Stabilized heat transfer fluid compositions

Abstract

To provide stabilized compositions comprising methyl perfluoroheptene ether for use in refrigeration and heat transfer applications.SOLUTION: There is provided a composition, comprising methyl perfluoroheptene ether; and a specific quantity of butylated hydroxy toluene; or hydroquinone monomethyl ether; or butylated hydroxy toluene and 1,2-epoxybutane; or hydroquinone monomethyl ether and 1,3-dioxolane; or hydroquinone monomethyl ether and 1,2-epoxybutane; or butylated hydroxy toluene and 1,3-dioxolane; or 2-tert-butyl-6-methylphenol; or 2-tert-butyl-5-methylphenol; or 2-tert-butyl-4-ethylphenol or the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This application relates to stabilized compositions (e.g., stabilized heat transfer fluids) containing methyl perfluoroheptene ether for use in refrigeration and heat transfer applications. The stabilized compositions of the present invention exhibit reduced decomposition compared to methyl perfluoroheptene ether and are useful in methods for producing cooling and heating, refrigerant replacement, and refrigeration, air conditioning, and heat pump devices. [Background technology]

[0002] Many of today's semiconductor manufacturing processes, power electronics, power avionics, and computing data centers require advanced, environmentally sustainable, safe, non-flammable, non-conductive, non-corrosive, and thermally stable heat transfer fluids to maintain optimal performance over long periods of time. Perfluorocarbons (PFCs) have been successfully and widely used in heat transfer applications due to their combination of excellent safety and health properties, dielectric properties, and thermal stability. However, PFCs have atmospheric lifetimes ranging from several hundred to over 10,000 years and are potent greenhouse gases, with a global warming potential (GWP) of over 8,600 (100-year ITH). Recent environmental concerns and government regulations have focused on mitigating global warming. Summary of the Invention [Means for solving the problem]

[0003] The present application relates, inter alia, to i) methyl perfluoroheptene ether; ii) a second component selected from the group consisting of butylated hydroxy toluene (BHT), hydroquinone monomethyl ether (HQMME), 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol and 2-tert-butyl-4-ethylphenol, 1,3-dioxolane, 1,2-epoxybutane, and nitromethane, or any mixture thereof.

[0004] The present application further provides a method for reducing acid decomposition of a working fluid comprising methyl perfluoroheptene ether, the method comprising mixing the working fluid with a second component selected from the group consisting of one or more antioxidants and one or more acid scavengers, or any mixture thereof, thereby forming a stabilized working fluid as provided herein.

[0005] The present application further provides a process for dissolving a solute, the process comprising contacting and mixing the solute with a sufficient amount of a composition provided herein.

[0006] The present application further provides a process for cleaning a surface, the process comprising contacting the surface with a composition provided herein.

[0007] The present application further provides a process for removing at least a portion of water from the surface of a wet substrate, the process comprising contacting the substrate with a composition provided herein and then removing the substrate from contact with the composition.

[0008] The present application further provides a process for depositing a fluorolubricant on a surface, the process comprising: a) combining a fluorolubricant and a solvent to form a lubricant / solvent combination, wherein the solvent comprises a composition provided herein; b) contacting the lubricant / solvent combination with the surface; c) evaporating the solvent from the surface to form a fluorolubricant coating on the surface.

[0009] The present application further provides a process for producing cooling, the process comprising condensing a composition provided herein and then evaporating the composition in the vicinity of a body to be cooled.

[0010] The present application further provides a process for producing heating, the process comprising evaporating a composition provided herein and then condensing the composition in the vicinity of a body to be heated.

[0011] The present application further provides a method for producing cooling, the method comprising circulating a heat transfer fluid comprising a composition provided herein in the vicinity of a body to be cooled, the heat transfer fluid being a working fluid that removes heat from, adds heat to, or maintains a temperature in the vicinity of the body to be cooled.

[0012] The present application further provides a method of replacing a heat transfer fluid in a refrigeration fluid distribution unit, a refrigeration system, or a heat pump system, the method comprising providing a composition provided herein as a replacement for the heat transfer fluid. [Brief explanation of the drawings]

[0013] [Figure 1] 1 shows the results of a total acid number (TAN) analysis at 75° C. of a representative composition of the present invention. [Figure 2] 1 shows the results of a total acid number (TAN) analysis at 90° C. of a representative composition of the present invention. [Figure 3] 1 shows the results of a total acid number (TAN) analysis at 100° C. of a representative composition of the present invention. [Figure 4] Comparative Total Acid Number (TAN) analysis performed at 75° C. over a 6 day period is shown. DETAILED DESCRIPTION OF THE INVENTION

[0014] Methylperfluoroheptene ether (MPHE) is a hydrofluoroolefin (HFO)-based fluorinated fluid with a low GPW of 2.5 (100-year ITH) and zero ODP. MPHE exhibits an application profile similar to PFCs but with a significantly lower GPW. However, due to its low GWP, its performance may be susceptible to hydrolysis and other forms of degradation. It has been observed that measurable acidity in MPHE is higher than its product specification upon storage at elevated temperatures and long-term storage at room temperature. Acidity formation in fluids under these conditions can lead to shortened shelf life and, without appropriate mitigation measures, potentially damage equipment. Therefore, the present application provides stabilized compositions that exhibit lower decomposition rates than MPHE over extended periods and at elevated temperatures.

[0015] composition The present application provides a composition comprising methyl perfluoroheptene ether (MPHE) and a second component selected from the group consisting of one or more antioxidants and one or more acid scavengers, or any mixture thereof.

[0016] In some embodiments, the one or more acid antioxidants are selected from butylated hydroxytoluene (BHT), hydroquinone monomethyl ether (HQMME), 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, and 2-tert-butyl-4-ethylphenol.

[0017] In some embodiments, the one or more scavengers are selected from 1,3-dioxolane, 1,2-epoxybutane, and nitromethane.

[0018] In some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from one or more antioxidants, hi some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from one or two antioxidants.

[0019] In some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from one or more acid scavengers, hi some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from one or two acid scavengers.

[0020] In some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from a mixture of one or more antioxidants and one or more acid scavengers. In some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from a mixture of one or two antioxidants and one or two acid scavengers. In some embodiments, the composition comprises methyl perfluoroheptene ether and a second component selected from a mixture of one antioxidant and one acid scavengers.

[0021] In some embodiments, the compositions provided herein comprise: i) methyl perfluoroheptene ether; ii) a second component selected from the group consisting of butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol and 2-tert-butyl-4-ethylphenol, 1,3-dioxolane, 1,2-epoxybutane, and nitromethane, or any mixture thereof.

[0022] In some embodiments, the compositions provided herein comprise: i) methyl perfluoroheptene ether; ii) a second component selected from the group consisting of butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol and 2-tert-butyl-4-ethylphenol, 1,3-dioxolane, 1,2-epoxybutane, and nitromethane, or any mixture thereof.

[0023] In some embodiments, the compositions provided herein comprise: i) methyl perfluoroheptene ether; ii) a second component selected from the group consisting of butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol and 2-tert-butyl-4-ethylphenol, 1,3-dioxolane, 1,2-epoxybutane, and nitromethane, or any mixture thereof.

[0024] In some embodiments, the second component is present in the composition in an amount effective to maintain the total acid number of the composition at about 0.2 mg KOH / g or less, e.g., about 0.1 mg KOH / g or less, about 0.075 mg KOH / g or less, about 0.050 mg KOH / g or less, about 0.025 mg KOH / g or less, or about 0.01 mg KOH / g or less. In some embodiments, the second component is present in the composition in an amount effective to maintain the total acid number of the composition at about 0.1 mg KOH / g or less.

[0025] In some embodiments, the second component increases the total acid number of the composition by about 0.01 mg KOH / g to about 0.2 mg KOH / g, e.g., about 0.01 mg KOH / g to about 0.15 mg KOH / g, about 0.01 mg KOH / g to about 0.1 mg KOH / g, about 0.01 mg KOH / g to about 0.075 mg KOH / g, about 0.01 mg KOH / g to about 0.050 mg KOH / g, about 0.01 mg KOH / g to about 0.025 mg KOH / g, about 0.025 mg KOH / g to about 0.2 mg KOH / g, about 0.025 mg KOH / g to about 0.15 mg KOH / g, about 0.025 mg KOH / g to about 0.1 mg KOH / g, or about 0.025 mg KOH / g to about 0.075 mg KOH / g, about 0.025mg KOH / g to about 0.050mg KOH / g, about 0.050mg KOH / g to about 0.2mg KOH / g, about 0.050mg KOH / g to about 0.15mg KOH / g, about 0.050mg KOH / g to about 0.1mg KOH / g, about 0.050mg KOH / g to about 0.075mg KOH / g, about 0.075mg KOH / g to about 0.2mg KOH / g, about 0.075mg KOH / g to about 0.15mg KOH / g, about 0.075mg KOH / g to about 0.1mg KOH / g, about 0.1mg KOH / g to about 0.2mg KOH / g, about 0.1mg KOH / g to about 0.15mg KOH / g, or about 0.15mg KOH / g to about 0.2mg In some embodiments, the second component is present in the composition in an amount effective to maintain a total acid number of the composition between about 0.01 mg KOH / g and about 0.1 mg KOH / g. In some embodiments, the second component is present in the composition in an amount effective to maintain a total acid number of the composition between about 0.01 mg KOH / g and about 0.1 mg KOH / g. In some embodiments, the second component is present in the composition in an amount effective to maintain a total acid number of the composition between about 0.1 mg KOH / g.

[0026] In some embodiments, the methyl perfluoroheptene ether comprises a mixture of about 48 to about 52 weight percent 5-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent 3-methoxyperfluoro-3-heptene, about 18 to about 22 weight percent 4-methoxyperfluoro-2-heptene, and about 6 to about 10 weight percent 4-methoxyperfluoro-3-heptene.

[0027] In some embodiments, the methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxyperfluoro-3-heptene, about 20 weight percent 3-methoxyperfluoro-3-heptene, about 20 weight percent 4-methoxyperfluoro-2-heptene, and about 8 weight percent 4-methoxyperfluoro-3-heptene.

[0028] In some embodiments, the methyl perfluoroheptene ether comprises a mixture of about 48 to about 52 weight percent 5-methoxy(E)-perfluoro-3-heptene, about 12 to about 16 weight percent 3-methoxy(E)-perfluoro-3-heptene, about 4 to about 8 weight percent 3-methoxy(Z)-perfluoro-3-heptene, about 18 to about 22 weight percent 4-methoxy(E)-perfluoro-2-heptene, about 1 to about 3 weight percent 4-methoxy(Z)-perfluoro-3-heptene, and about 4 to about 8 weight percent 4-methoxy(E)-perfluoro-3-heptene.

[0029] In some embodiments, the methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxy(E)-perfluoro-3-heptene, about 14 weight percent 3-methoxy(E)-perfluoro-3-heptene, about 6 weight percent 3-methoxy(Z)-perfluoro-3-heptene, about 20 weight percent 4-methoxy(E)-perfluoro-2-heptene, about 2 weight percent 4-methoxy(Z)-perfluoro-3-heptene, and about 6 weight percent 4-methoxy(E)-perfluoro-3-heptene.

[0030] In some embodiments, the second component is selected from the group consisting of 1,3-dioxolane, butylated hydroxytoluene, and hydroquinone monomethyl ether. In some embodiments, the second component is selected from the group consisting of butylated hydroxytoluene and hydroquinone monomethyl ether.

[0031] In some embodiments, the second component is butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-ethylphenol, a mixture of butylated hydroxytoluene and 1,2-epoxybutane, a mixture of hydroquinone monomethyl ether and 1,3-dioxolane, a mixture of hydroquinone monomethyl ether and 1,2-epoxybutane, a mixture of 2-tert-butyl-6-methylphenol and 1,2-epoxybutane, a mixture of 2-tert-butyl-6-methylphenol and nitromethane, and The solvent is selected from the group consisting of a mixture of butylated hydroxytoluene and 1,3-dioxolane.

[0032] In some embodiments, the composition may have a saturation concentration of about 100 ppm to about 1100 ppm, e.g., about 100 ppm to about 1000 ppm, about 100 ppm to about 900 ppm, about 100 ppm to about 800 ppm, about 100 ppm to about 700 ppm, about 100 ppm to about 600 ppm, about 100 ppm to about 500 ppm, about 100 ppm to about 400 ppm, about 100 ppm to about 300 ppm, about 100 ppm to about 200 ppm, about 200 ppm to about 1100 ppm, about 200 ppm to about 1000 ppm, about 200 ppm to about 900 ppm, Approximately 200ppm to approximately 800ppm, approximately 200ppm to approximately 700ppm, approximately 200ppm to approximately 600ppm, approximately 200ppm to approximately 500ppm, approximately 200ppm to approximately 400ppm, approximately 200ppm to approximately 300ppm, approximately 300ppm to approximately 1100ppm, approximately 30 0ppm to about 1000ppm, about 300ppm to about 900ppm, about 300ppm to about 800ppm, about 300ppm to about 700ppm, about 300ppm to about 600ppm, about 300ppm to about 500ppm, about 300ppm to about 400ppm, about 400ppm ~1100ppm, 400ppm~1000ppm, 400ppm~900ppm, 400ppm~800ppm, 400ppm~700ppm, 400ppm~600ppm, 400ppm~500ppm, 500ppm~approx. 1100ppm, about 500ppm to about 1000ppm, about 500ppm to about 900ppm, about 500ppm to about 800ppm, about 500ppm to about 700ppm, about 500ppm to about 600ppm, about 600ppm to about 1100ppm, about 600ppm to about 10 In some embodiments, the composition comprises about 100 ppm to about 1100 ppm of the second component. In some embodiments, the composition comprises about 100 ppm to about 1100 ppm of the second component.

[0033] In some embodiments, the composition comprises about 100 ppm to about 550 ppm, e.g., about 100 ppm to about 500 ppm, about 100 ppm to about 400 ppm, about 100 ppm to about 300 ppm, about 100 ppm to about 200 ppm, about 200 ppm to about 550 ppm, about 200 ppm to about 500 ppm, about 200 ppm to about 400 ppm, about 200 ppm to about 300 ppm, about 300 ppm to about 550 ppm, about 300 ppm to about 500 ppm, about 300 ppm to about 400 ppm, about 400 ppm to about 550 ppm, about 400 ppm to about 500 ppm, or about 500 ppm to about 550 ppm of the second component. In some embodiments, the composition comprises from about 100 ppm to about 550 ppm of the second component, hi some embodiments, the composition comprises from about 140 ppm to about 500 ppm of the second component.

[0034] In some embodiments, the composition comprises from about 0.01% to about 0.15% by weight, e.g., from about 0.01% to about 0.011% by weight, from about 0.01% to about 0.01% by weight, from about 0.01% to about 0.075% by weight, from about 0.01% to about 0.050% by weight, from about 0.01% to about 0.025% by weight, from about 0.025% to about 0.15% by weight, from about 0.025% to about 0.11% by weight, from about 0.025% to about 0.1% by weight, from about 0.025% to about 0.075% by weight, from about 0.025% to about 0.075% by weight, from about 0.025% to about 0.050% by weight, The composition may comprise about 0.050 wt%, about 0.050 wt% to about 0.15 wt%, about 0.050 wt% to about 0.11 wt%, about 0.050 wt% to about 0.1 wt%, about 0.050 wt% to about 0.1 wt%, about 0.050 wt% to about 0.075 wt%, about 0.075 wt% to about 0.1 wt%, about 0.075 wt% to about 0.15 wt%, about 0.075 wt% to about 0.11 wt%, about 0.075 wt% to about 0.1 wt%, about 0.1 wt% to about 0.15 wt%, about 0.1 wt% to about 0.11 wt%, or about 0.11 wt% to about 0.15 wt% of the second component. In some embodiments, the composition comprises about 0.01 wt% to about 0.11 wt% of the second component. In some embodiments, the composition comprises about 0.01 wt% to about 0.05 wt% of the second component. In some embodiments, the composition comprises from about 0.01% to about 0.045% by weight of the second component, hi some embodiments, the composition comprises from about 0.01% to about 0.11% by weight of the second component.

[0035] In some embodiments, the composition comprises methyl perfluoroheptene ether and about 450 ppm to about 550 ppm of butylated hydroxytoluene, or about 100 ppm to about 200 ppm of hydroquinone monomethyl ether, or about 400 ppm to about 550 ppm of butylated hydroxytoluene and about 450 ppm to about 550 ppm of 1,2-epoxybutane, or about 100 ppm to about 200 ppm hydroquinone monomethyl ether and about 450 ppm to about 550 ppm 1,3-dioxolane, or about 100 ppm to about 200 ppm hydroquinone monomethyl ether and about 450 ppm to about 550 ppm 1,2-epoxybutane, or about 450 ppm to about 550 ppm of butylated hydroxytoluene and about 450 ppm to about 550 ppm of 1,3-dioxolane, or about 50 to about 500 ppm of 2-tert-butyl-6-methylphenol, or about 50 to about 500 ppm of 2-tert-butyl-5-methylphenol, or about 50 to about 500 ppm of 2-tert-butyl-4-ethylphenol, or about 50 to about 500 ppm 2-tert-butyl-6-methylphenol and about 200 to about 600 ppm 1,2-epoxybutane, or about 50 to about 500 ppm 2-tert-butyl-6-methylphenol and about 200 to about 600 ppm nitromethane, or about 300 ppm of 2-tert-butyl-6-methylphenol, or about 300 ppm of 2-tert-butyl-5-methylphenol, or about 300 ppm of 2-tert-butyl-4-ethylphenol, or about 300 ppm 2-tert-butyl-6-methylphenol and about 400 ppm 1,2-epoxybutane, or Approximately 300 ppm of 2-tert-butyl-6-methylphenol and approximately 400 ppm of nitromethane.

[0036] In some embodiments, the composition comprises methyl perfluoroheptene ether and approximately 140 ppm hydroquinone monomethyl ether, or about 500 ppm butylated hydroxytoluene, or about 140 ppm hydroquinone monomethyl ether and about 500 ppm 1,2-epoxybutane, or about 500 ppm butylated hydroxytoluene and about 500 ppm 1,2-epoxybutane, or about 500 ppm butylated hydroxytoluene and about 500 ppm 1,3-dioxolane; about 140 ppm hydroquinone monomethyl ether and about 500 ppm 1,3-dioxolane, or about 450 ppm butylated hydroxytoluene and about 500 ppm 1,2-epoxybutane.

[0037] How to use The present application provides a method for reducing acid decomposition of a working fluid comprising methyl perfluoroheptene ether. In some embodiments, the method includes mixing the working fluid with a second component selected from the group consisting of one or more antioxidants and one or more acid scavengers, or any mixture thereof, to thereby form a stabilized working fluid.

[0038] In some embodiments, the method includes reducing the total acid number (TAN) of the working fluid compared to an unstabilized working fluid (e.g., a composition comprising methyl perfluoroheptene ether in the absence of one or more antioxidants and one or more acid scavengers, or any mixture thereof).

[0039] In some embodiments, the method includes reducing the total acid number (TAN) of the working fluid at a temperature greater than about 50°C, e.g., greater than about 50°C, greater than about 60°C, greater than about 70°C, greater than about 80°C, greater than about 90°C, or greater than about 100°C, compared to an unstabilized working fluid (e.g., a composition comprising methyl perfluoroheptene ether in the absence of one or more antioxidants and one or more acid scavengers, or any mixture thereof).

[0040] In some embodiments, the present application provides a method for improving the stability of a working fluid that includes methyl perfluoroheptene ether.

[0041] In some embodiments, the present application provides a method for improving the stability of a working fluid comprising methyl perfluoroheptene ether at temperatures greater than about 50°C, e.g., greater than about 50°C, greater than about 60°C, greater than about 70°C, greater than about 80°C, greater than about 90°C, or greater than about 100°C.

[0042] In some embodiments, the present application describes the stability of working fluids comprising methyl perfluoroheptene ether at temperatures greater than about 50° C. for a period of about 1 day to about 12 months, e.g., about 1 day to about 6 months, about 1 day to about 5 months, about 1 day to about 4 months, about 1 day to about 3 months, about 1 day to about 2 months, about 1 day to about 1 month, about 1 month to about 12 months, about 1 month to about 6 months, about 1 month to about 5 months, about 1 month to about 4 months, about 1 month to about 3 months, about The present invention provides a method for improving symptoms over a period of 1 month to about 2 months, about 2 months to about 12 months, about 2 months to about 6 months, about 2 months to about 5 months, about 2 months to about 4 months, about 2 months to about 3 months, about 3 months to about 12 months, about 3 months to about 6 months, about 3 months to about 5 months, about 3 months to about 4 months, about 4 months to about 12 months, about 4 months to about 6 months, about 4 months to about 5 months, about 5 months to about 12 months, about 5 months to about 6 months, or about 6 months to about 12 months.

[0043] The compositions provided herein can act as working fluids used to transfer heat from a heat source to a heat sink. Such heat transfer compositions can also be useful as refrigerants in cycles where the fluid undergoes a phase change, i.e., from liquid to gas or vice versa, or as single-phase working fluids (e.g., as chiller heat transfer fluids (HFT) or circulating fluids). Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high-temperature heat pumps, mobile refrigerators, mobile air conditioning units, immersion cooling systems, data center cooling systems, and combinations thereof. It is understood that exemplary heat transfer systems can include components useful for single-phase heat transfer. Accordingly, the present application provides heat transfer systems (e.g., heat transfer devices) described herein that include the compositions provided herein. In some embodiments, the compositions provided herein are useful as working fluids or heat transfer fluids in heat transfer systems (e.g., working fluids for refrigeration or heating applications). In some embodiments, the compositions provided herein are useful in an apparatus or system comprising a high temperature heat pump (e.g., a heat pump including a heat exchanger operating at a temperature above about 50°C). In some embodiments, the high temperature heat pump comprises a centrifugal compressor. In some embodiments, the compositions provided herein are useful in an apparatus or system comprising a chiller. In some embodiments, the compositions provided herein are useful in an apparatus or system comprising a centrifugal chiller. In some embodiments, the compositions provided herein are useful in a centrifugal high temperature heat pump.

[0044] In some embodiments, provided compositions can be useful as heat transfer fluids (e.g., chiller heat transfer fluids or circulating fluids). As used herein, a heat transfer fluid (HFT), or circulating fluid, is a working fluid that can remove heat, add heat, or maintain temperature in the vicinity of an object to be cooled (e.g., the refrigeration circuit of a chiller). In an exemplary heat transfer system, a pumping system circulates cooled heat transfer fluid from a chiller to a process (or, for example, a semiconductor manufacturing tool). The heat transfer fluid removes heat from the process, and the warmed heat transfer fluid returns to the chiller tank via a heat exchanger. The heat transfer fluid is recooled in the heat exchanger and circulated back to the heat-receiving process. The process requires temperature control, and the circulating fluid must remain single-phase throughout the entire process temperature range. In systems using single-phase heat transfer fluids, the fluid properties (e.g., viscosity, boiling point, etc.) must remain relatively constant. In some embodiments, the compositions provided herein are useful as heat transfer fluids, wherein the compositions maintain a single phase (e.g., liquid) over the operating temperature range of the heat transfer system (e.g., from about −140° C. to about 120° C.).

[0045] Mechanical vapor-compression refrigeration, air conditioning, and heat pump systems include an evaporator, a compressor, a condenser, and an expansion device. Refrigeration cycles reuse refrigerant in multiple steps, producing a cooling effect in one step and a heating effect in a different step. A multiphase cycle (e.g., condensation / evaporation) can be described as follows: liquid refrigerant enters an evaporator through an expansion device, where it boils at a low temperature by removing heat from the environment to form a gas, producing cooling. Often, air or a heat-transfer fluid flows over or around the evaporator to transfer the cooling effect created by the evaporation of the refrigerant in the evaporator to the object to be cooled. Low-pressure gas enters a compressor, where the gas is compressed, increasing its pressure and temperature. The high-pressure (compressed) gaseous refrigerant then enters a condenser, where the refrigerant condenses and releases its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher pressure level in the condenser to the lower pressure level in the evaporator, thus repeating the cycle.

[0046] An object to be cooled or heated may be defined as any space, location, object, or body to which it is desirable to provide cooling or heating. Examples include spaces (open or enclosed) requiring air conditioning, cooling, or heating, such as rooms, apartments, or buildings, such as apartment buildings, college dormitories, townhouses, or other tenement or single-family homes, hospitals, office buildings, supermarkets, classrooms or administrative buildings at a college or university, and passenger compartments in automobiles or trucks. Additionally, objects to be cooled may include electronic devices such as computer equipment, central processing units (CPUs), data centers, server banks, and personal computers, among others.

[0047] "Proximate" means that the evaporator of a system containing a refrigerant is located either within or in close proximity to the object to be cooled, such that air moving over the evaporator moves through or around the object to be cooled. In a process for producing heating, "proximate" means that the condenser of a system containing a refrigerant is located either within or in close proximity to the object to be heated, such that air moving over the evaporator moves through or around the object to be heated. In some embodiments, with respect to heat transfer, "proximate" can mean, for example, that the object to be cooled is directly immersed in the heat transfer composition, or that a tube containing the heat transfer composition flows into, through, and out of electronic equipment.

[0048] Exemplary refrigeration systems include, but are not limited to, commercial, industrial, or residential refrigerators and freezers, ice makers, built-in coolers and freezers, vending machines, flooded evaporative chillers, direct expansion chillers, water chillers, centrifugal chillers, walk-in and reach-in coolers and freezers, and combined systems. In some embodiments, the compositions provided herein may be used in supermarket refrigeration systems. Additionally, stationary applications may utilize secondary loop systems that use a primary refrigerant to generate cooling in one location and transport it to a remote location via a secondary heat transfer fluid.

[0049] In some embodiments, the compositions provided herein are useful in single-phase refrigerator systems (e.g., refrigerators that can operate using a single-phase heat transfer composition). In some embodiments, the single-phase refrigerator system comprises a single-phase semiconductor refrigerator. In some embodiments, the compositions provided herein are useful over a wide range of temperatures for cooling and heating applications. For example, the compositions provided herein are useful over a wide range of temperatures from about -140°C to about 120°C, e.g., from about -140°C to about 110°C, from about -140°C to about 100°C, from about -140°C to about 50°C, from about -140°C to about 25°C, from about -140°C to about 0°C, from about -140°C to about -25°C, from about -140°C to about -50°C, from about -140°C to about -100°C, from about -140°C to about -120°C, from about -120°C to about 120°C, from about -120°C to about 110°C, from about -120°C to about 10°C, 0°C, about -120°C to about 50°C, about -120°C to about 25°C, about -120°C to about 0°C, about -120°C to about -25°C, about -120°C to about -50°C, about -120°C to about -100°C, about -100°C to about 120°C, about -100°C to about 110°C, about -100°C to about 100°C, about -100°C to about 50°C, about -100°C to about 25°C, about -100°C to about 0°C, about -100°C to about -25°C, about -100°C to about -50°C, about -75°C to about 120 °C, about -75°C to about 110°C, about -75°C to about 100°C, about -75°C to about 50°C, about -75°C to about 25°C, about -75°C to about 0°C, about -75°C to about -25°C, about -50°C to about 120°C, about -50°C to about 110°C, about -50°C to about 100°C, about -50°C to about 50°C, about -50°C to about 25°C, about -50°C to about 0°C, about -25°C to about 120°C, about -25°C to about 110°C, about -25°C to about 100°C, about -25°C to about 50°C, about -2 They may be suitable as working fluids at temperatures from 5°C to about 25°C, from about 0°C to about 120°C, from about 0°C to about 110°C, from about 0°C to about 100°C, from about 0°C to about 50°C, from about 0°C to about 25°C, from about 25°C to about 120°C, from about 25°C to about 110°C, from about 25°C to about 100°C, from about 25°C to about 50°C, from about 50°C to about 120°C, from about 50°C to about 110°C, from about 50°C to about 100°C, from about 100°C to about 120°C, from about 100°C to about 110°C, or from about 110°C to about 120°C. In some embodiments, the compositions provided herein may be suitable as working fluids at temperatures from -135°C to about 110°C.In some embodiments, the compositions provided herein may be suitable as working fluids at temperatures from −95° C. to about 100° C. In some embodiments, the compositions provided herein may be suitable as working fluids at temperatures from −70° C. to about 60° C.

[0050] In some embodiments, the compositions provided herein are useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices. In some embodiments, the compositions are useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices.

[0051] As used herein, a mobile refrigeration, air conditioning, or heat pump system refers to any refrigeration, air conditioning, or heat pump device incorporated into a road, rail, sea, or air transportation unit. The mobile air conditioning or heat pump system may be used in an automobile, truck, train, or other transportation system. Mobile refrigeration can include transport refrigeration for trucks, planes, or trains. Additionally, devices intended to provide refrigeration for any mobile carrier-independent system, known as an "intermodal" system, are included in the present invention. Such intermodal systems include "containers" (sea / land intermodal) and "swap bodies" (road and rail intermodal).

[0052] As used herein, a stationary air conditioning or heat pump system is a system that is fixed in place during operation. Stationary air conditioning or heat pump systems can be associated with or attached to any of a variety of buildings. These stationary applications can include, but are not limited to, chillers, heat pumps, including residential high temperature heat pumps, residential, commercial, or industrial air conditioning systems, as well as stationary air conditioning and heat pumps, including those externally connected to buildings such as window, ductless, ducted packaged terminals, rooftop systems, etc.

[0053] Stationary heat transfer may refer to systems for cooling electronic equipment such as immersion cooling systems, submersion cooling systems, phase change cooling systems, data center cooling systems, or simply liquid cooling systems.

[0054] In some embodiments, a method is provided for using the composition as a heat transfer fluid, the method comprising transporting the composition from a heat source to a heat sink.

[0055] In some embodiments, a method for producing cooling is provided, comprising evaporating one of the compounds or compositions in the vicinity of a body to be cooled and then condensing the composition.

[0056] In some embodiments, a method for producing heating is provided, comprising condensing any of the present compositions in the vicinity of a body to be heated and then evaporating the composition.

[0057] In some embodiments, the composition is for use in heat transfer and the working fluid is a heat transfer component.

[0058] In some embodiments, the compositions of the present invention are for use in refrigeration or air conditioning.

[0059] In some embodiments, the compositions of the present invention may be useful for reducing or eliminating the flammability of flammable refrigerants provided herein. In some embodiments, the present application provides a method for reducing the flammability of a flammable refrigerant, the method comprising adding to the flammable refrigerant a composition comprising a composition disclosed herein.

[0060] The compositions provided herein may be useful as replacements for currently used ("current") refrigerants or oils. As used herein, the terms "current refrigerant" or "current oil" should be understood to mean the refrigerant or oil that a heat transfer system is designed to operate against or that is present within the heat transfer system. In some embodiments, the compositions provided herein may be useful as replacements for a current refrigerant selected from perfluorocarbons, perfluoropolyethers, silicone oils, hydrocarbon oils, and aqueous ethylene glycol solutions. In some embodiments, the current refrigerant is methylperfluoroheptene ether (MPHE).

[0061] In some embodiments, the alternative compositions (i.e., the compositions provided herein) increase the operating temperature range of a refrigeration or heat pump system compared to heat transfer fluids (e.g., increasing the operating temperature to temperatures from about −140° C. to about 120° C., as described herein).

[0062] In many cases, replacement refrigerants are most useful if they can be used in the original refrigeration equipment designed for a different refrigerant, e.g., with minimal to no system modifications. In many applications, some embodiments of the compositions of the present disclosure are useful as refrigerants, providing cooling performance (meaning cooling capacity) at least equivalent to the refrigerant for which replacement is sought.

[0063] In some embodiments, the high temperature heat pump comprises a condenser that operates at a temperature greater than about 50° C. In some embodiments, the high temperature heat pump comprises a condenser that operates at a temperature greater than about 100° C. In some embodiments, the high temperature heat pump comprises a condenser that operates at a temperature greater than about 120° C. In some embodiments, the high temperature heat pump comprises a condenser that operates at a temperature greater than about 150° C.

[0064] In some embodiments, the present application provides methods for improving the energy efficiency of a heat transfer system or device comprising an incumbent refrigerant, the method comprising substantially replacing the incumbent refrigerant with an alternative refrigerant composition provided herein, thereby improving the efficiency of the heat transfer system. In some embodiments, the heat transfer system is a chiller system or chiller provided herein.

[0065] In some embodiments, a method is provided for operating a heat transfer system designed to operate with a current refrigerant or for transferring heat by filling an empty system with a composition of the present invention or by substantially replacing the current refrigerant with a composition of the present invention.

[0066] As used herein, the term "substantially replace" should be understood to mean draining the current refrigerant from the system or pumping the current refrigerant from the system and then charging the system with the composition of the present invention. The system may be flushed with one or more quantities of the replacement refrigerant before charging. It should be understood that in some embodiments, some small amount of the current refrigerant may be present in the system after it has been charged with the composition of the present invention.

[0067] In another embodiment, a method is provided for recharging a heat transfer system containing a current refrigerant and a lubricant, the method comprising substantially removing the current refrigerant from the system while retaining a substantial portion of the lubricant within the heat transfer system, and introducing one of the present compositions into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced.

[0068] In some embodiments, the compositions of the present invention may be used to make up the refrigerant charge in a cooling system. For example, if the performance of a cooling system using a current refrigerant is reduced due to a refrigerant leak, the compositions disclosed herein can be added to restore performance to original specifications.

[0069] In some embodiments, a heat exchange system containing any of the compositions disclosed herein is provided, the heat exchange system being selected from the group consisting of systems having an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporative cooler, a direct expansion cooler, a walk-in cooler, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and combinations thereof. Additionally, the compositions provided herein may be useful in secondary loop systems in which the compositions function as a primary refrigerant to provide cooling for a secondary heat transfer fluid, which in turn cools a remote location.

[0070] In some embodiments, the systems described herein may operate more efficiently if the heat exchangers are operating in a countercurrent mode or a cross-current mode with a countercurrent tendency. Countercurrent tendency means that the closer the heat exchanger is to a countercurrent mode as possible, the more efficient the heat transfer. Therefore, air conditioning heat exchangers, particularly evaporators, are designed to provide some aspect of a countercurrent tendency.

[0071] In some embodiments, the present application provides an air conditioning or heat pump system that includes one or more heat exchangers (evaporators, condensers, or both) operating in a countercurrent mode or a crosscurrent mode with a countercurrent tendency.

[0072] In some embodiments, a refrigeration system is provided herein, the system including one or more heat exchangers (evaporators, condensers, or both) operating in a countercurrent mode or a crosscurrent mode with a countercurrent tendency.

[0073] In some embodiments, the refrigeration, air conditioning, or heat pump system is a stationary refrigeration, air conditioning, or heat pump system. In some embodiments, the refrigeration, air conditioning, or heat pump system is a mobile refrigeration, air conditioning, or heat pump system.

[0074] Additionally, in some embodiments, the disclosed compositions can function as a primary refrigerant in a secondary loop system that provides cooling to a remote location through the use of a secondary heat transfer fluid, which can include water, a salt solution (e.g., calcium chloride), glycol, carbon dioxide, or a fluorinated hydrocarbon fluid (HFC, HCFC, hydrofluoroolefin ("HFO"), hydrochlorofluoroolefin ("HCFO"), chlorofluoroolefin ("CFO"), or perfluorocarbon ("perfluorocarbon, PFC"). In this case, the secondary heat transfer fluid is adjacent to the evaporator and is cooled before being transferred to a second, remote object to be cooled, and therefore is the object to be cooled. In some embodiments, the disclosed compositions function as a secondary heat transfer fluid, thereby transferring or providing cooling (or heating) to a remote location.

[0075] In some embodiments, the compositions provided herein further comprise one or more additives selected from the group consisting of lubricants, dyes (including UV dyes), solubilizers, compatibilizers, tracers, antiwear agents, extreme pressure additives, polymerization inhibitors, metal surface energy reducers, metal surface deactivators, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity modifiers, and mixtures thereof (e.g., a composition comprising methyl perfluoroheptene ether, a second component selected from the group consisting of one or more antioxidants and one or more acid scavengers, and one or more additives). Indeed, many of the optional additives described herein fit into one or more of these categories and may themselves possess qualities that aid in achieving one or more performance characteristics.

[0076] In some embodiments, one or more additives (i.e., additive components) are present in small amounts relative to the overall composition. In some embodiments, the concentration of the additive(s) in the disclosed compositions ranges from less than about 0.1 weight percent to as much as about 5 weight percent of the total composition. In some embodiments of the present invention, the additive is present in the disclosed compositions in an amount of about 0.1 weight percent to about 5 weight percent or about 0.1 weight percent to about 3.5 weight percent of the total composition. The additive component(s) selected for the compositions provided herein can be selected based on the utility and / or requirements of the individual equipment component or system.

[0077] In some embodiments, the lubricant is selected from the group consisting of mineral oil, alkyl benzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, silicone, silicate ester, phosphate ester, paraffin, naphthene, polyalphaolefin, and combinations thereof.

[0078] The lubricants disclosed herein may be commercially available lubricants. For example, the lubricant may be a paraffinic mineral oil sold by BVA Oil under the tradename BVM100N, a naphthenic mineral oil sold by Crompton Co. under the tradename Suniso® 1GS, Suniso® 3GS, and Suniso® 5GS, a naphthenic mineral oil sold by Pennzoil under the tradename Sontex® 372LT, a naphthenic mineral oil sold by Calumet Lubricants under the tradename Calumet® RO-30, a linear alkyl benzene sold by Shrieve Chemicals under the tradename Zerol® 75, Zerol® 150, and Zerol® 500, a branched alkyl benzene sold by Nippon Oil under the tradename HAB22, a polyol ester (POE) sold by Castrol, United Kingdom under the tradename Castrol® 100, a propylene glycol stearate (PGS) sold by Dow (Dow). and polyalkylene glycols (PAGs) such as RL-488A from GE Healthcare Chemical, Midland, Michigan, as well as mixtures thereof.

[0079] Notwithstanding the weight ratios of the compositions disclosed herein, it is understood that in some heat transfer systems, additional lubricant may be obtained from one or more equipment components of such heat transfer systems while the compositions are in use. For example, some refrigeration, air conditioning, and heat pump systems may charge lubricant in the compressor and / or compressor lubrication sump. Such lubricant may be present in the refrigerant of such systems, in addition to any lubricant additives. During use, when in the compressor, the refrigerant may pick up a certain amount of equipment lubricant, altering the refrigerant-lubricant composition from the starting ratio.

[0080] In some embodiments, the compositions provided herein further comprise at least one dye. The dye may be at least one ultraviolet (UV) dye. As used herein, an "ultraviolet" dye is defined as an ultraviolet fluorescent or phosphorescent composition that absorbs light in the ultraviolet or "near" ultraviolet region of the electromagnetic spectrum. Fluorescence produced by the ultraviolet fluorescent dye can be detected under ultraviolet irradiation, emitting at least some radiation having a wavelength in the range of 10 nanometers to about 775 nanometers.

[0081] Ultraviolet dyes are useful components for detecting leaking compositions because the fluorescence of the dye can be observed at or near the point of a leak in an apparatus (e.g., a refrigeration unit, air conditioner, or heat pump). The ultraviolet emission (e.g., fluorescence from the dye) can be observed under ultraviolet light. Thus, if a composition containing such an ultraviolet dye leaks from a given point in the apparatus, the fluorescence can be detected at or near the point of the leak.

[0082] In some embodiments, the ultraviolet dye may be a fluorescent dye, hi some embodiments, the fluorescent dye is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthene, thioxanthene, naphthoxanthene, fluorescein, and derivatives thereof, and combinations thereof.

[0083] In some embodiments, the compositions provided herein further comprise at least one solubilizing agent, e.g., selected to improve the solubility of one or more dyes in the compositions provided herein. In some embodiments, the weight ratio of dye to solubilizing agent ranges from about 99:1 to about 1:1. The solubilizing agent can include at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes, and mixtures thereof.

[0084] In some embodiments, the compositions provided herein further comprise at least one compatibilizer, for example, to improve the compatibility of the compositions provided herein with one or more lubricants. The compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof (meaning mixtures of any of the compatibilizers disclosed in this paragraph).

[0085] The solubilizer and / or compatibilizer may be selected from the group consisting of hydrocarbon ethers consisting of ethers containing only carbon, hydrogen, and oxygen (e.g., dimethyl ether (DME)), and mixtures thereof (meaning mixtures of any of the hydrocarbon ethers disclosed in this paragraph).

[0086] The compatibilizer may be a linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing 3 to 15 carbon atoms. The compatibilizer may be at least one hydrocarbon selected from the group consisting of, inter alia, at least: propane, including propylene and propane; butane, including n-butane and isobutene; pentane, including n-pentane, isopentane, neopentane, and cyclopentane; hexane; octane; nonane; and decane. Commercially available hydrocarbon compatibilizers include, but are not limited to, those sold under the trade name Isopar® H by Exxon Chemical (USA); undecane (C 11 ) and dodecane (C 12 ) mixture (high purity C 11 ~C 12 Isoparaffin), Aromatic 150 (C9~C 11 Aromatic200(C9~C 15 aromatic) and Naptha 140 (C5-C 11 mixtures of paraffins, naphthenes and aromatic hydrocarbons) and mixtures thereof (meaning mixtures of any of the hydrocarbons disclosed in this paragraph).

[0087] The compatibilizer may alternatively be at least one polymeric compatibilizer. The polymeric compatibilizer may be a random copolymer of fluorinated and non-fluorinated acrylates, the polymer having the formula CH═C(R 1 )CO2R 2 , CH2=C(R 3 )C6H4R 4 , and CH2=C(R 5 )C6H4XR 6 wherein X is oxygen or sulfur, and R 1 , R 3 , and R 5 are independently selected from the group consisting of H and C1-C4 alkyl groups; R 2 , R 4 , and R 6are independently selected from the group consisting of carbon chain-based radicals containing C and F, and may further contain H, Cl, ether oxygen, or sulfur in the form of thioether, sulfoxide, or sulfone groups, and mixtures thereof. Examples of such polymeric compatibilizers include those commercially available from EI du Pont de Nemours and Company (Wilmington, DE, 19898, USA) under the trade name Zonyl® PHS. Zonyl® PHS is a polymeric compound containing 40 weight percent CH═C(CH₃)CO₂CH₂CH₂(CF₂CF₂) m F (also known as Zonyl® fluoromethacrylate or ZFM), where m is 1 to 12, primarily 2 to 8, and 60 weight percent lauryl methacrylate (CH═C(CH)CO(CH) 11 It is a random copolymer made by polymerizing CH3, also known as LMA.

[0088] In some embodiments, the compatibilizer component contains about 0.01 to 30 weight percent (based on the total weight of the compatibilizer) of an additive that reduces the surface energy of metallic copper, aluminum, steel, or other metals and their alloys found in heat exchangers in a manner that reduces the adhesion of the lubricant to the metal. Examples of metal surface energy reducing additives include those available from DuPont under the trade names Zonyl® FSA, Zonyl® FSP, and Zonyl® FSJ.

[0089] In some embodiments, the compositions provided herein further comprise a metal surface passivator. In some embodiments, the metal surface passivator is selected from the group consisting of areoxalyl bis(benzylidene)hydrazide (CAS Registry Number 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS Registry Number 32687-78-8), 2,2,'-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (CAS Registry Number 70331-94-1), N,N'-(disalicyclidene)-1,2-diaminopropane (CAS Registry Number 94-91-7), and ethylenediaminetetraacetic acid (CAS Registry Number 60-00-4) and salts thereof, and mixtures thereof (meaning mixtures of any of the metal surface passivators disclosed in this paragraph).

[0090] In some embodiments, the compositions provided herein further comprise a tracer. The tracer may be two or more tracer compounds of the same class of compound or different classes of compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 parts per million (ppm) to about 1000 ppm by weight, based on the weight of the total composition. In some embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0091] The tracer may be selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, perfluorocarbons (e.g., additional perfluorocarbons), fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof. In some embodiments, the tracer is selected from the group consisting of trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca), 1,1,1,2,2,3-hexafluoropropane (HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1 ,2,2-tetrafluoropropane (HFC-254cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1-trifluoropropane (HFC-263fb), 2,2-difluoropropane (HFC-272ca), 2-fluoropropane (HFC-281ea), 1-fluoropropane (HFC-281fa), 1,1,1,2,2,3,3,4-nonafluorobutane (HFC-329p), 1,1, 1-trifluoro-2-methylpropane (HFC-329mmz), 1,1,1,2,2,4,4,4-octafluorobutane (HFC-338mf), 1,1,2,2,3,3,4,4-octafluorobutane (HFC-338pcc), 1,1,1,2,2,3,3-heptafluorobutane (HFC-347s), hexafluoroethane (perfluoroethane, PFC-116), perfluorocyclopropane (PFC-C216 ), perfluoropropane (PFC-218), perfluoro-cyclobutane (PFC-C318), perfluorobutane (PFC-31-10mc), perfluoro-2-methylpropane (CF3CF(CF3)2), perfluoro-1,3-dimethylcyclobutane (PFC-C51-12mycm), trans-perfluoro-2,3-dimethylcyclobutane (PFC-C51-12mym, trans), cis-perfluoro-2,The tracer may be selected from the group consisting of 3-dimethylcyclobutane (PFC-C51-12mym, cis), perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho, meta, or para), perfluoroethylcyclohexane, perfluoroindane, perfluorotrimethylcyclohexane and its isomers, perfluoroisopropylcyclohexane, cis-perfluorodecalin, trans-perfluorodecalin, cis- or trans-perfluoromethyldecalin, and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons or one hydrofluorocarbon combined with one or more perfluorocarbons.

[0092] Tracers may be added to the compositions of the present invention in predetermined amounts to allow for the detection of any dilution, contamination, or other alteration of the composition.

[0093] The additives that may be used in the compositions of the present invention may alternatively be perfluoropolyethers as described in U.S. Patent Application Publication No. 2007 / 0284555, the disclosure of which is incorporated herein by reference in its entirety.

[0094] It will be understood that the particular additives described above are identified as potential refrigerants, however, in accordance with the present invention, when used, these additives are not present in amounts that affect the novel and fundamental characteristics of the refrigerant mixtures of the present invention.

[0095] In some embodiments, the refrigerant compositions disclosed herein may be prepared by any convenient method for combining the desired amounts of the individual components, as is standard in the art. A preferred method is to weigh the desired component amounts and then combine the components in a suitable vessel. Agitation may be used if desired. [Example]

[0096] The present invention will now be described in more detail by way of specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize a variety of non-critical parameters that can be changed or modified to achieve essentially the same results.

[0097] Example 1. Methyl perfluoroheptene ether composition The following stabilized compositions were prepared for analysis in the degradation studies. The compositions were prepared from MPHE and the stabilizers shown in Table 1. HQMME = hydroquinone monomethyl ether. BHT = butylated hydroxytoluene.

[0098] [Table 1]

[0099] Example 2. Total Acid Number (TAN) Analysis The total acid number (TAN) of a representative stabilized composition was analyzed according to the following procedure. A known amount of MPHE (typically 2 g to 5 g) was added directly to 100 mL of a TAN solvent mixture (50 wt. % toluene, 49.5 wt. % propan-2-ol, and 0.5 wt. % water) and titrated (in mL) with 0.1 N KOH to the potentiometric inflection point. To account for the acidity provided by the TAN solvent, the experiment was repeated with 100 mL of TAN solvent alone (no sample added) as a control, titrated to the same inflection point (in mL). The baseline endpoint was subtracted from the sample endpoint to determine the true titration volume of the MPHE sample. The total acid number was calculated according to Equation 1, where V S = volume of sample titration, V B = volume of blank titration, mmol / mL = molar concentration of titrant (0.1N), 56 mg / mmol = molecular weight of KOH, M MPHE = mass of MPHE analyzed in grams (g). The acidity specification for MPHE products is ≦0.1 mg KOH / g.

[0100] Formula 1. TAN(mg KOH / g)=(V S -V B ) * 0.1 mmol / mL * 56mg / mmol) / M MPHE

[0101] The effectiveness of representative stabilized compositions, analyzed as total acid number (TAN), compared to unstabilized MPHE is shown in Figures 1-4 and Table 2 below.

[0102] [Table 2]

[0103] As shown in Figures 1-4 and Table 2, the stabilized compositions effectively mitigated the formation of decomposition by-products (e.g., acidic by-products) and effectively stabilized both the liquid and gas phases of the MPHE. Therefore, Compositions 1-6 may be useful as working fluids that effectively prevent metal corrosion of chiller components during normal operation.

[0104] The stabilized MPHE exhibited no closed cup flash point and an NVR (non-volatile residue) of less than 1 ppm.

[0105] Example 3. Methyl perfluoroheptene ether composition The following stabilized compositions were prepared for analysis in the degradation studies. The compositions were prepared from MPHE and the stabilizers shown in Table 3: 2tB6M = 2-tert-butyl-methylphenol. 2tB5M = 2-tert-butyl-5-methylphenol. 2tB4E = 2-tert-butyl-4-ethylphenol.

[0106] [Table 3]

[0107] Example 4. Total Acid Number (TAN) Analysis The total acid number (TAN) of the representative stabilized compositions listed in Table 3 was analyzed according to the procedure described in Example 2. The efficacy of representative stabilized compositions 9-14, analyzed as total acid number (TAN), is shown in Table 4 below.

[0108] [Table 4]

[0109] Comparative Example 1 Comparative TAN analysis was performed according to the procedure described in Example 2 using MPHE compositions containing an initial stabilizer concentration of (1) 1 wt. % 1,3-dioxane or (2) 0.1 wt. % of a mixture of BHT and 1,3-dioxolane. As shown in Table 5 and Figure 5, the stabilized composition containing 0.1 wt. % BHT and 1,3-dioxolane exhibited a TAN of 0.03 mg KOH / g after 6 days at a temperature of 75°C. This is significantly below the MPHE product specification (0.1 mg KOH / g). In contrast, the composition containing 1 wt. % 1,3-dioxane exhibited a TAN of 0.43 mg KOH / g.

[0110] [Table 5]

[0111] Other embodiments 1. In some embodiments, the present application provides: i) methyl perfluoroheptene ether; ii) a second component selected from the group consisting of butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-ethylphenol, 1,3-dioxolane, 1,2-epoxybutane, and nitromethane, or any mixture thereof. 2. The composition of embodiment 1, wherein the second component is present in the composition in an amount effective to maintain a total acid number of the composition at or below about 0.1 mg KOH / g. 3. The composition of embodiment 1 or 2, wherein the methyl perfluoroheptene ether comprises a mixture of about 50 weight percent 5-methoxyperfluoro-3-heptene, about 20 weight percent 3-methoxyperfluoro-3-heptene, about 20 weight percent 4-methoxyperfluoro-2-heptene, and about 8 weight percent 4-methoxyperfluoro-3-heptene. 4. The composition of any one of embodiments 1-3, wherein the second component is selected from the group consisting of butylated hydroxytoluene and hydroquinone monomethyl ether. 5. The composition of any one of embodiments 1-4, wherein the composition comprises from about 100 ppm to about 550 ppm of the second component. 6. The second component is butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-ethylphenol, a mixture of butylated hydroxytoluene and 1,2-epoxybutane, a mixture of hydroquinone monomethyl ether and 1,3-dioxolane, a mixture of hydroquinone monomethyl ether and 1,2-epoxybutane, a mixture of butylated hydroxytoluene and 1,3-dioxolane, a mixture of 2-tert-butyl-6-methylphenol and 1,2-epoxybutane, and Mixture of 2-tert-butyl-6-methylphenol and nitromethane 6. The composition of any one of embodiments 1 to 3 and 5, selected from the group consisting of: 7. The composition of any one of embodiments 1-6, wherein the composition comprises from about 100 ppm to about 1100 ppm of the second component. 8. The composition comprises methyl perfluoroheptene ether, about 450 ppm to about 550 ppm of butylated hydroxytoluene, or about 100 ppm to about 200 ppm of hydroquinone monomethyl ether, or about 400 ppm to about 550 ppm of butylated hydroxytoluene and about 450 ppm to about 550 ppm of 1,2-epoxybutane, or about 100 ppm to about 200 ppm hydroquinone monomethyl ether and about 450 ppm to about 550 ppm 1,3-dioxolane, or about 100 ppm to about 200 ppm hydroquinone monomethyl ether and about 450 ppm to about 550 ppm 1,2-epoxybutane, or about 450 ppm to about 550 ppm of butylated hydroxytoluene and about 450 ppm to about 550 ppm of 1,3-dioxolane, or about 50 to about 500 ppm of 2-tert-butyl-6-methylphenol, or about 50 to about 500 ppm of 2-tert-butyl-5-methylphenol, or about 50 to about 500 ppm of 2-tert-butyl-4-ethylphenol, or about 50 to about 500 ppm 2-tert-butyl-6-methylphenol and about 200 to about 600 ppm 1,2-epoxybutane, or about 50 to about 500 ppm 2-tert-butyl-6-methylphenol and about 200 to about 600 ppm nitromethane, or about 300 ppm of 2-tert-butyl-6-methylphenol, or about 300 ppm of 2-tert-butyl-5-methylphenol, or about 300 ppm of 2-tert-butyl-4-ethylphenol, or about 300 ppm 2-tert-butyl-6-methylphenol and about 400 ppm 1,2-epoxybutane, or about 300 ppm 2-tert-butyl-6-methylphenol and about 400 ppm nitromethane; and 9. The composition comprises methyl perfluoroheptene ether, approximately 140 ppm hydroquinone monomethyl ether, or about 500 ppm butylated hydroxytoluene, or about 140 ppm hydroquinone monomethyl ether and about 500 ppm 1,2-epoxybutane, or about 500 ppm butylated hydroxytoluene and about 500 ppm 1,2-epoxybutane, or about 500 ppm butylated hydroxytoluene and about 500 ppm 1,3-dioxolane; about 140 ppm hydroquinone monomethyl ether and about 500 ppm 1,3-dioxolane, or About 450 ppm butylated hydroxytoluene and about 500 ppm 1,2-epoxybutane and 10. In some embodiments, the present application further provides a method for reducing acid decomposition of a working fluid comprising methyl perfluoroheptene ether, the method comprising mixing the working fluid with a second component selected from the group consisting of one or more antioxidants and one or more acid scavengers, or any mixture thereof, thereby forming a stabilized working fluid. 11. The method of embodiment 10, wherein the second component is selected from the group consisting of one or more antioxidants. 12. The method of embodiment 10 or 11, wherein the second component is selected from the group consisting of butylated hydroxytoluene, hydroquinone monomethyl ether, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, and 2-tert-butyl-4-ethylphenol, or mixtures thereof. 13. The second component is butylated hydroxytoluene, 2-tert-butyl-6-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-4-ethylphenol, hydroquinone monomethyl ether, a mixture of butylated hydroxytoluene and 1,2-epoxybutane, a mixture of hydroquinone monomethyl ether and 1,3-dioxolane, a mixture of hydroquinone monomethyl ether and 1,2-epoxybutane, a mixture of 2-tert-butyl-6-methylphenol and 1,2-epoxybutane, a mixture of 2-tert-butyl-6-methylphenol and nitromethane, and 12. The method of claim 10 or 11, wherein the hydroxyl group is selected from the group consisting of a mixture of butylated hydroxytoluene and 1,3-dioxolane. 14. In some embodiments, the present application further provides a process for dissolving a solute, comprising contacting and mixing the solute with a sufficient amount of the composition of any one of embodiments 1-9. 15. In some embodiments, the present application further provides a process for cleaning a surface, comprising contacting the surface with a composition of any one of embodiments 1-9. 16. In some embodiments, the present application further provides a process for removing at least a portion of water from a surface of a wet substrate, comprising contacting the substrate with the composition of any one of embodiments 1-9, and then removing the substrate from contact with the composition. 17. The process of embodiment 16, wherein the composition further comprises at least one surfactant suitable for dehydrating or drying the substrate. 18. In some embodiments, the present application further provides a process for depositing a fluorolubricant on a surface, the process comprising: a) combining a fluorolubricant and a solvent to form a lubricant / solvent combination, wherein the solvent comprises the composition of any one of embodiments 1-9; b) contacting the lubricant / solvent combination with the surface; c) evaporating the solvent from the surface to form a fluorolubricant coating on the surface. 19. In some embodiments, the present application further provides a process for producing cooling, comprising condensing a composition of any one of embodiments 1-9 and then evaporating the composition in the vicinity of a body to be cooled. 20. In some embodiments, the present application further provides a process for producing heating, the process comprising evaporating a composition of any one of embodiments 1-9 and then condensing the composition in the vicinity of a body to be heated. 21. In some embodiments, the present application further provides a method for producing cooling, comprising circulating a heat transfer fluid comprising the composition of any one of embodiments 1-9 in the vicinity of a body to be cooled, wherein the heat transfer fluid is a working fluid that removes heat from, adds heat to, or maintains a temperature in the vicinity of the body to be cooled. 22. In some embodiments, the present application further provides a method of replacing a heat transfer fluid in a refrigeration fluid distribution unit, a refrigeration system, or a heat pump system, the method comprising providing a composition of any one of embodiments 1-9 as a replacement for the heat transfer fluid. 23. The embodiment of embodiment 22, wherein the refrigeration system or heat pump system comprises a single-phase cooling device. 24. The embodiment of embodiment 22 or 23, wherein the cooling device is a single-phase solid-state cooling device.

[0112] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, but not limit, the scope of the invention as defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art to which this invention pertains that any of the features described herein with respect to any particular aspect and / or embodiment of the invention may be combined with one or more of any of the other features of any other aspect and / or embodiment of the invention described herein, mutating appropriately to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. A composition comprising: methyl perfluoroheptene ether, based on the total weight of the composition, 450 ppm to 550 ppm of butylated hydroxytoluene, or 100 ppm to 200 ppm of hydroquinone monomethyl ether, or 400 ppm to 550 ppm of butylated hydroxytoluene and 450 ppm to 550 ppm of 1,2-epoxybutane, or 100 ppm to 200 ppm of hydroquinone monomethyl ether and 450 ppm to 550 ppm of 1,3-dioxolane, or 100 ppm to 200 ppm of hydroquinone monomethyl ether and 450 ppm to 550 ppm of 1,2-epoxybutane, or 450 ppm to 550 ppm of butylated hydroxytoluene and 450 ppm to 550 ppm of 1,3-dioxolane, or 50 to 500 ppm of 2-tert-butyl-6-methylphenol, or 50 to 500 ppm of 2-tert-butyl-5-methylphenol, or 50 to 500 ppm of 2-tert-butyl-4-ethylphenol, or 50 to 500 ppm of 2-tert-butyl-6-methylphenol and 200 to 600 ppm of 1,2-epoxybutane, or 50 to 500 ppm 2-tert-butyl-6-methylphenol and 200 to 600 ppm nitromethane, or 300 ppm 2-tert-butyl-6-methylphenol, or 300 ppm 2-tert-butyl-5-methylphenol, or 300 ppm 2-tert-butyl-4-ethylphenol, or 300 ppm 2-tert-butyl-6-methylphenol and 400 ppm 1,2-epoxybutane, or 300 ppm 2-tert-butyl-6-methylphenol and 400 ppm nitromethane and a composition comprising:

2. The composition comprises methyl perfluoroheptene ether and, based on the total weight of the composition, 140 ppm hydroquinone monomethyl ether, or 500 ppm butylated hydroxytoluene, or 140 ppm hydroquinone monomethyl ether and 500 ppm 1,2-epoxybutane, or 500 ppm butylated hydroxytoluene and 500 ppm 1,2-epoxybutane, or 500 ppm butylated hydroxytoluene and 500 ppm 1,3-dioxolane; 140 ppm hydroquinone monomethyl ether and 500 ppm 1,3-dioxolane, or 450 ppm butylated hydroxytoluene and 500 ppm 1,2-epoxybutane The composition of claim 1 comprising:

3. 10. A process for dissolving a solute, comprising contacting and mixing said solute with a sufficient amount of the composition of claim 1.

4. 10. A process for cleaning a surface, comprising contacting the surface with the composition of claim 1.

5. 10. A process for removing at least a portion of water from a surface of a wet substrate, comprising contacting the substrate with the composition of claim 1 and then removing the substrate from contact with the composition.

6. The process of claim 5 , wherein the composition further comprises at least one surfactant suitable for dewatering or drying the substrate.

7. 1. A process for depositing a fluorolubricant on a surface, comprising: a) combining a fluorolubricant and a solvent to form a lubricant / solvent combination, wherein the solvent comprises the composition of claim 1; b) contacting the lubricant / solvent combination with the surface; c) evaporating the solvent from the surface to form a fluorolubricant coating on the surface.

8. 10. A process for producing cooling, comprising condensing the composition of claim 1 and then evaporating said composition in the vicinity of a body to be cooled.

9. 10. A process for producing heat, comprising evaporating the composition of claim 1 and then condensing said composition in the vicinity of a body to be heated.

10. 10. A method for producing cooling, comprising circulating a heat transfer fluid comprising the composition of claim 1 in the vicinity of a body to be cooled, the heat transfer fluid being a working fluid that removes heat from, adds heat to, or maintains a temperature in the vicinity of the body to be cooled.

11. 10. A method of replacing a heat transfer fluid in a refrigeration fluid distribution unit, a refrigeration system, or a heat pump system, comprising providing the composition of claim 1 as a replacement for the heat transfer fluid.

12. The method of claim 11 , wherein the refrigeration or heat pump system comprises a single-phase cooling device.

13. The method of claim 12 , wherein the cooling device is a single-phase solid-state cooling device.

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