U.S. patent application number 15/670111 was filed with the patent office on 2017-11-23 for azeotrope-like compositions comprising trans-1-chloro-3,3,3-trifluoropropene.
The applicant listed for this patent is HONEYWELL INTERNATIONAL INC.. Invention is credited to Rajat S. Basu, Leslie Bement, Kane D. Cook, Ryan Hulse, Gary M. Knopeck, Hang T. Pham, Rajiv R. Singh.
Application Number | 20170335081 15/670111 |
Document ID | / |
Family ID | 42116591 |
Filed Date | 2017-11-23 |
United States Patent
Application |
20170335081 |
Kind Code |
A1 |
Basu; Rajat S. ; et
al. |
November 23, 2017 |
Azeotrope-Like Compositions Comprising
Trans-1-Chloro-3,3,3-Trifluoropropene
Abstract
An azeotrope-like mixture consisting essentially of
chlorotrifluoropropene and at least one component selected from the
group consisting of pentane, hexane, methanol, and
trans-1,2-dichloroethene.
Inventors: |
Basu; Rajat S.; (East
Amherst, NY) ; Cook; Kane D.; (Eggertsville, NY)
; Bement; Leslie; (Buffalo, NY) ; Knopeck; Gary
M.; (Lakeview, NY) ; Singh; Rajiv R.;
(Getzsville, NY) ; Hulse; Ryan; (Getzville,
NY) ; Pham; Hang T.; (Amherst, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HONEYWELL INTERNATIONAL INC. |
MORRIS PLAINS |
NJ |
US |
|
|
Family ID: |
42116591 |
Appl. No.: |
15/670111 |
Filed: |
August 7, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14457549 |
Aug 12, 2014 |
9725570 |
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15670111 |
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13072881 |
Mar 28, 2011 |
8802743 |
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14457549 |
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12259694 |
Oct 28, 2008 |
7935268 |
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13072881 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 7/5077 20130101;
C11D 7/5072 20130101; C23G 5/02809 20130101; C08J 2203/182
20130101; C08J 2203/14 20130101; C09K 3/30 20130101; C08J 9/149
20130101; C23G 5/02825 20130101; C09K 5/044 20130101; C11D 7/5068
20130101; C09K 2205/34 20130101; C11D 7/5059 20130101; C08J
2203/162 20130101; C08J 2203/12 20130101 |
International
Class: |
C08J 9/14 20060101
C08J009/14; C09K 5/04 20060101 C09K005/04; C09K 3/30 20060101
C09K003/30; C11D 7/50 20060101 C11D007/50; C23G 5/028 20060101
C23G005/028 |
Claims
1. A composition comprising an azeotrope-like mixture consisting
essentially of trans-1-chloro-3,3,3-trifluoropropene and at least
one component selected from the group consisting of pentane,
hexane, methanol, and trans-1,2-dichloroethene.
2. The composition of claim 1 wherein said azeotrope-like mixture
is a binary mixture consisting essentially of
trans-1-chloro-3,3,3-trifluoropropene and a compound selected from
the group consisting of pentane, hexane, methanol, and
trans-1,2-dichloroethylene.
3. The composition of claim 1 wherein said azeotrope-like mixture
is a ternary mixture consisting essentially of
trans-1-chloro-3,3,3-trifluoropropene and two compounds selected
from the group consisting of pentane, hexane, methanol, and
trans-1,2-dichloroethylene.
4. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
methanol.
5. The composition of claim 4 wherein said azeotrope-like mixture
consists essentially of about 70 to about 99.95 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 0.05 to about 30
wt. % methanol at a temperature of about 17.15.+-.1.degree. C. and
at pressure of about 14 psia.
6. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
n-pentane.
7. The composition of claim 6 wherein said azeotrope-like mixture
consists essentially of about 65 to about 99.95 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 0.05 to about 35
wt. % n-pentane at a temperature of about 17.4.+-.1.degree. C. and
at pressure of about 14 psia.
8. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
isopentane.
9. The composition of claim 8 wherein said azeotrope-like mixture
consists essentially of about 60 to about 99.95 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 0.05 to about 40
wt. % isopentane at a temperature of about 16.8.+-.1.degree. C. and
at pressure of about 14 psi.
10. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
neopentane.
11. The composition of claim 10 wherein said azeotrope-like mixture
consists essentially of about 5 to about 70 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 30 to about 95 wt.
% neopentane at a temperature of about 7.7.+-.1.degree. C. and at
pressure of about 14 psia.
12. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
isohexane.
13. The composition of claim 12 wherein said azeotrope-like mixture
consists essentially of about 60 to about 99.95 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 0.05 to about 40
wt. % isohexane at a temperature of about 17.4.+-.1.degree. C. and
at pressure of about 14 psia.
14. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene and
trans-1,2-dichloroethene.
15. The composition of claim 14 wherein said azeotrope-like mixture
consists essentially of about 60 to about 99.95 wt. %
trans-1-chloro-3,3,3-trifluoropropene and about 0.05 to about 40
wt. % transl,2-dichloroethene at a temperature of about
17.8.+-.1.degree. C. and at pressure of about 14 psia.
16. The composition of claim 1 wherein said azeotrope-like mixture
consists essentially of trans-1-chloro-3,3,3-trifluoropropene,
methanol, and n-pentane.
17. The composition of claim 16 wherein said azeotrope-like mixture
consists essentially of about 55 to about 99.90 wt. %
trans-1-chloro-3,3,3-trifluoropropene, about 0.05 to about 10 wt. %
methanol, and about 0.05 to about 35 wt. % n-pentane at a
temperature of about 17.4.+-.1.degree. C. and at pressure of about
14 psia.
18. The composition of claim 1 wherein said azeotrope-like mixture
further comprises nitromethane.
19. A blowing agent comprising an azeotrope-like mixture according
to claim 1, and, optionally, co-blowing agents, fillers, vapor
pressure modifiers, flame suppressants, and stabilizers.
20. A sprayable composition comprising an azeotrope-like mixture
according to claim 1, an active ingredient, and, optionally, inert
ingredients and/or solvents.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser.
No. 14/457,549, filed Aug. 12, 2014, which is a Continuation of
U.S. application Ser. No. 13/072,881, filed Mar. 28, 2011, (now
U.S. Pat. No. 8,802,743, issued on Aug. 12, 2014), which is a
Continuation of U.S. application Ser. No. 12/259,694, filed on Oct.
28, 2008, (now U.S. Pat. No. 7,935,268, issued on May 3, 2011),
which are incorporated herein by reference.
BACKGROUND
Field of Invention
[0002] The present invention relates generally to compositions
comprising trans-1-chloro-3,3,3-trifluoropropene. More
specifically, the present invention provides azeotrope-like
compositions comprising trans-1-chloro-3,3,3-trifluoropropene and
uses thereof.
Description of Related Art
[0003] Fluorocarbon based fluids, including chlorofluorocarbons
("CFCs") or hydrochlorofluorocarbons ("HCFCs"), have properties
that are desirable in industrial refrigerants, blowing agents, heat
transfer media, solvents, gaseous dielectrics, and other
applications. For these applications, the use of single component
fluids or azeotrope-like mixtures, i.e., those which do not
substantially fractionate on boiling and evaporation, are
particularly desirable.
[0004] Unfortunately, suspected environmental problems, such as
global warming and ozone depletion, have been attributed to the use
of some of these fluids, thereby limiting their contemporary use.
Hydrofluoroolefins ("HFOs") have been proposed as possible
replacements for such CFCs, HCFCs, and HFCs. However, the
identification of new, environmentally-safe, non-fractionating
mixtures comprising HFOs are complicated due to the fact that
azeotrope formation is not readily predictable. Therefore, industry
is continually seeking new HFO-based mixtures that are acceptable
and environmentally safer substitutes for CFCs, HCFCs, and HFCs.
This invention satisfies these needs among others.
SUMMARY OF INVENTION
[0005] Applicants have discovered that azeotrope-like compositions
are formed upon mixing trans-1-chloro-3,3,3-trifluoropropene
("trans-HFO-1233zd") with a second component selected from pentane,
hexane, methanol, trans-1,2-dichloroethene, and mixtures of two or
more of these, and optionally nitromethane. Preferred
azeotrope-like mixtures of the invention exhibit characteristics
which make them particularly desirable for number of applications,
including as refrigerants, as blowing agents in the manufacture of
insulating foams, as solvents in a number of cleaning and other
applications, including in aerosols and other sprayable
compositions. In particular, applicants have recognized that these
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.
[0006] Accordingly, one aspect of the present invention involves a
composition comprising an azeotrope-like mixture consisting
essentially of trans-1-chloro-3,3,3-trifluoropropene and at least
one component selected from the group consisting of pentane,
hexane, methanol, and trans-1,2-dichloroethene.
[0007] Another aspect of the invention provides a blowing agent
comprising at least about 15 wt. % of an azeotrope-like mixture as
described herein, and, optionally, co-blowing agents, fillers,
vapor pressure modifiers, flame suppressants, and stabilizers.
[0008] Another aspect of the invention provides a sprayable
composition comprising an azeotrope-like mixture as described
herein, an active ingredient, and, optionally, inert ingredients
and/or solvents and aerosol propellants.
[0009] Yet another aspect of the invention provides a closed cell
foam comprising a polyurethane-, polyisocyanurate-, or
phenolic-based cell wall and a cell gas comprising the novel
azeotrope-like mixture as described herein.
[0010] According to another aspect of the invention, provided is a
polyol premix comprising the novel azeotrope-like mixture as
described herein.
[0011] According to another aspect of the invention provided, is a
foamable composition comprising the novel azeotrope-like mixture as
described herein.
[0012] According to another aspect of the invention provided, is a
method for producing thermoset foam comprising (a) adding a blowing
agent comprising a novel azeotrope-like mixture as described herein
to a foamable mixture comprising a thermosetting resin; (b)
reacting said foamable mixture to produce a thermoset foam; and (c)
volatilizing said azeotrope-like composition during said
reacting.
[0013] According to another aspect of the invention provided, is a
method for producing thermoplastic foam comprising (a) adding a
blowing agent comprising a novel azeotrope-like mixture as
described herein to a foamable mixture comprising a thermoplastic
resin; (b) reacting said foamable mixture to produce a
thermoplastic foam; and (c) volatilizing said azeotrope-like
composition during said reacting.
[0014] According to another aspect of the invention, provided is a
thermoplastic foam having a cell wall comprising a thermoplastic
polymer and a cell gas comprising a novel azeotrope-like mixture as
described herein. Preferably, the thermoplastic foam comprises a
cell gas having an azeotrope-like mixture consisting essentially of
trans-1-chloro-3,3,3-trifluoropropene and methanol and a cell wall
of a thermoplastic polymer selected from polystyrene, polyethylene,
polypropylene, polyvinyl chloride, polytheyeneterephthalate or
combinations thereof.
[0015] According to another aspect of the invention, provided is a
thermoset foam having a cell wall comprising a thermosetting
polymer and a cell gas comprising a novel azeotrope-like mixture as
described herein. Preferably, the thermosetting foam comprises a
cell gas having an azeotrope-like mixture consisting essentially of
trans-1-chloro-3,3,3-trifluoropropene and methanol and a cell wall
of a thermoset polymer selected from polyurethane,
polyisocyanurate, phenolic, epoxy, or combinations thereof.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0016] According to certain embodiments, the present invention
provides azeotrope-like compositions comprising, and preferably
consisting essentially of, trans-HFO-1233zd and at least one
compound component selected from the group consisting of alcohols,
hydrocarbons, chlorinated hydrocarbon and mixtures thereof, and
optionally nitromethane. In certain embodiments, the novel
composition comprises an azeotrope-like mixture consisting
essentially of trans-HFO-1233zd and at least one component selected
from the group consisting of pentane, hexane, methanol, and
trans-1-12-dichloroethene. Thus, the present invention overcomes
the aforementioned shortcomings by providing azeotrope-like
compositions that are, in preferred embodiments, substantially free
of CFCs, HCFCs, and HFCs and have very low global warming
potentials have low ozone depletion, and which exhibit relatively
constant boiling point and vapor pressure characteristics.
[0017] As used herein, the term "azeotrope-like" relates to
compositions that are strictly azeotropic or that generally behave
like azeotropic mixtures. 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 or essentially constant-boiling and generally
cannot be thermodynamically separated during a phase change. The
vapor composition formed by boiling or evaporation of an azeotropic
mixture is identical, or substantially identical, to the original
liquid composition. Thus, the concentration of components in the
liquid and vapor phases of azeotrope-like compositions change only
minimally, if at all, as the composition boils or otherwise
evaporates. In contrast, boiling or evaporating non-azeotropic
mixtures changes the component concentrations in the liquid phase
to a significant degree.
[0018] As used herein, the term "consisting essentially of", with
respect to the components of an azeotrope-like composition, means
the composition contains the indicated components in an
azeotrope-like ratio, and may contain additional components
provided that the additional components do not form new
azeotrope-like systems. For example, azeotrope-like mixtures
consisting essentially of two compounds are those that form binary
azeotropes, which optionally may include one or more additional
components, provided that the additional components do not render
the mixture non-azeotropic and do not form an azeotrope with either
or both of the compounds.
[0019] 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.
[0020] In preferred embodiments, the amount trans-HO-1233zd
relative to all isomers of HFO-1233zd in azeotrope-like
compositions of the present invention is at least about 95%, more
preferably at least about 98%, even more preferably at least about
99%, even more preferably at least about 99.9%. In certain
preferred embodiments, the trans-HFO-1233zd component in
azeotrope-like compositions of the present invention is essentially
pure trans-HFO-1233zd.
[0021] As used herein, the term "pentane" includes all isomers of
C5 alkane. Preferred pentanes include the structural isomers
n-pentane (CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.3), isopentane
(2-methylbutane), and neopentane (2,2-dimethylpropane), with
n-pentane and isopentane being particularly preferred.
[0022] As used herein, the term "hexane" includes all isomers of C6
alkanes. Preferred hexanes include the structural isomers n-hexane
(CH.sub.3CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3), isohexane
(2-methylpentane), 3-methylpentane, 2,3-dimethylbutane, and
neohexane (2,2-dimethylbutane), with isohexane being particularly
preferred.
[0023] The azeotrope-like compositions of the present invention can
be produced by combining effective amounts of trans-HFO-1233zd with
one or more other components, preferably in fluid form. 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. For example, trans-HFO-1233zd and methanol 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.
[0024] Fluoropropenes, such as CF.sub.3CCl.dbd.CH.sub.2, can be
produced by known methods such as catalytic vapor phase
fluorination of various saturated and unsaturated
halogen-containing C3 compounds, including the method described in
U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is
incorporated herein by reference.
[0025] EP 974,571, also incorporated herein by reference, discloses
the preparation of 1,1,1,3-chlorotrifluoropropene 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.
The end product is approximately 90% by weight of the trans isomer
and 10% by weight cis. Preferably, the cis isomers are
substantially separated from the trans forms so that the resultant
preferred form of 1-chloro-3,3,3-trifluoropropene is more enriched
in the trans isomer. Because the cis isomer has a boiling point of
about 40.degree. C. in contrast with the trans isomer boiling point
of about 20.degree. C., the two can easily be separated by any
number of distillation methods known in the art. However, a
preferred method is batch distillation. According to this method, a
mixture of cis and trans 1-chloro-3,3,3-trifluoropropene is charged
to the reboiler. The trans isomer is removed in the overhead
leaving the cis isomer in the reboiler. The distillation can also
be run in a continuous distillation where the trans isomer is
removed in the overhead and the cis isomer is removed in the
bottom. This distillation process can yield about 99.9+% pure
trans-1-chloro-3,3,3-trifluoropropene and 99.9+%
cis-1-chloro-3,3,3-trifluoropropene.
Trans-HFO-1233zd/Methanol Azeotrope-Like Compositions:
[0026] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and methanol. More
preferably, these binary azeotrope-like compositions consist
essentially of about 70 to about 99.95 wt. % trans-HFO-1233zd and
from about 0.05 to about 30 wt. % methanol, more preferably from
about 90 to about 99.95 wt. % trans-HFO-1233zd and about 0.05 to
about 10 wt. % methanol, and even more preferably from about 95 to
about 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 5
wt. % methanol.
[0027] Preferably, the trans-HFO-1233zd/methanol compositions of
the present invention have a boiling point of from about 17.degree.
C. to about 19.degree. C., more preferably about 17.degree. C. to
about 18.degree. C., even more preferably about 17.degree. C. to
about 17.5.degree. C., and most preferably about 17.15.degree.
C..+-.1.degree. C., all measured at a pressure of about 14
psia.
Trans-HFO-1233zd/n-Pentane Azeotrope-Like Compositions:
[0028] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and n-pentane. More
preferably, these binary azeotrope-like compositions consist
essentially of about 65 to about 99.95 wt. % trans-HFO-1233zd and
from about 0.05 to about 35 wt. % n-pentane, more preferably from
about 84 to about 99.9 wt. % trans-HFO-1233zd and about 0.1 to
about 16 wt. % n-pentane, and even more preferably from about 92 to
about 99.5 wt. % trans-HFO-1233zd and from about 0.5 to about 8 wt.
% n-pentane.
[0029] Preferably, the trans-HFO-1233zd/n-pentane compositions of
the present invention have a boiling of from about 17.degree. C. to
about 19.degree. C., more preferably about 17.degree. C. to about
18.degree. C., even more preferably about 17.3.degree. C. to about
17.6.degree. C., and most preferably about 17.4.degree.
C..+-.1.degree. C., all measured at pressure of about 14 psia.
Trans-HFO-1233zd/Isopentane Azeotrope-Like Compositions:
[0030] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and isopentane.
More preferably, these binary azeotrope-like compositions consist
essentially of about 60 to about 99.95 wt. % trans-HFO-1233zd and
from about 0.05 to about 40 wt. % isopentane, more preferably from
about 70 to about 95 wt. % trans-HFO-1233zd and about 5 to about 30
wt. % isopentane, and even more preferably from about 80 to about
90 wt. % trans-HFO-1233zd and from about 10 to about 20 wt. %
isopentane.
[0031] Preferably, the trans-HFO-1233zd/isopentane compositions of
the present invention have a boiling of from about 15.degree. C. to
about 18.degree. C., more preferably about 16.degree. C. to about
17.degree. C., even more preferably about 16.7.degree. C. to about
16.9.degree. C., and most preferably about 16.8.degree.
C..+-.1.degree. C., all measured at a pressure of about 14
psia.
Trans-HFO-1233zd/Neopentane Azeotrope-Like Compositions:
[0032] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and neopentane.
More preferably, these binary azeotrope-like compositions consist
essentially of about 5 to about 70 wt. % trans-HFO-1233zd and from
about 30 to about 95 wt. % neopentane, more preferably from about
15 to about 55 wt. % trans-HFO-1233zd and about 45 to about 85 wt.
% neopentane, and even more preferably from about 20 to about 50
wt. % trans-HFO-1233zd and from about 50 to about 80 wt. %
neopentane.
[0033] Preferably, the trans-HFO-1233zd/neopentane compositions of
the present invention have a boiling of from about 7.7.degree. C.
to about 8.4.degree. C., more preferably about 7.7.degree. C. to
about 8.0.degree. C., and most preferably about 7.7.degree.
C..+-.1.degree. C., all measured at a pressure of about 14
psia.
Trans-HFO-1233zd/Isohexane Azeotrope-Like Compositions:
[0034] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and isohexane. More
preferably, these binary azeotrope-like compositions consist
essentially of about 60 to about 99.95 wt. % trans-HFO-1233zd and
from about 0.05 to about 40 wt. % isohexane, more preferably from
70 wt. % to about 99.95 wt. % trans-HFO-1233zd and about 0.05 to
about 30 wt. % isohexane, and even more preferably from about 80 to
about 99.95 wt. % trans-HFO-1233zd and from about 0.05 to about 20
wt. % isohexane.
[0035] Preferably, the trans-HFO-1233zd/isohexane compositions of
the present invention have a boiling of from about 17.degree. C. to
about 19.degree. C., more preferably about 17.degree. C. to about
18.degree. C., even more preferably about 17.3.degree. C. to about
17.6.degree. C., and most preferably about 17.4.degree.
C..+-.1.degree. C., all measured at a pressure of about 14
psia.
Trans-HFO-1233zd/trans-1,2-DCE Azeotrope-Like Compositions:
[0036] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd and trans-1,2-DCE.
More preferably, these binary azeotrope-like compositions consist
essentially of about 60 to about 99.99 wt. % trans-HFO-1233zd and
from about 0.01 to about 40 wt. % trans-1,2-DCE, more preferably
from about 75 to about 99.99 wt. % trans-HFO-1233zd and about 0.01
to about 25 wt. % trans-1,2-DCE, and even more preferably from
about 95 weight percent to about 99.99 wt % trans-HFO-1233zd and
from about 0.01 to about 5 wt. % trans-1,2-DCE.
[0037] Preferably, the trans-HFO-1233zd/trans-1,2-DCE compositions
of the present invention have a boiling of from about 17.degree. C.
to about 19.degree. C., more preferably about 17.5.degree. C. to
about 18.5.degree. C., even more preferably about 17.5.degree. C.
to about 18.degree. C., and most preferably about 17.8.degree.
C..+-.1.degree. C., all measured at a pressure of about 14
psia.
Trans-HFO-1233zd/Methanolln-Pentane Azeotrope-Like
Compositions:
[0038] In a preferred embodiment, the azeotrope-like composition
comprises effective amounts of trans-HFO-1233zd, methanol, and
n-pentane. More preferably, these ternary azeotrope-like
compositions consist essentially of about 55 to about 99.90 wt. %
trans-HFO-1233zd, from about 0.05 to about 10 wt. % methanol, and
from about 0.05 to about 35 wt. % n-pentane, even more preferably
from about 79 to about 98 wt. % trans-HFO-1233zd, from about 0.1 to
about 5 wt. % methanol, and about 1.9 to about 16 wt. % n-pentane,
and most preferably from about 88 to about 96 wt. %
trans-HFO-1233zd, from about 0.5 to about 4 wt. % methanol, and
from about 3.5 to about 8 wt. % n-pentane.
[0039] Preferably, the trans-HFO-1233zd/methanol/n-pentane
compositions of the present invention have a boiling point of from
about 17.degree. C. to about 19.degree. C., more preferably about
17.degree. C. to about 18.degree. C., even more preferably about
17.1.degree. C. to about 17.6.degree. C., and most preferably about
17.4.degree. C..+-.1.degree. C., all measured at a pressure of
about 14 psia.
[0040] The azeotrope-like compositions of the present invention may
further include a variety of optional additives including, but not
limited to, lubricants, stabilizers, metal passivators, corrosion
inhibitors, flammability suppressants, and the like. Examples of
suitable stabilizers include 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. Preferably, these optional
additives do not affect the basic azeotrope-like characteristic of
the composition.
Blowing Agents:
[0041] In another embodiment of the invention, provided are blowing
agents comprising at least one azeotrope-like mixture described
herein. In respect to the preparation of polymer foams comprising
the blowing agent described herein, and of the polymers and methods
used to prepare these foams can be employed. Specifically, polymer
foams are generally of two general classes, thermoplastic foams and
thermoset foams.
[0042] Thermoplastic foams are produced generally via any method
known in the art, including those described in Throne,
Thermoplastic Foams, 1996, Sherwood Publishers, Hinkley, Ohio. or
Klempner and Sendijarevic, Polymeric Foams and Foam Technology,
2.sup.nd Edition 2004, Hander Gardner Publications. Inc,
Cincinnati, Ohio. For example, extruded thermoplastic foams can be
prepared by an extrusion process whereby a solution of blowing
agent in molten polymer, formed in an extruded under pressure, is
forced through an orifice onto a moving belt at ambient temperature
or pressure or optionally at reduced pressure to aid in foam
expansion. The blowing agent vaporizes and causes the polymer to
expand. The polymer simultaneously expands and cools under
conditions that give it enough strength to maintain dimensional
stability at the time corresponding to maximum expansion. Polymers
used for the production of extruded thermoplastic foams include,
but are not limited to, polystyrene, polyethylene (HDPE, LDPE, and
LLDPE), polypropylene, polyethylene terephthalate, ethylene vinyl
acetate, and mixtures thereof. A number of additives are optionally
added to the molten polymer solution to optimize foam processing
and properties including, but not limited to, nucleating agents
(e.g., talc), flame retardants, colorants, processing aids (e.g.,
waxes), cross linking agents, permeability modifiers, and the like.
Additional processing steps such as irradiation to increase cross
linking, lamination of a surface film to improve foam skin quality,
trimming and planning to achieve foam dimension requirements, and
other processes may also be included in the manufacturing
process.
[0043] 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
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 azeotrope-like
mixtures, one or more co-blowing agents, fillers, vapor pressure
modifiers, flame suppressants, stabilizers, and like adjuvants.
[0044] In certain preferred embodiments, the blowing agent is
characterized as a physical (i.e., volatile) blowing agent
comprising the azeotrope-like mixture of the present invention. In
general, the amount of blowing agent present in the blended mixture
is dictated by the desired foam densities of the final foams
products and by the pressure and solubility limits of the process.
For example, the proportions of blowing agent in parts by weight
can fall within the range of about 1 to about 45 parts, more
preferably from about 4 to about 30 parts, of blowing agent per 100
parts by weight of polymer. The blowing agent may comprise
additional components mixed with the azeotrope-like composition,
including chlorofluorocarbons such as trichlorofluoromethane
(CFC-11), dichlorodifluoromethane (CFC-12),
hydrochlorofluorocarbons such as 1,1-dichloro-1-fluoroethane
(HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b),
chlorodifluoromethane (HCFC-22), hydrofluorocarbons such as
1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane
(HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and
1,1,1,3,3-pentafluorobutane (HFC-365mfc), hydrocarbons such as
propane, butane, isobutane, cyclopentane, carbon dioxide,
chlorinated hydrocarbons alcohols, ethers, ketones and mixtures
thereof.
[0045] In certain embodiments, the blowing agent is characterized
as a chemical blowing agents. Chemical blowing agents are materials
that, when exposed to temperature and pressure conditions in the
extruder, decompose to liberate a gas, generally carbon dioxide,
carbon monoxide, nitrogen, hydrogen, ammonia, nitrous oxide, of
mixtures thereof. The amount of chemical blowing agent present is
dependent on the desired final foam density. The proportions in
parts by weight of the total chemical blowing agent blend can fall
within the range of from less than 1 to about 15 parts, preferably
from about 1 to about 10 parts, of blowing agent per 100 parts by
weight of polymer.
[0046] 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 include flame retardants or
suppressants such as tri(2-hloroethyl)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.
[0047] With respect to thermoset foams, in general any thermoset
polymer can be used, including but not limited to polyurethane,
polyisocyanurate, phenolic, epoxy, and combinations thereof. In
general these foams are produces by bringing together chemically
reactive components in the presence of one or more blowing agents,
including the azeotrope-like composition of this invention and
optionally other additives, including but no limited to cell
stabilizers, solubility enhancers, catalysts, flame retardants,
auxiliary blowing agents, inert fillers, dyes, and the like.
[0048] With respect to the preparation of polyurethane or
polyisocyanurate foams using the azeotrope like compositions
described in the invention, any of the methods well known in the
art can be employed, see Saunders and Frisch, Volumes I and II
Polyurethanes Chemistry and technology, 1962, John Wiley and Sons,
New York, N.Y. In general, polyurethane or polyisocyanurate foams
are prepared by combining an isocyanate, a polyol or mixture of
polyols, a blowing agent or mixture of blowing agents, and other
materials such as catalysts, surfactants, and optionally, flame
retardants, colorants, or other additives.
[0049] It is convenient in many applications to provide the
components for polyurethane or polyisocyanurate foams in preblended
formulations. Most typically, the foam formulation is preblended
into two components. The isocyanate and optionally certain
surfactants and blowing agents comprise the first component,
commonly referred to as the "A" component. The polyol or polyol
mixture, surfactant, catalysts, blowing agents, flame retardant,
and other isocyanate reactive components comprise the second
component, commonly referred to as the "B" component. Accordingly,
polyurethane or polyisocyanurate foams are readily prepared by
bringing together the A and B side components either by hand mix
for small preparations and, preferably, machine mix techniques to
form blocks, slabs, laminates, pour-in-place panels and other
items, spray applied foams, froths, and the like. Optionally, other
ingredients such as fire retardants, colorants, auxiliary blowing
agents, water, and even other polyols can be added as a third
stream to the mix head or reaction site. Most conveniently,
however, they are all incorporated into one B Component as
described above.
[0050] Any organic polyisocyanate can be employed in polyurethane
or polyisocyanurate foam synthesis inclusive of aliphatic and
aromatic polyisocyanates. Preferred as a class are the aromatic
polyisocyanates. Typical aliphatic polyisocyanates are alkylene
diisocyanates such as tri, tetra, and hexamethylene diisocyanate,
isophorene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate),
and the like; typical aromatic polyisocyanates include m-, and
p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2,4-
and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitoylene
isocyanate, naphthylene 1,4-diisocyanate,
bis(4-isocyanatophenyl)methene,
bis(2-methyl-4-isocyanatophenyl)methane, and the like.
[0051] Preferred polyisocyanates are the polymethylene polyphenyl
isocyanates, particularly the mixtures containing from about 30 to
about 85 percent by weight of methylenebis(phenyl isocyanate) with
the remainder of the mixture comprising the polymethylene
polyphenyl polyisocyanates of functionality higher than 2.
[0052] Typical polyols used in the manufacture of polyurethane
foams include, but are not limited to, aromatic amino-based
polyether polyols such as those based on mixtures of 2,4- and
2,6-toluenediamine condensed with ethylene oxide and/or propylene
oxide. These polyols find utility in pour-in-place molded foams.
Another example is aromatic alkylamino-based polyether polyols such
as those based on ethoxylated and/or propoxylated aminoethylated
nonylphenol derivatives. These polyols generally find utility in
spray applied polyurethane foams. Another example is sucrose-based
polyols such as those based on sucrose derivatives and/or mixtures
of sucrose and glycerine derivatives condensed with ethylene oxide
and/or propylene oxide.
[0053] Examples of polyols used in polyurethane modified
polyisocyanurate foams include, but are not limited to, aromatic
polyester polyols such as those based on complex mixtures of
phthalate-type or terephthalate-type esters formed from polyols
such as ethylene glycol, diethylene glycol, or propylene glycol.
These polyols are used in rigid laminated boardstock, can be
blended with other types of polyols such as sucrose based polyols,
and used in other polyurethane foam applications such as described
above.
[0054] Catalysts used in the manufacture of polyurethane foams are
typically tertiary amines including, but not limited to,
N-alkylmorpholines, N-alkylalkanolamines,
N,N-dialkylcyclohexylamines, and alkylamines where the alkyl groups
are methyl, ethyl, propyl, butyl, and the like and isomeric forms
thereof; and hetrocyclic amines. Typical, but not limiting examples
are triethylenediamine, tetramethylethylenediamine,
bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine,
tributylamine, triamylamine, pyridine, quinoline,
dimethylpiperazine, piperazine, N,N-dimethylcyclohexylamine,
N-ethylmorpholine, 2-methylpiperazine, N,N-dimethylethanolamine,
tetramethylpropanediamine, methyltriethylenediamine, and the like,
and mixtures thereof.
[0055] Optionally, non-amine polyurethane catalysts are used.
Typical of such catalysts are organometallic compounds of bismuth,
lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium,
aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium,
copper, manganese, zirconium, and the like. Included as
illustrative are bismuth nitrate, lead 2-ethylhexoate, lead
benzoate, ferric chloride, antimony trichloride and antimony
glycolate. A preferred organo-tin class includes the stannous salts
of carboxylic acids such as stannous octoate, stannous
2-ethylhexoate, stannous laurate, and the like, as well as dialkyl
tin salts of carboxylic acids such as dibutyl tin diacetate,
dibutyl tin dilaurate, dioctyl tin diacetate, and the like.
[0056] In the preparation of polyisocyanurate foams, trimerization
catalysts are used for the purpose of converting the blends in
conjunction with excess A component to
polyisocyanurate-polyurethane foams. The trimerization catalysts
employed can be any catalyst known to one skilled in the art,
including, but not limited to, glycine salts and tertiary amine
trimerization catalysts and alkali metal carboxylic acid salts and
mixtures of the various types of catalysts. Preferred species
within the classes are potassium acetate, potassium octoate, and
N-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.
[0057] Dispersing agents, cell stabilizers, and surfactants can be
incorporated into the present blends. Surfactants, 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, which are incorporated herein by reference.
[0058] Other optional additives for the blends can include flame
retardants such as tris(2-chloroethyl)phosphate,
tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate,
tris(1,3-dichloropropyl)phosphate, diammonium phosphate, various
halogenated aromatic compounds, antimony oxide, aluminum
trihydrate, polyvinyl chloride, and the like. Other optional
ingredients can include from 0 to about 3 percent water, which
chemically reacts with the isocyanate to produce carbon dioxide.
This carbon dioxide acts as an auxillary blowing agent.
[0059] Also included in the mixture are blowing agents or blowing
agent blends as disclosed in this invention. Generally speaking,
the amount present in the blended mixture are dictated by the
desired foam densities of the final polyurethane or
polyisocyanurate foams produces. The proportions in parts by weight
of the total blowing agent blend can fall within the range of from
1 to about 45 parts of blowing agent per 100 parts of polyol ,
preferably from about 4 to about 30 parts.
[0060] The polyurethane foams produced can vary in density from
about 0.5 pound per cubic foot to about 40 pounds per cubic foot,
preferably from about 1.0 to 20.0 pounds per cubic foot, and most
preferably from about 1.5 to 6.0 pounds per cubic foot. The density
obtained is a function of how much of the blowing agent or blowing
agent mixture disclosed in this invention is present in the A
and/or B components, or alternatively added at the time the foam is
prepared.
Foams and Foamable Compositions:
[0061] Certain embodiments of the present invention involve a foam
comprising a polyurethane-, polyisocyanurate-, or phenolic-based
cell wall and a cell gas disposed within at least a portion of the
cells, wherein the cell gas comprises the azeotrope-like mixture
described herein. In certain embodiments, the foams are extruded
thermoplastic foams. Preferred foams have a density ranging from
about 0.5 pounds per cubic foot to about 60 pounds per cubic foot,
preferably from about 1.0 to 20.0 pounds per cubic foot, and most
preferably from about 1.5 to 6.0 pounds per cubic foot. The foam
density is a function of how much of the blowing agent or blowing
agent mixture (i.e., the azeotrope-like mixture and any auxiliary
blowing agent, such as carbon dioxide, chemical blowing agent or
other co-blowing agent is present in the molten polymer). These
foams are generally rigid but can be made in various grades of
softness to suit the end use requirements. The foams can have a
closed cell structure, an open cell structure or a mixture of open
and closed cells, with closed cell structures being preferred.
These foams are used in a variety of well known applications,
including but not limited to thermal insulation, flotation,
packaging, void filling, crafts and decorative, and shock
absorption.
[0062] 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,
such as polyurethane, polyisocyanurate, and phenolic-based
compositions, and a blowing agent comprising at least one
azeotrope-like mixture described herein. In certain embodiments,
the foamable composition comprises thermoplastic materials,
particularly thermoplastic polymers and/or resins. Examples of
thermoplastic foam components include polyolefins, such as
polystyrene (PS), polyethylene (PE), polypropylene (PP) and
polyethyleneterepthalate (PET), and foams formed therefrom,
preferably low-density foams. In certain embodiments, the
thermoplastic foamable composition is an extrudable
composition.
[0063] In certain embodiments, provided is a method for producing
such foams. 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 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 to mix in advance the various
components of the blowing agent. In certain embodiments, the
components of the foamable composition are not mixed in advance of
introduction to the extrusion equipment or 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. In certain other 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.
Refrigerants and Heat Transfer Systems:
[0064] Another embodiment of the present invention relates to
refrigerant compositions comprising the azeotrope-like compositions
described herein. The refrigerant compositions of the present
invention may be used in any of a wide variety of refrigeration
systems including air-conditioning, refrigeration, heat-pump
systems, and the like. In certain preferred embodiments, the
compositions of the present invention are used in refrigeration
systems originally designed for use with a CFC, HCFC, or HFC
refrigerant, such as, for example, HFC-134a and the like. 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
as, or lower than, that of conventional HFC refrigerants. In
addition, the relatively constant boiling nature of the
compositions of the present invention makes them more desirable
than certain conventional HFCs for use as refrigerants in many
applications.
[0065] 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, such as mineral oils, silicone oils, and
the like. Preferably, the present methods involve recharging a
refrigerant system that contains a refrigerant to be replaced and a
lubricant, the method comprising the steps of (a) removing at least
a substantial portion of 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
refrigerant comprising an azeotrope-like mixture as described
herein. As used herein, the term "substantial portion" refers
generally to a quantity of lubricant or refrigerant which is at
least about 50% (by weight) of the quantity of lubricant or
refrigerant, respectively, contained in the refrigeration system
prior to removal of the previous, less environmentally friendly
refrigerant. Preferably, the substantial portion of lubricant or
refrigerant in the system according to the present invention is a
quantity of at least about 60% of the lubricant or refrigerant,
respectively, 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.
[0066] 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 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. Those of ordinary skill in the art also will
be readily able to remove the lubricants from refrigeration systems
and to provide a refrigeration system having therein a lubricant
and refrigerant according to the present invention.
[0067] 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,
are 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.
[0068] According to certain other embodiments, the present
invention provides refrigeration systems comprising a refrigerant
of the present invention and methods of producing heating or
cooling by condensing and/or evaporating a composition of the
present invention. In certain preferred embodiments, the methods
for cooling an article according to the present invention comprise
condensing a refrigerant composition comprising an azeotrope-like
composition of the present invention and thereafter evaporating
said refrigerant composition in the vicinity of the article to be
cooled. Certain preferred methods for heating an article comprise
condensing a refrigerant composition comprising an azeotrope-like
composition of the present invention in the vicinity of the article
to be heated and thereafter evaporating said refrigerant
composition.
[0069] 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.
Sprayable Compositions:
[0070] In a preferred embodiment, the azeotrope-like compositions
of this invention may be used as solvents in sprayable
compositions, either alone or in combination with other known
propellants. The solvent composition comprises, more preferably
consists essentially of, and, even more preferably, consists of the
azeotrope-like compositions of the invention. In certain
embodiments, the sprayable composition is an aerosol.
[0071] In certain preferred embodiments, provided is a sprayable
composition comprising a solvent as described above, an active
ingredient, and optionally, other components such as inert
ingredients, solvents, and the like.
[0072] Suitable active materials to be sprayed include, without
limitation, cosmetic materials such as deodorants, perfumes, hair
sprays, cleaning solvents, lubricants, insecticides 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.
[0073] Solvents and Cleaning Compositions:
[0074] In another embodiment of the invention, the azeotrope-like
compositions described herein can be used as a solvent in cleaning
various soils such as mineral oil, rosin based fluxes, lubricants,
etc., from various substrates by wiping, vapor degreasing, or other
means. In certain preferred embodiments, the cleaning composition
is an aerosol.
EXAMPLES
[0075] 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
[0076] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 10 cc of trans-HFO-1233zd was charged
to the ebulliometer and then methanol was added in small, measured
increments. Temperature depression was observed when methanol was
added, indicating a binary minimum boiling azeotrope had been
formed. From greater than 0 to about 51 weight percent methanol,
the boiling point of the composition changes less than about
1.3.degree. C. The boiling points of the binary mixtures shown in
Table 1 changed by less than about 0.02.degree. C. Thus the
compositions exhibited azeotrope and/or azeotrope-like properties
over these ranges.
TABLE-US-00001 TABLE 1 Trans-HFO-1233zd/Methanol compositions at
14.40 psia Wt. % Trans- wt % Temp (.degree. C.) HFO-1233zd Methanol
17.15 (.degree. C.) 98.78 wt. % 1.22 wt. % 17.14 (.degree. C.)
98.58 wt. % 1.42 wt. % 17.14 (.degree. C.) 98.38 wt. % 1.62 wt. %
17.14 (.degree. C.) 98.18 wt. % 1.82 wt. % 17.14 (.degree. C.)
97.98 wt. % 2.02 wt. % 17.14 (.degree. C.) 97.78 wt. % 2.22 wt. %
17.15 (.degree. C.) 97.59 wt. % 2.41 wt. %
Example 2
[0077] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 35 g trans-HFO-1233zd is charged to the
ebulliometer and then n-pentane was added in small, measured
increments. Temperature depression was observed when n-pentane was
added to trans-HFO-1233zd, indicating a binary minimum boiling
azeotrope had been formed. From greater than 0 to about 30 weight
percent n-pentane, the boiling point of the composition changes
less than about 0.8.degree. C. The boiling points of the binary
mixtures shown in Table 2 changed by less than about 0.02.degree.
C. Thus the compositions exhibited azeotrope and/or azeotrope-like
properties over these ranges.
TABLE-US-00002 TABLE 2 Trans-HFO-1233zd/n-Pentane compositions at
14.20 psia Wt. % Trans- Wt % Temp (.degree. C.) HFO-1233zd
n-pentane 17.43 (.degree. C.) 97.76 wt. % 2.24 wt. % 17.42
(.degree. C.) 97.60 wt. % 2.40 wt. % 17.42 (.degree. C.) 97.45 wt.
% 2.55 wt. % 17.42 (.degree. C.) 97.29 wt. % 2.71 wt. % 17.42
(.degree. C.) 97.14 wt. % 2.86 wt. % 17.42 (.degree. C.) 96.98 wt.
% 3.02 wt. % 17.42 (.degree. C.) 96.83 wt. % 3.17 wt. % 17.42
(.degree. C.) 96.67 wt. % 3.33 wt. % 17.42 (.degree. C.) 96.52 wt.
% 3.48 wt. % 17.42 (.degree. C.) 96.37 wt. % 3.63 wt. % 17.42
(.degree. C.) 96.22 wt. % 3.78 wt. % 17.42 (.degree. C.) 96.07 wt.
% 3.93 wt. % 17.43 (.degree. C.) 95.92 wt. % 4.08 wt. %
Example 3
[0078] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 17 g trans-HFO-1233zd is charged to the
ebulliometer and then isopentane was added in small, measured
increments. Temperature depression was observed when isopentane was
added to trans-HFO-1233zd, indicating a binary minimum boiling
azeotrope had been formed. From greater than about 0 to about 30
weight percent isopentane, the boiling point of the composition
changed by about 0.8.degree. C. or less. The boiling points of the
binary mixtures shown in Table 3 changed by less than about
0.2.degree. C. Thus the compositions exhibited azeotrope and/or
azeotrope-like properties over these ranges.
TABLE-US-00003 TABLE 3 Trans-HFO-1233/isopentane compositions at
14.39 psia Wt % Trans- Wt % Temp(.degree. C.) HFO-1233zd isopentane
16.86 (.degree. C.) 92.39 wt. % 7.61 wt. % 16.78 (.degree. C.)
90.52 wt. % 9.48 wt. % 16.73 (.degree. C.) 88.73 wt. % 11.27 wt. %
16.70 (.degree. C.) 87.01 wt. % 12.99 wt. % 16.70 (.degree. C.)
85.35 wt. % 14.65 wt. % 16.69 (.degree. C.) 83.75 wt. % 16.25 wt. %
16.70 (.degree. C.) 82.21 wt. % 17.79 wt. % 16.72 (.degree. C.)
80.73 wt. % 19.27 wt. % 16.76 (.degree. C.) 79.13 wt. % 20.87 wt. %
16.85 (.degree. C.) 77.58 wt. % 22.42 wt. %
Example 4
[0079] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 17 g neopentane is charged to the
ebulliometer and then trans-HFO-1233zd was added in small, measured
increments. Temperature depression was observed when
trans-HFO-1233zd was added to,neopentane indicating a binary
minimum boiling azeotrope had been formed. As shown in Table 4,
compositions comprising from about 19 to about 49 weight percent
trans-HFO-1233zd had a change in boiling point of 0.1.degree. C. or
less. Thus the compositions exhibited azeotrope and/or
azeotrope-like properties over at least this range.
TABLE-US-00004 TABLE 4 Trans-HFO-1233zd/neopentane compositions at
14.2 psia Wt % Trans- Wt % Temp(.degree. C.) HFO-1233zd neopentane
8.54 (.degree. C.) 0.00 wt. % 100.00 wt. % 8.47 (.degree. C.) 1.36
wt. % 98.64 wt. % 8.42 (.degree. C.) 2.69 wt. % 97.31 wt. % 8.30
(.degree. C.) 5.23 wt. % 94.77 wt. % 8.21 (.degree. C.) 7.65 wt. %
92.35 wt. % 8.12 (.degree. C.) 9.94 wt. % 90.06 wt. % 7.95
(.degree. C.) 14.21 wt. % 85.79 wt. % 7.87 (.degree. C.) 19.00 wt.
% 81.00 wt. % 7.78 (.degree. C.) 23.29 wt. % 76.71 wt. % 7.72
(.degree. C.) 29.28 wt. % 70.72 wt. % 7.72 (.degree. C.) 34.40 wt.
% 65.60 wt. % 7.75 (.degree. C.) 38.83 wt. % 61.17 wt. % 7.81
(.degree. C.) 42.70 wt. % 57.30 wt. % 7.85 (.degree. C.) 46.11 wt.
% 53.89 wt. % 7.88 (.degree. C.) 49.14 wt. % 50.86 wt. %
Example 5
[0080] 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 trans-HFO-1233 is charged to the
ebulliometer and then trans-1,2-DCE was added in small, measured
increments. Temperature depression was observed when trans-1,2-DCE
was added to trans-HFO-1233, indicating a binary minimum boiling
azeotrope was formed. From greater than about 0.01 to about 53
weight percent trans-1,2-DCE, the boiling point of the composition
changed by about 0.7.degree. C. or less. The boiling points of the
binary mixtures shown in Table 4 changed by less than about
0.3.degree. C. Thus the compositions exhibited azeotrope and/or
azeotrope-like properties over these ranges.
TABLE-US-00005 TABLE 5 Trans-HFO-1233/tr-1,2DCE compositions at
14.40 Psia Wt. % Trans- Wt. % T(.degree. C.) HFO-1233zd tr-1,2-DCE
17.74 (.degree. C.) 100.00 wt. % 0.00 wt. % 17.74 (.degree. C.)
99.68 wt. % 0.32 wt. % 17.73 (.degree. C.) 99.35 wt. % 0.65 wt. %
17.76 (.degree. C.) 99.03 wt. % 0.97 wt. % 17.79 (.degree. C.)
98.72 wt. % 1.28 wt. % 17.82 (.degree. C.) 98.40 wt. % 1.60 wt. %
17.85 (.degree. C.) 98.08 wt. % 1.92 wt. % 17.88 (.degree. C.)
97.77 wt. % 2.23 wt. % 17.92 (.degree. C.) 97.46 wt. % 2.54 wt. %
17.96 (.degree. C.) 97.15 wt. % 2.85 wt. %
Example 6
[0081] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which is further equipped with a Quartz
Thermometer is used. An amount of trans-HFO-1233zd is charged to
the ebulliometer and then isohexane was added in small, measured
increments. Temperature depression was observed when isohexane was
added to trans-HFO-1233, indicating a binary minimum boiling
azeotrope was formed. From greater than about 0.01 to about 30
weight percent isohexane, the boiling point of the composition
changed by about 0.5.degree. C. or less. Thus the compositions
exhibited azeotrope and/or azeotrope-like properties over these
ranges.
Example 7
[0082] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 18 g of a mixture of
trans-HFO-1233zd/methanol (98/2 wt %) was charged to the
ebulliometer and then n-pentane was added in small, measured
increments. Temperature depression was observed as n-pentane was
added to trans-HFO-1233, indicating a ternary minimum boiling
azeotrope was formed. From greater than about 0 to about 18 weight
percent n-pentane, the boiling point of the composition changed by
about 0.3.degree. C. or less.
Example 8
[0083] An ebulliometer consisting of vacuum jacketed tube with a
condenser on top which was further equipped with a Quartz
Thermometer was used. About 18 g of a mixture of
trans-HFO-1233zd/MeOH (98/2 wt %) was charged to the ebulliometer
and then trans-1,2-DCE was added in small, measured increments.
Temperature changed very little as trans-1,2-DCE was added to the
mixture, indicating a ternary constant boiling azeotropic-like
mixture was formed. From greater than about 0 to about 18 weight
percent n-pentane, the boiling point of the composition changed by
about 0.7.degree. C. or less.
Example 9
[0084] Mixtures were prepared containing 98% by weight
trans-HFO-1233zd with about 2 weight percent methanol. Several
stainless steel coupons were soiled with mineral oil. Then these
coupons were immersed in these solvent blends. The blends could
remove the oils in a short period of time. The coupons were
observed visually and looked clean.
Example 10
[0085] A solvent blend was prepared containing 98% by wt of
trans-HFO-1233zd and 2% by wt of methanol. Kester 1544 Rosin
Soldering Flux was placed on stainless steel coupons and heated to
approximately 300-400 .degree. F., which simulates contact with a
wave soldier normally used to solder electronic components in the
manufacture of printed circuit boards. The coupons were then dipped
in the solvent mixture and removed after 15 seconds without
rinsing. Results show that the coupons appeared clean by visual
inspection.
Example 11 (Prophetic)
[0086] The procedure of Example 8 is repeated except that the
solvent blend is an azeotrope-like mixture of trans-HFO-1233zd and
n-pentane. Visual inspection of the coupon upon removal from the
solvent mixture will appear clean.
Example 12 (Prophetic)
[0087] The procedure of Example 8 is repeated except that the
solvent blend is an azeotrope-like mixture of trans-HFO-1233zd and
isopentane. Visual inspection of the coupon upon removal from the
solvent mixture will appear clean.
Example 13 (Prophetic)
[0088] The procedure of Example 8 is repeated except that the
solvent blend is an azeotrope-like mixture of trans-HFO-1233zd and
isohexane. Visual inspection of the coupon upon removal from the
solvent mixture will appear clean.
Example 14 (Prophetic)
[0089] The procedure of Example 8 is repeated except that the
solvent blend is an azeotrope-like mixture of trans-HFO-1233zd and
trans-1,2-DCE. Visual inspection of the coupon upon removal from
the solvent mixture will appear clean.
Example 15 (prophetic)
[0090] The procedure of Example 8 is repeated except that the
solvent blend is an azeotrope-like mixture of trans-HFOP-1233zd,
methanol, and n-pentane. Visual inspection of the coupon upon
removal from the solvent mixture will appear clean.
Examples 16-22 (Prophetic)
[0091] A mixture containing 98% by weight trans-HFO-1233zd with
about 2% by weight methanol is loaded into an aerosol can. An
aerosol valve is crimped into place and HFC-134a is added through
the valve to achieve a pressure in the can of about 20 PSIG. The
mixture is then sprayed onto a metal coupon soiled with solder
flux. The flux is removed and the coupon is visually clean. This
procedure is repeated except that the azeotrope-like compositions
of 9-13 were used instead of trans-HFO-1233zd and methanol. Similar
results are obtained.
Examples 23-28 (Prophetic)
[0092] A mixture containing 98% by wt trans-HFO-1233zd and 2% by wt
of methanol is prepared, silicone oil is mixed with the blend and
the solvent was left to evaporate, a thin coating of silicone oil
is left behind in the coupon. This indicated that the solvent
blends can be used for silicone oil deposition in various
substrates. This procedure is repeated except that the
azeotrope-like compositions of 9-13 were used instead of
trans-HFO-1233zd and methanol. Similar results are obtained.
[0093] Having thus described a few particular embodiments of the
invention, various alterations, modifications, and improvements
will readily occur to those skilled in the art. Such alterations,
modifications, and improvements, as are made obvious by this
disclosure, are intended to be part of this description though not
expressly stated herein, and are intended to be within the spirit
and scope of the invention. Accordingly, the foregoing description
is by way of example only, and not limiting. The invention is
limited only as defined in the following claims and equivalents
thereto.
* * * * *