USOO8383 004B2

(12) United States Patent (10) Patent No.: US 8,383,004 B2

Mouli et al. (45) Date of Patent: *Feb. 26, 2013

(54) AMINE STABILIZERS FOR 2006, O2931.95 A1 12/2006 Howell et al.

FLUOROOLEFNS 2007/00495O2 A1 3/2007 Howell et al.
2008, 0230738 A1 9, 2008 Minor et al.
2009, 0288.431 A1 11/2009 Rao et al.
(75) Inventors: Nandini C. Mouli, Reisterstown, MD 2010.0009155 A1 1/2010 Hashii et al.
(US); Barbara Haviland Minor, Elkton, 2010. 0288965 A1 11, 2010 Howell et al.
MD (US); Mario Joseph Nappa, 2010/0288966 A1 11/2010 Lecket al.
Newark, DE (US); Thomas J. Leck, 2010/030.1259 A1 12/2010 Lecket al.
Hockessin (DE) FOREIGN PATENT DOCUMENTS
(73) Assignee: E I du Pont de Nemours and E. 9:25: A. 6.E.
Company, Wilmington, DE (US) GB 1587907 A1 4f1981
JP O4110388 A 4f1992
(*) Notice: Subject to any disclaimer, the term of this JP 2006O461 O2 A 2, 2006
patent is extended or adjusted under 35 So 395. A. 5. 2.
U.S.C. 154(b) by 481 days. WO O3.004944 A2 1, 2003
This patent is Subject to a terminal dis- WO 2005044969 A1 5, 2005
claimer WO 2005094395 A2 10, 2005
WO 2005103.187 A1 11, 2005
WO 2005103.192 A1 11, 2005
(21) Appl. No.: 12/377,485 WO 2005.119143 A2 12/2005
WO 2006069362 A2 6, 2006
(22) PCT Fled: Aug. 31, 2007 WO 2006O943O3 A2 9, 2006
WO 2006130406 A2 12/2006
(86). PCT No.: PCT/US2007/019286 WO 2007053672 A2 5, 2007
WO 2007053697 A2 5/2007
S371 (c)(1), WO 2007 126760 A2 11/2007
WO 2008/027511 A1 3, 2008
(2), (4) Date: Aug. 4, 2010 WO 2008O2.7594 A2 3, 2008
(87) PCT Pub. No.: WO2008/042066 OTHER PUBLICATIONS
PCT Pub. Date: Apr. 10, 2008 F. Jeanneaux, et al., Journal of Fluorine Chemistry, vol. 4 (Jul. 1974)
pp. 261-270, France.
(65) Prior Publication Data
C. Coudures, et al., Journal of Fluorine Chemistry, vol. 24 (1984), pp.
US 2011 FOO41530 A1 Feb. 24, 2011 93-104, France.
Viacheslave A. Petrov et al., New Partially Fluorinated Epoxides by
Related U.S. Application Data Oxidation of Olefins with Sodium Hypohalites Under Phase Transfer
Catalysis,Journal of Fluorine Chemistry, vol. 125 (2004), pp. 99-105,
(60) Provisional application No. 60/841,976, filed on Sep. Russia.
1, 2006, provisional application No. 60/841,905, filed Ming H. Hung, et al., Direct Epoxidation of Fluorinated Olefins
on Sep. 1, 2006, provisional application No. Using the F2-H20-CH3CN System, Journal of Organic Chemistry,
60/921,516, filed on Apr. 2, 2007. vol. 56 (1991), pp. 3187-3189.
1990 Ashrae Handbook, Refrigeration Systems and Applications,
Chapter 8, titled “Lubricants in Refrigeration Systems.” pp. 8.1-8.21.
(51) Int. C. International Search Report, Dec. 11, 2007.
C09K3/04 (2006.01) E. N. Step et al., Mechanism of Polymer Stabilization by Hindered
(52) U.S. Cl. ............................................ 252/68; 252/67 Amine Light Stabilizers (HALS). Model Investigations of the Inter
(58) Field of Classification Search .................... 252/67, action of Peroxy Radicals with HALS Amines and Amino Ethers,
252/68 American Chemical Society, Macromolecules, vol. 27, No. 9, 1994,
See application file for complete search history. pp. 2529-2539.
U.S. Appl. No. 12/377,454, filed Feb. 13, 2009 (National filing of
(56) References Cited PCT/US2007/019140 filed Aug. 31, 2007; see WO2008/027511).

U.S. PATENT DOCUMENTS * cited by examiner

5,895,793 A 4, 1999 Kitamura et al. Primary Examiner — John Hardee
5,932,775 A * 8/1999 Lacroix et al. ................ 57Of 122
6,066,768 A 5/2000 Nappa et al. (57) ABSTRACT
6,184, 187 B1 2/2001 Howell et al.
7,708,903 B2 * 5/2010 Sievert et al. ................... 252/68 The present invention relates to compositions comprising at
8,075,796 B2 * 12/2011 Rao et al. ... 252/67 least one fluoroolefin and an effective amount of stabilizer
8,097,181 B2 * 1/2012 Lecket al. ... 252/67
8, 101,094 B2 * 1/2012 Howell et al. ................... 252/68 that may be an amine or a mixture of an amine with other
2005, 0151.113 A1 7/2005 Minor et al. stabilizers. The stabilized compositions may be useful in
2005/0233934 A1 10/2005 Singh et al. cooling apparatus. Such as refrigeration, air-conditioning,
2006/0022166 A1 2/2006 Wilson et al. chillers, and heat pumps, as well as in applications as foam
2006, OO33072 A1 2/2006 Wilson et al. blowing agents, solvents, aerosol propellants, fire extinguis
2006/0043330 A1 3f2006 Wilson et al. ................... 252/67
2006/0243944 A1 11/2006 Minor et al. hants, and sterilants.
2006/0243945 A1 11/2006 Minor et al.
2006/0287559 A1 12, 2006 Friesen et al. 11 Claims, No Drawings
 US 8,383,004 B2
1. 2
AMINE STABILIZERS FOR Also provided is a method for reducing reaction with oxy
FLUOROOLEFNS gen for a composition comprising at least one fluoroolefin,
said method comprising adding an effective amount of stabi
BACKGROUND OF THE INVENTION lizer comprising at least one amine to the composition com
prising at least one fluoroolefin.
1. Field of the Invention DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to compositions comprising
at least one fluoroolefin and a stabilizer. The stabilized com The present invention provides a composition comprising
positions may be useful in cooling systems as replacements 10
at least one fluoroolefin and an effective amount a stabilizer
for existing refrigerants with higher global warming poten comprising at least one amine.
tial. These compositions have a variety of utilities in working
2. Description of Related Art fluids, which include use as foaming agents, blowing agents,
New environmental regulations on working fluids have fire extinguishing agents, heat transfer mediums (such as heat
forced the refrigeration and air-conditioning industry to look transfer fluids and refrigerants for use in refrigeration sys
for new working fluids with low global warming potential
15 tems, refrigerators, air conditioning systems, heat pumps,
(GWP). chillers, and the like), to name a few.
A blowing agent is a volatile composition that expands a
Replacement working fluids are being sought that have low polymer matrix to form a cellular structure.
GWP no toxicity, non-flammability, reasonable cost and A solvent is a fluid that removes a soil from a substrate, or
excellent refrigeration performance. deposits a material onto a Substrate, or carries a material.
Fluoroolefins have been proposed as working fluids alone An aerosol propellant is a volatile composition of one or
or in mixtures. However, it has been observed that fluoroole more components that exerts a pressure greater than one
fins can exhibit degradation when exposed to high tempera atmosphere to expel a material from a container.
tures or when contacted with other compounds (e.g., mois A fire extinguishant is a volatile composition that extin
ture, oxygen, or other compounds with which they may 25 guishes or Suppresses a flame.
undergo condensation reactions. This degradation may occur A sterilant is a volatile biocidal fluid or blend containing a
volatile biocidal fluid that destroys a biologically active mate
when fluoroolefins are used as working fluids in heat transfer rial or the like.
equipment (refrigeration or air-conditioning equipment, for A heat transfer medium (also referred to herein as a heat
instance) or when used in some other application. This deg 30
transfer fluid, a heat transfer composition or a heat transfer
radation may occur by any number of different mechanisms. fluid composition) is a working fluid used to carry heat from
In one instance, the degradation may be caused by instability a heat Source to a heat sink.
of the compounds at extreme temperatures. In other A refrigerant is a compound or mixture of compounds that
instances, the degradation may be caused by oxidation in the function as a heat transfer fluid in a cycle wherein the fluid
presence of air that has inadvertently leaked into the system. 35
undergoes a phase change from a liquid to a gas and back.
Whatever the cause of such degradation, because of the insta The term fluoroolefins, as used herein, describes com
bility of the fluoroolefins, it may not be practical to incorpo pounds which comprise carbon atoms, fluorine atoms, and
rate these fluoroolefins into refrigeration or air-conditioning optionally hydrogen atoms. In one embodiment, the fluo
systems. Therefore, to take advantage of the many other roolefins used in the compositions of the present invention
attributes of fluoroolefins, means to reduce the degradation is 40
comprise compounds with 2 to 12 carbon atoms. In another
needed. embodiment the fluoroolefins comprise compounds with 3 to
10 carbon atoms, and in yet another embodiment the fluo
SUMMARY OF THE INVENTION roolefins comprise compounds with 3 to 7 carbon atoms.
Representative fluoroolefins include but are not limited to all
The present disclosure provides a composition comprising 45
compounds as listed in Table 1, Table 2, and Table 3.
at least one fluoroolefinand an effective amount of a stabilizer One embodiment of the present invention provides fluo
comprising at least one amine. roolefins having the formula E- or Z RCH=CHR (For
Also provided is a method for stabilizing a composition mula I), wherein R' and R are, independently, C, to C.
comprising at least one fluoroolefin, said method comprising perfluoroalkyl groups. Examples of RandR groups include,
adding an effective amount of a stabilizer comprising at least 50
but are not limited to, CF, CFs, CFCFCF, CF (CF).
one amine. CFCFCFCF, CF(CF)CFCF, CFCF(CF), C(CF),
Also provided is a method for reducing degradation of a CFCFCFCFCF, CFCFCF (CF), C(CF)CFs,
composition comprising at least one fluoroolefin, wherein CFCFCFCFCFCF, CF(CF)CFCFCFs, and
said degradation is caused by the presence of inadvertent air C(CF). CFCFs. In one embodiment the fluoroolefins of
in a refrigeration, air-conditioning or heat pump system, said 55
Formula I have at least about 4 carbonatoms in the molecule.
method comprising adding an effective amount a stabilizer In another embodiment, the fluoroolefins of Formula I have at
comprising at least one amine to the composition comprising least about 5 carbon atoms in the molecule. Exemplary, non
at least one fluoroolefin. limiting Formula I compounds are presented in Table 1.
TABLE 1.
Code Structure Chemical Name

F11E CFCH=CHCF, 1,1,144.4-hexafluorobut-2-ene

F1 2E CFCH=CHC-Fs 1,1,144.5.5.5-octafluoropent-2-ene
F13E CFCH=CHCFCF 1,1,144,5,5,6,6,6-decafluorohex-2-ene
F13iE CFCH=CHCF(CF), 1,1,145.5.5-heptafluoro-4-(trifluoromethyl)pent-2-ene
F22E CFCH=CHC-Fs 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene
 US 8,383,004 B2
TABLE 1-continued
Code Structure Chemical Name

F414tE (CF)CFCF-CH=CH-C(CF). 1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-

tris(trifluoromethyl)hept-3-ene
F4S4SE CFCF (CF)CH=CH-CF (CF)CFs 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-
bis(trifluoromethyl)oct-4-ene
F4s4tE CFCF (CF)CH=CH-C(CF). 1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-
tris(trifluoromethyl)hept-3-ene
F4t4tE (CF). CCH=CH-C(CF). 1,1,1,6,6,6-hexafluoro-2,2,5,5-
tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a potassium hydroxide. Said contacting of the trihydroiodop
perfluoroalkyl iodide of the formula R'I with a perfluoroalky erfluoroalkane with a basic Substance may take place in the
ltrihydroolefin of the formula RCH=CH to form a trihy 15 liquid phase preferably in the presence of a solvent capable of
droiodoperfluoroalkane of the formula R'CHCHIR. This dissolving at least a portion of both reactants. Solvents Suit
trihydroiodoperfluoroalkane can then be dehydroiodinated to able for the dehydroiodination step include one or more polar
form RCH=CHR. Alternatively, the olefin RCH=CHR organic solvents such as alcohols (e.g., methanol, ethanol,
may be prepared by dehydroiodination of a trihydroiodoper n-propanol, isopropanol, n-butanol, isobutanol, and tertiary
fluoroalkane of the formula RCHICHR formed in turn by butanol), nitriles (e.g., acetonitrile, propionitrile, butyroni
reacting a perfluoroalkyl iodide of the formula RI with a trile, benzonitrile, or adiponitrile), dimethylsulfoxide, N.N-
perfluoroalkyltrihydroolefin of the formula R'CH=CH2. dimethylformamide, N,N-dimethylacetamide, or sulfolane.
The contacting of a perfluoroalkyl iodide with a perfluo The choice of solvent may depend on the boiling point prod
roalkyltrihydroolefin may take place in batch mode by com 25 uct and the ease of separation of traces of the solvent from the
bining the reactants in a suitable reaction vessel capable of product during purification. Typically, ethanol or isopropanol
operating under the autogenous pressure of the reactants and are good solvents for the reaction.
products at reaction temperature. Suitable reaction vessels Typically, the dehydroiodination reaction may be carried
include fabricated from stainless steels, in particular of the out by addition of one of the reactants (either the basic sub
austenitic type, and the well-known high nickel alloys such as 30 stance or the trihydroiodoperfluoroalkane) to the other reac
Monel(R) nickel-copper alloys, Hastelloy(R) nickel based tant in a suitable reaction vessel. Said reaction may be fabri
alloys and Inconel(R) nickel-chromium alloys. cated from glass, ceramic, or metal and is preferably agitated
Alternatively, the reaction may take be conducted in semi with an impeller or stirring mechanism.
batch mode in which the perfluoroalkyltrihydroolefin reac Temperatures suitable for the dehydroiodination reaction
tant is added to the perfluoroalkyl iodide reactant by means of 35 are from about 10° C. to about 100° C., preferably from about
a suitable addition apparatus Such as a pump at the reaction 20° C. to about 70°C. The dehydroiodination reaction may be
temperature. carried out at ambient pressure or at reduced or elevated
The ratio of perfluoroalkyl iodide to perfluoroalkyltrihy pressure. Of note are dehydroiodination reactions in which
droolefin should be between about 1:1 to about 4:1, prefer the compound of Formula I is distilled out of the reaction
ably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to 40 vessel as it is formed.
result in large amounts of the 2:1 adduct as reported by Alternatively, the dehydroiodination reaction may be con
Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4. ducted by contacting an aqueous solution of said basic Sub
pages 261-270 (1974). stance with a solution of the trihydroiodoperfluoroalkane in
Preferred temperatures for contacting of said perfluoro one or more organic solvents of lower polarity Such as an
alkyl iodide with said perfluoroalkyltrihydroolefin are pref 45 alkane (e.g., hexane, heptane, or octane), aromatic hydrocar
erably within therange of about 150° C. to 300° C., preferably bon (e.g., toluene), halogenated hydrocarbon (e.g., methyl
from about 170° C. to about 250° C., and most preferably ene chloride, chloroform, carbon tetrachloride, or perchloro
from about 180° C. to about 230° C. ethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether,
Suitable contact times for the reaction of the perfluoroalkyl tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane,
iodide with the perfluoroalkyltrihydroolefin are from about 50 dimethoxyethane, diglyme, or tetraglyme) in the presence of
0.5 hour to 18 hours, preferably from about 4 to about 12 a phase transfer catalyst. Suitable phase transfer catalysts
hours. include quaternary ammonium halides (e.g., tetrabutylam
The trihydroiodoperfluoroalkane prepared by reaction of monium bromide, tetrabutylammonium hydrosulfate, trieth
the perfluoroalkyl iodide with the perfluoroalkyltrihydroole ylbenzylammonium chloride, dodecyltrimethylammonium
fin may be used directly in the dehydroiodination step or may 55 chloride, and tricaprylylmethylammonium chloride), quater
preferably be recovered and purified by distillation prior to nary phosphonium halides (e.g., triphenylmethylphospho
the dehydroiodination step. nium bromide and tetraphenylphosphonium chloride), or
The dehydroiodination step is carried out by contacting the cyclic polyether compounds known in the art as crown ethers
trihydroiodoperfluoroalkane with a basic substance. Suitable (e.g., 18-crown-6 and 15-crown-5).
basic Substances include alkali metal hydroxides (e.g., 60 Alternatively, the dehydroiodination reaction may be con
Sodium hydroxide or potassium hydroxide), alkali metal ducted in the absence of solvent by adding the trihydroiodop
oxide (for example, Sodium oxide), alkaline earth metal erfluoroalkane to a solid or liquid basic Substance.
hydroxides (e.g., calcium hydroxide), alkaline earth metal Suitable reaction times for the dehydroiodination reactions
oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., are from about 15 minutes to about six hours or more depend
Sodium methoxide or Sodium ethoxide), aqueous ammonia, 65 ing on the solubility of the reactants. Typically the dehydroio
Sodium amide, or mixtures of basic Substances such as Soda dination reaction is rapid and requires about 30 minutes to
lime. Preferred basic substances are sodium hydroxide and about three hours for completion. The compound of Formula
 US 8,383,004 B2
13 14
1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehy In one embodiment, the amine stabilizers comprise at least
drofluorination of 1,1,1,2,3,3,4-heptafluorobutane one compound selected from the group consisting of triethy
(CHFCFCHFCF) using solid KOH. lamine, tributylamine, diisopropylamine, triisopropylamine,
1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehy triisobutylamine, p-phenylenediamine, and diphenylamine.
drofluorination of 1,1,1,2,2,4,4-heptafluorobutane In another embodiment, the amine Stabilizers comprise
(CHFCHCFCF) using solid KOH. dialkylamines including (N-(1-methylethyl)-2-propylamine,
1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehy CAS reg. no. 108-18-9). In another embodiment the amine
drofluorination of 1,1,1,3,3,4,4-heptafluorobutane stabilizers include hindered amine antioxidants. Hindered
amine antioxidants include amines derived from Substituted
(CFCHCFCHF) using solid KOH. 10 piperidine compounds, in particular derivatives of an alkyl
1,1,1,2,4-pentafluoro-2-butene may be prepared by dehy Substituted piperidyl, piperidinyl, piperazinone, or alkoxypi
drofluorination of 1,1,1,2,2,3-hexafluorobutane peridinyl compounds. Representative hindered amine anti
(CHFCHCFCF) using solid KOH. oxidants include 2.2.6.6-tetramethyl-4-piperidone; 2.2.6.6-
1,1,1,3,4-pentafluoro-2-butene may be prepared by dehy tetramethyl-4-piperidinol: bis-(1.2.2.6.6-
drofluorination of 1,1,1,3,3,4-hexafluorobutane 15 pentamethylpiperidyl)sebacate (CAS reg. no. 41556-26-7);
(CFCHCFCHF) using solid KOH. di-(2.2.6.6-tetramethyl-4-piperidyl)sebacate, such as the hin
1,1,1,3-tetrafluoro-2-butene may be prepared by reacting dered amine commercially available under the trademark
1,1,1,3,3-pentafluorobutane (CFCHCFCH) with aqueous Tinuvin R. 770 by Ciba; poly-(N-hydroxyethyl-2.2.6,6-tet
KOH at 120° C. ramethyl-4-hydroxy-piperidyl Succinate (CAS reg. no.
1.1.1.4.4.5.5.5-octafluoro-2-pentene may be prepared 65447-77-0), such as that commercially available under the
from (CFCHICHCFCF) by reaction with KOH using a trademark Tinuvin R. 622LD from Ciba; alkylated paraphe
phase transfer catalyst at about 60° C. The synthesis of nylenediamines, such as N-phenyl-N'-(1,3-dimethylbutyl)-p-
4-iodo-1.1.1.2.2.5.5.5-octafluoropentane may be carried out phenylenediamine, or N,N'-di-sec-butyl-p-phenylenedi
by reaction of perfluoroethyliodide (CFCFI) and 3,3,3-tri amine; and hydroxylamines such as tallow amines or
fluoropropeneatabout 200° C. under autogenous pressure for 25 N-methylbis(hydrogenated tallow alkyl)amine. Some other
about 8 hours. hindered amine antioxidants include the amine antioxidant
1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared commercially available from Ciba under the trademark Tinu
from 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane vin R. 765, or commercially available from MayZo, Inc. under
(CFCFCHICHCFCF) by reaction with KOH using a the trademark BLS(R) 1944 and BLS(R) 1770. The amines also
phase transfer catalyst at about 60° C. The synthesis of 1,1, 30 include mixtures of any of the amines listed in this paragraph.
1.2.2.5.5,6,6,6-decafluoro-3-iodohexane may be carried out In another embodiment, the present invention further com
by reaction of perfluoroethyliodide (CFCFI) and 3.3.4.4.4- prises at least one additional stabilizer selected from the
pentafluoro-1-butene (CFCF-CH=CH-) at about 200° C. group consisting of phenols, thiophosphates, butylated triph
under autogenous pressure for about 8 hours. enylphosphorothionates, organo phosphates, phosphites, ter
1,1,1,4,5,5.5-heptafluoro-4-(trifluoromethyl)-2-pentene 35 penes, terpenoids, fullerenes, functionalized perfluoropoly
may be prepared by the dehydrofluorination of 1,1,1,2,5,5.5- ethers, polyoxyalkylated aromatics, alkylated aromatics,
heptafluoro-4-iodo-2-(trifluoromethyl)-pentane epoxides, fluorinated epoxides, oxetanes, ascorbic acid, thi
(CFCHICHCF(CF)) with KOH in isopropanol. ols, lactones, thioethers, nitromethane, alkylsilanes, ben
CFCHICHCF (CF) is made from reaction of (CF)CFI Zophenone derivatives, aryl sulfides, divinyl terephthalate,
with CFCH=CH at high temperature, such as about 200° 40 and diphenyl terephthalate, and mixtures thereof, meaning
C. mixtures of any of the stabilizers listed in this paragraph, and
1.1.1.4.4.5.5.6,6,6-decafluoro-2-hexene may be prepared in addition, mixtures of any stabilizer or combination of sta
by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene bilizers listed in this paragraph with any of the stabilizers or
(CFCH=CHCF) with tetrafluoroethylene (CF–CF) and combination of the amine stabilizers described above.
antimony pentafluoride (SbF). 45 In one embodiment, the additional stabilizers may com
2,3,3,4,4-pentafluoro-1-butene may be prepared by dehy prise at least one phenol. Phenol stabilizers are any substi
drofluorination of 1,1,2,2,3,3-hexafluorobutane over fluo tuted or unsubstituted phenol compounds including phenols
rided alumina at elevated temperature. comprising one or more substituted or unsubstituted cyclic,
2.3.3.4.4.5.5.5-octafluoro-1-pentene may be prepared by straight chain, or branched aliphatic Substituent group. Such
dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane 50 as, alkylated monophenols including 2,6-di-tert-butyl-4-me
over Solid KOH. thylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-
1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared by tertbutylphenol; tocopherol; and the like, hydroquinone and
dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane alkylated hydroquinones including t-butyl hydroquinone,
over fluorided alumina at elevated temperature. other derivatives of hydroquinone; and the like, hydroxylated
Many of the compounds of Formula I, Formula II, Table 1, 55 thiodiphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert
Table 2 and Table 3 exist as different configurational isomers butylphenol): 4,4'-thiobis(3-methyl-6-tertbutylphenol); 2,2'-
or stereoisomers. When the specific isomer is not designated, thiobis(4-methyl-6-tert-butylphenol); and the like, alky
the present invention is intended to include all single configu lidene-bisphenols including: 4,4'-methylenebis(2,6-di-tert
rational isomers, single Stereoisomers, or any combination butylphenol): 4,4'-bis(2,6-di-tert-butylphenol); derivatives of
thereof. For instance, F11E is meant to represent the E-iso 60 2,2'- or 4.4-biphenoldiols; 2,2'-methylenebis(4-ethyl-6-tert
mer, Z-isomer, or any combination or mixture of both isomers butylphenol); 2.2'-methylenebis(4-methyl-6-tertbutylphe
in any ratio. As another example, HFC-1225ye is meant to nol): 4,4-butylidenebis(3-methyl-6-tert-butylphenol); 4.4-
represent the E-isomer, Z-isomer, or any combination or mix isopropylidenebis(2,6-di-tert-butylphenol): 2,2'-
ture of both isomers in any ratio. methylenebis(4-methyl-6-nonylphenol); 2,2'-
In one embodiment, the present invention provides com 65 isobutylidenebis(4,6-dimethylphenol; 2.2'-methylenebis(4-
positions comprising at least one fluoroolefin and an effective methyl-6-cyclohexylphenol, 2.2- or 4.4-biphenyldiols
amount of a stabilizer comprising at least one amine. including 2,2'-methylenebis(4-ethyl-6-tert-butylphenol):
 US 8,383,004 B2
15 16
butylated hydroxytoluene (BHT), bisphenols comprising het West Lafayette, Ind.) under the trademark DuradR 620; and
eroatoms including 2,6-di-tert-alpha-dimethylamino-p- iso-propylated triphenyl phosphates, also commercially
cresol, 4,4-thiobis(6-tert-butyl-m-cresol); and the like; acy available from GLCC under the trademarks DuradR 220 and
laminophenols; 2,6-di-tert-butyl-4(N,N'- 110.
dimethylaminomethylphenol); sulfides including; bis(3- In another embodiment, the additional stabilizers may
methyl-4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di comprise at least one phosphite. Phosphite stabilizers may be
tert-butyl-4-hydroxybenzyl)sulfide; and the like. derived from substituted phosphites. In particular, hindered
In another embodiment, the additional stabilizers may phosphites are derivatives of alkyl, aryl or alkylaryl phosphite
comprise at least one thiophosphate. The thiophosphate sta compounds. Tris-(di-tert-butylphenyl)phosphite is sold
bilizers of the present invention are compounds derived from 10 under the trademark Irgafos(R 168, di-n-octyl phosphite is
phosphoric acids by substituting divalent sulfur for one or sold under the trademark Irgafos(ROPH, and iso-decyl diphe
more oxygen atoms. These may be monothiophosphates, nylphosphite) is sold under the trademark Irgafos(R DDPP, all
dithiophosphates or higher order. A representative dithio by Ciba.
phosphate is commercially available from Ciba Specialty In another embodiment, the additional stabilizers may
Chemicals of Basel, Switzerland (hereinafter “Ciba') under 15 comprise at least one terpene. Terpenes are hydrocarbon com
the trademark Irgalube(R) 63. In another embodiment, thio pounds characterized by structures containing more than one
phosphates include dialkylthiophosphate esters. A represen repeating isoprene (2-methyl-1,3-butadiene) unit. Terpenes
tative dialkylthiophosphate ester stabilizer is commercially may be acyclic or cyclic. Representative terpenes include but
available from Ciba under the trademark Irgalube.R. 353. are not limited to myrcene (2-methyl-6-methyl-eneocta-1,7-
In another embodiment, the additional stabilizers of the diene), allo-cimene, beta-ocimene, terebene, limonene (par
present invention comprise at least one butylated triph ticularly d-limonene), retinal, pinene, menthol, geraniol, far
enylphosphorothionate as depicted by Formula A. neSol, phytol, Vitamin A, terpinene, delta-3-carene,
terpinolene, phellandrene, fenchene, dipentene, and mixtures
thereof. Terpene stabilizers are commercially available or
Formula A 25 may be prepared by methods known in the art or isolated from
natural sources.
In another embodiment, the additional stabilizers may
comprise at least one terpenoid. Terpenoids are natural prod
ucts and related compounds characterized by structures con
30 taining more than one repeating isoprene unit and optionally
A butylated triphenylphosphorothionate, wherein each R is contain oxygen. Representative terpenoids include caro
independently selected from Hortert-butyl, is commercially tenoids, such as lycopene (CAS reg. no. 502-65-8), betac
available from Ciba under the trademark Irgalube.R. 232. arotene (CAS reg. no. 7235-40-7), and xanthophylls, i.e.
In another embodiment, the additional stabilizers may Zeaxanthin (CAS reg. no. 144-68-3); retinoids. Such as hep
comprise at least one organophosphate. The organophosphate 35 axanthin (CAS reg. no. 512-39-0), and isotretinoin (CAS
stabilizers include but are not limited to amine phosphates, reg. no. 4759-48-2); abietane (CAS reg. no. 640-43-7);
trialkyl phosphates, triaryl phosphates, mixed alkyl-aryl ambrosane (CAS reg. no. 24749-18-6); aristolane (CAS
phosphates (alkyldiaryl, dialkylaryl or alkylated aryl), and reg. no. 29788-49-6); atisane (CAS reg. no. 24379-83-7);
cyclic phosphates. A representative amine phosphate is com beyerane (CAS reg. no. 2359-83-3), bisabolane (CAS reg.
mercially available from Ciba under the trademark Irgalube(R) 40 no. 29799-19-7); bornane (CAS reg. no. 464-15-3); caryo
349. Representative trialkyl phosphates include: trimethyl phyllane (CAS reg. no. 20479-00-9); cedrane (CAS reg. no.
phosphate ((CH),PO Cas reg. no. 512-56-1); triethyl phos 13567-54-9); dammarane (CAS reg. no. 545-22-2); dri
phate ((CHCH-)PO, Cas reg. no. 78-40-0); tributyl phos mane (CAS reg. no. 5951-58-6); eremophilane (CAS reg.
phate ((CH3)PO, CAS reg. no. 126-73-8); trioctyl phos no.3242-05-5); eudesmane (CAS reg. no. 473-11-0); fen
phate ((CH2)PO CAS reg. no. 1806-54-8); and tri(2- 45 chane (CAS reg. no. 6248-88-0); gammacerane (CAS reg.
ethylhexyl)phosphate ((CH3CH(CHs)(CH)). PO, CAS no. 559-65-9); germacrane (CAS reg. no. 645-10-3); gib
reg. no. 78-42-2). Representative triaryl phosphates include: bane (CAS reg. no. 6902-95-0); grayanotoxane (CAS reg.
triphenyl phosphate ((CHO). PO, CAS reg. no. 115-86-6): no. 39907-73-8); guaiane (CAS reg. no. 489-80-5); him
tricresyl phosphate (TCP (CHCHO)PO, CAS reg. no. achalane (CAS reg. no. 20479-45-2); hopane (CAS reg. no.
1330-78-5); and trixylenyl phosphate (((CH)CHO)PO, 50 471-62-5); humulane (CAS reg. no. 430-19-3); kaurane
CAS reg. no. 25155-23-1). Representative mixed alkyl-aryl (CAS reg. no. 1573-40-6); labdane (CAS reg. no. 561-90
phosphates include: isopropylphenyl phenyl phosphate O); lanostane (CAS reg. no. 474-20-4); lupane (CAS reg.
(IPPP (CHO), ((CH)CHO)PO, CAS reg. no. 68782-95 no. 464-99-3); p-menthane (CAS reg. no. 99-82-1); ole
6) and bis(t-butylphenyl)phenylphosphate (TBPP (CHO), anane (CAS reg. no. 471-67-0); ophiobolane (CAS reg. no.
((CH),C)PO, CAS reg. no. 65652-41-7). Such phosphorus 55 20098-65-1); picrasane (CAS reg. no.35732-97-9); pima
compounds. All of the organophosphate stabilizers listed in rane (CAS reg. no. 30257-03-5); pinane (CAS reg. no.
this paragraph are available from multiple chemical Suppliers 473-55-2); podocarpane (CAS reg. no. 471-78-3); protos
such as Aldrich (Milwaukee, Wis.); Alfa Aesar (Ward Hill, tane (CAS reg. no. 70050-78-1); rosane (CAS reg. no.
Mass.); or Akzo Nobel (Arnhem, the Netherlands). The alky 6812-82-4I); taxane (CAS reg. no. 1605-68-1); thujane
lated triaryl phosphates include butylated triphenyl phos 60 (CAS reg. no. 471-12-5); trichothecane (CAS reg. no.
phates, tert-butylated triphenyl phosphate, iso-propylated 24706-08-9); and ursane (CAS reg. no. 464-93-7). The
triphenyl phosphates. Representative commercially available terpenoids of the present invention are commercially avail
alkylated triaryl phosphates include a butylated triphenyl able or may be prepared by methods known in the art or may
phosphate, commercially available from Akzo Nobel (Arn be isolated from the naturally occurring Source.
hem, the Netherlands) under the trademark Syn-O-AdR 65 In another embodiment, the additional stabilizers may
8784; a tert-butylated triphenyl phosphate commercially comprise at least one fullerene. Fullerenes are closed carbon
available from Great Lakes Chemical Corporation (GLCC, cages that are bonded as hexagonal carbon rings (benzene)
 US 8,383,004 B2
17 18
linked to each other partly via pentagons. The relationship c and dare numbers such that the ratio of c.d ranges from
between the number of apices (a, carbonatoms) and hexagon about 0.01 to about 0.5;
carbon rings (n) (pentagon rings always number 12) is given X is F, CF, or combinations thereof;
by: a 20n+10). While this formula provides for all theoretical Z is F. Clor CF;
structures, only those molecules with relatively low stress and J" is a fluoroalkyl group selected from the group consisting
distortion will be stable. Representative fullerenes include of CF, CFs, CF, CFC1, CFC1, and combinations of two
but are not limited to Buckminsterfullerene (C60, or “bucky or more thereof;
ball, CAS reg. no. 99685-96-8), and 5.6 fullerene-Co e and fare numbers such that the ratio of eff ranges from
(C70, CAS reg. no. 115383-22-7), fullerene-C7 (CAS reg. about 0.3 to about 5:
10
no. 135113-15-4), fullerene-Cs (CAS reg. no. 136316-32 Z' is For Cl;
O), and fullerene-Cs (CAS reg. no. 135113-16-5). J is CF, CF, or combinations thereof;
In another embodiment, the additional stabilizers may j is an average number such that the formula weight of R,
comprise at least one aryl alkyl ether. The aryl alkyl ether ranges from about 400 to about 15,000;
stabilizers of the present invention may be depicted by For J is selected from the group consisting of CF, CFs, CF,
mula B, whereinn is 1, 2 or 3 and R' is an alkyl group of 1 to 15
and combinations of two or more thereof;
16 carbon atoms.
k is an average number such that the formula weight of R,
ranges from about 400 to about 15,000;
Formula B each Q is independently F, Cl, or H:
N g, handi are numbers such that (g+h) ranges from about 1
21
H(OR), to about 50, the ratio of i:(g+h) ranges from about 0.1 to about
0.5;
J" is CF, CFs, or combinations thereof;
r is an average number such that the formula weight of R,
Representative aryl alkyl ethers include but are not limited to 25 ranges from about 400 to about 15,000; and
anisole, 1,4-dimethoxybenzene, 1,4-diethoxybenzene and each RandR' is independently H, a C-Clo alkyl, a halo
1,3,5-trimethoxybenzene. gen, OR, OH, SOM, NR, ROH, RSOM, RNR,
In another embodiment, the additional stabilizers may RNO, RCN, C(O)OR, C(O)CM, C(O)R, or C(O)NR,
comprise at least one functionalized perfluoropolyether. Such or combinations of two or more thereof;
functionalized perfluoropolyethers may be perfluoropoly 30 wherein
ether- or perfluoroalkyl-containing and phosphorus-contain R’ is independently H, C, -Co alkyl, or combinations of
ing partially esterified aryl phosphates, aryl phosphonates two or more thereof;
and salts thereof, containing either (i) a mono- or poly-alky R is a C-Clo alkyl; and
lene oxide linking group between the phosphorus and a fluo M is hydrogen or a metal, preferably not aluminum;
rocarbon group, or (ii) no linking group between the phos 35 t is equal to (6+u);
phorus and fluorocarbon group as described in U.S. Pat. No. u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;
6,184,187, and references therein. V is independently either 2 or 4:
In another embodiment, the functionalized perfluoropoly n is 0 or 1;
ether stabilizers may be compounds as represented by For E is P. As, or Sb; and
mula Babove, which contain either a perfluoroalkyl or per 40 m is greater than about 0.5 to about 3, provided that, when
fluoropolyether side chain. Further, the functionalized E=P, m-3.0 and t=6, R cannot be exclusively H or contain F;
perfluoropolyether stabilizers may be perfluoropolyether as described in U.S. patent application Ser. No. 1 1/167,330,
alkyl alcohols comprising a perfluoropolyether segment and filed Jun. 27, 2006.
one or more alcohols segments having a general formula, In another embodiment, the functionalized perfluoropoly
—CH2(CH2)OH, wherein CH2 represents a divalent lin 45 ether stabilizers of the present invention may comprise aryl
ear or branched alkyl radical where q is an integer from 1 to perfluoropolyethers, which are monofunctional aryl perfluo
about 10 as described in U.S. patent application Ser. No. ropolyethers having the formula of R (Y), (CR)—
11/156,348, filed Jun. 17, 2005. (O—CR') R, difunctional aryl perfluoropolyethers
In another embodiment, the functionalized perfluoropoly having the formula of R,-(Y), (CR)-(O—
ether stabilizers of the present invention may comprise sub 50 C.R (4) R2, or combinations thereof, wherein
stituted aryl pnictogen compositions having the structure each of R, and R has a formula weight of about 400 to
IR,-(CR).E(O),(CR' (1)3-), wherein R, is a about 15,000;
fluoropolyether chain having a formula weight ranging from R, comprises repeat units selected from the group consist
about 400 to about 15,000, comprises repeat units, and is ing of
selected from the group consisting of: 55 (a) J-O-(CF(CF)CFO) (CFXO)ACFZ ,
(a) J-O-(CF(CF)CFO) (CFXO) CFZ : (b) J-O-(CFCFO).(CFO),CFZ"—,
(b) J-O-(CFCFO).(CFO),CFZ"—; (c) J-O-(CF(CFs)CFO),CF(CF,)—,
(c) J-O-(CF(CFs)CFO),CF(CFs)CF, ; (d) J-O-(CQ-CFCF (O), CQ.-,
(d) J-O-(CQ-CFCF (O), CQ-CF : (e) J-O-(CF(CFs)CFO) (CFCFO),(CFX-O),
(e) J-O-(CF(CFs)CFO) (CFCFO),(CFXO), 60 CFZ ,
CFZ ; (f) J-O-(CFCFO), CF, , and
(f) J-O-(CFCFO),CF ; and (g) combinations of two or more thereof, and
(h) combinations of two or more thereof where
wherein the units with formulae CFCFO and CFO are randomly
J is a fluoroalkyl group selected from the group consisting 65 distributed along the chain;
of CF, CFs, CF, CFC1, CFC1, CFC1, and combina J is CF, CFs CF, CFC1, CFC1, CFC1, or combi
tions of two or more thereof; nations of two or more thereof;
 US 8,383,004 B2
19 20
c and d are numbers such that the c/d ratio ranges from In another embodiment, the additional stabilizer may com
about 0.01 to about 0.5; prise at least one polyoxyalkylated aromatic. The polyoxy
X is —F. —CF, or combinations thereof; alkylated aromatics are compounds represented by Formula
Z is —F. —Cl or CF; B wherein the R' group is a polyoxyalkylated group compris
Z' is - F or - C1, ing at least one —CHCHO— moiety. In another embodi
J" is CF, CFs, CF, CFC1, C.F.C1, or combinations of ment, the additional stabilizers may comprise at least one
two or more thereof; alkylated aromatic compound. Representative alkylated aro
e and fare numbers such that the e/fratio ranges from about matics which can be used as additional stabilizers according
0.3 to about 5: to the present invention include but are not limited to alkyl
J is —C.F.s. -CF, or combinations thereof; 10
benzene lubricants, both branched and linear, commercially
j is an average number such that the formula weight of R, available under the trademarks Zerol(R) 75, Zerol (R) 150 and
ranges from about 400 to about 15,000; Zerol R (linear alkylbenzenes) 500 from Shrieve Chemicals
J is CF, CFs, CF7, or combinations of two or more and HAB 22 (branched alkylbenzene) sold by Nippon Oil.
thereof In another embodiment, the additional stabilizers may
k is an average number such that the formula weight of R, 15 comprise at least one epoxide. Epoxides include 1,2-propy
ranges from about 400 to about 15,000; lene oxide (CAS reg. no. 75-56-9), 1.2-butylene oxide
each Q is independently —F. —Cl, or—H; (CAS reg. no. 106-88-7), butylphenylglycidyl ether, pen
g, handi are numbers such that (g+h) ranges from about 1 tylphenylglycidyl ether, hexylphenylglycidyl ether, hep
to about 50, the i/(g+h) ratio ranges from about 0.1 to about tylphenylglycidyl ether, octylphenylglycidyl ether, non
0.5; ylphenylglycidyl ether, decylphenylglycidyl ether, glycidyl
J" is CF, CFs, or combinations thereof; methylphenylether, 1,4-glycidyl phenyl diether, 4-methox
k is an average number such that the formula weight of R, yphenylglycidyl ether, naphthyl glycidyl ether, 1,4-digly
ranges from about 400 to about 15,000; cidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl
each R is independently —H, a halogen, —OH, -SOM, glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl
NR, NO, ROH, RSOM, RNR - RNO, 25 ether, allyl glycidyl ether, polypropylene glycol diglycidyl
RCN, C(O)OR, C(O)CM, C(O)R, C(O) ether, and mixtures thereof.
NR, or combinations of two or more thereof; except that In another embodiment, the additional stabilizers may
when b=0, R cannot be four hydrogen atoms and —OH, or comprise at least one fluorinated epoxide. The fluorinated
—Br, or —NH; or R cannot be solely H or —NO, or epoxide stabilizers of the present invention may be depicted
combinations thereof 30
by Formula C, wherein each of R through R is H, alkyl of 1
each R" is independently H, -R, OR, a halogen, to 6 carbon atoms or fluoroalkyl of 1 to 6 carbon atoms with
OH, -SOM, NR, NO, CN, ROH, the proviso that at least one of R through R is a fluoroalkyl
RSOM, RNR - RNO, RCN, C(O)OR, group.
—C(O)CM, C(O)R, C(O)NR, or combinations of two
or more thereofprovided that ifb=0, the combination of Rand 35
R cannot be four or more hydrogenatoms and -OH,-Br, Formula C
—NH, or—NO;
each R is independently H, C, -Cio alkyl, or combinations
of two or more thereof; SA R4
R is a C-C alkyl: 40
M is a hydrogen or metal ion;
a is 0 or 1; Representative fluorinated epoxide stabilizers include but are
b is 0-5; not limited to trifluoromethyloxirane and 1,1-bis(trifluorom
Y is a divalent radical —CHOCH2—, —(CH2). O—, ethyl)oxirane. Such compounds may be prepared by methods
—(CF), , —CFO—, —CFOCF, , —C(O)—, 45
known in the art, for instance by methods described in, Jour
—C(S) , or combinations of two or more thereof; nal of Fluorine Chemistry, volume 24, pages 93-104 (1984),
n is about 1 to about 5; Journal of Organic Chemistry, volume 56, pages 3.187 to
o is about 2 to about 5; 3189 (1991), and Journal of Fluorine Chemistry, volume
t is equal to 6+u; 125, pages 99-105 (2004).
u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16; 50
In another embodiment, the additional stabilizers may
V is independently either 2 or 4: comprise at least one oxetane. The oxetane stabilizers of the
Rf is (CFCFO) (CFO),CF, , —(CFO), present invention may be a compound with one or more
(CFCFO),(CFXO), CF, , oxetane groups and is represented by Formula D, wherein
—(CFCFO)(CFO)CF(CF) , CF(CF)O R1-R6 are the same or different and can be selected from
(CFO), Rf-O(CFO), CF(CF) , 55
hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.
—((CQ)CFCFO)CFCF, , or combinations oftwo or
more thereof;
where Formula D
e, f, X, and Q are as defined above:
p, q and rare numbers such that (p+q) ranges from 1 to 50 60
and r?(p+q) ranges from 0.1 to 0.05;
each w is independently 2 to 45:
Rf is linear or branched —CF :
m is 1-10; and
S is an average number Such that the formula weight of R 65 Representative oxetane stabilizers include but are not limited
ranges from 400 to 15,000, as described in U.S. patent appli to 3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toa
cation Ser. No. 1 1/218.259, filed Sep. 1, 2005. gosei Co., Ltd): 3-ethyl-3-(phenoxy)methyl)-oxetane, Such
 US 8,383,004 B2
21 22
as OXT-211 (Toagosei Co., Ltd); and 3-ethyl-3-((2-ethyl fluorobenzophenone; 2-amino-5-nitrobenzophenone;
hexyloxy)methyl)-oxetane, such as OXT-212 (Toagosei Co., 2-amino-5-nitro-2'-chlorobenzophenone; 2-amino-2,5-
Ltd). dichlorobenzophenone: 2-chloro-4'-fluorobenzophenone;
In another embodiment, the additional stabilizers may 2-hydroxy-4-methoxybenzophenone; 2-hydroxy-5-chlo
comprise ascorbic acid (CAS reg. no. 50-81-7). robenzophenone, 2-methylamino-5-chlorobenzophenone;
In another embodiment, the additional stabilizers may 3-methylbenzophenone; 3-nitrobenzophenone; 3-nitro-4'-
comprise at least one thiol, also known as mercaptain or chloro-4-fluorobenzophenone; 4-chlorobenzophenone;
hydrosulfide. Such thiol compounds are the sulfur analogs of 4-fluorobenzophenone: 4-hydroxybenzophenone: 4-meth
the hydroxyl group containing alcohols. Representative thiol oxybenzophenone, 4-methylbenzophenone: 4-nitroben
stabilizers include but are not limited to methanethiol (methyl 10 Zophenone: 4-phenylbenzophenone: 4-chloro-3-nitroben
mercaptan), ethanethiol (ethyl mercaptan), Coenzyme A Zophenone; 4-hydroxy-4'-chlorobenzophenone; 2,4-
(CAS reg. no. 85-61-0), dimercaptosuccinic acid (DMSA, dihydroxybenzophenone; 2,4-dimethylbenzophenone; 2.5-
CAS reg. no. 2418-14-6), grapefruit mercaptan ((R)-2-(4- dimethylbenzophenone; 3,4-diaminobenzophenone; 3,4-
methylcyclohex-3-enyl)propane-2-thiol, CAS reg. no. dichlorobenzophenone; 3,4-difluorobenzophenone; 3,4-
83150-78-1), cysteine ((R)-2-amino-3-sulfanyl-propanoic 15 dihydroxybenzophenone; 3,4-dimethylbenzophenone; 4,4'-
acid, CAS reg. no. 52-90-4), and lipoamide (1,2-dithiolane bis(diethylamine)benzophenone; 4,4'-bis(dimethylamine)
3-pentanamide, CAS reg. no. 940-69-2. benzophenone; 4,4'-dichlorobenzophenone; 4,4'-
In another embodiment, the additional stabilizers may difluorobenzophenone; 4,4'-dihydroxybenzophenone; and
comprise at least one lactone. Lactones are cyclic esters that 4,4'-dimethoxybenzophenone.
may be produced by the reaction of an alcohol group with a In another embodiment, the additional stabilizers may
carboxylic acid group in the same molecule. Representative comprise at least one arylsulfide. The aryl sulfide stabilizers
lactone stabilizers of the present invention include but are not comprise at least one selected from the group consisting of
limited to gamma-butyrolactone (CAS reg. no. 96-48-0), benzyl phenyl sulfide, diphenyl sulfide, and dibenzylsulfide.
delta-gluconolactone (CAS reg. no. 90-80-2), gamma-un In another embodiment, the additional stabilizers may
decalactone (CAS reg. no. 104-67-6), 6,7-dihydro-4(5H)- 25 comprise at least one terephthalate. The terephthalate stabi
benzofuranone (CAS reg. No. 16806-93-2), and 5.7-bis(1, lizers include divinyl terephthalate (CAS reg. no. 13486-19
1-dimethylethyl)-3-2.3 (or 3,4)-dimethylphenyl-2(3H)- O) and diphenyl terephthalate (CAS reg. no. 1539-04-4).
benzofuranone (CAS reg. no 201815-03-4) commercially Unless otherwise noted above, the stabilizers of the present
available from Ciba under the trademark Irganox(R) HP-136, invention are commercially available from various chemical
and mixtures thereof, meaning mixtures of any of the lactones 30 Supply houses.
listed in this paragraph. Single stabilizer compounds may be used in combination
In another embodiment, the additional stabilizers may in the present compositions comprising at least one fluoroole
comprise at least one thioether. Thioether stabilizers of the fin or multiple stabilizer compounds may be combined in any
present invention include but are not limited to benzyl phenyl proportion to serve as a stabilizer blend. The stabilizer blend
sulfide (CAS reg. no. 831-91-4), diphenyl sulfide (CAS reg. 35 may contain multiple stabilizer compounds from the same
no. 139-66-2), dioctadecyl 3,3'-thiodipropionate, commer class of compounds or multiple stabilizer compounds from
cially available from Ciba under the trademark IrganoxRPS different classes of compounds. For example, a stabilizer
802 (Ciba) and didodecyl 3,3'-thiopropionate, commercially blend may contain2 or more amine Stabilizers, or one or more
available from Ciba under the trademark Irganox R, PS 800 amine stabilizers in combination with one or more additional
(Ciba), and mixtures thereof, meaning mixtures of any of the 40 stabilizers (e.g. phenols, terpenes or lactones, for instance).
thioethers listed in this paragraph. Additionally, some of the stabilizer compounds exist as
In another embodiment, the additional stabilizers may multiple configurational isomers or stereoisomers. Single
comprise nitromethane (CHNO, CAS reg. no. 75-52-5). isomers or multiple isomers of the same compound may be
In another embodiment, the additional stabilizers may used in any proportion to prepare the stabilizer blend. Further,
comprise at least one alkyl silane. Silanes are compounds 45 single or multiple isomers of a given compound may be
similar to hydrocarbons wherein a silicon atom replaces each combined in any proportion with any number of other com
carbon. Alkylsilane stabilizers include but are not limited to pounds to serve as a stabilizer blend. The present invention is
bis(dimethylamino)methylsilane (DMAMS, CAS reg. no. intended to include all single configurational isomers, single
22705-33-5), tris(trimethylsilyl)silane (TTMSS, CAS reg. Stereoisomers or any combination or mixture thereof.
no. 1873-77-4), vinyltriethyoxysilane (VTES, CAS reg. no. 50 Of particular note are stabilizer compositions comprising
78-08-0), and vinyltrimethoxysilane (VTMO, CAS reg. no. combinations of compounds that provide an unexpected level
2768-02-7). of stabilization. Certain of these combinations may serve as
In another embodiment, the additional stabilizers may synergistic stabilizer compositions, that is, the compositions
comprise at least one benzophenone derivative. BenZophe of compounds that augment each others’ efficiency in a for
none derivative stabilizers comprise benzophenone that may 55 mulation and the stabilization obtained is larger than that
be substituted with side groups including halides, such as expected from the sum of the contributions of the individual
fluorine, chlorine, bromine or iodine, amino groups, hydroxyl components. Such synergistic stabilizer compositions may
groups, alkyl groups such as methyl, ethyl or propyl groups, comprise at least one phosphorus-containing compound and
aryl groups such as phenyl, nitro groups, or any combinations any of the compounds selected from the group consisting of
of Such groups. Representative benzophenone derivative sta 60 terpenes and terpenoids, fullerenes, epoxides, fluorinated
bilizers include but are not limited to: 2,5-difluorobenzophe epoxides, oxetanes, divinylterephthalate, and diphenylth
none; 2,5'-dihydroxyacetophenone; 2-aminobenzophenone; erephthalate, and mixtures thereof, meaning mixtures of any
2-chlorobenzophenone: 2-fluorobenzophenone: 2-hydroxy of the foregoing with a phosphorus-containing compound.
benzophenone, 2-methylbenzophenone; 2-amino-4'-chlo A limiting factor in the effectiveness of a stabilizer com
robenzophenone, 2-amino-4'-fluorobenzophenone; 2-amino 65 position is the consumption of stabilizer and loss of function
5-bromo-2'-chlorobenzophenone; 2-amino-5- ality over the time of active use. Of particular note are syner
chlorobenzophenone; 2-amino-5-chloro-2'- gistic stabilizer compositions comprising mixtures of
 US 8,383,004 B2
23 24
stabilizers that include components capable of regenerating riazole, 2-mercaptobenzothiazole, tolutriazole derivatives,
the consumed Stabilizer during active use, hereinafter and N,N-disalicylidene-1,2-diaminopropane.
referred to as regenerative stabilizers. Unlike multi-func In another embodiment, a stabilizer composition com
tional single, large Stabilizer compounds comprising multiple prises at least one amine, at least one phosphite and at least
stabilizing functional groups, regenerative stabilizers com one metal deactivator selected from the group consisting of
prising Small “synergistic' stabilizers function with higher areoxalyl bis(benzylidene)hydrazide: N,N'-bis(3,5-di-tert
mobility and higher stabilization rates (meaning higher rates butyl-4-hydroxyhydrocinnamoylhydrazine); 2,2'-oxami
of reaction by which the stabilization is occurring). Regen dobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate);
erative stabilizer composition contains one or more stabiliz N,N'-(disalicyclidene)-1,2-propanediamine; ethyenedi
ers that can replenish itself or themselves after use, so that 10 aminetetraacetic acid and salts thereof, triazoles; benzotria
over long-term use, the composition’s efficacy is maintained. Zole, 2-mercaptobenzothiazole, tolutriazole derivatives, and
An example of a regenerative stabilizer is an amine and at N,N-disalicylidene-1,2-diaminopropane.
least one phenol. The phenols for inclusion in the present In another embodiment, a stabilizer composition com
regenerative stabilizers may be any of the phenols mentioned prises at least one amine; at least one compound selected from
previously herein. Of particular note are the hindered phenols 15 the group consisting of epoxides, oxetanes, lactones, divinyl
derived from a substituted phenol, in particular derivatives of terephthalate, and diphenyl terephthalate; and at least one
alkyl, aryl phenolic compounds. Representative hindered metal deactivator selected from the group consisting of areOX
phenols are commercially available under the trademarks alyl bis(benzylidene)hydrazide: N,N'-bis(3,5-di-tert-butyl-4-
IrganoxRE201 (di-alpha-tocophenol), IrganoxR) 1010, Irga hydroxyhydrocinnamoylhydrazine); 2.2'-oxamidobis-ethyl
nox(R) 1976, Irganox RL109, Irganox RL134 (all from Ciba). (3,5-d-tert-butyl-4-hydroxyhydorcinnamate); N,N'-
Another example of regenerative stabilizer is a stabilizer (disalicyclidene)-1,2-propanediamine;
which comprises at least one amine combined with at least ethyenediaminetetraacetic acid and salts thereof, triazoles;
one phosphite. The phosphites for inclusion in the present benzotriazole, 2-mercaptobenzothiazole, tolutriazole deriva
regenerative stabilizer compositions may be any previously tives, and N,N-disalicylidene-1,2-diaminopropane.
described herein. In one embodiment, the phosphites may be 25 In another embodiment, a stabilizer composition com
hindered phosphites and can be derived from substituted prises at least one amine; at least one phosphorus containing
phosphites in particular, derivatives of alky, aryl phosphite compound selected from the group consisting of aryl phos
compounds. Representative hindered phosphites are com phites, phosphorus acid, and bis(2,4-bis(1,1-dimethylethyl)-
mercially available under the trademarks Irgafos 168 (Tris 6-methylphenol)ethyl ether; and at least one metal deactiva
(di-tert-butylphenyl)phosphite), Irgafos(R OPH (Di-n-octyl 30 tor selected from the group consisting of areoxalyl bis
phosphite) Irgafo(Rs DDPP (Iso-decyl diphenyl phosphite) (benzylidene)hydrazide; N,N'-bis(3,5-di-tert-butyl-4-
(all from Ciba). hydroxyhydrocinnamoylhydrazine); 2.2'-oxamidobis-ethyl
The amines for inclusion in the regenerative stabilizer (3,5-d-tert-butyl-4-hydroxyhydorcinnamate); N,N'-
compositions may comprise any of the amine stabilizers as (disalicyclidene)-1,2-propanediamine;
described previously herein. Of particular note, are those 35 ethyenediaminetetraacetic acid and salts thereof, triazoles;
hindered amines derived from substituted piperidine com benzotriazole, 2-mercaptobenzothiazole, tolutriazole deriva
pounds, in particular derivatives of an alkyl-substituted pip tives, and N,N-disalicylidene-1,2-diaminopropane.
eridyl, piperidinyl, piperazinone, or alkoxypiperidinyl com The compositions of the present invention may further
pounds. Representative hindered amine light stabilizers are comprise at least one additional compound selected from the
2.2.6.6-tetramethyl-4-piperidone; 2.2.6.6-tetramethyl-4-pip 40 group consisting of fluoroolefins (as described previously
eridinol; bis-(1.2.2.6,6-pentamethylpiperidyl)sebacate (CAS herein), hydrofluorocarbons, hydrocarbons, dimethyl ether,
reg. no. 41556-26-7); di-(2.2.6,6-tetramethyl-4-piperidyl) CFI, carbon dioxide (CO), and ammonia.
sebacate, such as the hindered amine commercially available In one embodiment, the additional compounds comprise
under the trademark Tinuvin R. 770 by Ciba; poly-(N-hy hydrofluorocarbon (HFC) compounds. Hydrofluorocarbons
droxyethyl-2.2.6,6-tetramethyl-4-hydroxy-piperidyl Succi 45 comprise Saturated compounds containing carbon, hydrogen,
nate (CAS reg. no. 65447-77-0), such as that commercially and fluorine. Of particular utility are hydrofluorocarbons hav
available under the trademark Tinuvin R. 622LD from Ciba; ing 1-7 carbon atoms and having a normal boiling point of
alkylated paraphenylenediamines, such as N-phenyl-N'-(1,3- from -90° C. to 80° C. Hydrofluorocarbons are commercial
dimethylbutyl)-p-phenylenediamine, or N,N'-di-sec-butyl-p- products available from a number of sources such as E. I. du
phenylenediamine; and hydroxylamines such as tallow 50 Pont de Nemours & Co., Fluoroproducts, Wilmington, Del.
amines or N-methylbis(hydrogenated tallow alkyl)amine. 19898, USA, or may be prepared by methods known in the
Some other hindered amine antioxidants include the amine art. Representative hydrofluorocarbon compounds include
antioxidant commercially available from Ciba under the but are not limited to fluoromethane (CHF, HFC-41), difluo
trademark Tinuvin R. 765, or commercially available from romethane (CHF, HFC-32), trifluoromethane(CHF, HFC
Mayzo, Inc. under the trademark BLS(R) 1944 and BLS(R) 55 23), pentafluoroethane (CFCHF, HFC-125), 1.1.2.2-tet
1770. The amines also include mixtures of any of the amines rafluoroethane (CHFCHF, HFC-134), 1,1,1,2-
listed in this paragraph. tetrafluoroethane (CFCHF, HFC-134a), 1,1,1-
In another embodiment, any stabilizer composition as trifluoroethane (CFCH. HFC-143a), 1,1-difluoroethane
described above herein may further comprise at least one (CHFCH, HFC-152a), fluoroethane (CHCH2F, HFC
metal deactivator selected from the group consisting of areOX 60 161), 1,1,1,2,2,3,3-heptafluoropropane (CFCFCHF,
alyl bis(benzylidene)hydrazide (CAS reg. no. 6629-10-3): HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane
N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydra (CFCHFCF, HFC-227ea), 1,1,2,2,3,3-hexafluoropropane
Zine) (CAS reg. no. 32687-78-8); 2,2'-oxamidobis-ethyl-(3. (CHFCFCHF, HFC-236ca), 1,1,1,2,2,3-hexafluoropro
5-d-tert-butyl-4-hydroxyhydorcinnamate) (CAS reg. no. pane (CFCFCHF, HFC-236cb), 1,1,1,2,3,3-hexafluoro
70331-94-1); N,N'-(disalicyclidene)-1,2-propanediamine 65 propane (CFCHFCHF, HFC-236ea), 1,1,1,3,3,3-hexafluo
(CAS reg. no. 94-91-1); ethyenediaminetetraacetic acid ropropane (CFCHCF, HFC-236fa), 1,1,2,2,3-
(CAS reg. no. 60-00-4) and salts thereof; triazoles; benzot pentafluoropropane (CHFCFCHF, HFC-245ca), 1,1,1,2,
 US 8,383,004 B2
25 26
2-pentafluoropropane (CFCFCH. HFC-245cb), 1,1,2,3,3- lubricants and their properties are discussed in the 1990
pentafluoropropane (CHFCHFCH F, HFC-245ea 1,1,1,2, ASHRAE Handbook, Refrigeration Systems and Applica
3-pentafluoropropane (CFCHFCHF, HFC-245eb), 1,1,3,3- tions, chapter 8, titled “Lubricants in Refrigeration Systems’.
pentafluoropropane (CFCHCHF, HFC-245fa), 1,2,2,3- pages 8.1 through 8.21, herein incorporated by reference.
tetrafluoropropane (CHFCFCHF, HFC-254ca), 1.1.2.2- Lubricants of the present invention may comprise those com
tetrafluoropropane (CHFCFCH. HFC-254cb), 1,1,2,3- monly known as “mineral oils” in the field of compression
tetrafluoropropane (CHFCHFCHF, HFC-254ea), 1,1,1,2- refrigeration lubrication. Mineral oils comprise paraffins (i.e.
tetrafluoropropane (CFCHFCH, HFC-254eb), 1,1,3,3- straight-chain and branched-carbon-chain, Saturated hydro
tetrafluoropropane (CHFCHCHF, HFC-254 fa), 1,1,1,3- carbons), naphthenes (i.e. cyclic or ring structure Saturated
tetrafluoropropane (CFCHCHF, HFC-254fb), 1,1,1- 10 hydrocarbons, which may be paraffins) and aromatics (i.e.
trifluoropropane (CFCHCH. HFC-263fb), 2.2- unsaturated, cyclic hydrocarbons containing one or more
difluoropropane (CHCFCH. HFC-272ca), 1.2- rings characterized by alternating double bonds). Lubricants
difluoropropane (CHFCHFCH, HFC-272ea), 1,3- of the present invention further comprise those commonly
difluoropropane (CHFCHCHF, HFC-272fa), 1,1- known as “synthetic oils” in the field of compression refrig
difluoropropane (CHFCHCH, HFC-272fb), 15 eration lubrication. Synthetic oils comprise alkylaryls (i.e.
2-fluoropropane (CHCHFCH, HFC-281 ea), 1-fluoropro linear and branched alkyl alkylbenzenes), synthetic paraffins
and naphthenes, silicones, and polyalphaolefins. Representa
pane (CHFCHCH. HFC-281 fa), 1,1,2,2,3,3,4,4-octafluo tive conventional lubricants of the present invention are the
robutane (CHF.CFCFCHF, HFC-338pcc), 1,1,1,2,2,4,4, commercially available BVM 100 N (paraffinic mineral oil
4-octafluorobutane (CFCHCFCF, HFC-338mf), 1,1,1,3, sold by BVA Oils), naphthenic mineral oil commercially
3-pentafluorobutane (CFCHCHF, HFC-365mfc), 1,1,1,2, available under the trademark from Suniso(R) 3GS and
3.44.5.5,5-decafluoropentane (CFCHFCHFCFCF, HFC Suniso(R) 5GS by Crompton Co., naphthenic mineral oil com
43-10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7- mercially available from Pennzoil under the trademark Son
tetradecafluoroheptane (CFCFCHFCHFCFCFCF, texR 372LT, naphthenic mineral oil commercially available
HFC-63-14 mee). from Calumet Lubricants under the trademark Calumet(R)
In another embodiment, the additional compounds com 25 RO-30, linear alkylbenzenes commercially available from
prise hydrocarbons. Hydrocarbons comprise compounds Shrieve Chemicals under the trademarks ZerolR 75, Zerol R.
having only carbon and hydrogen. Of particular utility are 150 and ZerolR 500 and branched alkylbenzene, sold by
compounds having 3-7 carbonatoms. Hydrocarbons are com Nippon Oil as HAB 22.
mercially available through numerous chemical Suppliers. Lubricants of the present invention further comprise those
Representative hydrocarbons include but are not limited to 30 which have been designed for use with hydrofluorocarbon
propane, n-butane, isobutane, cyclobutane, n-pentane, 2-me refrigerants and are miscible with refrigerants of the present
thylbutane, 2,2-dimethylpropane, cyclopentane, n-hexane, invention under compression refrigeration and air-condition
2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, ingapparatus operating conditions. Such lubricants and their
3-methylpentane, cyclohexane, n-heptane, and cycloheptane. properties are discussed in “Synthetic Lubricants and High
In another embodiment, additional compounds may also 35 Performance Fluids'. R. L. Shubkin, editor, Marcel Dekker,
comprise hydrocarbons containing heteroatoms, such as dim 1993, Chapters 2 and 4. Such lubricants include, but are not
ethylether (DME, CHOCH). DME is commercially avail limited to, polyol esters (POEs) such as Castrol(R) 100 (Cas
able. trol, United Kingdom), polyalkylene glycols (PAGs) Such as
In another embodiment, additional compounds may also RL-488A from Dow (Dow Chemical, Midland, Mich.), and
comprise iodotrifluoromethane (CFI), which is commer 40
polyvinyl ethers (PVEs).
cially available from various sources or may be prepared by Lubricants of the present invention are selected by consid
methods known in the art. ering a given compressor's requirements and the environment
In another embodiment, additional compounds may also to which the lubricant will be exposed.
comprise carbon dioxide (CO), which is commercially avail The compositions of the present invention may be prepared
able from various sources or may be prepared by methods by any convenient method to combine the desired amount of
known in the art. 45 the individual components. A preferred method is to weigh
In another embodiment, additional compounds may also the desired component amounts and thereafter combine the
comprise ammonia (NH), which is commercially available components in an appropriate vessel. Agitation may be used,
from various sources or may be prepared by methods known if desired.
in the art. Any suitable effective amount of stabilizer may be used in
Of particular note are additional compounds comprising 50 the compositions comprising at least one fluoroolefin. As
compositions including: HFC-1225ye and HFC-32; HFC described herein, the phrase “effective amount” refers to an
1225ye and HFC-134a: HFC-1225ye, HFC-134a, and HFC amount of stabilizer of the present invention which, when
32: HFC-1225ye and HFC-1234yf: HFC-1225ye, HFC added to a composition comprising at least one fluoroolefin,
1234yf, and HFC-32: HFC-1225ye, HFC-1234yf. HFC-32, results in a composition that will not degrade to produce as
and CFI; and HFC-1225ye, HFC-1234yf and HFC-125. 55 great a reduction in refrigeration performance when in use in
In another embodiment, additional compounds include a cooling apparatus as compared to the composition without
compositions comprising fluoroolefins as disclosed in U.S. stabilizer. Such effective amounts of stabilizer may be deter
patent application Ser. No. 1 1/369,227 filed Mar. 2, 2006: mined by way of testing under the conditions of standard test
U.S. patent application Ser. No. 1 1/393,109 filed Mar. 30, ASHRAE 97-2004. In a certain embodiment of the present
2006; and U.S. patent application Ser. No. 1 1/486,791 filed 60
invention, an effective amount may be said to be that amount
Jul. 13, 2006; are intended to be included within the scope of of stabilizer that when combined with a composition com
the present invention. prising at least one fluoroolefin allows a cooling apparatus
In one embodiment, compositions of the present invention utilizing said composition comprising at least one fluoroole
may further comprise at least one lubricant. Lubricants of the fin to perform at the same level of refrigeration performance
present invention comprise those Suitable for use with refrig and cooling capacity as if a composition comprising 1,1,1,2-
eration or air-conditioning apparatus. Among these lubricants 65 tetrafluoroethane (R-134a), or other standard refrigerant
are those conventionally used in compression refrigeration (R-12, R-22, R-502, R-507A, R-508, R401A, R401B,
apparatus utilizing chlorofluorocarbon refrigerants. Such R402A, R402B, R408, R-410A, R-404A, R407C, R-413A,
 US 8,383,004 B2
27 28
R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R-114, method comprising adding an effective amount of stabilizer
R-11, R-113, R-123, R-124, R236fa, or R-245fa) depending comprising at least one amine to the composition comprising
upon what refrigerant may have been used in a similar system at least one fluoroolefin.
in the past, were being utilized as the working fluid.
Certain embodiments include effective amounts of stabi EXAMPLE
lizer for use in the present invention that comprise from about
0.001 weight percent to about 10 weight percent, more pref Refrigeration System Chemical Stability
erably from about 0.01 weight percent to about 5 weight
percent, even more preferably from about 0.3 weight percent A chemical stability test is run under conditions described
to about 4 weight percent and even more preferably from in ASHRAE (American Society of Heating, Refrigerating
about 0.3 weight percent to about 1 weight percent based on " and Air-Conditioning Engineers) Standard 97-2004 to deter
the total weight of compositions comprising at least one fluo- mine chemical stability of the stabilized compositions of the
roolefin as described present invention as compared to compositions with no sta
The present invention further relates to a method for stabi- bilizers.
lizing a composition comprising at least one fluoroolefin, said The procedure is given here:
method comprising adding an effective amount of a stabilizer 15 1. Metal coupons of copper, aluminum and steel are placed in
comprising at least one amine to the composition comprising thick walled glass tubes.
at least one fluoroolefin. 2. Working fluid samples, including lubricant, are prepared
The present invention further relates to a process for pro- with and without stabilizers, and optionally with 2 volume
ducing cooling comprising condensing a composition com- % air added to the tube.
prising at least one fluoroolefin and an effective amount of 20 3. Samples are added to the glass tubes as described in the
Stabilizer comprising at least one amine, and thereafter evapo- standard.
rating said composition in the vicinity of a body to be cooled. 4. The tubes are sealed with a glass blowing torch.
A body to be cooled may be any space, location or object 5. The sealed tubes are heated in an oven for 14 days at the
requiring refrigeration or air-conditioning. In stationary specified temperature.
applications the body may be the interior of a structure, i.e. s 6. After 14 days, the sealed tubes are removed from the oven
residential or commercial, or a storage location for perish- and examined for metal/liquid appearance, proper volume
ables, such as food orpharmaceuticals. For mobile refrigera- of liquid, appearance of glass, and absence of extraneous
tion applications the body may be incorporated into a trans- materials such as metal fines.
portation unit for the road, rail, sea or air. Certain refrigeration 7. Ratings are assigned to each sample based upon the fol
Systems operate independently with regards to any moving lowing criteria (per industry practice):
carrier, these are known as “intermodal” systems. Such inter- 30 1-light changes on coupons and liquids;
modal systems include “containers' (combined sea/land 2-light to moderate changes on coupons or liquids;
transport) as well as “swap bodies' (combined road and rail 3-moderate to significant changes on coupons or liquids;
transport). 4-severe changes on coupons or liquids;
The present invention further relates to a process for pro- 5-extreme changes on coupons or liquids, i.e. black liquid
ducing heat comprising condensing a composition compris- 35 or coked with many deposits.
ing at least one fluoroolefin and an effective amount of stabi- Table 4 lists estimated results for stabilizers of the present
lizer comprising at least one amine in the vicinity of a body to invention as compared to unstabilized compositions. Ucon R
be heated, and thereafter evaporating said composition. PAG 488 is a trademark for a polyalkylene glycol lubricant
A body to be heated may be any space, location or object commercially available from The Dow Chemical Company.
requiring heat. These may be the interior of structures either 40 Irgalube(R) 63 is a trademark for a dithiophosphate commer
residential or commercial in a similar manner to the body to cially available from Ciba. Irgalube.R. 232 is a trademark for
be cooled. Additionally, mobile units as described for cooling abutylated triphenyl phosphorothionate commercially avail
may be similar to those requiring heating. Certain transport able from Ciba. Irgalube(R).349 is a trademark for a mixture of
units require heating to prevent the material being transported amine phosphates (an example of an organophosphate) com
from solidifying inside the transport container. as mercially available from Ciba. Irgalube R350 and Irgalube.R.
It is not uncommon for air to leak into a refrigeration, 353 are trademarks for dialkyl dithiophosphate esters from
air-conditioning system or heat pump. The oxygen in the air Ciba. Krytox(R) 157FSL is a trademark for a functionalized
may lead to oxidation of certain components of the system perfluoropolyether commercially available from DuPont.
including the working fluid. Thus, in another embodiment, ZerolR 150 is a trademark for an alkylbenzene lubricant sold
also disclosed is a method for reducing degradation of a by Shrieve Chemical. OXT-101 is 3-ethyl-3-hydroxymethy
composition comprising at least one fluoroolefin, wherein loxetane from Toagosei Company. Tinuvin R. 622LD is a
said degradation is caused by the presence of inadvertent air; trademark for a hindered amine antioxidant commercially
for example in a refrigeration, air-conditioning or heat pump available from Ciba. HP-136 is 5,7-di-t-butyl-3-(3-4-dimeth
System, said method comprising adding an effective amount ylphenyl)-3H-benzofuran-2-one (an example of a lactone)
of stabilizer comprising at least one amine to the composition from Ciba. The lubricant Ucon R. PAG 488 is combined with
comprising at least one fluoroolefin. In another embodiment, 55 the working fluid as set forth in Table 4 below to produce a
also disclosed is a method for reducing reaction with oxygen composition that was 50 wt % working fluid and 50 wt %
for a composition comprising at least one fluoroolefins, said lubricant.
TABLE 4
Stabilizer With
(wt % in refrig? 2 vol%. Temp
Working fluid Lubricant Stabilizer lubricant mixture) Air (C.) Rating
HFC-1225ye PAG 488. None O yes 175 4
HFC-1225ye PAG 488. None O IlC) 175 2
HFC-1225ye PAG 488 Irgalube (R) 63 2 yes 175 2
HFC-1225ye PAG 488 Irgalube (R) 63 2 IlC) 175 1
 US 8,383,004 B2
29 30
TABLE 4-continued
Stabilizer With
(wt % in refrig? 2 vol% Temp
Working fluid Lubricant Stabilizer lubricant mixture) Air (C.) Rating
HFC-1225ye PAG 488 Irgalube (R) 232 2 yes 75 2
HFC-1225ye PAG 488 Irgalube (R) 232 2 O 75
HFC-1225ye PAG 488 Irgalube (R) 349 2 yes 75 2
HFC-1225ye PAG 488 Irgalube (R) 349 2 O 75
HFC-1225ye PAG 488 Irgalube (R) 350 2 yes 75 2
HFC-1225ye PAG 488 Irgalube (R) 350 2 O 75
HFC-1225ye PAG 488 Irgalube (R) 353 2 yes 75 2
HFC-1225ye PAG 488 Irgalube (R) 353 2 O 75
HFC-1225ye PAG 488 d-limonene 2 yes 75 2
HFC-1225ye PAG 488 d-limonene 2 O 75
HFC-1225ye PAG 488 buckminsterfullerene 2 yes 75 2
HFC-1225ye PAG 488 buckminsterfullerene 2 O 75
HFC-1225ye PAG 488 graphite powder 2 yes 75 2
HFC-1225ye PAG 488 graphite powder 2 O 75
HFC-1225ye PAG 488 naphthalene 2 yes 75 2
HFC-1225ye PAG 488 naphthalene 2 O 75
HFC-1225ye PAG 488 Anisole 2 yes 75 2
HFC-1225ye PAG 488 Anisole 2 O 75
HFC-1225ye PAG 488 Krytox (R) 157FSL 2 yes 75 2
HFC-1225ye PAG 488 Krytox (R) 157FSL 2 O 75
HFC-1225ye PAG 488 Zerol (R) 150 2 yes 75 2
HFC-1225ye PAG 488 Zerol (R) 150 2 O 75
HFC-1225ye PAG 488 Trifluormethyloxirane 2 yes 75 2
HFC-1225ye PAG 488 Trifluormethyloxirane 2 O 75
HFC-1225ye PAG 488 OXT 101 2 yes 75 2
HFC-1225ye PAG 488 OXT 101 2 O 75
HFC-1225ye PAG 488 ascorbic acid 2 yes 75 2
HFC-1225ye PAG 488 ascorbic acid 2 O 75
HFC-1225ye PAG 488 methyl mercaptain 2 yes 75 2
HFC-1225ye PAG 488 methyl mercaptain 2 O 75
HFC-1225ye PAG 488 gamma-undecalactone 2 yes 75 2
HFC-1225ye PAG 488 gamma-undecalactone 2 O 75
HFC-1225ye PAG 488 benzyl phenylsulfide 2 yes 75 2
HFC-1225ye PAG 488 benzyl phenylsulfide 2 O 75
HFC-1225ye PAG 488 12-butylene oxide 2 yes 75 2
HFC-1225ye PAG 488 12-butylene oxide 2 O 75
HFC-1225ye PAG 488 diisopropylamine 2 yes 75 2
HFC-1225ye PAG 488 diisopropylamine 2 O 75
HFC-1225ye PAG 488 nitromethane 2 yes 75 2
HFC-1225ye PAG 488 nitromethane 2 O 75
HFC-1225ye PAG 488 tris(trimethylsilyl)silane 2 yes 75 2
HFC-1225ye PAG 488 tris(trimethylsilyl)silane 2 O 75
HFC-1225ye PAG 488 tocopherol 2 yes 75 2
HFC-1225ye PAG 488 tocopherol 2 O 75
HFC-1225ye PAG 488 hydroquinone 2 yes 75 2
HFC-1225ye PAG 488 hydroquinone 2 O 75
HFC-1225ye PAG 488 Butylated hydroxy 2 yes 75 2
toluene (BHT)
HFC-1225ye PAG 488 Butylated hydroxy 2 O 75
toluene (BHT)
HFC-1225ye PAG 488 Divinyl terephthalic acid 2 yes 75 2
HFC-1225ye PAG 488 Divinyl terephthalic acid 2 O 75
HFC-1225ye PAG 488 Tinuwin (R) 622LD 2 yes 75 2
HFC-1225ye PAG 488 Tinuwin (R) 622LD 2 O 75
HFC-1225ye PAG 488 Mn(Cl), with KCl 2 yes 75 2
HFC-1225ye PAG 488 Mn(Cl), with KCl 2 O 75
HFC-1225ye PAG 488 TiO, 2 yes 75 2
HFC-1225ye PAG 488 TiO, 2 O 75
HFC-1225ye PAG 488 Na2CO 2 yes 75 2
HFC-1225ye PAG 488 Na2CO 2 O 75
HFC-1225ye PAG 488 2-hydroxy-4- 2 yes 75 2
methoxybenzophenone
HFC-1225ye PAG 488 2-hydroxy-4- 2 O 75
methoxybenzophenone
HFC-1225ye PAG 488 2- 2 yes 75 2
hydroxybenzophenone
HFC-1225ye PAG 488 2- 2 O 75
hydroxybenzophenone
HFC-1225ye PAG 488 24- 2 yes 75 2
dihydroxybenzophenone
HFC-1225ye PAG 488 24- 2 O 75
dihydroxybenzophenone
HFC-1225ye PAG 488 24- 2 yes 75 2
dimethylbenzophenone
HFC-1225ye PAG 488 24- 2 O 75
dimethylbenzophenone
 US 8,383,004 B2
31
TABLE 4-continued
Stabilizer With
(wt % in refrig? 2 vol% Temp
Working fluid Lubricant Stabilizer lubricant mixture) Air (C.) Rating
HFC-1225ye PAG 488 3,4- 2 yes 175 2
diaminobenzophenone
HFC-1225ye PAG 488 3,4- 2 O 175 1
diaminobenzophenone
HFC-1225ye PAG 488 HP-136 2 yes 175 2
HFC-1225ye PAG 488 HP-136 2 O 175 1

Estimates indicate improved chemical stability in the pres 3. The composition of claim 1 consisting of the at least one
ence of stabilizers with and without air present. fluoroolefin and the lubricant selected from the groups con
15 sisting of mineral oils, alkylbenzenes, poly-alpha-olefins,
What is claimed is: silicone oils, polyoxyalkylene glycol ethers, polyol esters,
1. A composition consisting of at least one fluoroolefinand and polyvinyl ethers and mixtures thereof.
an effective amount of a stabilizer comprising at least one 4. The composition of claim 1 consisting of the at least one
amine selected from the group consisting of triethylamine; fluoroolefin and the at least one additional stabilizer com
tributylamine; diisopropylamine; triisopropylamine; tri pound selected from the group consisting of phenols, thio
isobutylamine; p-phenylenediamine; diphenylamine; dialky phosphates, butylated triphenylphosphorothionates, organo
lamines; (N-(1-methylethyl)-2-propylamine; alkyl-substi phosphates, phosphites, terpenes, terpenoids, fullerenes,
tuted piperidyl, piperidinyl, piperazinone, and functionalized perfluoropolyethers, polyoxyalkylated aro
alkoxypiperidinyl compounds; 2.2.6,6-tetramethyl-4-piperi matics, alkylated aromatics, epoxides, fluorinated epoxides,
done; 2.2.6,6-tetramethyl-4-piperidinol; bis-(1.2.2.6,6-pen 25 oxetanes, ascorbic acid, thiols, lactones, thioethers,
tamethylpiperidyl)sebacate; di-(2.2.6.6-tetramethyl-4-pip nitromethane, alkylsilanes, benzophenone derivatives, aryl
eridyl)sebacate; poly-(N-hydroxyethyl-2.2.6,6-tetramethyl sulfides, divinyl terephthalate, diphenyl terephthalate, and
4-hydroxy-piperidyl Succinate; 2.2.6.6-tetramethyl-4- mixtures thereof.
piperidone, 2.2.6,6-tetramethyl-4-piperidinol, bis-(1.2.2.6.6- 5. The composition of claim 4 wherein:
pentamethylpiperidyl)sebacate, di-(2.2.6.6-tetramethyl-4- 30 a. The phenols are selected from the group consisting of
piperidyl)sebacate, poly-(N-hydroxyethyl-2.2.6.6- 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-
tetramethyl-4-hydroxy-piperidyl Succinate, and mixtures ethylphenol; 2,4-dimethyl-6-tertbutylphenol; toco
thereof, and, pherol: hydroquinone; t-butyl hydroquinone; 4,4'-thio
a metal deactivator selected from the group consisting of bis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-
areoxalyl bis(benzylidene)hydrazide: N,N'-bis(3,5-di methyl-6-tertbutylphenol): 2,2'-thiobis(4-methyl-6-
tert-butyl-4-hydroxyhydrocinnamoylhydrazine); 2.2'- 35
tert-butylphenol): 4,4'-methylenebis(2,6-di-tert
oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydror butylphenol): 4,4'-bis(2,6-di-tert-butylphenol); 2.2'-
cinnamate); N,N'-(disalicyclidene)-1,2- methylenebis(4-ethyl-6-tertbutylphenol); 2,2'-
propanediamine; ethyenediaminetetraacetic acid and methylenebis(4-methyl-6-tert-butylphenol): 4.4-
salts thereof, triazoles; benzotriazole, 2-mercaptoben butylidenebis(3-methyl-6-tert-butylphenol); 4.4-
Zothiazole, tolutriazole derivatives, N,N-disalicylidene 40 isopropylidenebis(2,6-di-tert-butylphenol): 2,2'-
1.2-diaminopropane, and mixture thereof; methyleenbis(4-methyl-6-nonylphenol); 2,2'-
and optionally, isobutylidenebis(4,6-dimethylphenol; 2,2'-
at least one additional compound selected from the methylenebis(4-methyl-6-cyclohexylphenol, 2,2'-
group consisting of fluoroolefins, hydrofluorocar methylenebis(4-ethyl-6-tert-butylphenol); butylated
bons, hydrocarbons, dimethyl ether, carbon dioxide, 45 hydroxyl toluene (BHT); 2,6-di-tert-alpha-dimethy
and ammonia and mixtures thereof, lamino-p-cresol; 4,4-thiobis(6-tert-butyl-m-cresol; acy
and optionally, laminophenols; 2,6-di-tert-butyl-4(N,N'-dimethylami
a lubricant selected from the groups consisting of min nomethylphenol); bis(3-methyl-4-hydroxy-5-tert
eral oils, alkylbenzenes, poly-alpha-olefins, silicone butylbenzyl)sulfide: bis(3,5-di-tert-butyl-4-
oils, polyoxyalkylene glycol ethers, polyolesters, and 50 hydroxybenzyl)sulfide and mixtures thereof;
polyvinyl ethers and mixtures thereof, b. the thiophosphates are selected from the group consist
and optionally ing of monothiophosphates, dithiophosphates, trithio
at least one additional stabilizer compound selected phosphates, dialkylthiophosphate esters, and mixtures
from the group consisting of phenols, thiophosphates, thereof;
butylated triphenylphosphorothionates, organo phos 55
c. the butylated triphenylphosphorothionates are repre
phates, phosphites, terpenes, terpenoids, fullerenes, sented by formula A.
functionalized perfluoropolyethers, polyoxyalky Formula A
lated aromatics, alkylated aromatics, epoxides, fluori
nated epoxides, oxetanes, ascorbic acid, thiols, lac
tones, thioethers, nitromethane, alkylsilanes, 60
benzophenone derivatives, aryl sulfides, divinyl
terephthalate, diphenyl terephthalate, and mixtures
thereof. wherein each R is independently selected from H or
2. The composition of claim 1 consisting of the at least one tert-butyl:
fluoroolefinand the at least one additional compound selected d. the organophosphates are selected from the group con
from the group consisting of fluoroolefins, hydrofluorocar 65 sisting of amine phosphates, trialkyl phosphates, triaryl
bons, hydrocarbons, dimethyl ether, carbon dioxide, and phosphates, mixed alkyl-aryl phosphates, cyclic phos
ammonia and mixtures thereof. phates and mixtures thereof;
 US 8,383,004 B2
33 34
e. the phosphites are selected from the group consisting of n. the thiols are selected from the group consisting of
tris-(di-tert-butylphenyl) phosphite, di-n-octyl phos methanethiol, ethanethiol, Coenzyme A, dimercapto
phite, iso-decyl diphenyl phosphite, and mixtures Succinic acid, (R)-2-(4-methylcyclohex-3-enyl)pro
thereof; pane-2-thiol, cysteine, lipoamide, and mixtures thereof;
f, the terpenes are selected from the group consisting of 5 . the lactones are selected from the group consisting of
isoprene, myrcene, allo-cimene, beta-ocimene, ter gamma-butyrolactone, delta-gluconolactone, gamma
ebene, d-limonene, retinal, pinene, menthol, geraniol, undecalactone, 6,7-dihydro-4(5H)-benzofuranone, 5,7-
farnesol, phytol, Vitamin A, terpinene, delta-3-carene, bis(1,1-dimethylethyl)-3-2.3 (or 3,4)-dimethylphenyl
terpinolene, phellandrene, fenchene, dipentene, lyco 2(3H)-benzofuranone, and mixtures thereof;
pene, betacarotene, Zeaxanthin, hepaxanthin, isotretin- 10 . the thioethers are selected from the group consisting of
oin, and mixtures thereof; benzylphenylsulfide, diphenylsulfide, dioctadecyl 3,3'-
g. the terpenoids are selected from the group consisting of thiodipropionate, didodecyl 3,3'-thiopropionate, and
abietane, ambrosane, aristolane, atisane, beyerane, bis- mixtures thereof;
abolane, bornane, caryophyllane, cedrane, dammarane, . the alkylsilanes are selected from the group consisting
drimane, eremophilane, eudesmane, fenchane, gam- 15 of bis(dimethylamino)methylsilane, tris(trimethylsilyl)
macerane, germacrane, gibbane, grayanotoxane, gua- silane, vinyltriethyoxysilane, vinyltrimethoxysilane,
iane, himachalane, hopane, humulane, kaurane, lab- and mixtures thereof
dane, lanostane, lupane, p-menthane, oleanane, r. the benzophenone derivatives are selected from the group
ophiobolane, picrasane, pimarane, pinane, podocar- consisting of 2,5-difluorobenzophenone; 2',5'-dihy
pane, protostane, rosane, taxane, thujane, trichothecane, 20 droxyacetophenone; 2-aminobenzophenone; 2-chlo
ursane, and mixtures thereof; robenzophenone; 2-fluorobenzophenone; 2-hydroxy
. the fullerenes are selected from the group consisting of benzophenone; 2-methylbenzophenone: 2-amino-4'-
Buckminsterfullerene, 5.6 fullerene-Co. fullerene- chlorobenzophenone: 2-amino-4'-fluorobenzophenone;
C76. fullerene-Cs. fullerene-Cs. and mixtures thereof 2-amino- 5-bromo-2'-chlorobenzophenone; 2-amino-5-
i. the polyoxyalkylated aromatics are compounds repre- 25 chlorobenzophenone: 2-amino-5-chloro-2'-fluoroben
sented by Formula B. Zophenone; 2-amino-5-nitrobenzophenone: 2-amino-5-
Formula B
nitro-2'-chlorobenzophenone; 2-amino-2,5-
dichlorobenzophenone; 2-chloro-4'-
N fluorobenzophenone; 2-hydroxy-4-
--(OR), 30 methoxybenzophenone; 2-hydroxy-5-
2 chlorobenzophenone; 2-methylamino-5-
wherein the R' group is a polyoxyalkylated group com-
prising at least one —CH2CH2O— moiety;
sheets 3-ni its phens
-n1trO enzop enone; -n1trO- se OO-4-UOOC
j. the alkylated aromatics are linear or branched alkylben- Zophenone: 4-chlorobenzophenone: 4-fluorobenzophe
Zene lubricants; 35 none: 4-hydroxybenzophenone; 4-methoxybenzophe
k. the epoxide stabilizers are selected from the group con- none: 4-methylbenzophenone; 4-nitrobenzophenone;
sisting of 1,2-propylene oxide, 1.2-butylene oxide, 4-phenylbenzophenone 4-chloro-3-nitrobenzophe
butylphenylglycidyl ether, pentylphenylglycidyl ether, none: 4-hydroxy-4'-chlorobenzophenone; 2,4-dihy
hexylphenylglycidyl ether, heptylphenylglycidyl ether, droxybenzophenone; 2,4-dimethylbenzophenone; 2.5-
octylphenylglycidyl ether, nonylphenylglycidyl ether, 40 dimethylbenzophenone; 3,4-diaminobenzophenone;
decylphenylglycidyl ether, glycidyl methylphenyl ether, 3,4-dichlorobenzophenone; 3,4-difluorobenzophenone;
1,4-glycidyl phenyl diether, 4-methoxyphenylglycidyl 3,4-dihydroxybenzophenone; 3,4-dimethylbenzophe
ether, naphthyl glycidyl ether, 1,4-diglycidyl naphthyl none; 4,4'-bis(diethylamine)benzophenone; 4,4'-bis
diether, butylphenyl glycidyl ether, n-butyl glycidyl (dimethylamine)benzophenone; 4,4'-dichloroben
ether, isobutyl glycidyl ether, hexanediol diglycidyl 45 Zophenone; 4,4'-difluorobenzophenone; 4,4'-
ether, allyl glycidyl ether, polypropylene glycol digly- dihydroxybenzophenone; 4,4'-
cidyl ether and mixtures thereof; dimethoxybenzophenone, and mixtures thereof, and
1. the fluorinated epoxides are represented by formula C S. the aryl Sulfides are selected from the group consisting of
Formula C
benzylphenylsulfide, diphenylsulfide, dibenzylsulfide,
O 50 and mixtures thereof.
R2 R4 6. The composition of claim 1 wherein said fluoroolefinis
at least one compound selected from the group consisting of
R3 R3 (i) fluoroolefins of the formula E- or Z R'CH=CHR,
wherein R' and Rare, independently, C to C perfluo
wherein each of R through R is H, alkyl of 1-6 carbon ss roalkyl groups;
atoms or fluoroalkyl of 1-6 carbon atoms with the (ii) cyclic fluoroolefins of the formula cyclo-CX—CY
proviso that at least one of R through R is a fluoro (CZW), , wherein X, Y, Z, and W, independently, are
alkyl group; H or F, and n is an integer from 2 to 5; and
m. the oxetanes are represented by formula D (iii) fluoroolefins selected from the group consisting of
Formula D 60 1,2,3,3,3-pentafluoro-1-propene (CHF=CFCF), 1.1.3.3.
R3 R4 3-pentafluoro-1-propene (CF–CHCF), 1,1,2,3,3-
R2><< R5 pentafluoro-1-propene
rafluoro-1-propene
(CF=CFCHF), 1,2,3,3-tet
(CHF—CFCHF), 2,3,3,3-
R O R6 tetrafluoro-1-propene (CH=CFCF), 1,3,3,3-
65 tetrafluoro-1-propenecHF=CHCF), 1,1,2,3-
wherein R1-R6 are independently selected from hydro- tetrafluoro-1-propene (CF=CFCHF), 1,1,3,3-
gen, alkyl or Substituted alkyl, aryl or substituted aryl; tetrafluoro-1-propene (CF=CHCHF), 1,2,3,3-
 US 8,383,004 B2
37 38
3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (CFCF 10. A method for reducing degradation of a composition
CF=CFCFCF); 1,1,1,3,4,4,5,5,6,6,7,7,7-tridecaf consisting of at least one fluoroolefin,
luoro-2-heptene (CFCH=CFCFCFCFs); 1,1,1,2,4, and optionally
4.5,5,6,6,7,7,7-tridecafluoro-2-heptene (CFCF at least one additional compound selected from the
CHCFCFCFs); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecaf group consisting of fluoroolefins, hydrofluorocar
luoro-3-heptene (CFCF-CH=CFCFCFs); and 1,1,1, bons, hydrocarbons, dimethyl ether, carbon dioxide,
2.2.3,5,5,6,6,7,7,7-tridecafluoro-3-heptene and ammonia and mixtures thereof,
(CFCFCF-CHCFCF). and optionally
7. A method for stabilizing a composition consisting of at 10
a lubricant selected from the groups consisting of min
least one fluoroolefin, eral oils, alkylbenzenes, poly-alpha-olefins, silicone
and optionally oils, polyoxyalkylene glycol ethers, polyolesters, and
at least one additional compound selected from the polyvinyl ethers and mixtures thereof,
group consisting of fluoroolefins, hydrofluorocar wherein said degradation is caused by the presence of
bons, hydrocarbons, dimethyl ether, carbon dioxide, 15 inadvertent air in a refrigeration, air-conditioning or
and ammonia and mixtures thereof, heat pump system, said method comprising adding to
and optionally the composition consisting of at least one olefin,
a lubricant selected from the groups consisting of min a metal deactivator selected from the group consisting
eral oils, alkylbenzenes, poly-alpha-olefins, silicone of areoxalyl bis(benzylidene)hydrazide; N.N'-bis
oils, polyoxyalkylene glycol ethers, polyolesters, and (3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhy
polyvinyl ethers and mixtures thereof, drazine); 2.2'-oxamidobis-ethyl-(3,5-d-tert-butyl
said method comprising adding to the composition consist 4-hydroxyhydrorcinnamate); N,N'-
ing of at least one fluoroolefine, a metal deactivator (disalicyclidene)-1,2-propanediamine;
Selected from the group consisting of areoxalyl bis(ben ethyenediaminetetraacetic acid and salts thereof.
Zylidene)hydrazide: N,N'-bis(3,5-di-tert-butyl-4-hy 25 triazoles; benzotriazole, 2-mercaptobenzothiazole,
droxyhydrocinnamoylhydrazine); 2,2'-oxamidobis tolutriazole derivatives, N,N-disalicylidene-1,2-di
ethyl-(3,5-d-tert-butyl-4-hydroxyhydrorcinnamate); aminopropane, and mixtures thereof, and
N,N'-(disalicyclidene)-1,2-propanediamine; ethyenedi an effective amount of a stabilizer consisting of at
aminetetraacetic acid and salts thereof; triazoles; benzo least one amine,
triazole, 2-mercaptobenzothiazole, tolutriazole deriva 30 and optionally,
tives, N,N-disalicylidene-1,2-diaminopropane, and at least one additional stabilizer compound selected
mixtures thereof, and, an effective amount of a stabilizer from the group consisting of phenols, thiophos
consisting of at least one amine; phates, butylated triphenylphosphorothionates,
and optionally, organo phosphates, phosphites, terpenes, terpe
at least one additional stabilizer compound selected 35 noids, fullerenes, functionalized perfluoropoly
from the group consisting of phenols, thiophosphates, ethers, polyoxyalkylated aromatics, alkylated aro
butylated triphenylphosphorothionates, organo phos matics, epoxides, fluorinated epoxides, oxetanes,
phates, phosphites, terpenes, terpenoids, fullerenes, ascorbic acid, thiols, lactones, thioethers,
functionalized perfluoropolyethers, polyoxyalky nitromethane, alkylsilanes, benzophenone deriva
lated aromatics, alkylated aromatics, epoxides, fluori 40 tives, aryl sulfides, divinyl terephthalate, diphenyl
nated epoxides, oxetanes, ascorbic acid, thiols, lac terephthalate, and mixtures thereof,
tones, thioethers, nitromethane, alkylsilanes, wherein the at least one amine is selected from the group
benzophenone derivatives, aryl sulfides, divinyl consisting of triethylamine; tributylamine; diisopropy
terephthalate, diphenyl terephthalate, and mixtures lamine; triisopropylamine; triisobutylamine; p-phe
thereof, 45 nylenediamine; diphenylamine; dialkylamines; (N-(1-
wherein the at least one amine is selected from the group methylethyl)-2-propylamine; alkyl-substituted
consisting of triethylamine; tributylamine; diisopropy piperidyl, piperidinyl, piperazinone, and alkoxypip
lamine; triisopropylamine; triisobutylamine; p-phe eridinyl compounds; 2.2.6,6-tetramethyl-4-piperidone;
nylenediamine; diphenylamine; dialkylamines; (N-(1- 2.2.6.6-tetramethyl-4-piperidinol; bis-(1.2.2.6,6-pen
methylethyl)-2-propylamine; alkyl-substituted 50 tamethylpiperidyl)sebacate; di-(2.2.6,6-tetramethyl-4-
piperidyl, piperidinyl, piperazinone, and alkoxypip piperidyl)sebacate; poly-(N-hydroxyethyl-2.2.6,6-tet
eridinyl compounds; 2.2.6,6-tetramethyl-4-piperidone; ramethyl-4-hydroxy-piperidyl Succinate; 2.2.6.6-
2.2.6.6-tetramethyl-4-piperidinol; bis-(1.2.2.6,6-pen tetramethyl-4-piperidone, 2.2.6,6-tetramethyl-4-
tamethylpiperidyl)sebacate; di-(2.2.6,6-tetramethyl-4- piperidinol, bis-(1.2.2.6,6-pentamethylpiperidyl)
piperidyl)sebacate; poly-(N-hydroxyethyl-2.2.6,6-tet 55 Sebacate, di-(2.2.6,6-tetramethyl-4-piperidyl)sebacate,
ramethyl-4-hydroxy-piperidyl Succinate; 2.2.6.6- poly-(N-hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxy
tetramethyl-4-piperidone, 2.2.6,6-tetramethyl-4- piperidyl Succinate, and mixtures thereof.
piperidinol, bis-(1.2.2.6,6-pentamethylpiperidyl) 11. A method for reducing reaction with oxygen for a
Sebacate, di-(2.2.6,6-tetramethyl-4-piperidyl)sebacate, composition consisting of at least one fluoroolefin,
poly-(N-hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxy 60 and optionally,
piperidyl Succinate, and mixtures thereof. at least one additional compound selected from the
8. A process for producing cooling comprising condensing group consisting of fluoroolefins, hydrofluorocar
the composition of claim 1 and thereafter evaporating said bons, hydrocarbons, dimethyl ether, carbon dioxide,
composition in the vicinity of a body to be cooled. and ammonia and mixtures thereof,
9. A process for producing heat comprising condensing the 65 and optionally
composition of claim 1 in the vicinity of a body to be heated, a lubricant selected from the groups consisting of min
and thereafter evaporating said composition. eral oils, alkylbenzenes, poly-alpha-olefins, silicone
 US 8,383,004 B2
39 40
oils, polyoxyalkylene glycol ethers, polyolesters, and tones, thioethers, nitromethane, alkylsilanes, ben
polyvinyl ethers and mixtures thereof, Zophenone derivatives, aryl sulfides, divinyl tereph
said method comprising adding a metal deactivator thalate, diphenyl terephthalate, and mixtures thereof,
Selected from the group consisting of areoxalyl bis(ben wherein the at least one amine is selected from the group
Zylidene)hydrazide: N,N'-bis(3,5-di-tert-butyl-4-hy consisting of triethylamine; tributylamine; diisopro
droxyhydrocinnamoylhydrazine); 2,2'-oxamidobis pylamine; triisopropylamine; triisobutylamine;
ethyl-(3,5-d-tert-butyl-4-hydroxyhydrorcinnamate); p-phenylenediamine; diphenylamine; dialkylamines;
N,N'-(disalicyclidene)-1,2-propanediamine; (N-(1-methylethyl)-2-propylamine; alkyl-substituted
ethyenediaminetetraacetic acid and salts thereof, triazoles; piperidyl, piperidinyl, piperazinone, and alkoxypip
benzotriazole, 2-mercaptobenzothiazole, tolutriazole 10 eridinyl compounds; 2.2.6.6-tetramethyl-4-piperi
derivatives, N,N-disalicylidene-1,2-diaminopropane, done; 2.2.6,6-tetramethyl-4-piperidinol; bis-(1.2.2.6.
and mixture thereof, and an effective amount of stabi
6-pentamethylpiperidyl)sebacate; di-(2.2.6,6-
lizer consisting of at least one amine; tetramethyl-4-piperidyl)sebacate; poly-(N-
and optionally, hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxy
15 piperidyl Succinate; 2.2.6,6-tetramethyl-4-
at least one additional stabilizer compound selected piperidone, 2.2.6.6-tetramethyl-4-piperidinol, bis-(1,
from the group consisting of phenols, thiophosphates, 2.2.6,6-pentamethylpiperidyl)sebacate, di-(2.2.6.6-
butylated triphenylphosphorothionates, organo phos tetramethyl-4-piperidyl)sebacate, poly-(N-
phates, phosphites, terpenes, terpenoids, fullerenes, hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxy
functionalized perfluoropolyethers, polyoxyalky piperidyl Succinate, and mixtures thereof.
lated aromatics, alkylated aromatics, epoxides, fluori
nated epoxides, oxetanes, ascorbic acid, thiols, lac k k k k k