WO2008027519A1 - Stabilisants d'oxéthane pour fluorooléfines - Google Patents

Stabilisants d'oxéthane pour fluorooléfines Download PDF

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Publication number
WO2008027519A1
WO2008027519A1 PCT/US2007/019148 US2007019148W WO2008027519A1 WO 2008027519 A1 WO2008027519 A1 WO 2008027519A1 US 2007019148 W US2007019148 W US 2007019148W WO 2008027519 A1 WO2008027519 A1 WO 2008027519A1
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Prior art keywords
butene
chf
cfcf
pentene
trifluoromethyl
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PCT/US2007/019148
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English (en)
Inventor
Jon Lee Howell
Barbara Haviland Minor
Mario Joseph Nappa
Andrew Edward Feiring
Viacheslav A. Petrov
Nandini Mouli
Thomas J. Leck
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E. I. Du Pont De Nemours And Company
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Publication of WO2008027519A1 publication Critical patent/WO2008027519A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons

Definitions

  • the present invention relates to compositions comprising at least one fluoroolefin and a stabilizer.
  • the stabilized compositions may be useful in cooling systems as replacements for existing refrigerants with higher global warming potential.
  • Fluoroolefins have been proposed as working fluids alone or in mixtures. However, it has been observed that fluoroolefins can exhibit degradation when exposed to high temperatures or when contacted with other compounds (e.g., moisture, oxygen, or other compounds with which they may undergo condensation reactions. This degradation may occur when fluoroolefins are used as working fluids in heat transfer equipment (refrigeration or air-conditioning equipment, for instance) or when used in some other application. This degradation may occur by any number of different mechanisms. In one instance, the degradation may be caused by instability of the compounds at extreme temperatures. In other instances, the degradation may be caused by oxidation in the presence of air that has inadvertently leaked into the system.
  • other compounds e.g., moisture, oxygen, or other compounds with which they may undergo condensation reactions. This degradation may occur when fluoroolefins are used as working fluids in heat transfer equipment (refrigeration or air-conditioning equipment, for instance) or when used in some other application. This degradation
  • composition comprising at least one fi ⁇ oroolefin and an effective amount of a stabilizer comprising at least one oxetane represented by Formula A,
  • R-i-R ⁇ are the same or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl. Also provided is a method for stabilizing a composition comprising at least one fiuoroolefin, said method comprising adding an effective amount of a stabilizer comprising at least one epoxide, fluorinated epoxide, or oxetane.
  • the present invention provides a composition comprising at least one fluoroolefin and an effective amount of a stabilizer comprising at least one oxetane.
  • These compositions have a variety of utilities in working fluids, which include use as These compositions have a variety of utilities in working fluids, which include use as foaming agents, blowing agents, fire extinguishing agents, heat transfer mediums (such as heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, and the like), to name a few.
  • a solvent is a fluid that removes a soil from a substrate, or deposits a material onto a substrate, or carries a material.
  • An aerosol propellant is a volatile composition of one or more components that exerts a pressure greater than one atmosphere to expel a material from a container.
  • a fire extinguishant is a volatile composition that extinguishes or suppresses a flame.
  • a refrigerant is a compound or mixture of compounds that function as a heat transfer fluid in a cycle wherein the fluid undergoes a phase change from a liquid to a gas and back.
  • R 1 and R 2 groups include, but are not limited to, CF 3 , C 2 F 6 , CF 2 CF 2 CF 3 , CF(CF 3 ) 2 , CF 2 CF 2 CF 2 CF 3 , CF(CF 3 )CF 2 CF 3 , CF 2 CF(CFs) 2 , C(CF 3 ) 3 , CF 2 CF 2 CF 2 CF 2 CF 3 , CF 2 CF 2 CF(CFa) 2 , C(CFj) 2 C 2 F 5 , CF 2 CF 2 CF 2 CF 2 CF 3 , CF(CF 3 ) CF 2 CF 2 C 2 Fs, and C(CF 3 ) 2 CF 2 C 2 Fs.
  • Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature.
  • Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.
  • reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.
  • a suitable addition apparatus such as a pump at the reaction temperature.
  • Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150 0 C to 300 0 C, preferably from about 17O 0 C to about 250 0 C, and most preferably from about 180 0 C to about 230 0 C.
  • Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.
  • the dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance.
  • Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime.
  • Preferred basic substances are sodium hydroxide and potassium hydroxide.
  • Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dirnethylacetamide, or sulfolane.
  • solvents e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol
  • nitriles e.g., acetonitrile, propionitrile, butyronitrile, benzonit
  • Temperatures suitable for the dehydroiodination reaction are from about 10 0 C to about 10O 0 C 1 preferably from about 20 0 C to about 70 0 C.
  • the dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure.
  • dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.
  • the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst.
  • an alkane e.g., hexane, heptane, or oc
  • Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).
  • the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substance.
  • Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.
  • the compound of formula I may be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.
  • the fluoroolefins of Formula II have at least about 3 carbon atoms in the molecule.
  • the fluoroolefins of Formula Il have at least about 4 carbon atoms in the molecule.
  • the fluoroolefins of Formula Il have at least about 5 carbon atoms in the molecule.
  • Representative cyclic fluoroolefins of Formula Il are listed in Table 2.
  • 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.
  • fluoroolefins may comprise those compounds listed in Table 3.
  • 1,1,1, 4,4, 4-hexafluoro-2-butene may be prepared from 1,1,1,4,4,4- hexafluoro-2-iodobutane (CF3CHICH 2 CF3) by reaction with KOH using a phase transfer catalyst at about 60 0 C.
  • 1,1 ,1 ,2,3,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1,2,3,3,4-heptafluorobutane (CH 2 FCF 2 CHFCF 3 ) using solid KOH.
  • 1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1, 2,2,4,4-heptafluorobutane (CHF 2 CH 2 CF 2 CF 3 ) using solid KOH.
  • 1,1,1 ) 3,4,4-hexafluoro2-butene may be prepared by dehydrofluorination of 1,1,1, 3,3,4,4-heptafluorobutane (CF 3 CH 2 CF 2 CHF 2 ) using solid KOH.
  • 1,1,1,2,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1, 2,2,3-hexafluorobutane (CH 2 FCH 2 CF 2 CF 3 ) using solid KOH.
  • 1,1,1 ,3,4-pentafluoro-2-butene may be prepared by dehydrofluorination of 1,1,1, 3,3,4-hexafluorobutane (CF 3 CH 2 CF 2 CH 2 F) using solid KOH.
  • 1 ,1 ,1 ,3-tetrafluoro-2-butene may be prepared by reacting 1 ,1 ,1 ,3,3- pentafluorobutane ( CF 3 CH 2 CF 2 CH 3 ) with aqueous KOH at 120 °C.
  • 5-octafIuoro-2-pentene may be prepared from (CF 3 CHICH 2 CF 2 CF 3 ) by reaction with KOH using a phase transfer catalyst at about 6O 0 C.
  • the synthesis of 4-iodo-1 ,1 ,1 ,2, 2,5, 5,5-octafluoropentane may be carried out by reaction of perfluoroethyliodide (CF 3 CF 2 I) and 3,3,3- trifluoropropene at about 200 0 C under autogenous pressure for about 8 hours.
  • 1 ,1 ,1 ,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared from 1 ,1 ,1 , 2,2, 5,5,6,6,6-decafluoro-3-iodohexane (CF 3 CFaCHICH 2 CF 2 CF 3 ) by reaction with KOH using a phase transfer catalyst at about 6O 0 C.
  • perfluoroethyliodide CF 3 CF 2 I
  • CF 3 CF 2 CH CH 2
  • 1 , 1 ,1 ,4,5,5,5-heptafluoro-4-(trifluoromethyl)-2-pentene may be prepared by the dehydrofluorination of 1 ,1 ,1 ,2,5,5,5-heptafluoro-4-iodo-2- (trifluoromethyl)-pentane (CF 3 CHICH 2 CF(CF 3 ) 2 ) with KOH in isopropanol.
  • F11E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.
  • HFC-1225ye is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.
  • the present invention provides compositions comprising at least one fluoroolefin and a stabilizer comprising at least one oxetane.
  • the present invention provides compositions comprising at least one fluoroolefin and a stabilizer comprising at least one oxetane combined with at least one additional stabilizer comprising at least one compound selected from the group consisting of phenols, thiophosphates, butylated triphenylphosphorothionates, organo phosphates, phosphites, terpenes, terpenoids, fullerenes, aryl alkyl ethers, functionalized perfluoropolyethers, polyoxyalkylated aromatics, alkylated aromatics, ascorbic acid, thiols, lactones, thioethers, amines, nitromethane, alkylsilanes, benzophenone derivatives, aryl sulfides, divinyl terephthalate, and diphenyl terephthalate
  • the stabilizers of the present invention comprise at least one oxetane.
  • the oxetane stabilizers of the present invention may be a compound with one or more oxetane groups and is represented by Formula A, wherein Ri-R 6 are the same or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.
  • oxetane stabilizers include but are not limited to 3-ethyl-3- hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3- ((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co., Ltd); and 3- ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212 (Toagosei Co., Ltd).
  • 3-ethyl-3- hydroxymethyl-oxetane such as OXT-101 (Toagosei Co., Ltd)
  • 3-ethyl-3- ((phenoxy)methyl)-oxetane such as OXT-211 (Toagosei Co., Ltd)
  • the additional stabilizers of the present invention may comprise at least one phenol.
  • Phenol stabilizers are any substituted or unsubstituted phenol compound including phenols comprising one or more substituted or unsubstituted cyclic, straight chain, or branched aliphatic substituent group, such as, alkylated monophenois including 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinone and alkylated hydroquinones including t-butyl hydroquinone, other derivatives of hydroquinone; and the like, hydroxylated throdiphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6- tertbutylphenol); 2,2'-thiobis(4
  • the additional stabilizers of the present invention comprise at least one thiophosphate.
  • the thiophosphate stabilizers of the present invention are compounds derived from phosphoric acids by substituting divalent sulfur for one or more oxygen atoms. These may be monothiophosphates, dithiophosphates or higher order.
  • a representative dithiophosphate is commercially available from Ciba Specialty Chemicals of Basel, Switzerland (hereinafter "Ciba") under the trademark Irgalube ® 63.
  • thiophosphates include dialkylthiophosphate esters.
  • a representative dialkylthiophosphate ester stabilizer is commercially available from Ciba under the trademark Irgalube ® 353.
  • the additional stabilizers of the present invention comprise at least one butylated triphenylphosphorothionate as depicted by Formula B.
  • a butylated triphenylphosphorothionate, wherein each R is independently selected from H or tert-butyl. is Irgalube® 232 (Ciba).
  • the additional stabilizers of the present invention comprise at least one organophosphate.
  • the organophosphate stabilizers include but are not limited to amine phosphates, trialkyl phosphates, triaryl phosphates, mixed alkyl-aryl phosphates (alkyldiaryl, dialkylaryl or alkylated aryl), and cyclic phosphates.
  • a representative amine phosphate is commercially available from Ciba under the trademark Irgalube ® 349.
  • Representative trialkyl phosphates include: trimethyl phosphate ((CHs) 3 PO 4 , Cas reg. no. 512-56-1); triethyl phosphate ((CH 3 CH 2 ) 3 P ⁇ 4 , Cas reg.
  • triaryl phosphates include: triphenyl phosphate ((C 6 H 5 O) 3 PO, CAS reg. no. 115-86-6); tricresyl phosphate (TCP, (CH 3 C 6 H 4 O) 3 PO, CAS reg. no. 1330-78-5); and trixylenyl phosphate (((CHs) 2 C 6 H 3 O) 3 PO, CAS reg. no. 25155-23-1).
  • Representative mixed alkyl-aryl phosphates include: isopropylphenyl phenyl phosphate (IPPP, (C 6 H 5 O) 2 ((CH 3 ) 2 CHO)PO ) CAS reg. no. 68782- 95-6) and bis(t-butylphenyl) phenyl phosphate (TBPP, (C 6 H 5 O) 2 ((CH 3 ) 3 C)PO, CAS reg. no. 65652-41-7).
  • IPPP isopropylphenyl phenyl phenyl phosphate
  • TBPP bis(t-butylphenyl) phenyl phosphate
  • Such phosphorus compounds are available from multiple chemical suppliers such as Aldrich (Milwaukee, Wisconsin); Alfa Aesar (Ward Hill, MA); or Akzo Nobel (Arnhem, the Netherlands).
  • hindered phosphites are derivatives of alkyl, aryl or alkylaryl phosphite compounds.
  • Tris-(di- tert-butylphenyl) phosphite is sold under the trademark Irgafos ® 168
  • di-n- octyl phosphite is sold under the trademark Irgafos ® OPH
  • iso-decyl diphenyl phosphite) is sold under the trademark Irgafos ® DDPP, all by Ciba.
  • the additional stabilizers of the present invention comprise at least one terpene.
  • Terpenes are hydrocarbon compounds characterized by structures containing one or more repeating isoprene (2-methyl-1 ,3-butadiene) unit. Terpenes may be acyclic or cyclic. Representative terpenes include but are not limited to isoprene, myrcene (2-methyl-6-methyl-eneocta-1 ,7-diene), allo-cimene, beta-ocimene, terebene, limonene (in particular d-limonene), retinal, pinene, menthol, geraniol, farnesol, phytol, Vitamin A, terpinene, delta-3-carene, terpinolene, phellandrene, fenchene, dipentene, and mixtures thereof. Terpene stabilizers are commercially available or may be prepared by methods known in the art or isolated from natural sources.
  • the additional stabilizers of the present invention comprise at least one terpenoid.
  • Terpenoids are natural products and related compounds characterized by structures containing more than one repeating isoprene unit and usually contain oxygen.
  • terpenoids include carotenoids, such as lycopene (CAS reg. no. [502-65-8]), betacarotene (CAS reg. no. [7235-40-7]), and xanthophylls, i.e. zeaxanthin (CAS 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.
  • the additional stabilizers of the present invention comprise at least one fullerene.
  • Fullerenes are closed carbon cages that are bonded as hexagonal carbon rings (benzene) linked to each other partly via pentagons.
  • Representative fullerenes include but are not limited to Buckminsterfullerene (C60, or "bucky ball", CAS reg. no. [99685- 96-8]), and [5,6]fullerene-C 70 ( C70 ( CAS reg. no.
  • fullerene-C 7 6 (CAS reg. no. [135113-15-4]), fullerene-C 78 (CAS reg. no. [136316-32-0]), and fullerene-C 84 (CAS reg. no. [135113-16-5]).
  • Z is F, Cl or CF 3 ;
  • J ⁇ is a fluoroalkyl group selected from the group consisting of CF3, C2F5, C 3 F/, CF2CI, C2F4CI, and combinations of two or more thereof; e and f are numbers such that the ratio of e:f ranges from about 0.3 to about 5;
  • Z1 is F or Cl
  • J 2 is C2F5, C3F7, or combinations thereof; j is an average number such that the formula weight of Rf ranges from about 400 to about 15,000; J3 is selected from the group consisting of CF 3 , C2F5, C3F7, and combinations of two or more thereof; k is an average number such that the formula weight of Rf ranges from about 400 to about 15,000; each Q is independently F, Cl, or H; g, h and i 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; j4 is CF 3 , C2F5, or combinations thereof; r is an average number such that the formula weight of Rf ranges from about 400 to about 15,000; and each R and R ⁇ is independently H, a C ⁇
  • R 2 is independently H, C-J-C-I O alkyl, or combinations of two or more thereof;
  • R 3 is a C-
  • the functionalized perfluoropolyether stabilizers of the present invention may comprise aryl perfluoropolyethers, which are monofunctional aryl perfluoropolyethers having the formula of Rf-(Y)a-(CtR( U+ v))-(O-C,R 1 ⁇ u+v))b-R, difunctional aryl perfluoropolyethers having the formula of Rf 1 -[(Y)a-(CtR( U + V ))-(O-CtR 1 ( U +v))b-R]2, or combinations thereof, wherein each of R f and Rf 1 has a formula weight of about 400 to about 15,000;
  • R f comprises repeat units selected from the group consisting of (a) J-O-(CF(CF 3 )CF 2 O)c(CFXO) d CFZ-, (b) J 1 -O-(CF 2 CF2O)e(CF 2 O)fCFZ 1 -, (C) J 2 -O-(CF(CF 3 )CF 2 O) j CF(CF 3 )-, (d) J 3 -O-(CQ 2 -CF 2 CF 2 -O) k -CQ 2 -,
  • J is CF 3 , C 2 F 5 , C 3 F 7 , CF 2 CI, C 2 F 4 CI, C 3 F 6 CI, or combinations of two or more thereof; c and d are numbers such that the c/d ratio ranges from about 0.01 to about 0.5; X is -F, -CF 3 , or combinations thereof;
  • Z is -F, -Cl or -CF 3 ;
  • Z 1 is -F or -Cl,
  • J 1 is CF 3 , C 2 F 5 , C 3 F 7 , CF 2 CI, C 2 F 4 CI, or combinations of two or more thereof; e and f are numbers such that the e/f ratio ranges from about 0.3 to about 5;
  • Y is a divalent radical -CH 2 OCH 2 -, -(CH 2 ) 0 -O-, -(CF 2 ) n -, -CF 2 O-, - CF 2 OCF 2 -, -C(O)-, -C(S)-, or combinations of two or more thereof; n is about 1 to about 5; o is about 2 to about 5; t is equal to 6+u; u is any combination of O, 2, 4, 6, 8, 10, 12, 14, 16; v is independently either 2 or 4;
  • Rf 1 is -(CF 2 CF 2 O) 6 (CF 2 O)ICF 2 -, -(C3F 6 O)p(CF2CF 2 O)q(CFXO) r CF2-, -(CF 2 CF 2 OX C 3 F 6 O)WCF(CF 3 )-. -CF(CF 3 )O(C 3 F 6 O) W -Rf 2 -O ( C 3 F 6 O)wCF(CF 3 )-,
  • the additional stabilizer may comprise at least one polyoxyalkylated aromatic.
  • the polyoxyalkylated aromatics are compounds represented by Formula C wherein the R 1 group is a polyoxyalkylated group comprising at least one -CH2CH2O- moiety.
  • the additional stabilizers of the present invention comprise at least one alkylated aromatic compound.
  • alkylated aromatics include but are not limited to alkylbenzene lubricants, both branched and linear, such as Zerol ® 75, Zerol ® 150 and Zerol ® 500 (linear alkylbenzenes sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).
  • the additional stabilizers of the present invention comprise ascorbic acid (CAS reg. no. [50-81-7]).
  • the additional stabilizers of the present invention comprise at least one thiol compound, also known as mercaptans or hydrosulfides.
  • thiol compounds are the sulfur analogs of the hydroxyl group containing alcohols.
  • Representative thiol stabilizers include but are not limited to methanethiol (methyl mercaptan), ethanethiol (ethyl mercaptan), Coenzyme A (CAS reg. no. [85-61-0]), dimercaptosuccinic acid (DMSA, CAS reg. no. [2418-14-6]), grapefruit mercaptan (( R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol, CAS reg. no.
  • cysteine ( R)-2-amino-3-sulfanyl-propanoic acid, CAS reg. no. [52-90-4]
  • lipoamide (1 ,2-dithiolane-3-pentanamide, CAS reg. no. [940-69-2].
  • the additional stabilizers of the present invention comprise at least one lactone.
  • Lactones are cyclic esters that may be produced by the reaction of an alcohol group with a carboxylic acid group in the same molecule.
  • Representative lactone stabilizers of the present invention include but are not limited to gamma-butyrolactone (CAS reg. no. [96-48-0]), delta-gluconolactone (CAS reg. no. [90-80-2]), gamma- undecalactone (CAS reg. no. [104-67-6]), 6,7-dihydro-4(5H)- benzofuranone (CAS reg. No.
  • the additional stabilizers of the present invention comprise at least one thioether.
  • Thioether stabilizers of the present invention include but are not limited to benzyl phenyl sulfide (CAS reg. no. [831-91-4]), diphenyl sulfide (CAS reg. no.
  • Hindered amine antioxidants include amines derived from substituted piperidine compounds, in particular derivatives of an alkyl-substituted piperidyl, piperidinyl, piperazinone, or alkoxypiperidinyl compounds.
  • Representative hindered amine antioxidants include 2,2,6,6- tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-(1 ,2,2,6,6- pentamethylpiperidy])sebacate (CAS reg. no.
  • di-(2,2,6,6- tetramethyl-4-piperidyl)sebacate such as that commercially available under the trademark Tinuvin ® 622LD from Ciba
  • alkylated paraphenylenediamines such as N-phenyl-N'-(1 ,3-dimethylbutyl)-p- phenylenediamine, or N.N'-di-sec-butyl-p-phenylenediamine
  • hydroxylamines such as tallow amines or N-methylbis(hydrogenated tallow alkyl)amine,.
  • hindered amine antioxidants include the amine antioxidant commercially available from Ciba under the trademark Tinuvin ® 765, or commercially available from Mayzo, Inc. under the trademark BLS ® 1944 and BLS ® 1770.
  • the amines also include mixtures of any of the amines listed in this paragraph.
  • the additional stabilizers of the present invention comprise nitromethane (CH 3 NO2, CAS reg. no. [75-52-5]).
  • the additional stabilizers of the present invention comprise at least one alkyl silane.
  • Silanes are compounds similar to hydrocarbons wherein a silicon atom replaces each carbon.
  • Alkyl silane stabilizers include but are not limited to bis(dimethylamino)methylsilane (DMAMS, CAS reg. no. [22705-33-5]), tris(trimethylsilyl)silane (TTMSS, CAS reg. no. [1873-77-4]), vinyltriethyoxysilane (VTES, CAS reg. no. [78-08-0]), and vinyltrimethoxysilane (VTMO, CAS reg. no. [2768-02-7]).
  • DMAMS bis(dimethylamino)methylsilane
  • TTMSS tris(trimethylsilyl)silane
  • VTES vinyltriethyoxysilane
  • VTMO vinyltrimethoxysilane
  • the additional stabilizers of the present invention comprise at least one benzophenone derivative.
  • Benzophenone derivative stabilizers comprise benzophenone that may be substituted with side groups including halides, such as fluorine, chlorine, bromine or iodine, amino groups, hydroxyl groups, alkyl groups such as methyl, ethyl or propyl groups, aryl groups such as phenyl, nitro groups, or any combinations of such groups.
  • benzophenone derivative stabilizers include but are not limited to: 2,5-difluorobenzophenone; 2', 5'- dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone; 2-fluorobenzophenone; 2-hydroxybenzophenone; 2-methylbenzophenone; 2-amino-4'-chlorobenzophenone; 2-amino-4'-fluorobenzophenone; 2- amino-5-bromo-2'-chlorobenzophenone; 2-amino-5-chlorobenzophenone; 2-amino-5-chloro-2'-fluorobenzophenone; 2-amino-5-nitrobenzophenone; 2-amino-5-nitro-2'-chlorobenzophenone; 2-amino-2',5- dichlorobenzophenone; 2-chloro-4'-fluorobenzophenone; 2-hydroxy-4- methoxybenzophenone; 2-hydroxy-5-chlorobenzophenone; 2- methylamino-5-ch
  • the additional stabilizers of the present invention comprise at least one aryl sulfide.
  • the aryl sulfide stabilizers comprise at least one selected from the group consisting of benzyl phenyl sulfide, diphenyl sulfide, and dibenzyl sulfide.
  • the additional stabilizers of the present invention comprise at least one terephthalic acid.
  • the terephthalate stabilizers include divinyl terephthalate (CAS reg. no. [13486-19-0]) and diphenyl terephthalate (CAS reg. no. [1539-04-4]).
  • the additional stabilizers of the present invention comprise at least one epoxide. Epoxides include 1 ,2-propylene oxide (CAS reg. no. [75-56-9]), 1 ,2-butylene oxide (CAS reg. no.
  • butylphenylglycidyl ether pentylphenylglycidyl ether, hexylphenylglycidyl ether, heptylphenylglycidyl ether, octylphenylglycidyl ether, nonylphenylglycidyl ether, decylphenylglycidyl ether, glycidyl methylphenylether, 1 ,4-glycidyl phenyl diether, 4-methoxyphenylglycidyl ether, naphthyl glycidyl ether, 1 ,4-diglycidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether, ally
  • the additional stabilizers of the present 5 invention comprise at least one fluorinated epoxide.
  • the fluorinated epoxide stabilizers of the present invention may be depicted by Formula
  • Representative fluorinated epoxide stabilizers include but are not limited to trifluoromethyloxirane and 1 ,1-bis(trifluoromethyl)oxirane. Such compounds may be prepared by methods known in the art, for instance by methods described in, Journal of Fluorine Chemistry, volume 24, pages 93-104 (1984), Journal of Organic Chemistry, volume 56, pages 3187 to
  • the stabilizers of the present invention are commercially available from various chemical supply houses. Single stabilizer compounds may be used in combination in the
  • the stabilizer compounds exist as multiple configurational isomers or stereoisomers. Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the stabilizer blend. Further, single or multiple isomers of a given compound may be combined in any proportion with any number of other compounds to serve as a stabilizer blend.
  • the present invention is intended to include all single configurational isomers, single stereoisomers or any combination or mixture thereof.
  • the present invention further provides a composition comprising at least one fluoroolefin selected from the group consisting of HFC-1225ye, HFC-1234yf, HFC-1234ze and HFC-1243zf, and an effective amount of a stabilizer comprising at least one oxetane.
  • stabilizer compositions comprising combinations of compounds that provide an unexpected level of stabilization. Certain of these combinations may serve as synergistic stabilizer compositions, that is, the compositions of compounds that augment each others' efficiency in a formulation and the stabilization obtained is larger than that expected from the sum of the contributions of the individual components.
  • Such synergistic stabilizer compositions may comprise at least one oxetane and any of the additional compounds selected from the group consisting of phosphites, terpenes and terpenoids, fullerenes, epoxides, fluorinated epoxides, amines, phenols, divinylterephthalate, and diphenylterephthalate, and mixtures thereof, meaning mixtures of any of the foregoing additional compounds with an oxetane.
  • a limiting factor in the effectiveness of a stabilizer composition is the consumption of stabilizer and loss of functionality over the time of active use.
  • synergistic stabilizer compositions comprising mixtures of stabilizers that include components capable of regenerating the consumed stabilizer during active use, hereinafter referred to as regenerative stabilizers.
  • regenerative stabilizers comprising small "synergistic" stabilizers function with higher mobility and higher stabilization rates (meaning higher rates of reaction by which the stabilization is occurring).
  • Regenerative stabilizer composition contains one or more stabilizers that can replenish itself or themselves after use, so that over long-term use, the composition's efficacy is maintained.
  • a regenerative stabilizer is an oxetane and at least one amine.
  • Amines for inclusion in the regenerative stabilizer compositions may comprise any of the hindered amine antioxidants as described previously herein.
  • hindered amine antioxidants are 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6- tetramethyl-4-piperidinol; bis-(1 ,2,2,6,6-pentamethylpiperidyl) sebacate (CAS reg. no. [41556-26-7]); di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, such as Tinuvin ® 770; poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy- piperidyl succinate (CAS reg. no. [65447-77-0]), such as Tinuvin ® 622LD (Ciba).
  • Some additional hindered amine antioxidants include Tinuvin ® 765 (Ciba), BLS ® 1944 (Mayzo, Inc.), and BLS ® 1770 (Mayzo), and mixtures thereof, including mixtures of any of the hindered amines described in this paragraph.
  • Another example of regenerative stabilizer is a stabilizer which comprises at least one oxetane combined with at least one phosphite.
  • phosphites which can be derived from substituted phosphites in particular, derivatives of alky, aryl phosphite compounds.
  • any stabilizer composition as described above herein may further comprise at least one metal deactivator selected from the group consisting of areoxalyl bis(benzylidene)hydrazide (CAS reg. no. 6629-10-3); N,N'-bis(3,5-di-tert- butyl-4-hydroxyhydrocinnamoylhydrazine) (CAS reg. no. 32687-78-8); 2,2'-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhydorcinnamate) (CAS reg. no. 70331-94-1 ); N,N'-(disalicyclidene)-1 ,2-propanediamine (CAS reg. no.
  • a synergistic stabilizer composition comprises at least one oxetane; at least one phosphite; and at least one metal deactivator selected from the group consisting of areoxalyl bis(benzylidene)hydrazide; N.N'-bisfS, 5-di-tert-butyl-4- hydroxyhydrocinnamoylhydrazine); 2,2'-oxamidobis-ethyl-(3,5-d-tert-butyl- 4-hydroxyhydorcinnamate); N,N'-(disalicyclidene)-1 ,2-propanediamine; ethyenediaminetetraacetic acid and salts thereof; triazoles; benzotriazole, 2-mercaptobenzothiazole, tolutriazole derivatives, N,N-disalicylidene-1 ,2- diaminopropane and mixtures thereof.
  • a synergistic stabilizer composition comprises at least one oxetane; at least one amine; and at least one metal deactivator selected from the group consisting of areoxalyl bis(benzylidene)hydrazide; N,N'-bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamoylhydrazine); 2,2'-oxamidobis-ethyl-(3,5-d-tert-butyl- 4-hydroxyhydorcinnamate); N,N'-(disalicyclidene)-1 ,2-propanediamine; ethyenediaminetetraacetic acid and salts thereof; triazoles; benzotriazole, 2-mercaptobenzothiazole, tolutriazole derivatives, N,N-disalicylidene-1 ,2- diaminopropane, and mixtures thereof.
  • compositions of the present invention may further comprise at least one additional compound selected from the group consisting of fluoroolefins (as described previously herein), hydrofluorocarbons, hydrocarbons, dimethyl ether, CF 3 I, carbon dioxide (CO 2 ), ammonia, and mixtures thereof.
  • the additional compounds comprise at least one hydrocarbon.
  • the hydrocarbon refrigerants of the present invention comprise compounds having only carbon and hydrogen. Of particular utility are compounds having 3-7 carbon atoms.
  • Hydrocarbons are commercially available through numerous chemical suppliers. Representative hydrocarbons include but are not limited to propane, n- butane, isobutane, cyclobutane, n-pentane, 2-methylbutane, 2,2- dimethylpropa ⁇ e, cyclopentane, n-hexane, 2-methylpentane, 2,2- dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, cyclohexane, n- heptane, and cycloheptane.
  • the additional compounds may also comprise hydrocarbons containing heteroatoms, such as dimethylether (DME, CH 3 OCH 3 ). DME is commercially available.
  • the additional compounds may also comprise iodotrifluoromethane (CF 3 I), which is commercially available from various sources or may be prepared by methods known in the art.
  • the additional compounds may also comprise carbon dioxide (CO2), which is commercially available from various sources or may be prepared by methods known in the art.
  • the additional compounds may also comprise ammonia (NH 3 ), which is commercially available from various sources or may be prepared by methods known in the art.
  • NH 3 ammonia
  • compositions comprising: HFC-1225ye and HFC-32; HFC-1225ye and HFC-134a; HFC-1225ye, HFC-134a, and HFC-32; HFC ⁇ 1225ye and HFC- 1234yf; HFC-1225ye, HFC-1234yf, and HFC-32; and HFC-1225ye, HFC- 1234yf and HFC-125.
  • the additional compounds include compositions comprising fluoroolefins as disclosed in U.S. Patent application no. 11/369,227 filed March 2, 2006; U.S. Patent application no. 11/393,109 filed March 30, 2006; and U. S. Patent application no. 11/486,791 filed July 13, 2006; are intended to be included within the scope of the present invention.
  • compositions of the present invention may further comprise at least one lubricant.
  • Lubricants of the present invention comprise those suitable for use with refrigeration or air-conditioning apparatus. Among these lubricants are those conventionally used in compression refrigeration apparatus utilizing chlorofluorocarbon refrigerants. Such lubricants and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled “Lubricants in Refrigeration Systems", pages 8.1 through 8.21, herein incorporated by reference.
  • Lubricants of the present invention may comprise those commonly known as "mineral oils” in the field of compression refrigeration lubrication. Mineral oils comprise paraffins (i.e. straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (i.e.
  • Lubricants of the present invention further comprise those commonly known as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, silicones, and polyalphaolefins.
  • Lubricants of the present invention further comprise those which have been designed for use with hydrofluorocarbon refrigerants and are miscible with refrigerants of the present invention under compression refrigeration and air-conditioning apparatus' operating conditions.
  • Such lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", R. L. Shubkin, editor, Marcel Dekker, 1993.
  • Such lubricants include, but are not limited to, polyol esters (POEs) such as a commercially available POE sold under the trademark Castrol ® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVEs).
  • Lubricants of the present invention are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed.
  • compositions of the present invention that may be prepared by any convenient method to combine the desired amount of the individual components.
  • a preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • an effective amount may be said to be that amount of stabilizer that when combined with a composition comprising at least one fluoroolefin allows a cooling apparatus utilizing said composition comprising at least one fluoroolefin to perform at the same level of refrigeration performance and cooling capacity as if a composition comprising 1 ,1 ,1 ,2-tetrafluoroethane (R-134a), or other standard refrigerant (R12, R22, R502, R507A, R508, R401A, R401 B, R402A, R402B, R408, R410A, R404A, R407C, R413A, R417A, R422A, R422B, R422C, R422D, R423, R114, R11 , R113, R123, R124, R236fa, or R245fa) depending upon what refrigerant may have been used in a similar system in the past, were being utilized as the working
  • the present invention further relates to a process for producing cooling comprising condensing a composition comprising at least one fluoroolefin and an effective amount of stabilizer comprising at least one oxetane, and thereafter evaporating said composition in the vicinity of a body to be cooled.
  • a body to be cooled may be any space, location or object requiring refrigeration or air-conditioning.
  • the body In stationary applications the body may be the interior of a structure, i.e. residential or commercial, or a storage location for perishables, such as food or pharmaceuticals.
  • the body For mobile refrigeration applications the body may be incorporated into a transportation unit for the road, rail, sea or air.
  • Certain refrigeration systems operate independently with regards to any moving carrier, these are known as “intermodal" systems. Such intermodal systems include “containers" (combined sea/land transport) as well as “swap bodies” (combined road and rail transport).
  • the present invention further relates to a process for producing heat comprising condensing a composition comprising at least one fluoroolefin and an effective amount of stabilizer comprising at least one oxetane in the vicinity of a body to be heated, and thereafter evaporating said composition.
  • a body to be heated may be any space, location or object requiring heat. These may be the interior of structures either residential or commercial in a similar manner to the body to be cooled. Additionally, mobile units as described for cooling may be similar to those requiring heating. Certain transport units require heating to prevent the material being transported from solidifying inside the transport container. It is not uncommon for air to leak into a refrigeration, air- conditioning system or heat pump. The oxygen in the air may lead to oxidation of certain components of the system including the working fluid.
  • a method for reducing degradation of a composition comprising at least one fluoroolefin wherein said degradation is caused by the presence of inadvertent air; for example in a refrigeration, air-conditioning or heat pump system, said method comprising adding an effective amount of a stabilizer comprising at least one oxetane to the composition comprising at least one fluoroolefin.
  • a method for reducing reaction with oxygen for a composition comprising at least one fluoroolefin comprising adding an effective amount of stabilizer comprising at least one oxetane to the composition comprising at least one fluoroolefin.
  • a chemical stability test is run under conditions described in ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers) Standard 97-2004 to determine chemical stability of the stabilized compositions of the present invention as compared to compositions with no stabilizers.
  • ASHRAE American Society of Heating, Refrigerating and Air-Conditioning Engineers
  • the tubes are sealed with a glass blowing torch.
  • the sealed tubes are heated in an oven for 14 days at the specified temperature.
  • the sealed tubes are removed from the oven and examined for metal/liquid appearance, proper volume of liquid, appearance of glass, and absence of extraneous materials such as metal fines.
  • Ucon ® PAG 488 is a trademark for a polyalkylene glycol lubricant commercially available from The Dow Chemical Company.
  • Irgalube ® 63 is a trademark for a dithiophosphate commercially available from Ciba.
  • Irgalube ® 232 is a trademark for a butylated triphenyl phosphorothionate commercially available from Ciba.
  • Irgalube ® 349 is a trademark for a mixture of amine phosphates (an example of an organophosphate) commercially available from Ciba.
  • Irgalube ® 350 and Irgalube ® 353 are trademarks for dialkyl dithiophosphate esters from Ciba.
  • Krytox ® 157FSL is a trademark for a functionalized perfluoropolyether commercially available from DuPont.
  • Zerol ® 150 is a trademark for an alkyl benzene lubricant sold by Shrieve Chemical.
  • OXT-101 is 3-ethyl-3-hydroxymethyloxetane from Toagosei Company.
  • Tinuvin ® 622LD is a trademark for a hindered amine antioxidant commercially available from Ciba.

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Abstract

La présente invention concerne des compositions contenant au moins une fluorooléfine et une quantité efficace d'un stabilisant pouvant être constitué d'un époxyde, d'un époxyde ou oxétane fluoré ou d'un mélange de ceux-ci avec d'autres stabilisants. Les compositions stabilisées peuvent être utilisées dans des appareils de refroidissement, par exemple des appareils de réfrigération, de climatisation, des refroidisseurs et des pompes à chaleur, ainsi que dans des applications telles que des agents gonflants pour mousse, des solvants, des agents propulseurs d'aérosol, des agents extincteurs et des stérilisants.
PCT/US2007/019148 2006-09-01 2007-08-31 Stabilisants d'oxéthane pour fluorooléfines WO2008027519A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012168607A1 (fr) 2011-06-07 2012-12-13 Arkema France Compositions binaires de 1,3,3,3-tetrafluoropropene et d'ammoniac
US9175201B2 (en) 2004-12-21 2015-11-03 Honeywell International Inc. Stabilized iodocarbon compositions
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005044969A1 (fr) * 2003-11-04 2005-05-19 Honeywell International Inc. Compositions de solvants contenant des chlorofluoroolefines ou des hydrochloroolefines
WO2005067555A2 (fr) * 2004-01-14 2005-07-28 E.I. Dupont De Nemours And Company Compositions liquides de 1,1,1,3,3-pentafluorobutane frigorigenes ou de transfert thermique comprenant des hydrofluorocarbones et utilisations
WO2005119143A2 (fr) * 2004-05-26 2005-12-15 E.I. Dupont De Nemours And Company Mélanges de 1, 1, 1, 2, 2, 4, 5, 5, 5-nonafluoro-4-(trifluoromethyle)-3-pentanone et leurs utilisations
WO2006069362A2 (fr) * 2004-12-21 2006-06-29 Honeywell International Inc. Compositions d'iodocarbone stabilisees
WO2007053697A2 (fr) * 2005-11-01 2007-05-10 E. I. Du Pont De Nemours And Company Compositions comprenant des olefines fluorees et leurs utilisations

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005044969A1 (fr) * 2003-11-04 2005-05-19 Honeywell International Inc. Compositions de solvants contenant des chlorofluoroolefines ou des hydrochloroolefines
WO2005067555A2 (fr) * 2004-01-14 2005-07-28 E.I. Dupont De Nemours And Company Compositions liquides de 1,1,1,3,3-pentafluorobutane frigorigenes ou de transfert thermique comprenant des hydrofluorocarbones et utilisations
WO2005119143A2 (fr) * 2004-05-26 2005-12-15 E.I. Dupont De Nemours And Company Mélanges de 1, 1, 1, 2, 2, 4, 5, 5, 5-nonafluoro-4-(trifluoromethyle)-3-pentanone et leurs utilisations
WO2006069362A2 (fr) * 2004-12-21 2006-06-29 Honeywell International Inc. Compositions d'iodocarbone stabilisees
WO2007053697A2 (fr) * 2005-11-01 2007-05-10 E. I. Du Pont De Nemours And Company Compositions comprenant des olefines fluorees et leurs utilisations

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9175201B2 (en) 2004-12-21 2015-11-03 Honeywell International Inc. Stabilized iodocarbon compositions
WO2012168607A1 (fr) 2011-06-07 2012-12-13 Arkema France Compositions binaires de 1,3,3,3-tetrafluoropropene et d'ammoniac
US8951432B2 (en) 2011-06-07 2015-02-10 Arkema France Binary compositions of 1,3,3,3-tetrafluoropropene and ammonia
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

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