WO2020132035A1 - Solutions inhibées de hfo-1234yf - Google Patents

Solutions inhibées de hfo-1234yf Download PDF

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Publication number
WO2020132035A1
WO2020132035A1 PCT/US2019/067124 US2019067124W WO2020132035A1 WO 2020132035 A1 WO2020132035 A1 WO 2020132035A1 US 2019067124 W US2019067124 W US 2019067124W WO 2020132035 A1 WO2020132035 A1 WO 2020132035A1
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WIPO (PCT)
Prior art keywords
hfo
ppm
composition
nvr
numbered embodiment
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PCT/US2019/067124
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English (en)
Inventor
David Nalewajek
Rajiv Ratna Singh
Rajiv Banavali
Gregory Laurence Smith
Original Assignee
Honeywell International Inc.
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Priority claimed from US16/713,476 external-priority patent/US11230655B2/en
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Publication of WO2020132035A1 publication Critical patent/WO2020132035A1/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
    • 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
    • C09K2205/24—Only one single fluoro component present

Definitions

  • HFO-1234yf 2,3,3,3-Tetrafluoropropene
  • HFO-1234yf is a hydrofluoroolefin, which is useful in a variety of applications including: heat transfer uses such as refrigeration, air conditioning (especially automobile air conditioning), heat pumps, chillers, and organic Rankine cycle; foam blowing agents; and aerosol propellants.
  • HFO-1234yf has been widely adopted to replace HFC-134a in a host of applications including automotive air conditioning.
  • HFOs and HCFOs make these molecules more likely to undergo chemical reaction including during transportation, storage, handling or use than the predecessor saturated molecules such as the HFCs.
  • Such undesirable reactions generally occur at lower temperatures than for HFCs and the rate of reactivity generally exceeds that of the HFCs at a given temperature.
  • HFOs and HCFOs are at greater risk than HFCs for undergoing reaction during transport.
  • HFO-1234yf does not undergo unwanted polymerization reactions during storage, handling or use as a refrigerant in heat transfer and other applications.
  • HFO-1234yf can undergo polymerization reactions to an unwanted, undesirable and disadvantageous extent.
  • the containers or vessels which hold HFO-1234yf, particularly during certain storage conditions can expose the HFO-1234yf to an increased likelihood of polymerization reactions.
  • the terms“polymerization” and“HFO-1234yf polymers” refer to materials and reactions that include HFO-1234yf homo oligomers and oligomers of HFO- 1234yf containing a heteroatom (hetero-oligomers), as well as polymers of HFO-1234yf.
  • An exemplary hetero-oligomer of HFO-1234yf has the formula [(CF 3 )(F)-C-C-(H)(H)-0-] x .
  • An exemplary polymer of HFO-1234yf has the following formula [(CF3)(F)-C-C-(H)(H)] n where n>10.
  • Figure 1 shows the NMR spectra for the monomer of HFO-1234yf and homopolymer of HFO-1234yf.
  • the unwanted polymer of HFO-1234yf can have the formula [(CF 3 )(F)-C-C-(H)(H)] n [(CF 3 )(F)-C-C- (H)(H)-0-]x where the ratio of n/x is 400 or greater.
  • Non-Volatile Residue or High Boiling Residue (NVR-Criteria)
  • the inhibiting effect of the additive of the invention can be measured by determining the formation of polymerization products measured as non-volatile residue (i.e. , NVR), using the gravimetric determination option of Part 3 “Determination of High Boiling Residue in New and Reclaimed Refrigerants by Volumetric and/or Gravimetric Measurement and Determination of Particulate Residue by Visual Indication” according to AHRI Standard 700-2014 - Normative, which incorporates and relies upon the 2008 version of Appendix C for Analytical Procedures (hereinafter“The NVR Test”).
  • a quantitative value or range of values for“the NVR” of HFO-1234yf refer to the value as determined by the NVR Test as described in this paragraph.
  • the NVR of HFO-1234yf according to the present invention should not exceed 0.01 weight % (100 ppm), which is consistent with AHRI Standard 700-2017 with Addendum 1 , Specification for Refrigerants. It is preferable that the compositions, methods and containers of the present invention have an NVR of HFO-1234yf that is less than or equal to 25 ppm, more preferably less than or equal to 15 ppm and still more preferably less than or equal to 10 ppm. It is most preferable that the compositions, methods and containers of the present invention have an NVR of HFO-1234yf less than or equal to 5 ppm.
  • the HFO-1234yf polymer that is produced at the relatively low end of the above-noted temperature range, i.e. , about -10°C tends to be of particularly high molecular and particularly disadvantageous to use of the HFO-1234yf, and that invention as described herein is able to effectively inhibit the production of such polymers at such low temperatures.
  • the compositions, methods and containers of the present invention have an NVR of HFO-1234yf that is not greater than 0.01 weight % (100 ppm) after storage in a container or vessel at a temperature of about -10°C over a 30 day period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is not greater than 0.01 weight % (100 ppm) after storage in a container or vessel at any temperature in the range of temperatures of from about -10°C to about 50 °C over a 30 day period and/or over a over a 3 month period and/or over a 6 month period.
  • the NVR of HFO-1234yf is less than or equal to 25 ppm, more preferably less than or equal to 15 ppm and still more preferably less than or equal to 10 ppm after storage at up to 50°C over any of the following periods: 30 days, at least 3 months or at least 6 months.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than or equal to 5 ppm after storage in a container or vessel at a temperature in the range of from about -10°C to about 50°C over a 30 day period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than or equal to 5 ppm after storage in a container or vessel at a temperature in the range of from about -10°C to about 50°C over a 3 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than or equal to 5 ppm after storage in a container or vessel at a temperature of about -10°C over a 30 day period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than or equal to 5 ppm after storage in a container or vessel at a temperature ofabout -10°C over a 3 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than or equal to 5 ppm after storage in a container or vessel at a temperature of about -10°C over a 6 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 5 ppm after storage in a container or vessel at any temperature in the range of temperatures of from about -10°C to about 50 °C over a 30 day period and/or over a over a 3 month period and/or over a 6 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is from about 5 ppm to about 15 ppm.
  • the present invention includes compositions in which the NVR of HFO-1234yf is from about 5 ppm to about 10 ppm.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at a temperature in the range of from about -10°C to about 50°C over a 30 day period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at a temperature in the range of from about -10°C to about 50°C over a 6 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at a temperature of about -10°C over a 30 day period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at a temperature of about -10°C over a 3 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at a temperature of about -10°C over a 6 month period.
  • the present invention includes compositions in which the NVR of HFO-1234yf is less than 10 ppm after storage in a container or vessel at any temperature in the range of temperatures of from about -10°C to about 50 °C over a 30 day period and/or over a over a 3 month period and/or over a 6 month period.
  • compositions of the invention have broad applicability including in automotive air conditioning systems and devices, commercial refrigeration systems and devices, chillers, residential refrigerator and freezers, general air conditioning systems, heat pumps, and the like.
  • the compositions of the invention are useful as foam blowing agents and propellants.
  • the presence of a-terpinene in the compositions of the invention does not detract from the environmentally desirable properties or from the performance of HFO-1234yf in these uses.
  • the present invention provides a heat transfer composition comprising or consisting essentially of or consisting of a composition of the first aspect of the invention.
  • the heat transfer composition may comprise, consist essentially of or consist of one or more other refrigerants besides HFO-1234yf, lubricants or other materials typically found in heat transfer compositions.
  • Other refrigerants besides HFO-1234yf which may be present in the heat transfer composition include without limitation hydrocarbons (such as propane, butane or isobutane), CO2, saturated HFCs (such as 134a, 152a, 227ea, 32, 125, CF3I), and HFOs (such as 1234ze, 1233zd, 1336mzzm) or combinations of these.
  • the amounts of these other refrigerants may vary widely depending on the application.
  • the other refrigerants may be present in an amount of from about 1 to about 99 weight % or from about 5 to about 95 weight % or from about 10 to about 90 weight % of the heat transfer composition.
  • the heat transfer compositions of the invention may contain one or more lubricants.
  • lubricant When lubricant is included in the heat transfer composition it may be present in widely ranging amounts including for example in an amount of from about 5 to about 30 percent by weight of the heat transfer composition.
  • Commonly used lubricants such as polyol esters (POEs) and poly alkylene glycols (PAGs), poly vinyl ethers, silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin) (PAO) may be used with the compositions of the present invention.
  • PEO poly(alpha-olefin)
  • the heat transfer compositions of the invention may be used in automotive air conditioning systems and devices, commercial refrigeration systems and devices, chillers, residential refrigerator and freezers, general air conditioning systems, heat pumps, and the like. The presence of a-terpinene in the compositions of the invention does not detract from the environmentally desirable properties or from the performance of HFO-1234yf in these
  • a HFO-1234yf and a-terpinene composition as defined in the first aspect of the invention as a refrigerant including in a heat transfer composition.
  • the present invention relates to the use of an additive to inhibit the formation of HFO-1234yf polymerization products comprising combining a-terpinene and HFO-1234yf to produce a composition comprising HFO-1234yf and a-terpinene.
  • the invention relates to a method of inhibiting the formation of HFO-1234yf polymerization products in a fluid comprising, consisting essentially of or consisting of HFO-1234yf comprising combining a-terpinene and the fluid to produce a composition comprising HFO-1234yf and a-terpinene.
  • the present invention includes methods and uses which combine a-terpinene and HFO-1234yf in amounts effectiveto meet any one of and/or each of the NVR limitations and ranges defined under the heading NVR Criteria discussed above.
  • the a-terpinene is present in an amount of at least about 1 ppm by weight based on the amount of HFO-1234yf and the a-terpinene present in the composition. Specifically the a-terpinene is present in an amount of from about 1 ppm to about 10,000 ppm by weight or from about 100 ppm to about 1000 ppm by weight or from about 150 ppm to about 500 ppm by weight or from about 300 ppm to about 500 ppm present in the composition, in each case based on the amount of HFO-1234yf and the a-terpinene present in the composition.
  • the a-terpinene is present in an amount of from about 150 ppm to about 500 ppm and the NVR of HFO-1234yf is less than 10 ppm, or the a-terpinene is present in an amount of from about 300 ppm to about 500 ppm and the NVR of HFO-1234yf is from about 5 to about 10 ppm or the a-terpinene is present after storage in a container or vessel at a temperature in the range of from about -10°C to about 50°C over any one or more of the following periods: 30 days, 3 months, 6 months.
  • the invention further provides a container comprising a composition comprising, consisting essentially of or consisting of HFO-1234yf and a-terpinene according to the present invention, including particularly in amounts effective to meet any one of and/or each of the NVR limitations and ranges defined under the heading NVR Criteria discussed above.
  • the container is fitted with a threaded valve and wherein the sealant on the threaded valve contains a peroxide, preferably cumene hydroperoxide.
  • the cumene hydroperoxide comprises 1 to 5 weight percent of the sealant.
  • the HFO-1234yf in said container preferably has a NVR of less than 0.01 weight percent (100 ppm), or has a NVR of less than or equal to 25 ppm, or has a NVR of less than or equal to 15 ppm, or has a NVR of less than or equal to 10 ppm, or has a NVR of less than or equal to 5 ppm or the HFO-1234yf in said container has a NVR of from about 5 ppm to 15 ppm, or has a NVR of from about 5 ppm to 10 ppm or has a NVR of less than 10 ppm, in each case after storage for at least 30 days at a temperature of in the range of from about -10°C to about 50°C or after storage for at least 3 months at a temperature in the range of from about -10°C to about 50°C or after storage for at least 6 months at a temperature in the range of from about -10°C to about 50°C.
  • the HFO-1234yf in said container preferably has a NVR of less than 0.01 weight percent (100 ppm), or has a NVR of less than or equal to 25 ppm, or has a NVR of less than or equal to 15 ppm, or has a NVR of less than or equal to 10 ppm, or has a NVR of less than or equal to 5 ppm or the HFO-1234yf in said container has a NVR of from about 5 ppm to 15 ppm, or has a NVR of from about 5 ppm to 10 ppm or has a NVR of less than 10 ppm, in each case after storage for at least 30 days at a temperature of about - 10°C to about 50°C or after storage for at least 3 months at a temperature about -10°C to about 50°C or after storage for at least 6 months at a temperature of about -10°C.
  • HFO-1234yf (2,3,3,3-tetrafluoropropene) may be prepared by any means known in the art. See for example the process disclosed in EP 1968922 A2. HFO-1234yf should meet AHRI Standard 700-2017 with Addendum 1 , Specification for Refrigerants. HFO- 1234yf is commercially available from Honeywell International Inc. as Solstice® 1234yf refrigerant. a-terpinene is commercially available, for example, from Millipore-Sigma.
  • Figure 1 shows the NMR spectra for the monomer of HFO-1234yf and homopolymer of HFO-1234yf.
  • the -70 to -80 region is the chemical shift for the CF3 group
  • the CF shift at -125 represents the CF in the monomer
  • the shift at -170 to- 180 represents the CF group in the polymer.
  • the monomer and polymer are distinct and it is easy to detect the formation of a homopolymer of HFO-1234yf when the additive fails in suppressing the reaction.
  • NVR means the value as determined by The NVR Test method.
  • successfully meeting the NVR specification of HFO-1234yf means an NVR maximum of 0.01 weight % (100 ppm).
  • initiator means peroxide or thread sealant containing cumene hydroperoxide.
  • Control 1 describes the preparation of a polymer of HFO-1234yf produced through the reaction of HFO-1234yf of >99.5% purity. For each of the Control, Examples, and Comparative Examples HFO-1234yf of >99.5 % purity was used. A free radical was generated by thermal bond cleavage by heating t- butylperoxypivalate (a peroxide) to 56-60°C. This serves as the base line for the quantity of polymer that can be generated under the conditions of the experiment. 2, 3,3,3- Tetrafluoropropene (245g, 2.15mol) was added to an evacuated 1 L Hastelloy autoclave.
  • the initiator t-butylperoxypivalate (0.47g of a 70wt% solution, 1343 ppm), was added in one portion.
  • the temperature of the Hastelloy autoclave was raised to 58°C ⁇ 2°C over a 0.5 hour period with agitation. The reaction was continued for 24 hours.
  • 42.9g (-17% yield) of the homo polymer of HFO- 1234yf was recovered having a molecular weight of 27.8K Daltons by GPC and a poly dispersity of 1.7. No additive was used in this Control.
  • Control 2 Control 1 was repeated to establish a base line for polymer formation using an approximate ten-fold decrease in the amount of radical initiator (100 ppm) compared to Control 1.
  • the equipment and reaction conditions described above were used with the following quantities of reactants: HFO-1234yf (249g, 2.18mol) and t- butylperoxypivalate (0.036g of a 70wt% solution, 101 ppm of active initiator).
  • HFO-1234yf 249g, 2.18mol
  • t- butylperoxypivalate 0.036g of a 70wt% solution, 101 ppm of active initiator.
  • the formed homo polymer of HFO-1234yf 6.6g, ( ⁇ 3% yield) was isolated. No additive was used in this Control.
  • Control 3 Control 1 was repeated to serve as a baseline value using an approximate one hundred-fold decrease in the amount of radical initiator of only 10 ppm of initiator compared to Control 1 and extending the reaction time to seven days.
  • the following reagents and values were charged into the autoclave.
  • HFO-1234yf 243.1 g, 2.13 mol
  • t-butylperoxypivalate 0.0036g of a 70wt% solution, 10 ppm.
  • the formed polymer of HFO-1234yf was isolated (0.6425 gram, 0.26% yield). No additive was used in this Control.
  • the Examples of the invention used the same equipment and reaction conditions as Control 1 except that an additive was added and t-butylperoxypivalate in a 70 wt. solution was used as the initiator.
  • Comparative Examples A, B, C, E, F, H, and I the same equipment and reaction conditions as Control 1 were used and various terpenes outside the scope of the invention were used as the additive.
  • Comparative Example D isobutylene was used as the additive and in example G, 1 ,4-hydroquinone, a known phenol stabilizer for preventing the decomposition of lubricants and refrigerants, was used as the additive.
  • the reaction conditions for Comparatives D and G were the same as Control 1.
  • Control 4 Control 1 was repeated except that the initiator was thread sealant instead of peroxide, the amount of HFO-1234yf was 500 g, the reaction time was 30 days, and the reaction temperature was about 20°C. No stabilizer was used in this Control.
  • Comparative Examples J and K used the same conditions as Control 4 and various terpenes outside the scope of the invention were used as the stabilizer.
  • Examples 4 and 5 used the same conditions as Control 4 except a-terpinene in an amount of 500 ppm or 300 ppm respectively was added as inhibitor.
  • a composition comprising HFO-1234yf and a-terpinene.
  • composition of Numbered Embodiment 1 wherein the composition consists essentially of HFO-1234yf and a-terpinene.
  • composition of Numbered Embodiment 1 wherein the composition consists of HFO- 1234yf and a-terpinene.
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • composition of any one of Numbered Embodiments 1 to 13, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 15 ppm.
  • composition of any one of Numbered Embodiments 1 to 14, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 10 ppm.
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • composition of any one of Numbered Embodiments 1 to 21 wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is less than or equal to 25 ppm after storage for a period of at least 3 months.
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • composition of any one of Numbered Embodiments 1 to 31 wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is less than or equal to 5 ppm after storage for a period of at least 6 months.
  • NVR Non-Volatile Residue
  • composition of any one of Numbered Embodiments 1 to 32, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 15 ppm after storage for a period of at least 30 days.
  • composition of any one of Numbered Embodiments 1 to 33, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 15 ppm after storage for a period of at least 3 months.
  • composition of any one of Numbered Embodiments 1 to 34, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 15 ppm after storage for a period of at least 6 months.
  • composition of any one of Numbered Embodiments 1 to 35, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 10 ppm after storage for a period of at least 30 days.
  • composition of any one of Numbered Embodiments 1 to 36, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 10 ppm after storage for a period of at least 3 months.
  • NVR Non-Volatile Residue
  • composition of any one of Numbered Embodiments 1 to 37, wherein the Non-Volatile Residue (NVR) of the HFO-1234yf is from about 5 ppm to 10 ppm after storage for a period of at least 6 months.
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • NVR Non-Volatile Residue
  • a heat transfer composition comprising a composition of any one of Numbered Embodiments 1 to 41.
  • Numbered Embodiment 60 where the a-terpinene is added in an amount of from about 300 to about 500 weight in each case based on the amount of HFO-1234yf and a-terpinene.
  • Numbered Embodiment 60 wherein the a-terpinene is added in an amount of from about 300 to about 500 percent by weight based on the amount of HFO-1234yf and a-terpinene and the NVR of HFO-1234yf is from about 5 to about 10 ppm after storage for a period of at least 3 months.
  • Numbered Embodiment 60 wherein the a-terpinene is added in an amount of from about 300 to about 500 percent by weight based on the amount of HFO-1234yf and a-terpinene and the NVR of HFO-1234yf is from about 5 to about 10 ppm after storage for a period of at least 6 months.
  • Numbered Embodiment 60 wherein the a-terpinene is added in an amount of from about 300 to about 500 percent by weight based on the amount of HFO-1234yf and a-terpinene and the NVR of HFO-1234yf is from about 5 to about 10 ppm after storage for a period of at least 3 months.
  • composition of any one of Numbered Embodiments 18 to 41 wherein said NVR values are achieved when the temperature of said composition is about -10 °C during said period of storage.
  • composition of any one of Numbered Embodiments 18 to 41 wherein said NVR values are achieved when the temperature of said composition is about 50 °C during said period of storage.
  • composition of any one of Numbered Embodiments 18 to 41 wherein said NVR values are achieved when said composition is at any temperature in the range of temperatures of from about -10 °C to about 50 °C during said period of storage.

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Abstract

La présente invention concerne une composition comprenant du 2,3,3,3-tétrafluoropropène et de l'α-terpinène, particulièrement utile dans des systèmes et des dispositifs de climatisation automobile, des systèmes et des dispositifs de réfrigération d'usage commercial, des refroidisseurs, des réfrigérateurs et des congélateurs d'usage domestique, des systèmes de climatisation d'usage général, des pompes à chaleur et similaires.
PCT/US2019/067124 2018-12-18 2019-12-18 Solutions inhibées de hfo-1234yf WO2020132035A1 (fr)

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US201862781333P 2018-12-18 2018-12-18
US62/781,333 2018-12-18
US201962911987P 2019-10-07 2019-10-07
US201962911945P 2019-10-07 2019-10-07
US62/911,945 2019-10-07
US62/911,987 2019-10-07
US16/713,476 US11230655B2 (en) 2018-12-18 2019-12-13 HFO-1234yf inhibited solutions
US16/713,476 2019-12-13

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