U.S. patent application number 12/667121 was filed with the patent office on 2011-01-06 for stable formulated systems with chloro-3,3,3-trifluoropropene.
This patent application is currently assigned to ARKEMA INC.. Invention is credited to Philippe Bonnet, Benjamin Bin Chen, Maher Y. Elsheikh, Brett L. Van Horn.
Application Number | 20110001080 12/667121 |
Document ID | / |
Family ID | 41127779 |
Filed Date | 2011-01-06 |
United States Patent
Application |
20110001080 |
Kind Code |
A1 |
Van Horn; Brett L. ; et
al. |
January 6, 2011 |
STABLE FORMULATED SYSTEMS WITH CHLORO-3,3,3-TRIFLUOROPROPENE
Abstract
The present invention relates to formulated systems of
1-chloro-3,3,3-trifluoropropene (R-1233zd) and/or
2-chloro-3,3,3-trifluoropropene (R-1233xf) that are sufficiently
thermally and chemically stable such that they can be effectively
used sans additional stabilizers. The formulations of the present
invention are particularly useful compositions for refrigeration,
heat transfer, and foam pre-mixes.
Inventors: |
Van Horn; Brett L.; (King of
Pussia, PA) ; Elsheikh; Maher Y.; (Wayne, PA)
; Chen; Benjamin Bin; (Wayne, PA) ; Bonnet;
Philippe; (Lower Merion, PA) |
Correspondence
Address: |
ARKEMA INC.;PATENT DEPARTMENT - 26TH FLOOR
2000 MARKET STREET
PHILADELPHIA
PA
19103-3222
US
|
Assignee: |
ARKEMA INC.
PHILADELPHIA, PENNSYLAVNIA
PA
|
Family ID: |
41127779 |
Appl. No.: |
12/667121 |
Filed: |
March 6, 2009 |
PCT Filed: |
March 6, 2009 |
PCT NO: |
PCT/US09/36267 |
371 Date: |
December 29, 2009 |
Current U.S.
Class: |
252/68 ; 252/67;
570/135 |
Current CPC
Class: |
C10M 2203/065 20130101;
C10M 2209/043 20130101; C10M 2205/0285 20130101; C09K 5/00
20130101; C10M 171/008 20130101; C09K 5/04 20130101; B01F 17/0085
20130101; C09K 5/044 20130101; C10M 2207/2835 20130101; C10N
2020/101 20200501; C10M 2209/1033 20130101 |
Class at
Publication: |
252/68 ; 570/135;
252/67 |
International
Class: |
C09K 5/04 20060101
C09K005/04; C07C 21/18 20060101 C07C021/18 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 7, 2008 |
US |
61/034513 |
Claims
1. A halogenated olefin composition stable in the presence of
lubricants, metals, water, a polyol B-side formulation, and
mixtures thereof comprising 1-chloro-3,3,3-trifluorpropene and/or
2-chloro-3,3,3-trifluorpropene sans a stabilizer.
2. The halogenated olefin composition of claim 1 wherein said
lubricant is selected from the group consisting of mineral oils,
alkyl benzene oils, polyol ester oils, polyalkylene glycol oils,
polyvinyl ether oils, poly(alphaolefin) oils and mixtures
thereof.
3. The halogenated olefin composition of claim 1 wherein said metal
is selected from the group consisting of steel, stainless steel,
aluminum, iron, copper, and mixtures thereof.
4. The halogenated olefin composition of claim 1 wherein said
polyol B-side formulation comprises at least one polyol and
optionally catalysts, surfactants water, and mixtures thereof.
5. The halogenated olefin composition of claim 1 wherein said
1-chloro-3,3,3-trifluoropropene is predominantly
trans-1-chloro-3,3,3-trifluoropropene.
6. The halogenated olefin composition of claim 1 wherein said
1-chloro-3,3,3-trifluoropropene is greater than about 70%
trans-1-chloro-3,3,3-trifluoropropene.
7. The halogenated olefin composition of claim 1 wherein said
1-chloro-3,3,3-trifluorpropene is consists essentially of
trans-1-chloro-3,3,3-trifluoropropene.
8. A halogenated olefin composition comprising
1-chloro-3,3,3-trifluoropropene sans stabilizer and at least one
component selected from the group consisting of lubricants and
metals.
9. A refrigeration system, air conditioning system, or heat
transfer system containing the halogenated olefin composition of
claim 8.
10. The halogenated olefin composition of claim 1 further
comprising a component selected from the group consisting of
hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins,
hydrofluorochlorocarbons, hydrocarbons, hydrofluoroethers,
fluoroketones, chlorofluorocarbons, trans-1,2-dichloroethylene,
carbon dioxide, ammonia, and mixtures thereof.
11. The halogenated olefin composition of claim 10 wherein said
hydrofluorocarbon is selected from the group consisting of
difluoromethane (HFC-32); 1-fluoroethane (HFC-161);
1,1-difluoroethane (HFC-152a); 1,2-difluoroethane (HFC-152);
1,1,1-trifluoroethane (HFC-143a); 1,1,2-trifluoroethane (HFC-143);
1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2,2-tetrafluoroethane
(HFC-134); 1,1,1,2,2-pentafluoroethane (HFC-125);
1,1,1,3,3-pentafluoropropane (HFC-245fa);
1,1,2,2,3-pentafluoropropane (HFC-245ca);
1,1,1,2,3-pentafluoropropane (HFC-245eb);
1,1,1,3,3,3-hexafluoropropane (HFC-236fa);
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);
1,1,1,3,3-pentafluorobutane (HFC-365mfc),
1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310), and mixtures
thereof.
12. The halogenated olefin composition of claim 10 wherein said
hydrochlorofluorocarbon is selected from the group consisting of
chlorodifluoromethane (HCFC-22), 1,1-dichloro-2,2,2-trifluoroethane
(HCFC-123), 1-chloro-2,2,2-trifluoroethane (HCFC-124),
1,1-dichloro-1-fluoroethane (HCFC-141b),
1-chloro-1,1-difluoroethane (HCFC-142b), and mixtures thereof.
13. The halogenated olefin composition of claim 10 wherein said
chlorofluorocarbon is selected from the group consisting of
trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12),
1,1,2-trifluoro-1,2,2-trifluoroethane (R-113),
1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114),
chloro-pentafluoroethane (R-115) and mixtures thereof.
14. The halogenated olefin composition of claim 10 wherein said
hydrocarbon is selected from the group consisting of propane,
butane, isobutane, n-pentane, iso-pentane, neo-pentane,
cyclopentane, and mixtures thereof.
15. The halogenated olefin composition of claim 10 wherein said
hydrofluoroolefin is selected from the group consisting of
3,3,3-trifluorpropene (HFO-1234zf), E-1,3,3,3-trtrafluoropropene,
2,3,3,3-trtrafluoropropene (HFO-1234yf),
E-1,2,3,3,-pentafluoropropene (E-HFO-1255ye),
Z-1,2,3,3,3-pentafluoropropene (Z--HFO-125ye),
E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336m/z),
Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z--HFO-1336m/z),
1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) and mixtures
thereof.
16. The halogenated olefin composition of claim 10 wherein said
hydrofluoroether is 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane,
1,1,1,2,2,3,3,4,4,-nonafluoro-4-methoxy-butane and mixtures
thereof.
17. The halogenated olefin composition of claim 10 wherein said
fluoroketone is
1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-3-pentanone.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to formulated systems of
1-chloro-3,3,3-trifluoropropene (R-1233zd) and/or
2-chloro-3,3,3-trifluoropropene (R-1233xf) that are sufficiently
thermally and chemically stable such that they can be effectively
used without the need for additional stabilizers. The formulations
of the present invention are particularly useful compositions for
refrigeration, heat transfer, and foam pre-mixes.
BACKGROUND OF THE INVENTION
[0002] With continued regulatory pressure there is a growing need
to identify more environmentally sustainable replacements for
refrigerants, heat transfer fluids, foam blowing agents, solvents,
and aerosols with lower ozone depleting and global warming
potentials. Chlorofluorocarbon (CFC) and hydrochlorofluorocarbons
(HCFC), widely used for these applications, are ozone depleting
substances and are being phased out in accordance with guidelines
of the Montreal Protocol. Hydrofluorocarbons (HFC) are a leading
replacement for CFCs and HCFCs in many applications. Though they
are deemed "friendly" to the ozone layer they still generally
possess high global warming potentials. One new class of compounds
that has been identified to replace ozone depleting or high global
warming substances are halogenated olefins, such as
hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO).
Because of the presence of alkene linkage it is expected that the
HFOs and HCFOs will be chemically unstable, relative to HCFCs or
CFCs. The inherent chemical instability of these materials in the
lower atmosphere results in short atmospheric lifetimes, which
provide the low global warming potential and zero or near zero
ozone depletion properties desired. However, such inherent
instability is believed to also impact the commercial application
of such materials, which may degrade during storage, handling and
use.
[0003] WO 2009/003165 discloses stabilized formulations of HFOs and
HCFOs in a variety of applications and compositions. This patent
application discloses that stabilizers can be used to inhibit
decomposition of HCFO-1233zd during use. WO 2007/002625 discloses
the use of various tetrafluoropropenes in a variety of applications
including heat transfer systems. The patent application discloses
the stability of HFO-1234ze, HFO-1243zf, and HFO-1225ye with
selected PAG lubricating oils and compares the results to that of
CFC-12 in a mineral oil, using the results to state the
refrigerants and compositions of that patent application have
better stability than many commonly used refrigerants.
[0004] WO08027596, WO08027595, WO08027518, WO08027517, WO08027516,
WO08027515, WO08027513, WO08027512, WO08027514 all are directed
towards stabilized systems of fluoroolefins. These applications
disclose that fluoroolefins can exhibit degradation when exposed to
high temperatures or when contacted with other compounds e.g.,
moisture, oxygen, or other compounds with which they may undergo
condensation reactions. It is disclosed that the degradation may
occur when fluoroolefins are used as working fluids in heat
transfer equipment (refrigeration or air-conditioning equipment,
for instance) or when used in some other application. It is
disclosed that because of the instability of the fluoroolefins, it
may not be practical to incorporate these fluoroolefins into
refrigeration or air-conditioning systems. Therefore, to take
advantage of the many other attributes of fluoroolefins, means to
reduce the degradation via the addition of a stabilizer is
needed.
[0005] In the present invention, it was discovered that HCFO-1233zd
(trans- and/or cis-isomers) and HCFO-1233xf are unexpectedly stable
during storage and use without the need for an added stabilizer,
being as stable or significantly more stable the many HCFCs and
CFCs while being more environmentally sustainable.
SUMMARY OF THE INVENTION
[0006] The present invention relates to formulated systems of
trans- and/or cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd)
and/or 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) that are
sufficiently thermally and chemically stable such that they can be
effectively used without the need for additional stabilizers. The
formulations of the present invention are particularly useful
compositions for refrigeration, heat transfer, and foam pre-mixes.
Stability results for select HCFCs are provided in "Chemical and
Thermal Stability of Refrigerant-Lubricant Mixtures with Metals",
by DF Huttenlocher of Spauschus Inc., in DOE/CE/23810-5 (1992). The
stated findings were that R-123 is approximately ten times more
stable than R-11, and that R-141b and R-142b are more stable than
R-123. EP0539719 discloses that R-141b should be used with a
stabilizer, such as alpha-methylstyrene, to inhibit the formation
of the toxic byproduct 1-chloro-1-fluoroethylene (HCFO-1131a). The
present inventors discovered that HCFO-1233zd, without any
additional stabilizer, was at least as stable as R-141b, and by
extension it is also more stable than R-123 and R-11.
DETAILED DESCRIPTION OF THE INVENTION
[0007] With continued regulatory pressure there is a growing need
to identify more environmentally sustainable replacements for
refrigerants, heat transfer fluids, foam blowing agents, solvents,
and aerosols with lower ozone depleting and global warming
potentials. Chlorofluorocarbon (CFC) and hydrochlorofluorocarbons
(HCFC), widely used for these applications, are ozone depleting
substances and are being phased out in accordance with guidelines
of the Montreal Protocol. Hydrofluorocarbons (HFC) are a leading
replacement for CFCs and HCFCs in many applications; though they
are deemed "friendly" to the ozone layer they still generally
possess high global warming potentials. One new class of compounds
that has been identified to replace ozone depleting or high global
warming substances are halogenated olefins, such as
hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO).
Because of the presence of alkene linkage it is expected that the
HFOs and HCFOs will be chemically unstable, relative to preceding
HCFC or CFC. The inherent chemical instability of these materials
in the lower atmosphere results in short atmospheric lifetimes,
which provide the low global warming potential and zero or near
zero ozone depletion properties desired. However, such inherent
instability is believed to also impact the commercial application
of such materials, which may degrade during storage, handling and
use, such as when exposed to high temperatures or when contacted
with other compounds e.g., moisture, oxygen, or other compounds
with which they may undergo condensation reactions. This
degradation may occur when halo-olefins are used as working fluids
in heat transfer equipment (refrigeration or air-conditioning
equipment, for instance) or when used in some other application.
This degradation may occur by any number of different mechanisms.
In one instance, the degradation may be caused by instability of
the compounds at extreme temperatures. In other instances, the
degradation may be caused by oxidation in the presence of air that
has inadvertently leaked into the system. Whatever the cause of
such degradation, because of the instability of the halo-olefins,
it may not be practical to incorporate these halo-olefins into
refrigeration or air-conditioning systems, or in other applications
such as in foam polyol pre-mixes.
[0008] Good understanding of the chemical interactions of the
refrigerant, lubricant, and metals in a refrigeration system is
necessary for designing systems that are reliable and have a long
service life. Incompatibility between the refrigerant and other
components of or within a refrigeration or heat transfer system can
lead to decomposition of the refrigerant, lubricant, and/or other
components, the formation of undesirable byproducts, corrosion or
degradation of mechanical parts, loss of efficiency, or a general
shortening of the service life of the equipment, refrigerant and/or
lubricant.
[0009] In the present invention, it was discovered that the
halogenated olefins HCFO-1233zd and/or HCFO-1233xf are unexpectedly
stable, sans additional stabilizing agents, in systems typical of
refrigeration, air conditioning, heat transfer systems, including
within the presence of lubricants, metals, and moisture. It was
discovered that halogenated olefins HCFO-1233zd and/or HCFO-1233xf
is at least if not more stable than similar HCFC and CFC
refrigerants, including R-141b, R-123, and R-11, and can therefore
be particularly useful as a refrigerant or heat transfer fluid
while providing both the benefits of an extended service life as
well as greater environmental sustainability.
[0010] In a refrigeration, air conditioning, or heat transfer
system, lubricating oil and refrigerant are expected to be in
contact with each other in at least some parts of the system, if
not most of the system, as explained in the ASHRAE Handbook: HVAC
Systems and Equipment. Therefore, whether the lubricant and
refrigerant are added separately or as part of a pre-mixed package
to a refrigeration, air conditioning, or heat transfer system, they
are still expected to be in contact within the system and must
therefore be compatible.
[0011] In one embodiment of the present invention, the stable
halogentaed olefin systems are refrigeration, air conditioning, or
heat transfer systems comprising chloro-3,3,3-trifluoropropene,
preferrably HCFO-1233zd. In such a system the HCFO-1233zd will be
in contact with various metals and other components and must remain
stable for extended operation. Typical materials which are present
in such systems include steel, stainless steel, aluminum, iron,
copper, and mixtures thereof. In another embodiment of the present
invention said stable systems also comprising lubricants, including
mineral oils, alkyl benzene oils, polyvinyl ether oils, polyol
ester oils, polyalkylene glycol oils, poly(alphaolefin) oils, and
mixtures thereof.
[0012] The stable halogenated olefin systems comprising
chloro-3,3,3-trifluoropropene, preferrably
1-chloro-3,3,3-trifluoropropene (R-1233 zd),
2-chloro-3,3,3-trifluoropropene (R-12330xf), and mixtures thereof,
and even more preferrably trans-1-chloro-3,3,3-trifluoropropene are
intended to include new systems, servicing of existing systems, and
retrofitting of existing systems. The preferred
chloro-3,3,3-trifluorpropene is
trans-1-chloro-3,3,3-trifluoropropene comprising greater than 70 wt
% trans isomer. For example, due to the stability of
chloro-3,3,3-trifluoropropene with lubricants and metals,
chloro-3,3,3-trifluoropropene can be used to service existing
equipment already containing other refrigerants including, but not
limited to, HCFC-123 and/or CFC-11, without worsening the system
stability. This can include adding chloro-3,3,3-trifluoropropene,
either alone or in combination with other refrigerants, to said
existing equipment in order to top-off a refrigerant charge or by
removing part or all of said existing refrigerant and then
replacing it with chloro-3,3,3-trifluoropropene, alone or in
combination with other refrigerants.
[0013] Chloro-3,3,3-trifluoropropene can also be charged to new
equipment, alone or in combination with other refrigerants such as
hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins,
hydrofluorochlorocarbons, hydrocarbons, hydrofluoroethers,
fluoroketones, chlorofluorocarbons, trans-1,2-dichloroethylene,
carbon dioxide, ammonia, and mixtures thereof. Exemplary
hydrofluorocarbons include difluoromethane (HFC-32); 1-fluoroethane
(HFC-161); 1,1-difluoroethane (HFC-152a); 1,2-difluoroethane
(HFC-152); 1,1,1-trifluoroethane (HFC-143a); 1,1,2-trifluoroethane
(HFC-143); 1,1,1,2-tetrafluoroethane (HFC-134a);
1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2,2-pentafluoroethane
(HFC-125); 1,1,1,3,3-pentafluoropropane (HFC-245fa);
1,1,2,2,3-pentafluoropropane (HFC-245ca);
1,1,1,2,3-pentafluoropropane (HFC-245eb);
1,1,1,3,3,3-hexafluoropropane (HFC-236fa);
1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);
1,1,1,3,3-pentafluorobutane (HFC-365mfc),
1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310), and mixtures
thereof. Exemplary chlorofluorocarbons include
trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12),
1,1,2-trifluoro-1,2,2-trifluoroethane (R-113),
1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114),
chloro-pentafluoroethane (R-115) and mixtures thereof. Exemplary
hydrocarbons include propane, butane, isobutane, n-pentane,
iso-pentane, neo-pentane, cyclopentane, and mixtures thereof.
Exemplary hydrofluoroolefins include 3,3,3-trifluorpropene
(HFO-1234zf), E-1,3,3,3-trtrafluoropropene,
2,3,3,3-trtrafluoropropene (HFO-1234yf),
E-1,2,3,3,-pentafluoropropene (E-HFO-1255ye),
Z-1,2,3,3,3-pentafluoropropene (Z--HFO-125ye),
E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336m/z),
Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z--HFO-1336m/z),
1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) and mixtures
thereof. Exemplary hydrofluoroethers include
1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane,
1,1,1,2,2,3,3,4,4,-nonafluoro-4-methoxy-butane and mixtures
thereof. An exemplary fluoroketone is
1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-3-pentanone.
[0014] In another embodiment of the present invention, a stable
pre-blend formulation can be prepared by mixing
chloro-3,3,3-trifluoropropene, alone or in combination with other
refrigerants, with a lubricant sans additional stabilizer. The
stable system refrigerant/lubricant pre-blend can then be charged
to a refrigeration, air conditioning, or heat transfer system.
[0015] For the production of polyurethane foams, it is typical to
prepare a polyol pre-mixture (typically referred to as the B-side)
that contains the blowing agent. This B-side foam pre-mix will form
foam when mixed with a polymeric MDI mixture (typically referred to
as the A-side). The B-side foam pre-mix formulation must remain
chemically and thermally stable before being mixed with the A-side
formulation to prevent problems such as the creation of undesirable
byproducts, decomposition of B-side components, undesired
polymerization etc. These can decrease the efficiency of the
foaming formulation, produce toxic or reactive components, produce
more volatile components that could increase the pressure of the
B-side container, etc. It was discovered in the present invention
that HCFO-1233zd and/or HCFO-1233xf are unexpectedly stable in
B-side polyol foam pre-mixes sans additional stabilizer, being at
least if not more stable than preceding HCFC blowing agents in
polyol foam pre-mixes, such as HCFC-141b. Foam pre-mixes containing
HFCO-1233zd and/or HCFO-1233xf will bring the benefit of added
shelf life compared to pre-mixes of HCFC-141b.
[0016] The following non-limiting examples are hereby provided as
reference:
EXAMPLES
[0017] The compatibility and stability of refrigerants in the
presence of lubricating oils, moisture, and metals was tested at
elevated temperatures in 300 mL stainless steel autoclaves. The 300
mL autoclaves were first loaded with approximately 10 g of oil, 1 g
of water, and coupons or chips of active metals: aluminum, copper,
and iron. To each autoclave was added approximately approximately
10 to 11 g of refrigerant. The autoclaves were sealed and placed in
a constant temperature oven at 140.degree. C. for 48 hours.
Afterwhich the autoclaves were allowed to cool and then the vapor
space was analyzed by gas chromatography (GC) to check for
decomposition and identify degradation products.
[0018] In calculating the purity of the refrigerant, some of the
impurities contained in the starting material were subtracted from
the GC scans to better reflect changes in purity of the refrigerant
and better identify the appearance of degradation products.
Example 1
[0019] The compatibility and stability of trans-HCFO-1233zd in the
presence of lubricating oils and metals was tested at elevated
temperatures in stainless steel autoclaves following the procedure
described previously. The lubricants tested in three separate
autoclaves were AB-150, MO-150, and POE-22. In a fourth autoclave,
trans-HCFO-1233zd was tested without lubricant, moisture, or the
metal chips to be used as a reference sample. The original
HCFO-1233zd contained from 1 to 2% impurities, primarily HFO-1234ze
and HFC-245fa, which were subtracted out of the GC scans as
described previously.
[0020] Table 1 shows the purity of the samples following the
stability tests. The purity of the HCFO-1233zd remained greater
than 99% in all cases. The primary impurities in the samples
containing oil were dimethyl terephthalate and diethylphthalate
which were not decomposition products of the HCFO-1233zd.
Comparative Example 2
[0021] The compatibility and stability of HCFC-141bin the presence
of lubricating oils and metals was tested at elevated temperatures
in stainless steel autoclaves following the procedure of example 1,
except replacing the HCFO-1233zd with HCFC-141b. The HCFC-141b
contained approximately 0.02% alpha-methylstyrene as a stabilizer.
The HCFC-141b taken from the reference sample remained fairly pure
at greater than 99.9%. The HCFC-141b showed signs of significant
decomposition when in the presence of lubricating oils, metals, and
moisture, with the appearance of numerous degradation products,
such as 1,1-dichloroethylene, and particularly with a significant
increase in the level of 1-chloro-1-fluoroethylene (HCFO-1131a),
from less than 15 ppm for the reference sample to over 1500 ppm or
even over 3300 ppm for the samples containing the oils. These
results are shown in Table 1. The stainless steel autoclaves
containing lubricants showed significant discoloration (darkening)
or corrosion in areas contacted by the other metals. This corrosion
could not be removed by simple scrubbing or washing. Corrosion of
this type was not observed in Example 1. Comparative Example 2
shows that HCFO-1233zd is at least as stable as HCFC-141b, even
when the HCFC-141b is stabilized to inhibit decomposition.
TABLE-US-00001 TABLE 1 Refrigerant purity following stability
testing with lubricants Example Refrigerant Reference AB-150 MO-150
POE-22 1 1233zd 99.97% 99.43% 99.18% 99.59% 2 141b 99.98% 98.49%
99.07% 99.08% (1131a) (13 ppm) (~1500 ppm) (~3300 (~1800 ppm)
ppm)
Examples 3 and 4 and Comparative Examples 5 and 6
[0022] The compatibility and stability of trans-HCFO-1233zd and
HCFC-141b were tested in the presence of lubricating oils similar
to as in Example 1 and comparative example 3, with the following
modifications: In examples 3 and 4, two autoclaves were prepared
with HCFO-1233zd with MO-150 and POE-22 respectively, as was done
in example 1. In comparative examples 5 and 6, two autoclaves were
prepared with HCFC-141b, containing alpha-methylstyrene as a
stabilizer, with MO-150 and POE-22 respectively, as was done in
comparative example 2. The autoclaves were maintained at
140.degree. C. for 96 hours, instead of 48 hours. The vapor space
of each autoclave was sampled and tested by GC/MS both before and
after the stability tests. The results are shown in Table 2.
[0023] The purity of the HCFO-1233zd changed by only 0.03% or less
while the purity of the HCFC-141b changed by greater than 0.3%. The
primary decomposition byproduct for HCFO-141b was HCFO-1131a,
increasing from 11 ppm to over 1400 ppm.
TABLE-US-00002 TABLE 2 Refrigerant purity following stability
testing with lubricants Purity Example Refrigerant Oil Before After
Change 3 HCFO- MO-150 99.99% 99.98% 0.01% 1233zd 4 HCFO- POE-22
99.97% 99.94% 0.03% 1233zd 5 HCFC-141b MO-150 99.95% 99.64% 0.31%
(1131a) (11 ppm) (~1900 ppm) 6 HCFC-141b POE-22 99.71% 98.97% 0.74%
(1131a) (11 ppm) (~1400 ppm)
Example 7
[0024] A sample of HCFO-1233zd, containing trans- and cis-isomers
in a ratio of approximately 7:3, was stored in a clear glass vial
for over ten years in uncontrolled ambient conditions. Following
the storage period the sample was visually observed and tested by
GC analysis. The sample still looked clear and unchanged and GC
analysis showed no significant change in sample composition. This
example shows that HCFO-1233zd is stable during extended storage
conditions.
Comparative Example 8
[0025] A sample of R-11 from 1981 was stored in a 30 gallon steel
drum. Following the storage period, the sample had turned yellow
and emitted a strong odor. This example shows that HCFO-1233zd will
be more stable than R-11 in storage and in use, especially in the
presence of active metals, lubricants, and moisture.
Example 9 and Comparative Example 10
[0026] The chemical and thermal stability of HCFO-1233zd and
HFO-1234ze in B-side polyol formulations were tested in stainless
steel autoclaves as follows:
[0027] Each foam pre-mix formulation was loaded into a 300 mL
stainless steel autoclave. The autoclaves were heated in a constant
temperature oven for 24 hours at 100.degree. C. The autoclaves were
then removed from the oven and kept at ambient temperature for 72
hours, after which for each a sample of the vapor space composition
was collected into a Tedlar.RTM. GC sample bag for subsequent
analysis by GC/MS.
[0028] To each autoclave was added the base B-side formulation
shown in Table 3:
TABLE-US-00003 TABLE 3 B-side formulation B-Side Parts Wt % B
Jeffol SG-360 35.0 39.2 sucrose polyol Jeffol R-425-X 10.0 11.2
mannich polyol SF-265 20.0 22.4 triethanol amine polyol DEG 5.0 5.6
diethylene glycol Dabco 33-LV 0.5 0.6 amine catalyst Jeffcat ZR-70
0.5 0.6 amine catalyst Tegostab B 8465 2.1 2.4 siloxane based
surfactant NP 9.5 15.1 16.9 nonpehnol Added water 1.0 1.1 Total
(w/o blowing 89.2 100% agent)
[0029] Foam pre-mix formulations were then prepared by adding the
blowing agents to the B-side formulations at a loading of 25 parts
blowing agent to 75 parts B-side. One foam pre-mix formulation was
prepared with HCFO-1233zd, example 9, and another with HFO-1234ze,
comparative example 10. The foam pre-mix formulations were then
subjected to the stability test.
[0030] The GC/MS analysis of the vapor phase composition of example
9 showed no significant degradation in the HCFO-1233zd. Most
degradation byproducts were attributable to decomposition of
HFO-1234ze, which was present at about 2% of the original
HCFO-1233zd sample.
[0031] The HFO-1234ze of comparative example 10 showed more
significant decomposition as shown by the GC/MS data provided in
Table 4. The presence of the fluorinated silane products came from
evolution of HF from trans-HF0-1234ze, which in turn can react with
more HFO-1234ze to yield HFC-245a and with the siloxane-based
surfactants used in the formulation:
CF.sub.3--CH.dbd.CHF.fwdarw.CF.sub.3--C.ident.CH+HF 1)
HF+SiMe.sub.3(OsiMe.sub.2)nOSiMe.sub.3.fwdarw.SiFMe.sub.3+nSiF.sub.2Me.s-
ub.2+H.sub.2O 2)
TABLE-US-00004 TABLE 4 Vapor analysis of Comparative Example 10 GC
Area % original 1234ze After aging trans-HFO-1234ze 99.963 97.97
HFC-245fa 0 0.10 Difluorodimethyl silane 0 1.50 Fluorotrimethyl
silane 0 0.17
[0032] Example 9 and comparative example 10 show that
trans-HCFO-1233zd was ore stable than the analogous
hydrofluoroolefin trans-HFO-1234ze.
[0033] These examples show that chloro-3,3,3-trifluoropropenes,
particularly HCFO-1233zd, are unexpectedly stable during both
storage and use and at least as stable as prior HCFCs and CFCs,
especially in combination with lubricants, moisture, active metals,
polyol B-side formulations and mixtures thereof.
* * * * *