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Patent 2879541 Summary

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(12) Patent Application: (11) CA 2879541
(54) English Title: AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS OF E-1,3,4,4,4-PENTAFLUORO-3-TRIFLUOROMETHYL-1-BUTENE AND Z-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE AND USES THEREOF
(54) French Title: COMPOSITIONS AZEOTROPES ET DE TYPE AZEOTROPE DE E-1,3,4,4,4-PENTAFLUORO-3-TRIFLUOROMETHYL-1-BUTENE ET Z-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE ET LEURS UTILISATIONS
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • C08J 9/14 (2006.01)
  • C09K 5/04 (2006.01)
(72) Inventors :
  • ROBIN, MARK L. (United States of America)
(73) Owners :
  • E. I. DU PONT DE NEMOURS AND COMPANY (United States of America)
(71) Applicants :
  • E. I. DU PONT DE NEMOURS AND COMPANY (United States of America)
(74) Agent: TORYS LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2013-08-01
(87) Open to Public Inspection: 2014-02-06
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2013/053175
(87) International Publication Number: WO2014/022638
(85) National Entry: 2015-01-19

(30) Application Priority Data:
Application No. Country/Territory Date
61/678,260 United States of America 2012-08-01

Abstracts

English Abstract

Azeotropic or azeotrope-like compositions are disclosed. The azeotropic or azeotrope-like compositions are mixtures of E-1,3,4,4,4-pentafluoro-3-trifluoromethyl-1-butene and Z-1,1,1,4,4,4-hexafluoro-2-butene. Also disclosed is a process of preparing a thermoplastic or thermoset foam by using such azeotropic or azeotrope-like compositions as blowing agents. Also disclosed is a process of producing refrigeration by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as solvents. Also disclosed is a process of producing an aerosol product by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as heat transfer media. Also disclosed is a process of extinguishing or suppressing a fire by using such azeotropic or azeotrope-like compositions. Also disclosed is a process of using such azeotropic or azeotrope-like compositions as dielectrics.


French Abstract

L'invention concerne des compositions azéotropes ou de type azéotrope. Les compositions azéotropes ou de type azéotrope sont des mélanges de E-1,3,4,4,4-pentafluoro-3-trifluorométhyl-1-butène et de Z-1,1,1,4,4,4-hexafluoro-2-butène. L'invention concerne aussi un procédé de préparation d'une mousse thermoplastique ou thermodurcissable en utilisant ces compositions azéotropes ou de type azéotrope en tant qu'agents gonflants. L'invention concerne aussi un procédé de production de réfrigération en utilisant ces compositions azéotropes ou de type azéotrope. L'invention concerne aussi un procédé d'utilisation de ces compositions azéotropes ou de type azéotrope en tant que solvants. L'invention concerne aussi un procédé de production d'un produit d'aérosol en utilisant ces compositions azéotropes ou de type azéotrope. L'invention concerne aussi un procédé d'utilisation de ces compositions azéotropes ou de type azéotrope en tant que milieux de transfert de chaleur. L'invention concerne aussi un procédé d'extinction ou de suppression d'un feu en utilisant ces compositions azéotropes ou de type azéotrope. L'invention concerne aussi un procédé d'utilisation de ces compositions azéotropes ou de type azéotrope en tant que diélectriques.

Claims

Note: Claims are shown in the official language in which they were submitted.



CLAIMS
1. A composition consisting essentially of:
E-1,3,4,4,4-pentafluoro-3-trifluoromethyl-1-butene and a second
component, wherein the second component is Z-1,1,1,4,4,4-hexafluoro-2-
butene or cyclopentane and wherein the second component is present in
an effective amount to form an azeotropic combination with the E-
1,3,4,4,4-pentafluoro-3-trifluoromethyl-1-butene.
2. A composition consisting essentially of:
E-1,3,4,4,4-pentafluoro-3-trifluoromethyl-1-butene and a second
component, wherein the second component is Z-1,1,1,4,4,4-hexafluoro-2-
butene or cyclopentane, and
wherein the second component is present in an effective amount to
form an azeotrope-like combination with the E-1,3,4,4,4-pentafluoro-3-
trifluoromethyl-1-butene.
3. A process for preparing a thermoplastic or thermoset foam
comprising mixing the the azeotropic composition of Claim 1 with a with a
polyol or a resin.
4. A process for preparing a thermoplastic or thermoset foam
comprisingmixing the azeotrope-like composition of Claim 2 with a polyol
or resin.
5. A process for producing refrigeration comprising condensing
the azeotropic composition of Claim 1 and thereafter evaporating said
azeotropic composition in the vicinity of the body to be cooled.
6. A process for producing refrigeration comprising condensing
the azeotrope-like composition of Claim 2 and thereafter evaporating said
azeotrope-like composition in the vicinity of the body to be cooled.
7. A process comprising using the azeotropic composition of
Claim 1 as a solvent.
8. A process comprising using the azeotrope-like composition of
Claim 2 as a solvent.
9. A process for producing an aerosol product comprising using
the azeotropic composition of Claim 1 as a propellant.
17



10. A process for producing an aerosol product comprising using
the azeotrope-like composition of Claim 2 as a propellant.
11. A process comprising using the azeotropic composition of
Claim 1 as a heat transfer media.
12. A process comprising using the azeotrope-like composition of
Claim 2 as a heat transfer media.
13. A process for extinguishing or suppressing a fire comprising
using the azeotropic composition of Claim 1 as a fire extinguishing or
suppression agent.
14. A process for extinguishing or suppressing a fire comprising
using the azeotrope-like composition of Claim 2 as a fire extinguishing or
suppression agent.
15. A process comprising using the azeotropic composition of
Claim 1 as dielectrics.
16. A process comprising using the azeotrope-like composition of
Claim 2 as dielectrics.
18

Description

Note: Descriptions are shown in the official language in which they were submitted.


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TITLE OF INVENTION
AZEOTROPIC AND AZEOTROPE-LIKE COMPOSITIONS OF E-
1,3,4,4,4-PENTAFLUOR0-3-TRIFLUOROMETHYL-1-BUTENE AND Z-
1,1,1,4,4,4-HEXAFLUOR0-2-BUTENE AND USES THEREOF
Cross Reference to Related Applications
This application claims the benefit of priority of U.S. Provisional
Application 61/678,260, filed August 1,2012, and incorporated herein by
reference. This application also claims benefit of priority of U.S.
Provisional Application 61/678,257, filed August 1,2012, titled "Azeotropic
and Azeotrope-Like Compositions of E-1,3,4,4,4-Pentafluoro-3-
Triffluoromethy1-1-Butene and Cyclopentane and Uses Thereof", also
incorporated herein by reference.
Field of the Disclosure
The present disclosure relates to azeotropic and azeotrope-like
compositions of E-1,3,4,4,4-pentafluoro-3-trifluoromethy1-1-butene and Z-
1,1,1,4,4,4-hexafluoro-2-butene.
Description of Related Art
Many industries have been working for the past few decades to find
replacements for the ozone depleting chlorofluorocarbons (CFCs) and
hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been
employed in a wide range of applications, including their use as aerosol
propellants, refrigerants, cleaning agents, expansion agents for
thermoplastic and thermoset foams, heat transfer media, gaseous
dielectrics, fire extinguishing and suppression agents, power cycle working
fluids, polymerization media, particulate removal fluids, carrier fluids,
buffing abrasive agents, and displacement drying agents. In the search
for replacements for these versatile compounds, many industries have
turned to the use of hydrofluorocarbons (HFCs).
The HFCs do not contribute to the destruction of stratospheric
ozone, but are of concern due to their contribution to the "greenhouse
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effect", i.e., they contribute to global warming. As a result of their
contribution to global warming, the HFCs have come under scrutiny, and
their widespread use may also be limited in the future. Thus, there is a
need for compositions that do not contribute to the destruction of
stratospheric ozone and also have low global warming potentials (GWPs).
SUMMARY OF THE INVENTION
This disclosure provides a composition consisting essentially of (a)
E-HF0-1438ezy and a second component present in an effective amount
to form an azeotrope or azeotrope like mixture. In one embodiment the
disclosure, the second component includes Z-HF0-1336mzz or
cyclopentane.
BRIEF SUMMARY OF THE DRAWINGS
FIG. 1 - FIG. 1 is a graphical representation of an azeotropic composition
of E-HF0-1438ezy and Z-HF0-1336mzz at a temperature of about 25 C.
FIG. 2 - FIG. 2 is a graphical representation of an azeotropic composition
of E-HF0-1438ezy and cyclopentane at a temperature of about 25.0 C.
DETAILED DESCRIPTION OF THE INVENTION
It was found that 1,3,4,4,4-pentafluoro-3-trifluoromethy1-1-butene
(HF0-1438ezy, (CF3)2CFCH=CHF), 1,1,1,4,4,4-hexafluoro-2-butene
(CF3CH=CHCF3, HF0-1336mzz) and cyclopentane do not contribute to
the destruction of stratospheric ozone and also have low global warming
potentials (GWPs).
In many applications, the use of a pure single component or an
azeotropic or azeotrope-like mixture is desirable. For example, when a
blowing agent composition (also known as foam expansion agents or foam
expansion compositions) is not a pure single component or an azeotropic
or azeotrope-like mixture, the composition may change during its
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application in the foam forming process. Such change in composition
could detrimentally affect processing or cause poor performance in the
application. Also, in refrigeration applications, a refrigerant is often lost
during operation through leaks in shaft seals, hose connections, soldered
joints and broken lines. In addition, the refrigerant may be released to the
atmosphere during maintenance procedures on refrigeration equipment. If
the refrigerant is not a pure single component or an azeotropic or
azeotrope-like composition, the refrigerant composition may change when
leaked or discharged to the atmosphere from the refrigeration equipment.
The change in refrigerant composition may cause the refrigerant to
become flammable or to have poor refrigeration performance. Accordingly,
there is a need for using azeotropic or azeotrope-like mixtures in these
and other applications, for example azeotropic or azeotrope-like mixtures
containing E-1,3,4,4,4-pentafluoro-3-trifluoromethy1-1-butene (trans-
1,3,4,4,4-pentafluoro-3-trifluoromethy1-1-butene, E-HF0-1438ezy, trans-
HF0-1438ezy, E-(CF3)2CFCH=CHF, trans-(CF3)2CFCH=CHF) and at least
one other component, where preferably, the second component also does
not harm the environment relative to incumbent products. Preferably, the
second component is Z-1,1,1,4,4,4-hexafluoro-2-butene (cis-1,1,1,4,4,4-
hexafluoro-2-butene, Z-CF3CH=CHCF3, cis-CF3CH=CHCF3, Z-HFO-
1336mzz, cis-HF0-1336mzz) or cyclopentane.
Before addressing details of embodiments described below, some
terms are defined or clarified.
HF0-1438ezy may exist as one of two configurational isomers, E or
Z. HF0-1438ezy as used herein refers to the isomers, Z-HF0-1438ezy or
E-HF0-1438ezy, as well as any combinations or mixtures of such isomers.
HF0-1336mzz may exist as one of two configurational isomers, E
or Z. HF0-1336mzz as used herein refers to the isomers, Z-HFO-
1336mzz or E-HF0-1336mzz, as well as any combinations or mixtures of
such isomers.
As used herein, the terms "comprises," "comprising," "includes,"
"including," "has," "having" or any other variation thereof, are intended to
cover a non-exclusive inclusion. For example, a process, method, article,
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or apparatus that comprises a list of elements is not necessarily limited to
only those elements but may include other elements not expressly listed or
inherent to such process, method, article, or apparatus. Further, unless
expressly stated to the contrary, "or" refers to an inclusive or and not to an
exclusive or. For example, a condition A or B is satisfied by any one of the
following: A is true (or present) and B is false (or not present), A is false
(or not present) and B is true (or present), and both A and B are true (or
present).
Also, use of "a" or "an" are employed to describe elements and
components described herein. This is done merely for convenience and to
give a general sense of the scope of the invention. This description
should be read to include one or at least one and the singular also
includes the plural unless it is obvious that it is meant otherwise.
Unless otherwise defined, all technical and scientific terms used
herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. In case of
conflict,
the present specification, including definitions, will control. Although
methods and materials similar or equivalent to those described herein can
be used in the practice or testing of embodiments of the present invention,
suitable methods and materials are described below. In addition, the
materials, methods, and examples are illustrative only and not intended to
be limiting.
When an amount, concentration, or other value or parameter is
given as either a range, preferred range or a list of upper preferable values
and/or lower preferable values, this is to be understood as specifically
disclosing all ranges formed from any pair of any upper range limit or
preferred value and any lower range limit or preferred value, regardless of
whether ranges are separately disclosed. Where a range of numerical
values is recited herein, unless otherwise stated, the range is intended to
include the endpoints thereof, and all integers and fractions within the
range.
HF0-1438ezy is a known compound, and can be made through a
catalytic addition reaction between (CF3)2CFI and CH2=CHF, followed by
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an elimination reaction to remove HI, such as disclosed in U.S. Patent No.
8,148,584.
Z-HF0-1336mzz is a known compound, and can be made by the
selective hydrogenation of hexafluoro-2-butyne with a Lindlar catalyst and
hydrogen, such as disclosed in U.S. Patent Publication No. 2008-
0269532.
This application includes compositions consisting essentially of (a)
E-HF0-1438ezy and (b) Z-HF0-1336mzz; wherein the Z-HF0-1336mzz is
present in an effective amount to form an azeotropic or azeotrope-like
mixture with E-HF0-1438ezy.
By effective amount is meant an amount of Z-HF0-1336mzz,
which, when combined with E-HF0-1438ezy, results in the formation of an
azeotropic or azeotrope-like mixture.
By effective amount is meant an amount of cyclopentane, which,
when combined with E-HF0-1438ezy, results in the formation of an
azeotropic or azeotrope-like mixture.
This definition includes the amounts of each component, which
amounts may vary depending on the pressure applied to the composition
so long as the azeotropic or azeotrope-like compositions continue to exist
at the different pressures, but with possible different boiling points.
Therefore, effective amount includes the amounts, such as may be
expressed in weight or mole percentages, of each component of the
compositions of the instant invention which form azeotropic or azeotrope-
like compositions at temperatures or pressures other than as described
herein.
As recognized in the art, an azeotropic composition is an admixture
of two or more different components which, when in liquid form under a
given pressure, will boil at a substantially constant temperature, which
temperature may be higher or lower than the boiling temperatures of the
individual components, and which will provide a vapor composition
essentially identical to the overall liquid composition undergoing boiling.
(see, e.g., M. F. Doherty and M.F. Malone, Conceptual Design of
Distillation Systems, McGraw-Hill (New York), 2001, 185-186, 351-359).
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Accordingly, the essential features of an azeotropic composition are
that at a given pressure, the boiling point of the liquid composition is fixed

and that the composition of the vapor above the boiling composition is
essentially that of the overall boiling liquid composition (i.e., no
fractionation of the components of the liquid composition takes place). It is
also recognized in the art that both the boiling point and the weight
percentages of each component of the azeotropic composition may
change when the azeotropic composition is subjected to boiling at different
pressures. Thus, an azeotropic composition may be defined in terms of
the unique relationship that exists among the components or in terms of
the compositional ranges of the components or in terms of exact weight
percentages of each component of the composition characterized by a
fixed boiling point at a specified pressure.
For the purpose of this invention, an azeotrope-like composition
means a composition that behaves like an azeotropic composition (i.e.,
has constant boiling characteristics or a tendency not to fractionate upon
boiling or evaporation). Hence, during boiling or evaporation, the vapor
and liquid compositions, if they change at all, change only to a minimal or
negligible extent. This is to be contrasted with non-azeotrope-like
compositions in which during boiling or evaporation, the vapor and liquid
compositions change to a substantial degree.
Additionally, azeotrope-like compositions exhibit dew point pressure
and bubble point pressure with virtually no pressure differential. That is to
say that the difference in the dew point pressure and bubble point
pressure at a given temperature will be a small value. In this invention,
compositions with a difference in dew point pressure and bubble point
pressure of less than or equal to 5 percent (based upon the bubble point
pressure) is considered to be azeotrope-like.
It is recognized in this field that when the relative volatility of a
system approaches 1.0, the system is defined as forming an azeotropic or
azeotrope-like composition. Relative volatility is the ratio of the volatility
of
component 1 to the volatility of component 2. The ratio of the mole fraction
of a component in vapor to that in liquid is the volatility of the component.
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To determine the relative volatility of any two compounds, a method
known as the PTx method can be used. The vapor-liquid equilibrium
(VLE), and hence relative volatility, can be determined either isothermally
or isobarically. The isothermal method requires measurement of the total
pressure of mixtures of known composition at constant temperature. In this
procedure, the total absolute pressure in a cell of known volume is
measured at a constant temperature for various compositions of the two
compounds. The isobaric method requires measurement of the
temperature of mixtures of known composition at constant pressure. In
this procedure, the temperature in a cell of known volume is measured at
a constant pressure for various compositions of the two compounds. Use
of the PTx Method is described in detail in "Phase Equilibrium in Process
Design", Wiley-Interscience Publisher, 1970, written by Harold R. Null, on
pages 124 to 126.
These measurements can be converted into equilibrium vapor and
liquid compositions in the PTx cell by using an activity coefficient equation
model, such as the Non-Random, Two-Liquid (NRTL) equation, to
represent liquid phase nonidealities. Use of an activity coefficient equation,

such as the NRTL equation is described in detail in "The Properties of
Gases and Liquids," 4th edition, published by McGraw Hill, written by
Reid, Prausnitz and Poling, on pages 241 to 387, and in "Phase Equilibria
in Chemical Engineering," published by Butterworth Publishers, 1985,
written by Stanley M. Walas, pages 165 to 244. Without wishing to be
bound by any theory or explanation, it is believed that the NRTL equation,
together with the PTx cell data, can sufficiently predict the relative
volatilities of the E-HF0-1438ezy/Z-HF0-1336mzz compositions of the
present invention and can therefore predict the behavior of these mixtures
in multi-stage separation equipment such as distillation columns.
It was found through experiments that E-HF0-1438ezy and Z-HFO-
1336mzz form azeotropic or azeotrope-like compositions.
To determine the relative volatility of this binary pair, the PTx
method described above was used. The pressure in a PTx cell of known
volume was measured at constant temperature for various binary
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compositions. These measurements were then reduced to equilibrium
vapor and liquid compositions in the cell using the NRTL equation.
Example 1
The pressures measured versus the compositions in the PTx cell
for E-HF0-1438ezy/Z-HF0-1336mzz mixtures are shown in FIG. 1, which
graphically illustrates the formation of an azeotropic composition
consisting essentially of E-HF0-1438ezy and Z-HF0-1336mzz as
indicated by a mixture of about 63.7 mole % E-HF0-1438ezy and about
36.3 mole % Z-HF0-1336mzz having the highest pressure over the range
of compositions at about 25 C. Based upon these findings, it has been
calculated that E-HF0-1438ezy and Z-HF0-1336mzz form azeotropic
compositions ranging from about 64.0 mole percent to about 61.3 mole
percent E-HF0-1438ezy and from about 36.0 mole percent to about 38.7
mole percent Z-HF0-1336mzz (which form azeotropic compositions
boiling at a temperature of from about -50 C to about 14000 and at a
pressure of from about 0.2 psia (1.4 kPa) to about 261 psia (1799 kPa)).
For example, at about 25 C and about 12.4 psia (85 kPa) the azeotropic
composition consists essentially of about 63.7 mole % E-HF0-1438ezy
and about 36.3 mole % Z-HF0-1336mzz. For another example, at about
29.500 and about atmospheric pressure (14.7 psia, 101 kPa) the
azeotropic composition consists essentially of about 63.8 mole % E-HFO-
1438ezy and about 36.2 mole % Z-HF0-1336mzz. Some embodiments of
azeotropic compositions are listed in Table 1.
Table 1 Azeotropic compositions
Azeotropic Azeotropic E-HF0-
1438ezy Z-HF0-1336mzz
Temperature Pressure (psia) (mole %) (mole %)
( C)
-50 0.2 61.3 38.7
-40 0.4 61.8 38.2
-30 0.8 62.2 37.8
-20 1.5 62.6 37.4
-10 2.6 62.9 37.1
0 4.3 63.2 36.8
10 6.7 63.4 36.6
20 10.2 63.7 36.3
25 12.4 63.7 36.3
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30 15.0 63.8 36.2
40 21.3 63.9 36.1
50 29.5 64.0 36.0
60 40.0 64.0 36.0
70 53.2 64.0 36.0
80 69.4 64.0 36.0
90 89.1 63.9 36.1
100 112.8 63.8 36.2
110 141.1 63.7 36.3
120 174.6 63.5 36.5
130 214.1 63.3 36.7
140 260.7 63.0 37.0
Additionally, azeotrope-like compositions containing E-HFO-
1438ezy and Z-HF0-1336mzz may also be formed. In some embodiments
of this invention, an azeotrope-like composition consists essentially of 1-99
mole % E-HF0-1438ezy and 99-1 mole % Z-HF0-1336mzz at a
temperature ranging from about -40 C to about 140 C (i.e., over this
temperature range, the difference in dew point pressure and bubble point
pressure of the composition at a particular temperature is less than or
equal to 5 percent (based upon the bubble point pressure)). In some
embodiments of this invention, an azeotrope-like composition consists
essentially of 5-95 mole % E-HF0-1438ezy and 95-5 mole % Z-HFO-
1336mzz at a temperature ranging from about 4000- to
about 14000 (i.e.,
over this temperature range, the difference in dew point pressure and
bubble point pressure of the composition at a particular temperature is
less than or equal to 5 percent (based upon the bubble point pressure)).
Such azeotrope-like compositions exist around azeotropic
compositions. Some embodiments of azeotrope-like compositions are
listed in Table 2. Additional embodiments of azeotrope-like compositions
are listed in Table 3.
Table 2 Azeotrope-like compositions
COMPONENTS T ( C) Mole
Percentage
Range
E-HF0-1438ezy/Z-HF0-1336mzz -40 1 - 99/1 -99
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E-H F0-1438ezy/Z-H F0-1336mzz -20 1 ¨ 99/1 -99
E-HF0-1438ezy/Z-HF0-1336mzz 0 1 ¨ 99/1 -99
E-HF0-1438ezy/Z-HF0-1336mzz 40 1 ¨ 99/1 -99
E-HF0-1438ezy/Z-HF0-1336mzz 80 1 ¨ 99/1 -99
E-HF0-1438ezy/Z-HF0-1336mzz 120 1 ¨ 99/1 -99
E-HF0-1438ezy/Z-HF0-1336mzz 140 1 ¨ 99/1 -99
Table 3 Azeotrope-like compositions
Mole Percentage
COMPONENTS T ( C) Range
E-HF0-1438ezy/Z-HF0-1336mzz -40 5 ¨ 95/5 - 95
E-HF0-1438ezy/Z-HF0-1336mzz -20 5 ¨ 95/5 - 95
E-HF0-1438ezy/Z-HF0-1336mzz 0 5 ¨ 95/5 - 95
E-HF0-1438ezy/Z-HF0-1336mzz 40 5 ¨ 95/5 - 95
E-HF0-1438ezy/Z-HF0-1336mzz 80 5 ¨ 95/5 - 95
E-H F0-1438ezy/Z-H F0-1336mzz 120 5 ¨ 95/5 - 95
E-H F0-1438ezy/Z-H F0-1336mzz 140 5 ¨ 95/5 - 95
The azeotropic or azeotrope-like compositions of the present
invention can be prepared by any convenient method including mixing or
combining the desired amounts. In one embodiment of this invention, an
azeotropic or azeotrope-like composition can be prepared by weighing the
desired component amounts and thereafter combining them in an
appropriate container.
The azeotropic or azeotrope-like compositions of the present
invention can be used in a wide range of applications, including their use
as aerosol propellants, refrigerants, solvents, cleaning agents, blowing
agents (foam expansion agents) for thermoplastic and thermoset foams,
heat transfer media, gaseous dielectrics, fire extinguishing and
suppression agents, power cycle working fluids, polymerization media,

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particulate removal fluids, carrier fluids, buffing abrasive agents, and
displacement drying agents.
One embodiment of this invention provides a process for preparing
a thermoplastic or thermoset foam. The process comprises using an
azeotropic or azeotrope-like composition as a blowing agent, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and Z-HF0-1336mzz. For thermoplastic foams, this process
includes mixing the blowing agent with a liquid resin under elevatged
temperatures and pressures, and extruding the resin to form the foam.
For thermoset foams, this process includes mixing the blowing agent with
a polyol, and mixing the polyol with an isocyanate to form the foam
Another embodiment of this invention provides a process for
producing refrigeration. The process comprises condensing an azeotropic
or azeotrope-like composition and thereafter evaporating said azeotropic
or azeotrope-like composition in the vicinity of the body to be cooled,
wherein said azeotropic or azeotrope-like composition consists essentially
of E-HF0-1438ezy and Z-HF0-1336mzz.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as a solvent, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and Z-HF0-1336mzz. This process includes the step of
contacting the composition to a surface to be cleaned and then removing
the composition or removing the surface.
Another embodiment of this invention provides a process for
producing an aerosol product. The process comprises using an azeotropic
or azeotrope-like composition as a propellant, wherein said azeotropic or
azeotrope-like composition consists essentially of E-HF0-1438ezy and Z-
HF0-1336mzz.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as a heat transfer media,
wherein said azeotropic or azeotrope-like composition consists essentially
of E-HF0-1438ezy and Z-HF0-1336mzz.
11

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Another embodiment of this invention provides a process for
extinguishing or suppressing a fire. The process comprises using an
azeotropic or azeotrope-like composition as a fire extinguishing or
suppression agent, wherein said azeotropic or azeotrope-like composition
consists essentially of E-HF0-1438ezy and Z-HF0-1336mzz. The
process includes detecting a fire or incipient ignition, and delivering a
sufficient amount of the composition to the fire or incipient ignition to
reach
an extinguishing concentration that suppresses or extinguishes the fire.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as dielectrics, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and Z-HF0-1336mzz.
Example 2
The pressures measured versus the compositions in the PTx cell
for E-HF0-1438ezy/cyclopentane mixtures are shown in FIG. 1, which
graphically illustrates the formation of an azeotropic composition
consisting essentially of E-HF0-1438ezy and cyclopentane as indicated
by a mixture of about 67.7 mole % E-HF0-1438ezy and about 32.3 mole
% cyclopentane having the highest pressure over the range of
compositions at about 25.0 C. Based upon these findings, it has been
calculated that E-HF0-1438ezy and cyclopentane form azeotropic
compositions ranging from about 66.8 mole percent to about 95.2 mole
percent E-HF0-1438ezy and from about 33.2 mole percent to about 4.8
mole percent cyclopentane (which form azeotropic compositions boiling at
a temperature of from about -50 C to about 14000 and at a pressure of
from about 0.2 psia (1.4 kPa) to about 250 psia (1724 kPa)). For example,
at about 25.000 and about 13.5 psia (93 kPa) the azeotropic composition
consists essentially of about 67.7 mole % E-HF0-1438ezy and about 32.3
mole % cyclopentane. For another example, at about 27.3 C and about
atmospheric pressure (14.7 psia, 101 kPa) the azeotropic composition
consists essentially of about 67.9 mole % E-HF0-1438ezy and about 32.1
12

CA 02879541 2015-01-19
WO 2014/022638 PCT/US2013/053175
mole % cyclopentane. Some embodiments of azeotropic compositions are
listed in Table 1.
Table 1 Azeotropic compositions
Azeotropic Azeotropic E-HF0-1438ezy Cyclopentane
Temperature Pressure (psia) (mole %) (mole %)
( C)
-50 0.2 67.2 32.8
-40 0.5 67.0 33.0
-30 1.0 66.9 33.1
-20 1.7 66.8 33.2
-10 3.0 66.9 33.1
0 4.8 67.0 33.0
7.5 67.2 32.8
11.2 67.5 32.5
13.5 67.7 32.3
16.2 68.0 32.0
22.8 68.5 31.5
31.2 69.2 30.8
41.9 70.1 29.9
55.0 71.2 28.8
70.9 72.6 27.4
90.0 74.3 25.7
100 112.7 76.4 23.6
110 139.3 79.2 20.8
120 170.5 82.8 17.2
130 206.8 87.8 12.2
140 249.5 95.2 4.8
5 Additionally, azeotrope-like compositions containing E-HFO-
1438ezy and cyclopentane may also be formed. In some embodiments of
this invention, an azeotrope-like composition consists essentially of 99-48
mole % E-HF0-1438ezy and 1-52 mole % cyclopentane at a temperature
ranging from about -40 C to about 14000 (i.e., over this temperature
10 range, the difference in dew point pressure and bubble point pressure of
the composition at a particular temperature is less than or equal to 5
percent (based upon the bubble point pressure)). In some embodiments of
this invention, an azeotrope-like composition consists essentially of 1-4
mole % E-HF0-1438ezy and 99-96 mole % cyclopentane at a temperature
15 ranging from about 12000 to about 14000 (i.e., over this temperature
range, the difference in dew point pressure and bubble point pressure of
the composition at a particular temperature is less than or equal to 5
13

CA 02879541 2015-01-19
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PCT/US2013/053175
percent (based upon the bubble point pressure)). In some embodiments of
this invention, an azeotrope-like composition consists essentially of 48-95
mole % E-HF0-1438ezy and 52-5 mole % cyclopentane at a temperature
ranging from about -40 C to about 14000 (i.e., over this temperature
range, the difference in dew point pressure and bubble point pressure of
the composition at a particular temperature is less than or equal to 5
percent (based upon the bubble point pressure)).
Such azeotrope-like compositions exist around azeotropic
compositions. Some embodiments of azeotrope-like compositions are
listed in Table 2. Additional embodiments of azeotrope-like compositions
are listed in Table 3.
Table 2 Azeotrope-like compositions
COMPONENTS T ( C) Mole Percentage
Range
E-HF0-1438ezy/Cyclopentane -40 60 ¨ 77 / 40 - 23
E-HF0-1438ezy/Cyclopentane 98 ¨99 / 2 ¨ 1 and
-20 60 - 79 / 40 - 21
E-HF0-1438ezy/Cyclopentane 0 95 - 99 / 5¨ 1 and
59 - 83 /41 -17
E-HF0-1438ezy/Cyclopentane 20 58 - 99 / 42 - 1
E-HF0-1438ezy/Cyclopentane 40 56 - 99 / 44 - 1
E-HF0-1438ezy/Cyclopentane 60 55 - 99 / 45 - 1
E-HF0-1438ezy/Cyclopentane 80 54 - 99 / 46 - 1
E-HF0-1438ezy/Cyclopentane 100 52 -99 / 48 - 1
E-HF0-1438ezy/Cyclopentane 51 - 99 / 49¨ 1 and
120 1 -2 /99 - 98
E-HF0-1438ezy/Cyclopentane 48 - 99 / 52 ¨ 1 and
140 1 -4 /99 - 96
Table 3 Azeotrope-like compositions
Mole Percentage
COMPONENTS T ( C) Range
E-HF0-1438ezy/Cyclopentane -40 61 - 74 / 39 - 26
14

CA 02879541 2015-01-19
WO 2014/022638
PCT/US2013/053175
E-HF0-1438ezy/Cyclopentane - 20 61 - 75 / 39 -
25
E-HF0-1438ezy/Cyclopentane 0 60 - 78 / 40 -
22
E-HF0-1438ezy/Cyclopentane 20 60 - 82 / 40-
18
E-HF0-1438ezy/Cyclopentane 40 56 - 95 / 44 -
5
E-HF0-1438ezy/Cyclopentane 60 55 - 95 / 45 -
5
E-HF0-1438ezy/Cyclopentane 80 54 - 95 / 46 -
5
E-HF0-1438ezy/Cyclopentane 100 52 -95 / 48 -
5
E-HF0-1438ezy/Cyclopentane 120 51 -95 / 49-5
E-HF0-1438ezy/Cyclopentane 140 48 - 95 / 52 -
5
The azeotropic or azeotrope-like compositions of the present
invention can be prepared by any convenient method including mixing or
combining the desired amounts. In one embodiment of this invention, an
azeotropic or azeotrope-like composition can be prepared by weighing the
desired component amounts and thereafter combining them in an
appropriate container.
The azeotropic or azeotrope-like compositions of the present
invention can be used in a wide range of applications, including their use
as aerosol propellants, refrigerants, solvents, cleaning agents, blowing
agents (foam expansion agents) for thermoplastic and thermoset foams,
heat transfer media, gaseous dielectrics, fire extinguishing and
suppression agents, power cycle working fluids, polymerization media,
particulate removal fluids, carrier fluids, buffing abrasive agents, and
displacement drying agents.
One embodiment of this invention provides a process for preparing
a thermoplastic or thermoset foam. The process comprises using an
azeotropic or azeotrope-like composition as a blowing agent, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and cyclopentane. For thermoplastic foams, this process
includes mixing the blowing agent with a liquid resin under elevatged
temperatures and pressures, and extruding the resin to form the foam.

CA 02879541 2015-01-19
WO 2014/022638
PCT/US2013/053175
For thermoset foams, this process includes mixing the blowing agent with
a polyol, and mixing the polyol with an isocyanate to form the foam
Another embodiment of this invention provides a process for
producing refrigeration. The process comprises condensing an azeotropic
or azeotrope-like composition and thereafter evaporating said azeotropic
or azeotrope-like composition in the vicinity of the body to be cooled,
wherein said azeotropic or azeotrope-like composition consists essentially
of E-HF0-1438ezy and cyclopentane.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as a solvent, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and cyclopentane. This process includes the step of contacting
the composition to a surface to be cleaned and then removing the
composition or removing the surface.
Another embodiment of this invention provides a process for
producing an aerosol product. The process comprises using an azeotropic
or azeotrope-like composition as a propellant, wherein said azeotropic or
azeotrope-like composition consists essentially of E-HF0-1438ezy and
cyclopentane.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as a heat transfer media,
wherein said azeotropic or azeotrope-like composition consists essentially
of E-HF0-1438ezy and cyclopentane.
Another embodiment of this invention provides a process for
extinguishing or suppressing a fire. The process comprises using an
azeotropic or azeotrope-like composition as a fire extinguishing or
suppression agent, wherein said azeotropic or azeotrope-like composition
consists essentially of E-HF0-1438ezy and cyclopentane.
Another embodiment of this invention provides a process using an
azeotropic or azeotrope-like composition as dielectrics, wherein said
azeotropic or azeotrope-like composition consists essentially of E-HFO-
1438ezy and cyclopentane.
16

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 2013-08-01
(87) PCT Publication Date 2014-02-06
(85) National Entry 2015-01-19
Dead Application 2018-08-01

Abandonment History

Abandonment Date Reason Reinstatement Date
2017-08-01 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $400.00 2015-01-19
Maintenance Fee - Application - New Act 2 2015-08-03 $100.00 2015-01-19
Maintenance Fee - Application - New Act 3 2016-08-01 $100.00 2016-07-22
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
E. I. DU PONT DE NEMOURS AND COMPANY
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2015-01-19 1 62
Claims 2015-01-19 2 59
Drawings 2015-01-19 2 13
Description 2015-01-19 16 697
Cover Page 2015-03-06 1 41
PCT 2015-01-19 2 75
Assignment 2015-01-19 3 106