Note: Descriptions are shown in the official language in which they were submitted.
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AZEOTROPE-LIKE COMPOSITION OF 1,1,1,2,2,3,3-HEPTAFLITOR0-3-
METHOXYPROPANE AND 1-CHLOR0-3,3,3-TRIFLUOROPROPENE
FIELD OF INVENTION
The present invention relates to azeotrope-like compositions of 1,1,1,2,2,3,3-
heptafluom-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd)
and
uses thereof.
BACKGROUND
Fluorocarbon based fluids have found widespread use in industry in a number of
applications, including as refrigerants, aerosol propellants, blowing agents,
heat
transfer media, and gaseous dielectrics. Because of the suspected
environmental
problems associated with the use of some of these fluids, including the
relatively high
global warming potentials associated therewith, it is desirable to use fluids
having low
or even zero ozone depletion potential. Additionally, the use of single
component
fluids or azeotropic mixtures, which do not fractionate on boiling and
evaporation, is
desirable. However, the identification of new, environmentally safe, non-
fractionating
mixtures is complicated due to the fact that azeotrope foimation is not
readily
predictable.
The industry is continually seeking new fluorocarbon based mixtures that offer
alternatives, and are considered environmentally safer substitutes for CFCs
and
HCFCs.
The Montreal Protocol for the protection of the ozone layer, signed in October
1987,
mandate the phase out of the use of chlorofluorocarbons (CFCs). Materials more
"friendly" to the ozone layer, such as hydrofluorocarbons (HFCs) eg HFC-134a
replaced chlorofluorocarbons. The latter compounds have proven to be green
house
gases, causing global warming and were regulated by the Kyoto Protocol on
Climate
Change, signed in 1998. The emerging replacement materials.
hydrofluoropropenes,
were shown to be environmentally acceptable ie has zero ozone depletion
potential
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(ODP) and acceptable low GWP.
Currently proposed replacement refrigerants for hydrofluorocarbons such as RFC-
134a include HFC-152a, pure hydrocarbons such as butane or propane. or
"natural"
refrigerants such as CO,. Many of these suggested replacements are, flammable,
and/or have low energy efficiency. Therefore, new alternative refrigerants are
being
sought. Fluoroolefin materials such as hydrofluoropropenes and/or
hydrochlorofluoropropenes have generated interest as replacements for HFCs.
The object of the present invention is to provide novel compositions that can
serve as
refrigerants, heat transfer fluids, blowing agents, solvents, de-fluxing
agents,
degreasers, aerosols, etc. that provide unique characteristics to meet the
demands of
low or zero ozone depletion potential and lower global warming potential as
compared to the current HFCs.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is graph of Pressure (bar) versus molar ratio of 1,1,1,2,2,3.3-
heptafluoro-3-
methoxypropane.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present inventors have developed several compositions that help to satisfy
the
continuing need for alternatives to CFCs and HCFCs. According to certain
embodiments, the present invention provides azeotrope-like compositions
comprising
1,1,1,2,2,3,3-heptafluoro-3-methoxypropane with E-1-chloro-3,3,3-
trifluoropropene
(E-12337d).
The preferred compositions of the invention tend both to be non-flammable and
to
exhibit relatively low global warming potentials ("GWPs"). Accordingly,
applicants
have recognized that such compositions can be used to great advantage in a
number of
applications, including as replacements for CFCs, IICFCs, and IIFCs (such as
HCFC123, HFC134a, HFC 245fa, HFC 365mfc etc.) in refrigerant, aerosol, and
other
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applications.
Additionally, applicants have recognized surprisingly that azeotrope-like
compositions of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane with E-1-chloro-
3,3,3-
trifluoropropene (E-1233zd) can be formed. Accordingly, in other embodiments,
the
present invention provides methods of producing an azeotrope-like composition
comprising combining 1,1,1,2,2,3,3-heptatluoro-3-methoxypropane with E-1-
chloro-
3,3,3-trifluoropropene (E-1233zd) in amounts effective to produce an azeotrope-
like
composition.
In addition, applicants have recognized that the azeotrope-like compositions
of the
present invention exhibit properties that make them advantageous for use as,
or in,
refrigerant compositions and in foam blowing agents. Accordingly, in yet other
embodiments, the present invention provides refrigerant compositions and/or
flowing
blowing agents, and solvents comprising an azeotrope-like composition of
1,1,1,2,2,3,3-heptafluoro-3-methoxypropane with E-1-chloro-3,3,3-
trifluoropropene
(E-1233zd).
Azeotrope-Like Compositions
As used herein, the term "azeotrope-like" is intended in its broad sense to
include both
compositions that are strictly azeotropic and compositions that behave like
azeotropic
mixtures. From fundamental principles, the thermodynamic state of a fluid is
defined
by pressure, temperature, liquid composition, and vapor composition. An
azeotropic
.. mixture is a system of two or more components in which the liquid
composition and
vapor composition are equal at the stated pressure and temperature. In
practice, this
means that the components of an azeotropic mixture are constant boiling and
cannot
he separated during a phase change.
The azeotrope-like compositions of the present invention may include
additional
components that do not form new azeotrope-like systems, or additional
components
that are not in the first distillation cut. The first distillation cut is the
first cut taken
after the distillation column displays steady state operation under total
reflux
conditions. One way to determine whether the addition of a component foims a
new
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azeotrope-like system so as to be outside of this invention is to distill a
sample of the
composition with the component under conditions that would be expected to
separate
a non-azeotropic mixture into its separate components. If the mixture
containing the
additional component is non-azeotrope-like, the additional component will
fractionate
.. from the azeotrope-like components. If the mixture is azeotrope-like, some
finite
amount of a first distillation cut will be obtained that contains all of the
mixture
components that is constant boiling or behaves as a single substance.
It follows from this that another characteristic of azeotrope-like
compositions is that
.. there is a range of compositions containing the same components in varying
proportions that are azeotrope-like or constant boiling. All such compositions
are
intended to be covered by the terms "azeotrope-like" and "constant boiling".
As an
example, it is well known that at differing pressures, the composition of a
given
azeotrope will vary at least slightly, as does the boiling point of the
composition.
Thus, an azeotrope of A and B represents a unique type of relationship, but
with a
variable composition depending on temperature and/or pressure. It follows
that, for
azeotrope-like compositions, there is a range of compositions containing the
same
components in varying proportions that are azeotrope-like. All such
compositions are
intended to be covered by the term azeotrope-like as used herein.
It is well recognized in the art that it is not possible to predict the
formation of
azeotropes. Applicants have discovered unexpectedly that 1,1,1,2,2,3,3-
heptafluoro-3-
methoxypropane with E-1-chloro-3,3,3-trifluoropropene (E-1233zd) form
azeotrope-
like compositions.
According to certain preferred embodiments, the azeotrope-like compositions of
the
present invention comprise, and preferably consist essentially of, effective
azeotrope-
like amounts of l ,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-
3,3,3-
trifluoropropene (E-1233zd). The teim "effective azeotrope-like amounts" as
used
herein refers to the amount of each component which upon combination with the
other component, results in the formation of an azeotrope-like composition of
the
present invention. Preferably, the present azeotrope-like compositions
comprise, and
preferably consist essentially of, from about 99 to about 1 weight percent
1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and from about 1 to about 99 weight
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percent of E-1-chloro-3,3,3-trifluoropropene (E-1233zd). More preferably, the
azeotrope-like compositions comprise, and preferably consist essentially of,
from
about 85 to about 10 weight percent 1,1,1,2,2,3,3-heptafluoro-3- and from
about 15 to
about 90 weight percent of -1-chloro-3,3,3-trifluoropropene (E-1233zd). Even
more
preferably, the azeotrope-like compositions comprise, and preferably consist
essentially of, from about 75 to about 20 weight percent 1,1,1,2,2,3,3-
heptafluoro-3-
and from about 25 to about 80 weight percent of E-1-chloro-3,3,3-
trifluoropropene
(E-1233zd). Unless otherwise indicated, the weight percents disclosed herein
are
based on the total weight of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-
1-
chloro-3,3,3-trifluoropropene (E-1233zd) in a composition.
The azeotrope-like compositions described herein preferably have a boiling
point of
from about 10 C to about 34 C at a pressure of about 1.013 bar. In certain
more
preferred embodiments, the present azeotrope-like compositions have a boiling
point
of from about 12 C to about 28 C at a pressure of about 1.013 bar amd more
preferably boiling point of from about 14 C to about 26 C at a pressure of
about
1.013 bar.
The azeotrope-like compositions of the present invention can be produced by
combining effective azeotrope-like amounts of 1,1,1,2,2,3,3-heptafluoro-3-
methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd). Any of a wide
variety of methods known in the art for combining two or more components to
form a
composition can be adapted for use in the present methods to produce an
azeotrope-
like composition. For example, 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and
E-1-
chloro-3,3,3-trifluoropropene (E-1233zd) can be mixed, blended, or otherwise
contacted by hand and/or by machine, as part of a batch or continuous reaction
and/or
process, or via combinations of two or more such steps. In light of the
disclosure
herein, those of skill in the art will be readily able to prepare azeotrope-
like
compositions according to the present invention without undue experimentation.
Composition Additives
The azeotrope-like compositions of the present invention may further include
any of a
variety of optional additives including stabilizers, metal passivators,
corrosion
5
inhibitors, and the like.
In certain preferred embodiments, the compositions of the present invention
further
comprise a lubricant. Any of a variety of conventional lubricants may be used
in the
compositions of the present invention. An important requirement for the
lubricant is
that, when in use in a refrigerant system, there must be sufficient lubricant
returning
to the compressor of the system such that the compressor is lubricated. Thus,
suitability of a lubricant for any given system is determined partly by the
refrigerant/lubricant characteristics and partly by the characteristics of the
system in
which it is intended to be used. Examples of suitable lubricants include
mineral oil,
alkyl benzenes, polyvinyl ethers, polyalpha olefns, polyol esters, including
polyalkylene glycols, PAG oil, and the like. Mineral oil, which comprises
paraffin oil
or naphthenic oil, is commercially available. Commercially available mineral
oils
include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered
trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015
from Calumet. Commercially available alkyl benzene lubricants include Zerol
150
(registered trademark). Commercially available esters include neopentyl glycol
dipelargonate which is available as Emery 2917 (registered trademark) and
Hatcol
2370 (registered trademark). Other useful esters include phosphate esters,
dibasic acid
esters, and fluoroesters. Preferred lubricants include polyalkylene glycols
and esters.
Certain more preferred lubricants include polyalkylene glycols.
Uses of the Compositions
The present compositions have utility in a wide range of applications. For
example,
one embodiment of the present invention relates to refrigerant compositions
comprising the present azeotrope-like compositions.
The refrigerant compositions of the present invention may be used in any of a
wide
variety of refrigeration systems including air-conditioning, refrigeration,
heat-pump,
chiller, heat engines, high temperature heat pumps, HVAC systems, and the
like.
Vapor-compression refrigeration, air-conditioning, or heat pump systems
typically
include an evaporator, a compressor, a condenser, and an expansion device. A
vapor-
compression cycle re-uses refrigerant in multiple steps producing a cooling
effect in
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one step and a heating effect in a different step. A typical cycle can be
described
simply as follows: liquid refrigerant enters an evaporator through an
expansion
device, and the liquid refrigerant boils in the evaporator at a low
temperature to foun
a gas and produce cooling. The low-pressure gas enters a compressor where the
gas is
compressed to raise its pressure and temperature. The higher-pressure
(compressed)
gaseous refrigerant then enters the condenser in which the refrigerant
condenses and
discharges its heat to the environment. The refrigerant returns to the
expansion device
through which the liquid expands from the higher-pressure level in the
condenser to
the low-pressure level in the evaporator, thus repeating the cycle. A heat
pump is a
device typically used to move heat from one source (a "source") to another (a
"sink");
a reversible heat pump can be used to heat or cool, depending upon operation.
In
HVACR operations, a heat pump is typically a vapor-compression refrigerating
device that includes a reversing valve to reverse the direction of heat flow.
Heat
engines, such as Rankine Cycles and Organic Rankine Cycles, are typically used
to
convert heat energy into mechanical work, particularly for power generation.
In certain preferred embodiments, the compositions of the present invention
are used
in refrigeration systems originally designed for use with an HCFC refrigerant,
such as,
for example, HCFC123. The preferred compositions of the present invention tend
to
exhibit many of the desirable characteristics of HCFC123 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. In addition,
the
relatively constant boiling nature of the compositions of the present
invention makes
them even more desirable than certain conventional IIFCs for use as
refrigerants in
many applications.
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, silicone oils, 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.
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Such refrigeration systems include, for example, air conditioners, electric
refrigerators, chillers, transport refrigeration systems, commercial
refrigeration
systems and the like.
Any of a wide range of methods for introducing the present refrigerant
compositions
to a refrigeration system can he used in the present invention. For example,
one
method comprises attaching a refrigerant container to the low-pressure side of
a
refrigeration system and turning on the refrigeration system compressor to
pull the
refrigerant into the system. In such embodiments, the refrigerant container
may be
placed on a scale such that the amount of refrigerant composition entering the
system
can be monitored. When a desired amount of refrigerant composition has been
introduced into the system, charging is stopped. Alternatively, a wide range
of
charging tools, known to those of skill in the art, is commercially available.
Accordingly, in light of the above disclosure, those of skill in the art will
be readily
able to introduce the refrigerant compositions of the present invention into
refrigeration systems according to the present invention without undue
experimentation.
According to certain other embodiments, the present invention provides
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 an
article
according to the present invention comprise condensing a refrigerant
composition
comprising an azeotrope-like composition of the present invention and
thereafter
evaporating said refrigerant composition in the vicinity of the article to be
cooled.
Certain preferred methods for heating an article comprise condensing a
refrigerant
composition comprising an azeotrope-like composition of the present invention
in the
vicinity of the article 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.
In another embodiment, the azeotrope-like compositions of this invention may
be
used as propellants in sprayable compositions, either alone or in combination
with
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known propellants. The propellant composition comprises, more preferably
consists
essentially of, and, even more preferably, consists of the azeotrope-like
compositions
of the invention. The active ingredient to be sprayed together with inert
ingredients,
solvents, and other materials may also be present in the sprayable mixture.
Preferably,
the sprayable composition is an aerosol. Suitable active materials to be
sprayed
include, without limitation, cosmetic materials such as deodorants, perfumes,
hair
sprays, cleansers, and polishing agents as well as medicinal materials such as
anti-
asthma and anti-halitosis medications.
Yet another embodiment of the present invention relates to a blowing agent
comprising one or more azeotrope-like compositions of the invention. In other
embodiments, the invention provides foamable compositions, and preferably
polyurethane and polyisocyanurate foam compositions, and methods of preparing
foams. In such foam embodiments, one or more of the present azeotrope-like
.. compositions are included as a blowing agent in a foamable composition,
which
composition preferably includes one or more additional components capable of
reacting and foaming under the proper conditions to form a foam or cellular
structure,
as is well known in the art. Any of the methods well known in the art, may be
used or
adapted for use in accordance with the foam embodiments of the present
invention.
Another embodiment of this invention relates to a process for preparing a
foamed
thermoplastic product is as follows: Prepare a foamable polymer composition by
blending together components comprising foamable polymer composition in any
order. Typically, a foamable polymer composition is prepared by plasticizing a
polymer resin and then blending in components of a blowing agent composition
at an
initial pressure. A common process of plasticizing a polymer resin is heat
plasticization, which involves heating a polymer resin enough to soften it
sufficiently
to blend in a blowing agent composition. Generally, heat plasticization
involves
heating a thermoplastic polymer resin to or near to its glass transition
temperature
(Tg), or melt temperature (Tm) for crystalline polymers.
Other uses of the present azeotrope-like compositions include use as solvents,
cleaning agents, and the like. Examples include vapor degreasing, precision
cleaning,
electronics cleaning, drying cleaning, solvent etching cleaning, carrier
solvents for
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depositing lubricants and release agents, and other solvent or surface
treatment. Those
of skill in the art will be readily able to adapt the present compositions for
use in such
applications without undue experimentation.
EXAMPLES
The invention is further illustrated in the following examples which are
intended to be
illustrative, but not limiting in any manner.
Example 1
Vapor-liquid equilibrium measurements for a binary system of 1,1,1,2,2,3,3-
heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene were taken
in a
vacuum cell equipped with a saphir tube is heated at 100 C using an oil bath.
Once
temperature equilibrium was reached, the cell was charged with a known amount
of
E-1-chloro-3,3,3-trifluoropropene the product with the lowest boiling point,
and the
pressure at which equilibrium was reached was recorded. A known amount of
1,1,1,2,2,3,3-heptafluoro-3-methoxypropane was introduced in the cell and the
content was mixed in order to accelerate equilibrium. At equilibrium, a very
small
quantity of a sample was taken from the gaseous phase as well as the liquid
phase to
be analysed by gas chromatography with thermal detector. Figure 1 is a graph
of
pressure in bar versus the molar ratio of 1,1,1,2,2,3,3-heptafluoro-3-
methoxypropane
for a binary system of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-
chloro-
3,3,3-trifluoropropene showing the azeotrope-like properties of the
combination of the
present invention.
Although the invention is illustrated and described herein with reference to
specific
embodiments, it is not intended that the appended claims be limited to the
details
shown. Rather, it is expected that various modifications may be made in these
details
by those skilled in the art, which modifications may still be within the
spirit and scope
of the claimed subject matter and it is intended that these claims be
construed
accordingly.
