U.S. patent application number 15/995751 was filed with the patent office on 2019-05-09 for azeotrope-like compositions of tetrafluoropropene and hydrofluorocarbons.
The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to GARY M. KNOPECK, HANG T. PHAM, RAJIV R. SINGH.
Application Number | 20190136107 15/995751 |
Document ID | / |
Family ID | 34967705 |
Filed Date | 2019-05-09 |
United States Patent
Application |
20190136107 |
Kind Code |
A1 |
SINGH; RAJIV R. ; et
al. |
May 9, 2019 |
Azeotrope-Like Compositions of Tetrafluoropropene And
Hydrofluorocarbons
Abstract
Provided are azeotrope-like compositions comprising
tetrafluoropropene and hydrofluorocarbons and uses thereof,
including use in refrigerant compositions, refrigeration systems,
blowing agent compositions, and aerosol propellants.
Inventors: |
SINGH; RAJIV R.; (Getzville,
NY) ; PHAM; HANG T.; (Amherst, NY) ; KNOPECK;
GARY M.; (Lakeview, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
Morris Plains |
NJ |
US |
|
|
Family ID: |
34967705 |
Appl. No.: |
15/995751 |
Filed: |
June 1, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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15367825 |
Dec 2, 2016 |
9988567 |
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15995751 |
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14538335 |
Nov 11, 2014 |
9657208 |
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15367825 |
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14084080 |
Nov 19, 2013 |
8883708 |
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14538335 |
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13429806 |
Mar 26, 2012 |
8741829 |
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14084080 |
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12511018 |
Jul 28, 2009 |
8148317 |
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13429806 |
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11119053 |
Apr 29, 2005 |
7767638 |
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12511018 |
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10837526 |
Apr 29, 2004 |
7524805 |
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11119053 |
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10694273 |
Oct 27, 2003 |
7534366 |
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10837526 |
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10827525 |
Apr 20, 2004 |
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10694273 |
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10837521 |
Apr 29, 2004 |
7655610 |
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10827525 |
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10695212 |
Oct 27, 2003 |
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10837521 |
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10694272 |
Oct 27, 2003 |
7230146 |
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10695212 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01F 17/0085 20130101;
C09K 3/30 20130101; C11D 7/5018 20130101; C09K 2205/40 20130101;
C09K 2205/126 20130101; C09K 2205/34 20130101; C09K 2205/22
20130101; A01N 29/02 20130101; C11D 7/505 20130101; C09K 2205/122
20130101; C09K 2205/32 20130101; F25B 1/00 20130101; C09K 5/045
20130101; F25B 31/002 20130101 |
International
Class: |
C09K 5/04 20060101
C09K005/04; B01F 17/00 20060101 B01F017/00; C09K 3/30 20060101
C09K003/30; F25B 31/00 20060101 F25B031/00; F25B 1/00 20060101
F25B001/00; A01N 29/02 20060101 A01N029/02 |
Claims
1. An azeotrope-like composition consisting essentially of (a)
trans-1,3,3,3-tetrafluoropropene (transHFO-1234ze) and (b)
1,1-difluoroethane ("HFC-152a"), said HFC-152a being present in the
azeotrope-like composition in a range of from about 50 wt % to less
than 100 wt %.
2. A heat transfer composition comprising the azeotrope-like
composition of claim 1.
3. The heat transfer composition of claim 2 wherein said
azeotrope-like composition has a boiling point of from about
-23.degree. C.+/-1.degree. C. at a pressure of about 14.4 psia.
4. A refrigeration system comprising the heat transfer composition
of claim 2.
5. An air conditioning system comprising the heat transfer
composition of claim 2.
6. A refrigeration system originally designed for use with HFC-134a
and comprising the heat transfer composition of claim 2.
7. The heat transfer composition of claim 1 wherein said heat
transfer composition is non-flammable.
8. The heat transfer composition of claim 7 further comprising a
lubricant.
9. An azeotrope-like composition consisting of (a)
trans-1,3,3,3-tetrafluoropropene (transHFO-1234ze) and (b)
1,1,1,2,2-pentafluoroethane ("HFC-125"), said HFC-125 being present
in the azeotrope-like composition in a range of from about 60 wt %
to less than about 99 wt %, wherein said composition range includes
a minimum boiling azeotrope having a liquid composition component
concentration equal to the vapor composition component
concentration, whereby at a pressure of about 14.4 psia said
azeotrope-like composition has a boiling point of -47.degree.
C.+/-2.degree. C.
10. A heat transfer composition comprising the azeotrope-like
composition of claim 9.
11. A refrigeration system comprising the heat transfer composition
of claim 10.
12. The heat transfer composition of claim 11 wherein said heat
transfer composition is non-flammable.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a Continuation of U.S.
application Ser. No. 15/367,825, filed Dec. 2, 2016, (now pending),
which application is a Continuation of U.S. application Ser. No.
14/538,335, filed Nov. 11, 2014, (now U.S. Pat. No. 9,657,208,
issued May 23, 2017), which is a Division of U.S. application Ser.
No. 14/084,080, filed Nov. 19, 2013 (now U.S. Pat. No. 8,883,708,
issued Nov. 11, 2014), which is a Continuation of U.S. application
Ser. No. 13/429,806, filed on Mar. 26, 2012 (now U.S. Pat. No.
8,741,829, issued Jun. 3, 2014), which is a Continuation of U.S.
application Ser. No. 12/511,018, filed on Jul. 28, 2009 (now U.S.
Pat. No. 8,148,317, issued Apr. 3, 2012), which is a Divisional of
U.S. application Ser. No. 11/119,053 filed on Apr. 29, 2005 (now
U.S. Pat. No. 7,767,638, issued Aug. 3, 2010), which is a
Continuation-in-Part of U.S. application Ser. No. 10/837,526 filed
on Apr. 29, 2004 (now U.S. Pat. No. 7,524,805, issued Apr. 28,
2009), all of which are incorporated by reference.
[0002] The present application is also related to and incorporates
by reference each of the following United States patent
application: U.S. application Ser. No. 10/837,525, filed Apr. 29,
2004; Ser. No. 10/837,521, filed Apr. 29, 2004, Ser. No.
10/694,273, filed Oct. 27, 2003; Ser. No. 10/695,212, filed Oct.
27, 2003; and Ser. No. 10/694,272 filed Oct. 27, 2003.
FIELD OF INVENTION
[0003] The present invention relates generally to compositions
comprising 1,1,3,3-tetrafluoropropene. More specifically, the
present invention provides azeotrope-like compositions comprising
1,1,1,3-tetrafluoropropene and uses thereof.
BACKGROUND
[0004] 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, 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 hydrofluorocarbon
or other fluorinated fluids having global warming potentials as low
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. However, the identification
of new, environmentally-safe, non-fractionating mixtures is
complicated due to the fact that azeotrope formation is not readily
predictable.
[0005] The industry is continually seeking new fluorocarbon based
mixtures that offer alternatives, and are considered
environmentally safer substitutes for CFCs and HCFCs. Of particular
interest are mixtures containing both hydrofluorocarbons and other
fluorinated compounds, both of low ozone depletion potentials. Such
mixtures and their uses are the subject of this invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0006] 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, or consisting
essentially of, 1,1,1,3-tetrafluoropropene ("HFO-1234ze"),
preferably trans-1,1,1,3-tetrafluoropropene ("transHFO-1234ze") and
at least one compound component selected from the group consisting
of 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetraafluoethane ("HFC-134a"), 1,1,1,2,2-pentafluoroethane
("HFC-125") and combinations of two or more of these. Thus, the
present invention overcomes the aforementioned shortcomings by
providing azeotrope-like compositions that are, in preferred
embodiments, substantially free of CFCs and HCFCs and which exhibit
relatively constant boiling point and vapor pressure
characteristics.
[0007] The preferred compositions of the invention tend to exhibit
characteristics which make them particularly desirable for use in a
number of applications, including as refrigerants in automotive air
conditioning and heat pump systems, and in stationary air
conditioning and refrigeration. In particular, applicants have
recognized that 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. Preferred embodiments of the present
compositions tend also to have similar or higher refrigeration
capacity than many conventional HFC refrigerants, for example,
HFC-134a. Accordingly, applicants have recognized that such
compositions can be used to great advantage in a number of
applications, including as replacements for CFCs such as
dichlorodifluormethane (CFC-12), HCFCs, such as
chlorodifluoromethane (HCFC-22), and 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 73.8:26.2 mass ratio being
known as R-500) in refrigerant, aerosol, and other
applications.
[0008] Additionally, applicants have recognized surprisingly that
the azeotrope-like compositions of the present invention exist and
can be readily formed in view of the teachings contained herein.
Accordingly, one aspect of the present invention provides methods
of producing azeotrope-like compositions comprising the step of
combining HFO-1234, preferably HFO-1234ze, and even more preferably
transHFO-1234ze, and a compound selected from the group consisting
of 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetraafluoethane ("HFC-134a"), 1,1,1,2,2-pentafluoroethane
("HFC-125") and combinations of two or more of these, in amounts
effective to produce an azeotrope-like composition.
[0009] The term "HFO-1234" is used herein to refer to all
tetrafluoropropenes. Among the tetrafluoropropenes are included
HFO-1234yf and both cis- and trans-1,3,3,3-tetrafluoropropene
(HFO-1234ze). The term HFO-1234ze is used herein generically to
refer to 1,3,3,3-tetrafluoropropene, independent of whether it is
the cis- or trans-form. The terms "cisHFO-1234ze" and
"transHFO-1234ze" are used herein to describe the cis- and
trans-forms of 1,3,3,3-tetrafluoropropene respectively. The term
"HFO-1234ze" therefore includes within its scope cisHFO-1234ze,
transHFO-1234ze, and all combinations and mixtures of these.
[0010] Although the properties of cisHFO-1234ze and transHFO-1234ze
differ in at least some respects, and while the present
azeotrope-like compositions are based mainly on transHFO-1234ze, it
is contemplated that the cisHFO-1234ze form may be present in
certain embodiments in amounts which do not negate the essential
nature of the azeotrope-like composition. Accordingly, it is to be
understood that the terms "HFO-1234ze" and
1,3,3,3-tetrafluoropropene refer to both stereo isomers, and the
use of this term is intended to indicate that each of the cis- and
trans-forms applies and/or is useful for the stated purpose unless
otherwise indicated.
[0011] HFO-1234 compounds are known materials and are listed in
Chemical Abstracts databases. The production of fluoropropenes such
as CF3CH.dbd.CH2 by catalytic vapor phase fluorination of various
saturated and unsaturated halogen-containing C3 compounds is
described in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786,
each of which is incorporated herein by reference. EP 974,571, also
incorporated herein by reference, discloses the preparation of
1,1,1,3-tetrafluoropropene by contacting
1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a
chromium-based catalyst at elevated temperature, or in the liquid
phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2.
In addition, methods for producing compounds in accordance with the
present invention are described generally in connection with
pending United States patent application entitled "Process for
Producing Fluoropropenes" bearing attorney docket No. H0003789
(U.S. application Ser. No. 13/226,019, now U.S. Pat. No.
8,247,625), which is also incorporated herein by reference.
[0012] 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, numerous
applications, including as heat transfer compositions (including as
refrigerants in automotive air conditioning and heat pump systems,
and in stationary air conditioning, heat pump and refrigeration
systems), blowing agents, propellants and sterilizing agents.
Accordingly, yet other aspects of the present invention provide one
or more azeotrope-like compositions of the present invention and
methods associated with these and other uses.
[0013] In another embodiment, the compositions of this invention
may be used as propellants in sprayable compositions, either alone
or in combination with known propellants. The propellant
compositions comprise, more preferably consists essentially of,
and, even more preferably consist of the 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, cleaning solvents, lubricants, as well as medicinal
materials such as anti-asthma medications.
[0014] The present compositions find particular advantage in
methods and systems involving aerosol compositions, particularly in
medicinal compositions, cleaning composition, and other sprayable
compositions. Those of skill in the art will be readily able to
adapt the present compositions for use in such applications without
undue experimentation.
Azeotrope-Like Compositions
[0015] 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 be separated during a phase change.
[0016] Azeotrope-like compositions are constant boiling or
essentially constant boiling. In other words, for azeotrope-like
compositions, the composition of the vapor formed during boiling or
evaporation is identical, or substantially identical, to the
original liquid composition. Thus, with boiling or evaporation, the
liquid composition changes, if at all, only to a minimal or
negligible extent. This is to be contrasted with non-azeotrope-like
compositions in which, during boiling or evaporation, the liquid
composition changes to a substantial degree. All azeotrope-like
compositions of the invention within the indicated ranges as well
as certain compositions outside these ranges are
azeotrope-like.
[0017] The azeotrope-like compositions of the 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 forms a new 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.
[0018] 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.
[0019] It is well-recognized in the art that it is not possible to
predict the formation of azeotropes. (See, for example, U.S. Pat.
No. 5,648,017 (column 3, lines 64-65) and U.S. Pat. No. 5,182,040
(column 3, lines 62-63), both of which are incorporated herein by
reference). Applicants have discovered unexpectedly that HFO-1234
and HFCs, particularly the HFCs described above, form
azeotrope-like compositions.
[0020] According to certain preferred embodiments, the
azeotrope-like compositions of the present invention comprise, and
preferably consist essentially of, effective amounts of HFO-1234
and the above-noted HFCs. The term "effective 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.
[0021] The azeotrope-like compositions of the present invention can
be produced by combining effective amounts of HFO-1234 and a
component, preferably in fluid form, selected from the group
consisting of 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetrafluroethane ("HFC-134a"), 1,1,1,2,2-pentafluoroethane
("HFC-125") and combinations of two or more of these. 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, transHFO-1234ze and HFC-152a can be mixed, blended, or
otherwise combined 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.
[0022] Preferably, such azeotrope-like compositions comprise,
preferably consist essentially of, from greater than zero to about
99 wt. % of of HFO-1234, preferably transHFO-1234ze, and from about
1 wt. % to less than 100 wt. % of one or more components selected
from the group consisting 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetrafluroethane ("HFC-134a"), and
1,1,1,2,2-pentafluoroethane ("HFC-125"). It will be appreciated by
those skilled in the art that the production transHFO-1234ze will
commonly result in product which includes a small proportion of
compound which are not transHFO-1234ze. For example, it would be
common in expected for a product designated as transHFO-1234ze to
include a minor percentage, for example about 0.5 wt. % up to about
1 wt. % of other components, including particularly cisHFO-1234ze
and/or HFO-1234yf. The term "consisting essentially of
transHFO-1234ze" used herein is intended to generally include such
compositions.
[0023] More preferably, the present azeotrope-like compositions
comprise, and preferably consist essentially of, from about 5 wt. %
to about 90 wt. % of HFO-1234, preferably transHFO-1234ze, and from
about 10 wt. % to about 90 wt. % of one or more components selected
from the group consisting of 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetrafluroethane ("HFC-134a"), and
1,1,1,2,2-pentafluoroethane ("HFC-125"). Other preferred
compositions comprise, or consist essentially of, greater than zero
to about 60 wt. % of HFO-1234, preferably transHFO-1234ze, and from
about 40 wt. % to less than 100 wt. % of one or more components
selected from the group consisting 1,1-difluoroethane ("HFC-152a"),
1,1,1,2,3,3,3-heptafluoropropane ("HFC-227ea"),
1,1,1,2,-tetrafluroethane ("HFC-134a"), and
1,1,1,2,2-pentafluoroethane ("HFC-125"). Unless otherwise
indicated, all weight percents reported herein are based on the
total weight of the HFO-1234 and the one or more components
selected from the indicated group in the azeotrope-like
composition.
[0024] According to certain preferred embodiments, the present
transHFO-1234ze azeotrope-like compositions have a boiling point of
from about -15.degree. C. to about -50.degree. C., and even more
preferably from about -28.degree. C. to about -50.degree. C., at
about 14 psia. In certain preferred embodiments, the present
compositions have a boiling point of about -23.degree.
C..+-.2.degree. C. In other preferred embodiments, the present
compositions have a boiling point of about -18.degree. C..+-.1 C.
Additionally, in other preferred embodiments the present
compositions have a boiling point of about -47.degree.
C..+-.2.degree. C. Preferably, the HFO-1234 containing compositions
of the present invention are substantially homogenous
azeotrope-like compositions.
HFO-1234/HFC-134a
[0025] Certain preferred embodiments of the present invention
provide azeotrope-like compositions comprising transHFO-1234ze and
HFC-134a. Preferably, the novel azeotrope-like compositions of the
present invention comprise effective amounts of transHFO-1234ze and
HFO-134a. These embodiments preferably provide azeotrope-like
compositions comprising, and preferably consisting essentially of,
from greater than zero to about 75 weight percent transHFO-1234ze
and from about 25 wt. % to less than 100 wt. % HFC-134a, more
preferably from greater than zero to about 60 wt. % transHFO-1234ze
and from about 40 wt. % to less than 100 wt. % HFO-134a, and even
more preferably from about 1% to about 40 weight percent
transHFO-1234ze and from about 60 wt. % to about 99 wt. % HFC-134a.
In certain preferred embodiments, the azeotrope-like compositions
comprise, and preferably consist essentially of, from about 5 wt. %
to about 35 wt % transHFO-1234ze and from about 65 wt. % to about
95 wt. % HFO-134a.
[0026] Preferably, the HFO-1234/HFC-134a compositions of the
present invention have a boiling of from about -26.degree. C. to
about -23.degree. C. at about 14 psia.
[0027] Preferably, the HFO-1234/HFO-134a compositions of the
present invention have a boiling of about -25.degree.
C..+-.3.degree. C. at about 14 psia. In certain embodiments, the
compositions have a boiling point of preferably about -25.degree.
C..+-.2.degree. C., and even more preferably -25.degree.
C..+-.1.degree. C., all measured at about 14 psia.
[0028] Preferably the HFO-1234 of these embodiments is
transHFO-1234ze.
HFO-1234/HFC-125
[0029] In certain other preferred embodiments, the present
invention provides azeotrope-like compositions comprising
transHFO-1234ze and HFC-125. Preferably, such novel azeotrope-like
compositions of the present invention comprise, or consist
essentially of, effective amounts of transHFO-1234ze and HFC-125.
These embodiments preferably provide azeotrope-like compositions
comprising, and preferably consisting essentially of, from greater
than zero to about 99 weight percent transHFO-1234ze and from about
1 wt. % to less than 100 wt. % HFC-125, more preferably from
greater than zero to about 75 wt. % transHFO-1234ze and from about
25 wt. % to less than 100 wt. % HFC-125, even more preferably from
about greater than zero to about 60 wt. % transHFO-1234ze and from
about 40 to less than 100 wt. % HFC-125, and even more preferably
from about 1% to about 40 weight percent transHFO-1234ze and from
about 60 wt. % to about 99 wt. % HFC-125. In certain preferred
embodiments, the azeotrope-like compositions comprise, and
preferably consist essentially of, from about 2 wt. % to about 15
wt % transHFO-1234ze and from about 85 wt. % to about 98 wt. %
HFO-125.
[0030] Other preferred compositions comprise, or consist
essentially of, from greater than zero to about 45 wt. %
transHFO-1234ze and from about 55 to less than 100 wt. %
HFC-125.
[0031] Preferably, the HFO-1234/HFC-125 compositions of the present
invention have a boiling of about -44.degree. C. to about
-50.degree. C., at about 14 psia.
[0032] Preferably the HFO-1234/HFC-125 compositions of the present
invention have a boiling of about -47.degree. C..+-.2.degree. C.,
preferably -47.degree. C..+-.1.degree. C. at about 14 psia.
HFO-1234/HFC-152a
[0033] In certain other preferred embodiments, the present
invention provides azeotrope-like compositions comprising
transHFO-1234ze and HFC-152a. Preferably, such novel azeotrope-like
compositions of the present invention comprise, or consist
essentially of, effective amounts of transHFO-1234ze and HFC-152a.
These embodiments preferably provide azeotrope-like compositions
comprising, and preferably consisting essentially of, from greater
than zero to about 99 weight percent transHFO-1234ze and from about
1 wt. % to less than 100 wt. % HFC-152a, more preferably from
greater than zero to about 50 wt. % transHFO-1234ze and from about
50 wt. % to less than 100 wt. % HFC-152a, and even more preferably
from about greater than zero to about 40 wt. % transHFO-1234ze and
from about 60% to less than 100 wt. % HFC-227ea. In certain
preferred embodiments, the azeotrope-like compositions comprise,
and preferably consist essentially of, from about 15 wt. % to about
30 wt % transHFO-1234ze and from about 70 wt. % to about 85 wt. %
HFO-152a.
[0034] Preferably, the HFO-1234/HFC-152a compositions of the
present invention have a boiling of from about -22.degree. C. to
about -24.degree. C. at about 14 psia.
[0035] Preferably, the HFO-1234/HFO-152a compositions of the
present invention have a boiling of about -23.degree.
C..+-.2.degree. C. at about 14 psia. In certain embodiments, the
compositions have a boiling point of preferably about -23.degree.
C..+-.1.degree. C. measured at about 14 psia.
[0036] Preferably the HFO-1234 of these embodiments is
transHFO-1234ze.
HFO-1234/HFC-227ea
[0037] Certain preferred embodiments of the present invention
provide azeotrope-like compositions comprising transHFO-1234ze and
HFC-227ea. Preferably, the novel azeotrope-like compositions of the
present invention comprise effective amounts of transHFO-1234ze and
HFO-227ea. These embodiments preferably provide azeotrope-like
compositions comprising, and preferably consisting essentially of,
from greater than zero to about 75 weight percent HFC-227ea and
from about 25 wt. % to less than 100 wt. % transHFO-1234ze, more
preferably from greater than zero to about 60 wt. % HFC-227ea and
from about 40 wt. % to less than 100 wt. % transHFC-1234ze, and
even more preferably from about 1% to about 40 weight percent
HFC-227ea and from about 60 wt. % to about 99 wt. %
transHFO-1234ze. In certain preferred embodiments, the
azeotrope-like compositions comprise, and preferably consist
essentially of, from about 5 wt. % to about 35 wt % HFC-227ea and
from about 65 wt. % to about 95 wt. % transHFO-1234ze.
[0038] Preferably, the HFO-1234/HFC-227ea compositions of the
present invention have a boiling of from about -17.degree. C. to
about -19.degree. C. at about 14 psia.
[0039] Preferably, the HFO-1234/HFO-227ea compositions of the
present invention have a boiling of about -18.degree.
C..+-.2.degree. C. at about 14 psia, and even more preferably about
-18.degree. C..+-.1.degree. C., measured at about 14 psia.
[0040] Preferably the HFO-1234 of these embodiments is
transHFO-1234ze.
Composition Additives
[0041] The azeotrope-like compositions of the present invention may
further include any of a variety of optional additives including
lubricants, stabilizers, metal passivators, corrosion inhibitors,
flammability suppressants, and the like.
[0042] According to certain embodiments, the azeotrope-like
compositions of the present invention further comprise a
stabilizer. Any of a variety of compounds suitable for stabilizing
an azeotrope-like composition of the present invention may be used.
Examples of certain preferred stabilizers include stabilizer
compositions comprising stabilizing diene-based compounds, and/or
phenol compounds, and/or epoxides selected from the group
consisting of aromatic epoxides, alkyl epoxides, alkenyl epoxides,
and combinations of two or more thereof.
[0043] In certain preferred embodiments, the compositions of the
present invention further comprise a lubricant. Any of a variety of
conventional and unconventional 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, which are generally those
commonly used in refrigeration machinery using or designed to use
hydrofluorocarbon (HFC) refrigerants, chlorofluorocarbon
refrigerants and hydrochlorofluorocarbons refrigerants, include
mineral oil, silicone oil, polyalkyl benzenes (sometimes referred
to as (PABs), polyol esters (sometimes referred to as (POEs),
polyalkylene glycols (sometimes referred to as (PAGs), polyalkylene
glycol esters (sometimes referred to as PAG esters), polyvinyl
ethers (sometimes referred to as PVEs), poly(alpha-olefin)
(sometimes referred to as PAOs) and halocarbon oils, particularly
poly(chlorotrifluorethylene) 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 polyalkyl 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). Commercially available PAGs include Motorcraft PAG
Refrigerant Compressor Oil, available from Ford, with similar
products being available from Dow. Commercially available PAOs
include CP-4600 from CPI Engineering. Commercially available PVEs
are available from Idemitsu Kosan. Commercially available PAG
esters are available from Chrysler. Other useful esters include
phosphate esters, dibasic acid esters, and fluoroesters.
[0044] For refrigeration systems using or designed to use HFCs, it
is generally preferred to use as lubricants PAGs, PAG esters, PVEs,
and POEs, particularly for systems comprising compression
refrigeration, air-conditioning (especially for automotive air
conditioning) and heat pumps. For refrigeration systems using or
designed to use CFCs or HCFCs, it is generally preferred to use as
lubricants mineral oil or PAB. In certain preferred embodiments,
the lubricants of this invention are organic compounds which are
comprised of carbon, hydrogen and oxygen with a ratio of oxygen to
carbon and are included to provide, in combination with the amounts
used, effective solubility and/or miscibility with the refrigerant
to ensure sufficient return of the lubricant to the compressor.
This solubility or miscibility preferably exists at at least one
temperature from about -30.degree. C. and 70.degree. C.
[0045] PAGs and PAG esters are highly preferred in certain
embodiments because they are currently in use in particular
applications such as original equipment mobile air-conditioning
systems. Polyol esters are highly preferred in other certain
embodiments because they are currently in use in particular
non-mobile applications such as residential, commercial, and
industrial air conditioning and refrigeration. Of course, different
mixtures of different types of lubricants may be used.
Uses of the Compositions
[0046] The present compositions have utility in a wide range of
applications. For example, one embodiment of the present invention
relates to heat transfer compositions, such as refrigerant
compositions, comprising an azeotrope-like composition of the
present invention. The heat transfer compositions of the present
invention are generally adaptable for use in heat transfer
applications, that is, as a heating and/or cooling medium. Although
it is contemplated that the compositions of the present invention
may include the present azeotrope-like composition in combination
with one or more other compounds or combinations of compounds in
widely ranging amounts, it is generally preferred that heat
transfer compositions of the present invention, including
refrigerant compositions, consist essentially of, and in some
embodiments consist of the present azeotrope-like compositions.
[0047] The heat transfer compositions of the present invention may
be used in any of a wide variety of refrigeration systems including
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 non-flammability, and a GWP that is as
low, or lower than that of conventional HFC-refrigerants and a
capacity that is as substantially similar to or substantially
matches, and preferably is as high as or higher than such
refrigerants. In particular, applicants have recognized that 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
the compositions of the present invention 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 23:25:52 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. The present compositions are also believed
to be suitable as replacements for the above noted compositions in
other applications, such as aerosols, blowing agents and the
like.
[0048] In certain other preferred embodiments, the present
compositions are used in heat transfer systems in general, and in
refrigeration systems in particular, 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 glycols, and the like,
or may be used with other lubricants traditionally used with HFC
refrigerants.
[0049] 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 (including chillers
using centrifugal compressors), transport refrigeration systems,
commercial refrigeration systems and the like.
[0050] In certain embodiments, the compositions of the present
invention may be used to retrofit refrigeration systems containing
HFC, HCFC, and/or CFC-refrigerants and lubricants used
conventionally therewith. Preferably, the present methods involve
recharging a refrigerant system that contains a refrigerant to be
replaced and a lubricant comprising the steps of (a) removing the
refrigerant to be replaced from the refrigeration system while
retaining a substantial portion of the lubricant in said system;
and (b) introducing to the system a composition of the present
invention.
[0051] As used herein, the term "substantial portion" refers
generally to a quantity of lubricant which is at least about 50%
(by weight) of the quantity of lubricant contained in the
refrigeration system prior to removal of the chlorine-containing
refrigerant. Preferably, the substantial portion of lubricant in
the system according to the present invention is a quantity of at
least about 60% of the lubricant contained originally in the
refrigeration system, and more preferably a quantity of at least
about 70%. 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, transport
refrigeration systems, commercial refrigeration systems and the
like.
[0052] 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 smaller
systems currently based on certain refrigerants, for example those
requiring a small refrigerating capacity and thereby dictating a
need for relatively small compressor displacement. 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 azeotrope-like 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. Heat transfer compositions of the
present invention are particularly preferred as replacements for
R-22, R-32, R-404A, R-407A, R-407C, R-407D, R-410A and R-507A. The
present compositions are also believed to be suitable as
replacements for the above noted compositions in other
applications, such as aerosols, blowing agents and the like.
[0053] 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.
It is contemplated that the compositions of the present also have
advantage (either in original systems or when used as a replacement
for refrigerants such as CFC-12, HCFC-22, HFC-134a, HFC-152a
R-404A, R-410A, R-407C, R-500 and R-507A), in chillers typically
used in connection with commercial air conditioning and
refrigeration systems. In certain of such embodiments it is
preferred to including in the present compositions from about 0.5
to about 30%, and in certain cases more preferably 0.5% to about
15% by weight of a supplemental flammability suppressant. In this
regard it is noted that the HFO-1234ze component and the other
compound in the azeotrope-like composition of the present
compositions may in certain embodiments act as a flammability
suppressant with respect to other components in the composition.
For example, in cases where other components more flammable than
HFO-1234ze are included in the composition, HFO1234-ze may function
to suppress the flammability of such other component. Thus, any
additional components which have flammability suppressant
functionality in the composition will sometimes be referred to
herein as a supplemental flammability suppressant.
[0054] In certain embodiments, co-refrigerants, including for
example HFCs, HCFCs and CFCs may be included in the heat transfer
compositions of the present invention, including one or more of the
following compounds, including any and all isomers thereof:
Trichlorofluoromethane (CFC-11)
Dichlorodifluoromethane (CFC-12)
Difluoromethane (HFC-32)
[0055] 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
CO2
[0056] The relative amount of any of the above noted components, as
well as any additional components which may be included in present
compositions, may be incorporated in amounts depending on the
particular application for the composition, and all such relative
amounts are considered to be within the scope hereof, provided
preferably that such components do not negate the azeotrope-like
nature of the preferred compositions described herein.
[0057] The present methods, systems and compositions are thus
adaptable for use in connection with automotive air conditioning
systems and devices, commercial refrigeration systems and devices,
chillers (including systems which utilize centrifugal compressors),
residential refrigerator and freezers, general air conditioning
systems, heat pumps, and the like.
[0058] Any of a wide range of known methods can be used to remove
refrigerants to be replaced from a refrigeration system while
removing less than a major portion of the lubricant contained in
the system. For example, because refrigerants are quite volatile
relative to traditional hydrocarbon-based lubricants (the boiling
points of refrigerants are generally less than 10.degree. C.
whereas the boiling points of mineral oils are generally more than
200.degree. C.), in embodiments wherein the lubricant is a
hydrocarbon-based lubricant, the removal step may readily be
performed by pumping chlorine-containing refrigerants in the
gaseous state out of a refrigeration system containing liquid state
lubricants. Such removal can be achieved in any of a number of ways
known in the art, including, the use of a refrigerant recovery
system, such as the recovery system manufactured by Robinair of
Ohio. Alternatively, a cooled, evacuated refrigerant container can
be attached to the low pressure side of a refrigeration system such
that the gaseous refrigerant is drawn into the evacuated container
and removed. Moreover, a compressor may be attached to a
refrigeration system to pump the refrigerant from the system to an
evacuated container. In light of the above disclosure, those of
ordinary skill in the art will be readily able to remove
chlorine-containing lubricants from refrigeration systems and to
provide a refrigeration system having therein a hydrocarbon-based
lubricant and substantially no chlorine-containing refrigerant
according to the present invention.
[0059] Any of a wide range of methods for introducing the present
refrigerant compositions to a refrigeration system can be 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.
[0060] 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 including cooling of other fluid either directly or
indirectly or a body directly or indirectly, 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 fluid or body 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 fluid
or body to be heated and thereafter evaporating said refrigerant
composition. 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 particular. For
example, certain aspects of the present invention involved
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. 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.
[0061] Applicants have found that in the systems 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 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 refrigerant of the present invention. 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 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 system capacity 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 system capacity
prior to replacement.
[0062] In another embodiment, the azeotrope-like compositions of
this invention may be used as propellants in sprayable
compositions, either alone or in combination with 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, and cleaning solvents, 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, diagnostic, pain
relief, and similar treatments, and as such would include for
example drugs and biologically active substances.
[0063] Yet another embodiment of the present invention relates to a
blowing agent comprising one or more azeotrope-like compositions of
the invention. In general, the blowing agent may include the
azeotrope-like compositions of the present invention in widely
ranging amounts. It is generally preferred, however, that the
blowing agents comprise the present azeotrope-like compositions in
amounts at least about 5% by weight, and even more preferably at
least about 15% by weight, of the blowing agent. 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
azeotrope-like composition. In certain preferred embodiments, the
blowing agent includes, in addition to the present compositions,
one or more of co-blowing agents, fillers, vapor pressure
modifiers, flame suppressants, stabilizers and like adjuvants.
[0064] 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. and methods of preparing foams. In such thermosetting
foam embodiments, one or more of the present azeotrope-like
compositions are included as a blowing agent in a foamable
composition, or as a part of a two or more part 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. 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 polyethyleneterephthalate
(PET), and foams formed therefrom, preferably low-density foams. In
certain embodiments, the thermoplastic foamable composition is an
extrudable composition.
[0065] It will be appreciated by those skilled in the art,
especially in view of the 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.
[0066] The invention also relates to foam, and preferably closed
cell foam, prepared from a polymer foam formulation containing a
composition of the invention, preferably as part of blowing
agent.
[0067] In certain preferred embodiments, dispersing agents, cell
stabilizers, surfactants and other additives may also be
incorporated into the blowing agent compositions of the present
invention. Surfactants are optionally but preferably added to serve
as cell stabilizers. Some representative materials are sold under
the names of DC-193, B-8404, and L-5340 which are, generally,
polysiloxane polyoxyalkylene block co-polymers such as those
disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458,
each of which is incorporated herein by reference. Other optional
additives for the blowing agent mixture may include flame
retardants or suppressants such as tri(2-chloroethyl)phosphate,
tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)-phosphate,
tri(1,3-dichloropropyl) phosphate, diammonium phosphate, various
halogenated aromatic compounds, antimony oxide, aluminum
trihydrate, polyvinyl chloride, and the like.
[0068] Any of the methods well known in the art, such as those
described in "Polyurethanes Chemistry and Technology," Volumes I
and II, Saunders and Frisch, 1962, John Wiley and Sons, New York,
N.Y., which is incorporated herein by reference, may be used or
adapted for use in accordance with the foam embodiments of the
present invention.
[0069] Other uses of the present azeotrope-like compositions
include use as solvents, cleaning agents, and the like. Those of
skill in the art will be readily able to adapt the present
compositions for use in such applications without undue
experimentation.
EXAMPLES
[0070] The invention is further illustrated in the following
example which is intended to be illustrative, but not limiting in
any manner. For examples 1-4, a ebulliometer of the general type
described by Swietolslowski in his book Ebulliometric Measurements
(Reinhold, 1945) was used.
Example 1
[0071] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which is further equipped with a Quartz
Thermometer is used. About 21 g HFC-134a is charged to the
ebulliometer and then HFO-1234ze is added in small, measured
increments. Temperature depression is observed when HFO-1234 is
added to HFC-134a, indicating a binary minimum boiling azeotrope is
formed. From greater than about 0 to about 51 weight percent
HFO-1234ze, the boiling point of the composition changed by about
1.3.degree. C. or less. The binary mixtures shown in Table 1 were
studied and the boiling point of the compositions changed by less
than about 2.degree. C. The compositions exhibit azeotrope and/or
azeotrope-like properties over this range.
TABLE-US-00001 TABLE 1 HFO-1234/HFC-134a compositions at 14.41 psia
Wt. % Wt. % Trans- T (C.) 134a 1234ze -25.288 100.00 0.00 -25.522
99.07 0.93 -25.581 95.01 4.99 -25.513 91.74 8.26 -25.444 86.21
13.79 -25.366 77.87 22.13 -24.926 67.47 32.53 -24.633 61.67 38.33
-24.291 55.23 44.77 -23.998 51.05 48.95
Example 2
[0072] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which is further equipped with a Quartz
Thermometer is used. About 35 g HFC-125 is charged to the
ebulliometer and then HFO-1234ze is added in small, measured
increments. Temperature depression is observed when HFO-1234ze is
added to HFC-125, indicating a binary minimum boiling azeotrope is
formed. From greater than about 0 to about 24 weight percent
HFO-1234ze, the boiling point of the composition changed by about
2.degree. C. or less. The binary mixtures shown in Table 1 were
studied and the boiling point of the compositions changed by less
than about 6.degree. C. The compositions exhibit azeotrope and/or
azeotrope-like properties over this range.
TABLE-US-00002 TABLE 2 HFO-1234/HFC-125 compositions at 14.40 psia
Wt. % Wt. % Trans- T (C.) 125 1234ze -48.446 100.00 0.00 -48.546
99.42 0.58 -48.898 96.35 3.65 -48.697 92.27 7.73 -47.842 84.68
15.32 -46.686 77.49 22.51 -44.856 68.02 31.98 -43.177 59.57 40.43
-42.513 56.97 43.03
Example 3
[0073] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which is further equipped with a Quartz
Thermometer is used. About 17 g HFC-152a is charged to the
ebulliometer and then HFO-1234 is added in small, measured
increments. Temperature depression is observed when HFO-1234 is
added to HFC-152a, indicating a binary minimum boiling azeotrope is
formed. From greater than about 0 to about 30 weight percent
HFO-1234, the boiling point of the composition changed by about
0.8.degree. C. or less. The binary mixtures shown in Table 1 were
studied and the boiling point of the compositions changed by less
than about 1.degree. C. The compositions exhibit azeotrope and/or
azeotrope-like properties over this range.
TABLE-US-00003 TABLE 3 HFO-1234/HFC-152a compositions at 14.39 psia
Wt. % Wt. % Trans- T (C.) 152a 1234ze -23.455 100.00 0.00 -23.504
99.34 0.66 -23.631 96.83 3.17 -23.778 94.99 5.01 -23.817 87.22
12.78 -24.160 81.49 18.51 -23.797 70.59 29.41
Example 4
[0074] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which is further equipped with a Quartz
Thermometer is used. About 18 g HFO-1234 is charged to the
ebulliometer and then HFC-227ea is added in small, measured
increments. Temperature depression is observed when HFC-227ea is
added to HFO-1234, indicating a binary minimum boiling azeotrope is
formed. From greater than about 0 to about 53 weight percent
HFC-227ea, the boiling point of the composition changed by about
0.7.degree. C. or less. The binary mixtures shown in Table 1 were
studied and the boiling point of the compositions changed by less
than about 1.degree. C. The compositions exhibit azeotrope and/or
azeotrope-like properties over this range.
TABLE-US-00004 TABLE 4 HFO-1234/HFC-227ea compositions at 14.44
psia Wt. % Trans- Wt. % T (C.) 1234ze 227ea -18.124 100.00 0.00
-18.310 98.87 1.13 -18.506 93.23 6.77 -18.653 86.62 13.38 -18.741
76.24 23.76 -18.555 66.40 33.60 -18.359 58.18 41.82 -18.114 52.63
47.37 -18.055 46.56 53.44
* * * * *