U.S. patent application number 15/925892 was filed with the patent office on 2018-09-20 for compositions and uses of trans-1,1,1,4,4,4-hexafluoro-2-butene.
The applicant listed for this patent is THE CHEMOURS COMPANY FC, LLC. Invention is credited to KONSTANTINOS KONTOMARIS, MARK L. ROBIN.
Application Number | 20180264303 15/925892 |
Document ID | / |
Family ID | 62044959 |
Filed Date | 2018-09-20 |
United States Patent
Application |
20180264303 |
Kind Code |
A1 |
ROBIN; MARK L. ; et
al. |
September 20, 2018 |
COMPOSITIONS AND USES OF TRANS-1,1,1,4,4,4-HEXAFLUORO-2-BUTENE
Abstract
Disclosed is a mixture comprising the compound
trans-1,1,1,4,4,4-hexafluoro-2-butene and at least one additional
compound selected from the group consisting of HFOs, HFCs, HFEs,
CFCs, CO2, olefins, organic acids, alcohols, hydrocarbons, ethers,
aldehydes, ketones, and others such as methyl formate, formic acid,
trans-1,2 dichloroethylene, carbon dioxide,
cis-HFO-1234ze+HFO-1225yez; mixtures of these plus water; mixtures
of these plus CO2; mixtures of these trans 1,2-dichloroethylene
(DCE); mixtures of these plus methyl formate; mixtures with
cis-HFO-1234ze+CO2; mixtures with cis-HFO-1234ze+HFO-1225yez+CO2;
and mixtures with cis-HFO-1234ze+HFC-245fa. Also disclosed are
methods of using and products of using the above compositions as
blowing agents, solvents, heat transfer compositions, aerosol
propellant compositions, fire extinguishing and suppressant
compositions.
Inventors: |
ROBIN; MARK L.; (MIDDLETOWN,
DE) ; KONTOMARIS; KONSTANTINOS; (WILMINGTON,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
THE CHEMOURS COMPANY FC, LLC |
Wilmington |
DE |
US |
|
|
Family ID: |
62044959 |
Appl. No.: |
15/925892 |
Filed: |
March 20, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62473989 |
Mar 20, 2017 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A62D 1/0071 20130101;
C08J 9/144 20130101; C09K 5/045 20130101; C10M 2203/045 20130101;
C11D 7/5018 20130101; H05F 3/04 20130101; C08J 2300/22 20130101;
A62D 1/0057 20130101; C08J 9/141 20130101; C09K 5/00 20130101; C09K
2205/24 20130101; C08J 2300/24 20130101; H01B 3/24 20130101; A01N
29/00 20130101; C08J 2203/182 20130101; C09K 2205/126 20130101;
C08J 2203/162 20130101; C08J 9/146 20130101; C09K 2205/32 20130101;
C09K 5/048 20130101; C08J 2203/202 20130101; C09K 2205/12 20130101;
B01D 11/0288 20130101; C09K 5/044 20130101; C09K 3/30 20130101;
H01B 3/56 20130101; C10M 105/04 20130101; C08J 2367/00 20130101;
C08J 2375/04 20130101; C10M 105/52 20130101; C10M 2211/0225
20130101; A62D 1/0092 20130101 |
International
Class: |
A62D 1/00 20060101
A62D001/00; C08J 9/14 20060101 C08J009/14; C09K 5/04 20060101
C09K005/04; C09K 3/30 20060101 C09K003/30; C10M 105/52 20060101
C10M105/52; C10M 105/04 20060101 C10M105/04; A01N 29/00 20060101
A01N029/00; C11D 7/50 20060101 C11D007/50; H01B 3/56 20060101
H01B003/56; H05F 3/04 20060101 H05F003/04; B01D 11/02 20060101
B01D011/02 |
Claims
1. A composition comprising an azeotropic or near-azeotropic
composition of trans-1,1,1,4,4,4-hexafluoro-2-butene and
cyclopentane.
2. The azeotropic composition of claim 1, wherein the composition
comprises from about 89.6 to about 97.8 mole percent
trans-1,1,1,4,4,4-hexafluoro-2-butene and about 2.2 to about 10.4
mole percent cyclopentane.
3. The composition of claim 2, which exhibits a vapor pressure of
from about 1.43 psia to about 83.12 psia at a temperature of from
-40.degree. C. to 60.degree. C.
4. The near-azeotropic composition of claim 1, comprising from
about 82.4 to about 99.8 mole percent
trans-1,1,1,4,4,4-hexafluoro-2-butene and from about 0.2 to about
17.6 mole percent cyclopentane.
5. A mixture comprising the compound
trans-1,1,1,4,4,4-hexafluoro-2-butene and at least one additional
compound selected from the group consisting of HFOs, HCFOs, HFCs,
HFEs, HCFCs, CFCs, CO2, olefins, hydrochloroolefins, chlorinated
hydrocarbons, organic acids, alcohols, hydrocarbons, ethers,
aldehydes, ketones, water, and others such as methyl formate, ethyl
formate, formic acid, trans-1,2-dichloroethylene (DCE), carbon
dioxide, 3,3,3-trifluoropropyne, cis-HFO-1234ze+HFO-1225yez;
mixtures of these plus water; mixtures of these plus CO2; mixtures
of these plus trans-1,2-dichloroethylene; mixtures of these plus
methyl formate; mixtures with cis-HFO-1234ze+CO2; mixtures with
cis-HFO-1234ze+HFO-1225yez+CO2; and mixtures with
cis-HFO-1234ze+HFC-245fa.
6. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of trans-1,2-dichloroethylene; carbon dioxide;
cis-HFO-1234ze; HFO-1225yez; low molecular weight alcohols; low
global warming potential olefins; chlorofluorocarbons; ketones;
aldehydes; organic acids; and alkanes.
7. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of cis-HFO-1234ze; trans-HFO-1234ze; HFO-1234yf; HFO
1225ye(Z); HFO-1225ye(E); HFO-1225yc; HFO-1233zd (E&Z);
HFC-1233xf; HCFO-1224yd (E&Z); (CF3)2CFCH.dbd.CHF (E & Z);
(CF3)2CFCH.dbd.CF2; CF3CHFC.dbd.CHF (E & Z); and
(C2F5)(CF3)C.dbd.CH2.
8. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of HFC-245eb; HFC-245ca; HFC-227ea; HFC-236ea;
HFC-236fa; HFC-134a; HFC-134; HFC-152a; HFC-32; HFC-125; HFC-143a;
HFC-365mfc; HFC-161; and HFC-43-10mee.
9. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of CHF2-O--CHF2; CHF2-O--CH2F; CH2F--O--CH2F;
CH2F--O--CH3; cyclo-CF2-CH2-CF2-O; cyclo-CF2-CF2-CH2-O;
CHF2-O--CF2-CHF2; CF3-CF2-O--CH2F; CHF2-O--CHF--CF3;
CHF2-O--CF2-CHF2; CH2F--O--CF2-CHF2; CF3-O--CF2-CH3;
CHF2-CHF--O--CHF2; CF3-O--CHF--CH2F; CF3-CHF--O--CH2F;
CF3-O--CH2-CHF2; CHF2-O--CH2-CF3; CH2F--CF2-O--CH2F;
CHF2-O--CF2-CH3; CHF2-CF2-O--CH3; CH2F--O--CHF--CH2F;
CHF2-CHF--O--CH2F; CF3-O--CHF--CH3; CF3-CHF--O--CH3;
CHF2-O--CH2-CHF2; CF3-O--CH2-CH2F; CF3-CH2-O--CH2F; and
CF2H--CF2-CF2-O--CH3.
10. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of propane; butane; isobutane; neopentane; isopentane;
n-hexane; isohexane; and heptane.
11. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of dimethylether; methylethylether; diethyl ether;
methylpropylether; methylisopropylether; ethylpropylether;
ethylisopropylether; dipropylether; diisopropylether;
dimethyloxymethane; diethoxymethane; dipropoxymethane; and
dibutoxymethane.
12. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of formaldehyde; acetaldehyde; propanal; butanal; and
isobutanal.
13. The mixture of claim 5, wherein the additional compound
comprises one or more of the compounds selected from the group
consisting of acetone; methylethylketone; and
methylisobutylketone.
14. A process of forming a foam comprising: (a) adding a foamable
composition to a blowing agent; and, (b) reacting said foamable
composition under conditions effective to form a foam, wherein said
blowing agent comprises the composition according to claim 5.
15. A foam formed by the process according to claim 14.
16. A foam comprising a polymer and the composition according to
claim 5.
17. A pre-mix composition comprising a foamable component and a
blowing agent, said blowing agent comprising the composition
according to claim 5.
18. A process for producing refrigeration comprising; (a)
condensing the composition according to claim 5; and, (b)
evaporating said composition in the vicinity of a body to be
cooled.
19. A heat transfer system comprising a heat transfer medium,
wherein said heat transfer medium comprises the composition
according to claim 5.
20. A method of cleaning a surface comprising bringing the
composition according to claim 5 into contact with said
surface.
21. An aerosol product comprising a component to be dispensed and a
propellant, wherein said propellant comprises the composition
according to claim 5.
22. A method for extinguishing or suppressing a flame comprising
dispensing the composition according to claim 5 at said flame.
23. A system for preventing or suppressing a flame comprising a
vessel containing the composition according to claim 5 and a nozzle
to dispense said composition toward an anticipated or actual
location of said flame.
24. A process for dissolving a solute comprising contacting and
mixing said solute with a sufficient quantity of the composition
according to claim 5.
25. A method for preventing or rapidly quenching an electric
discharge in a space in a high voltage device comprising injecting
a gaseous dielectric into said space, wherein said gaseous
dielectric comprises the composition according to claim 5.
26. A high voltage device comprising a gaseous dielectric, wherein
said gaseous dielectric comprises the composition according to
claim 5.
27. The high voltage device according to claim 26 selected from the
group consisting of a transformer, a circuit breaker, a switch and
a radar waveguide.
Description
BACKGROUND INFORMATION
Field of the Disclosure
[0001] This disclosure relates to compositions, methods and systems
having utility in numerous applications, and in particular, uses
for compositions containing the compound
trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz).
Description of the Related Art
[0002] Many industries have been working for the past few decades
to find replacements for the ozone depleting chlorofluorocarbons
(CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs
have been employed in a wide range of applications, including their
use as aerosol propellants, refrigerants, cleaning agents,
expansion agents for thermoplastic and thermoset foams, heat
transfer media, gaseous dielectrics, fire extinguishing and
suppression agents, power cycle working fluids, polymerization
media, particulate removal fluids, carrier fluids, buffing abrasive
agents, and displacement drying agents. In the search for
replacements for these versatile compounds, many industries have
turned to the use of hydrofluorocarbons (HFCs).
[0003] The HFCs do not contribute to the destruction of
stratospheric ozone, but are of concern due to their contribution
to the "greenhouse effect", i.e., they contribute to global
warming. As a result of their contribution to global warming, the
HFCs have come under scrutiny, and their widespread use may also be
limited in the future. Thus, there is a need for compositions that
do not contribute to the destruction of stratospheric ozone and
also have low global warming potentials (GWPs). Certain
hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene
(CF.sub.3CH.dbd.CHCF.sub.3, FC-1336mzz, HFO-1336mzz) is believed to
meet both goals. 1,1,1,4,4,4-Hexafluoro-2-butene exists as two
different stereoisomers, which have different boiling points, and
therefore possibly perform differently in different
applications.
SUMMARY
[0004] This invention relates to compositions, methods and systems
having utility in numerous applications, and in particular, uses
for compositions containing the compound
trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz), which has
the following structure:
##STR00001##
[0005] Embodiments of the present invention comprise the compound
E-HFO-1336mzz, either alone or in combination with one or more
other compounds as described in detail herein below. Mixtures
containing the compound E-HFO-1336mzz can be azeotropic,
azeotrope-like or non-azeotropic (zeotropic).
DETAILED DESCRIPTION
[0006] The compositions of the present invention all include the
compound E-HFO-1336mzz. Certain embodiments of the invention,
particularly those employed as blowing agent compositions or
foamable compositions, can optionally include other ingredients,
some of which are described in detail below.
[0007] In addition to the compound E-HFO-1336mzz, certain
embodiments of the present invention are directed to compositions
comprising, or consisting essentially of, at least one additional
fluoroalkene containing from 2 to 6, preferably 3 to 5 carbon
atoms, more preferably 3 to 4 carbon atoms, and in certain
embodiments most preferably three carbon atoms, and at least one
carbon-carbon double bond. The fluoroalkene compounds of the
present invention are sometimes referred to herein for the purpose
of convenience as hydrofluoro-olefins or "HFOs" if they contain at
least one hydrogen.
[0008] Applicants have developed several compositions which include
as an essential component the compound E-HFO-1336mzz and at least
one additional compound such as HFOs, HFCs, hydrofluoroethers
(HFEs), hydrocarbons, ethers, aldehydes, ketones, and others such
as methyl formate, formic acid, trans-1,2-dichloroethylene (DCE),
carbon dioxide (CO2), cis-HFO-1234ze+HFO-1225yez; mixtures of these
plus water; mixtures of these plus CO2; mixtures of these plus DCE;
mixtures of these plus methyl formate; mixtures with
cis-HFO-1234ze+CO2; mixtures with cis-HFO-1234ze+HFO-1225yez+CO2;
and mixtures with cis-HFO-1234ze+HFC-245fa. In such compositions,
the amount of the compound E-HFO-1336mzz may vary widely, including
in all cases constituting the balance of the composition after all
other components in composition are accounted for.
[0009] In certain preferred embodiments, the amount of the compound
E-HFO-1336mzz in the composition can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %.
[0010] The preferred compositions of the present invention are
environmentally acceptable and do not contribute to the depletion
of the earth's stratospheric ozone layer. The compounds and
compositions of the present invention have no substantial ozone
depletion potential (ODP), preferably an ODP of not greater than
about 0.5 and even more preferably an ODP of not greater than about
0.25, most preferably an ODP of not greater than about 0.1; and/or
a global warming potential (GWP) of not greater than about 150, and
even more preferably, a GWP of not greater than about 50.
[0011] As used herein, ODP is defined in the "Scientific Assessment
of Ozone Depletion, 2002," a report of the World Meteorological
association, incorporated here by reference. As used herein, GWP is
defined relative to that of carbon dioxide and over a 100 year time
horizon, and defined in the same reference as for the ODP mentioned
above.
[0012] Preferred compositions of this type are described below in
Table 1 (with all percentages being in percent by weight and being
understood to be proceeded by the word "about").
TABLE-US-00001 TABLE 1 Blend Composition Preferred More Preferred
Most Preferred Compound Mixed with E-HFO- Ranges Ranges Ranges
1336mzz wt % wt % wt % HFOs HFO-1234ze (E&Z) 1 to 99 5 to 95 10
to 90 HFO-1234yf 1 to 99 5 to 95 10 to 90 HFO-1225ye (E&Z) 1 to
99 5 to 95 10 to 90 HFO-1225yc 1 to 99 5 to 95 10 to 90 HFO-1216 1
to 99 5 to 95 10 to 90 HFO-1233zd (E&Z) 1 to 99 5 to 95 10 to
90 HFO-1233xf 1 to 99 5 to 95 10 to 90 HFO-1243zf 1 to 99 5 to 95
10 to 90 HFO-1336mzz (Z) 1 to 99 5 to 95 10 to 90
(CF3)2CFCH.dbd.CHF (E&Z) 1 to 99 5 to 95 10 to 90
(C2F5)(CF3)C.dbd.CH2 1 to 99 5 to 95 10 to 90 (CF3)2CFCH.dbd.CF2 1
to 99 5 to 95 10 to 90 (CF3)2CFCF.dbd.CHF (E&Z) 1 to 99 5 to 95
10 to 90 HFCs HFC-245fa 1 to 99 5 to 95 10 to 90 HFC-245cb 1 to 99
5 to 95 10 to 90 HFC-245ca 1 to 99 5 to 95 10 to 90 HFC-245eb 1 to
99 5 to 95 10 to 90 HFC-245ea 1 to 99 5 to 95 10 to 90 HFC-227ea 1
to 99 5 to 95 10 to 90 HFC-254eb 1 to 99 5 to 95 10 to 90 HFC-236ea
1 to 99 5 to 95 10 to 90 HFC-236fa 1 to 99 5 to 95 10 to 90 HFC-134
1 to 99 5 to 95 10 to 90 HFC-134a 1 to 99 5 to 95 10 to 90 HFC-152
1 to 99 5 to 95 10 to 90 HFC-152a 1 to 99 5 to 95 10 to 90 HFC-32 1
to 99 5 to 95 10 to 90 HFC-125 1 to 99 5 to 95 10 to 90 HFC-143a 1
to 99 5 to 95 10 to 90 HFC-365mfc 1 to 99 5 to 95 10 to 90 HFC-161
1 to 99 5 to 95 10 to 90 HFC-43-10mee 1 to 99 5 to 95 10 to 90
HFC-23 1 to 99 5 to 95 10 to 90 HFEs CHF2--O--CHF2 1 to 99 5 to 95
10 to 90 CHF2--O--CH2F 1 to 99 5 to 95 10 to 90 CH2F--O--CH2F 1 to
99 5 to 95 10 to 90 CH2F--O--CH3 1 to 99 5 to 95 10 to 90
cyclo-CF2--CH2--CF2--O 1 to 99 5 to 95 10 to 90
cyclo-CF2--CF2--CH2--O 1 to 99 5 to 95 10 to 90 CHF2--O--CF2--CHF2
1 to 99 5 to 95 10 to 90 CF3--CF2--O--CH2F 1 to 99 5 to 95 10 to 90
CHF2--O--CHF--CF3 1 to 99 5 to 95 10 to 90 CHF2--O--CF2--CHF2 1 to
99 5 to 95 10 to 90 CH2F--O--CF2--CHF2 1 to 99 5 to 95 10 to 90
CF3--O--CF2--CH3 1 to 99 5 to 95 10 to 90 CHF2--CHF--O--CHF2 1 to
99 5 to 95 10 to 90 CF3--O--CHF--CH2F 1 to 99 5 to 95 10 to 90
CF3--CHF--O--CH2F 1 to 99 5 to 95 10 to 90 CF3--O--CH2--CHF2 1 to
99 5 to 95 10 to 90 CHF2--O--CH2--CF3 1 to 99 5 to 95 10 to 90
CH2F--CF2--O--CH2F 1 to 99 5 to 95 10 to 90 CHF2--O--CF2--CH3 1 to
99 5 to 95 10 to 90 CHF2--CF2--O--CH3 1 to 99 5 to 95 10 to 90
CH2F--O--CHF--CH2F 1 to 99 5 to 95 10 to 90 CHF2--CHF--O--CH2F 1 to
99 5 to 95 10 to 90 CF3--O--CHF--CH3 1 to 99 5 to 95 10 to 90
CF3--CHF--O--CH3 1 to 99 5 to 95 10 to 90 CHF2--O--CH2--CHF2 1 to
99 5 to 95 10 to 90 CF3--O--CH2--CH2F 1 to 99 5 to 95 10 to 90
CF3--CH2--O--CH2F 1 to 99 5 to 95 10 to 90 CF2H--CF2--CF2--O--CH3 1
to 99 5 to 95 10 to 90 Hydrocarbons propane 1 to 99 5 to 95 10 to
90 butane 1 to 99 5 to 95 10 to 90 isobutane 1 to 99 5 to 95 10 to
90 n-pentane (high HFO) 1 to 99 50 to 99 60 to 99 n-pentane (high
n-pentane) 1 to 99 1 to 30 1 to 20 isopentane (high HFO) 1 to 99 50
to 99 60 to 90 isopentane (high isopentane) 1 to 99 1 to 30 1 to 20
neopentane (high HFO) 1 to 99 50 to 99 60 to 99 neopentane (high
neopentane) 1 to 99 1 to 30 1 to 20 cyclopentane (high HFO) 1 to 99
50 to 99 60 to 99 cyclopentane (high cyclopentane) 1 to 99 1 to 30
1 to 20 n-hexane 1 to 99 5 to 95 10 to 90 isohexane 1 to 99 5 to 95
10 to 90 heptane 1 to 99 5 to 95 10 to 90 Ethers dimethyl ether 1
to 99 5 to 95 10 to 90 methylethyl ether 1 to 99 5 to 95 10 to 90
diethyl ether 1 to 99 5 to 95 10 to 90 methylpropyl ether 1 to 99 5
to 95 10 to 90 methylisopropyl ether 1 to 99 5 to 95 10 to 90
ethylpropyl ether 1 to 99 5 to 95 10 to 90 ethylisopropyl ether 1
to 99 5 to 95 10 to 90 dipropyl ether 1 to 99 5 to 95 10 to 90
diisopropyl ether 1 to 99 5 to 95 10 to 90 dimethoxymethane 1 to 99
5 to 95 10 to 90 diethoxymethane 1 to 99 5 to 95 10 to 90
dipropoxymethane 1 to 99 5 to 95 10 to 90 dibutoxymethane 1 to 99 5
to 95 10 to 90 Aldehydes formaldehyde 1 to 99 5 to 95 10 to 90
acetaldehyde 1 to 99 5 to 95 10 to 90 propanal 1 to 99 5 to 95 10
to 90 butanal 1 to 99 5 to 95 10 to 90 isobutanal 1 to 99 5 to 95
10 to 90 Ketones Acetone 1 to 99 5 to 95 10 to 90 Methylethylketone
1 to 99 5 to 95 10 to 90 methylisobutylketone 1 to 99 5 to 95 10 to
90 perfluoroethylisopropylketone 1 to 99 5 to 95 10 to 90
(C2F5C(O)CF(CF3)2 Others water 1 to 99 5 to 95 10 to 90 methyl
formate 1 to 99 5 to 95 10 to 90 ethyl formate 1 to 99 5 to 95 10
to 90 formic acid 1 to 99 5 to 95 10 to 90
trans-1,2-dichloroethylene (t-DCE) 1 to 99 5 to 95 10 to 90
CO.sub.2 1 to 99 5 to 95 10 to 90 HCFO-1232xf 1 to 99 5 to 95 10 to
90 HCFO-1223xd 1 to 99 5 to 95 10 to 90 HCFO-1233xf 1 to 99 5 to 95
10 to 90 HCFO-1233zd (E&Z) 1 to 99 5 to 95 10 to 90 HCFO-1224yd
(E&Z) 1 to 99 5 to 95 10 to 90 CFC-13 (CF3Cl) 1 to 99 5 to 95
10 to 90 HCFO-1121a (CHF.dbd.CCl2) 1 to 99 5 to 95 10 to 90
HCFO-1121 (CFCl.dbd.CHCl) 1 to 99 5 to 95 10 to 90 HCFO-1131a
(CH2.dbd.CFCl) 1 to 99 5 to 95 10 to 90 HCFO-1131 (CHF.dbd.CHCl) 1
to 99 5 to 95 10 to 90 HCFO-1122 (CF2.dbd.CHCl) 1 to 99 5 to 95 10
to 90 HCFO-1113 (CF2.dbd.CFCl) 1 to 99 5 to 95 10 to 90
CH2.dbd.CHCl 1 to 99 5 to 95 10 to 90 CH3Cl 1 to 99 5 to 95 10 to
90 HCFC-133a (CF3CH2Cl) 1 to 99 5 to 95 10 to 90 CFC-115 (CF3CF2Cl)
1 to 99 5 to 95 10 to 90 3,3,3-Trifluoropropyne 1 to 99 5 to 95 10
to 90 HCFC-124 (CF3CHFCl) 1 to 99 5 to 95 10 to 90 HCC-40 (CH3Cl) 1
to 99 5 to 95 10 to 90 HCFC-22 (CF2HCl) 1 to 99 5 to 95 10 to 90
cis-HFO-1234ze + HFO-1225yeZ 1 to 99 5 to 95 10 to 90 Mixtures of
any of the above plus 1 to 99% 5 to 95% 10 to 90% water H2O H2O H2O
Mixtures of any of the above plus 1 to 99% 5 to 95% 10 to 90% CO2
CO2 CO2 CO2 Mixtures of any of the above plus t- 1 to 99% t- 5 to
95% t- 10 to 90% DCE DCE DCE t-DCE Mixtures of any of the above
plus 1 to 99% 5 to 95% MF 10 to 90% methyl formate MF MF Mixtures
with cis-HFO-1234ze + CO2 1 to 99 5 to 95 10 to 90 Mixtures with
cis-HFO-1234ze + 1 to 99 5 to 95 10 to 90 CO2 + 1225yeZ Mixtures
with cis-HFO-1234ze + 1 to 99 5 to 95 10 to 90 HFC-245fa
Azeotrope Compositions
[0013] Some of the compositions of E-HFO-1336mzz have been formed
to form azeotropic or azeotrope-like compositions with some blend
components.
[0014] As used herein, an azeotropic composition is a constant
boiling liquid admixture of two or more substances wherein the
admixture distills without substantial composition change and
behaves as a constant boiling composition. Constant boiling
compositions, which are characterized as azeotropic, exhibit either
a maximum or a minimum boiling point, as compared with that of the
non-azeotropic mixtures of the same substances. Azeotropic
compositions as used herein include homogeneous azeotropes which
are liquid admixtures of two or more substances that behave as a
single substance, in that the vapor, produced by partial
evaporation or distillation of the liquid, has the same composition
as the liquid. Azeotropic compositions as used herein also include
heterogeneous azeotropes where the liquid phase splits into two or
more liquid phases. In these embodiments, at the azeotropic point,
the vapor phase is in equilibrium with two liquid phases and all
three phases have different compositions. If the two equilibrium
liquid phases of a heterogeneous azeotrope are combined and the
composition of the overall liquid phase calculated, this would be
identical to the composition of the vapor phase.
[0015] For the purpose of this discussion, near-azeotropic
composition means a composition that behaves like an azeotrope
(i.e., has constant boiling characteristics or a tendency not to
fractionate upon boiling or evaporation). Thus, the composition of
the vapor formed during boiling or evaporation is the same as or
substantially the same as the original liquid composition. Hence,
during boiling or evaporation, the liquid composition, if it
changes at all, changes only to a minimal or negligible extent.
This is to be contrasted with non-azeotropic compositions in which
during boiling or evaporation, the liquid composition changes to a
substantial degree.
[0016] Near-azeotropic compositions exhibit dew point pressure and
bubble point pressure with virtually no pressure differential. That
is to say that the difference in the dew point pressure and bubble
point pressure at a given temperature will be a small value. It may
be stated that compositions with a difference in dew point pressure
and bubble point pressure of less than or equal to 3 percent (based
upon the bubble point pressure) may be considered to be a
near-azeotropic.
[0017] It is also recognized that both the boiling point and the
weight percentages of each component of the azeotropic or
near-azeotropic liquid composition may change when the azeotropic
or near-azeotropic liquid composition is subjected to boiling at
different pressures. Thus, an azeotropic or a near-azeotropic
composition may be defined in terms of the unique relationship that
exists among the components or in terms of the compositional ranges
of the components or in terms of exact weight percentages of each
component of the composition characterized by a fixed boiling point
at a specified pressure. It is also recognized in the art that
various azeotropic compositions (including their boiling points at
particular pressures) may be calculated (see, e.g., W. Schotte Ind.
Eng. Chem. Process Des. Dev. (1980) 19, 432-439). Experimental
identification of azeotropic compositions involving the same
components may be used to confirm the accuracy of such calculations
and/or to modify the calculations at the same or other temperatures
and pressures.
[0018] In one embodiment, the present inventors have determined
that E-1336mzz forms azeotropic compositions with cyclopentane. In
one embodiment, these include compositions comprising from about
89.6 mole percent to about 97.8 mole percent E-1336mzz and from
about 2.2 mole percent to about 10.4 mole percent cyclopentane
(which forms an azeotrope boiling at a temperature from between
about -40.degree. C. and about 60.degree. C. and at a pressure of
from between about 1.43 psia and about 83.12 psia).
[0019] In another embodiment, compositions may be formed that
consist essentially of E-1336mzz and cyclopentane. These include
compositions consisting essentially of from about 89.6 mole percent
to about 97.8 mole percent E-1336mzz and from about 2.2 mole
percent to about 10.4 mole percent cyclopentane (which forms an
azeotrope boiling at a temperature from between about -40.degree.
C. and about 60.degree. C. and at a pressure of from between about
1.43 psia and about 83.12 psia).
[0020] In yet another embodiment, near-azeotropic compositions
comprising E-1336mzz and cyclopentane may also be formed. Such
near-azeotropic compositions comprise from about 82.4 mole percent
to about 99.8 mole percent E-1336mzz and from about 0.2 mole
percent to about 17.6 mole percent cyclopentane at temperatures
ranging from about -40.degree. C. to about 100.degree. C.
[0021] In yet another embodiment, near-azeotropic compositions
consisting essentially of E-1336mzz and cyclopentane may also be
formed. Such near-azeotopic compositions consist essentially of
from about 82.4 mole percent to about 99.8 mole percent E-1336mzz
and from about 0.2 mole percent to about 17.6 mole percent
cyclopentane at temperatures ranging from about -40.degree. C. to
about 100.degree. C.
[0022] At one atmosphere pressure the composition of the azeotropic
composition comprise about 90 mole percent E-1336mzz and about 10
mole percent cyclopentane, which exhibits a normal boiling point of
6.8.degree. C.
Uses of the Compositions
[0023] As described above, the compositions of the present
invention may be used in a wide variety of applications as
substitutes for CFCs and for compositions containing less desirable
HCFCs. For example, the present compositions are useful as blowing
agents, refrigerants, heating agents, power cycle agents, cleaning
agents, aerosol propellants, sterilization agents, lubricants,
flavor and fragrance extractants, flammability reducing agents, and
flame suppression agents, to name a few preferred uses. Each of
these uses will be discussed in greater detail below.
Blowing Agents
[0024] Thus, the present invention includes methods and systems
which include using E-HFO-1336mzz as a blowing agent, optionally
with one or more optional additional compounds which include, but
are not limited to, other compounds which also act as blowing
agents (hereinafter referred to for convenience but not by way of
limitation as co-blowing agents), surfactants, polyols, catalysts,
flame retardants, polymer modifiers, colorants, dyes, solubility
enhancers, rheology modifiers, plasticizing agents, fillers,
nucleating agents, viscosity reduction agents, vapor pressure
modifiers, stabilizers, and the like. Preferred blends for blowing
agents used for foams, especially spray foams and panel foams
include blends of E-HFO-1336mzz with hydrocarbons (especially the
pentanes, including cyclopentane), and with each of HFC-245fa,
HFC-365mfc, HCFO-1233zd and HCFO-1224yd. While the cis isomer of
HFO-1336mzz is preferred, it is anticipated that the trans isomer
and/or mixtures of the isomers, including the racemate, will be
useful in certain foam types.
[0025] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0026] 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. Certain 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 copolymers 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 such as tris(2-chloroethyl)phosphate,
tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)-phosphate,
tris(1,3-dichloro-propyl)phosphate, diammonium phosphate, various
halogenated aromatic compounds, antimony oxide, aluminum
trihydrate, polyvinyl chloride, and the like. With respect to
nucleating agents, all known compounds and materials having
nucleating functionality are available for use in the present
invention, including particularly talc.
[0027] Of course other compounds and/or components that modulate a
particular property of the compositions (such as cost for example)
may also be included in the present compositions, and the presence
of all such compounds and components is within the broad scope of
the invention.
[0028] The co-blowing agent in accordance with the present
invention can comprise a physical blowing agent, a chemical blowing
agent (which preferably in certain embodiments comprises water) or
a blowing agent having a combination of physical and chemical
blowing agent properties.
[0029] Although it is contemplated that a wide range of co-blowing
agents may be used in accordance with the present invention, in
certain embodiments it is preferred that the blowing agent
compositions of the present invention include one or more HFCs as
co-blowing agents, more preferably one or more C1-C4 HFCs, and/or
one or more hydrocarbons, more preferably C4-C6 hydrocarbons. For
example, with respect to HFCs, the present blowing agent
compositions may include one or more of difluoromethane (HFC-32),
fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane
(HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane
(HFC-125), pentafluoropropane (HFC-245), hexafluoropropane
(HFC-236), heptafluoropropane (HFC-227), pentafluorobutane
(HFC-365), hexafluorobutane (HFC-356) and all isomers of all such
HFC's.
[0030] With respect to hydrocarbons, the present blowing agent
compositions may include in certain preferred embodiments, for
example, iso, normal and/or cyclopentane for thermoset foams and
butane or isobutane for thermoplastic foams. Of course other
materials, such as water, CO2, CFCs (such as trichlorofluoromethane
(CFC-11) and dichlorodifluoromethane (CFC-12), hydrochlorocarbons
(HCCs such as dichloroethylene (preferably
trans-1,2-dichloroethylene), ethyl chloride and chloropropane),
HCFCs, C1-C5 alcohols (such as, for example, ethanol and/or
propanol and/or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4
ethers (including ethers (such as dimethyl ether and diethyl
ether), diethers (such as dimethoxy methane and diethoxy methane),
and methyl formate including combinations of any of these may be
included, although such components are contemplated to be not
preferred in many embodiments due to negative environmental
impact.
[0031] In certain embodiments, one or more of the following HFC
isomers are preferred for use as co-blowing agents in the
compositions of the present invention: [0032]
1,1,1,2,2-pentafluoroethane (HFC-125) [0033]
1,1,2,2-tetrafluoroethane (HFC-134) [0034]
1,1,1,2-tetrafluoroethane (HFC-134a) [0035] 1,1-difluoroethane
(HFC-152a) [0036] 1,1,1,2,3,3,3-heptafluoropropane (HFC-227 ea)
[0037] 1,1,1,3,3,3-hexafluoropropane (HFC-236fa) [0038]
1,1,1,3,3-pentafluoropropane (HFC-245 fa) and [0039]
1,1,1,3,3-pentafluorobutane (HFC-365mfc).
[0040] The relative amount of any of the above noted additional
co-blowing agents, as well as any additional components which may
be included in present compositions, can vary widely within the
general broad scope of the present invention according to the
particular application for the composition, and all such relative
amounts are considered to be within the scope hereof.
[0041] In certain embodiments it is preferred that the blowing
agent composition of the present invention comprise at least one
co-blowing agent and an amount of E-HFO-1336mzz sufficient to
produce a blowing agent composition which is overall
nonflammable.
[0042] The blowing agent compositions of the present invention may
include the compound E-HFO-1336mzz in widely ranging amounts. It is
generally preferred, however, that for preferred compositions for
use as blowing agents in accordance with the present invention,
E-HFO-1336mzz is present in an amount that is at least about 1% by
weight, more preferably at least about 5% by weight, and even more
preferably at least about 15% by weight, of the composition.
[0043] In certain preferred embodiments, the blowing agent
comprises at least about 50% by weight of the present blowing agent
compound(s), and in certain embodiments the blowing agent consists
essentially of E-HFO-1336mzz. In this regard, it is noted that the
use of one or more co-blowing agents is consistent with the novel
and basic features of the present invention. For example, it is
contemplated that water will be used as either a co-blowing or in
combination with other co-blowing agents (such as, for example,
pentane, particularly cyclopentane) in a large number of
embodiments.
[0044] In certain preferred embodiments, the blowing agent
composition comprises from about 30% to about 95% by weight of
E-HFO-1336mzz and from about 5% to about 90% by weight, more
preferably from about 5% to about 65% by weight of co-blowing
agent. In certain of such embodiments the co-blowing agent
comprises, and preferably consists essentially of, H2O, HFCs,
hydrocarbons, alcohols (preferably C2, C3 and/or C4 alcohols), CO2,
and combinations of these.
[0045] In preferred embodiments in which the co-blowing agent
comprises H2O, the composition comprises H2O in an amount of from
about 5% by weight to about 50% by weight of the total blowing
agent composition, more preferably from about 10% by weight to
about 40% by weight, and even more preferably of from about 10% to
about 20% by weight of the total blowing agent.
[0046] In preferred embodiments in which the co-blowing agent
comprises CO2, the composition comprises CO2 in an amount of from
about 5% by weight to about 60% by weight of the total blowing
agent composition, more preferably from about 20% by weight to
about 50% by weight, and even more preferably of from about 40% to
about 50% by weight of the total blowing agent.
[0047] In preferred embodiments in which the co-blowing agent
comprises alcohols, (preferably C2, C3 and/or C4 alcohols), the
composition comprises alcohol in an amount of from about 5% by
weight to about 40% by weight of the total blowing agent
composition, more preferably from about 10% by weight to about 40%
by weight, and even more preferably of from about 15% to about 25%
by weight of the total blowing agent.
[0048] For compositions which include HFC co-blowing agents, the
HFC co-blowing agent (preferably C2, C3, C4 and/or C5 HFC), and
even more preferably difluoroethane (HFC-152a being particularly
preferred for extruded thermoplastics) and/or pentafluoropropane
(HFC-245)), is preferably present in the composition in amounts of
from of from about 5% by weight to about 80% by weight of the total
blowing agent composition, more preferably from about 10% by weight
to about 75% by weight, and even more preferably of from about 25%
to about 75% by weight of the total blowing agent. Furthermore, in
such embodiments, the HFC is preferably C2-C4 HFC, and even more
preferably C3 HFC, with penta-fluorinated C3 HFC, such as
HFC-245fa, being highly preferred in certain embodiments.
[0049] For compositions which include HC co-blowing agents, the HC
co-blowing agent (preferably C3, C4 and/or C5 HC) is preferably
present in the composition in amounts of from of from about 5% by
weight to about 80% by weight of the total blowing agent
composition, and even more preferably from about 20% by weight to
about 60% by weight of the total blowing agent.
BLOWING AGENT EXAMPLES
Example 1--Foaming Using Z-1,1,1,4,4,4-hexafluoro-2-butene and
E-1,1,1,4,4,4-hexafluoro-2-butene Mixtures as the Blowing Agent
[0050] The foaming was carried out at 1000 psi (6.9 MPa) sprayer
gauge pressure using different mixtures of these blowing agents and
at different foaming temperatures. The results are reported in
Table 2.
TABLE-US-00002 TABLE 2 Use of Mixtures of the Z- and E-Isomers as
Blowing Agent Thermal Conductivity Isomer Foaming Temp Density
(BTU-in/hr- Mixture, % (.degree. F.) (PCF) ft.sup.2-.degree. F.)
40Z/60E poor quality foam -- -- 50Z/50E poor quality foam -- --
60Z/40E 100 2.46 0.1593 (5.57) 60Z/40E 140 2.63 0.1553 (5.43)
70Z/30E 100 2.51 0.1555 (5.44) 70Z/30E 140 2.73 0.1559 (5.45)
80Z/20E 100 2.86 0.1654 (5.78)
[0051] The numerical amounts of Z and E in the Isomer mixture
column are the wt % s of the isomer in the mixture. Thus, isomer
mixture Z40/E60 means the mixture is 40 wt % Z-isomer and 60 wt %
E-isomer. The poor quality of the sprayed foam for the 40Z/60E and
50Z/50E compositions is exhibited by the foam structure being
frothy, i.e. exhibiting large open cells, and non-uniform foam
structure across the thickness of the foamed structure. In
contrast, the remaining blowing agents in Table 2 produced sprayed
foams of the same thickness as the poor quality foams, but
exhibiting no frothing, uniform density across the foam structure
thickness, and an average of at least 95% closed cell. The units of
thermal conductivity are the same as in Table 1. The k-factors in
parentheses are values X10-5. The temperature at which thermal
conductivity is measured is 75.degree. F.
[0052] The results in Table 2 reveal that greater than 50 wt % of
the Z-isomer is required in the mixture with the E-isomer and that
80 wt % Z isomer is too much. The results also reveal that the
thermal conductivity is not appreciably changed over this broad
foaming temperature range. The change for the 60Z-40E mixture is
2.6% (calculation: (0.1593-0.01553).times.100)). The change for the
70Z/30E mixture is 0.3%. This enables foam applicators broad
discretion in the choice of foaming application without sacrifice
in foam quality, and/or permits quality foaming application when
the equipment temperature is in error.
[0053] The A-side composition used in the Comparison Example and in
Example 1 was a polymeric aromatic isocyanate with an --NCO content
of 31.5 wt % and a viscosity of 200 cps at 25.degree. C., present
in an amount sufficient for index of 105-110.
[0054] The B-side composition used in Example 1 is set forth in
Table 3.
TABLE-US-00003 TABLE 3 B-Side Composition Ingredient Polyester
polyol Mannich polyol Ethylamine, 2'2-oxybis[N,N-dimethyl-catalyst
2(-N,N-dimethylaminoethyl-N-methylamino)ethanol catalyst
1.3-propanediamine, N-[3-dimethylamino)propyl]-N,N',N'-
Trimethyl-catalyst 2-butoxy ethanol co-solvent Tris(chloropropyl)
phosphate (TCPP) Glycerin Silicone surfactant Water Z/E isomer
mixture (Table 2) Total
[0055] The polyester polyol has a hydroxyl number of 307 mg KOH/g,
nominal functionality of 2.2, and dynamic viscosity of 5500 cps at
25.degree. C.
[0056] The Mannich polyol has a hydroxyl number of 470 mg KOH/g,
nominal functionality of 4, and dynamic viscosity of 10000 cps at
25.degree. C.
Example 2--Solubility of Blowing Agent in Polyol of B-Side
[0057] E-1,1,1,4,4,4-hexafluoro-2-butene has a boiling temperature
of 7.5.degree. F. (1 atm) and causes the polyisocyanate/polyol
reaction product to froth uncontrollably when the E-isomer is used
by itself as the blowing agent, which disrupts the spray pattern
when this method of application is used. This disruption of the
spray pattern causes the deposited foamed structure to exhibit a
rough exterior surface arising from expansion of the E-isomer that
is not dissolved in the polyol of the B-side composition. A
"frothed" foam lacks integrity by being easily collapsed. A
comparison of solubilities when the E-isomer is the only blowing
agent and when 10 wt % (based on the weight of the polyol of the
B-side composition) of the Z-isomer is supplemented by the E-isomer
is presented in Table 4.
TABLE-US-00004 TABLE 4 Comparison of Solubilities of Blowing Agent
in Polyol of B-side Composition E-Isomer Solubility in Blowing
Agent Polyol (wt %) E-isomer less than 1.48 E-isomer/10 wt %
Z-isomer 6.11
[0058] As shown in Table 4, the E-isomer by itself has very low
solubility in the polyol of the B-side composition, and this
solubility is improved by adding the indicated amount of the
Z-isomer to the polyol of the B-side composition. The improvement
in solubility using the Z-isomer addition is greater than 400%. The
combination of the 10 wt % Z-isomer and 6.11 wt % E-isomer
dissolved in the polyol of the B-side composition corresponds to a
blowing agent composition of 62.5 wt % Z-isomer and 37.5 wt %
E-isomer.
[0059] The low boiling temperature of 7.5.degree. F. for the
E-isomer together with its low ODP and GWP make this isomer an
attractive candidate as blowing agent for the polyisocyanate/polyol
reaction product. The uncontrolled frothing of the reaction product
caused by the insolubility of the E-isomer limits the use of the
E-isomer for this purpose. The solubilization of the E-isomer by
the presence of the Z-isomer as described above enables the
E-isomer to be advantageously be used in the spray application
foaming of the polyisocyanate/polyol reaction product without the
detriment of uncontrolled frothing. Advantages include improvement
in the foaming process and in the performance of the resultant
foamed reaction product.
[0060] An example of the B-side composition which contains the
polyol used in the solubility test is presented in Table 5.
TABLE-US-00005 TABLE 5 B-side Composition Ingredient Wt % Polyester
polyol (same as Table 3) 35.00 Mannich polyol 32.30 Catalyst:
2-{[2-(dimethylamino)ethyl] methylamino}ethanol 1.90 Catalyst:
bis(dimetylaminoethyl)ether 0.10 Catalyst:
2-{[2-(dimethylamino)ethyl]methylamino}ethanol 0.23 Silicone
surfactant 1.10 Tris(chloropropyl) phosphate (TCPP) 15.40 Water
1.70 Blowing agent (Table 3) 12.25 Total 100.00
[0061] The Mannich polyol has a hydroxyl number of 425 mg KOH/g, a
nominal functionality of 3.2, and a dynamic viscosity of 4500 cps
at 25.degree. C.
[0062] The procedure for determining solubility (under ambient
conditions--temperature of 15.degree. C. to 25.degree. C. and
atmospheric pressure) is as follows: 50.000 g of the polyol is
added to a tared, 120 ml aerosol flask and weighed. Then, in small
increments, the blowing agent is introduced via the gas inlet and
the contents are mixed thoroughly then allowed to stand. When both
isomers are used, they are introduced sequentially: first 5.0 g of
the Z-isomer, followed by increments of the E-isomer until 2 phase
behavior is first observed, indicating the limit of solubility of
the E-isomer in the polyol. The addition of the 5.0 g of Z-isomer
to the polyol forms a single phase, indicating complete solubility
of this proportion (10 wt %) of the Z-isomer in the polyol. The
total weight of E-isomer present in and thus dissolved in the
single phase is the weight gain over the combination of 50.000 g of
polyol and 5.0 g of Z-isomer in the single phase. The 6.11 wt %
E-isomer reported in Table 4 is the amount of dissolved E-isomer
compared to the 50.000 g of polyol. On this basis, the polyol
contains in solution 10 wt % of the Z isomer and 6.11 w % of the
E-isomer.
[0063] The mixture of the Z-isomer with the E-isomer has the effect
of minimizing/controlling to eliminating the frothing associated
with the E-isomer when used by itself in spray application and
providing certain blowing agent mixtures that exhibit foaming
insensitivity to produce high quality foams over a wide range of
elevated foaming temperatures.
Foamable Compositions
[0064] One embodiment of the present invention provides foamable
compositions. As is known to those skilled in the art, foamable
compositions generally include one or more components capable of
forming foam. As used herein, the term "foam foaming agent" is used
to refer to a component, or a combination on components, which are
capable of forming a foam structure, preferably a generally
cellular foam structure. The foamable compositions of the present
invention include such component(s) and a blowing agent compound,
preferably E-HFO-1336mzz.
[0065] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0066] In certain embodiments, the one or more components capable
of forming foam 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. This reaction and foaming process may be enhanced
through the use of various additives such as catalysts and
surfactant materials that serve to control and adjust cell size and
to stabilize the foam structure during formation. Furthermore, it
is contemplated that any one or more of the additional components
described above with respect to the blowing agent compositions of
the present invention could be incorporated into the foamable
composition of the present invention. In such thermosetting foam
embodiments, one or more of the present compositions are included
as or part of a blowing agent in a foamable composition, or as a
part of a two or more part foamable composition, which preferably
includes one or more of the components capable of reacting and/or
foaming under the proper conditions to form a foam or cellular
structure.
[0067] In certain other embodiments of the present invention, the
one or more components capable of foaming comprise thermoplastic
materials, particularly thermoplastic polymers and/or resins.
Examples of thermoplastic foam components include polyolefins, such
as for example monovinyl aromatic compounds of the formula
Ar--CH.dbd.CH2 wherein Ar is an aromatic hydrocarbon radical of the
benzene series such as polystyrene (PS). Other examples of suitable
polyolefin resins in accordance with the invention include the
various ethylene resins including the ethylene homopolymers such as
polyethylene and ethylene copolymers, polypropylene (PP) and
polyethylene-terephthalate (PET). In certain embodiments, the
thermoplastic foamable composition is an extrudable
composition.
[0068] It is contemplated that all presently known and available
methods and systems for forming foam are readily adaptable for use
in connection with the present invention. For example, the methods
of the present invention generally require incorporating a blowing
agent in accordance with the present invention into a foamable or
foam forming composition and then foaming the composition,
preferably by a step or series of steps which include causing
volumetric expansion of the blowing agent in accordance with the
present invention.
[0069] In general, it is contemplated that the presently used
systems and devices for incorporation of blowing agent and for
foaming are readily adaptable for use in accordance with the
present invention. In fact, it is believed that one advantage of
the present invention is the provision of an improved blowing agent
which is generally compatible with existing foaming methods and
systems.
[0070] Thus, it will be appreciated by those skilled in the art
that the present invention comprises methods and systems for
foaming all types of foams, including thermosetting foams,
thermoplastic foams and formed-in-place foams. Thus, one aspect of
the present invention is the use of the present blowing agents in
connection with conventional foaming equipment, such as
polyurethane foaming equipment, at conventional processing
conditions. The present methods therefore include polyol premix
type operations, blending type operations, third stream blowing
agent addition, and blowing agent addition at the foam head.
[0071] With respect to thermoplastic foams, the preferred methods
generally comprise introducing a blowing agent in accordance with
the present invention into a thermoplastic material, preferably
thermoplastic polymer such as polyolefin, and then subjecting the
thermoplastic material to conditions effective to cause foaming.
For example, the step of introducing the blowing agent into the
thermoplastic material may comprise introducing the blowing agent
into a screw extruder containing the thermoplastic, and the step of
causing foaming may comprise lowering the pressure on the
thermoplastic material and thereby causing expansion of the blowing
agent and contributing to the foaming of the material.
[0072] 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 foamable 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. Moreover, the blowing agent can be introduced either
directly or as part of a premix, which is then further added to
other parts of the foamable composition.
[0073] 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.
Foams
[0074] One embodiment of the present invention relates to methods
of forming foams, especially panel foams and spray foams, and
preferably such foams made from polyurethane and polyisocyanurate.
The methods generally comprise providing a blowing agent
composition of the present inventions, adding (directly or
indirectly) the blowing agent composition to a foamable
composition, and reacting the foamable composition under the
conditions effective to form a foam or cellular structure, as is
well known in the art. Any of the methods well known in the art,
such as those described in "Polyurethanes Chemistry and
Technology," Volumes I and II, Saunders and Frisch, 1962, John
Wiley and Sons, New York, 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.
[0075] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0076] In general, such preferred methods comprise preparing
polyurethane or polyisocyanurate foams by combining an isocyanate,
a polyol or mixture of polyols, a blowing agent or mixture of
blowing agents comprising one or more of the present compositions,
and other materials such as catalysts, surfactants, and optionally,
flame retardants, colorants, or other additives.
[0077] It is convenient in many applications to provide the
components for polyurethane or polyisocyanurate foams in
pre-blended formulations. Most typically, the foam formulation is
pre-blended into two components. The isocyanate and optionally
certain surfactants and blowing agents comprise the first
component, commonly referred to as the "A" component. The polyol or
polyol mixture, surfactant, catalysts, blowing agents, flame
retardant, and other isocyanate reactive components comprise the
second component, commonly referred to as the "B" component.
Accordingly, polyurethane or polyisocyanurate foams are readily
prepared by bringing together the A and B side components either by
hand mix for small preparations and, preferably, machine mix
techniques to form blocks, slabs, laminates, pour-in-place panels
and other items, spray applied foams, froths, and the like.
Optionally, other ingredients such as fire retardants, colorants,
auxiliary blowing agents, and even other polyols can be added as
one or more additional streams to the mix head or reaction site.
Most preferably, however, they are all incorporated into one
B-component as described above.
[0078] The present methods and systems also include forming a one
component foam, preferably polyurethane foam, containing a blowing
agent in accordance with the present invention. In certain
preferably embodiments, a portion of the blowing agent is contained
in the foam forming agent, preferably by being dissolved in a foam
forming agent which is liquid at the pressure within the container,
a second portion of the blowing agent is present as a separate gas
phase. In such systems, the contained/dissolved blowing agent
performs, in large part, to cause the expansion of the foam, and
the separate gas phase operates to impart propulsive force to the
foam forming agent.
[0079] Such one component systems are typically and preferably
packaged in a container, such as an aerosol type can, and the
blowing agent of the present invention thus preferably provides for
expansion of the foam and/or the energy to transport the
foam/foamable material from the package, and preferably both. In
certain embodiments, such systems and methods comprise charging the
package with a fully formulated system (preferably
isocyanate/polyol system) and incorporating a gaseous blowing agent
in accordance with the present invention into the package,
preferably an aerosol type can.
[0080] It is contemplated also that in certain embodiments it may
be desirable to utilize the present compositions when in the
supercritical or near supercritical state as a blowing agent.
[0081] The present invention also relates to all foams, including
but not limited to closed cell foam, open cell foam, spray foams,
panel foams, rigid foam, flexible foam, integral skin and the like,
prepared from a polymer foam formulation containing a blowing agent
comprising, or consisting essentially of, E-HFO-1336mzz, either
alone or in combination with one or more other compounds.
[0082] Applicants have found that one advantage of the foams, and
particularly thermoset foams such as polyurethane foams, in
accordance with the present invention is the ability to achieve,
preferably in connection with thermoset foam embodiments,
exceptional thermal performance, such as can be measured by the
K-factor or lambda, particularly and preferably under low
temperature conditions, as shown in FIG. 1. Although it is
contemplated that the present foams, particularly thermoset foams
of the present invention, may be used in a wide variety of
applications, in certain preferred embodiments the present
invention comprises appliance foams in accordance with the present
invention, including refrigerator foams, freezer foams,
refrigerator/freezer foams, panel foams, and other cold or
cryogenic manufacturing applications.
[0083] The foams in accordance with the present invention, in
certain preferred embodiments, provide one or more exceptional
features, characteristics and/or properties, including: thermal
insulation efficiency (particularly for thermoset foams),
dimensional stability, compressive strength, aging of thermal
insulation properties, all in addition to the low ozone depletion
potential and low global warming potential associated with many of
the preferred blowing agents of the present invention. In certain
highly preferred embodiments, the present invention provides
thermoset foam, including such foam formed into foam articles,
which exhibit improved thermal conductivity relative to foams made
using the same blowing agent (or a commonly used blowing agent such
as HFC-245fa) in the same amount but without the compound
E-HFO-1336mzz.
[0084] In other preferred embodiments, the present foams exhibit
improved mechanical properties relative to foams produced with
blowing agents outside the scope of the present invention. For
example, certain preferred embodiments of the present invention
provide foams and foam articles having a compressive strength which
is superior to, and preferably at least about 10 relative percent,
and even more preferably at least about 15 relative percent greater
than a foam produced under substantially identical conditions by
utilizing a blowing agent consisting of cyclopentane.
[0085] Furthermore, it is preferred in certain embodiments that the
foams produced in accordance with the present invention have
compressive strengths that are on a commercial basis comparable to
the compressive strength produced by making a foam under
substantially the same conditions except wherein the blowing agent
consists of HFC-245fa. In certain preferred embodiments, the foams
of the present invention exhibit a compressive strength of at least
about 12.5% yield (in the parallel and perpendicular directions),
and even more preferably at least about 13% yield in each of said
directions.
Methods and Systems
[0086] Table 1 describes compositions of this invention which
comprise, or consist essentially of E-HFO-1336mzz. These
compositions are useful in connection with numerous methods and
systems, including as heat transfer fluids in methods and systems
for transferring heat, such as refrigerants used in refrigeration,
air conditioning, including vehicle air conditioning systems, and
heat pump systems. The compositions of this invention are also
advantageous for in use in systems and methods of generating
aerosols, preferably comprising or consisting of the aerosol
propellant in such systems and methods. Methods of forming foams
and methods of extinguishing and suppressing fire are also included
as embodiments of this invention. The present invention also
provides in certain aspects methods of removing residue from
articles in which the present compositions are used as solvent
compositions in such methods and systems.
Heat Transfer Methods
[0087] The preferred heat transfer methods generally comprise
providing a composition comprising, or consisting essentially of
E-HFO-1336mzz, particularly blends as described in Table 6, and
causing heat to be transferred to or from the composition changing
the phase of the composition. For example, the present methods
provide cooling by absorbing heat from a fluid or article,
preferably by evaporating the present refrigerant composition in
the vicinity of the body or fluid to be cooled to produce vapor
comprising, or consisting essentially of, E-HFO-1336mzz.
[0088] In particular, Table 6 shows specific compositions and
ranges that are useful in heat transfer methods.
TABLE-US-00006 TABLE 6 Blend Composition More Preferred Most
Compound Mixed with E-HFO- Preferred Ranges Preferred 1336mzz
Ranges wt % wt % Ranges wt % HFOs HFO-1234ze (E&Z) 10 to 90 25
to 75 40-60, 45-55, or 50/50 HFO-1234yf 10 to 90 25 to 75 40-60,
45-55, or 50/50 HFO-1225ye (E&Z) 10 to 90 25 to 75 40-60,
45-55, or 50/50 HFO-1225yc 10 to 90 25 to 75 40-60, 45-55, or 50/50
HFO-1216 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFO-1233zd
(E&Z) 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFO-1233xf 10 to
90 25 to 75 40-60, 45-55, or 50/50 HFO-1243zf 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFO-1336mzz (Z) 10 to 90 25 to 75 40-60,
45-55, or 50/50 (CF3)2CFCH.dbd.CHF (E&Z) 10 to 90 25 to 75
40-60, 45-55, or 50/50 (C2F5)(CF3)C.dbd.CH2 10 to 90 25 to 75
40-60, 45-55, or 50/50 (CF3)2CFCH.dbd.CF2 10 to 90 25 to 75 40-60,
45-55, or 50/50 (CF3)2CFCF.dbd.CHF (E&Z) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFCs HFC-245fa 10 to 90 25 to 75 40-60,
45-55, or 50/50 HFC-245cb 10 to 90 25 to 75 40-60, 45-55, or 50/50
HFC-245ca 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-245eb 10 to
90 25 to 75 40-60, 45-55, or 50/50 HFC-227ea 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFC-254eb 10 to 90 25 to 75 40-60, 45-55, or
50/50 HFC-236ea 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-236fa
10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-134 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFC-134a 10 to 90 25 to 75 40-60, 45-55, or
50/50 HFC-152 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-152a 10
to 90 25 to 75 40-60, 45-55, or 50/50 HFC-32 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFC-125 10 to 90 25 to 75 40-60, 45-55, or
50/50 HFC-143a 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-365mfc
10 to 90 25 to 75 40-60, 45-55, or 50/50 HFC-161 10 to 90 25 to 75
40-60, 45-55, or 50/50 HFC-43-10mee 10 to 90 25 to 75 40-60, 45-55,
or 50/50 HFC-23 10 to 90 25 to 75 40-60, 45-55, or 50/50 HFEs
CHF2--O--CHF2 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CH2F--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50 CH2F--O--CH3
10 to 90 25 to 75 40-60, 45-55, or 50/50 cyclo-CF2--CH2--CF2--O 10
to 90 25 to 75 40-60, 45-55, or 50/50 cyclo-CF2--CF2--CH2--O 10 to
90 25 to 75 40-60, 45-55, or 50/50 CHF2--O--CF2--CHF2 10 to 90 25
to 75 40-60, 45-55, or 50/50 CF3--CF2--O--CH2F 10 to 90 25 to 75
40-60, 45-55, or 50/50 CHF2--O--CHF--CF3 10 to 90 25 to 75 40-60,
45-55, or 50/50 CHF2--O--CF2--CHF2 10 to 90 25 to 75 40-60, 45-55,
or 50/50 CH2F--O--CF2--CHF2 10 to 90 25 to 75 40-60, 45-55, or
50/50 CF3--O--CF2--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--CHF--O--CHF2 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--O--CHF--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--CHF--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--O--CH2--CHF2 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--O--CH2--CF3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CH2F--CF2--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--O--CF2--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--CF2--O--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CH2F--O--CHF--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--CHF--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--O--CHF--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--CHF--O--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
CHF2--O--CH2--CHF2 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--O--CH2--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF3--CH2--O--CH2F 10 to 90 25 to 75 40-60, 45-55, or 50/50
CF2H--CF2--CF2--O--CH3 10 to 90 25 to 75 40-60, 45-55, or 50/50
Hydrocarbons propane 10 to 90 25 to 75 40-60, 45-55, or 50/50
butane 10 to 90 25 to 75 40-60, 45-55, or 50/50 isobutane 10 to 90
25 to 75 40-60, 45-55, or 50/50 n-pentane (high HFO) 10 to 90 25 to
75 40-60, 45-55, or 50/50 n-pentane (high n-pentane) 10 to 90 25 to
75 40-60, 45-55, or 50/50 isopentane (high HFO) 10 to 90 25 to 75
40-60, 45-55, or 50/50 isopentane (high isopentane) 10 to 90 25 to
75 40-60, 45-55, or 50/50 neopentane (high HFO) 10 to 90 25 to 75
40-60, 45-55, or 50/50 neopentane (high neopentane) 10 to 90 25 to
75 40-60, 45-55, or 50/50 cyclopentane (high HFO) 10 to 90 25 to 75
40-60, 45-55, or 50/50 cyclopentane (high cyclopentane) 10 to 90 25
to 75 40-60, 45-55, or 50/50 n-hexane 10 to 90 25 to 75 40-60,
45-55, or 50/50 isohexane 10 to 90 25 to 75 40-60, 45-55, or 50/50
heptane 10 to 90 25 to 75 40-60, 45-55, or 50/50 Ethers dimethyl
ether 10 to 90 25 to 75 40-60, 45-55, or 50/50 methylethyl ether 10
to 90 25 to 75 40-60, 45-55, or 50/50 diethyl ether 10 to 90 25 to
75 40-60, 45-55, or 50/50 methylpropyl ether 10 to 90 25 to 75
40-60, 45-55, or 50/50 methylisopropyl ether 10 to 90 25 to 75
40-60, 45-55, or 50/50 ethylpropyl ether 10 to 90 25 to 75 40-60,
45-55, or 50/50 ethylisopropyl ether 10 to 90 25 to 75 40-60,
45-55, or 50/50 dipropyl ether 10 to 90 25 to 75 40-60, 45-55, or
50/50 diisopropyl ether 10 to 90 25 to 75 40-60, 45-55, or 50/50
dimethoxymethane 10 to 90 25 to 75 40-60, 45-55, or 50/50
diethoxymethane 10 to 90 25 to 75 40-60, 45-55, or 50/50
dipropoxymethane 10 to 90 25 to 75 40-60, 45-55, or 50/50
dibutoxymethane 10 to 90 25 to 75 40-60, 45-55, or 50/50 Aldehydes
formaldehyde 10 to 90 25 to 75 40-60, 45-55, or 50/50 acetaldehyde
10 to 90 25 to 75 40-60, 45-55, or 50/50 propanal 10 to 90 25 to 75
40-60, 45-55, or 50/50 butanal 10 to 90 25 to 75 40-60, 45-55, or
50/50 isobutanal 10 to 90 25 to 75 40-60, 45-55, or 50/50 Ketones
Acetone 10 to 90 25 to 75 40-60, 45-55, or 50/50 Methylethylketone
10 to 90 25 to 75 40-60, 45-55, or 50/50 methylisobutylketone 10 to
90 25 to 75 40-60, 45-55, or 50/50 perfluoroethylisopropylketone 10
to 90 25 to 75 40-60, 45-55, (C2F5C(O)CF(CF3)2 or 50/50 Others
water 10 to 90 25 to 75 40-60, 45-55, or 50/50 methyl formate 10 to
90 25 to 75 40-60, 45-55, or 50/50 ethyl formate 10 to 90 25 to 75
40-60, 45-55, or 50/50 formic acid 10 to 90 25 to 75 40-60, 45-55,
or 50/50 trans-1,2-dichloroethylene (t- 10 to 90 25 to 75 40-60,
45-55, DCE) or 50/50 CO.sub.2 10 to 90 25 to 75 40-60, 45-55, or
50/50 HCFO-1232xf 10 to 90 25 to 75 40-60, 45-55, or 50/50
HCFO-1223xd 10 to 90 25 to 75 40-60, 45-55, or 50/50 HCFO-1233xf 10
to 90 25 to 75 40-60, 45-55, or 50/50 HCFO-1233zd (E&Z) 10 to
90 25 to 75 40-60, 45-55, or 50/50 HCFO-1224yd (E&Z) 10 to 90
25 to 75 40-60, 45-55, or 50/50 CFC-13 (CF3Cl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1121a (CHF.dbd.CCl2) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1121 (CFCl.dbd.CHCl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1131a (CH2.dbd.CFCl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1131 (CHF.dbd.CHCl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1122 (CF2.dbd.CHCl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 HCFO-1113 (CF2.dbd.CFCl) 10 to 90 25 to 75
40-60, 45-55, or 50/50 CH2.dbd.CHCl 10 to 90 25 to 75 40-60, 45-55,
or 50/50 CH3Cl 10 to 90 25 to 75 40-60, 45-55, or 50/50 HCFC-133a
(CF3CH2Cl) 10 to 90 25 to 75 40-60, 45-55, or 50/50 CFC-115
(CF3CF2Cl) 10 to 90 25 to 75 40-60, 45-55,
or 50/50 3,3,3-Trifluoropropyne 10 to 90 25 to 75 40-60, 45-55, or
50/50 HCFC-124 (CF3CHFCl) 10 to 90 25 to 75 40-60, 45-55, or 50/50
HCC-40 (CH3Cl) 10 to 90 25 to 75 40-60, 45-55, or 50/50 HCFC-22
(CF2HCl) 10 to 90 25 to 75 40-60, 45-55, or 50/50 cis-HFO-1234ze +
HFO-1225yeZ 10 to 90 25 to 75 40-60, 45-55, or 50/50 Mixtures of
any of the above plus 1 to 99% H2O 5 to 95% 10 to 90% water H2O H2O
Mixtures of any of the above plus 1 to 99% CO2 5 to 95% 10 to 90%
CO2 CO2 CO2 Mixtures of any of the above plus 1 to 99% t- 5 to 95%
t- 10 to 90% t- t-DCE DCE DCE DCE Mixtures of any of the above plus
1 to 99% MF 5 to 95% MF 10 to 90% MF methyl formate Mixtures with
cis-HFO-1234ze + 10 to 90 5 to 95 10 to 90 CO2 Mixtures with
cis-HFO-1234ze + 10 to 90 5 to 95 10 to 90 CO2 + 1225yeZ Mixtures
with cis-HFO-1234ze + 10 to 90 5 to 95 10 to 90 HFC-245fa
[0089] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1A.
[0090] Preferably the methods include the further step of
compressing the refrigerant vapor, usually with a compressor or
similar equipment to produce vapor of the present composition at a
relatively elevated pressure. Generally, the step of compressing
the vapor results in the addition of heat to the vapor, thus
causing an increase in the temperature of the relatively
high-pressure vapor. Preferably, the present methods include
removing from this relatively high temperature, high pressure vapor
at least a portion of the heat added by the evaporation and
compression steps. The heat removal step preferably includes
condensing the high temperature, high-pressure vapor while the
vapor is in a relatively high-pressure condition to produce a
relatively high-pressure liquid comprising, or consisting
essentially of, E-HFO-1336mzz. This relatively high-pressure liquid
preferably then undergoes a nominally isoenthalpic reduction in
pressure to produce a relatively low temperature, low-pressure
liquid. In such embodiments, it is this reduced temperature
refrigerant liquid which is then vaporized by heat transferred from
the body or fluid to be cooled.
[0091] In one embodiment of the invention, the compositions of the
invention may be used in a method for producing cooling which
comprises evaporating a refrigerant comprising, or consisting
essentially of, E-HFO-1336mzz, particularly blends as described in
Table 1A, in the vicinity of a liquid or body to be cooled.
[0092] In another embodiment of the invention, the compositions of
the invention may be used in a method for producing heating which
comprises condensing a refrigerant comprising, or consisting
essentially of, E-HFO-1336mzz, particularly blends as described in
Table 1, in the vicinity of a liquid or body to be heated. Such
methods, as mentioned herein before, frequently are reverse cycles
to the refrigeration cycle described above.
[0093] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1A, and those
amounts are likewise applicable for this use of the composition of
the invention.
Refrigerant Compositions
[0094] The present methods, systems and compositions comprising, or
consisting essentially of E-HFO-1336mzz, and in particular, blends
as described in Table 1, are thus adaptable for use in connection
with air conditioning systems and devices, including automotive air
conditioning systems, commercial refrigeration systems and devices
(including medium and low temperature systems and transport
refrigeration), chillers, residential refrigerator and freezers,
general air conditioning systems, including residential and window
air conditioners, chillers, heat pumps, including high temperature
heat pumps (with condenser temperatures greater than 55.degree. C.,
70.degree. C., or 100.degree. C.) and the like.
[0095] Many existing refrigeration systems are currently adapted
for use in connection with existing refrigerants, and the
compositions of the present invention are believed to be adaptable
for use in many of such systems, either with or without system
modification. In many applications the compositions of the present
invention may provide an advantage as a replacement in systems,
which are currently based on refrigerants having a relatively high
capacity. Furthermore, in embodiments where it is desired to use a
lower capacity refrigerant composition of the present invention,
for reasons of 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 comprising, or consisting
essentially of, E-HFO-1336mzz, either alone or in combination with
one or more other compounds, particularly blends as described in
Table 1A, as a replacement for existing refrigerants, such as
CFC-11, CFC-12, CFC-113, CFC-114 or CFC-114a, HCFC-123, HCFC-124,
HCFC-22, HFC-134a, HFC-236fa, HFC-245fa, R-404A, R-407C, R-407A,
R-407F, R-407H, R410A and R507 among others. 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 HCFC-123 or HFC-134a. Therefore, the
refrigerant compositions of the present invention, particularly
compositions comprising, or consisting essentially of,
E-HFO-1336mzz, provide the possibility of achieving a competitive
advantage on an energy basis for refrigerant replacement
applications.
[0096] Although, as described above, it is contemplated that the
compositions of the present invention may include the compounds of
the present invention in widely ranging amounts, it is generally
preferred that refrigerant compositions of the present invention
comprise E-HFO-1336mzz, in an amount that is at least about 50% by
weight, and even more preferably at least about 70% by weight, of
the composition.
[0097] The compositions of the present invention may include other
components for the purpose of enhancing or providing certain
functionality to the composition, or in some cases to reduce the
cost of the composition. For example, refrigerant compositions
according to the present invention, especially those used in vapor
compression systems, include a lubricant, generally in amounts of
from about 5 to about 50 percent by weight of the composition. Or
in another embodiment, the compositions useful as a refrigerant
may, in use, include a lubricant, from about 30 to about 50 percent
by weight of the composition Furthermore, the present compositions
may also include a compatibilizer, such as propane, for the purpose
of aiding compatibility and/or solubility of the lubricant. Such
compatibilizers, including propane, butanes and pentanes, are
preferably present in amounts of from about 0.5 to about 5 percent
by weight of the composition.
[0098] Combinations of surfactants and solubilizing agents may also
be added to the present compositions to aid oil solubility, as
disclosed by U.S. Pat. No. 6,516,837, the disclosure of which is
incorporated by reference. Commonly used refrigeration lubricants
such as Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs),
polyvinyl ethers (PVEs), fluorinated and perfluorinated oils (e.g.,
perfluoropolyethers, PFPEs), polycarbonates, silicone oil, mineral
oil, alkyl benzenes (ABs) and poly(alpha-olefin) (PAO) that are
used in refrigeration machinery with hydrofluorocarbon (HFC)
refrigerants may be used with the refrigerant compositions of the
present invention.
[0099] It is contemplated that the compositions of the present,
including particularly those comprising, or consisting essentially
of, E-HFO-1336mzz, and particularly blends as set forth in Table
1A, also have advantage (either in original systems or when used as
a replacement for refrigerants such as R-12 and R-500), in chillers
typically used in connection with commercial air conditioning
systems. In certain of such embodiments it is preferred to
including in the present E-HFO-1336mzz compositions from about 0.5
to about 5% of a flammability suppressant, such as CF3I.
[0100] In certain preferred embodiments, the compositions of the
present invention further comprise a lubricant. Any of a variety of
conventional lubricants may be used in the compositions of the
present invention. An important requirement for the lubricant is
that, when in use in a refrigerant system, there must be sufficient
lubricant returning to the compressor of the system such that the
compressor is lubricated. Thus, suitability of a lubricant for any
given system is determined partly by the refrigerant/lubricant
characteristics and partly by the characteristics of the system in
which it is intended to be used. Examples of suitable lubricants
include mineral oil, alkyl benzenes, polyol esters, including
polyalkylene glycols, PAG oil, and the like. Mineral oil, which
comprises paraffin oil or naphthenic oil, is commercially
available. Commercially available mineral oils include Witco LP
250.TM. from Witco, Zerol 300.TM. from Shrieve Chemical, Sunisco
3GS from Witco, and Calumet R015 from Calumet. Commercially
available alkyl benzene lubricants include Zerol 150.TM..
Commercially available esters include neopentyl glycol
dipelargonate which is available as Emery 2917.TM. and Hatcol
2370.TM.. Other useful esters include phosphate esters, dibasic
acid esters, and fluoroesters.
[0101] Additionally, perfluoropolyethers (PFPEs), such as
Krytox.RTM., Galden.RTM., Fomblin.RTM. and the like may serve as
refrigerant lubricants or performance enhancing additives.
[0102] Preferred lubricants include polyalkylene glycols and polyol
esters. Certain more preferred lubricants include polyalkylene
glycols. Certain more preferred lubricants include polyol
ethers.
[0103] 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.
Power Cycle Use
[0104] Rankine cycle systems are known to be a simple and reliable
means to convert heat energy into mechanical shaft power. Organic
working fluids are useful in place of water/steam when low-grade
thermal energy is encountered. Water/steam systems operating with
low-grade thermal energy (typically 400.degree. F. and lower) will
have associated high volumes and low pressures. To keep system size
small and efficiency high, organic working fluids with boiling
points near room temperature are employed. Such fluids would have
higher gas densities lending to higher capacity and favorable
transport and heat transfer properties lending to higher efficiency
as compared to water at low operating temperatures. In industrial
settings there are more opportunities to use flammable working
fluids such as toluene and pentane, particularly when the
industrial setting has large quantities of flammables already on
site in processes or storage. For instances where the risk
associated with use of a flammable working fluid is not acceptable,
such as power generation in populous areas or near buildings, other
fluids such as CFC-113 and CFC-11 were used. Although these
materials were non-flammable, they were a risk to the environment
because of their ozone-depletion potential. Ideally, the organic
working fluid should be environmentally acceptable, non-flammable,
of a low order of toxicity, and operate at positive pressures.
[0105] Organic Rankine Cycle (ORC) systems are often used to
recover waste heat from industrial processes. In combined heat and
power (cogeneration) applications, waste heat from combustion of
fuel used to drive the prime mover of a generator set is recovered
and used to make hot water for building heat, for example, or for
supplying heat to operate an absorption chiller to provide cooling.
In some cases, the demand for hot water is small or does not exist.
The most difficult case is when the thermal requirement is variable
and load matching becomes difficult, confounding efficient
operation of the combined heat and power system. In such an
instance, it is more useful to convert the waste heat to shaft
power by using an organic Rankine cycle system. The shaft power can
be used to operate pumps, for example, or it may be used to
generate electricity. By using this approach, the overall system
efficiency is higher and fuel utilization is greater. Air emissions
from fuel combustion can be decreased since more electric power can
be generated for the same amount of fuel input.
[0106] The process that produces waste heat is at least one
selected from the group consisting of fuel cells, internal
combustion engines, internal compression engines, external
combustion engines, and turbines. Other sources of waste heat can
be found in association with operations at oil refineries,
petrochemical plants, oil and gas pipelines, chemical industry,
commercial buildings, hotels, shopping malls, supermarkets,
bakeries, food processing industries, restaurants, paint curing
ovens, furniture making, plastics molders, cement kilns, lumber
kilns (drying), calcining operations, steel industry, glass
industry, foundries, smelting, air-conditioning, refrigeration, and
central heating. See U.S. Pat. No. 7,428,816, the disclosure of
which is hereby incorporated herein by reference.
[0107] Preferred compositions for ORC power cycle use are described
below in Table 7 (with all percentages being in percent by weight
and being understood to be proceeded by the word "about").
TABLE-US-00007 TABLE 7 ORC Blends More Most Preferred Preferred
Preferred Compound Mixed with E-HFO- Ranges Ranges Ranges 1336mzz
wt % wt % wt % HFOs HFO-1234ze (E&Z) 1 to 99 5 to 95 10 to 90
HFO-1234yf 1 to 99 5 to 95 10 to 90 HFO-1225ye (E&Z) 1 to 99 5
to 95 10 to 90 HFO-1225yc 1 to 99 5 to 95 10 to 90 HFO-1233zd
(E&Z) 1 to 99 5 to 95 10 to 90 HFO-1233xf 1 to 99 5 to 95 10 to
90 HFO-1336mzz (Z) 1 to 99 64-94 6-36 (CF3)2CFCH.dbd.CHF (E&Z)
1 to 99 5 to 95 10 to 90 (C2F5)(CF3)C.dbd.CH2 1 to 99 5 to 95 10 to
90 (CF3)2CFCH.dbd.CF2 1 to 99 5 to 95 10 to 90 (CF3)2CFCF.dbd.CHF
(E&Z) 1 to 99 5 to 95 10 to 90 HFCs HFC-245fa 1 to 99 5 to 95
10 to 90 HFC-245cb 1 to 99 5 to 95 10 to 90 HFC-245ca 1 to 99 5 to
95 10 to 90 HFC-227ea 1 to 99 5 to 95 10 to 90 HFC-236ea 1 to 99 5
to 95 10 to 90 HFC-236fa 1 to 99 5 to 95 10 to 90 HFC-134 1 to 99 5
to 95 10 to 90 HFC-134a 1 to 99 5 to 95 10 to 90 HFC-152 1 to 99 5
to 95 10 to 90 HFC-152a 1 to 99 5 to 95 10 to 90 HFC-32 1 to 99 5
to 95 10 to 90 HFC-125 1 to 99 5 to 95 10 to 90 HFC-143a 1 to 99 5
to 95 10 to 90 HFC-365mfc 1 to 99 5 to 95 10 to 90 HFC-161 1 to 99
5 to 95 10 to 90 HFC-43-10mee 1 to 99 5 to 95 10 to 90 HFEs
CHF2--O--CHF2 1 to 99 5 to 95 10 to 90 CHF2--O--CH2F 1 to 99 5 to
95 10 to 90 CH2F--O--CH2F 1 to 99 5 to 95 10 to 90 CH2F--O--CH3 1
to 99 5 to 95 10 to 90 cyclo-CF2--CH2--CF2--O 1 to 99 5 to 95 10 to
90 cyclo-CF2--CF2--CH2--O 1 to 99 5 to 95 10 to 90
CHF2--O--CF2--CHF2 1 to 99 5 to 95 10 to 90 CF3--CF2--O--CH2F 1 to
99 5 to 95 10 to 90 CHF2--O--CHF--CF3 1 to 99 5 to 95 10 to 90
CHF2--O--CF2--CHF2 1 to 99 5 to 95 10 to 90 CH2F--O--CF2--CHF2 1 to
99 5 to 95 10 to 90 CF3--O--CF2--CH3 1 to 99 5 to 95 10 to 90
CHF2--CHF--O--CHF2 1 to 99 5 to 95 10 to 90 CF3--O--CHF--CH2F 1 to
99 5 to 95 10 to 90 CF3--CHF--O--CH2F 1 to 99 5 to 95 10 to 90
CF3--O--CH2--CHF2 1 to 99 5 to 95 10 to 90 CHF2--O--CH2--CF3 1 to
99 5 to 95 10 to 90 CH2F--CF2--O--CH2F 1 to 99 5 to 95 10 to 90
CHF2--O--CF2--CH3 1 to 99 5 to 95 10 to 90 CHF2--CF2--O--CH3 1 to
99 5 to 95 10 to 90 CH2F--O--CHF--CH2F 1 to 99 5 to 95 10 to 90
CHF2--CHF--O--CH2F 1 to 99 5 to 95 10 to 90 CF3--O--CHF--CH3 1 to
99 5 to 95 10 to 90 CF3--CHF--O--CH3 1 to 99 5 to 95 10 to 90
CHF2--O--CH2--CHF2 1 to 99 5 to 95 10 to 90 CF3--O--CH2--CH2F 1 to
99 5 to 95 10 to 90 CF3--CH2--O--CH2F 1 to 99 5 to 95 10 to 90
CF2H--CF2--CF2--O--CH3 1 to 99 5 to 95 10 to 90 Hydrocarbons
propane 1 to 99 5 to 95 10 to 90 butane 1 to 99 5 to 95 10 to 90
isobutane 1 to 99 5 to 95 10 to 90 n-pentane (high HFO) 1 to 99 50
to 99 60 to 99 n-pentane (high n-pentane) 1 to 99 1 to 30 1 to 20
isopentane (high HFO) 1 to 99 50 to 99 60 to 90 isopentane (high
isopentane) 1 to 99 1 to 30 1 to 20 neopentane (high HFO) 1 to 99
50 to 99 60 to 99 neopentane (high neopentane) 1 to 99 1 to 30 1 to
20 cyclopentane (high HFO) 1 to 99 50 to 99 60 to 99 cyclopentane
(high cyclopentane) 1 to 99 1 to 30 1 to 20 n-hexane 1 to 99 5 to
95 10 to 90 isohexane 1 to 99 5 to 95 10 to 90 heptane 1 to 99 5 to
95 10 to 90 Ethers dimethyl ether 1 to 99 5 to 95 10 to 90
methylethyl ether 1 to 99 5 to 95 10 to 90 diethyl ether 1 to 99 5
to 95 10 to 90 methylpropyl ether 1 to 99 5 to 95 10 to 90
methylisopropyl ether 1 to 99 5 to 95 10 to 90 ethylpropyl ether 1
to 99 5 to 95 10 to 90 ethylisopropyl ether 1 to 99 5 to 95 10 to
90 dipropyl ether 1 to 99 5 to 95 10 to 90 diisopropyl ether 1 to
99 5 to 95 10 to 90 dimethoxymethane 1 to 99 5 to 95 10 to 90
diethoxymethane 1 to 99 5 to 95 10 to 90 dipropoxymethane 1 to 99 5
to 95 10 to 90 dibutoxymethane 1 to 99 5 to 95 10 to 90 Aldehydes
formaldehyde 1 to 99 5 to 95 10 to 90 acetaldehyde 1 to 99 5 to 95
10 to 90 propanal 1 to 99 5 to 95 10 to 90 butanal 1 to 99 5 to 95
10 to 90 isobutanal 1 to 99 5 to 95 10 to 90 Ketones Acetone 1 to
99 5 to 95 10 to 90 Methylethylketone 1 to 99 5 to 95 10 to 90
methylisobutylketone 1 to 99 5 to 95 10 to 90
perfluoroethylisopropylketone 1 to 99 5 to 95 10 to 90
(C2F5C(O)CF(CF3)2 Others water 1 to 99 5 to 95 10 to 90 methyl
formate 1 to 99 5 to 95 10 to 90 ethyl formate 1 to 99 5 to 95 10
to 90 formic acid 1 to 99 5 to 95 10 to 90
trans-1,2-dichloroethylene (t-DCE) 1 to 99 5 to 95 10 to 90 CO2 1
to 99 5 to 95 10 to 90 cis-HFO-1234ze + HFO-1225yeZ Mixtures of any
of the above plus 1 to 99% 5 to 95% 10 to 90% water H2O H2O H2O
Mixtures of any of the above plus 1 to 99% 5 to 95% 10 to 90% CO2
CO2 CO2 CO2 Mixtures of any of the above plus t- 1 to 99% 5 to 95%
10 to 90% DCE t-DCE t-DCE t-DCE Mixtures of any of the above plus 1
to 99% 5 to 95% 10 to 90% methyl formate MF MF MF Mixtures with
cis-HFO-1234ze + 1 to 99 5 to 95 10 to 90 CO2 Mixtures with
cis-HFO-1234ze + 1 to 99 5 to 95 10 to 90 CO2 + 1225yeZ Mixtures
with cis-HFO-1234ze + 1 to 99 5 to 95 10 to 90 HFC-245fa
[0108] One specific embodiment of a power cycle use of this
compound is a process for recovering waste heat in an Organic
Rankine Cycle system in which the working fluid is a composition
comprising, or consisting essentially of, E-HFO-1336mzz and
optionally, one or more additional compounds, as set forth above in
Table 6.
Power Cycle Example
Example 3
[0109] HFO-1336mzz(E)/HFO-1336mzz(Z) Blends Approximating the
Volumetric Capacity for Power Generation of HFC-245Fa without
Exceeding the Equipment Maximum Permissible Working Pressure
[0110] Table 8 compares the performance of Rankine cycles operated
at an evaporating temperature of 120.degree. C. with
HFO-1336mzz-E/HFO-1336mzz-Z blends of various compositions to
performance of a Rankine cycle operated at the same evaporating
temperature with HFC-245fa. The volumetric capacity for power
generation with blend A.1 is within 5% of that with HFC-245fa. The
volumetric capacity for power generation with blend A.2 matches
that with HFC-245fa with an evaporating pressure not exceeding that
of HFC-245fa. The volumetric capacity for power generation with
blend A.3 exceeds that with HFC-245fa by about 5% with an
evaporating pressure not exceeding 2.18 MPa. Finally, the
volumetric capacity for power generation with blend A.4 is the
maximum possible (higher than that with HFC-245fa by about 12.5%)
with an evaporating pressure not exceeding 2.18 MPa.
HFO-1336mzz(E)/HFO-1336mzz(Z) blends containing 66.50 to 94 wt %
HFO-1336mzz(E) would be advantageous as replacements for HFC-245fa
in ORCs.
TABLE-US-00008 TABLE 8 Subcritical ORC performance with
HFO-1336mzz-E/HFO-1336mzz-Z Blends at an evaporating temperature of
120.degree. C. BLEND A.1 BLEND A.2 BLEND A.3 BLEND A.4 HFO- HFO-
HFO- HFO- 1336mzz- 1336mzz- 1336mzz- 1336mzz- E/HFO- E/HFO- E/HFO-
E/HFO- 1336mzz-Z 1336mzz-Z 1336mzz-Z 1336mzz-Z Blend Blend HFC-
Blend Blend 66.50/33.50 wt % 74.50/25.50 wt % 245fa 82.30/17.70 wt
% 94.00/06.00 wt % Tevap, .degree. C. 120 120 120 120 120 Tcond,
.degree. C. 35 35 35 35 35 .DELTA.Tsuph, .degree. C. 0 0 0 0 0
.DELTA.Tsubc, .degree. C. 0 0 0 0 0 EFF_expn 0.85 0.85 0.85 0.85
0.85 EFF_comp 0.85 0.85 0.85 0.85 0.85 Pevap, MPa 1.83 1.93 1.93
2.03 2.18 Pcond, MPa 0.21 0.22 0.21 0.24 0.26 Texpn_out, .degree.
C. 65.12 63.47 61.28 61.76 59.02 CAP_e, kJ/m.sup.3 343.02 361.39
361.47 379.51 406.57 (Volumetric Capacity for power generation)
Cleaning and Contaminant Removal
[0111] The present invention also provides methods of removing
containments from a product, part, component, substrate, or any
other article or portion thereof by applying to the article a
composition of the present invention comprising, or consisting
essentially of, E-HFO-1336mzz, and in particular, the blends set
forth in Table 1. For the purposes of convenience, the term
"article" is used herein to refer to all such products, parts,
components, substrates, and the like and is further intended to
refer to any surface or portion thereof. Furthermore, the term
"contaminant" is intended to refer to any unwanted material or
substance present on the article, even if such substance is placed
on the article intentionally. For example, in the manufacture of
semiconductor devices it is common to deposit a photoresist
material onto a substrate to form a mask for the etching operation
and to subsequently remove the photoresist material from the
substrate. The term "contaminant" as used herein is intended to
cover and encompass such a photo resist material.
[0112] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0113] Preferred methods of the present invention comprise applying
the present composition to the article. Although it is contemplated
that numerous and varied cleaning techniques can employ the
compositions of the present invention to good advantage, it is
considered to be particularly advantageous to use the present
compositions in connection with supercritical cleaning techniques.
Supercritical cleaning is disclosed in U.S. Pat. No. 6,589,355,
which is incorporated herein by reference.
[0114] For supercritical cleaning applications, it is preferred in
certain embodiments to include in the present cleaning
compositions, in addition to the composition of the present
invention, another component, such as CO2 and other additional
components known for use in connection with supercritical cleaning
applications.
[0115] It may also be possible and desirable in certain embodiments
to use the present cleaning compositions in connection with
particular sub-critical vapor degreasing and solvent cleaning
methods. For all solvent uses, compositions containing the compound
E-HFO-1336mzz may preferably be blended with one or more of the
following compounds; cis-1234ze, cis-1233zd, HFC-245fa, Methylal
(dimethoxymethane), methylethylketone, methylisobutylketone, and/or
HFC-134a. More preferred blends comprise E-HFO-1336mzz blended with
one or more of the following compounds; pentanes, hexanes, HFC-365,
C.sub.4F.sub.9OCH.sub.3, C.sub.4F.sub.9OC.sub.2H.sub.5, propane,
butane, isobutane, and/or dimethylether. Most preferred blends
comprise E-HFO-1336mzz blended with one or more of the following
compounds; trans-1,2-dichloroethylene, trans-HFO-1234ze,
trans-HCFO-1233zd, trans-1336, HFC-43-10, HFC-152a, methanol,
ethanol, isopropanol, and/or acetone.
[0116] Another cleaning embodiment of the invention comprises the
removal of contaminants from vapor compression systems and their
ancillary components when these systems are manufactured and
serviced. As used herein, the term "contaminants" refers to
processing fluids, lubricants, particulates, sludge, and/or other
materials that are used in the manufacture of these systems or
generated during their use. In general, these contaminants comprise
compounds such as alkylbenzenes, mineral oils, esters,
polyalkyleneglycols, polyvinylethers and other compounds that are
made primarily of carbon, hydrogen and oxygen. The compositions of
the present invention will be useful for this purpose.
Propellants for Sprayable Compositions
[0117] In another embodiment, the compositions of this invention
comprising, or consisting essentially of, E-HFO-1336mzz, and in
particular, blends as described in Table 1, may be used as
propellants in sprayable compositions, either alone or in
combination with known propellants. For this use, the amount of the
compound E-HFO-1336mzz in the composition of the invention can be
in accordance with the following ranges: from about 1 wt % to about
99 wt %; from about 30 wt % to about 99 wt %; from about 50 wt % to
about 99 wt %; from about 75 wt % to about 99 wt %; from about 85
wt % to about 99 wt %; from about 20 wt % to about 80 wt %; from
about 90 wt % to about 99 wt %; from about 95 wt % to about 99 wt
%; from about 1 wt % to about 20 wt %; from about 1 wt % to about
40 wt %; from about 1 wt % to about 50 wt %; from about 5 wt % to
about 20 wt %; from about 5 wt % to about 40 wt %; from about 5 wt
% to about 60 wt %; from about 10 wt % to about 80 wt %; from about
10 wt % to about 90 wt %; from about 20 wt % to about 80 wt %; from
about 20 wt % to about 90 wt %. Other ranges of amounts are shown
in Table 1, and those amounts are likewise applicable for this use
of the composition of the invention.
[0118] The sprayable composition includes a material to be sprayed
and a propellant comprising, or consisting essentially of
E-HFO-1336mzz, and in particular, blends as described in Table 1.
Inert ingredients, solvents, and other materials may also be
present in the sprayable mixture. Preferably, the sprayable
composition is an aerosol. Suitable materials to be sprayed
include, without limitation, cosmetic materials such as deodorants,
perfumes, hair sprays, cleansers, and polishing agents as well as
medicinal materials such as anti-asthma and anti-halitosis
medications.
[0119] For aerosol uses, compositions containing the compound
trans-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) may
preferably be blended with one or more of the following compounds;
cis-HFO-1234ze, cis-HCFO-1233zd, HFC-245fa, Methylal
(dimethoxymethane), methylethylketone, methylisobutylketone, and/or
HFC-134a. More preferred blends comprise E-HFO-1336mzz blended with
one or more of the following compounds; pentanes, hexanes, HFC-365,
C.sub.4F.sub.9OCH.sub.3 and/or C.sub.4F.sub.9OC.sub.2H.sub.5. Most
preferred blends comprise E-HFO-1336mzz blended with one or more of
the following compounds; trans-1,2-dichloroethylene,
trans-HFO-1234ze, trans-HCFO-1233zd, cis-HFO-1336mzz, HFC-43-10,
HFC-152a, methanol, ethanol, isopropanol, propane, butane,
isobutane, dimethylether and/or acetone.
[0120] In this use, the active ingredient to be sprayed is mixed
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, lubricants, insecticides, cleaners,
cosmetic materials such as deodorants, perfumes and hair sprays,
polishing agents, as well as medicinal materials such as skin
cooling agents (sunburn treatment), topical anesthetics and
anti-asthma medications.
[0121] In another aspect, the present invention provides propellant
comprising, or consisting essentially of, E-HFO-1336mzz, either
alone or in combination with one or more other compounds, in
particular blends as set forth in Table 1, such propellant
composition preferably being a sprayable composition. The
propellant compositions of the present invention preferably
comprise a material to be sprayed and a propellant comprising, or
consisting essentially of, E-HFO-1336mzz. Inert ingredients,
solvents, and other materials may also be present in the sprayable
mixture. Preferably, the sprayable composition is an aerosol.
Suitable materials to be sprayed include, without limitation,
lubricants, insecticides, cleaners, cosmetic materials such as
deodorants, perfumes and hair sprays, polishing agents as well as
medicinal materials such as anti-asthma components, and any other
medication or the like, including preferably any other medicament
or agent intended to be inhaled. The medicament or other
therapeutic agent is preferably present in the composition in a
therapeutic amount, with a substantial portion of the balance of
the composition comprising, or consisting essentially of,
E-HFO-1336mzz.
[0122] Aerosol products for industrial, consumer or medical use
typically contain one or more propellants along with one or more
active ingredients, inert ingredients or solvents. The propellant
provides the force that expels the product in aerosolized form.
While some aerosol products are propelled with compressed gases
like carbon dioxide, nitrogen, nitrous oxide and even air, most
commercial aerosols use liquefied gas propellants. The most
commonly used liquefied gas propellants are hydrocarbons such as
butane, isobutane, and propane. Dimethyl ether and HFC-152a
(1,1-difluoroethane) are also used, either alone or in blends with
the hydrocarbon propellants. Unfortunately, all of these liquefied
gas propellants are highly flammable and their incorporation into
aerosol formulations will often result in flammable aerosol
products.
[0123] Applicants have come to appreciate the continuing need for
nonflammable, liquefied gas propellants with which to formulate
aerosol products. The present invention provides compositions of
the present invention, particularly and preferably compositions
comprising, or consisting essentially of, E-HFO-1336mzz, and in
particular, those blends set forth in Table 1, for use in certain
industrial aerosol products, including for example spray cleaners,
lubricants, and the like, and in medicinal aerosols, including for
example to deliver medications to the lungs or mucosal membranes.
Examples of this includes metered dose inhalers (MDIs) for the
treatment of asthma and other chronic obstructive pulmonary
diseases and for delivery of medicaments to accessible mucous
membranes or intranasally. The present invention thus includes
methods for treating ailments, diseases and similar health related
problems of an organism (such as a human or animal) comprising
applying a composition of the present invention containing a
medicament or other therapeutic component to the organism in need
of treatment. In certain preferred embodiments, the step of
applying the present composition comprises providing a MDI
containing the composition of the present invention (for example,
introducing the composition into the MDI) and then discharging the
present composition from the MDI.
[0124] As used herein, the term "nonflammable" refers to compounds
and compositions of the present invention which do not exhibit a
flashpoint as measured by one of the standard flash point methods,
for example ASTM-1310-86 "Flash point of liquids by tag Open-cup
apparatus."
[0125] The present compositions can be used to formulate a variety
of industrial aerosols or other sprayable compositions such as
contact cleaners, dusters, lubricant sprays, and the like, and
consumer aerosols such as personal care products, household
products and automotive products. E-HFO-1336mzz is particularly
preferred for use as an important component of propellant
compositions for in medicinal aerosols such as metered dose
inhalers. The medicinal aerosol and/or propellant and/or sprayable
compositions of the present invention in many applications include,
in addition to E-HFO-1336mzz, a medicament such as a beta-agonist,
a corticosteroid or other medicament, and, optionally, other
ingredients, such as surfactants, solvents, other propellants,
flavorants and other excipients.
Sterilization
[0126] Many articles, devices and materials, particularly for use
in the medical field, must be sterilized prior to use for the
health and safety reasons, such as the health and safety of
patients and hospital staff. The present invention provides methods
of sterilizing comprising contacting the articles, devices or
material to be sterilized with a composition of the present
invention comprising, or consisting essentially of, E-HFO-1336mzz,
and in particular, the blends defined in Table 1, and optionally in
combination with one or more additional sterilizing agents.
[0127] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0128] While many sterilizing agents are known in the art and are
considered to be adaptable for use in connection with the present
invention, in certain preferred embodiments sterilizing agent
comprises ethylene oxide, formaldehyde, hydrogen peroxide, chlorine
dioxide, ozone and combinations of these. In certain embodiments,
ethylene oxide is the preferred sterilizing agent. Those skilled in
the art, in view of the teachings contained herein, will be able to
readily determine the relative proportions of sterilizing agent and
the present compound(s) to be used in connection with the present
sterilizing compositions and methods, and all such ranges are
within the broad scope hereof.
[0129] As is known to those skilled in the art, certain sterilizing
agents, such as ethylene oxide, are extremely flammable components,
and the compound(s) in accordance with the present invention are
included in the present compositions in amounts effective, together
with other components present in the composition, to reduce the
flammability of the sterilizing composition to acceptable levels.
The sterilization methods of the present invention may be either
high or low-temperature sterilization of the present invention
involves the use of a compound or composition of the present
invention at a temperature of from about 250.degree. F. to about
270.degree. F., preferably in a substantially sealed chamber. The
process can be completed usually in less than about two hours.
However, some articles, such as plastic articles and electrical
components, cannot withstand such high temperatures and require
low-temperature sterilization.
Sterilization Examples
[0130] In low temperature sterilization methods, the article to be
sterilized is exposed to a fluid comprising, or consisting
essentially of, E-HFO-1336mzz at a temperature of from about room
temperature to about 200.degree. F., more preferably at a
temperature of from about room temperature to about 100.degree.
F.
[0131] The low-temperature sterilization of the present invention
is preferably at least a two-step process performed in a
substantially sealed, preferably air tight, chamber. In the first
step (the sterilization step), the articles having been cleaned and
wrapped in gas permeable bags are placed in the chamber.
[0132] Air is then evacuated from the chamber by pulling a vacuum
and perhaps by displacing the air with steam. In certain
embodiments, it is preferable to inject steam into the chamber to
achieve a relative humidity that ranges preferably from about 30%
to about 70%. Such humidities may maximize the sterilizing
effectiveness of the sterilant, which is introduced into the
chamber after the desired relative humidity is achieved. After a
period of time sufficient for the sterilant to permeate the
wrapping and reach the interstices of the article, the sterilant
and steam are evacuated from the chamber.
[0133] In the preferred second step of the process (the aeration
step), the articles are aerated to remove sterilant residues.
Removing such residues is particularly important in the case of
toxic sterilants, although it is optional in those cases in which
the substantially non-toxic compounds of the present invention are
used. Typical aeration processes include air washes, continuous
aeration, and a combination of the two. An air wash is a batch
process and usually comprises evacuating the chamber for a
relatively short period, for example, 12 minutes, and then
introducing air at atmospheric pressure or higher into the
chamber.
[0134] As used herein the term "non-toxic" refers to compounds and
compositions of the present invention which have an acute toxicity
level substantially less than, and preferably at least about 30
relative percent less than, the toxicity level of HFO-1223xd, as
measured by the method published in Anesthesiology, Vol. 14, pp.
466-472, 1953, incorporated here by reference.
[0135] This cycle is repeated any number of times until the desired
removal of sterilant is achieved. Continuous aeration typically
involves introducing air through an inlet at one side of the
chamber and then drawing it out through an outlet on the other side
of the chamber by applying a slight vacuum to the outlet.
Frequently, the two approaches are combined. For example, a common
approach involves performing air washes and then an aeration
cycle.
Lubricants
[0136] In certain preferred embodiments, the compositions of the
present invention comprising, or consisting essentially of,
E-HFO-1336mzz, and in particular, the blends defined in Table 1,
may further comprise a lubricant. Any of a variety of conventional
lubricants may be used in the compositions of the present
invention. An important requirement for the lubricant is that, when
in use in a refrigerant system, there must be sufficient lubricant
returning to the compressor of the system such that the compressor
is lubricated. Thus, suitability of a lubricant for any given
system is determined partly by the refrigerant/lubricant
characteristics and partly by the characteristics of the system in
which it is intended to be used.
[0137] Examples of suitable lubricants include mineral oil, alkyl
benzenes, polyol esters, including polyalkylene glycols, PAG oil,
PVE, polycarbonate and the like. Mineral oil, which comprises
paraffin oil or naphthenic oil, is commercially available.
Commercially available mineral oils include Witco LP 250.TM. from
Witco, Zerol 300.TM. from Shrieve Chemical, Sunisco 3GS from Witco,
and Calumet R015 from Calumet. Commercially available alkyl benzene
lubricants include Zerol 150.TM.. Commercially available esters
include neopentyl glycol dipelargonate which is available as Emery
2917.TM. and Hatcol 2370.TM.. Other useful esters include phosphate
esters, dibasic acid esters, and fluoroesters. Preferred lubricants
include polyalkylene glycols and esters. Certain more preferred
lubricants include polyalkylene glycols.
Extraction of Flavors and Fragrances
[0138] The compositions of the present invention comprising, or
consisting essentially of E-HFO-1336mzz, and in particular, the
blends as described in Table 1, also provide advantage when used to
carry, extract or separate desirable materials from biomass. These
materials include, but are not limited to, essential oils such as
flavors and fragrances, oils which may be used as fuel, medicinals,
nutraceuticals, etc.
[0139] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
Extraction Example
[0140] The suitability of the present compositions for this purpose
is demonstrated by a test procedure in which a sample of Jasmone is
put into a heavy walled glass tube. A suitable amount of a
E-HFO-1336mzz containing composition of the present invention is
added to the glass tube. The tube is then frozen and sealed. Upon
thawing the tube, when the mixture has one liquid phase containing
Jasome and the E-HFO-1336mzz containing composition of this
invention; this test establishes the favorable use of the
composition as an extractant, carrier or part of delivery system
for flavor and fragrance formulations, in aerosol and other
formulations. It also establishes its potential as an extractant of
flavors and fragrances, including from plant matter.
Flammability Reduction Methods
[0141] According to certain other preferred embodiments, the
present invention provides methods for reducing the flammability of
fluids, said methods comprising adding a E-HFO-1336mzz containing
composition, such as the blends defined in Table 1, to said fluid.
The flammability associated with any of a wide range of otherwise
flammable fluids may be reduced according to the present invention.
For example, the flammability associated with fluids such as
ethylene oxide, flammable hydrofluorocarbons and hydrocarbons,
including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a),
difluoromethane (HFC-32), propane, hexane, octane, and the like can
be reduced according to the present invention. For the purposes of
the present invention, a flammable fluid may be any fluid
exhibiting flammability ranges in air as measured via any standard
conventional test method, such as ASTM E-681, and the like.
[0142] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0143] Any suitable amounts of the present compounds or
compositions may be added to reduce flammability of a fluid
according to the present invention. As will be recognized by those
of skill in the art, the amount added will depend, at least in
part, on the degree to which the subject fluid is flammable and the
degree to which it is desired to reduce the flammability thereof.
In certain preferred embodiments, the amount of compound or
composition added to the flammable fluid is effective to render the
resulting fluid substantially non-flammable.
Flame Suppression Methods
[0144] The present invention further provides methods of
suppressing a flame, said methods comprising contacting a flame
with a E-HFO-1336mzz containing composition of the present
invention, particularly the blends described in Table 1. If
desired, additional flame suppressing agents can also be used with
the composition of the present invention, either in admixture, or
as a secondary flame suppressing agent. One class of compounds for
this purpose is the fluoroketones. One especially preferred
fluoroketone is dodecafluoro-2-methylpentan-3-one, which is sold by
the 3M Company under the trade name Novec 1230.
[0145] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0146] Any suitable methods for contacting the flame with the
present composition may be used. For example, a composition of the
present invention may be sprayed, poured, and the like onto the
flame, or at least a portion of the flame may be immersed in the
composition.
Flame Suppression Example
[0147] This example demonstrates the use of the compositions
comprising, or consisting essentially of E-HFO-1336mzz, and in
particular, the blends as described in Table 1, for use as a flame
suppression composition.
[0148] For this use, the amount of the compound E-HFO-1336mzz in
the composition of the invention can be in accordance with the
following ranges: from about 1 wt % to about 99 wt %; from about 30
wt % to about 99 wt %; from about 50 wt % to about 99 wt %; from
about 75 wt % to about 99 wt %; from about 85 wt % to about 99 wt
%; from about 20 wt % to about 80 wt %; from about 90 wt % to about
99 wt %; from about 95 wt % to about 99 wt %; from about 1 wt % to
about 20 wt %; from about 1 wt % to about 40 wt %; from about 1 wt
% to about 50 wt %; from about 5 wt % to about 20 wt %; from about
5 wt % to about 40 wt %; from about 5 wt % to about 60 wt %; from
about 10 wt % to about 80 wt %; from about 10 wt % to about 90 wt
%; from about 20 wt % to about 80 wt %; from about 20 wt % to about
90 wt %. Other ranges of amounts are shown in Table 1, and those
amounts are likewise applicable for this use of the composition of
the invention.
[0149] To evaluate total flooding fire suppression applications the
NFPA 2001 cup burner was used. Here a small fire of the fuel of
interest is located in a chimney which has air flowing around the
flame to supply the needed oxygen. To this air stream E-HFO-1336mzz
is added until the flame is extinguished. Table 9 shows the
extinguishing concentrations for several fuels using E-HFO-1336mzz
as the fire extinguishant.
TABLE-US-00009 TABLE 9 Flame Extinguishment by E-HFO-1336mzz %
E-HFO-1336mzz for Fuel Flame Extingishment heptane 7.0 methanol
10.4 acetone 6.9
[0150] While the present invention has been particularly shown and
described with reference to preferred embodiments, it will be
readily appreciated by those of ordinary skill in the art that
various changes and modifications may be made without departing
from the scope of the invention. It is intended that the claims be
interpreted to cover the disclosed embodiment, those alternatives
which have been discussed above and all equivalents thereto.
[0151] As used herein, the terms "comprises," "comprising,"
"includes," "including," "has," "having" or any other variation
thereof, are intended to cover a non-exclusive inclusion. For
example, a process, method, article, or apparatus that comprises a
list of elements is not necessarily limited to only those elements
but may include other elements not expressly listed or inherent to
such process, method, article, or apparatus. Further, unless
expressly stated to the contrary, "or" refers to an inclusive or
and not to an exclusive or. For example, a condition A or B is
satisfied by any one of the following: A is true (or present) and B
is false (or not present), A is false (or not present) and B is
true (or present), and both A and B are true (or present).
[0152] The transitional phrase "consisting of" excludes any
element, step, or ingredient not specified. If in the claim such
would close the claim to the inclusion of materials other than
those recited except for impurities ordinarily associated
therewith. When the phrase "consists of" appears in a clause of the
body of a claim, rather than immediately following the preamble, it
limits only the element set forth in that clause; other elements
are not excluded from the claim as a whole.
[0153] As used herein, the phrase "consisting essentially of" is
intended to cover a partially exclusive inclusion. For example, a
composition, method, process or apparatus that consists essentially
of elements is not limited to only those elements, but may only
include other elements that do not materially change the intended
advantageous properties of the composition, method, process or
apparatus.
[0154] Also, use of "a" or "an" are employed to describe elements
and components described herein. This is done merely for
convenience and to give a general sense of the scope of the
invention. This description should be read to include one or at
least one and the singular also includes the plural unless it is
obvious that it is meant otherwise.
[0155] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
methods and materials similar or equivalent to those described
herein can be used in the practice or testing of embodiments of the
present invention, suitable methods and materials are described
below. All publications, patent applications, patents, and other
references mentioned herein are incorporated by reference in their
entirety, unless a particular passage is cited in case of conflict,
the present specification, including definitions, will control. In
addition, the materials, methods, and examples are illustrative
only and not intended to be limiting.
[0156] Note that not all of the activities described above in the
general description or the examples are required, that a portion of
a specific activity may not be required, and that one or more
further activities may be performed in addition to those described.
Still further, the order in which activities are listed are not
necessarily the order in which they are performed.
[0157] In the foregoing specification, the concepts have been
described with reference to specific embodiments. However, one of
ordinary skill in the art appreciates that various modifications
and changes can be made without departing from the scope of the
invention as set forth in the claims below. Accordingly, the
specification and figures are to be regarded in an illustrative
rather than a restrictive sense, and all such modifications are
intended to be included within the scope of invention.
[0158] Benefits, other advantages, and solutions to problems have
been described above with regard to specific embodiments. However,
the benefits, advantages, solutions to problems, and any feature(s)
that may cause any benefit, advantage, or solution to occur or
become more pronounced are not to be construed as a critical,
required, or essential feature of any or all the claims.
[0159] It is to be appreciated that certain features are, for
clarity, described herein in the context of separate embodiments,
may also be provided in combination in a single embodiment.
Conversely, various features that are, for brevity, described in
the context of a single embodiment, may also be provided separately
or in any subcombination. Further, reference to values stated in
ranges include each and every value within that range.
Example 4
Phase Studies of Mixture of E-1336Mzz and Cyclopentane
[0160] A phase study was performed for a composition consisting
essentially of E-1336mzz and cyclopentane, wherein the composition
was varied and the vapor pressures were measured at 29.89.degree.
C. Based upon the data from the phase studies, azeotropic
compositions at other temperature and pressures have been
calculated.
[0161] Table 10 provides a compilation of experimental and
calculated azeotropic compositions for E-1336mzz and cyclopentane
at specified temperatures and pressures.
TABLE-US-00010 TABLE 10 Temperature Mole % E- Mole % .degree. C.
Pressure psia 1336mzz cyclopentane -40 1.43 90.30% 9.70% -30 2.57
89.89% 10.11% -20 4.39 89.66% 10.34% -10 7.14 89.63% 10.37% 0 11.11
89.81% 10.19% 10 16.65 90.25% 9.75% 20 24.16 90.96% 9.04% 30 34.05
92.00% 8.00% 40 46.81 93.42% 6.58% 50 62.96 95.31% 4.69% 60 83.12
97.76% 2.24% 70 108.03 100.00% 0
Example 5
[0162] Example 2 demonstrates dew point and bubble point vapor
pressures for mixtures of E-1336mzz and cyclopentane.
[0163] The dew point and bubble point vapor pressures for
compositions disclosed herein were calculated from measured and
calculated thermodynamic properties. The near-azeotrope range is
indicated by the minimum and maximum concentration of E-1336mzz and
cyclopentane (mole percent, mol %) for which the difference in dew
point and bubble point pressures is less than or equal to 3% (based
upon bubble point pressure). The results are summarized in Table
11.
TABLE-US-00011 TABLE 11 Azeotrope Near azeotrope compositions,
Temperature, composition, mol % E-1336mzz .degree. C. mol %
E-1336mzz Minimum Maximum -40 90.3 88.0 99.8 -20 89.7 85.8 99.8 0
89.8 84.2 99.8 20 91.0 83.0 99.8 29.89 92.0 82.6 99.8 40 93.4 82.4
99.8 60 97.8 82.6 99.8 80 -- 83.6 99.8 100 -- 85.6 99.8
Example 6
[0164] The chemical stability of E-HFO-1336mzz in the presence of
metals was tested according to the sealed tube testing methodology
of ANSI/ASHRAE Standard 97-2007. The stock of E-HFO-1336mzz used in
the sealed tube tests contained virtually no water or air. Sealed
glass tubes, each containing three metal coupons made of steel,
copper, and aluminum immersed in E-HFO-1336mzz, were aged in a
heated oven at 175.degree. C., 225.degree. C. and 250.degree. C.
for 14 days. Visual inspection of the tubes after thermal aging
indicated clear liquids with no discoloration or other visible
deterioration of the fluid. The concentration of fluoride ion in
the aged liquid samples, measured by ion chromatography, was below
detection limit (3 ppm) even after two weeks of aging at
250.degree. C. The concentration of fluoride ion can be interpreted
as an indicator of the degree of E-HFO-1336mzz degradation.
Therefore, E-HFO-1336mzz degradation was minimal. Gas
chromatography (GC) analyses of the E-HFO-1336mzz samples after
aging for 14 days at 175.degree. C., 225.degree. C. and 250.degree.
C. indicated negligible chemical conversion of E-HFO-1336mzz and
negligible formation of new compounds.
* * * * *