Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITIONS CONTAINING FLUORINE SUBSTITUTED OLEFINS
FIELD OF THE INVENTION
This invention relates to compositions, methods and systems having utility in
numerous applications, including particularly heat transfer systems such as
refrigeration
systems. In preferred aspects, the present invention is directed to
refrigerant
compositions which comprise at least one multi-fluorinated olefin of the
present
invention.
BACKGROUND
Fluorocarbon based fluids have found widespread use in many commercial and
industrial applications, including as the working fluid in systems such as air
conditioning,
heat pump and refrigeration systems, as aerosol propellants, as blowing
agents, as heat
transfer media, and as gaseous dielectrics. Because of certain suspected
environmental problems, including the relatively high global warming
potentials,
associated with the use of some of the compositions that have heretofore been
used in
these applications, it has become increasingly desirable to use fluids having
low or even
zero ozone depletion potential, such as hydrofluorocarbons ("HFCs"). Thus, the
use of
fluids that do not contain chlorofluorocarbons ("CFCs") or
hydrochlorofluorocarbons
("HCFCs") is desirable. Furthermore, some HFC fluids may have relatively high
global
warming potentials associated therewith, and it is desirable to use
hydrofiuorocarbon or
other fluorinated fluids having as low global warming potentials as possible
while
maintaining the desired performance in use properties. Additionally, the use
of single
component fluids or azeotrope-like mixtures, which do not substantially
fractionate on
boiling and evaporation, is desirable in certain circumstances.
Certain fluorocarbons have been a preferred component in many heat exchange
fluids, such as refrigerants, for many years in many applications. For,
example,
fluoroalkanes, such as chlorofluoromethane and chlorofluoroethane derivatives,
have
gained widespread use as refrigerants in applications including air
conditioning and heat
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pump applications owing to their unique combination of chemical and physical
properties. Many of the refrigerants commonly utilized in vapor compression
systems
are either single components fluids or azeotropic mixtures.
As suggested above, concern has been increasing in recent years about
potential damage to the earth's atmosphere and climate, and certain chlorine-
based
compounds have been identified as particularly problematic in this regard. The
use of
chlorine-containing compositions (such as chlorofluorocarbons (CFC's),
hydrochlorofluorocarbons (HCF's) and the like) as the working fluid in heat
transfer
systems, such as in refrigeration and air-conditioning systems, has become
disfavored
because of the ozone-depleting properties associated with many of such
compounds.
There has thus been an increasing need for new fluorocarbon and
hydrofluorocarbon
compounds and compositions that are attractive alternatives to the
compositions
heretofore used in these and other applications. For example, it has become
desirable
to retrofit chlorine-containing refrigeration systems by replacing chlorine-
containing
refrigerants with non-chlorine-containing refrigerant compounds that will not
deplete the
ozone layer, such as hydrofluorocarbons (HFC's). Industry in general and the
heat
transfer industry in particular are continually seeking new fluorocarbon based
mixtures
that offer alternatives to, and are considered environmentally safer
substitutes for, CFCs
and HCFCs. It is generally considered important, however, at least with
respect to heat
transfer fluids, that any potential substitute must also possess those
properties present
in many of the most widely used fluids, such as excellent heat transfer
properties,
chemical stability, low- or no- toxicity, non-flammability and/or lubricant
compatibility,
among others.
Applicants have come to appreciate that lubricant compatibility is of
particular
importance in many of applications. More particularly, it is highly desirably
for
refrigeration fluids to be compatible with the lubricant utilized in the
compressor unit,
used in most refrigeration systems. Unfortunately, many non-chlorine-
containing
refrigeration fluids, including HFC's, are relatively insoluble and/or
immiscible in the
types of lubricants used traditionally with CFC's and HFC's, including, for
example,
mineral oils, alkylbenzenes or poly(alpha-olefins). In order for a
refrigeration fluid-
lubricant combination to work at a desirable level of efficiently within a
compression
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refrigeration, air-conditioning and/or heat pump system, the lubricant should
be
sufficiently soluble in the refrigeration liquid over a wide range of
operating
temperatures. Such solubility lowers the viscosity of the lubricant and allows
it to flow
more easily throughout the system. In the absence of such solubility,
lubricants tend to
become lodged in the coils of the evaporator of the refrigeration, air-
conditioning or heat
pump system, as well as other parts of the system, and thus reduce the system
efficiency.
With regard to efficiency in use, it is important to note that a loss in
refrigerant
thermodynamic performance or energy efficiency may have secondary
environmental
impacts through increased fossil fuel usage arising from an increased demand
for
electrical energy.
Furthermore, it is generally considered desirably for CFC refrigerant
substitutes
to be effective without major engineering changes to conventional vapor
compression
technology currently used with CFC refrigerants.
Flammability is another important property for many applications. That is, it
is
considered either important or essential in many applications, including
particularly in
heat transfer applications, to use compositions which are non-flammable. Thus,
it is
frequently beneficial to use in such compositions compounds which are
nonflammable.
As used herein, the term 'nonflammable" refers to compounds or compositions
which
are determined to be nonflammable as determined In accordance with ASTM
standard
E-681, dated 2002. Unfortunately, many
HFC's which might otherwise be desirable for used in refrigerant compositions
are not
nonflammable. For example, the fluoroalkane difluoroethane (HFC-152a) and the
fluoroalkene 1,1,1¨tiifluorpropene (HF0-1243g) are each flammable and
therefore not
viable for use in many applications.
Higher fluomalkenes, that is fluorine-substituted alkenes having at least five
carbon atoms, have been suggested for use as refrigerants. U.S. Patent No.
4,788,352
¨ Smutny is directed to production of fluorinated C5 to Ce, compounds having
at least
some degree of unsaturation. The Smutny patent Identifies such higher olefins
as being
known to have utility as refrigerants, pesticides, dielectric fluids, heat
transfer fluids,
solvents, and intermediates in various chemical reactions. (See column 1,
lines 11 ¨
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22).
While the fluorinated olefins described in Smutny may have some level of
effectiveness in heat transfer applications, it is believed that such
compounds may also
have certain disadvantages. For example, some of these compounds may tend to
attack substrates, particularly general-purpose plastics such as acrylic
resins and ABS
resins. Furthermore, the higher olefinic compounds described in Smutny may
also be
undesirable in certain applications because of the potential level of toxicity
of such
compounds which may arise as a result of pesticide activity noted in Smutny.
Also,
such compounds may have a boiling point which is too high to make them useful
as a
refrigerant in certain applications.
Bromofiuoromethane and bromochlorofluoromethane derivatives, particularly
bromotrifluoromethane (HaIon 1301) and bromochlorodifluoromethane (HaIon 1211)
have gained widespread use as fire extinguishing agents in enclosed areas such
as
airplane cabins and computer rooms. However, the use of various halons is
being
phased out due to their high ozone depletion. Moreover, as halons are
frequently used
in areas where humans are present, suitable replacements must also be safe to
humans at concentrations necessary to suppress or extinguish fire.
Applicants have thus come to appreciate a need for compositions, and
particularly heat transfer compositions, fire extinguishing/suppression
compositions,
blowing agents, solvent compositions, and compatabilizing agents, that are
potentially
useful in numerous applications, including vapor compression heating and
cooling
systems and methods, while avoiding one or more of the disadvantages noted
above.
SUMMARY
Applicants have found that the above-noted need, and other needs, can be =
satisfied by compositions, preferably heat transfer compositions, comprising
one or
more C3 to C6 fluorakenes, and more preferably one or more C3, C4, or C5
fluoroalkenes, preferably compounds having Formula las follows:
XCFzR3-z (I)
where Xis a C2, C3, C4 or C5 unsaturated, substituted or unsubstituted,
radical, each R
is independently Cl, F, Br, I or H, and z is 1 to 3. In certain preferred
embodiments, the
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fluoroalkene of the present invention has at least four (4) halogen
substituents, at least
three of which are F and even more preferably none of which are Br. In certain
preferred embodiments, the compound of formula one comprises a compound, and
preferably a three carbon compound, in which each non-terminal unsaturated
carbon
has a fluorine substituent
For embodiments in which at least one Br substituent is present, it is
preferred
that the compound includes no hydrogen. In such embodiments it also generally
preferred that the Br substituent is on an unsaturated carbon, and even more
preferably
the Br substituent is on an non-terminal unsaturated carbon. One particularly
preferred
embodiment in this class is CF3CBr=CF2, including all of its isomers.
In certain embodiments it is highly preferred that the compounds of Formula I
comprise propenes, butenes, pentanes and hexanes having from 3 to 5 fluorine
substituents, with other substituents being either present or not present In
certain
preferred embodiments, no R is Br, and preferably the unsaturated radical
contains no
Br substituents. Among the propenes, tetrafluoropropenes (HFO-1234) and
fluorochloroporpenes (such as trifluoro,monochloropropenes (HFCO-1233), and
even
more preferably CF3CCI=CH2 (HF0-1233xf) and CF3CH=CHCI (HF0-1233zd)) are
especially preferred in certain embodiments.
In certain embodiments, pentafluoropropenes are preferred, including
particularly
those pentafiuoropropenes in which there is a hydrogen substituent on the
terminal
unsaturated carbon, such as CF3CF=CFH (HF0-1225yez and/or yz), particularly
since
applicants have discovered that such compounds have a relatively low degree of
toxicity
in comparison to at least the compound CF3CH=CF2(HF0-1225zc).
Among the butenes, fluorochlorobutenes are especially preferred in certain
embodiments.
The term "HFO-1234" is used herein to refer to all tetrafluoropropenes. Among
the tetrafluoropropenes are included 1,1,1,2-tetrafluoropropene (HF0-1234y0
and both
cis- and trans-1, 1, 1, 3-tetrafluoropropene (HF0-1234ze). The term HF0-1234ze
is
used herein generically to refer to 1, 1,1, 3-tetrafluoropropene, independent
of whether
it is the cis- or trans-form. The terms "cisHF0-1234ze" and "transHF0-1234ze"
are
used herein to describe the cis- and trans- forms of 1, 1, I. 3-
tetrafluoropropene
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respectively. The term "HF0-1234ze" therefore includes within its scope cisHF0-
1234ze, transHF0-1234ze, and all combinations and mixtures of these.
The term "HFO-1233" is used herein to refer to all
trifluoroymonochloropropenes.
Among the trifluoro,monochloropropenes are included 1,1,1,trifluoro-2,chloro-
propene
(HFC0-1233xf), both cis- and trans-1,1,1-trifluo-3,chlororopropene (HFC0-
1233zd).
The term HFC0-1233zd is used herein generically to refer to 1,1 ,1-trifluo-
3,chloro-
propene, independent of whether it is the cis- or trans- form. The terms
"cisHFC0-
1233zd" and "transHFC0-1233zd" are used herein to describe the cis- and trans-
forms
of 1, 1, 1-trifluo,3-chlororopropene, respectively. The term "HFC0-1233zd"
therefore
includes within its scope cisHFC0-1233zd, transHFC0-1233zd, and all
combinations
and mixtures of these.
The term "HFO-1225" is used herein to refer to all pentafluoropropenes. Among
such molecules are included 1,1,1,2,3 pentafluoropropene (HF0-1225yez), both
cis-
and trans- forms thereof. The term HF0-1225yez is thus used herein generically
to
refer to 1,1,1,2,3 pentafluoropropene, independent of whether it is the cis-
or trans-
form. The term "HF0-1225yez" therefore includes within its scope cisHF0-
1225yez,
transHF0-1225yez, and all combinations and mixtures of these.
In certain preferred embodiments, the present compositions comprise a
combination of two or more compounds of Formula I. In one such preferred
embodiment the composition comprises at least one tetrafluoropropene and at
least one
pentafluoropropene compound, preferably with each compound being present in
the
composition in an amount of from about 20% by weight to about 80% by weight,
more
preferably from about 30% by weight to about 70% by weight, and even more
preferably
from about 40% by weight to about 60% by weight. In certain of such
embodiments,
the tetrafluoropropene comprises, and preferably consists essentially of HFO-
1234
(most preferably HF0-1234yf) and HF01225 (most preferably HF0-1225yez).
The present invention provides also methods and systems which utilize the
compositions of the present invention, including methods and systems for heat
transfer,
for retrofitting existing heat transfer equipment, for replacing the existing
heat transfer
fluids in an existing heat transfer system. In certain cases, the present
compositions
may also be used in connection with foam blowing, solvating, flavor and
fragrance
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extraction and/or delivery, aerosol generation, non-aerosol propellants and as
inflating
agents.
Brief Description of the Drawings
Figure 1 is a schematic illustration of the foam testing apparatus described
in the Examples.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
THE COMPOSITIONS
The preferred embodiments of the present invention are directed to
compositions
comprising at least one fluoroalkene containing from 3 to 6 carbon atoms,
preferably 3
to five carbon atoms, and in certain highly preferred embodiments three carbon
atoms,
and at least one carbon-carbon double bond. The fluoroalkene compounds of the
present invention are sometimes referred to herein for the purpose of
convenience as
hydrofluoro-olefins or "HFOs" if they contain at least one hydrogen. Although
it is
contemplated that the HFOs of the present invention may contain two carbon ¨
carbon
double bonds, such compounds at the present time are not considered to be
preferred.
For HFOs which also contain at least one chlorine atom, the designation HFCO
is
sometimes used herein
As mentioned above, the present compositions comprise one or more
compounds in accordance with Formula I. In preferred embodiments, the
compositions
include compounds of Formula ll below:
(II)
where each R is independently Cl, F, Br, I or H,
R' is (CR2)nY,
Y is CRF2
and n is 0, 1, 2 or 3, preferably 0 or 1, it being generally preferred however
that
when Br is present in the compound there is no hydrogen in the compound. In
certain
embodiments, Br is not present in the compound.
In highly preferred embodiments, Y is CF3, n is 0 or 1 (most preferably 0) and
at
least one of the remaining Rs is F, and preferably no R is Br or when Br is
present,
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there is no hydrogen in the compound.
Applicants believe that, in general, the compounds of the above identified
Formulas I and II are generally effective and exhibit utility in heat transfer
compositions
generally and in refrigerant compositions particularly. The compositions of
the present
invention also find use as blowing agent compositions, compatibilzers,
aerosols,
propellants, fragrances, flavor formulations, solvent compositions and
inflating agent
composition. 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 CF3, n is 0 or 1, wherein at least one R on the unsaturated
terminal carbon
is H, and at least one of the remaining Rs is F or Cl. Applicants believe also
that all
structural, geometric and stereoisomers of such compounds are effective and of
beneficially low toxicity.
In certain preferred embodiments the compounds of the present invention
=
comprise one or more comprises a C3 or C4 HFO, preferably a C3 HFO, and
preferably
a compound accordance with Formula I in which X is a halogen substituted C3
alkylene
and z is 3. In certain of such embodiments X is fluorine and/or chlorine
substituted C3
alkylene, with the following C3 alkylene radicals being preferred in certain
embodiments:
-CH=CF-CH3
-CF=CH-CH3
-CH2-CF=CH2
-CH2-CH=CFH,
Such embodiments therefore comprise the following preferred compounds: CF3-
CH=CF-CH3; CF3-CF=CH-CH3; CF3-CH2-CF=CH2; CF3-CHrCH=CFH; and
combinations of these with one another and/or with other compounds in
accordance
with Formula I,
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In certain preferred embodiments, the compound of the present invention
comprises a C3 or C4 HFCO, preferably a C3 HFCO, and more preferably a
compound
in accordance with Formula 11 in which Y is CF3, n is 0, at least one R on the
Unsaturated terminal carbon is H, and at least one of the remaining Rs is Cl.
HFCO-
1233 is an example of such a preferred compound.
In highly preferred embodiments, especially embodiments which comprise 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, including HF0-1234yf, (cis)HF0-1234ze and (trans)HF0-
1234ze,
with HF0-1234ze being generally preferred. Although the properties of (cis)HF0-
1234ze and (trans)HF0-1234ze 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 stereo isomer, in connection with each of the
applications,
methods and systems described herein. For example, (trans)HF0-1234ze may be
preferred for use in certain systems because of its relatively low boiling
point (-19 C),
while (cis)HF0-1234ze, with a boiling point of +9 C, may be preferred in
other
applications. Of course, it is likely that combinations of the cis- and trans-
Isomers will
be acceptable and/or preferred in many embodiments. Accordingly, it is to be
understood that the terms "HF0-1234ze" 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.
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. Patent Nos. 2,889,379; 4,798,818 and 4,465,786.
EP 974,571 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 generally in connection
with
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United States Patent number 7,230,146, entitled "Process for Producing
Fluorpropenes" bearing attorney docket number (H0003789 (26267)) .
Other preferred compounds for use in accordance with the present invention
include pentafiuoropropenes, including all isomers thereof (eg., HF0-1225),
tetra- and
penta-fluorobutenes, including all isomers thereof (eg., HFO-1354 and HFO-
1345). Of
course, the present compositions may comprise combinations of any two or more
compounds within the broad scope of the invention or within any preferred
scope of the
invention.
The present compositions, particularly those comprising HFO-1234 (including
HF0-1234ze and HF0-1234y0, 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.
Of course other compounds and/or components that modulate a particular
property of the compositions (such as cost for example) may also be included
in the
present compositions, and the presence of all such compounds and components is
within the broad scope of the invention.
In certain preferred forms, compositions of the present invention 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. In
certain
embodiments, the GWP of the present compositions is not greater than about 100
and
even more preferably 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"
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In certain preferred forms, the present compositions also preferably have an
Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not
greater
than 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 " -
The amount of the Formula I compounds, particularly HFO-1234, and even more
preferably HF0-1234yf, contained in the present compositions can vary widely,
depending the particular application, and compositions containing more than
trace
amounts and less than 100% of the compound are within broad the scope of the
present invention. Moreover, the compositions of the present invention can be
azeotropic, azeotrope-like or non-azeotropic. In preferred embodiments, the
present
compositions comprise Formula I compounds, preferably HFO-1234 and more
preferably HF0-1234ze and/or HF0-1234yf, preferably HF0-1234ze and/or HFO-
1234yf, in amounts from about 5% by weight to about 99% by weight, and even
more
preferably from about 5% to about 95%. Many additional compounds or
components,
including lubricants, stabilizers, metal passivators, corrosion inhibitors,
flammability
suppressants, and other compounds and/or components that modulate a particular
property of the compositions (such as cost for example) may be included in the
present
compositions, and the presence of all such compounds and components is within
the
broad scope of the invention. In certain preferred embodiments, the present
compositions include, in addition to the compounds of formula I (including
particularly
HF0-1234ze and/or HF0-1234y1), one or more of the following:
Trichiorofluoromethane (CFC-11)
Dichlorodifluoromethane (CFC-12)
Difluoromethane (HFC-32)
Pentafiuoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
1,1,1,2-Tetrafluoroethane (HFC-134a)
Difluoroethane (HFC-152a)
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1 ,1 ,1,2,3,3,3-Heptafluoropropane (HFC-227ea)
11111 ,3,3,3-hexafluoropropane (HFC-236fa)
1,1,1,3,3-pentafluoropropane (HFC-245fa)
1,1,1,3,3-pentafluorobutane (HFC-365mfc)
water
CO2
The relative amount of any of the above noted compounds of the present
invention, as well as any additional components which may be included in
present
compositions, can vary widely within the general broad scope of the present
invention
according to the particular application for the composition, and all such
relative amounts
are considered to be within the scope hereof.
Accordingly, applicants have recognized that certain compositions of the
present
invention can be used to great advantage in a number of applications. For
example,
included in the present invention are methods and compositions relating to
heat transfer
applications, foam and blowing agent applications, propellant applications,
sprayable
composition applications, sterilization applications, aerosol applications,
compatibilizer
application, fragrance and flavor applications, solvent applications, cleaning
applications, inflating agent applications and others. It is believed that
those of skill in
the art will be readily able to adapt the present compositions for use in any
and all such
applications without undue experimentation.
The present compositions are generally useful as replacements for CFCs, such
as dichlorodifluormethane (CFC-12), HCFCs, such as chlorodifluoromethane (HCFC-
22), HFCs, such as tetrafluoroethane (HFC-134a), and combinations of HFCs and
CFCs, such as the combination of CFC-12 and 1,1-difluorethane (HFC-152a) (the
combination CFC-12:HFC-152a in a 73.8:262 mass ratio being known as R-500) in
refrigerant, aerosol, and other applications.
HEAT TRANSFER COMPOSITIONS
The compositions of the present invention are generally adaptable for use in
heat
transfer applications, that is, as a heating and/or cooling medium, including
as
evaporative cooling agents.
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In connection with evaporative cooling applications, the compositions of the
present invention are brought in contact, either directly or indirectly, with
a body to be
cooled and thereafter permitted to evaporate or boil while in such contact,
with the
preferred result that the boiling gas in accordance with the present
composition absorbs
heat from the body. to be cooled. In such applications it may be preferred to
utilize the
compositions of the present invention, preferably in liquid form, by spraying
or otherwise
applying the liquid to the body to be cooled. In other evaporative cooling
applications, it
may be preferred to permit a liquid composition in accordance with the present
intention
to escape from a relatively high pressure container into a relatively lower
pressure
environment wherein the body to be cooled is in contact, either directly or
indirectly, with
the container enclosing the liquid composition of the present invention,
preferably
without recovering or recompressing the escaped gas. One particular
application for .
this type of embodiment is the self cooling of a beverage, food item, novelty
item or the
like. Previous to the invention described herein, prior compositions, such as
HFC-152a
and HFC-134a were used for such applications. However, such .compositions have
recently been looked upon negatively in such application because of the
negative
environmental impact caused by release of these materials into the atmosphere.
For
example, the United States EPA has determined that the use of such prior
chemicals in
this application is unacceptable due to the high global warming nature of
these
chemicals and the resulting detrimental effect on the environment that may
result from
their use. The compositions of the present invention should have a distinct
advantage
in this regard due to their low global warming potential and low ozone
depletion
potential, as described herein. Additionally, the present compositions are
expected to
also find substantial utility in connection with the cooling of electrical or
electronic
components, either during manufacture or during accelerated lifetime testing.
In a
accelerated lifetime testing, the component is sequentially heated and cooled
in rapid
succession to simulate the use of the component. Such uses would therefore be
of
particular advantage in the semiconductor and computer board manufacturing
industry.
Another advantage of the present compositions in this regard is they are
expected to
exhibit as contagious electrical properties when used in cannection with such
applications. Another evaporative cooling application comprises methods for
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temporarily causing a discontinuation of the flow of fluid through a conduit.
Preferably,
such methods would include contacting the conduit, such as a water pipe
through which
water is flowing, with a liquid composition according to the present invention
and
allowing the liquid composition of the present invention to evaporate while in
contact
with the conduit so as to freeze liquid contained therein and thereby
temporarily stop the
flow of fluid through the conduit. Such methods have distinct advantage in
connection
with enabling the service or other work to be performed on such conduits, or
systems
connected to such conduits, at a location downstream of the location at which
the
present composition is applied.
Although it is contemplated that the compositions of the present invention may
include the compounds of the present invention in widely ranging amounts, it
is
generally preferred that refrigerant compositions of the present invention
comprise
compound(s) in accordance with Formula 1, more preferably in accordance with
Formula
and even more preferably HFO-1234 (including HF0-1234ze and HF0-1234yf), in an
amount that is at least about 50% by weight, and even more preferably at least
about 70
% by weight, of the composition. In certain embodiments, it is preferred that
the heat
transfer compositions of the present invention comprise transHF0-1234ze. In
certain
preferred embodiments, it is preferred that the heat transfer compositions of
the present
invention comprise at least about 80%, and even more preferably at least about
90% by
weight of HFO-1234, and even more preferably HF0-1234yf and/or HF0-1234ze. The
heat transfer compositions of the present invention comprise in certain
embodiments a
combination of cisHF0-1234ze and transHF01234ze, preferably in a cis:trans
weight
ratio of from about 1:99 to about 10:99, more preferably from about 1:99 to
about 5:95,
and even more preferably from about 1:99 to about 3:97.
The relative amount of the hydrofluoroolefln used in accordance with the
present
invention is preferably selected to produce a heat transfer fluid which has
the required
heat transfer capacity, particularly refrigeration capacity, and preferably is
at the same
time non-flammable. As used herein, the term non-flammable refers to a fluid
which is
non-flammable in all proportions in air as measured by ASTM E-681.
The compositions of the present invention may include other components for the
purpose of enhancing or providing certain functionality to the composition, or
in some
14
CA 02822739 2013-08-02
cases to reduce the cost of the composition. For example, refrigerant
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 percent
by weight of the composition. Furthermore, the present compositions may also
include
a co-refrigerant, or compatibilzer, 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. Patent No. 6,516,837.
Commonly used refrigeration lubricants such as Polyol Esters (POEs) and Poly
Alkylene Glycols (PACs), PAG oils, silicone oil, mineral oil, alkyl benzenes
(ABS) and
poly(alpha-olefin) (PAO) that are used in refrigeration machinery with
hydrofluorocarbon
(HFC) refrigerants may be used with the refrigerant compositions of the
present
invention. 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 Retool 2370 (registered trademark). Other
useful
esters include phosphate esters, dibasic acid esters, and fiuoroesters. .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 polyaikylene 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.
In certain preferred embodiments, the heat transfer composition comprises from
about 10% to about 95 % by weight of a compound of Formula I, more preferably
a
compound of Formula II, and even more preferably one or more HFO-1234
compounds,
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and from about 5% to about 90% by weight of an adjuvant, particular in certain
embodiments a co-refrigerant (such as HFC-152, HFC-125 and/or CF3I). The use
of the
term co-refrigerant is not intended for use herein in a limiting sense
regarding the
relative performance of the compound of Formula I compounds, but is used in
stead
used to identify other components of the refrigerant composition generally
that
contribute to the desirable heat transfer characteristics of the composition
for a desired
application. In certain of such embodiments the co-refrigerant comprises, and
preferably consists essentially of, one or more HFCs and/or one or more
fluoroiodo Cl
¨ C3 compounds, such as trifluroiodomethane, and combinations of these with
each
other and with other components.
In preferred embodiments in which the co-refrigerant comprises HFC, preferably
HFC-125. the composition comprises HFC in an amount of from about 50% by
weight
to about 95% by weight of the total heat transfer composition, more preferably
from
about 60% by weight to about 90% by weight, and even more preferably of from
about
70% to about 90% by weight of the composition. In such embodiments the
compound
of the present invention preferably comprises, and even more preferably
consists
essentially of, HF0-1234,and even more preferably HF0-1234y1 and/or HF0-1234ze
in
an amount of from about 5% by weight to about 50% by weight of the total heat
transfer
composition, more preferably from about 10% by weight to about 40% by weight,
and
even more preferably of from about 10% to about 30% by weight of the
composition.
In preferred embodiments in which the co-refrigerant comprises
fluoriodocarbon,
preferably CF3I, the composition comprises fluoriodocarbon in an amount of
from about
15% by weight to about 50% by weight of the total heat transfer composition,
more
preferably from about 20% by weight to about 40% by weight, and even more
preferably
of from about 25% to about 35% by weight of the composition. In such
embodiments the
compound of the present invention preferably comprises, and even more
preferably
consists essentially of, HF0-1234,and even more preferably HF0-1234yf in an
amount
of from about 50% by weight to about 90% by weight of the total heat transfer
composition, more preferably from about 60% by weight to about 80% by weight,
and
even more preferably of from about 65% to about 75% by weight of the
composition.
The present methods, systems and compositions are thus adaptable for use in
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=
connection with a wide variety of heat transfer systems in general and
refrigeration
systems in particular, such as air-conditioning (including both stationary and
mobile air
conditioning systems), refrigeration, heat-pump systems, and the like. In
certain
preferred embodiments, the compositions of the present invention are used in
refrigeration systems originally designed for use with an HFC refrigerant,
such as, for
example, HFC-134a, or an HCFC refrigerant, such as, for example, HCFC-22. The
preferred compositions of the present invention tend to exhibit many of the
desirable
characteristics of HFC-134a and other HFC refrigerants, including a GWP that
is as low,
or lower than that of conventional HFC refrigerants and a capacity that is as
high or
higher than such refrigerants and a capacity that is substantially similar to
or
substantially matches, and preferably is as high as or higher than such
refrigerants. In
particular, applicants have recognized that certain preferred embodiments of
the
present compositions tend to exhibit relatively low global warming potentials
("GWPs"),
preferably less than about 1000, more preferably less than about 500, and even
more
preferably less than about 150. In addition, the relatively constant boiling
nature of
certain of the present compositions, makes them
even more desirable than certain conventional HFCs, such as R-404A or
combinations
of HFC-32, HFC-125 and HFC-134a (the combination HFC-32:HFC-125:HFC134a in
approximate 23:25:62 weight ratio Is referred to as R-407C), for use as
refrigerants in
many applications. Heat transfer compositions of the present invention are
particularly
preferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500.
In certain other preferred embodiments, the present compositions are used in
refrigeration systems originally designed for use with a CFC-refrigerant.
Preferred
refrigeration compositions of the present invention may be used in
refrigeration systems
containing a lubricant used conventionally with CFC-refrigerants, such as
mineral oils,
polyalkylbenzene, polyalkylene glycol oils, and the like, or may be used with
other
lubricants traditionally used with HFC refrigerants_ As used herein the term
"refrigeration system" refers generally to any system or apparatus, or any
part or portion
of such a system or apparatus, which employs a refrigerant to provide cooling.
Such
refrigeration systems include, for example, air conditioners, electric
refrigerators, chillers
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(including chillers using centrifugal compressors), transport refrigeration
systems,
commercial refrigeration systems and the like.
Many existing refrigeration systems are currently adapted for use in
connection
with existing refrigerants, and the compositions of the present invention are
believed to
be adaptable for use in many of such systems, either with or without system
modification. Many applications the compositions of the present invention may
provide
an advantage as a replacement in smaller systems currently based on certain
refrigerants, for example those requiring a small refrigerating capacity and
thereby
dictating a need for relatively small compressor displacements. Furthermore,
in
embodiments where it is desired to use a lower capacity refrigerant
composition of the
present invention, for reasons of efficiency 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 consisting essentially of the present compositions, as a
replacement for existing refrigerants, such as: HFC-134a; CFC-12; HCFC-22; HFC-
152a; combinations of pentfluoroethane (HFC-125), trifluorethane (HFC-143a)
and
tetrafluoroethane (HFC-134a) (the combination HFC-125:HFC-143a:HFC134a in
approximate 44:52:4 weight ratio is referred to as R-404A); combinations of
HFC-32,
HFC-125 and HFC-134a (the combination HFC-32:HFC-125:HFC134a in approximate
23:25:52 weight ratio is referred to as R-407C); combinations of methylene
fluoride
(HFC-32) and pentfluoroethane (HFC-125) (the combination HFC-32:HFC-125 in
approximate 50:50 weight ratio is referred to as R-410A); the combination of
CFC-12
and 1,1-difluorethane (HFC-152a) (the combination CFC-12:HFC-152a in a
73.8:26.2
weight ratio is referred to R-500); and combinations of HFC-125 and HFC-143a
(the
combination HFC-125:HFC143a in approximate 50:50 weight ratio is referred to
as R-
507A). In certain embodiments it may also be beneficial to use the present
compositions in connection with the replacement of refrigerants formed from
the
combination HFC-32:HFC-125:HFC134a in approximate 20:40:40 weight ratio, which
is
referred to as R-407A, or in approximate 15:15:70 weight ratio, which is
referred to as
R-407D. The present compositions are also believed to be suitable as
replacements for
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WO 2007/002625 PCT/US2006/024886
the above noted compositions in other applications, such as aerosols, blowing
agents
and the like, as explained elsewhere herein.
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 provide the possibility of achieving a
competitive
advantage on an energy basis for refrigerant replacement applications,
including
automotive air conditioning systems and devices, commercial refrigeration
systems and
devices, chillers, residential refrigerator and freezers, general air
conditioning systems,
- heat pumps and the like.
Many existing refrigeration systems are currently adapted for use in
connection
with existing refrigerants, and the 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 consisting essentially of, HFO-1234 (preferably HF0-1234ze and/or
HFO-
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 HF0-1234yf and /or
HFO-
1234ze (preferably transHF0-1234ze), provide the possibility of achieving a
competitive
advantage on an energy basis for refrigerant replacement applications.
It is contemplated that the compositions of the present, including
particularly
those which comprise HF0-1234yf and/or HF0-1234ze, also have advantage (either
in
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WO 2007/002625 PCT/US2006/024886
original systems or when used as a replacement for refrigerants such as CFC-
11, CFC-
12, HCFC-22, HFC-134a, HFC-152a, R-500 and R-507A), in chillers typically used
in
connection with commercial air conditioning systems. In certain of such
embodiments it
is preferred to include in the present compositions, particularly those
comprising HFO-
1234yf and/or HF0-1234ze, from about 0.5 to about 30% of a supplemental
flammability suppressant, and in certain cases more preferably 0.5% to about
15% by
weight and even more preferably from about 0.5 to about 10% on a weight basis.
In this
regard it is noted that the certain of HFO-1234 and/or HFO-1225 components of
the
present compositions may in certain embodiments act as flammability
suppressants
with respect to other components in the composition. Thus, components other
than
HFO-1234 and HF0-1225 which have flammability suppressant functionality in the
composition will sometimes be referred to herein as a supplemental
flammability
suppressant.
In certain preferred embodiments, the present compositions include, in
addition
to the compounds of formula 1, particularly HFO-1234 (including HF0-1234ze and
HF0-
1234y0, one or more of the following additional compounds that may be included
primarily for their impact on the heat transfer characteristics, cost and the
like. The
following components may thus be included in the compositions as co-heat
transfer
fluids (or co-refrigerants in the case of cooling operations):
Trichlorofluoromethane (CFC-11)
Dichlorodifluoromethane (CFC-12)
Difluoromethane (HFC-32)
Pentafluoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFC-134)
111 ,1,2-Tetrafluoroethane (HFC-134a)
Difluoroethane (HFC-152a)
1,1,1,2,3,3,3-Heptafluoropropane (lFC-227ea)
1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
1,1,1,3,3-pentafluoropropane (HFC-245fa)
1,1,1,3,3-pentafluorobutane (HFC-365mfc)
water
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CO2
BLOWING AGENTS, FOAMS AND FOAMABLE COMPOSITIONS
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 compounds 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, compound(s) in accordance with
Formula I,
and even more preferably Formula II, are present in an amount that is at least
about 5
% by weight, and even more preferably at least about 15 % by weight, of the
composition. In certain preferred embodiments, the blowing agent comprises at
least
about 50% by weight of the present compositions, and in certain embodiments
the
blowing agent consists essentially of the present compositions. In certain
preferred
embodiments, the blowing agent compositions of the present invention and
include, in
addition to HFO-1234 (preferably HF0-1234ze and/or HF0-123414) one or more of
co-
blowing agents, fillers, vapor pressure modifiers, flame suppressants,
stabilizers and
like adjuvants. By way of example, one or more of the following components may
included in certain preferred blowing agent of the present invention in widely
varying
amounts:
Difluoromethane (HFC-32)
Pentafluoroethane (HFC-125)
1,1,2,2-tetrafluoroethane (HFG-134)
1,1,1 ,2-Tetrafluoroethane (HFC-134a)
Difluoroethane (HFC-152a)
1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)
1,1,1,3,3,3-hexafluoropropane (HFC-236fa)
1,1,1,3,3-pentafluoropropane (HFC-245fa)
1,1,1,3,3-pentafluorobutane (IFC-365mfc)
water
CO2
It is contemplated that the blowing agent compositions of the present
invention may
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comprise, preferably in amounts of at least about 15% by weight of the
composition,
HF0-1234yf, cisHF0-1234ze, transHF01234ze or combinations of two or more of
these. In certain preferred embodiments, the blowing agent compositions of the
present
invention comprise a combination of cisHF0-1234ze and transHF01234ze in a
cis:trans
weight ratio of from about 1:99 to about 10:99, and even more preferably from
about
1:99 to about 5:95.
In other embodiments, the invention provides foamable compositions. The
foamable compositions of the present invention generally include one or more
components capable of forming foam having a generally cellular structure and a
blowing
agent in accordance with the present invention. In certain embodiments, the
one or
more components comprise a thermosetting composition capable of forming foam
and/or foamable compositions. Examples of thermosetting compositions include
polyurethane and polyisocyanurate foam compositions, and also phenolic foam
compositions. In such thermosetting foam embodiments, one or more of the
present
compositions are included as or part of a blowing agent in a foamable
composition, or
as a part of a two or more part foamable composition, which preferably
includes one or
more of the components capable of reacting and/or foaming under the proper
conditions
to form a foam or cellular structure. In certain other embodiments, the one or
more
components comprise thermoplastic materials, particularly thermoplastic
polymers
and/or resins. Examples of thermoplastic foam components include polyolefins,
such
as polystyrene (PS), polyethylene (PE), polypropylene (PP) and
polyethyleneterepthalate (PET), and foams formed there from, preferably low-
density
foams. In certain embodiments, the thermoplastic foamable composition is an
extrudable composition.
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 or polyolefin foams, such as
polystyrene (PS), polyethylene (PE), polypropylene (PP) and
polyethyleneterpthalate
(PET) foams, preferably low-density foams.
It will be appreciated by those skilled in the art, especially in view of the
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=
disclosure contained herein, that the order and manner in which the blowing
agent of
the present invention is formed and/or added to the foamable composition does
not
generally affect the operability of the present invention. For example, in the
case of
extrudable foams, it is possible that the various components of the blowing
agent, and
even the components of the present composition, be not be mixed in advance of
introduction to the extrusion equipment, or even that the components are not
added to
the same location in the extrusion equipment. Thus, in certain embodiments it
may be
desired to introduce one or more components of the blowing agent at first
location in the
extruder, which is upstream of the place of addition of one or more other
components of
the blowing agent, with the expectation that the components will come together
in the
extruder and/or operate more effectively in this manner. Nevertheless, in
certain
embodiments, two or more components of the blowing agent are combined in
advance
and introduced together into the foamable composition, either directly or as
part of
premix which is then further added to other parts of the foamable composition.
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. Patent Nos. 2,834,748, 2,917,480, and
2,846,458. 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-dibromopropyI)-
phosphate,
tri(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated
aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride,
and the
like.
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, NY,
may be used or adapted for use in accordance with the foam embodiments of the
present invention.
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PROPELLANT AND AEROSOL COMPOSITIONS
In another aspect, the present invention provides propellant compositions
comprising or consisting essentially of a composition of the present
invention. In certain
preferred embodiments, such propellant composition is preferably a sprayable
composition, either alone or in combination with other known propellants.
In one aspect, the present compositions may be used for propelling objects,
including solid and/or liquid objects and/or gaseous objects, by applying to
such objects
a force generated by the present composition, such as would occur through the
expansion of the compositions of the present invention. For example, such
force may
preferably be provided, at least in part, by the change of phase of the
compositions of
the present invention from liquid to gas, and/or by the force released as a
result of a
substantial pressure reduction as the composition of the present invention
exits from a
pressurized container. In this way, the compositions of the present invention
may be
used to apply a burst of force, or a sustained force to an object to be
propelled.
Accordingly, the present invention comprises systems, containers and devices
which
include compositions of the present invention and which are configured to
propel or
move an object, either a liquid object or a solid object or a gaseous object,
with the
desired amount of force. Examples of such uses include containers (such as
pressurized cans and similar devices) which may be used, through the
propellant force,
to unblock drains, pipes or blockages in conduits, channels or nozzles.
Another
application includes use of the present composition to propel solid objects
through the
environment, particularly the ambient air, such as bullets, pellets, grenades,
nets,
canisters, bean bags, electrodes or other individual tethered or untethered
projectiles.
In other embodiments, the present compositions may be used to impart motion,
such as
a spitting motion, to gyroscopes, centrifuges, toys or other bodies to be
rotated, or to
impart a propelling force to solid objects, such as fireworks, confetti,
pellets, munitions
and other solid objects. In other applications, the force provided by the
compositions of
the present invention may be used to push or steer bodies in motion, including
rockets
or other projectiles.
The propellant compositions of the present invention preferably comprise a
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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,
cleaning solvents, and lubricants, as well as medicinal materials such as anti-
asthma
medications. The term medicinal materials is used herein in its broadest sense
to
include any and all materials which are, or at least are believe to be,
effective in
connection with therapeutic treatments, diagnostic methods, pain relief, and
similar
treatments, and as such would Include for example drugs and biologically
active
substances. The medicinal material in certain preferred embodiments are
adapted 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 HF0-1234ze and/or HF0-1234y1.
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 theforce 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.
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 HF0-1234ze, 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
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lungs or mucosa, 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.
The compositions of the present invention, particularly compositions which
comprise or consist essentially of HF0-1234ze, 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. HF0-1234ze 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 HF0-1234ze), 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.
FLAVORANTS AND FRAGRANCES
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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 favorable use a carrier for flavor formulations and
fragrances. It also
establishes its potential as an extractant of biologically active compounds
(such as
Biomass) and fragrances, including from plant matter. In certain embodiments,
it may
be preferred to use the present composition for in extraction applications
with the
present fluid in its supercritical state. This an other applications of
involving use of the
present compositions in the supercritical or near supercritical state are
described
hereinafter.
INFLATING AGENTS
One potential advantage of the compositions of the present invention is that
the
preferred compositions are in a gaseous state under most ambient conditions.
This
characteristic allows them to fill the space while not adding significantly to
the weight of
the space being spilled. Furthermore, the compositions of the present
invention are
able to be compressed or liquefied for relatively easy transportation and
storage. Thus,
for example, the compositions of the present invention may be included,
preferably but
not necessarily in liquid form, in a closed container, such as a pressurized
can, which
has a nozzle therein adapted to release the composition into another
environment in
which it will exist, at least for a period of time, as a pressurized gas. For
example, such
an application may include including the present compositions in a can adapted
to
connect to tires such as may be used on transportation vehicles (including
cars, trucks
and aircraft). Other examples in accordance with this embodiment include the
use of
the present compositions, in a similar arrangement, to inflate air bags or
other bladders
(including other protective bladders) adapted to contain, at least for a
period of time, a
gaseous material under pressure. Alternatively to the use of a fixed
container, such as
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can, the present compositions may be applied In accordance with this aspect of
the
invention through a hose or other system that contains the present
composition, either
in liquid or gaseous form, and through which it can be introduced into such a
pressurized environment as is required for the particular application.
METHODS AND SYSTEMS
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 in
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.
HEAT TRANSFER METHODS AND SYSTEMS
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,
either by sensible heat transfer, phase change heat transfer, or a combination
of these.
For example, in certain preferred embodiments the present methods provide
refrigeration systems comprising a refrigerant of the present invention and
methods of
producing heating or cooling by condensing and/or evaporating a composition of
the
present invention. In certain preferred embodiments, the methods for cooling,
including
cooling of other fluid either directly or indirectly or a body directly or
indirectly, comprise
condensing a refrigerant composition comprising a composition of the present
invention
and thereafter evaporating said refrigerant composition in the vicinity of the
article to be
cooled. As used herein, the term 'body" is intended to refer not only to
inanimate
objects but also to living tissue, including animal tissue in general and
human tissue in
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particular. For example, certain aspects of the present invention involve
application of
the present composition to human tissue for one or more therapeutic purposes,
such as
a pain killing technique, as a preparatory anesthetic, or as part of a therapy
involving
reducing the temperature of the body being treated. In certain embodiments,
the
application to the body comprises providing the present compositions in liquid
form
under pressure, preferably in a pressurized container having a one-way
discharge valve
and/or nozzle, and releasing the liquid from the pressurized container by
spraying or
otherwise applying the composition to the body. As the liquid evaporates from
the
surface being sprayed, the surface cools.
Certain preferred methods for heating a fluid or body comprise condensing a
refrigerant composition comprising a composition of the present invention in
the vicinity
of the fluid or body to be heated and thereafter evaporating said refrigerant
composition.
In light of the disclosure herein, those of skill in the art will be readily
able to heat and
cool articles according to the present inventions without undue
experimentation.
Applicants have found that in the systems and methods of the present invention
many of the important refrigeration system performance parameters are
relatively close
to the parameters for R-134a. Since many existing refrigeration systems have
been
designed for R-134a, or for other refrigerants with properties similar to R-
134a, those
skilled in the art will appreciate the substantial advantage of a low GWP
and/or a low
ozone depleting refrigerant that can be used as replacement for R-134a or like
refrigerants with relatively minimal modifications to the system. It is
contemplated that
in certain embodiments the present invention provides retrofitting methods
which
comprise replacing the heat transfer fluid (such as a refrigerant) in an
existing system
with a composition of the present invention, without substantial modification
of the
system. In certain preferred embodiments the replacement step is a drop-in
replacement in the sense that no substantial redesign of the system is
required and no
major item of equipment needs to be replaced in order to accommodate the
composition
of the present invention as the heat transfer fluid. In certain preferred
embodiments, the
methods comprise a drop-in replacement in which the capacity of the system is
at least
about 70%, preferably at least about 85%, and even more preferably at least
about 90%
of the system capacity prior to replacement. In certain preferred embodiments,
the
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methods comprise a drop-in replacement in which the suction pressure and/or
the
discharge pressure of the system, and even more preferably both, is/are at
least about
70%, more preferably at least about 90% and even more preferably at least
about 95%
of the suction pressure and/or the discharge pressure prior to replacement. In
certain
preferred embodiments, the methods comprise a drop-in replacement in which the
mass
flow of the system is at least about 80%, and even more preferably at least
90% of the
mass flow prior to replacement.
In certain embodiments the present invention provides cooling by absorbing
heat
from a fluid or body, 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
in such
embodiments 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.
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.
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FOAM BLOWING METHODS
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 inventions,
adding
(directly or indirectly) the blowing agent composition to a foamabie
composition, and
reacting the foamable composition under the 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, NY,
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.
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, auxiliary blowing agents, and even other polyols can be added 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.
It is also possible to produce thermoplastic foams using the compositions of
the
invention. For example, conventional polystyrene and polyethylene formulations
may be
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combined with the compositions in a conventional manner to produce rigid
foams.
CLEANING METHODS
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.
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 US Patent No.6,589,365 .
For supercritical cleaning
applications, is preferred in certain embodiments to include in the present
cleaning
compositions, in addition to the HFO-1234 (preferably HF0-1234ze), one or more
additional components, such as CO2 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.
FLAMMABILITY REDUCTION METHODS
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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 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.
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.
FLAME SUPPRESSION METHODS
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.
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STERILIZATION METHODS
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 comprising a compound of
Formula I,
preferably HFO-1234, and even more preferably HFO-1234ze, in combination with
one
or more sterilizing agents. While many sterilizing agents are known in the art
and are
considered to be adaptable for use in connection with the present invention,
in certain
preferred embodiments sterilizing agent comprises ethylene oxide,
formaldehyde,
hydrogen peroxide, chlorine dioxide, ozone and combinations of these. In
certain
embodiments, ethylene oxide is the preferred sterilizing agent. Those skilled
in the art,
in view of the teachings contained herein, will be able to readily determine
the relative
proportions of sterilizing agent and the present compound(s) to be used in
connection
with the present sterilizing compositions and methods, and all such ranges are
within
the broad scope hereof. As is known to those skilled in the art, certain
sterilizing
agents, such as ethylene oxide, are relatively flammable components, and the
compound(s) in accordance with the present invention are included in the
present
compositions in amounts effective, together with other components present in
the
composition, to reduce the flammability of the sterilizing composition to
acceptable
levels.
The sterilization methods of the present invention may be either high or 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 250 F to
about
270 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. In low temperature sterilization methods, the
article to be
sterilized is exposed to a fluid comprising a composition of the present
invention at a
temperature of from about room temperature to about 200 F, more preferably at
a
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temperature of from about room temperature to about 100 F.
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.
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.
SUPERCRITICAL METHODS
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
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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.
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.
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.
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.
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.
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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
The following examples are provided for the purpose of illustrating the
present
invention but without limiting the scope thereof.
EXAMPLE I
The coefficient of performance (COP) is a universally accepted measure of
refrigerant performance, especially useful in representing the relative
thermodynamic
efficiency of a refrigerant in a specific heating or cooling cycle involving
evaporation or
condensation of the refrigerant. In refrigeration engineering, this term
expresses the
ratio of useful refrigeration to the energy applied by the compressor in
compressing the
vapor. The capacity of a refrigerant represents the amount of cooling or
heating it
provides and provides some measure of the capability of a compressor to pump
quantities of heat for a given volumetric flow rate of refrigerant. In other
words, given a
specific compressor, a refrigerant with a higher capacity will deliver more
cooling or
heating power. One means for estimating COP of a refrigerant at specific
operating
conditions is from the thermodynamic properties of the refrigerant using
standard
refrigeration cycle analysis techniques (see for example, R.C. Downing,
FLUOROCARBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988).
A refrigeration /air conditioning cycle system is provided where the condenser
temperature is about 150 F and the evaporator temperature is about -35 F under
nominally isentropic compression with a compressor inlet temperature of about
50 F.
COP is determined for several compositions of the present invention over a
range of
condenser and evaporator temperatures and reported in Table 1 below, based
upon
HFC-134a having a COP value of 1.00, a capacity value of 1.00 and a discharge
temperature of 175 F.
TABLE I
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REFRIGERANT Relative COP Relative DISCHARGE
COMPOSTION CAPACITY TEMPERATURE
( F)
HFO 1225ve 1.02 0.76 158
HFO trans-1234ze 1.04 0.70 165
HFO cis-1234ze 1.13 0.36 155
HFO 1234vf 0.98 1.10 168
This example shows that certain of the preferred compounds for use with the
present compositions each have a better energy efficiency than HFC-134a (1.02,
1.04
and 1.13 compared to 1.00) and the compressor using the present refrigerant
compositions will produce discharge temperatures (158, 165 and 155 compared to
175),
which is advantageous since such result will likely leading to reduced
maintenance
problems. Moreover, it is evident from the above table that one embodiment of
the
present invention, namely one in which the refrigerant composition comprises,
and
preferably comprises at least about 70% by weight of HFO-1234yf, has a
dramatically
superior performance in terms of relative capacity in comparison not only to R-
134a, but
also to embodiments in which the refrigerant consists essentially of HFO-
1234ze. in
certain preferred embodiments, therefore the present invention provides
methods for
heating or cooling an article or fluid comprising using a composition
comprising at least
about 80% by weight of HFO-1234yf, and even more preferably at least about 90%
by
weight, and in which the capacity of the refrigeration system is at least
about 100%,
more preferably at least about 105%, of the capacity of the same system with R-
134a
used as the refrigerant.
EXAMPLE 2
The miscibility of HFO-1225ye and HFO-1234ze with various refrigeration
lubricants is tested. The lubricants tested are mineral oil (C3), alkyl
benzene (Zerol
150), ester oil (Mobil EAL 22 cc and Solest 120), polyalkylene glycol (PAG)
oil
(Goodwrench Refrigeration Oil for 134a systems), and a poly(alpha-olefin) oil
(CP-6005-
100). For each refrigerant/oil combination, three compositions are tested,
namely 5,20
and 50 weight percent of lubricant, with the balance of each being the
compound of the
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present invention being tested
The lubricant compositions are placed in heavy-walled glass tubes. The tubes
are evacuated, the refrigerant compound in accordance with the present
invention is
added, and the tubes are then sealed. The tubes are then put into an air bath
environmental chamber, the temperature of which is varied from about -50 C to
70 C.
At roughly 10 C intervals, visual observations of the tube contents are made
for the
existence of one or more liquid phases. In a case where more than one liquid
phase is
observed, the mixture is reported to be immiscible. In a case where there is
only one
liquid phase observed, the mixture is reported to be miscible. In those cases
where two
liquid phases were observed, but with one of the liquid phases occupying only
a very
small volume, the mixture is reported to be partially miscible.
The polyalkylene glycol and ester oil lubricants were judged to be miscible in
all
tested proportions over the entire temperature range, except that for the HF0-
1225ye
mixtures with polyalkylene glycol, the refrigerant mixture was found to be
immiscible
over the temperature range of ¨50 C to ¨30 C and to be partially miscible=over
from ¨20
to 50 C. At 50 weight percent concentration of the PAG in refrigerant and at
60 , the
refrigerant/PAG mixture was miscible. At 70 C, it was miscible from 5 weight
percent
lubricant in refrigerant to 50 weight percent lubricants in refrigerant.
EXAMPLE 3
The compatibility of the refrigerant compounds and compositions of the present
invention with PAG lubricating oils while in contact with metals used in
refrigeration and
air conditioning systems is tested at 350 C, representing conditions much
more severe
than are found in many refrigeration and air conditioning applications.
Aluminum, copper and steel coupons are added to heavy walled glass tubes.
Two grams of oil are added to the tubes. The tubes are then evacuated and one
gram
of refrigerant is added. The tubes are put into an oven at 350 F for one week
and visual
observations are made. At the end of the exposure period, the tubes are
removed.
This procedure was done for the following combinations of oil and the compound
of the present invention:
a) HFC-1234ze and GM Goodwrench PAG oil
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b) HFC1243 zf and GM Goodwrench oil PAG oil
C) HFC-1234ze and MOPAR-56 PAG oil
d) HFC-1243 zf and MOPAR-56 PAG oil
e) HFC-1225 ye and MOPAR-56 PAG oil.
In all cases, there is minimal change in the appearance of the contents of the
tube. This indicates that the refrigerant compounds and compositions of the
present
invention are stable in contact with aluminum, steel and copper found in
refrigeration
and air conditioning systems, and the types of lubricating oils that are
likely to be
included in such compositions or used with such compositions in these types of
systems.
COMPARATIVE EXAMPLE
Aluminum, copper and steel coupons are added to a heavy walled glass tube
with mineral oil and CFC-12 and heated for one week at 350 C, as in Example 3.
At the
end of the exposure period, the tube is removed and visual observations are
made.
The liquid contents are observed to turn black, indicating there is severe
decomposition
of the contents of the tube.
CFC-12 and mineral oil have heretofore been the combination of choice in many
refrigerant systems and methods. Thus, the refrigerant compounds and
compositions
of the present invention possess significantly better stability with many
commonly used
lubricating oils than the widely-used prior art refrigerant-lubricating oil
combination.
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EXAMPLE 4¨ POLYOL FOAM
This example illustrates the use of blowing agent in accordance with one of
the
preferred embodiments of the present invention, namely the use of HF0-1234ze,
and
the production of polyol foams in accordance with the present invention. The
components of a polyol foam formulation are prepared in accordance with the
following
Table 2:
TABLE 2
PoIvo, Component PBW
Voranol 490 50
Voranol*391 50
Water 0.5
B-8462 (surfactant) 2.0
Polycat*8 0.3
Polycat*41 3.0 =
HF0-1234ze 35
Total 140.8
lsocvanate
M-20S 123.8 Index 1.10
*Voranol 490 is a sucrose-based polyol and Voranol 391 is a toluene
diamine based polyol, and each are from Dow Chemical. B-8462 is a
surfactant available from Degussa-Goldschmidt. Polytat catalysts
= are tertiary amine based and are available from Air Products.
Isocyanate M-20S is a product of Bayer LLC.
The foam is prepared by first mixing the ingredients thereof, but without the
addition of
blowing agent Two Fisher-Porter tubes are each filled with about 52.6 grams of
the
polyol mixture (without blowing agent) and sealed and placed in a refrigerator
to cool
and form a slight vacuum. Using gas burets, about 17.4 grams of HF0-1234ze are
added to each tube, and the tubes are then placed in an ultrasound bath in
warm water
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.
.
and allowed to sit for 30 minutes. The solution produced is hazy, and a vapor
pressure
measurement at room temperature indicates a vapor pressure of about 70 psig
indicating that the blowing agent is not in solution. The tubes are then
placed in a
freezer at 27 F for 2 hours. The vapor pressure was again measured and found
to be
14-psig. The isocyanate mixture, about 87.9 grams, is placed into a metal
container
and placed in a refrigerator and allowed to cool to about 50 F. The polyol
tubes were
then opened and weighed into a metal mixing container (about 100 grams of
polyol
blend are used). The isocyanate from the cooled metal container is then
immediately
poured into the polyol and mixed with an air mixer with double propellers at
3000 RPM's
for 10 seconds. The blend immediately begins to froth with the agitation and
is then
poured into an 8x8x4 inch box and allowed to foam. Because of the froth, a
cream time
can not be measured. The foam has a 4-minute gel time and a 5-minute tack free
time.
The foam is then allowed to cure for two days at room temperature.
The foam is then cut to samples suitable for measuring physical properties and
is found
to have a density of 2.14 pcf. K-factors are measured and found to be as
indicated in
the following Table 3:
TABLE 3
Temperature K, BTU In / Ft2 h F
40 F 0.1464
75 F 0.1640
110 F 0.1808
EXAMPLE 5¨ POLSTYRENE FOAM
This example illustrates the use of blowing agent in accordance with two
preferred
embodiments of the present invention, namely the use of HF0-1234ze and HF0-
1234yf, and the production of polystyrene foam. A testing apparatus and
protocol has
been established as an aid to determining whether a specific blowing agent and
polymer are capable of producing a foam and the quality of the foam. Ground
polymer
(Dow Polystyrene 685D) and blowing agent consisting essentially of HF0-1234ze
are
combined in a vessel. A sketch of the vessel is illustrated below. The vessel
volume is
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200 cm3 and it is made from two pipe flanges and a section of 2-inch diameter
schedule
40 stainless steel pipe 4 inches long. The vessel_ shown in figure 1 is placed
in an oven, with
temperature set at from about 190 F to about 285 F, preferably for polystyrene
at 265 F, and
remains there until temperature equilibrium is reached.
The pressure in the vessel is then released, quickly producing a foamed
polymer. The
blowing agent plasticizes the polymer as it dissolves into it. The resulting
density of the
Iwo foams thus produced using this method are given in Table 4 and graphed in
Figure
1 as the density of the foams produced using trans-HF0-1234ze and HF0-1234yf.
The
data show that foam polystyrene is obtainable in accordance with the present
invention.
The die temperature for R1234ze with polystyrene is about 250 F.
TABLE 4
Dow polystyrene 685D
Foam density (Ibtft3)
T F transHF0-1234zeIHF0-1234yi
275 55.15
260 22.14 14.27
250 7.28 24.17
240 16.93
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EXAMPLE 6
This example illustrates the performance of one embodiment of the present
invention in which a refrigerant composition comprises HFO-1234 wherein a
large
proportion, and preferably at least about 75% by weight and even more
preferably at
least about 90% by weight, of the HF0-1234 is HF0-1234yf. More particularly,
such a
composition is used as a replacement for HFC-134a in four refrigerant systems.
The
first system is one have an evaporator temperature (ET) of about 20 F and
condenser
temperature (CT) of about 130 F (Example 6A). For the purposes of convenience,
such heat transfer systems, that is, systems having an ET of from about 0 to
about 35
and a CT of from about 80 F to about 130 F, are referred to herein as "medium
temperature" systems. The second system is one have an ET of about -10 F and a
CT
of about 110 F (Example 6B). For the purposes of convenience, such heat
transfer
systems, that is, systems having an evaporator temperature of from about -20 F
to
about 20 F and a CT of from about 80 F to about 130 F, are referred to herein
as
"refrigifreezer systems. The third system is one have an ET of about of 35 F
and a CT
of about 150 F (Example 6C). For the purposes of convenience, such heat
transfer
systems, that is, systems having an evaporator temperature of from about 30 F
to about
60 F and a CT of from about 90 F to about 200 F, are referred to herein as
"automotive
AC" systems. The fourth system is one have an ET of about 40 F and a CT of
about
60 F (Example 6D). For the purposes of convenience, such heat transfer
systems, that
is, systems having an evaporator temperature of from about 35 F to about 50 F
and a
CT of from about 80 F to about 120 F, are referred to herein as "chiller" or
"chiller AC"
systems The operation of each of such systems using R-134a and a refrigeration
composition comprising at least about 90% by weight of HF0-1234yf is reported
in
Tables 6A - D below:
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TABLE 6A - Medium Temp Conditions 20 F ET and 130 F CT
R-134a HF0-1234y1
Performance Property Units
Capacity* Btu/hr 2541 2519
Re! to R-134a 99.1%
COP 2.31 2.27
Re! to R-134a 98.3%
Discharge Press. psig 198.7 190.3.
Re! to R-134a 95.8%
Suction Press. psig 18.4 22.5
Re! to R-134a 122.3%
Mass Flow lb/hr 0.673 0.958
Rel to R-134a 142.3%
*Capacity per CFM of compressor displacement (Volumetric Capacity)
TABLE 6B ¨ Refrig/Freezer Temp Conditions 10 F ET and 110 F CT
R-134a HF0-1234yf
Performance Property Units
Capacity* Btu/hr 1234 1293
Re! to R-134a 104.8%
COP 1.77 1.71
=
Rel to R-134a 96.6%
Discharge Press. psig 146.4 145.4
Re! to R-134a 99.3%
Suction Press. psig 1.9 6.0
Re! to R-134a 315.8%
Mass Flow lb/hr 0.342 0.427
Re! to R-134a 124.9%
* Capacity per CFM of compressor displacement (Volumetric Capacity)
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TABLE 6C ¨ Auto AC Temp Conditions 35 F ET and 150 F CT
R-134a HF0-1234y1
Performance Property Units
Capacity* Btu/hr 2754 2612
Rel to R-134a 94.8%
COP 1.91 1.84
Rel to R-134a 96.3%
Discharge Press. psig 262.9 247.3
Re! to R-134a 94.1%
Suction Press. psIg 30.4 34.5
Rel to R-134a 113.5%
Mass Flow lb/hr 0.891 1.235
Rel to R-134a 138.6%
* Capacity per CFM of compressor displacement (Volumetric Capacity)
TABLE 6D ¨ Chiller Temp Conditions 40 F ET and 95 F CT
R-134a HF0-1234yf
Performance Property Units
Capacity* Btu/hr 4236 4060
Rel to R-134a
95.8%
COP 6.34 6.23
Re! to R-134a 98.3%
Discharge Press. psig 113.9 113.5
Rel to R-134a 99.6%
Suction Press. psig 35.0 38.7
Rel to R-134a 110.6%
Mass Flow lb/hr 1.034 1.268
Re! to R-134a 122.6%
* Capacity per CFM of compressor displacement (Volumetric Capacity)
As can be seen from the Tables above, many of the important refrigeration
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system performance parameters are relatively close to the parameters for R-
134a.
Since many existing refrigeration systems have been designed for R-134a, or
for other
refrigerants with properties similar to R-134a, those skilled in the art will
appreciate the
substantial advantage of a low GWP and/or a low ozone depleting refrigerant
that can
be used as replacement for R-134a or like refrigerants with relatively minimal
modifications to the system. It is contemplated that in certain embodiments
the present
invention provided retrofitting methods which comprise replacing the
refrigerant in an
existing system with a composition of the present invention, preferably a
composition
comprising at least about 90% by weight and/or consists essentially of HFO-
1234 and
even more preferably HF0-1234yf, without substantial modification of the
system. In
certain preferred embodiments the replacement step is a drop-in replacement in
the
sense that no substantial redesign of the system is required and no major item
of
equipment needs to be replaced in order to accommodate the refrigerant of the
present
invention.
47
