US8663494

USOO8663494 B2
(12) United States Patent (10) Patent No.: US 8,663,494 B2

HOWell et al. (45) Date of Patent: *Mar. 4, 2014
(54) TERPENE,TERPENOID, AND FULLERENE 6,260,380 B1* 7/2001 Arman et al. ................... 62.646
STABILIZERS FOR FLUOROOLEFNS 6,653,511 B2 11/2003 Howell et al.
6,982, 173 B2 1/2006 Marchionni et al.
(75) Inventors: Jon Lee Howell, Bear, DE (US); 25, E: $39, St. st al.
Velliyur Nott Mallikarjuna Rao, 8,049,046 B2 11/2011 Lecket al.
Wilmington, DE (US); Thomas J. Leck, 8,075,796 B2 * 12/2011 Rao et al. ........................ 252,67
Hockessin, DE (US); Barbara Haviland R. E: : 38: E. al
J. W. J. OWell Gal. ...................
53.
Minor, Elkton, MD (US); Marigloseph 8, 188,323 B2 5, 2012 Lecket al.
Nappa, Newark, DE (US); Nandini C. 8,383,004 B2 * 2/2013 Mouli et al. .................... 252,68
Mouli, Reisterstown, MD (US); 8,426,657 B2 4/2013 Lecket al.
Ekaterina N. Swearingen, Wilmington, 2003/0027732 A1 2/2003 Howell et al.
DE- (US); Andrew Edward Feiring, SSA 3.58. Sea
Ingh et al. ..................... 252/71
Wilmington, DE (US) 2005.0029488 A1* 2, 2005 Li et al. ...... 252,68
2005.01099.78 A1 5/2005 Lecket al.
(73) Assignee: E I du Pont de Nemours and 2005. O151113 A1 7, 2005 Minor et al.
Company, Wilmington, DE (US) 2005/0233.934 A1 10/2005 Singh et al.
2006/0022166 A1 2, 2006 Wilson et al.
(*) Notice: Subject to any disclaimer, the term of this 2006, OO33072 A1 2.2006 Wilson et al.
p
atent is extended or adiusted under 35 2006.0043330 A1
2006/0243944 A1
3/2006 Wilson et al.
11/2006 Minor et al.
U.S.C. 154(b) by 5 days. 2006/0243945 A1 11/2006 Minor et al.
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This patent is subject to a terminal dis- 2006, O2931.95 A1 12/2006 Howell et al.
claimer. 2007/00495O2 A1 3/2007 Howell et al.
2008/0157022 A1* 7/2008 Singh et al. ..................... 252,68
(21) Appl. No.: 13/325,966 2008, 0230738 A1 9, 2008 Minor et al.
2009, 0288.431 A1 11/2009 Rao et al.
1-1. 2010.0009155 A1 1/2010 Hashii et al.
(22) Filed Dec.e -14,rs 2011
(Continued)
(65) Prior Publication Data
FOREIGN PATENT DOCUMENTS
US 2012/OO851 1 O A1 Apr. 12, 2012
EP O 432273 A1 6, 1991
Related U.S. Application Data EP O885952 A1 12/1998
- - - (Continued)
(62) Division of application No. 12/377,645, filed as OTHER PUBLICATIONS
application No. PCT/US2007/019143 on Aug. 31,
2007, now Pat. No. 8,101,094. F. Jeanneaux, et al., Journal of Fluorine Chemistry, vol. 4 (Jul. 1974)
pp. 261-270, France.
(60) Provisional application No. 60/841,835, filed on Sep. C. Coudures, et al., Journal of Fluorine Chemistry, vol. 24 (1984), pp.
1, 2006, provisional application No. 60/841,943, filed 93-104, France.
on Sep. 1, 2006, provisional application No. Viacheslave A. Petrov et al., New Partially Fluorinated Epoxides by
60/841,891, filed on Sep. 1, 2006, provisional Oxidation of Olefins with Sodium Hypohalites Under Phase Transfer
application No. 60/841,975, filed on Sep. 1, 2006, Catalysis,Journal of Fluorine Chemistry, vol. 125 (2004), pp. 99-105,
Russia.
provisional application No. 60/921,528, filed on Apr. Ming H. Hung, et al., Direct Epoxidation of Fluorinated Olefins
2, 2007. Using the F2-H20-CH3CN System, Journal of Organic Chemistry,
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(51) Int. C. 1990 ASHRAE Handbook, Refrigeration Systems and Applications,
C09K3/04 (2006.01) Chapter 8, titled “Lubricants in Refrigeration Systems.” pp. 8.1-8.21.
(52) U.S. C. “Synthetic Lubricants and High-Performance Fluids.” Marcel Dek
USPC ............................................................ 252/68 ker, Inc., 1993, Chapter 2, titled “Esters' by Steven James Randles,
pp. 41-65 and Chapter 4, titled “Polyalkylene Glycols” by Paul L.
(58) Field of Classification Search Matlocket. al., pp. 101-123.
USPC ............................................................ 252/68 International Search Report, mailed Dec. 11, 2007.
See application file for complete search history.
(Continued)
(56) References Cited Primary Examiner — John Hardee
U.S. PATENT DOCUMENTS (57) ABSTRACT
The present invention relates to compositions comprising at
5,202,044 A * 4, 1993 Hagihara et al. ................ 252/68 least one fluoroolefin and an effective amount of stabilizer
5,221,494 A 6, 1993 Ikeda et al. that may be a terpene, terpenoid or fullerene; or a mixture of
5,376,359 A 12/1994 Johnson a terpene, terpenoid or fullerene with other stabilizers. The
5,413,728 A 5, 1995 Mall et al. stabilized compositions may be useful in cooling apparatus,
5,454,963 A 10, 1995 Kaneko Such as refrigeration, air-conditioning, chillers, and heat
5,543,068 A 8, 1996 Kaimai et al. pumps, as well as in applications as foam blowing agents,
5,895,793 A 4, 1999 Kitamura et al. Solvents, aerosol propellants, fire extinguishants, and ster
6,066,768 A 5/2000 Nappa et al. ilants.
6,184, 187 B1 2/2001 Howell et al.
6,221,273 B1 4/2001 Basile et al. 17 Claims, No Drawings
US 8,663,494 B2
Page 2
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WO 2005.119143 A2 12/2005
U.S. PATENT DOCUMENTS WO 2006069362 A2 6, 2006
WO 2006O943O3 A2 9, 2006
2010/0288966 A1 11/2010 Lecket al. WO 2006130406 A2 12/2006
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WO 2008/042066 A1 4, 2008
EP O947572 A1 10, 1999
EP 1275 678 A2 1, 2003 OTHER PUBLICATIONS
EP 1306 417 A2 5, 2003 E. N. Step et al., Mechanism of Polymer Stabilization by Hindered
EP 1325949 A2 7, 2003 Amine Light Stabilizers (HALS). Model Investigations of the Inter
GB 1587907 A1 4f1981 action of Peroxy Radicals with HALS Amines and Amino Ethers,
JP O4110388 A 4f1992 American Chemical Society, Macromolecules, vol. 27, No. 9, 1994,
JP 2006O461 O2 A 2, 2006
RU 2O73058 C1 2/1997 pp. 2529-2539.
WO 9708116 A1 3, 1997 U.S. Appl. No. 12/377,454, filed Feb. 13, 2009 (National filing of
WO O2/38718 A2 5, 2002 PCT/US2007/019140 filed Aug. 31, 2007; see WO2008/027511).
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US 8,663,494 B2
1. 2
TERPENE,TERPENOID, AND FULLERENE Also provided is a composition comprising: a) at least one
STABILIZERS FOR FLUOROOLEFINS fluoroolefin; and b) an effective amount of a stabilizer com
prising: i) at least one terpene, terpenoid, fullerene, or mixture
This application is a divisional of U.S. Application No. thereof; ii) at least one phosphite, phenol, epoxide, fluori
12/377,645 filed Mar. 16 2009 now U.S. Pat. No. 8,101,094, 5 nated epoxide, or mixture thereof, and iii) at least one metal
which represents a national filing under 35 U.S.C. 371 of deactivator selected from the group consisting of areoxalyl
International Application No. PCT/US2007/019143 filed bis(benzylidene)hydrazide: N,N'-bis(3,5-di-tert-butyl-4-hy
Aug. 31, 2007, and claims priority of U.S. Provisional Appli droxyhydrocinnamoylhydrazine); 2.2'-oxamidobis-ethyl-(3.
cation No. 60/841,835 filed Sep. 1, 2006, U.S. Provisional 10
5-d-tert-butyl-4-hydroxyhydrorcinnamate); N,N'-(disalicy
Application No. 60/841,943 filed Sep. 1, 2006, U.S. Provi clidene)-1,2-propanediamine; ethyenediaminetetraacetic
sional Application No. 60/841,891 filed Sep. 1, 2006, U.S. acid and salts thereof, triazoles; benzotriazole, 2-mercapto
Provisional Application No. 60/841,975 filed Sep. 1, 2006, benzothiazole, tolutriazole derivatives, N,N-disalicylidene-1,
and U.S. Provisional Application No. 60/921,528 filed Apr. 2, 2-diaminopropane, and mixtures thereof.
2007. 15 Also provided is a method for stabilizing a composition
comprising at least one fluoroolefin, said method comprising
BACKGROUND OF THE INVENTION adding an effective amount of a stabilizer comprising at least
one terpene, terpenoid, or fullerene, and at least one com
1. Field of the Invention pound selected from the group consisting of thiophosphates,
The present invention relates to compositions comprising butylated triphenylphosphorothionates, organo phosphates,
at least one fluoroolefin and a stabilizer comprising at least functionalized perfluoropolyethers, polyoxyalkylated aro
one terpene, terpenoid or fullerene. The stabilized composi matics, alkylated aromatics, oxetanes, ascorbic acid, thiols,
tions may be useful in cooling systems as replacements for lactones, thioethers, amines, nitromethane, alkylsilanes, ben
existing refrigerants with higher global warming potential. Zophenone derivatives, aryl sulfides, divinyl terephthalate,
2. Description of Related Art 25 diphenyl terephthalate, and mixtures thereof to said at least
New environmental regulations on working fluids have one fluoroolefin.
forced the refrigeration and air-conditioning industry to look Also provided is a method for reducing degradation of a
for new refrigerants with low global warming potential composition comprising at least one fluoroolefin, wherein
(GWP). said degradation is caused by the presence of inadvertent air
Replacement working fluids are being sought that have low 30 in a refrigeration, air-conditioning or heat pump system, said
GWP no toxicity, non-flammability, reasonable cost and method comprising adding an effective amount of a stabilizer
excellent refrigeration performance. comprising at least one terpene, terpenoid, or fullerene, and at
Fluoroolefins have been proposed as working fluids alone least one compound selected from the group consisting of
or in mixtures. However, it has been observed that fluoroole thiophosphates, butylated triphenylphosphorothionates,
fins can exhibit degradation when exposed to high tempera 35 organo phosphates, functionalized perfluoropolyethers, poly
tures or when contacted with other compounds (e.g., mois oxyalkylated aromatics, alkylated aromatics, oxetanes, ascor
ture, oxygen, or other compounds with which they may bic acid, thiols, lactones, thioethers, amines, nitromethane,
undergo condensation reactions. This degradation may occur alkylsilanes, benzophenone derivatives, aryl Sulfides, divinyl
when fluoroolefins are used as working fluids in heat transfer terephthalate, diphenylterephthalate, and mixtures thereof to
equipment (refrigeration or air-conditioning equipment, for 40 the composition comprising at least one fluoroolefin.
instance) or when used in some other application. This deg Also provided is a method for reducing reaction with oxy
radation may occur by any number of different mechanisms. gen for a composition comprising at least one fluoroolefin,
In one instance, the degradation may be caused by instability said method comprising adding an effective amount of stabi
of the compounds at extreme temperatures. In other lizer comprising a stabilizer comprising at least one terpene,
instances, the degradation may be caused by oxidation in the 45 terpenoid, or fullerene, and at least one compound selected
presence of air that has inadvertently leaked into the system. from the group consisting of thiophosphates, butylated triph
Whatever the cause of such degradation, because of the insta enylphosphorothionates, organo phosphates, functionalized
bility of the fluoroolefins, it may not be practical to incorpo perfluoropolyethers, polyoxyalkylated aromatics, alkylated
rate these fluoroolefins into refrigeration or air-conditioning aromatics, oxetanes, ascorbic acid, thiols, lactones, thioet
systems. Therefore, to take advantage of the many other 50 hers, amines, nitromethane, alkylsilanes, benzophenone
attributes of fluoroolefins, means to reduce the degradation is derivatives, aryl sulfides, divinyl terephthalate, diphenyl
needed. terephthalate, and mixtures thereof to the composition com
prising at least one fluoroolefin.
SUMMARY OF THE INVENTION
55 DETAILED DESCRIPTION OF THE INVENTION
The present disclosure provides a composition comprising:
at least one fluoroolefin; and an effective amount of a stabi The present invention provides a composition comprising
lizer comprising at least one terpene, terpenoid, fullerene, or at least one fluoroolefinand an effective amount of a stabilizer
mixture thereof, and at least one compound selected from the comprising at least one terpene, terpenoid, or fullerene.
group consisting of thiophosphates, butylated triphenylphos 60 These compositions have a variety of utilities in working
phorothionates, organo phosphates, aryl alkyl ethers, func fluids, which include blowing agents, solvents, aerosol pro
tionalized perfluoropolyethers, polyoxyalkylated aromatics, pellants, fire extinguishants, sterilants or heat transfer medi
alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones, ums (such as heat transfer fluids and refrigerants for use in
thioethers, amines, nitromethane, alkylsilanes, benzophe refrigeration systems, refrigerators, air conditioning systems,
none derivatives, arylsulfides, divinylterephthalate, diphenyl 65 heat pumps, chillers, and the like), to name a few.
terephthalate, graphite, polycyclic aromatics, and mixtures A blowing agent is a volatile composition that expands a
thereof. polymer matrix to form a cellular structure.
US 8,663,494 B2
3 4
A solvent is a fluid that removes a soil from a substrate, or in the compositions as disclosed herein comprise compounds
deposits a material onto a Substrate, or carries a material. with 2 to 12 carbon atoms, in another embodiment the fluo
An aerosol propellant is a volatile composition of one or roolefins comprise compounds with 3 to 10 carbonatoms, and
more components that exerts a pressure greater than one in yet another embodiment the fluoroolefins comprise com
atmosphere to expel a material from a container. pounds with 3 to 7 carbonatoms. Representative fluoroolefins
A fire extinguishant is a volatile composition that extin include but are not limited to all compounds as listed in Table
guishes or Suppresses a flame. 1, Table 2, and Table 3.
A sterilant is a volatile biocidal fluid or blend containing a One embodiment of the present invention provides fluo
volatile biocidal fluid that destroys a biologically active mate roolefins having the formula E- or Z-R'CH=CHR (Formula
rial or the like. 10 I), wherein R' and Rare, independently, C, to Ce perfluoro
A heat transfer medium (also referred to herein as a heat alkyl groups. Examples of R and R groups include, but are
transfer fluid, a heat transfer composition or a heat transfer not limited to, CF, CFs, CFCFCF, CF (CF).
fluid composition) is a working fluid used to carry heat from CFCFCFCF, CF(CF)CFCF, CFCF(CF), C(CF),
a heat Source to a heat sink. CFCFCFCFCF, CFCFCF (CF), C(CF),CF,
A refrigerant is a compound or mixture of compounds that 15 CFCFCFCFCFCF, CF(CF) CFCFCFs, and
function as a heat transfer fluid in a cycle wherein the fluid C(CF). CFCFs. In one embodiment the fluoroolefins of
undergoes a phase change from a liquid to a gas and back. Formula I, have at least about 4 carbonatoms in the molecule.
In one embodiment, the fluoroolefins are compounds In another embodiment, the fluoroolefins of Formula I have at
which comprise carbon atoms, fluorine atoms and optionally least about 5 carbon atoms in the molecule. Exemplary, non
hydrogen atoms. In one embodiment, the fluoroolefins used limiting Formula I compounds are presented in Table 1.
TABLE 1.
Code Structure Chemical Name
E CFCH=CHCF, 1,144.4-hexafluorobut-2-ene
E CFCH=CHC-Fs 1,144.5.5.5-octafluoropent-2-ene
E CFCH=CHCFCFs 1,144,5,5,6,6,6-decafluorohex-2-ene
F13iE CFCH=CHCF(CF), 1,145.5.5-heptafluoro-4-(trifluoromethyl)pent-2-ene
F22E CFCH=CHC-Fs ,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene
F14E CFCH=CH(CF)CF 1,144,5,5,6,6,7,7,7-dodecafluorohept-2-ene
F14iE CFCH=CHCFCF (CF), 1,144,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene
F14sE CFCH=CHCF(CF) CFs ,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene
F14tF, CFCH=CHC(CF), ,1,1,5,5,5-hexafluoro-44-bis(trifluoromethyl)pent-2-ene
F23E CFCH=CHCFCFs ,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene
F23i E. CFCH=CHCF (CF), ,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene
F15E CFCH=CH(CF)CF, 1,144,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene
F15iE CFCH=CH-CFCF-CF (CF), 1,144,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept
2-ene
F15tE CFCH=CH-C(CF)CFs ,1,1,5,5,6,6,6-octafluoro-44-bis(trifluoromethyl)hex-2-
tle
F24E CFCH=CH(CF)CF ,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene
F24iE CFCH=CHCFCF (CF), ,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept
3-ene
F24sE CFCH=CHCF (CF) CFs ,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept
3-ene
F24tE CFCH=CHC(CF). ,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-
tle
F33E CFCF-CH=CH-CFCFs ,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene
F3i3iE (CF)CFCH=CH-CF (CF), ,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-
tle
F33iE CFCF-CH=CH-CF(CF), ,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept
3-ene
F16E CFCH=CH(CF)CF 1,144,5,5,6,6,7,7,8,8,9,9.9-hexadecafluoronon-2-ene
F16sE CFCH=CHCF(CF) (CF)CFs 1,145,5,6,6,7,7,8,8,8-tridecafluoro-4-
(trifluoromethyl)hept-2-ene
F16tE CFCH=CHC(CF). CFCFs ,1,1,6,6,6-octafluoro-44-bis(trifluoromethyl)hept-2-ene
F25E CFCH=CH(CF). CF ,1,1,2,2,5,5,6,6,7,7,8,8,9,9.9-hexadecafluoronon-3-ene
F25iE CFCH=CH-CFCF-CF (CF), ,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-
(trifluoromethyl)oct-3-ene
F25tE CFCH=CH-C(CF)2C2Fs ,1,1,2,2,6,6,7,7,7-decafluoro-5,5-
bis(trifluoromethyl) hept-3-ene
F34E CFCF-CH=CH-(CF)CF ,1,1,2,2,3,3,6,6,7,7,8,8,9,9.9-hexadecafluoronon-4-ene
F34iE CFCF-CH=CH-CFCF(CF), ,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-
F34sE CFCF-CH=CH-CF (CF)CFs ,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-
F34tE CFCF-CH=CH-C(CF). ,1,1,5,5,6,6,7,7,7-decafluoro-2,2-
F314E (CF). CFCH=CH-(CF)CF, ,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro
2(trifluoromethyl)oct-3-ene
F314iE (CF)CFCH=CH-CFCF (CF), ,1,1,2,5,5,6,7,7,7-decafluoro-2,6-
F3I4SE (CF)CFCH=CH-CF (CF)CFs ,1,1,2,5,6,6,7,7,7-decafluoro-2,5-
US 8,663,494 B2
TABLE 1-continued
Code Structure Chemical Name
F314tF (CF)CFCH=CH-C(CF). sks 2,66,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-

tle
F26E CFCH=CH(CF)CF sks 2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec
3-ene
F26sE CFCH=CHCF (CF) (CF)CFs ,1,1,2,2,5,6,6,7,7,8,8,9,9.9-pentadecafluoro-5-
(trifluoromethyl)non-3-ene
F26tE CFCH=CHC(CF). CFC-Fs ,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-
bis(trifluoromethyl)oct-3-ene
F35E CFCF-CH=CH-(CF)CF sks 2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec
4-ene
F35iE CFCF-CH=CH-CFCF-CF (CF),,1,1,2,2,3,3,6,6,7,7,8,9,9.9-pentadecafluoro-8-
F35tE CFCF-CH=CH-C(CF)2C2Fs ,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-
F3i5E (CF)CFCH=CH (CF)CF ,1,1,2,5,5,6,6,7,7,8,8,9,9.9-pentadecafluoro-2-
F3i5iE (CF)CFCH=CH-CFCFCF (CF), 1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-
F3i5tE (CF)CFCH=CH-C(CF)2C2Fs 12,6,6,7,7,7-nonafluoro-2.5.5-
tris(trifluoromethyl) hept-3-ene
F44E CF (CF)CH=CH-(CF)CF sks 2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec
5-ene
F44iE CF (CF)-CH=CH-CFCF (CF), ,1,1,2,3,3,6,6,7,7,8,8,9,9.9-pentadecafluoro-2-
F44sE CF (CF)CH=CH-CF (CF)C2Fs ,1,1,2,2,3,6,6,7,7,8,8,9,9.9-pentadecafluoro-3-
F44tE CF (CF)CH=CH-C(CF). ,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2-
F4i4iE (CF)CFCF-CH=CH-CFCF (CF), 1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-
F4i4sE (CF)CFCF-CH=CH-CF (CF)C2Fs 1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-
F414tE (CF). CFCF-CH=CH-C(CF). ,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-
F4s4SE CFCF (CF)CH=CH-CF (CF)CFs 1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-
F4s4tE CFCF (CF)CH=CH-C(CF). ,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-
F4t4tE (CF). CCH=CH-C(CF). ,1,1,6,6,6-hexafluoro-2,2,5,5-
etrakis(trifluoromethyl)hex-3-ene
Compounds of Formula I may be prepared by contacting a erably within therange of about 150° C. to 300° C., preferably
perfluoroalkyl iodide of the formula R'I with a perfluoroalky 40 from about 170° C. to about 250° C., and most preferably
itrihydroolefin of the formula RCH=CH to form a trihy from about 180° C. to about 230° C.
droiodoperfluoroalkane of the formula RCHCHIR. This Suitable contact times for the reaction of the perfluoroalkyl
trihydroiodoperfluoroalkane can then be dehydroiodinated to iodide with the perfluoroalkyltrihydroolefin are from about
form R'CH-CHR. Alternatively, the olefin RCH=CHR 0.5 hour to 18 hours, preferably from about 4 to about 12
may be prepared by dehydroiodination of a trihydroiodoper hours.
fluoroalkane of the formula RCHICHR formed in turn by 45 The trihydroiodoperfluoroalkane prepared by reaction of
reacting a perfluoroalkyl iodide of the formula RI with a the perfluoroalkyl iodide with the perfluoroalkyltrihydroole
perfluoroalkyltrihydroolefin of the formula R'CH=CH. fin may be used directly in the dehydroiodination step or may
Said contacting of a perfluoroalkyl iodide with a perfluoro preferably be recovered and purified by distillation prior to
alkyltrihydroolefin may take place in batch mode by combin the dehydroiodination step.
ing the reactants in a Suitable reaction vessel capable of oper 50 The dehydroiodination step is carried out by contacting the
ating under the autogenous pressure of the reactants and trihydroiodoperfluoroalkane with a basic substance. Suitable
products at reaction temperature. Suitable reaction vessels basic Substances include alkali metal hydroxides (e.g.,
include fabricated from stainless steels, in particular of the Sodium hydroxide or potassium hydroxide), alkali metal
austenitic type, and the well-known high nickel alloys such as oxide (for example, Sodium oxide), alkaline earth metal
Monel(R) nickel-copper alloys, Hastelloy(R) nickel based hydroxides (e.g., calcium hydroxide), alkaline earth metal
alloys and Inconel(R) nickel-chromium alloys. 55 oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,
Alternatively, the reaction may take be conducted in semi Sodium methoxide or Sodium ethoxide), aqueous ammonia,
batch mode in which the perfluoroalkyltrihydroolefin reac Sodium amide, or mixtures of basic Substances such as Soda
tant is added to the perfluoroalkyl iodide reactant by means of lime. Preferred basic substances are sodium hydroxide and
a suitable addition apparatus Such as a pump at the reaction potassium hydroxide. Said contacting of the trihydroiodop
temperature. 60 erfluoroalkane with a basic Substance may take place in the
The ratio of perfluoroalkyl iodide to perfluoroalkyltrihy liquid phase preferably in the presence of a solvent capable of
droolefin should be between about 1:1 to about 4:1, prefer dissolving at least a portion of both reactants. Solvents Suit
ably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to able for the dehydroiodination step include one or more polar
result in large amounts of the 2:1 adduct as reported by organic solvents such as alcohols (e.g., methanol, ethanol,
Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4. n-propanol, isopropanol, n-butanol, isobutanol, and tertiary
pages 261-270 (1974). 65 butanol), nitriles (e.g., acetonitrile, propionitrile, butyroni
Preferred temperatures for contacting of said perfluoro trile, benzonitrile, or adiponitrile), dimethylsulfoxide, N.N-
alkyl iodide with said perfluoroalkyltrihydroolefin are pref dimethylformamide, N,N-dimethylacetamide, or sulfolane.
US 8,663,494 B2
7 8
The choice of solvent may depend on the boiling point prod monium bromide, tetrabutylammonium hydrosulfate, trieth
uct and the ease of separation of traces of the solvent from the ylbenzylammonium chloride, dodecyltrimethylammonium
product during purification. Typically, ethanol or isopropanol chloride, and tricaprylylmethylammonium chloride), quater
are good solvents for the reaction. nary phosphonium halides (e.g., triphenylmethylphospho
Typically, the dehydroiodination reaction may be carried 5 nium bromide and tetraphenylphosphonium chloride), or
out by addition of one of the reactants (either the basic sub cyclic polyether compounds known in the art as crown ethers
stance or the trihydroiodoperfluoroalkane) to the other reac (e.g., 18-crown-6 and 15-crown-5).
tant in a suitable reaction vessel. Said reaction may be fabri Alternatively, the dehydroiodination reaction may be con
cated from glass, ceramic, or metal and is preferably agitated ducted in the absence of solvent by adding the trihydroiodop
with an impeller or stirring mechanism. 10 erfluoroalkane to a solid or liquid basic Substance.
Temperatures suitable for the dehydroiodination reaction Suitable reaction times for the dehydroiodination reactions
are from about 10° C. to about 100° C., preferably from about are from about 15 minutes to about six hours or more depend
20°C. to about 70°C. The dehydroiodination reaction may be ing on the solubility of the reactants. Typically the dehydroio
carried out at ambient pressure or at reduced or elevated dination reaction is rapid and requires about 30 minutes to
pressure. Of note are dehydroiodination reactions in which 15 about three hours for completion. The compound of formula
the compound of Formula I is distilled out of the reaction I may be recovered from the dehydroiodination reaction mix
vessel as it is formed. ture by phase separation after addition of water, by distilla
Alternatively, the dehydroiodination reaction may be con tion, or by a combination thereof.
ducted by contacting an aqueous solution of said basic Sub In another embodiment of the present invention, fluoroole
stance with a solution of the trihydroiodoperfluoroalkane in 20 fins comprise cyclic fluoroolefins (cyclo-CX—CY
one or more organic solvents of lower polarity Such as an (CZW), (Formula II), wherein X, Y, Z, and W are inde
alkane (e.g., hexane, heptane, or octane), aromatic hydrocar pendently selected from Hand F, and n is an integer from 2 to
bon (e.g., toluene), halogenated hydrocarbon (e.g., methyl 5). In one embodiment the fluoroolefins of Formula II, have at
ene chloride, chloroform, carbon tetrachloride, or perchloro least about 3 carbon atoms in the molecule. In another
ethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, 25 embodiment, the fluoroolefins of Formula II have at least
tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, about 4 carbonatoms in the molecule. In yet another embodi
dimethoxyethane, diglyme, or tetraglyme) in the presence of ment, the fluoroolefins of Formula II have at least about 5
a phase transfer catalyst. Suitable phase transfer catalysts carbon atoms in the molecule. Representative cyclic fluo
include quaternary ammonium halides (e.g., tetrabutylam roolefins of Formula II are listed in Table 2.
TABLE 2
Cyclic
fluoroolefins Structure Chemical name
FC-C13.16cc cyclo-CFCF-CF=CF 1,2,3,3,4,4-hexafluorocyclobutene
HFC-C1334cc. cyclo-CFCF-CH=CH 3,3,4,4-tetrafluorocyclobutene
HFC-C1436 cyclo-CFCFCF-CH=CH 3,3,4,4,5,5-hexafluorocyclopentene
FC-C1418y cyclo-CFCF-CFCFCF 1,2,3,3,4,4,5,5-octafluorocyclopentene
FC-C151-10y cyclo-CFCF-CFCF-CFCF – 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene
40
The compositions of the present invention may comprise a
single compound of Formula I or formula II, for example, one
of the compounds in Table 1 or Table 2, or may comprise a
combination of compounds of Formula I or formula II.
In another embodiment, fluoroolefins may comprise those
compounds listed in Table 3.
TABLE 3
Structure Chemical name
225ye CFCF-CHF 2,3,3,3-pentafluoro-1-propene

225zc CFCH=CF, ,1,3,3,3-pentafluoro-1-propene
225yc CHF.CF–CF, ,1,2,3,3-pentafluoro-1-propene
234ye CHF.CF=CHF ,2,3,3-tetrafluoro-1-propene
234yf CFCF-CH 2,3,3,3-tetrafluoro-1-propene
234ze CFCH=CHF ,3,3,3-tetrafluoro-1-propene
234yc CHFCF-CF, ,1,2,3-tetrafluoro-1-propene
234zc CHF.CH=CF, ,1,3,3-tetrafluoro-1-propene
243yf CHF.CF–CH, 2,3,3-trifluoro-1-propene
243Zf CFCH=CH- 3,3,3-trifluoro-1-propene
243yc CHCF=CF, 12-trifluoro-1-propene
243Zc CHFCH=CF, 1,3-trifluoro-1-propene
243ye CHFCF-CHF 2,3-trifluoro-1-propene
243Ze CHF CH-CHF ,3,3-trifluoro-1-propene
FC-1318my CFCF-CFCF ,1,1,2,3,444-octafluoro-2-butene
FC-1318cy CFCFCF-CF, ,1,2,3,3,444-octafluoro-1-butene
327my CFCF-CHCF, ,1,1,2,4,44-heptafluoro-2-butene
327ye CHF-CFCFCF 2,3,3,444-heptafluoro-1-butene
327py CHF.CF–CFCF ,1,1,2,3,4,4-heptafluoro-2-butene
US 8,663,494 B2
13 14
TABLE 3-continued
Name Structure Chemical name
FC-161-14mcyy CFCFCF-CFCF-C2Fs 1,1,1,2,2,3,4,5,5,6,6,7,7,7-

tetradecafluoro-2-heptene
HFC-162-13mzy CFCH=CFCFCFCF 1,1,1,3,4,4,5,5,6,6,7,7,7-
tridecafluoro-2-heptene
HFC 162-13myz CFCF-CHCFCF-C-Fs 1,1,1,2,4,4,5,5,6,6,7,7,7-
HFC-162-13mczy CFCF-CH=CFCF-C-Fs 1,1,1,2,2,4,5,5,6,6,7,7,7-
HFC-162-13mcyz CFCF-CF=CHCFC-Fs 1,1,1,2,2,3,5,5,6,6,7,7,7-
PEVE pentafluoroethyl trifluorovinyl ether
PMVE trifluoromethyl trifluorovinyl ether
15
The compounds listed in Table 2 and Table 3 are available 1.2.2.5.5,6,6,6-decafluoro-3-iodohexane may be carried out
commercially or may be prepared by processes known in the by reaction of perfluoroethyliodide (CFCFI) and 3.3.4.4.4-
art or as described herein. pentafluoro-1-butene (CFCF-CH=CH-) at about 200° C.
1,1,1,4,4-pentafluoro-2-butene may be prepared from 1.1, under autogenous pressure for about 8 hours.
1,2,4,4-hexafluorobutane (CHFCHCHFCF) by dehydrof 1,1,1,4,5,5.5-heptafluoro-4-(trifluoromethyl)-2-pentene
luorination over solid KOH in the vapor phase at room tem may be prepared by the dehydrofluorination of 1,1,1,2,5,5.5-
perature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is heptafluoro-4-iodo-2-(trifluoromethyl)-pentane
described in U.S. Pat. No. 6,066,768, incorporated herein by (CFCHICHCF(CF)) with KOH in isopropanol.
reference. 25 CFCHICHCF(CF) is made from reaction of (CF),CFI
1.1.1.4.4.4-hexafluoro-2-butene may be prepared from with CFCH=CH at high temperature, such as about 200°
1,1,14.4.4-hexafluoro-2-iodobutane (CFCHICHCF) by C.
reaction with KOHusing a phase transfer catalyst at about 60° 1.1.1.4.4.5,5,6,6,6-decafluoro-2-hexene may be prepared
C. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane may by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene
be carried out by reaction of perfluoromethyl iodide (CFI) 30 (CFCH=CHCF) with tetrafluoroethylene (CF=CF) and
and 3,3,3-trifluoropropene (CFCH=CH-) at about 200° C. antimony pentafluoride (SbF).
under autogenous pressure for about 8 hours. 2,3,3,4,4-pentafluoro-1-butene may be prepared by dehy
3.4.4.5.5.5-hexafluoro-2-pentene may be prepared by drofluorination of 1,1,2,2,3,3-hexafluorobutane over fluo
dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane rided alumina at elevated temperature.
(CFCFCFCHCH) using solid KOH or over a carbon 35 2.3.3.4.4.5.5.5-octafluoro-1-pentene may be prepared by
catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentane may dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane
be prepared by hydrogenation of 3.3.4.4.5.5.5-heptafluoro-1- over Solid KOH.
pentene (CFCFCF-CH=CH-). 1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared by
1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehy dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane
drofluorination of 1,1,1,2,3,3,4-heptafluorobutane 40 over fluorided alumina at elevated temperature.
(CHFCFCHFCF) using solid KOH. Many of the compounds of Formula I, Formula II, Table 1,
1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehy Table 2, and Table 3 exist as different configurational isomers
drofluorination of 1,1,1,2,2,4,4-heptafluorobutane or stereoisomers. When the specific isomer is not designated,
(CHFCHCFCF) using solid KOH. the present invention is intended to include all single configu
1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehy 45 rational isomers, single Stereoisomers, or any combination
drofluorination of 1,1,1,3,3,4,4-heptafluorobutane thereof. For instance, F11E is meant to represent the E-iso
(CFCHCFCHF) using solid KOH. mer, Z-isomer, or any combination or mixture of both isomers
1,1,1,2,4-pentafluoro-2-butene may be prepared by dehy in any ratio. As another example, HFC-1225ye is meant to
drofluorination of 1,1,1,2,2,3-hexafluorobutane represent the E-isomer, Z-isomer, or any combination or mix
(CHFCHCFCF) using solid KOH. 50 ture of both isomers in any ratio.
1,1,1,3,4-pentafluoro-2-butene may be prepared by dehy The present invention provides compositions comprising at
drofluorination of 1,1,1,3,3,4-hexafluorobutane least one fluoroolefin and at least one stabilizer comprising an
(CFCHCFCHF) using solid KOH. effective amount of a stabilizer comprising at least one ter
1,1,1,3-tetrafluoro-2-butene may be prepared by reacting pene, terpenoid, or fullerene, and at least one compound
1,1,1,3,3-pentafluorobutane (CFCHCFCH) with aqueous 55 selected from the group consisting of thiophosphates, buty
KOH at 120° C. lated triphenylphosphorothionates, organo phosphates, func
1.1.1.4.4.5.5.5-octafluoro-2-pentene may be prepared tionalized perfluoropolyethers, polyoxyalkylated aromatics,
from (CFCHICHCFCF) by reaction with KOH using a alkylated aromatics, oxetanes, ascorbic acid, thiols, lactones,
phase transfer catalyst at about 60° C. The synthesis of thioethers, amines, nitromethane, alkylsilanes, benzophe
4-iodo-1.1.1.2.2.5.5.5-octafluoropentane may be carried out 60 none derivatives, arylsulfides, divinylterephthalate, diphenyl
by reaction of perfluoroethyliodide (CFCFI) and 3,3,3-tri terephthalate, graphite, polycyclic aromatics, and mixtures
fluoropropeneatabout 200° C. under autogenous pressure for thereof.
about 8 hours. In one embodiment, the stabilizer comprises at least one
1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared terpene. Terpenes comprise hydrocarbon compounds charac
from 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane 65 terized by structures containing more than one repeating iso
(CFCFCHICHCFCF) by reaction with KOH using a prene (2-methyl-1,3-butadiene) unit. Representative terpenes
phase transfer catalyst at about 60° C. The synthesis of 1,1, include but are not limited to myrcene (2-methyl-6-methyl
US 8,663,494 B2
15 16
eneocta-1,7-diene), allo-ocimene, beta-ocimene, terebene, dithiophosphate is commercially available from Ciba Spe
limonene (in particulard-limonene), retinal, pinene, menthol, cialty Chemicals of Basel, Switzerland (hereinafter “Ciba')
geraniol, farnesol, phytol, Vitamin A, terpinene, delta-3- under the trademark Irgalube(R) 63. In another embodiment,
carene, terpinolene, phellandrene, fenchene, dipentene, and thiophosphates include dialkylthiophosphate esters. A repre
mixtures thereof. Terpene stabilizers are commercially avail 5 sentative dialkylthiophosphate ester stabilizer is commer
able or may be prepared by methods known in the art or cially available from Ciba under the trademark Irgalube(R)
isolated from natural sources. 353.
In another embodiment, the stabilizer comprises at least In another embodiment, the additional stabilizers of the
one terpenoid. Terpenoids comprise natural products and 10
present invention comprise at least one butylated triph
related compounds characterized by structures containing enylphosphorothionate as depicted by Formula A.
more than one repeating isoprene unit and usually contain
oxygen. Representative terpenoids include carotenoids, Such
as lycopene (CAS reg. no. 502-65-8), beta carotene (CAS Formula A
reg. no. 7235-40-7), and xanthophylls, i.e. zeaxanthin (CAS 15
reg. no. 144-68-3); retinoids, such as hepaxanthin (CAS reg.
no. 512-39-0), and isotretinoin (CAS reg. no. 4759-48-2);
abietane (CAS reg. no. 640-43-7); ambrosane (CAS reg. no.
24749-18-6); aristolane (CAS reg. no. 29788-49-6); ati A butylated triphenylphosphorothionate, wherein each R is
sane (CAS reg. no. 24379-83-7); beyerane (CAS reg. no. independently selected from H or tert-butyl, is commercially
2359-83-3), bisabolane (CAS reg. no. 29799-19-7); bor available from Ciba under the trademark Irgalube(R) 232
nane (CAS reg. no. 464-15-3); caryophyllane (CAS reg. no.
20479-00-9); cedrane (CAS reg. no. 13567-54-9); dam (Ciba).
marane (CAS reg. no. 545-22-2); drimane (CAS reg. no. In another embodiment, the additional stabilizers of the
5951-58-6); eremophilane (CAS reg. no. 3242-05-5]); 25 present invention comprise at least one organophosphate. The
eudesmane (CAS reg. no. 473-11-0); fenchane (CAS reg. organophosphate stabilizers include but are not limited to
no. 6248-88-0); gammacerane (CAS reg. no. 559-65-9); amine phosphates, trialkyl phosphates, triaryl phosphates,
germacrane (CAS reg. no. 645-10-3); gibbane (CAS reg. mixed alkyl-aryl phosphates (alkyldiaryl, dialkylaryl or alky
no. 6902-95-0); grayanotoxane (CAS reg. no. 39907-73 lated aryl), and cyclic phosphates. A representative amine
8); guaiane (CAS reg. no. 489-80-5); himachalane (CAS 30
phosphate is commercially available from Ciba under the
reg. no. 20479-45-2); hopane (CAS reg. no. 471-62-5); trademark Irgalube.R. 349 (Ciba). Representative trialkyl
humulane (CAS reg. no. 430-19-3); kaurane (CAS reg. no.
1573-40-6); labdane (CAS reg. no. 561-90-0); lanostane phosphates include: trimethyl phosphate ((CH)-PO, Cas
(CAS reg. no. 474-20-4); lupane (CAS reg. no. 464-99-3); reg. no. 512-56-1); triethyl phosphate ((CHCH-)PO, Cas
p-menthane (CAS reg. no. 99-82-1); oleanane (CAS reg. no. 35 reg. no. 78-40-0); tributyl phosphate ((CH3)PO, CAS reg.
471-67-0); ophiobolane (CAS reg. no. 20098-65-1): no. 126-73-8); trioctyl phosphate ((CH4)PO, CAS reg.
picrasane (CAS reg. no. 35732-97-9); pimarane (CAS reg. no. 1806-54-8); and tri(2-ethylhexyl)phosphate ((CHCH
no. 30257-03-5]); pinane (CAS reg. no. 473-55-2); (CHs)(CH))PO CAS reg. no. 78-42-2). Representative
podocarpane (CAS reg. no. 471-78-3); protostane (CAS
reg. no. 70050-78-1); rosane (CAS reg. no. 6812-82-4I); 40 triaryl phosphates include: triphenyl phosphate ((CHO).
taxane (CAS reg. no. 1605-68-1); thujane (CAS reg. no. PO, CAS reg. no. 115-86-6); tricresyl phosphate (TCP,
471-12-5); trichothecane (CAS reg. no. 24706-08-9); and (CHCHO). PO, CAS reg. no. 1330-78-5); and trixylenyl
ursane (CAS reg. no. 464-93-7). The terpenoids of the phosphate (((CH),CHO)PO, CAS reg. no. 25155-23-1).
present invention are commercially available or may be pre Representative mixed alkyl-aryl phosphates include: isopro
pared by methods known in the art or may be isolated from the 45
pylphenyl phenyl phosphate (IPPP (CHO) ((CH3)2CHO)
naturally occurring source. PO, CAS reg. no. 68782-95-6) and bis(t-butylphenyl)phenyl
In another embodiment the stabilizers of the present inven phosphate (TBPP (CHO)((CH),C)PO, CAS reg. no.
tion comprise at least one fullerene. Fullerenes comprise
closed carbon cages that are bonded as hexagonal carbon 65652-41-7). Such phosphorus compounds are available
rings (benzene) linked to each other partly via pentagons. The 50 from multiple chemical suppliers such as Aldrich (Milwau
relationship between the number of apices (a, carbon atoms) kee, Wis.); Alfa Aesar (Ward Hill, Mass.); or Akzo Nobel
and hexagon carbon rings (n) (pentagon rings always number (Arnhem, the Netherlands). Representative commercially
12) is given by: a-2(n+10). While this formula provides for available alkylated triaryl phosphates include a butylated
all theoretical structures, only those molecules with relatively triphenyl phosphate, commercially available from AkZo
low stress and distortion will be stable. Representative 55
Nobel (Arnhem, the Netherlands) under the trademark Syn
fullerenes includebutare not limited to Buckminsterfullerene
O-AdR 8784; a tert-butylated triphenyl phosphate commer
(C60, or “bucky ball, CAS reg. no. 99685-96-8), and 5.6 cially available from Great Lakes Chemical Corporation
fullerene-C7 (C70, CAS reg. no. 115383-22-7), fullerene (GLCC, West Lafayette, Ind.) under the trademark DuradR
Cze (CAS reg. no. 135113-15-4), fullerene-Cs (CAS reg. 620; and iso-propylated triphenyl phosphates, also commer
no. 136316-32-0), and fullerene-Cs (CAS reg. no. 60
135113-16-5). Fullerenes are commercially available. cially available from GLCC under the trademarks DuradR
In one embodiment, the additional stabilizers of the present 220 and 110.
invention comprise at least one thiophosphate. The thiophos In another embodiment, the additional stabilizers of the
phate stabilizers of the present invention are compounds present invention comprise at least one aryl alkyl ether. The
derived from phosphoric acids by substituting divalent sulfur 65 aryl alkyl ether stabilizers of the present invention may be
for one or more oxygenatoms. These may be monothiophos depicted by Formula B, whereinn is 1, 2 or 3 and R' is an alkyl
phates, dithiophosphates or higher order. A representative group of 1 to 16 carbon atoms.
US 8,663,494 B2
17 18
k is an average number such that the formula weight of R,
Formula B ranges from about 400 to about 15,000;
N each Q is independently F, Cl, or H:
2
H(OR), g, handi are numbers such that (g+h) ranges from about 1
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;
Representative aryl alkyl ethers include but are not limited to r is an average number such that the formula weight of R,
anisole, 1,4-dimethoxybenzene, 1,4-diethoxybenzene and ranges from about 400 to about 15,000; and
1,3,5-trimethoxybenzene. 10 each R and R' is independently H, a C-Clo alkyl, a halo
In another embodiment, the additional stabilizers of the gen, OR, OH, SOM, NR, ROH, RSOM, RNR,
present invention comprise at least one functionalized per RNO, RCN, C(O)OR, C(O)OM, C(O)R, or C(O)NR,
fluoropolyether. Such functionalized perfluoropolyethers or combinations of two or more thereof;
comprise perfluoropolyether- or perfluoroalkyl-containing wherein
and phosphorus-containing partially esterified aryl phos 15 R’ is independently H, C, -Co alkyl, or combinations of
phates, aryl phosphonates and salts thereof, containing either two or more thereof;
(i) a mono- or poly-alkylene oxide linking group between the R is a C-Clo alkyl; and
phosphorus and a fluorocarbon group, or (ii) no linking group M is hydrogen or a metal, preferably not aluminum;
between the phosphorus and fluorocarbon group as described t is equal to (6+u);
in U.S. Pat. No. 6,184,187, and references therein. Addition u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;
ally, the functionalized perfluoropolyether stabilizers may be V is independently either 2 or 4:
compounds as represented by Formula Babove, which con n is 0 or 1;
tain either a perfluoroalkyl or perfluoropolyether side chain. E is P. As, or Sb; and
Further, the functionalized perfluoropolyether stabilizers m is greater than about 0.5 to about 3, provided that, when
may be perfluoropolyether alkyl alcohols comprising a per 25 E=P, m-3.0 and t=6, R cannot be exclusively H or contain F;
fluoropolyether segment and one or more alcohols segments as described in U.S. patent application Ser. No. 1 1/167,330,
having a general formula, —CH2(CH2)OH, wherein— filed Jun. 27, 2006.
CH, represents a divalent linear or branched alkyl radical In another embodiment, the functionalized perfluoropoly
where q is an integer from 1 to about 10 as described in U.S. ether stabilizers of the present invention may comprise aryl
patent application Ser. No. 1 1/156,348, filed Jun. 17, 2005. 30 perfluoropolyethers, which are monofunctional aryl perfluo
In another embodiment, the functionalized perfluoropoly ropolyethers having the formula of R (Y), (CR)—
ether stabilizers of the present invention may comprise sub (O C.R") R, difunctional aryl perfluoropolyethers
stituted aryl pnictogen compositions having the structure having the formula of R,-(Y), (CR)-(O—
IR,-(CR).E(O),(CRe)s. wherein C.R (4) R2, or combinations thereof, wherein
R is a fluoropolyether chain having a formula weight rang 35 each of R, and R has a formula weight of about 400 to
ing from about 400 to about 15,000, comprises repeat units, about 15,000;
and is selected from the group consisting of: R, comprises repeat units selected from the group consist
(a) J-O-(CF(CF)CFO) (CFXO)ACFZ : ing of
(a) J-O-(CF(CF)CFO) (CFXO)ACFZ ,
(b) J'-O-(CFCFO).(CFO),CFZ"—; 40 (b) J-O-(CFCFO).(CFO),CFZ"—,
(c) J-O-(CF(CF,)CFO)CF(CF,)CF, ; (c) J-O-(CF(CFs)CFO),CF(CF,)—,
(d) J-O-(CQ-CFCF. O), CQ-CF : (d) J-O (CQ-CFCF (O), CQ.-,
(e) J-O-(CF(CFs)CFO) (CFCFO),(CFXO), (e) J-O-(CF(CFs)CFO) (CF.CFO),(CFX-O),
CFZ ; CFZ ,
(f) J-O-(CFCFO), CF ; and 45 (f) J-O-(CFCFO), 'CF , and
(h) combinations of two or more thereof (g) combinations of two or more thereof, and
where
wherein
J is a fluoroalkyl group selected from the group consisting the units with formulae CFCFO and CFO are randomly
distributed along the chain;
of CF, CFs, CF, CFC1, CFC1, CFC1, and combina 50 J is CF, CFs CF, CFC1, CFC1, CFC1, or combi
tions of two or more thereof; nations of two or more thereof;
c and dare numbers such that the ratio of c.d ranges from c and d are numbers such that the cid ratio ranges from
about 0.01 to about 0.5; about 0.01 to about 0.5;
X is F, CF, or combinations thereof; X is —F. —CF, or combinations thereof;
Z is F, C1 or CF; 55 Z is —F. —Cl or —CF;
J" is a fluoroalkyl group selected from the group consisting Z' is - F or - C1,
of CF, CF, CF, CFC1, CFC1, and combinations of two J" is CF, CFs, CF, CFC1, C.F.C1, or combinations of
or more thereof; two or more thereof;
e and fare numbers such that the ratio of e:f ranges from e and fare numbers such that the effratio ranges from about
about 0.3 to about 5: 60 0.3 to about 5:
Z' is For Cl; J is —C.F.s, —CF, or combinations thereof;
J is C.F.s, CF, or combinations thereof; j is an average number such that the formula weight of R,
ranges from about 400 to about 15,000;
j is an average number such that the formula weight of R, J is CF, CFs, CF, or combinations of two or more
ranges from about 400 to about 15,000; 65 thereof;
J is selected from the group consisting of CF, CFs, CF7, k is an average number such that the formula weight of R,
and combinations of two or more thereof; ranges from about 400 to about 15,000;
US 8,663,494 B2
19 20
each Q is independently —F. —Cl, or—H; one or more oxetane groups and is represented by Formula C,
g, handi are numbers such that (g+h) ranges from about 1 wherein R1-R6 are the same or different and can be selected
to about 50, the i/(g+h) ratio ranges from about 0.1 to about from hydrogen, alkyl or substituted alkyl, aryl or substituted
0.5; aryl.
J" is CF, CFs, or combinations thereof; 5
k is an average number such that the formula weight of R,
ranges from about 400 to about 15,000; Formula C
each R is independently —H, a halogen, —OH, -SOM,
NR, NO, ROH, -RSO.M. - RNR - RNO,
RCN, C(O)OR, C(O)CM, C(O)R, C(O) 10
NR, or combinations of two or more thereof; except that
when b=0, R cannot be four hydrogen atoms and —OH, or
—Br, or —NH; or R cannot be solely H or —NO, or
combinations thereof Representative oxetane stabilizers include but are not limited
each R" is independently H, -R, OR, a halogen, 15 to 3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toa
–OH, -SOM, NR, NO, CN, ROH, gosei Co., Ltd): 3-ethyl-3-(phenoxy)methyl)-oxetane, Such
RSOM, RNR - RNO, RCN, C(O)OR, as OXT-211 (Toagosei Co., Ltd); and 3-ethyl-3-((2-ethyl
—C(O)CM, C(O)R, C(O)NR, or combinations of two hexyloxy)methyl)-oxetane, such as OXT-212 (Toagosei Co.,
or more thereofprovided that ifb=0, the combination of Rand Ltd).
R cannot be four or more hydrogenatoms and -OH,-Br, In another embodiment, the additional stabilizers of the
—NH, or - NO; present invention comprise ascorbic acid (CAS reg. no. 50
each R is independently H, C, -Cio alkyl, or combinations 81-7).
of two or more thereof; In another embodiment, the additional stabilizers of the
R" is a C-Clo alkyl: present invention comprise at least one thiol compound, also
M is a hydrogen or metal ion; 25 known as mercaptains or hydrosulfides. Such thiol com
a is 0 or 1; pounds are the Sulfur analogs of the hydroxyl group contain
b is 0-5; ing alcohols. Representative thiol stabilizers include but are
Y is a divalent radical —CHOCH2—, —(CH), O—, not limited to methanethiol (methyl mercaptan), ethanethiol
—(CF), , —CFO—, —CFOCF, , —C(O)—, (ethyl mercaptan), Coenzyme A (CAS reg. no. 85-61-0),
—C(S) , or combinations of two or more thereof; 30 dimercaptosuccinic acid (DMSA, CAS reg. no. 2418-14-6),
n is about 1 to about 5; grapefruit mercaptan ((R)-2-(4-methylcyclohex-3-enyl)pro
o is about 2 to about 5: pane-2-thiol, CAS reg. no. 83150-78-1), cysteine ((R)-2-
t is equal to 6+u; amino-3-sulfanyl-propanoic acid, CAS reg. no. 52-90-4).
u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16; and lipoamide (1,2-dithiolane-3-pentanamide, CAS reg. no.
V is independently either 2 or 4: 35 940-69-2.
R is —(CFCFO) (CFO),CF, , —(CFO), In another embodiment, the additional stabilizers of the
(CFCFO),(CFXO), CF, , present invention comprise at least one lactone. Lactones are
cyclic esters that may be produced by the reaction of an
(CFO), Rf O (CFO), CF(CF) , alcohol group with a carboxylic acid group in the same mol
—((CQ)CFCFO)CFCF, , or combinations oftwo or 40 ecule. Representative lactone stabilizers of the present inven
more thereof; tion include but are not limited to gamma-butyrolactone
where (CAS reg. no. 96-48-0), delta-gluconolactone (CAS reg. no.
e, f, X, and Q are as defined above: 90-80-2), gamma-undecalactone (CAS reg. no. 104-67
p, q and rare numbers such that (p+q) ranges from 1 to 50 6), 6,7-dihydro-4(5H)-benzofuranone (CAS reg. No.
and r?(p+q) ranges from 0.1 to 0.05; 45 16806-93-2), and 5.7-bis(1,1-dimethylethyl)-3-2.3(or
each w is independently 2 to 45: 3,4)-dimethylphenyl-2(3H)-benzofuranone (CAS reg. no
Rf is linear or branched —CF : 201815-03-4) commercially available from Ciba under the
m is 1-10; and trademark Irganox RHP-136.
S is an average number Such that the formula weight of R In another embodiment, the additional stabilizers of the
ranges from 400 to 15,000, as described in U.S. patent appli 50 present invention comprise at least one thioether. Thioether
cation Ser. No. 1 1/218.259, filed Sep. 1, 2005. stabilizers of the present invention include but are not limited
In another embodiment, the additional stabilizer may com to benzyl phenyl sulfide (CAS reg. no. 831-91-4), diphenyl
prise at least one polyoxyalkylated aromatic. The polyoxy sulfide (CAS reg. no. 139-66-2), dioctadecyl 3,3'-thiodipro
alkylated aromatics are compounds represented by Formula pionate, commercially available from Ciba under the trade
B wherein the R' group is a polyoxyalkylated group compris 55 mark Irganox R, PS 802 (Ciba) and didodecyl 3,3'-thiopropi
ing at least one —CHCH-O-moiety. onate, commercially available from Ciba under the trademark
In another embodiment, the additional stabilizers of the Irganox(RPS800 (Ciba), and mixtures thereof, meaning mix
present invention comprise at least one alkylated aromatic tures of any of the thioethers listed in this paragraph.
compounds. Representative alkylated aromatics include but In another embodiment, the additional stabilizers of the
are not limited to alkylbenzene lubricants, both branched and 60 present invention comprise at least one amine. In one embodi
linear, commercially available under the trademarks ZerolR) ment the amine stabilizers comprise at least one compound
75, Zerol.R. 150 and Zerol R (linear alkylbenzenes) 500 from selected from the group consisting of triethylamine, tributy
Shrieve Chemicals and HAB 22 (branched alkylbenzene) lamine, diisopropylamine, triisopropylamine, triisobuty
sold by Nippon Oil. lamine, p-phenylenediamine, and diphenylamine. In another
In another embodiment, the additional stabilizers of the 65 embodiment, the amine stabilizers comprise dialkylamines
present invention comprise at least one oxetane. The oxetane including (N-(1-methylethyl)-2-propylamine, CAS reg. no.
stabilizers of the present invention may be a compound with 108-18-9). In another embodiment the amine stabilizers
US 8,663,494 B2
21 22
include hindered amine antioxidants. Hindered amine anti difluorobenzophenone; 4,4'-dihydroxybenzophenone; 4,4'-
oxidants include amines derived from substituted piperidine dimethoxybenzophenone, and mixtures thereof.
compounds, in particular derivatives of an alkyl-substituted In another embodiment, the additional stabilizers of the
piperidyl, piperidinyl, piperazinone, or alkoxypiperidinyl present invention comprise at least one aryl Sulfide. The aryl
compounds. Representative hindered amine antioxidants sulfide stabilizers comprise at least one selected from the
include 2.2.6.6-tetramethyl-4-piperidone; 2.2.6.6-tetram group consisting of benzyl phenyl sulfide, diphenyl sulfide,
ethyl-4-piperidinol; bis-(1.2.2.6,6-pentamethylpiperidyl)se dibenzylsulfide, and mixtures thereof.
bacate (CAS reg. no. 41556-26-7); di-(2.2.6,6-tetramethyl In another embodiment, the additional stabilizers of the
4-piperidyl)sebacate, such as the hindered amine present invention comprise at least one terephthalate. The
commercially available under the trademark Tinuvin R. 770 10 terephthalate stabilizers include divinyl terephthalate (CAS
by Ciba; poly-(N-hydroxyethyl-2.2.6,6-tetramethyl-4-hy reg. no. 13486-19-0), diphenyl terephthalate (CAS reg. no.
droxy-piperidyl succinate (CAS reg. no. 65447-77-0), such 1539-04-4), and mixtures thereof.
as that commercially available under the trademark Tinuvin R In another embodiment, the additional stabilizers of the
622LD from Ciba; alkylated paraphenylenediamines, such as present invention comprise graphite (CAS reg. no. 7782–42
N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, or 15 5), which is commercially available in multiple physical
N,N'-di-sec-butyl-p-phenylenediamine; and hydroxylamines forms.
such as tallow amines, N-methylbis(hydrogenated tallow In another embodiment, the additional stabilizers of the
alkyl)amine, or phenol-alpha-naphthylamine. Some other present invention comprise at least one polycyclic aromatic
hindered amine antioxidants include the amine antioxidant compound. Representative polycyclic aromatic compounds
commercially available from Ciba under the trademark Tinu include benzene, naphthalene (CAS reg. no. 91-20-3) and
vin R. 765, or commercially available from MayZo, Inc. under ferrocene (CAS reg. no. 102-54-5).
the trademark BLS(R) 1944 and BLS(R) 1770. The amines also Unless otherwise noted above, the stabilizers of the present
include mixtures of any of the amines listed in this paragraph. invention are commercially available from various chemical
In another embodiment, the additional stabilizers of the Supply houses.
present invention comprise nitromethane (CHNO, CAS 25 Single stabilizer compounds may be used in combination
reg. no. 75-52-5). in the present compositions comprising at least one fluoroole
In another embodiment, the additional stabilizers of the fin or multiple stabilizer compounds may be combined in any
present invention comprise at least one alkylsilane. Silanes proportion to serve as a stabilizer blend. The stabilizer blend
are compounds similar to hydrocarbons wherein a silicon may contain multiple stabilizer compounds from the same
atom replaces each carbon. Alkyl silane stabilizers include 30 class of compounds or multiple stabilizer compounds from
but are not limited to bis(dimethylamino)methylsilane different classes of compounds. For example, a stabilizer
(DMAMS, CAS reg. no. 22705-33-5), tris(trimethylsilyl) blend may contain2 or more terpenes or terpenoids, or one or
silane (TTMSS, CAS reg. no. 1873-77-4), vinyltriethoxysi more terpenes or terpenoids in combination with one or more
lane (VTES, CAS reg. no. 78-08-0), and vinyltrimethoxysi additional stabilizer compounds (e.g., lactones, amines, or
lane (VTMO, CAS reg. no. 2768-02-7). 35 phenols, for example).
In another embodiment, the additional stabilizers of the Additionally, some of the stabilizer compounds exist as
present invention comprise at least one benzophenone deriva multiple configurational isomers or stereoisomers. Single
tive. Benzophenone derivative stabilizers comprise ben isomers or multiple isomers of the same compound may be
Zophenone Substituted with side groups including halides, used in any proportion to prepare the stabilizer blend. Further,
Such as fluorine, chlorine, bromine or iodine, amino groups, 40 single or multiple isomers of a given compound may be
hydroxyl groups, alkyl groups such as methyl, ethyl or propyl combined in any proportion with any number of other com
groups, aryl groups such as phenyl, nitro groups, or any pounds to serve as a stabilizer blend. The present invention is
combinations of Such groups. Representative benzophenone intended to include all single configurational isomers, single
derivative stabilizers include but are not limited to: 2,5-dif Stereoisomers or any combination or mixture thereof.
luorobenzophenone; 2,5-dihydroxyacetophenone; 2-ami 45 Of particular note are stabilizer compositions comprising
nobenzophenone; 2-chlorobenzophenone; 2-fluoroben combinations of compounds that provide an unexpected level
Zophenone; 2-hydroxybenzophenone; of stabilization. Certain of these combinations may serve as
2-methylbenzophenone; 2-amino-4'-chlorobenzophenone; synergistic stabilizer compositions, that is, the combination
2-amino-4-fluorobenzophenone: 2-amino-5-bromo-2'-chlo of compounds that augment each others’ efficiency in a for
robenzophenone, 2-amino-5-chlorobenzophenone, 2-amino 50 mulation and the stabilization obtained is larger than that
5-chloro-2'-fluorobenzophenone: 2-amino-5-nitrobenzophe expected from the sum of the contributions of the individual
none; 2-amino-5-nitro-2'-chlorobenzophenone; 2-amino-2, components. Such synergistic stabilizer compositions may
5-dichlorobenzophenone: 2-chloro-4'-fluorobenzophenone; comprise at least one terpene, terpenoid, or fullerene, and any
2-hydroxy-4-methoxybenzophenone: 2-hydroxy-5-chlo of the compounds selected from the group consisting of thio
robenzophenone, 2-methylamino-5-chlorobenzophenone; 55 phosphates, butylated triphenylphosphorothionates, organo
3-methylbenzophenone; 3-nitrobenzophenone; 3-nitro-4'- phosphates, aryl alkyl ethers, functionalized perfluoropoly
chloro-4-fluorobenzophenone; 4-chlorobenzophenone; ethers, polyoxyalkylated aromatics, alkylated aromatics,
4-fluorobenzophenone: 4-hydroxybenzophenone, 4-meth oxetanes, ascorbic acid, thiols, lactones, thioethers, amines,
oxybenzophenone, 4-methylbenzophenone: 4-nitroben nitromethane, alkylsilanes, benzophenone derivatives, aryl
Zophenone, 4-phenylbenzophenone: 4-chloro-3-nitroben 60 Sulfides, divinyl terephthalate, diphenyl terephthalate, graph
Zophenone; 4-hydroxy-4'-chlorobenzophenone; 2,4- ite, polycyclic aromatics, and mixtures thereof, meaning mix
dihydroxybenzophenone; 2,4-dimethylbenzophenone; 2.5- tures of any of the foregoing with a terpene, terpenoid or
dimethylbenzophenone; 3,4-diaminobenzophenone; 3,4- fullerene.
dichlorobenzophenone; 3,4-difluorobenzophenone; 3,4- A limiting factor in the effectiveness of a stabilizer com
dihydroxybenzophenone; 3,4-dimethylbenzophenone; 4,4'- 65 position is the consumption of stabilizer and loss of function
bis(diethylamine)benzophenone; 4,4'-bis(dimethylamine) ality over the time of active use. Of particular note are syner
benzophenone; 4,4'-dichlorobenzophenone; 4,4'- gistic stabilizer compositions comprising mixtures of
US 8,663,494 B2
23 24
stabilizers that include components capable of regenerating Substituent group. Such as, alkylated monophenols including
the consumed Stabilizer during active use, hereinafter 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-eth
referred to as regenerative stabilizers. Unlike multi-func ylphenol; 2,4-dimethyl-6-tertbutylphenol; tocopherol; and
tional single, large Stabilizer compounds comprising multiple the like, hydroquinone and alkylated hydroquinones includ
stabilizing functional groups, regenerative stabilizers com ing t-butyl hydroquinone, other derivatives of hydroquinone;
prising Small “synergistic' stabilizers function with higher and the like, hydroxylated thiodiphenyl ethers, including 4,4'-
mobility and higher stabilization rates (meaning higher rates thio-bis(2-methyl-6-tert-butylphenol): 4,4'-thiobis(3-me
of reaction by which the stabilization is occurring). Regen thyl-6-tertbutylphenol): 2,2'-thiobis(4-methyl-6-tert-bu
erative stabilizer composition contains one or more stabiliz tylphenol); and the like, alkylidene-bisphenols including:
ers that can replenish itself or themselves after use, so that 10
4,4'-methylenebis(2,6-di-tert-butylphenol): 4,4'-bis(2,6-di
over long-term use, the composition’s efficacy is maintained. tert-butylphenol); derivatives of 2,2'- or 4.4-biphenoldiols;
An example of a regenerative stabilizer is a terpene, terpe 2,2'-methylenebis(4-ethyl-6-tertbutylphenol); 2.2'-methyl
noid, or a fullerene combined with at least one amine. enebis(4-methyl-6-tertbutylphenol): 4,4-butylidenebis(3-
In one embodiment, the amines for inclusion in the regen methyl-6-tert-butylphenol); 4.4-isopropylidenebis(2,6-di
erative stabilizer compositions may comprise any of the hin 15
tert-butylphenol): 2,2'-methylenebis(4-methyl-6-
dered amine antioxidants as described previously herein. Of nonylphenol); 2.2-isobutylidenebis(4,6-dimethylphenol;
particular note, are those hindered amines derived from sub
stituted piperidine compounds, in particular derivatives of an 2,2'-methylenebis(4-methyl-6-cyclohexylphenol, 2.2- or 4.4-
alkyl-substituted piperidyl, piperidinyl, piperazinone, or biphenyldiols including 2,2'-methylenebis(4-ethyl-6-tert-bu
alkoxypiperidinyl compounds. Representative hindered tylphenol); butylated hydroxy toluene (BHT), bisphenols
amine antioxidants are 2.2.6.6-tetramethyl-4-piperidone; comprising heteroatoms including 2,6-di-tert-alpha-dim
2.2.6.6-tetramethyl-4-piperidinol; bis-(1.2.2.6,6-pentameth ethylamino-p-cresol, 4.4-thiobis(6-tert-butyl-m-cresol); and
ylpiperidyl) sebacate (CAS reg. no. 41556-26-7); di-(2.2.6, the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N'-dim
6-tetramethyl-4-piperidyl)sebacate, such as Tinuvin R. 770; ethylaminomethylphenol); sulfides including: bis(3-methyl
poly-(N-hydroxyethyl-2.2.6,6-tetramethyl-4-hydroxy-pip 25 4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl
eridyl succinate (CAS reg. no. 65447-77-0), such as Tinu 4-hydroxybenzyl)sulfide; and the like; bis(2,4-bis(1,1-
vin R. 622LD (Ciba). Some others include Tinuvin R. 765 dimethylethyl)-6-methylphenol)ethyl ether; and mixtures
(Ciba), BLS(R) 1944 (MayZo, Inc.), and BLS(R) 1770 (MayZo). thereof. In another embodiment, the stabilizers of the present
In another embodiment, any of the compositions of the invention comprise at least one epoxide. Epoxides Suitable for
present invention as described above herein may further com 30
use in the above mentioned compositions include 1,2-propy
prise at least one metal deactivator selected from the group lene oxide (CAS reg. no. 75-56-9), 1.2-butylene oxide
consisting of areoxalyl bis(benzylidene)hydrazide (CAS reg. (CAS reg. no. 106-88-7), butylphenylglycidyl ether, pen
no. 6629-10-3): N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydro tylphenylglycidyl ether, hexylphenylglycidyl ether, hep
cinnamoylhydrazine) (CAS reg. no. 32687-78-8); 2.2'-Oxa tylphenylglycidyl ether, octylphenylglycidyl ether, non
midobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydrorcinnamate) 35
(CAS reg. no. 70331-94-1); N,N'-(disalicyclidene)-1,2-pro ylphenylglycidyl ether, decylphenylglycidyl ether, glycidyl
panediamine (CAS reg. no. 94-91-1); ethyenediaminetet methylphenylether, 1,4-glycidyl phenyl diether, 4-methox
raacetic acid (CAS reg. no. 60-00-4) and salts thereof; triaz yphenylglycidyl ether, naphthyl glycidyl ether, 1,4-digly
oles; benzotriazole, 2-mercaptobenzothiazole, tolutriazole cidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl
derivatives, N,N-disalicylidene-1,2-diaminopropane, and 40 glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl
mixtures thereof, meaning mixtures of any of the foregoing ether, allyl glycidyl ether, polypropylene glycol diglycidyl
metal deactivators listed in this paragraph. ether, and mixtures thereof. In another embodiment, the
In another embodiment, the compositions may comprise: epoxides of the present invention comprise fluorinated
at least one fluoroolefin; and an effective amount of a stabi epoxides. The fluorinated epoxide stabilizers of the present
lizer comprising at least one terpene, terpenoid, fullerene, or 45 invention may be depicted by Formula D, wherein each of R
mixture thereof; at least one phosphite, phenol, epoxide, flu through R is H, alkyl of 1 to 6 carbonatoms or fluoroalkyl of
orinated epoxide, or mixture thereof, and at least one metal 1 to 6 carbon atoms with the proviso that at least one of R
deactivator selected from the group consisting of areoxalyl through R is a fluoroalkyl group.
bis(benzylidene)hydrazide: N,N'-bis(3,5-di-tert-butyl-4-hy
droxyhydrocinnamoylhydrazine); 2.2'-oxamidobis-ethyl-(3. 50
5-d-tert-butyl-4-hydroxyhydrorcinnamate); N,N'-(disalicy Formula D
clidene)-1,2-propanediamine; ethyenediaminetetraacetic
acid and salts thereof triazoles; benzotriazole, 2-mercapto
benzothiazole, tolutriazole derivatives, N,N-disalicylidene-1, SA R4
2-diaminopropane, and mixtures thereof. Phosphites Suitable 55
for inclusion in the above mentioned compositions may be
hindered phosphites derived from substituted phosphites. In Representative fluorinated epoxide stabilizers include but are
particular, hindered phosphites are derivatives of alkyl, arylor not limited to trifluoromethyloxirane and 1,1-bis(trifluorom
alkylaryl phosphite compounds. Representative hindered ethyl)oxirane. Such compounds may be prepared by methods
phosphites are sold under the trademark Irgafos(R 168, (di-n- 60 known in the art, for instance by methods described in, Jour
octylphosphite), sold under the trademark Irgafos(ROPH and nal of Fluorine Chemistry, volume 24, pages 93-104 (1984),
(Iso-decyl diphenyl phosphite), sold under the trademark Journal of Organic Chemistry, volume 56, pages 3.187 to
Irgafos(R DDPP (all from Ciba), and phosphorous acid. Phe 3189 (1991), and Journal of Fluorine Chemistry, volume
nols suitable for inclusion in the above mentioned composi 125, pages 99-105 (2004).
tions are any Substituted or unsubstituted phenol compound 65 In one embodiment, the compositions of the present inven
including phenols comprising one or more substituted or tion may further comprise at least one additional compound
unsubstituted cyclic, straight chain, or branched aliphatic selected from the group consisting of fluoroolefins (as
US 8,663,494 B2
25 26
described previously herein), hydrofluorocarbons, hydrocar ethylether (DME, CHOCH), may be included as additional
bons, dimethyl ether, CFI, ammonia, carbon dioxide (CO). refrigerants of the present invention. DME is commercially
and mixtures thereof. available.
In one embodiment, additional compounds comprise In another embodiment, additional compounds may also
hydrofluorocarbons. The hydrofluorocarbon (HFC) com comprise iodotrifluoromethane (CFI), which is commer
pounds of the present invention comprise Saturated com cially available from various sources or may be prepared by
pounds containing carbon, hydrogen, and fluorine. Of par methods known in the art.
ticular utility are hydrofluorocarbons having 1-7 carbon In another embodiment, additional compounds may also
atoms and having a normal boiling point of from about -90° comprise carbon dioxide (CO), which is commercially avail
C. to about 80°C. Hydrofluorocarbons are commercial prod 10 able from various sources or may be prepared by methods
ucts available from a number of sources such as E. I. duPont known in the art.
de Nemours & Co., Fluoroproducts, Wilmington, Del. In another embodiment, additional compounds may also
comprise ammonia (NH), which is commercially available
19898, USA, or may be prepared by methods known in the from various sources or may be prepared by methods known
art. Representative hydrofluorocarbon compounds include 15 in the art.
but are not limited to fluoromethane (CHF, HFC-41), difluo In another embodiment, of particular note are composi
romethane (CHF, HFC-32), trifluoromethane (CHF, HFC tions comprising: HFC-1225ye and HFC-32: HFC-1225ye
23), pentafluoroethane (CFCHF, HFC-125), 1.1.2.2-tet and HFC-134a: HFC-1225ye, HFC-134a, and HFC-32:
rafluoroethane (CHFCHF HFC-134), 1,1,1,2- HFC-1225ye and HFC-1234yf: HFC-1225ye, HFC-1234yf,
tetrafluoroethane (CFCHF, HFC-134a), 1,1,1- and HFC-32: HFC-1225ye, HFC-1234yf. HFC-32, and CFI;
trifluoroethane (CFCH. HFC-143a), 1,1-difluoroethane and HFC-1225ye, HFC-1234yf and HFC-125.
(CHFCH, HFC-152a), fluoroethane (CHCHF, HFC In another embodiment, additional compounds include
161), 1,1,1,2,2,3,3-heptafluoropropane (CFCFCHF, compositions comprising fluoroolefins as disclosed in U.S.
HFC-227ca), 1,1,1,2,3,3,3-heptafluoropropane patent application Ser. No. 1 1/369,227 filed Mar. 2, 2006:
(CFCHFCF, HFC-227ea), 1,1,2,2,3,3-hexafluoropropane 25 U.S. patent application Ser. No. 1 1/393,109 filed Mar. 30,
(CHFCFCHF, HFC-236ca), 1,1,1,2,2,3-hexafluoropro 2006; and U.S. patent application Ser. No. 1 1/486,791 filed
pane (CFCFCHF, HFC-236cb), 1,1,1,2,3,3-hexafluoro Jul. 13, 2006; are intended to be included within the scope of
propane (CFCHFCHF, HFC-236ea), 1,1,1,3,3,3-hexafluo the present invention.
ropropane (CFCHCF, HFC-236fa), 1,1,2,2,3- The compositions of the present invention may further
pentafluoropropane (CHFCFCHF, HFC-245ca), 1,1,1,2, 30 comprise at least one lubricant. Lubricants of the present
2-pentafluoropropane (CFCFCH. HFC-245cb), 1,1,2,3,3- invention comprise those suitable for use with refrigeration or
pentafluoropropane (CHFCHFCHF, HFC-245ea), 1,1,1,2, air-conditioning apparatus. Among these lubricants are those
3-pentafluoropropane (CFCHFCHF, HFC-245eb), 1,1,1,3, conventionally used in compression refrigeration apparatus
3-pentafluoropropane (CFCHCHF, HFC-245fa), 1,2,2,3- utilizing chlorofluorocarbon refrigerants. Such lubricants and
tetrafluoropropane (CHFCFCHF, HFC-254ca), 1.1.2.2- 35 their properties are discussed in the 1990 ASHRAE Hand
tetrafluoropropane (CHFCFCH. HFC-254cb), 1,1,2,3- book, Refrigeration Systems and Applications, chapter 8,
tetrafluoropropane (CHFCHFCHF, HFC-254ea), 1,1,1,2- titled “Lubricants in Refrigeration Systems, pages 8.1
tetrafluoropropane (CFCHFCH, HFC-254eb), 1,1,3,3- through 8.21, herein incorporated by reference. Lubricants of
tetrafluoropropane (CHFCHCHF, HFC-254 fa), 1,1,1,3- the present invention may comprise those commonly known
tetrafluoropropane (CFCHCHF, HFC-254fb), 1,1,1- 40 as “mineral oils” in the field of compression refrigeration
trifluoropropane (CFCHCH. HFC-263fb), 2.2- lubrication. Mineral oils comprise paraffins (i.e. straight
difluoropropane (CHCFCH. HFC-272ca), 1.2- chain and branched-carbon-chain, Saturated hydrocarbons),
difluoropropane (CHFCHFCH, HFC-272ea), 1,3- naphthenes (i.e. cyclic or ring structure saturated hydrocar
difluoropropane (CHFCHCHF, HFC-272fa), 1,1- bons, which may be paraffins) and aromatics (i.e. unsaturated,
difluoropropane (CHFCHCH, HFC-272fb), 45 cyclic hydrocarbons containing one or more rings character
2-fluoropropane (CHCHFCH, HFC-281 ea), 1-fluoropro ized by alternating double bonds). Lubricants of the present
pane (CHFCHCH. HFC-281 fa), 1,1,2,2,3,3,4,4-octafluo invention further comprise those commonly known as “syn
robutane (CHFCFCFCHF, HFC-338 pcc), 1,1,1,2,2,4,4, thetic oils” in the field of compression refrigeration lubrica
4-octafluorobutane (CFCHCFCF, HFC-338mf), 1,1,1,3, tion. Synthetic oils comprise alkylaryls (i.e. linear and
3-pentafluorobutane (CFCHCHF, HFC-365mfc), 1,1,1,2, 50 branched alkyl alkylbenzenes), synthetic paraffins and naph
3.44.5.5,5-decafluoropentane (CFCHFCHFCFCF, HFC thenes, silicones, and poly-alpha-olefins. Representative con
43-10mee), and 1,1,1,2,2,3,4,5,5,6,6,7,7,7- ventional lubricants of the present invention are the commer
tetradecafluoroheptane (CFCFCHFCHFCFCFCF, cially available BVM 100 N (paraffinic mineral oil sold by
HFC-63-14 mee). BVA Oils), napthenic mineral oil commercially available
In another embodiment, additional compounds comprise 55 under the trademark from Suniso(R) 3GS and Suniso(R5GS by
hydrocarbons. The hydrocarbon compounds of the present Crompton Co., naphthenic mineral oil commercially avail
invention comprise compounds having only carbon and able from Pennzoil under the trademark Sontex.R. 372LT,
hydrogen. Of particular utility are compounds having 3-7 naphthenic mineral oil commercially available from Calumet
carbon atoms. Hydrocarbons are commercially available Lubricants under the trademark Calumet(R) RO-30, linear
through numerous chemical Suppliers. Representative hydro 60 alkylbenzenes commercially available from Shrieve Chemi
carbons include but are not limited to propane, n-butane, cals under the trademarks Zerol R75, ZerolR 150 and Zerol (R)
isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2-dim 500 and branched alkylbenzene, sold by Nippon Oil as HAB
ethylpropane, cyclopentane, n-hexane, 2-methylpentane, 22.
2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, Lubricants of the present invention further comprise those
cyclohexane, n-heptane, and cycloheptane. 65 which have been designed for use with hydrofluorocarbon
In another embodiment, additional compounds may also refrigerants and are miscible with refrigerants of the present
comprise hydrocarbons containing heteroatoms, such as dim invention under compression refrigeration and air-condition
US 8,663,494 B2
27 28
ingapparatus operating conditions. Such lubricants and their closed herein, and thereafter evaporating said composition in
properties are discussed in “Synthetic Lubricants and High the vicinity of a body to be cooled.
Performance Fluids'. R. L. Shubkin, editor, Marcel Dekker, A body to be cooled may be any space, location or object
1993. Such lubricants include, but are not limited to, polyol requiring refrigeration or air-conditioning. In stationary
esters (POEs) such as the commercially available POE sold applications the body may be the interior of a structure, i.e.
under the trademark Castrol(R) 100 (Castrol, United King residential or commercial, or a storage location for perish
dom), polyalkylene glycols (PAGs) such as RL-488A from ables, such as food or pharmaceuticals. For mobile refrigera
Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers tion applications the body may be incorporated into a trans
(PVEs). portation unit for the road, rail, Sea or air. Certain refrigeration
Lubricants of the present invention are selected by consid 10
systems operate independently with regards to any moving
ering a given compressor's requirements and the environment carrier, these are known as “intermodal” systems. Such inter
to which the lubricant will be exposed. modal systems include “containers' (combined seafland
The compositions of the present invention that may be transport) as well as “swap bodies' (combined road and rail
transport).
prepared by any convenient method to combine the desired The present invention further relates to a process for pro
amount of the individual components. A preferred method is 15 ducing heat comprising condensing a composition as dis
to weigh the desired component amounts and thereafter com closed herein in the vicinity of a body to be heated, and
bine the components in an appropriate vessel. Agitation may thereafter evaporating said composition.
be used, if desired. A body to be heated may be any space, location or object
Any suitable effective amount of stabilizer may be used in requiring heat. These may be the interior of structures either
the compositions comprising at least one fluoroolefin. As residential or commercial in a similar manner to the body to
described herein, the phrase “effective amount” refers to an be cooled. Additionally, mobile units as described for cooling
amount of stabilizer of the present invention which, when may be similar to those requiring heating. Certain transport
added to a composition comprising at least one fluoroolefin, units require heating to prevent the material being transported
results in a composition that will not degrade to produce as from Solidifying inside the transport container.
great a reduction in refrigeration performance when in use in 25 It is not uncommon for air to leak into a refrigeration,
a cooling apparatus as compared to the composition without air-conditioning system or heat pump. The oxygen in the air
stabilizer. Such effective amounts of stabilizer may be deter may lead to oxidation of certain components of the system
mined by way of testing under the conditions of standard test including the working fluid. Thus, in another embodiment,
ASHRAE 97-2004. In a certain embodiment of the present also disclosed is a method for reducing degradation of a
invention, an effective amount may be said to be that amount 30
composition comprising at least one fluoroolefin, wherein
of stabilizer that when combined with a composition com said degradation is caused by the presence of inadvertent air;
for example in a refrigeration, air-conditioning or heat pump
prising at least one fluoroolefin allows a cooling apparatus system, said method comprising adding an effective amount
utilizing said composition comprising at least one fluoroole of a stabilizer comprising at least one terpene, terpenoid, or
fin to perform at the same level of refrigeration performance fullerene, and at least one compound selected from the group
and cooling capacity as if a composition comprising 1,1,1,2- 35 consisting of thiophosphates, butylated triphenylphospho
tetrafluoroethane (R-134a), or other standard refrigerant rothionates, organo phosphates, functionalized perfluo
(R-12, R-22, R-502, R-507A, R-508, R401A, R401B, ropolyethers, polyoxyalkylated aromatics, alkylated aromat
R402A, R402B, R408, R-410A, R-404A, R407C, R-413A, ics, oxetanes, ascorbic acid, thiols, lactones, thioethers,
R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R-114, amines, nitromethane, alkylsilanes, benzophenone deriva
R-11, R-113, R-123, R-124, R236fa, or R-245fa) depending 40 tives, aryl sulfides, divinyl terephthalate, diphenyl terephtha
upon what refrigerant may have been used in a similar system late, and mixtures thereof to the composition comprising at
in the past, were being utilized as the working fluid. least one fluoroolefin.
Certain embodiments include effective amounts of stabi In another embodiment, also disclosed is a method for
lizer for use in the present invention that comprise from about reducing reaction with oxygen for a composition comprising
0.001 weight percent to about 10 weight percent, more pref 45 at least one fluoroolefin, said method comprising adding an
erably from about 0.01 weight percent to about 5 weight effective amount of stabilizer comprising at least one terpene,
percent, even more preferably from about 0.3 weight percent terpenoid, or fullerene, and at least one compound selected
to about 4 weight percent and even more preferably from from the group consisting of thiophosphates, butylated triph
about 0.3 weight percent to about 1 weight percent based on enylphosphorothionates, organo phosphates, functionalized
the total weight of compositions comprising at least one fluo 50
perfluoropolyethers, polyoxyalkylated aromatics, alkylated
roolefin as described herein. aromatics, oxetanes, ascorbic acid, thiols, lactones, thioet
hers, amines, nitromethane, alkylsilanes, benzophenone
The present invention further relates to a method for stabi derivatives, aryl sulfides, divinyl terephthalate, diphenyl
lizing a composition comprising at least one fluoroolefin, said terephthalate, and mixtures thereof to the composition com
method comprising adding an effective amount of a stabilizer prising at least one fluoroolefin.
comprising at least one fluoroolefin; and an effective amount 55 In another embodiment, the compositions of the present
of a stabilizer comprising at least one terpene, terpenoid, invention comprise at least one fluoroolefin and a stabilizer
fullerene, or mixture thereof, and at least one compound comprising graphite.
selected from the group consisting of thiophosphates, buty In another embodiment, the compositions of the present
lated triphenylphosphorothionates, organo phosphates, aryl invention comprise at least one fluoroolefin and a stabilizer
alkyl ethers, functionalized perfluoropolyethers, polyoxy 60 comprising at least one polycyclic aromatic.
alkylated aromatics, alkylated aromatics, oxetanes, ascorbic
acid, thiols, lactones, thioethers, amines, nitromethane, alkyl EXAMPLE
silanes, benzophenone derivatives, aryl Sulfides, divinyl
terephthalate, diphenyl terephthalate, graphite, polycyclic Refrigeration System Chemical Stability
aromatics, and mixtures thereof. 65
The present invention further relates to a process for pro A chemical stability test is run under conditions described
ducing cooling comprising condensing a composition as dis in ASHRAE (American Society of Heating, Refrigerating
US 8,663,494 B2
29 30
and Air-Conditioning Engineers) Standard 97-2004 to deter 5 extreme changes on coupons or liquids, i.e. black liquid
mine chemical stability of the stabilized compositions of the or coked with many deposits.
present invention as compared to compositions with no sta Table 4 lists estimated results for stabilizers of the present
bilizers. invention as compared to unstabilized compositions. Ucon R
The procedure is given here: 5 PAG 488 is a trademark for a polyalkylene glycol lubricant
. Metal coupons of copper, aluminum and steel are placed in commercially available from The Dow Chemical Company.
thick walled glass tubes. Irgalube(R) 63 is a trademark for a dithiophosphate commer
. Working fluid samples, including lubricant, are prepared cially available from Ciba. Irgalube(R) 232 is a trademark for
with and without stabilizers, and optionally with 2 abutylated triphenyl phosphorothionate commercially avail
Volume 96 air added to the tube. 10 able from Ciba. Irgalube(R).349 is a trademark for a mixture of
. Samples are added to the glass tubes as described in the amine phosphates (an example of an organophosphate) com
standard. mercially available from Ciba. Irgalube.R. 350 and Irgalube(R)
. The tubes are sealed with a glass blowing torch. 353 are trademarks for dialkyl dithiophosphate esters from
5 . The sealed tubes are heated in an oven for 14 days at the Ciba. KrytoxR 157FSL is a trademark for a functionalized
specified temperature. 15 perfluoropolyether commercially available from DuPont.
6. After 14 days, the sealed tubes are removed from the oven ZerolR 150 is a trademark for an alkylbenzene lubricant sold
and examined for metal/liquid appearance, proper Volume by Shrieve Chemical. OXT-101 is 3-ethyl-3-hydroxymethy
of liquid, appearance of glass, and absence of extraneous loxetane from Toagosei Company. Tinuvin R. 622LD is a
materials such as metal fines. trademark for a hindered amine antioxidant commercially
. Ratings are assigned to each sample based upon the fol- 20 available from Ciba. HP-136 is 5,7-di-t-butyl-3-(3-4-dimeth
lowing criteria (per industry practice): ylphenyl)-3H-benzofuran-2-one (an example of a lactone)
1=light changes on coupons and liquids; from Ciba. The lubricant Ucon R. PAG 488 is combined with
2 light to moderate changes on coupons or liquids; the working fluid as set forth in Table 4 below to produce a
3 moderate to significant changes on coupons or liquids; composition that was 50 wt % working fluid and 50 wt %
4-severe changes on coupons or liquids; lubricant.
TABLE 4
Stabilizer
wt % in With
refriq/lubricant 2 vol% Temp
Workin fluid Lubricant Stabilizer mixture Air (C.) Rating
HFC-1225ye PAG 488 None O yes 75 4
FC-1225ye PAG 488 None O O 75 2
225ye PAG 488 Irgalube (R) 63 2 yes 75 2
225ye PAG 488 Irgalube (R) 63 2 O 75
225ye PAG 488 d-limonene 2 yes 75 2
225ye PAG 488 d-limonene 2 O 75
225ye PAG 488 buckminsterfullerene 2 yes 75 2
225ye PAG 488 buckminsterfullerene 2 O 75
225ye PAG 488 graphite powder 2 yes 75 2
225ye PAG 488 graphite powder 2 O 75
225ye PAG 488 naphthalene 2 yes 75 2
225ye PAG 488 naphthalene 2 O 75
225ye PAG 488 Anisole 2 yes 75 2
225ye PAG 488 Anisole 2 O 75
225ye PAG 488 Krytox (R) 157FSL 2 yes 75 2
225ye PAG 488 Krytox (R) 157FSL 2 O 75
225ye PAG 488 Zero (R) 150 2 yes 75 2
225ye PAG 488 Zero (R) 150 2 O 75
225ye PAG 488 Trifluorimethyloxirane 2 yes 75 2
225ye PAG 488 Trifluorimethyloxirane 2 O 75
225ye PAG 488 OXT 101 2 yes 75 2
225ye PAG 488 OXT 101 2 O 75
225ye PAG 488 ascorbic acid 2 yes 75 2
225ye PAG 488 ascorbic acid 2 O 75
225ye PAG 488 methyl mercaptain 2 yes 75 2
225ye PAG 488 methyl mercaptain 2 O 75
225ye PAG 488 gamma-undecalactone 2 yes 75 2
225ye PAG 488 gamma-undecalactone 2 O 75
225ye PAG 488 benzyl phenylsulfide 2 yes 75 2
225ye PAG 488 benzyl phenylsulfide 2 O 75
225ye PAG 488 1,2-butylene oxide 2 yes 75 2
225ye PAG 488 1,2-butylene oxide 2 O 75
225ye PAG 488 diisopropylamine 2 yes 75 2
225ye PAG 488 diisopropylamine 2 O 75
225ye PAG 488 nitromethane 2 yes 75 2
US 8,663,494 B2
31 32
TABLE 4-continued
Stabilizer
wt % in With
refriq/lubricant 2 vol% Temp
Workin fluid Lubricant Stabilizer mixture Air (C.) Rating
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(CI) with KCl 2 yes 75 2
HFC-1225ye PAG 488 Mn(CI) with KCl 2 O 75
HFC-1225ye PAG 488 TiO2 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-hydroxybenzophenone 2 yes 75 2
HFC-1225ye PAG 488 2-hydroxybenzophenone 2 O 75
HFC-1225ye PAG 488 2,4-dihydroxybenzophenone 2 yes 75 2
HFC-1225ye PAG 488 2,4-dihydroxybenzophenone 2 O 75
HFC-1225ye PAG 488 2,4-dimethylbenzophenone 2 yes 75 2
HFC-1225ye PAG 488 2,4-dimethylbenzophenone 2 O 75
HFC-1225ye PAG 488 3,4-diaminobenzophenone 2 yes 75 2
HFC-1225ye PAG 488 3,4-diaminobenzophenone 2 O 75
HFC-1225ye PAG 488 HP-136 2 yes 75 2
HFC-1225ye PAG 488 HP-136 2 O 75
Estimates indicate improved chemical stability in the pres- 3. The composition of claim 1 wherein said fluoroolefin is
ence of stabilizers with and without air present. at least one compound selected from the group consisting of
the
What is claimed is: 40 (i) fluoroolefins of the formula E or Z R'CH=CHR,
1. A composition comprising: wherein R' and Rare, independently, C to C perfluo
a. a refrigerant consisting of at least one fluoroolefin and roalkyl groups;
optionally at least one additional compound selected (ii) cyclic fluoroolefins of the formula cyclo-CX—CY
from the group consisting of hydrofluorocarbons, as (CZW), ), wherein X, Y, Z, and W, independently, are
hydrocarbons, dimethyl ether, carbon dioxide, ammonia H or F, and n is an integer from 2 to 5; and
and mixtures thereof, and (iii) fluoroolefins selected from the group consisting of
b. an effective amount of a stabilizer comprising at least 1,2,3,3,3-pentafluoro-1-propene (CHF=CFCF), 1.1,
one terpene, terpenoid, fullerene, or mixture thereof; 3,3,3-pentafluoro-1-propene (CF=CHCF), 1.1.2,
and at least one compound selected from the group con- 50 3.3-pentafluoro-1-propene (CF=CFCHF), 1,2,3,3-
sisting of functionalized perfluoropolyethers. tetrafluoro-1-propene (CHF=CFCHF), 2,3,3,3-
2. The composition of claim 1 wherein the terpene, terpe- tetrafluoro-1-propene (CH=CFCF), 1,3,3,3-
noid, or fullerene stabilizer is selected from the group con- tetrafluoro-1-propene (CHF=CHCF), 1,1,2,3-
sisting of isoprene, myrcene, allo-cimene, beta-ocimene, ter- tetrafluoro-1-propene (CF=CFCHF), 1,1,3,3-
ebene, limonene, retinal, pinene, menthol, geraniol, farnesol. 55 tetrafluoro-1-propene (CF=CHCHF), 1,2,3,3-
phytol, Vitamin A, terpinene, delta-3-carene, terpinolene, tetrafluoro-1-propene (CHF=CFCHF), 3,3,3-
phellandrene, fenchene lycopene, betacarotene, Zeaxanthin, trifluoro-1-propene (CH2=CHCF), 2,3,3-trifluoro
hepaxanthin, and isotretinoin, abietane, ambrosane, aristo- 1-propene (CHFCF=CH-); 1,1,2-trifluoro-1-
lane, atisane, beyerane, bisabolane, bornane, caryophyllane, propene (CHCF=CF); 1,2,3-trifluoro-1-propene
cedrane, dammarane, drimane, eremophilane, eudesmane, 60 (CHFCF–CF); 1,1,3-trifluoro-1-propene
fenchane, gammacerane, germacrane, gibbane, grayanotox- (CHFCH=CF); 1,3,3-trifluoro-1-propene
ane, guaiane, himachalane, hopane, humulane, kaurane, lab- (CHF.CH-CHF); 1.1.1.2.3.4.4.4-octafluoro-2-
dane, lanostane, lupane, p-menthane, oleanane, ophiobolane, butene (CFCF–CFCF); 1,1,2,3,3,4,4,4-oc
picrasane, pimarane, pinane, podocarpane, protostane, tafluoro-1-butene (CFCFCF–CF); 1,1,1,2,4,4,4-
rosane, taxane, thujane, trichothecane, ursane, Buckminster- 65 heptafluoro-2-butene (CFCF–CHCF); 1.2.3.3.4.4,
fullerene, and 5.6 fullerene-Co, fullerene-C7, C.7s, and 4-heptafluoro-1-butene (CHF=CFCFCF); 1,1,1,2,
fullerene-Cs, and mixtures thereof. 3,4,4-heptafluoro-2-butane (CHFCF=CFCF); 1.3,
US 8,663,494 B2
35 36
7-tridecafluoro-2-heptene wherein
(CFCF–CHCFCFCF); 1,1,1,2,2,4,5,5,6,6,7,7, J is a fluoroalkyl group selected from the group consisting
7-tridecafluoro-3-heptene of CF, CFs, ClF7, CFC1, CFC1, CFC1, and com
(CFCF-CH=CFCFCFs); and 1,1,1,2,2,3,5,5,6,6, binations of two or more thereof;
7,7,7-tridecafluoro-3-heptene 5 c and dare numbers such that the ratio of c.d ranges from
(CFCFCF-CHCFCF). about 0.01 to about 0.5;
4. The composition of claim 1, wherein said fluoroolefin X is F, CF, or combinations thereof;
comprises at least one fluoroolefin selected from the group Z is F. Clor CF;
consisting of HFC-1225ye, HFC-1234yf. HFC-1234ze, and J" is a fluoroalkyl group selected from the group consisting
HFC-1243Zlf. 10 of CF, CFs, ClF7, CFC1, CFC1, and combinations
5. The composition of claim 1, further comprising at least of two or more thereof;
one metal deactivator selected from the group consisting of e and fare numbers such that the ratio of e:f ranges from
areoxalyl bis(benzylidene)hydrazide: N,N'-bis(3,5-di-tert about 0.3 to about 5:
butyl-4-hydroxyhydrocinnamoylhydrazine); 2,2'-oxami Z' is For Cl;
dobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate); 15 J’ is C.F.s, CF, or combinations thereof;
ethyenediaminetetraacetic acid and salts thereof, and mix j is an average number such that the formula weight of R,
tures thereof. ranges from about 400 to about 15,000;
6. A process for producing cooling comprising condensing J is selected from the group consisting of CF, CFs, CF7,
the composition of claim 1 and thereafter evaporating said and combinations of two or more thereof;
composition in the vicinity of a body to be cooled. k is an average number such that the formula weight of R,
7. A process for producing heat comprising condensing the ranges from about 400 to about 15,000;
composition of claim 1 in the vicinity of a body to be heated, each Q is independently F, Cl, or H:
and thereafter evaporating said composition. g, handi are numbers such that (g+h) ranges from about 1
8. The composition of claim 1, wherein said functionalized to about 50, the ratio of i:(g+h) ranges from about 0.1 to
perfluoropolyethers comprise perfluoropolyether- or perfluo 25 about 0.5;
roalkyl-containing and phosphorus-containing partially J" is CF, CFs, or combinations thereof;
esterified aryl phosphates, aryl phosphonates or salts thereof. r is an average number such that the formula weight of R,
9. The composition of claim8, wherein said functionalized ranges from about 400 to about 15,000; and
perfluoropolyethers contain either (i) a mono- or poly-alky each R and R' is independently H, a C-Clo alkyl, a halo
lene oxide linking group between the phosphorus and a fluo 30 gen, OR, OH, SOM, NR, ROH, RSOM, RNR,
rocarbon group, or (ii) no linking group between the phos RNO, RCN, C(O)OR, C(O)OM, C(O)R, or C(O)
phorus and fluorocarbon. NR, or combinations of two or more thereof;
10. The composition of claim 1 wherein said functional wherein
ized perfluoropolyether stabilizers are represented by For R’ is independently H, C, -Co alkyl, or combinations of
mula B, 35 two or more thereof;
R is a C-Clo alkyl; and
M is hydrogen or a metal, preferably not aluminum;
Formula B t is equal to (6+u);
N u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;
--(OR), 40 V is independently either 2 or 4:
21 n is 0 or 1;
E is P. As, or Sb; and
m is greater than about 0.5 to about 3, provided that, when
which contain either a perfluoroalkyl or perfluoropolyether E=P. m-3.0 and t=6, R cannot be exclusively H or con
side chain. 45 tain F.
11. The composition of claim 1 wherein said functional 13. The composition of claim 1 wherein the functionalized
ized perfluoropolyether stabilizers are perfluoropolyether perfluoropolyether stabilizers of the present invention com
alkyl alcohols comprising a perfluoropolyether segment and prise aryl perfluoropolyethers, which are monofunctional
one or more alcohols segments having a general formula, aryl perfluoropolyethers having the formula of R,-(Y) -
—CH2(CH2)OH, wherein-CH2 represents a divalent lin 50 (CR)–(O C.R.) R, difunctional aryl perfluo
ear or branched alkyl radical where q is an integer from 1 to ropolyethers having the formula of R—I(Y), (CR)—
about 10. (O—CR') R2, or combinations thereof, wherein
12. The composition of claim 1 wherein said functional each of R, and R has a formula weight of about 400 to
ized perfluoropolyether stabilizers comprise substituted aryl about 15,000;
pnictogen compositions having the structure R— 55 R, comprises repeat units selected from the group consist
(CR)l.E(O),(CR')s wherein R, is a fluo ing of
ropolyether chain having a formula weight ranging from (a) J-O-(CF(CF)CFO) (CFXO)ACFZ ,
about 400 to about 15,000, comprises repeat units, and is
selected from the group consisting of:
(b) J-O-(CFCFO).(CFO),CFZ"—,
(c) J-O-(CF(CFs)CFO),CF(CF,)—,
(a) J-O-(CF(CF)CFO) (CFXO)ACFZ : 60 (d) J-O-(CQ. CFCF. O), CQ, ,
(b) J-O-(CF.CFO) (CFO),CFZ"—; (e) J-O-(CF(CF,)CFO) (CFCFO),(CFX O),
(c) J-O-(CF(CFs)CFO),CF(CFs)CF, ; CFZ ,
(d) J-O-(CQ. CFCF-O)-CQ CF : (f) J-O-(CFCFO), CF, , and
(e) J-O-(CF(CFs)CFO) (CFCFO),(CFXO), (g) combinations of two or more thereof, and
where
CFZ ; 65
(f) J-O-(CFCFO), CF ; and the units with formulae CFCFO and CFO are randomly
(h) combinations of two or more thereof distributed along the chain;
US 8,663,494 B2
37 38
J is CF, CFs CF, CFC1, CFC1, CFC1, or combi a is 0 or 1;
nations of two or more thereof; b is 0-5:
c and d are numbers such that the c/d ratio ranges from Y is a divalent radical —CHOCH2—, —(CH2). O—,
about 0.01 to about 0.5; —(CF), , —CFO—, —CFOCF, , —C(O)—,
X is —F. —CF, or combinations thereof; —C(S)—, or combinations of two or more thereof;
Z is —F. —Cl or CF; n is about 1 to about 5;
Z' is - F or - C1, o is about 2 to about 5;
J" is CF, CFs, CF, CFC1, C.F.C1, or combinations of t is equal to 6+u;
two or more thereof; u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;
e and fare numbers such that the e/fratio ranges from about 10
V is independently either 2 or 4:
0.3 to about 5:
J is —CFs, —CF, or combinations thereof; Rf is (CFCFO).(CFO),CF, , -(CFO),
j is an average number such that the formula weight of R, (CFCFO) (CFXO), CF, , (CFCFO)(CFO),
ranges from about 400 to about 15,000; CF(CF) , —CF(CF)O(CFO), Rf O
J is CF, CFs, CF7, or combinations of two or more 15 (CFO), CF(CF)— —((CQ)CFCFO)CFCF ,
thereof; or combinations of two or more thereof;
where
k is an average number such that the formula weight of R, e, f, X, and Q are as defined above:
ranges from about 400 to about 15,000; p, q and rare numbers such that (p+q) ranges from 1 to 50
each Q is independently —F. —Cl, or—H; and r?(p+q) ranges from 0.1 to 0.05:
g, handi are numbers such that (g+h) ranges from about 1 each w is independently 2 to 45:
to about 50, the i/(g+h) ratio ranges from about 0.1 to
about 0.5; Rf is linear or branched —C.F. :
J" is CF, CFs, or combinations thereof; m is 1-10; and
k is an average number such that the formula weight of R, S is an average number Such that the formula weight of R
ranges from about 400 to about 15,000; 25 ranges from 400 to 15,000.
each R is independently —H, a halogen, —OH, -SOM, 14. The composition of claim 1 further comprising a lubri
NR, NO, ROH, RSOM, RNR, cant selected from the groups consisting of mineral oils,
- RNO, RCN, C(O)OR, C(O)OM, C(O) alkylbenzenes, polyalphaolefins, silicone oils, polyoxyalky
R. —C(O)NR, or combinations of two or more lene glycol ethers, polyol esters, polyvinylethers and mix
tures thereof.
thereof; except that when b=0, R cannot be four hydro 30
15. A method for stabilizing a composition comprising at
gen atoms and —OH, or—Br, or—NH, or R cannot be least one fluoroolefin, said method comprising adding an
solely H or —NO, or combinations thereof; effective amount of a stabilizer comprising at least one ter
each R" is independently H. R. —OR, a halogen, pene, terpenoid, or fullerene, and at least one compound
OH, -SOM, NR, NO, CN, ROH, selected from the group consisting of functionalized perfluo
- RSO.M. - RNR - RNO, RCN, C(O) 35
ropolyethers, to said composition comprising at least one
OR, C(O)CM, C(O)R, C(O)NR, or combina fluoroolefin.
tions of two or more thereof provided that if b=0, the 16. A method of claim 15 wherein degradation caused by
combination of RandR cannot be four or more hydro the presence of inadvertent air in a refrigeration, air-condi
gen atoms and —OH, - Br, —NH, or —NO; tioning or heat pump system, is reduced.
each R is independently H, C, -Co alkyl, or combinations 40
17. A method of claim 15 wherein reaction of at least one
of two or more thereof; original composition component with oxygen is reduced.
R is a C-C alkyl:
M is a hydrogen or metal ion; k k k k k

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USOO8663494 B2

(12) United States Patent (10) Patent No.: US 8,663,494 B2

(56) References Cited WO 2005103.192 A1 11, 2005

F314tF (CF)CFCH=CH-C(CF). sks 2,66,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-

225ye CFCF-CHF 2,3,3,3-pentafluoro-1-propene

FC-161-14mcyy CFCFCF-CFCF-C2Fs 1,1,1,2,2,3,4,5,5,6,6,7,7,7-

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