
any other medication or the like, including preferably any other
medicament or agent intended to be inhaled. The medicament or other
therapeutic agent is preferably present in the composition in a
therapeutic amount, with a substantial portion of the balance of
the composition comprising a compound of Formula I of the present
invention, preferably HFO-1234, and even more preferably
HFO-1234ze.
[0175] Aerosol products for industrial, consumer or medical use
typically contain one or more propellants along with one or more
active ingredients, inert ingredients or solvents. The propellant
provides the force that expels the product in aerosolized form.
While some aerosol products are propelled with compressed gases
like carbon dioxide, nitrogen, nitrous oxide and even air, most
commercial aerosols use liquefied gas propellants. The most
commonly used liquefied gas propellants are hydrocarbons such as
butane, isobutane, and propane. Dimethyl ether and HFC-152a
(1,1-difluoroethane) are also used, either alone or in blends with
the hydrocarbon propellants. Unfortunately, all of these liquefied
gas propellants are highly flammable and their incorporation into
aerosol formulations will often result in flammable aerosol
products.
[0176] Applicants have come to appreciate the continuing need for
nonflammable, liquefied gas propellants with which to formulate
aerosol products. The present invention provides compositions of
the present invention, particularly and preferably compositions
comprising HFO-1234, and even more preferably HFO-1234ze and/or
HFO-1234yf, for use in certain industrial aerosol products,
including for example spray cleaners, lubricants, and the like, and
in medicinal aerosols, including for example to deliver medications
to the lungs or mucosal membranes. Examples of this includes
metered dose inhalers (MDIs) for the treatment of asthma and other
chronic obstructive pulmonary diseases and for delivery of
medicaments to accessible mucous membranes or intranasally. The
present invention thus includes methods for treating ailments,
diseases and similar health related problems of an organism (such
as a human or animal) comprising applying a composition of the
present invention containing a medicament or other therapeutic
component to the organism in need of treatment. In certain
preferred embodiments, the step of applying the present composition
comprises providing a MDI containing the composition of the present
invention (for example, introducing the composition into the MDI)
and then discharging the present composition from the MDI.
[0177] The compositions of the present invention, particularly
compositions comprising or comprising in major proportion HFO-1234
(preferably HFO-1234ze and/or HFO-1234yf), are capable of providing
nonflammable, liquefied gas propellant and aerosols that do not
contribute substantially to global warming. The present
compositions can be used to formulate a variety of industrial
aerosols or other sprayable compositions such as contact cleaners,
dusters, lubricant sprays, and the like, and consumer aerosols such
as personal care products, household products and automotive
products. HFO-1234ze is particularly preferred for use as an
important component of propellant compositions for in medicinal
aerosols such as metered dose inhalers. The medicinal aerosol
and/or propellant and/or sprayable compositions of the present
invention in many applications include, in addition to compound of
formula (I) or (II) (preferably HFO-1234ze), a medicament such as a
beta-agonist, a corticosteroid or other medicament, and,
optionally, other ingredients, such as surfactants, solvents, other
propellants, flavorants and other excipients. The compositions of
the present invention, unlike many compositions previously used in
these applications, have good environmental properties and are not
considered to be potential contributors to global warming. The
present compositions therefore provide in certain preferred
embodiments substantially nonflammable, liquefied gas propellants
having very low Global Warming potentials.
V. Flavorants and Fragrances
[0178] The compositions of the present invention also provide
advantage when used as part of, and in particular as a carrier for,
flavor formulations and fragrance formulations. The suitability of
the present compositions for this purpose is demonstrated by a test
procedure in which 0.39 grams of Jasmone were put into a heavy
walled glass tube. 1.73 grams of R-1234ze were added to the glass
tube. The tube was then frozen and sealed. Upon thawing the tube,
it was found that the mixture had one liquid phase. The solution
contained 20 wt. % Jasome and 80 wt. % R-1234ze, thus establishing
its favorable use as a carrier or part of delivery system for
flavor formulations, in aerosol and other formulations. It also
establishes its potential as an extractant of fragrances, including
from plant matter. In certain embodiments, it may be preferred to
use the present composition in extraction applications with the
present fluid in its supercritical state. This and other
applications of involving use of the present compositions in the
supercritical or near supercritical state are described
hereinafter.
VI. Stabilizer Compositions
[0179] The present invention provides in one aspect a stabilizer
composition for use as an additive in any one of the above-noted
compositions, or more generally as an additive for any composition,
which contains or will be exposed to iodocarbon compound(s). In
such compositions, therefore, there is no requirement for the
presence of iodocarbon compound(s), but the presence of a
diene-based compound as described above is required. In preferred
embodiments, the stabilizer composition of the present invention
comprises a combination of diene-based compound(s) and at least one
additional stabilizer selected from the group of additional
stabilizers described above, preferably selected from the group
consisting of phenol compound(s), epoxy compound(s), phosphites,
phosphates and combinations of these.
VI. Methods and Systems
[0180] The compositions of the present invention are useful in
connection with numerous methods and systems, including as heat
transfer fluids in methods and systems for transferring heat, such
as refrigerants used in refrigeration, air conditioning and heat
pump systems. The present compositions are also advantageous for
use in systems and methods of generating aerosols, preferably
comprising or consisting of the aerosol propellant in such systems
and methods. Methods of forming foams and methods of extinguishing
and suppressing fire are also included in certain aspects of the
present invention. The present invention also provides in certain
aspects methods of removing residue from articles in which the
present compositions are used as solvent compositions in such
methods and systems.
[0181] A. Heat Transfer Methods
[0182] The preferred heat transfer methods generally comprise
providing a composition of the present invention and causing heat
to be transferred to or from the composition, preferably by
changing the phase of the composition and/or by sensible heat
transfer. For example, the present methods provide cooling by
absorbing heat from a fluid or article, preferably by evaporating
the present refrigerant composition in the vicinity of the body or
fluid to be cooled to produce vapor comprising the present
composition. Preferably the methods include the further step of
compressing the refrigerant vapor, usually with a compressor or
similar equipment to produce vapor of the present composition at a
relatively elevated pressure. Generally, the step of compressing
the vapor results in the addition of heat to the vapor, thus
causing an increase in the temperature of the relatively high
pressure vapor. Preferably, the present methods include removing
from this relatively high temperature, high pressure vapor at least
a portion of the heat added by the evaporation and compression
steps. The heat removal step preferably includes condensing the
high temperature, high pressure vapor while the vapor is in a
relatively high pressure condition to produce a relatively high
pressure liquid comprising a composition of the present invention.
This relatively high pressure liquid preferably then undergoes a
nominally isoenthalpic reduction in pressure to produce a
relatively low temperature, low pressure liquid. In such
embodiments, it is this reduced temperature refrigerant liquid
which is then vaporized by heat transferred from the body or fluid
to be cooled.
[0183] In another process embodiment of the invention, the
compositions of the invention may be used in a method for producing
heating which comprises condensing a refrigerant comprising the
compositions in the vicinity of a liquid or body to be heated. Such
methods, as mentioned hereinbefore, frequently are reverse cycles
to the refrigeration cycle described above.
[0184] B. Foam Blowing Methods
[0185] One embodiment of the present invention relates to methods
of forming foams, and preferably polyurethane and polyisocyanurate
foams. The methods generally comprise providing a blowing agent
composition of the present invention, adding (directly or
indirectly) the blowing agent composition to a foamable
composition, and reacting the foamable composition under conditions
effective to form a foam or cellular structure, as is well known in
the art. 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. In general, such preferred methods comprise
preparing polyurethane or polyisocyanurate foams by combining an
isocyanate, a polyol or mixture of polyols, a blowing agent or
mixture of blowing agents comprising one or more of the present
compositions, and other materials such as catalysts, surfactants,
and optionally, flame retardants, colorants, or other
additives.
[0186] It is convenient in many applications to provide the
components for polyurethane or polyisocyanurate foams in
pre-blended formulations. Most typically, the foam formulation is
pre-blended into two components. The isocyanate and optionally
certain surfactants and blowing agents comprise the first
component, commonly referred to as the "A" component. The polyol or
polyol mixture, surfactant, catalysts, blowing agents, flame
retardant, and other isocyanate reactive components comprise the
second component, commonly referred to as the "B" component.
Accordingly, polyurethane or polyisocyanurate foams are readily
prepared by bringing together the A and B side components either by
hand mix for small preparations and, preferably, machine mix
techniques to form blocks, slabs, laminates, pour-in-place panels
and other items, spray applied foams, froths, and the like.
Optionally, other ingredients such as fire retardants, colorants,
blowing agents, and even other polyols can be added as a third
stream to the mix head or reaction site. Also optionally, each of
these components can be added partially to the B-component and
partially as a third stream to the mix head or reaction site. Most
preferably, however, they are all incorporated into one B-component
as described above.
[0187] It is also possible to produce thermoplastic foams using the
compositions of the invention. For example, conventional
polystyrene and polyethylene formulations may be combined with the
compositions in a conventional manner to produce rigid foams.
[0188] C. Cleaning Methods
[0189] The present invention also provides methods of removing
containments from a product, part, component, substrate, or any
other article or portion thereof by applying to the article a
composition of the present invention. For the purposes of
convenience, the term "article" is used herein to refer to all such
products, parts, components, substrates, and the like and is
further intended to refer to any surface or portion thereof.
Furthermore, the term "contaminant" is intended to refer to any
unwanted material or substance present on the article, even if such
substance is placed on the article intentionally. For example, in
the manufacture of semiconductor devices it is common to deposit a
photoresist material onto a substrate to form a mask for the
etching operation and to subsequently remove the photoresist
material from the substrate. The term "contaminant" as used herein
is intended to cover and encompass such a photo resist
material.
[0190] Preferred methods of the present invention comprise applying
the present composition to the article. Although it is contemplated
that numerous and varied cleaning techniques can employ the
compositions of the present invention to good advantage, it is
considered to be particularly advantageous to use the present
compositions in connection with supercritical cleaning techniques.
Supercritical cleaning is disclosed in U.S. Pat. No. 6,589,355,
which is assigned to the assignee of the present invention and
incorporated herein by reference. For supercritical cleaning
applications, is preferred in certain embodiments to include in the
present cleaning compositions, in addition to the HFO-1234
(preferably HFO-1234ze), one or more additional components, such as
CO.sub.2 and other additional components known for use in
connection with supercritical cleaning applications. It may also be
possible and desirable in certain embodiments to use the present
cleaning compositions in connection with particular vapor
degreasing and solvent cleaning methods, with vapor degreasing and
solvent cleaning methods being particularly preferred for certain
applications, especially those involving intricate parts and
difficult to remove soils. Preferred vapor degreasing and solvent
cleaning methods consist of exposing an article, preferably at room
temperature, to the vapors of a boiling solvent. Vapors condensing
on the object have the advantage of providing a relatively clean,
distilled solvent to wash away grease or other contamination. Such
processes thus have an additional advantage in that final
evaporation of the present solvent composition from the object
leaves behind relatively little residue as compared to the case
where the object is simply washed in liquid solvent.
[0191] For applications in which the article includes contaminants
that are difficult to remove, it is preferred that the present
methods involve raising the temperature of the solvent composition
of the present invention above ambient or to any other temperature
that is effective in such application to substantially improve the
cleaning action of the solvent. Such processes are also generally
preferred for large volume assembly line operations where the
cleaning of the article, particularly metal parts and assemblies,
must be done efficiently and quickly.
[0192] In preferred embodiments, the cleaning methods of the
present invention comprise immersing the article to be cleaned in
liquid solvent at an elevated temperature, and even more preferably
at about the boiling point of the solvent. In such operations, this
step preferably removes a substantial amount, and even more
preferably a major portion, of the target contaminant from the
article. This step is then preferably followed by immersing the
article in solvent, preferably freshly distilled solvent, which is
at a temperature below the temperature of the liquid solvent in the
preceding immersion step, preferably at about ambient or room
temperature. The preferred methods also include the step of then
contacting the article with relatively hot vapor of the present
solvent composition, preferably by exposing the article to solvent
vapors rising from the hot/boiling solvent associated with the
first mentioned immersion step. This preferably results in
condensation of the solvent vapor on the article. In certain
preferred embodiments, the article may be sprayed with distilled
solvent before final rinsing.
[0193] It is contemplated that numerous varieties and types of
vapor degreasing equipment are adaptable for use in connection with
the present methods. One example of such equipment and its
operation is disclosed by Sherliker et al. in U.S. Pat. Ser. No.
3,085,918, which is incorporated herein by reference. The equipment
disclosed in Sherliker et al includes a boiling sump for containing
a solvent composition, a clean sump for containing distilled
solvent, a water separator, and other ancillary equipment.
[0194] The present cleaning methods may also comprise cold cleaning
in which the contaminated article is either immersed in the fluid
composition of the present invention under ambient or room
temperature conditions or wiped under such conditions with rags or
similar objects soaked in solvents.
[0195] Certain preferred cleaning methods comprise flushing the
substrate with a composition in accordance with the present
invention.
[0196] D. Flammability Reduction Methods
[0197] According to certain other preferred embodiments, the
present invention provides methods for reducing the flammability of
fluids, said methods comprising adding a compound or composition of
the present invention to said fluid. The flammability associated
with any of a wide range of otherwise flammable fluids may be
reduced according to the present invention. For example, the
flammability associated with fluids such as ethylene oxide,
flammable hydrofluorocarbons and hydrocarbons, including: HFC-152a,
1,1,1-trifluoroethane (HFC-143a), difluoromethane (HFC-32),
propane, hexane, octane, and the like can be reduced according to
the present invention. For example, certain compositions according
to the present invention may include CF.sub.3I and HFC-152a in
amounts, based on the total weight of these two components, of from
greater than 0 to about 38.5% of CF.sub.3I, more preferably from
greater than 0 to about 35% of CF.sub.3I, and from about 61.5 to
less than 100, and even more preferably from about 65 to less than
about 100 of HFC-152a. For the purposes of the present invention, a
flammable fluid may be any fluid exhibiting flammability ranges in
air as measured via any standard conventional test method, such as
ASTM E-681, and the like.
[0198] Any suitable amounts of the present compounds or
compositions may be added to reduce flammability of a fluid
according to the present invention. As will be recognized by those
of skill in the art, the amount added will depend, at least in
part, on the degree to which the subject fluid is flammable and the
degree to which it is desired to reduce the flammability thereof.
In certain preferred embodiments, the amount of compound or
composition added to the flammable fluid is effective to render the
resulting fluid substantially non-flammable.
[0199] E. Flame Suppression Methods
[0200] The present invention further provides methods of
suppressing a flame, said methods comprising contacting a flame
with a fluid comprising a compound or composition of the present
invention. Any suitable methods for contacting the flame with the
present composition may be used. For example, a composition of the
present invention may be sprayed, poured, and the like onto the
flame, or at least a portion of the flame may be immersed in the
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
invention.
[0201] F. Sterilization Methods
[0202] Many articles, devices and materials, particularly for use
in the medical field, must be sterilized prior to use for the
health and safety reasons, such as the health and safety of
patients and hospital staff. The present invention provides methods
of sterilizing comprising contacting the articles, devices or
material to be sterilized with a compound or composition of the
present invention. Such methods may be either high or
low-temperature sterilization methods. In certain embodiments,
high-temperature sterilization comprises exposing the articles,
device or material to be sterilized to a hot fluid comprising a
compound or composition of the present invention at a temperature
of from about 250.degree. F. to about 270.degree. F., preferably in
a substantially sealed chamber. The process can be completed
usually in less than about 2 hours. However, some articles, such as
plastic articles and electrical components, cannot withstand such
high temperatures and require low-temperature sterilization.
[0203] Low-temperature sterilization of the present invention
involves the use of a compound or composition of the present
invention at a temperature of from about 100 to about 200 EF. The
compounds of the present invention may be combined with other
common chemical sterilants, including, for example, ethylene oxide
(EO), formaldehyde, hydrogen peroxide, chlorine dioxide, and ozone
to form a sterilant composition of the present invention.
[0204] The low-temperature sterilization of the present invention
is preferably at least a two-step process performed in a
substantially sealed, preferably air tight, chamber. In the first
step (the sterilization step), the articles having been cleaned and
wrapped in gas permeable bags are placed in the chamber. Air is
then evacuated from the chamber by pulling a vacuum and perhaps by
displacing the air with steam. In certain embodiments, it is
preferable to inject steam into the chamber to achieve a relative
humidity that ranges preferably from about 30% to about 70%. Such
humidities may maximize the sterilizing effectiveness of the
sterilant, which is introduced into the chamber after the desired
relative humidity is achieved. After a period of time sufficient
for the sterilant to permeate the wrapping and reach the
interstices of the article, the sterilant and steam are evacuated
from the chamber.
[0205] In the preferred second step of the process (the aeration
step), the articles are aerated to remove sterilant residues.
Removing such residues is particularly important in the case of
toxic sterilants, although it is optional in those cases in which
the substantially non-toxic compounds of the present invention are
used. Typical aeration processes include air washes, continuous
aeration, and a combination of the two. An air wash is a batch
process and usually comprises evacuating the chamber for a
relatively short period, for example, 12 minutes, and then
introducing air at atmospheric pressure or higher into the chamber.
This cycle is repeated any number of times until the desired
removal of sterilant is achieved. Continuous aeration typically
involves introducing air through an inlet at one side of the
chamber and then drawing it out through an outlet on the other side
of the chamber by applying a slight vacuum to the outlet.
Frequently, the two approaches are combined. For example, a common
approach involves performing air washes and then an aeration
cycle.
[0206] G. Stabilization Methods
[0207] The present invention further provides methods for
stabilizing a composition comprising iodocarbons, such as
trifluoroiodomethane. The preferred method steps comprise providing
at least one iodocarbon compound and stabilizing said at least one
iodocarbon compound by exposing the compound to a diene-based
compound(s) of the present invention. In many embodiments, the
iodocarbon providing step comprises providing a composition,
including the specific types of compositions described above, and
adding to such composition and a diene-based compound of the
present invention, preferably by mixing an effective amount of a
stabilizer composition of the present invention with said
iodocarbon composition.
[0208] H. Supercritical Methods
[0209] It is contemplated that in general many of the uses and
methods described herein can be carried out with the present
compositions in the supercritical or near supercritical state. For
example, the present compositions may be utilized in solvent and
solvent extraction applications mentioned herein, particularly for
use in connection with materials such as alkaloids (which are
commonly derived from plant sources), for example caffeine, codeine
and papaverine, for organometallic materials such as metallocenes,
which are generally useful as catalysts, and for fragrances and
flavors such as Jasmone.
[0210] The present compositions, preferably in their supercritical
or near supercritical state, can be used in connection with methods
involving the deposit of catalysts, particularly organometallic
catalysts, on solid supports. In one preferred embodiment, these
methods include the step of generating finely divided catalyst
particles, preferably by precipitating such catalyst particles from
the present compositions in the supercritical or near supercritical
state. It is expected that in certain preferred embodiments
catalysts prepared in accordance with the present methods will
exhibit excellent activity.
[0211] It is also contemplated that certain of the MDI methods and
devices described herein may utilize medicaments in finely divided
form, and in such situations it is contemplated that the present
invention provides methods which include the step of incorporating
such finely divided medicament particles, such as albuterol, into
the present fluids, preferably by dissolving such particles, in the
present composition, preferably in the supercritical or near
supercritical state. In cases where the solubility of the materials
is relatively low when the present fluids are in the supercritical
or near supercritical state, it may be preferred to use entrainers
such as alcohols.
[0212] It is also contemplated that the present compositions in the
supercritical or near supercritical state may be used to clean
circuit boards and other electronic materials and articles.
[0213] Certain materials may have very limited solubility in the
present compositions, particularly when in the supercritical or
near supercritical state. For such situations, the present
compositions may be used as anti-solvents for the precipitation of
such low solubility solutes from solution in another supercritical
or near supercritical solvent, such as carbon dioxide. For example,
supercritical carbon dioxide is utilized frequently used in the
extrusion process of thermoplastic foams, and the present
compositions may be used to precipitation certain materials
contained therein.
[0214] It is contemplated also that in certain embodiments it may
be desirable to utilize the present compositions when in the
supercritical or near supercritical state as a blowing agent.
EXAMPLES
[0215] The application is further explained in light of the
following examples, which are illustrative and not intended to be
limiting in any manner.
Example I
Example I-1
[0216] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I, PAG oil, and isoprene.
[0217] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of a composition
containing 99% by weight of PAG oil and 1% by weight of isoprene.
The resulting mixture is placed into a glass tube with metal
coupons of aluminum, steel, and copper, and the tube is then
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed and
observed.
[0218] Upon observation, the mixture is one phase, indicating that
the refrigerant has during the period remained miscible and soluble
in the PAG oil. In addition, the liquid in the tube is clear with a
light yellow color. The steel coupon appears unchanged.
[0219] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is a decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
about 0.23.+-.0.07wt. %.
Example I-2
[0220] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I, PAG oil, and myrcene.
[0221] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of a composition
containing 99% by weight of PAG oil and 1% by weight of myrcene.
The resulting mixture is placed into a glass tube with metal
coupons of aluminum, steel, and copper, and the tube is then
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed and
observed.
[0222] Upon observation, the mixture is one phase, indicating that
the refrigerant has during the period remained miscible and soluble
in the PAG oil. In addition, the liquid in the tube is clear with a
light yellow color. The steel coupon appears unchanged.
[0223] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is a decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
0.27 wt. %. The experiment is repeated and the result is 0.28 wt %
of HFC-23.
Example I-3
[0224] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I, PAG oil, and farnesol.
[0225] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of a composition
containing 99% by weight of PAG oil and 1% by weight of farnesol.
The resulting mixture is placed into a glass tube with metal
coupons of aluminum, steel, and copper, and the tube is then
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed and
observed.
[0226] Upon observation, the mixture is one phase, indicating that
the refrigerant has during the period remained miscible and soluble
in the PAG oil. In addition, the liquid in the tube is clear with a
light yellow color. The steel coupon appears unchanged.
[0227] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is a decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
0.16 wt. %.
Example I-4
[0228] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I, PAG oil, and geraniol.
[0229] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of a composition
containing 99% by weight of PAG oil and 1% by weight of geraniol.
The resulting mixture is placed into a glass tube with metal
coupons of aluminum, steel, and copper, and the tube is then
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed and
observed.
[0230] Upon observation, the mixture is one phase, indicating that
the refrigerant has during the period remained miscible and soluble
in the PAG oil. In addition, the liquid in the tube is clear with a
light yellow color. The steel coupon appears unchanged.
[0231] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is a decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
0.14 wt. %.
Example I-5
[0232] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I, polyalkylene glycol
lubricant, and myrcene with a triphenylphosphite (DP213-available
from Dover Chemical) as additives in the oil. Each additive was
present at 0.5 wt. % in the oil.
[0233] A mixture of trifluoroiodomethane (about 9 wt. %) and
HFO-1234yf (about 91 wt. %) (1.6 grams) was added to 3 grams of a
composition containing 99% by weight of a polyalkylene glycol
lubricant (commercially available as Motorcraft PAG Refrigerant
Compressor Oil) and 1 wt. % of additive as described in the
paragraph above. The resulting mixture is placed into a glass tube
with metal coupons of aluminum, steel, and copper, and the tube is
then sealed. The sealed glass tube is put into an oven at
300.degree. F. for two weeks. After such time the tube is removed
and observed.
[0234] Upon observation, the mixture is one phase, indicating that
the iodocarbon compound during this period remains miscible and
soluble in the PAG oil. In addition, the liquid in the tube is
clear with a light yellow color. The steel coupon appears
unchanged.
[0235] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of HFC-23, which
is a decomposition product of the oil reacting with the
trifluoroiodide. The level of HFC-23 found is about 0.2 wt. %.
Example I-6
[0236] This example illustrates a stabilized composition of the
present invention comprising CF.sub.3I and polyalkylene glycol
lubricant, and a stabilizer consisting of myrcene.
[0237] Trifluoroiodomethane (1.6 grams) is added to 3 grams of the
polyalkylene glycol lubricant containing myrcene, with the myrcene
being present on the basis of 1 wt. % based on the total weight of
the lubricant. The resulting mixture is placed into a glass tube
with metal coupons of aluminum, steel, and copper and the tube is
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed and
observed.
[0238] Upon observation, the mixture is one phase, indicating that
the refrigerant is miscible and soluble in the PAG oil. In
addition, the liquid in the tube is clear with a light yellow
color. The steel coupon appears unchanged.
[0239] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
0.23 wt. %.
Example I-7
[0240] This example illustrates that the level of decomposition of
CF.sub.3I in mineral oil, is dramatically decreased by the
combination of additives myrcene and Doverphos DP 213.
[0241] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of mineral oil. The
mineral oil contained 0.5 wt. % of myrcene and 0.5 wt. % Doverphos
DP-213. The resulting mixture is placed into a glass tube with
metal coupons of aluminum, steel, and copper, and the tube is then
sealed. The sealed glass tube is put into an oven at 300.degree. F.
for two weeks. After such time the tube is removed.
[0242] The glass tube was opened and the gas was extracted. The gas
was examined by gas chromatography for the presence of
trifluoromethane (HFC-23), which is a decomposition product of the
oil reacting with the trifluoroiodide. The level of HFC-23 found is
0.08 wt. %. The experiment is repeated and the result is 0.08 wt%
of HFC-23.
Comparative Example I-1
[0243] A mixture of trifluoroiodomethane (about 9 wt. %) and
HFO-1234yf (about 91 wt. %) (1.6 grams) was added to 3 grams of a
composition containing 99% by weight of a polyalkylene glycol
lubricant (commercially available as Motorcraft PAG Refrigerant
Compressor Oil). No stabilizer additive is used. The resulting
mixture is placed into a glass tube with metal coupons of aluminum,
steel, and copper, and the tube is then sealed. The sealed glass
tube is put into an oven at 300.degree. F. for two weeks. After
such time the tube is removed and observed.
[0244] Upon observation, the mixture is one phase, indicating that
the refrigerant composition during this period remains miscible and
soluble in the mineral oil. After the exposure, the metal coupons
are discolored and the color of the lubricant is dark brown.
[0245] The glass tube is opened and the gas is extracted. The gas
is examined by gas chromatography for the presence of HFC-23 that
is decomposition product of the oil reacting with the
trifluoroiodide. The level of HFC-23 found is about 1.0 wt. %.
Comparative Example I-2
[0246] A mixture (1.6 grams) of trifluoroiodomethane (25 wt. %) and
HFO-1234yf (75 wt. %) is added to 3 grams of mineral oil. The
resulting mixture is placed into a glass tube with metal coupons of
aluminum, steel, and copper, and the tube is then sealed. The
sealed glass tube is put into an oven at 300.degree. F. for two
weeks.
[0247] The glass tube was opened after the two week exposure and
the gas was extracted. The gas was examined by gas chromatography
for the presence of trifluoromethane (HFC-23), which is a
decomposition product of the oil reacting with the trifluoroiodide.
The level of HFC-23 found is 0.76 wt. %. The experiment is repeated
and the result is 1.51 wt % of HFC-23.
EXAMPLE II
[0248] This example illustrates stabilized compositions of the
present invention comprising a 30/70 blend of CF.sub.3I/HFO-1234yf,
PAG oil (RL-897), and a stabilization compound. Four grams of
RL-897 and 1.62 grams of CF.sub.3I/HFO-1234yf blend were put into a
sealed glass tube along with a metal assembly made of aluminum,
steel and copper. The sealed tube was put into an oven at
300.degree. C. for 2 weeks. The tubes were removed from the oven,
cooled, opened, and the gas is extracted.
[0249] Under these conditions, the breakdown products of CF.sub.3I
will be R-23 in the gas phase. Accordingly, the gas was analyzed
for the amount of R23 in it. A baseline test with no additives was
also tested.
[0250] Since the concern is the breakdown of CF.sub.3I, additives
at 1% in the oil were tested for their effect on the level of the
breakdown products. The results are presented in Table I below.
TABLE-US-00005 TABLE I CF.sub.3I Breakdown in 30/70 Blend of
CF.sub.3I/HFO-1234yf. R23% Example Stabilizer Myrcene 0.12%
Geraniol 0.14% Farnesol 0.16% Limonene 0.36% Diphenyl Phosphite
(Doverphos 213; DOV213) 0.61% 1,2-epoxyhexene (HEXENE) 0.77%
Dilauryl hydrogen phosphite (Doverphos 274; DP274) 0.97%
2,4-dimethyl-6-tert-butylphenol (AO1) 1.62% Allyl glycidyl ether
(AGE) 1.98% Tocopherol (TOC) 2.19% Hexane gylcidyl ether (HDGE)
2.38% Comparative Stabilizer Phophorous acid
(1-methylethylidene)di-4,1-phenylene- 2.60% tetra-C.sub.12-15
alkylesters 2-ethyl hexyl glycidyl ether (2EHGE) 2.62% Tridecyl
gylcidylether (13R) 2.74% Phosphorous acid, 2-ethylhexyl diphenyl
ester (DOV9EH) 3.63% Trans2,3-epoxybutane 4.04% Dodecyl gylcidyl
ether (HAG12) 4.73% cis-2,3-epoxybutane 5.25% No additive 2.5%,
3.8%
[0251] Results for the stabilizers phosphate,
2,4-dimethyl-6-tert-butylphenol, allyl glycidyl ether, tocopherol,
and hexane glycidyl ether indicate that breakdown of CF.sub.3I to
R23 is reduced in the 30/70 blend of CF.sub.3I/HFO-1234yf. Results
for the stabilizers myrcene, geraniol, farnesol, limonene, diphenyl
phosphate, 1,2-epoxyhexene, dilauryl hydrogen indicated that
breakdown of CF.sub.3I to R23 is substantially reduced.
EXAMPLE III
[0252] This example illustrates stabilized compositions of the
present invention comprising a 30/70 blend of CF.sub.3I/HFC-32, PAG
oil (ND-8), and a stabilization compound. Two grams of ND-8 and two
grams of CF.sub.3I/HFC-32 blend were put into a sealed glass tube
along with a metal assembly made of aluminum, steel and copper. The
sealed tube was put into an oven at 300.degree. C. for 1 week. The
tubes were removed from the oven, cooled, opened, and the gas is
extracted.
[0253] Under these conditions, the breakdown products of CF.sub.3I
will be R-23 in the gas phase and iodide ions in the oil. The oil
was therefore analyzed for the amount of iodide in it. The gas was
analyzed for the amount of R23 in it.
[0254] In addition to the 30/70 blend, tests were done on a 10/90
blend of CF.sub.3I/HFC-32. A baseline test with no additives was
done for each blend. Since the concern is the breakdown of
CF.sub.3I, additives at 1% in the oil were tested for their effect
on the level of the breakdown products. The results are presented
in Table II and III below.
TABLE-US-00006 TABLE II CF.sub.3I Breakdown in 30/70 Blend of
CF.sub.3I/HFC-32. Iodide R23% (ppm) Comparative Stabilizer No
Additives 0.73% 195.5 1,2-butylene oxide 0.97% 479 Dodecyl glycidyl
ether 1.03% 188 Glycidyl 2-methylphenyl ether 0.82% 139 Example
Stabilizer Farnesol 0.16% 1 Myrcene 0.09% 9 Butadiene 0.33% 35
Napthyl glycidyl ether 0.43% 35
TABLE-US-00007 TABLE III CF.sub.3I Breakdown in 10/90 Blend of
CF.sub.3I/HFC-32. Iodide R23% (ppm) No Additives 0.29% 28 Farnesol
0.04% 7
[0255] The baseline for 30/70 blend produces 0.73% R23 and an
iodide concentration of 195 ppm. For the three comparative
additives, the amount of R23 produced is greater, indicating that
certain additives may be harmful. The corresponding iodide
concentrations are either greater or not much reduced.
[0256] Results for the stabilizers farnesol, myrcene, butadiene and
napthyl glycidyl ether indicate that breakdown of CF.sub.3I to R23
is substantially reduced in the 30/70 blend of CF.sub.3I/HFC-32.
Similarly the iodide concentrations are much lower than with no
additives or with one of the comparatives.
[0257] Results for farnesol as used in the 10/90 CF.sub.3I/HFC-32
blend demonstrates a reduction in both the R23 and iodide
concentrations.
* * * * *