Fluorobutene compositions comprising e-1, 1, 1, 4, 4, 4-hexafluoro-2-butene and uses thereof

Abstract

The present disclosure relates to a fluorobutene composition comprising E-1, 1, 1, 4, 4, 4-hexafluoro-2-butene and a fluorinated compound, in particular to a fluorobutene composition comprising E-1, 1, 1, 4, 4, 4-hexafluoro-2-butene and a fluorinated compound, the fluorobutene composition can be used as a refrigerant, a heat transfer composition, an aerosol propellant, a foaming agent, a blowing agent, a solvent, a cleaning agent, a carrier fluid, a displacement desiccant, a polishing wear agent, a polymerization medium, a swelling agent for polyolefins and polyurethanes, a gaseous dielectric, a power cycle working fluid, a fire extinguishing agent and a fire suppression agent in liquid or vapor form, and can be used in a method for detecting leaks.

Description

Technical Field

[0001] The present invention broadly relates to fluorobutene compositions comprising E-1,1,1,4,4,4-hexafluoro-2-butene (E-1336mzz) having improved performance, particularly in refrigeration applications. Background Art

[0002] New environmental regulations have led to a need for new compositions for a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particle removal fluids, carrier fluids, polishing abrasives, and displacement desiccants. Low ozone depletion and low global warming potential compounds are of particular interest. Certain hydrofluoroolefin compositions are believed to meet both of these goals.

[0003] E-HFO-1336mzz (E- or trans-1,1,1,4,4,4-hexafluoro-2-butene, trans-CF3CH=CHCF3) and Z-HFO-1336mzz (Z- or cis-1,1,1,4,4,4-hexafluoro-2-butene, cis-CF3CH=CHCF3) both have zero ozone depletion and low global warming potential and have been identified as potential refrigerants. WO 2007 / 53697 discloses compositions containing E- and / or Z-HFO-1336mzz and their use in various applications. Summary of the Invention

[0004] E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) can be used as a refrigerant, heat transfer fluid, foam expansion agent, power cycle working fluid, and other applications. Furthermore, E-HFO-1336mzz has been found to have a low global warming potential (GWP), with a GWP of 32. Therefore, fluorobutene compositions containing E-HFO-1336mzz can be good candidates for replacing higher GWP saturated compounds, such as CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), or HFCs (hydrofluorocarbons), in many applications.

[0005] The present disclosure provides fluorobutene compositions comprising E-1,1,1,4,4,4-hexafluoro-2-butene (referred to herein as E-1336mzz or E1336mzz). More specifically, the compositions comprise E-1336mzz and one or more fluorinated compounds. The fluorinated compounds enhance the properties of E-1336mzz in applications such as heat transfer fluids.

[0006] The present disclosure provides a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and a fluorinated compound selected from the group consisting of 1,1,1,2,4,4,4-heptafluorobutane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, and 2-chloro-3,3,3-trifluoropropene. The fluorobutene composition comprises at least 99% by weight of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0007] The fluorobutene compositions are useful as refrigerants, heat transfer compositions, working fluids in thermodynamic cycles (e.g., heating or cooling cycles), gaseous dielectrics, power cycle working fluids, and aerosol propellants, blowing agents (foaming agents), solvents, cleaning agents, carrier fluids, displacement desiccants, polishing abrasives, polymerization media, blowing agents for polyolefins and polyurethanes, fire extinguishing agents, and fire suppressants in liquid or gaseous form.

[0008] In some embodiments, the fluorobutene composition comprises 0.0001 wt% to 0.9 wt% of the fluorinated compound, or 0.0005 wt% to 0.4 wt% of the fluorinated compound, or 0.005 wt% to 0.2 wt% of the fluorinated compound.

[0009] In some embodiments, the fluorinated compound is 1,1,1,2,4,4,4-heptafluorobutane or 2-chloro-1,1,1-trifluoroethane, or E-1-chloro-3,3,3-trifluoropropene, or Z-1-chloro-3,3,3-trifluoropropene, or 2-chloro-3,3,3-trifluoropropene.

[0010] In some embodiments, the fluorobutene composition further comprises Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0011] In some embodiments, the fluorobutene composition comprises E-1336mzz and E-1233zd or E-1336mzz, E-1233zd, and Z-1336mzz.

[0012] In some embodiments, the fluorobutene compositions have improved refrigeration performance that is superior to the performance of E-1336mzz alone. In certain embodiments, the improved performance is higher cooling capacity. In certain embodiments, the improved performance is higher efficiency (COP).

[0013] In some embodiments, the fluorobutene compositions comprise a lubricant. In certain embodiments, such compositions exhibit improved solubility of the lubricant with E1336mzz and improved lubricity in heat transfer systems.

[0014] The fluorobutene compositions disclosed herein are non-flammable. DETAILED DESCRIPTION

[0015] Composition

[0016] E-HFO-1336mzz can be produced, for example, by the reaction of chlorohydro(fluoro)carbons such as CF3CHClCH2CCl3 (HCFC-343jfd) or CF3CHClCH2CF3 (HCFC-346mdf) or CCl3CHClCH2CCl3 (HCC-340jfd) or CCl2=CClCH=CCl2 (HCO-2320az) in the liquid or gas phase; or by the isomerization of Z-HFO-1336mzz. For example, methods for preparing E-HFO-1336mzz are disclosed in US 9,174,896, US10,479,745, US10,611,709, US2021 / 0188743, WO 2020 / 206247, and WO2020 / 206335. Such disclosures are incorporated herein by reference. Other methods for producing E-HFO-1336mzz are known to those skilled in the art.

[0017] In one embodiment, the present disclosure provides a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and a fluorinated compound selected from the group consisting of 1,1,1,2,4,4,4-heptafluorobutane, 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, and 2-chloro-3,3,3-trifluoropropene. The fluorobutene composition comprises at least 99% by weight of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0018] E-HFO-1336mzz and fluorinated compounds are commercially available or can be prepared by methods known in the art. Such compounds can be purchased from specialty fluorinated compound suppliers such as SynQuest Laboratories, Inc. (Alachua, Florida, USA).

[0019] E-HFO-1336mzz can be produced, for example, by the reaction of chlorohydro(fluoro)carbons such as CF3CHClCH2CCl3 (HCFC-343jfd) or CF3CHClCH2CF3 (HCFC-346mdf) or CCl3CHClCH2CCl3 (HCC-340jfd) or CCl2=CClCH=CCl2 (HCO-2320az) in the liquid or gas phase; or by the isomerization of Z-HFO-1336mzz. For example, methods for preparing E-HFO-1336mzz are disclosed in US 9,174,896, US10,479,745, US10,611,709, US2021 / 0188743, WO 2020 / 206247, and WO2020 / 206335. Such disclosures are incorporated herein by reference. Other methods for producing E-HFO-1336mzz are known to those skilled in the art.

[0020] The compositions of the present invention may comprise E-HFO-1336mzz and one fluorinated compound, or two fluorinated compounds, or three or more fluorinated compounds.

[0021] In one embodiment, the total amount of fluorinated compounds in the composition comprising E-HFO-1336mzz is in a range from greater than zero weight percent to less than 1.0 weight percent, based on the total weight of the composition. In another embodiment, the total amount of fluorinated compounds is in a range from greater than zero weight percent to less than 0.5 weight percent, based on the total weight of the composition. In another embodiment, the total amount of fluorinated compounds is in a range from 0.01 ppm (weight) to about 1 weight percent. In another embodiment, the total amount of fluorinated compounds is in a range from 0.1 ppm (weight) to about 1 weight percent. In another embodiment, the total amount of fluorinated compounds is in a range from 0.001 weight percent to about 1 weight percent. In another embodiment, the total amount of fluorinated compounds is in a range from 0.001 weight percent to about 0.5 weight percent.

[0022] Table 1 provides a list of fluorinated and other compounds that may be present in the fluorobutene compositions disclosed herein.

[0023] Table 1. Compound names and chemical formulas

[0024]

[0025] For refrigerant applications such as those used in air conditioning, heat pumps, refrigeration and power cycles (e.g., organic Rankine cycle), fluorinated compounds can provide improved solubility with refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic cycloalkanes, poly(α)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyethylene ethers (PVE) or perfluoropolyethers (PFPE), or mixtures thereof.

[0026] In certain embodiments, the fluorinated compound can provide improved solubility of the active ingredient in the polymer component of the aerosol or foam.

[0027] Fluorinated compounds can provide improved solubility of active ingredients in aerosol propellants or polymer components of foams.

[0028] Unsaturated fluorocarbons (such as E-HFO-1336mzz) exhibit solubility that differs from that of other commonly used fluorocarbon propellants. Their reduced solubility can make it difficult to prepare single-phase aqueous homogeneous aerosol formulations. The presence of low levels of certain fluorinated compounds can improve mixing and simplify the formulation and use of aerosol products.

[0029] Unsaturated fluorocarbons (such as E-HFO-1336mzz) also exhibit solubility that differs from that of other commonly used blowing agents. Their reduced solubility can promote small cell growth during the foaming reaction, but they can be difficult to mix. The presence of fluorinated compounds can improve mixing and foam processing properties without sacrificing the benefits of lower HFO solubility. In addition, fluorinated compounds can impart improved insulating properties to foam insulation products.

[0030] For refrigerant applications such as those used in air conditioning, heat pumps, refrigeration and power cycles (e.g., organic Rankine cycle), fluorinated compounds can provide improved solubility with refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic cycloalkanes, poly(α)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyethylene ethers (PVE) or perfluoropolyethers (PFPE), or mixtures thereof.

[0031] Furthermore, certain fluorinated compounds can be used to improve leak detection capabilities. Refrigerant leaks can result in refrigerant loss from the system, increasing operating costs due to the need for refrigerant recharge. Even minor refrigerant losses in the system can impact normal operation. Finally, refrigerant leaks can cause excessive environmental pollution. Specifically, even low levels of fluorinated compounds can increase the detectability of refrigerant leaks. This allows systems to be repaired or redesigned to prevent refrigerant leaks.

[0032] While the presence of a fluorinated compound (as defined herein) with E-1336mzz in the fluorobutene composition can enhance performance when the fluorobutene composition is used in many applications, the level of fluorination is kept low, e.g., so as not to detract from the advantages of using E1336mzz over high GWP alternatives and other options.

[0033] application

[0034] The fluorobutene compositions comprising E-HFO-1336mzz disclosed herein can be used as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, blowing agents, foaming agents, solvents, cleaning agents, carrier fluids, displacement desiccants, polishing abrasives, polymerization media, expansion agents for polyolefins and polyurethanes, gaseous dielectrics, fire extinguishing agents, and fire suppressants in liquid or gaseous form. The disclosed compositions can be used as working fluids for transporting heat from a heat source to a heat sink. Such heat transfer compositions can also be used as refrigerants in cycles where a fluid undergoes a phase change; that is, from liquid to gas and gas to liquid, or vice versa.

[0035] 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, heat pumps, mobile chillers, mobile air conditioning units, and combinations thereof.

[0036] In one embodiment, the composition comprising E-HFO-1336mzz can be used in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment. In another embodiment, the composition can be used in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment.

[0037] As used herein, a mobile heat transfer system refers to any refrigeration, air conditioning, or heating equipment that is incorporated into a road, rail, sea, or air transport unit. Furthermore, mobile refrigeration or air conditioning units include those that are independent of any mobile carrier and are referred to as "combined" systems. Such combined systems include "containers" (for combined sea / land transport) and "deconsolidated bodies" (for combined road / rail transport).

[0038] As used herein, a fixed heat transfer system is a system that is fixed in one location during operation. A fixed heat transfer system can be incorporated into or attached to any type of building, or can be a freestanding device located outside a door, such as a soft drink vending machine. These fixed applications can be fixed air conditioners and heat pumps (including but not limited to chillers, high temperature heat pumps, including transcritical heat pumps (wherein the condenser temperature is greater than 50°C, 70°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, or 200°C), residential, commercial or industrial air conditioning systems, and including window coolers, ductless coolers, ducted coolers, integral terminal coolers, and those that are outside the building but connected to the building, such as rooftop systems). In stationary refrigeration applications, the disclosed compositions can be used in high-temperature, medium-temperature, and / or low-temperature refrigeration equipment, including commercial, industrial, or residential refrigerators and freezers, ice machines, stand-alone chillers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems.

[0039] Thus, in accordance with the present invention, the compositions containing E-HFO-1336mzz disclosed herein can be used in methods of generating cooling, generating heating, and transferring heat.

[0040] In one embodiment, there is provided a method for producing cooling comprising vaporizing any of the compositions of the present invention comprising E-HFO-1336mzz in the vicinity of a body to be cooled, and then condensing the composition.

[0041] In another embodiment, there is provided a method for generating heat comprising condensing any of the compositions of the present invention comprising E-HFO-1336mzz in the vicinity of a body to be heated, and then evaporating the composition.

[0042] In another embodiment, a method of using a composition of the present invention comprising E-HFO-1336mzz as a heat transfer fluid composition is disclosed. The method comprises transferring the composition from a heat source to a heat sink.

[0043] In many applications, some embodiments of the compositions of the present invention comprising E-HFO-1336mzz can be used as refrigerants and provide at least comparable cooling performance (meaning cooling capacity and energy efficiency) as the refrigerant being replaced. In addition, the compositions of the present invention provide heating performance (meaning heating capacity and energy efficiency) comparable to the refrigerant being replaced.

[0044] In another embodiment, the compositions of the present invention comprising Z-HFO-1336mzz can be used as refrigerant charge in chillers. For example, if a chiller using HCFC-114 is experiencing performance degradation due to refrigerant leakage, the compositions disclosed herein can be added to bring performance back up to specification.

[0045] In another embodiment, a heat exchange system comprising any of the compositions of the present invention comprising E-HFO-1336mzz is provided, wherein the system is selected from the group consisting of an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporator chiller, a direct expansion chiller, a walk-in cooler, a heat pump, a mobile chiller, a mobile air conditioning unit, and combinations thereof. Additionally, the compositions comprising E-HFO-1336mzz can be used in secondary loop systems, wherein these compositions serve as the primary refrigerant, thereby providing cooling to a secondary heat transfer fluid, thereby cooling a remote location.

[0046] In one embodiment, a heat transfer system is provided containing any of the compositions of the present invention comprising E-HFO-1336mzz. In another embodiment, a refrigeration, air conditioning, or heat pump apparatus is disclosed containing any of the compositions of the present invention comprising E-HFO-1336mzz. In another embodiment, a stationary refrigeration or air conditioning apparatus is disclosed containing any of the compositions of the present invention comprising E-HFO-1336mzz. In another embodiment, a mobile refrigeration or air conditioning apparatus is disclosed containing a composition as disclosed herein.

[0047] In one embodiment, the present invention relates to a method for generating heat in a high temperature heat pump, the method comprising condensing a vapor working fluid comprising a composition comprising E-HFO-1336mzz in a condenser to produce a liquid working fluid. The high temperature heat pump can operate at a condenser temperature of at least about 100°C.

[0048] The high temperature heat pump may include a centrifugal compressor or a positive displacement compressor.

[0049] The method for generating heating may further comprise passing a heat transfer medium through a condenser, whereby condensation of the working fluid heats the heat transfer medium, and passing the heated heat transfer medium from the condenser to the body to be heated.

[0050] The subject to be heated can be any space, object, or fluid that can be heated, such as water or air for space heating. In one embodiment, the subject to be heated can be a room, a building, or the passenger compartment of a car. Alternatively, in another embodiment, the subject to be heated can be a second or medium or heat transfer fluid, such as a chemical process stream.

[0051] According to the present invention, a method for converting heat from a heat source into mechanical energy is provided. The method comprises: heating a working fluid using heat supplied from the heat source; and expanding the heated working fluid to reduce the pressure of the working fluid and generate mechanical energy as the pressure of the working fluid decreases. The method is characterized by using a working fluid comprising a fluorobutene composition disclosed herein. The method for converting heat from the heat source into mechanical energy is a power cycle, which may be an organic Rankine cycle (ORC).

[0052] The provided method for converting heat from a heat source into mechanical energy can be a subcritical power cycle, wherein the organic working fluid used in the cycle receives heat at a pressure below the critical pressure of the organic working fluid, and the working fluid is maintained below its critical pressure throughout the cycle.

[0053] The provided method for converting heat from a heat source into mechanical energy can be a transcritical power cycle, wherein the organic working fluid used in the cycle receives heat at a pressure above the critical pressure of the organic working fluid. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure before being heated, and then the working fluid pressure is reduced to below its critical pressure during expansion.

[0054] The provided method for converting heat from a heat source into mechanical energy can be a supercritical power cycle. In a supercritical cycle, the working fluid is maintained above its critical pressure throughout the cycle (eg, compression, heating, expansion, and cooling).

[0055] In another embodiment, the present invention relates to a foam expansion agent composition comprising E-HFO-1336mzz for use in preparing foam. In other embodiments, the present invention provides foamable compositions, preferably thermosetting (e.g., polyurethane, polyisocyanurate, or phenolic) foam compositions and thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions, and methods for preparing foams. In such foam embodiments, one or more of the compositions of the present invention comprising E-HFO-1336mzz are included as the foam expansion agent in the foamable composition, preferably comprising one or more additional components capable of reacting and / or mixing and foaming under appropriate conditions to form a foam or porous structure.

[0056] Disclosed herein are methods for preparing thermoplastic foams, comprising providing a foamable composition comprising a thermoplastic polymer and a blowing agent, wherein the blowing agent comprises a fluorobutylene composition comprising E-HFO-1336mzz, the thermoplastic polymer comprising a polystyrene homopolymer, a polystyrene copolymer, a styrene-acrylonitrile copolymer, or a blend of two or more thereof, and expanding the foamable composition to produce a closed-shell polymer foam.

[0057] The foamable composition used to prepare the thermoplastic foam may also include a co-blowing agent, a nucleating agent, a flame retardant, a cell stabilizer, a surfactant, a preservative colorant, an antioxidant, a reinforcing agent, a filler, an antistatic agent, an IR attenuating agent, an extrusion aid, a plasticizer, a viscosity modifier, and other known additives, all in amounts to achieve the desired effect. Examples of nucleating agents are talc, graphite, and magnesium silicate. Examples of flame retardants include tetrabromobisphenol A and polymeric flame retardants.

[0058] Disclosed herein is a method for preparing polyurethane or polyisocyanurate foams, comprising reacting a polyisocyanate with an active hydrogen-containing compound in the presence of a blowing agent to obtain the foaming reaction product, the blowing agent comprising a composition containing E-HFO-1336mzz. Examples of active hydrogen-containing compounds include polyols, such as polyether or polyester polyols. Some of the hydroxyl groups may be substituted with amine groups, such that the active hydrogen-containing compound contains both hydroxyl and amine groups. Although any suitable polyisocyanate may be employed in the inventive method, examples of polyisocyanates useful for preparing polyisocyanate-based foams include at least one of aromatic, aliphatic, and alicyclic polyisocyanates, and the like.

[0059] Typically, the active hydrogen-containing compound and optionally other additives are mixed with a blowing agent to form a foam-forming composition prior to reaction with a suitable polyisocyanate. Such foam-forming compositions are generally known in the art as isocyanate-reactive pre-blends or B-side compositions. The B-side composition contains the active hydrogen-containing compound and preferably also contains the blowing agent composition of the present invention. The A-side composition contains the polyisocyanate. The foam-forming composition comprising the A-side composition and the B-side composition can be prepared in any manner convenient to one skilled in the art, including simply weighing the desired amount of each component (ingredient) and then combining them in a suitable container at the desired temperature and pressure.

[0060] It is generally desirable to employ minor amounts of additives in the B-side composition. These additives include one or more members selected from the group consisting of catalysts, surfactants, flame retardants such as TCPP, preservatives, colorants, antioxidants, reinforcing agents, fillers, and antistatic agents, among others, as are well known in the art.

[0061] In the process of making polyurethane-based or polyisocyanurate-based foams or polyurethane / polyisocyanurate-based foams, an active hydrogen-containing compound, polyisocyanate, and other components are contacted, thoroughly mixed, and allowed to expand and cure into a cellular polymer.

[0062] Another embodiment of the present invention relates to the use of a composition of the present invention comprising E-HFO-1336mzz as a propellant in a sprayable composition. In addition, the present invention relates to a sprayable fluorobutylene composition comprising E-HFO-1336mzz. The active ingredient to be sprayed may also be present in the sprayable composition along with inert ingredients, solvents and other materials. In one embodiment, the sprayable composition is an aerosol. The composition of the present invention can be used to formulate various industrial aerosols or other sprayable compositions, such as contact cleaners, dusters, lubricant sprays, mold release sprays, insecticides, etc., as well as consumer aerosols, such as personal care products (e.g., hair sprays, deodorants and perfumes), household products (such as waxes, polishes, pot sprays, room fresheners and household insecticides) and automotive products (e.g., cleaners and polishes) and pharmaceuticals such as anti-asthma and anti-halitosis drugs. Examples include metered dose inhalers (MDIs) for treating asthma and other chronic obstructive pulmonary diseases and for delivering drugs to accessible mucous membranes or intranasally.

[0063] The present invention also relates to a method for producing an aerosol product, comprising the steps of adding a fluorobutene composition of the present invention comprising E-HFO-1336mzz to a formulation comprising an active ingredient in an aerosol container, wherein the composition serves as a propellant. Furthermore, the present invention relates to a method for producing an aerosol product, comprising the steps of adding a fluorobutene composition of the present invention comprising E-HFO-1336mzz to a barrier aerosol package (e.g., a bag-type can or piston can), wherein the composition remains separate from the other formulation ingredients in the aerosol container, and wherein the composition serves as a propellant. Furthermore, the present invention relates to a method for producing an aerosol product, comprising the steps of adding only a fluorobutene composition of the present invention comprising E-HFO-1336mzz to an aerosol package, wherein the composition serves as an active ingredient (e.g., a duster, or a cooling or freezing spray).

[0064] Also provided is a method for detecting a leak from a container, the method comprising sampling the air near the container and detecting at least one fluorinated compound using a device for detecting a leak, wherein the fluorobutene composition of the present invention comprising HFO-1336mzz-E is contained within the container.

[0065] The container can be any known container, system, or device that is filled with a fluorobutene composition comprising 1336mzz-E. The container can include, but is not limited to, storage containers, shipping containers, aerosol cans, fire extinguishing systems, chiller equipment, heat pump equipment, heat transfer containers, and power cycle equipment (e.g., an organic Rankine cycle system).

[0066] The device for detecting leakage can be any known sensor designed for detecting leakage. Specifically, the device for detecting leakage includes but is not limited to electrochemical, corona discharge and mass spectrometry leak detectors.

[0067] So-called "near" the container refers to within 12 inches from the outer surface of the container. Alternatively, near can be within 6 inches, within 3 inches or within 1 inch from the outer surface of the container.

[0068] Without further explanation, those skilled in the art should be able to make the most of the present invention based on the description herein. Therefore, the following specific embodiments should be understood as being merely illustrative and not restrictive of the rest of the present disclosure in any way.

[0069] Selected implementation plan

[0070] 1. This embodiment is a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and a fluorinated compound selected from the group consisting of: 1,1,1,2,4,4,4-heptafluorobutane, 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, and 2-chloro-3,3,3-trifluoropropene, wherein the composition comprises at least 99 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0071] 2. The composition of embodiment 1, wherein the fluorinated compound is present in an amount of 0.0001 wt% to 0.9 wt%.

[0072] 3. The composition of embodiment 1, wherein the fluorinated compound is present in an amount of 0.0005% to 0.4% by weight.

[0073] 4. The composition of embodiment 1, wherein the fluorinated compound is present in an amount of 0.005% to 0.2% by weight.

[0074] 5. The composition of any one of embodiments 1 to 4, further comprising a compound selected from the group consisting of vinyl chloride, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene, and 1,1,1,4,4,4-hexafluorobutane.

[0075] 6. The composition of any one of embodiments 1 to 5, further comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0076] 7. The composition of embodiment 6, comprising 1,1,1,2,4,4,4-heptafluorobutane.

[0077] 8. The composition of embodiment 6, comprising 2-chloro-1,1,1-trifluoroethane.

[0078] 9. The composition of embodiment 6, comprising E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, or a mixture of two or more thereof.

[0079] 10. The composition of any one of embodiments 1 to 9, wherein the composition comprises less than 0.1 wt% 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene.

[0080] 11. The composition of any one of embodiments 1 to 9, wherein the composition comprises less than 0.01 wt% vinyl chloride.

[0081] 12. The composition of any one of embodiments 1 to 9, wherein the composition comprises less than 0.1 wt% 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene and less than 0.01 wt% vinyl chloride.

[0082] 13. This embodiment is a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2,4,4,4-heptafluorobutane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, and 2-chloro-3,3,3-trifluoropropene, wherein the composition comprises greater than 99 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0083] 14. This embodiment is a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least two fluorinated compounds selected from the group consisting of: 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene.

[0084] 15. The fluorobutene composition of embodiment 15, wherein the composition comprises:

[0085] 1,1,1,3,3-pentafluoropropane and 2-chloro-1,1,1-trifluoroethane, or

[0086] 1,1,1,3,3-pentafluoropropane and E-1-chloro-3,3,3-trifluoropropene, or

[0087] 1,1,1,3,3-pentafluoropropane and Z-1-chloro-3,3,3-trifluoropropene, or

[0088] 1,1,1,3,3-pentafluoropropane and 2-chloro-3,3,3-trifluoropropene, or

[0089] 1,1,1,3,3-pentafluoropropane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0090] 1,1,1,3,3-pentafluoropropane and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0091] 2-Chloro-1,1,1-trifluoroethane and E-1-chloro-3,3,3-trifluoropropene, or

[0092] 2-Chloro-1,1,1-trifluoroethane and Z-1-chloro-3,3,3-trifluoropropene, or

[0093] 2-chloro-1,1,1-trifluoroethane and 2-chloro-3,3,3-trifluoropropene, or

[0094] 2-Chloro-1,1,1-trifluoroethane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0095] 2-Chloro-1,1,1-trifluoroethane and 1,1,1,2,4,4,4-heptafluoro-2-butene.

[0096] 16. This embodiment is a fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least three fluorinated compounds selected from the group consisting of: 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene (1327mz).

[0097] 17. The fluorobutene composition of embodiment 16, wherein the composition comprises:

[0098] 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and Z-1-chloro-3,3,3-trifluoropropene, or

[0099] 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and E-1-chloro-3,3,3-trifluoropropene, or

[0100] 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 2-chloro-3,3,3-trifluoropropene, or

[0101] 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0102] 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0103] 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, or

[0104] 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or

[0105] 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0106] 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0107] 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or

[0108] 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0109] 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0110] 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, or

[0111] 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or

[0112] 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0113] 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0114] 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or

[0115] 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0116] 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0117] 2-Chloro-1,1,1-trifluoroethane, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0118] 2-chloro-1,1,1-trifluoroethane, 2-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0119] 2-Chloro-1,1,1-trifluoroethane, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0120] E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or

[0121] E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0122] E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or

[0123] E-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0124] Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or

[0125] Z-1-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, and 1,1,1,2,4,4,4-heptafluoro-2-butene.

[0126] 18. The fluorobutene composition of any one of embodiments 1 to 17, further comprising a lubricant selected from the group consisting of mineral oils such as paraffins, cycloalkanes, and aromatics, alkylaryl compounds such as linear and branched alkyl alkylbenzenes, synthetic paraffins, synthetic cycloalkanes, poly(alpha olefins), polyol esters, polyalkylene glycols, and polyethylene ethers.

[0127] 19. This embodiment is a method of forming a foam, comprising: (a) adding a composition according to any one of embodiments 1 to 17 to a foamable composition; and (b) processing the foamable composition under conditions effective to form a foam.

[0128] 20. This embodiment is a method for preparing a thermoplastic foam, the method comprising providing a foamable composition comprising a thermoplastic polymer and a blowing agent, wherein the blowing agent comprises the composition of any one of embodiments 1 to 17.

[0129] 21. This embodiment is a method for preparing a polyurethane or polyisocyanurate foam, the method comprising reacting a polyisocyanate with an active hydrogen-containing compound in the presence of a blowing agent to obtain the foamed reaction product, the blowing agent comprising the composition according to any one of embodiments 1 to 17.

[0130] 22. This embodiment is a method for producing an aerosol product, comprising the steps of adding a composition according to any one of embodiments 1 to 17 to a formulation comprising an active ingredient in an aerosol container, wherein the composition serves as a propellant.

[0131] 23. This embodiment is a method for treating a surface, the method comprising: providing a surface; and contacting the surface with a treatment composition;

[0132] wherein the surface comprises a treatable material deposited thereon; and

[0133] wherein the treatment composition comprises the fluorobutene composition according to any one of embodiments 1 to 17.

[0134] 24. The method of embodiment 23, wherein the treatment composition substantially dissolves the treatable material.

[0135] 25. This embodiment is a method for forming a composition, the method comprising: providing a solute; and contacting the solute with a solvent;

[0136] wherein the solvent comprises the fluorobutene composition according to any one of embodiments 1 to 17.

[0137] 26. This embodiment is a method for producing cooling, the method comprising evaporating a composition according to any one of embodiments 1 to 18 in the vicinity of a body to be cooled, and then condensing the composition.

[0138] 27. This embodiment is a method for generating heat, comprising condensing a composition according to any one of embodiments 1 to 18 in the vicinity of a body to be heated, and then evaporating the composition.

[0139] 28. This embodiment is a method for transferring heat, the method comprising: providing an article; and contacting the article with a heat transfer medium;

[0140] wherein the heat transfer medium comprises the fluorobutene composition according to any one of embodiments 1 to 18.

[0141] 29. This embodiment is a method for converting heat into mechanical energy, the method comprising heating a working fluid comprising the composition according to any one of embodiments 1 to 18, and then expanding the heated working fluid.

[0142] 30. This embodiment is a refrigeration system, comprising: an evaporator; a condenser; a compressor; an expansion device; and a heat transfer medium;

[0143] wherein the heat transfer medium comprises the fluorobutene composition according to any one of embodiments 1 to 18.

[0144] 31. This embodiment is a cooler apparatus comprising the fluorobutene composition according to any one of embodiments 1 to 18.

[0145] 32. The fluorobutene composition of any one of embodiments 1 to 18 for use in a cooler apparatus, preferably a medium temperature cooler apparatus.

[0146] 33. This embodiment is the use of the fluorobutene composition according to any one of embodiments 1 to 18 in a cooler apparatus, preferably a medium-temperature cooler apparatus.

[0147] 34. This embodiment is a method of producing cooling, the method comprising: evaporating a composition according to any one of embodiments 1 to 18 in the vicinity of a body to be cooled, and then condensing the composition.

[0148] 35. This embodiment is a refrigeration device, air-conditioning device or heat pump device containing the composition according to any one of embodiments 1 to 18, wherein the refrigeration device is preferably a stationary or mobile refrigeration device, and the air-conditioning device is preferably a mobile air-conditioning device, more preferably a mobile air-conditioning device.

[0149] 36. This embodiment is a method for generating heating in a high temperature heat pump, the method comprising condensing a vapor working fluid comprising a composition according to any one of embodiments 1 to 18 in a condenser to produce a liquid working fluid.

[0150] 37. This embodiment is a method comprising: heating a working fluid using heat supplied from the heat source; and expanding the heated working fluid to reduce the pressure of the working fluid and generate mechanical energy as the pressure of the working fluid decreases, wherein the method is characterized in using a working fluid comprising a composition according to any one of embodiments 1 to 17.

[0151] Example

[0152] Material. The materials used to prepare the examples are either commercially available or can be prepared by known methods.

[0153] Examples 1 to 4. Preparation of E1336MZZ with Fluorinated Compounds

[0154] E-HFO-1336mzz was prepared as follows. A tube (0.5 inch (1.27 cm) OD, 10 inches (25.4 cm) long, 0.35 inches (0.89 cm wall thickness)) was the reactor and was filled with 6 cc of chromium catalyst. The catalyst was activated with HF. The reactor was operated at 80 psig. HCFC-343jfd and HF were fed in a 1 / 20 molar ratio. The contact time was 20 seconds.

[0155] Fluorobutene compositions comprising E1336 and the fluorinated compounds shown in Table 2 were prepared using the added compounds in the amounts provided.

[0156] Table 2. Compositions of Examples 1 to 4

[0157] Compound Example 1 Example 2 Example 3 Example 4 weight% weight% weight% weight% E-HFO-1336mzz 99.9 99.9 99.9 99.9 Z-HFO-1336mzz 0 0 0.001 0.001 HCFO-1233xf 0.01 0.01 0.01 0.015 HFO-1336ft 0.025 0.024 0.01 0.01 HCFC-133a 0.02 0.035 0.05 0.035 HCO-1140 0 0 0 0.0001 E-HCFO-1233zd 0.0013 0.001 0.002 0.0007 HFC-245fa 0.01 0.008 0.009 0.007 HFC-347mef 0.0001 0 0.001 0 HFO-1327mz 0.03 0.02 0.01 0.03 HFO-1243zf 0.0036 0.002 0.007 0.0012

[0158] Example 5. Performance test

[0159] Compositions were prepared by mixing these components in certain amounts, and the refrigeration properties of these compositions were measured and provided in Tables 3 and 4.

[0160] Loop input parameters:

[0161] Evaporator average temperature = 4.44°C

[0162] Evaporator superheat (K) = 6

[0163] Suction line superheat (K) = 0

[0164] Condenser average temperature = 37.78°C

[0165] Supercooling (K) = 0

[0166] Compressor isentropic efficiency = 0.85

[0167] Compressor volumetric efficiency = 0.95

[0168] Glide is defined as the average of the evaporator glide and the condenser glide.

[0169] Weighted averaging was used to calculate the average dipole moment and GWP.

[0170] Table 3. Properties of E1233zd-E1336mzz compositions

[0171]

[0172] Table 3. Properties of E1233zd-E1336mzz compositions (continued)

[0173]

[0174] Table 4. Properties of E1233zd-E1336mzz-Z1336mzz compositions

[0175]

[0176] Table 4. Properties of E1233zd-E1336mzz-Z1336mzz Compositions (Continued)

[0177]

[0178] As can be seen from the performance in Tables 3 and 4, the compositions of the present invention show improved energy efficiency (COP) compared to pure E1336mzz.

Claims

1. A fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and a fluorinated compound selected from the group consisting of 1,1,1,2,4,4,4-heptafluorobutane, 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, wherein the composition comprises at least 99 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

2. The composition of claim 1, wherein the fluorinated compound is present in an amount of 0.0001 wt% to 0.9 wt%.

3. The composition of claim 1, wherein the fluorinated compound is present in an amount of 0.0005 wt% to 0.4 wt%.

4. The composition of claim 1, wherein the fluorinated compound is present in an amount of 0.005 wt% to 0.2 wt%.

5. The composition according to any one of claims 1 to 4, further comprising a compound selected from the group consisting of vinyl chloride, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene and 1,1,1,4,4,4-hexafluorobutane.

6. The composition according to any one of claims 1 to 5, further comprising Z-1,1,1,4,4,4-hexafluoro-2-butene.

7. The composition of claim 6, comprising 1,1,1,2,4,4,4-heptafluorobutane.

8. The composition of claim 6, comprising 2-chloro-1,1,1-trifluoroethane.

9. The composition of claim 6, comprising E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, or a mixture of two or more thereof.

10. The composition of any one of claims 1 to 9, wherein the composition comprises less than 0.1 wt% 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene.

11. The composition of any one of claims 1 to 9, wherein the composition comprises less than 0.01 wt% vinyl chloride.

12. The composition of any one of claims 1 to 9, wherein the composition comprises less than 0.1 wt% 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene and less than 0.01 wt% vinyl chloride.

13. A fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene, Z-1,1,1,4,4,4-hexafluoro-2-butene, 1,1,1,2,4,4,4-heptafluorobutane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, wherein the composition comprises greater than 99 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

14. A fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least two fluorinated compounds selected from the group consisting of: 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene.

15. The fluorobutene composition of claim 15, wherein the composition comprises: 1,1,1,3,3-pentafluoropropane and 2-chloro-1,1,1-trifluoroethane, or 1,1,1,3,3-pentafluoropropane and E-1-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane and Z-1-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane and 2-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 1,1,1,3,3-pentafluoropropane and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 2-Chloro-1,1,1-trifluoroethane and E-1-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane and Z-1-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane and 2-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 2-Chloro-1,1,1-trifluoroethane and 1,1,1,2,4,4,4-heptafluoro-2-butene.

16. A fluorobutene composition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at least three fluorinated compounds selected from the group consisting of: 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 1,1,1,2,4,4,4-heptafluoro-2-butene (1327mz).

17. The fluorobutene composition of claim 16, wherein the composition comprises: 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and Z-1-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and E-1-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 2-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 1,1,1,3,3-pentafluoropropane, 2-chloro-1,1,1-trifluoroethane and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 1,1,1,3,3-pentafluoropropane, E-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 1,1,1,3,3-pentafluoropropane, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and Z-1-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 2-Chloro-1,1,1-trifluoroethane, E-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 2-Chloro-1,1,1-trifluoroethane, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 2-Chloro-1,1,1-trifluoroethane, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or 2-Chloro-1,1,1-trifluoroethane, 2-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or 2-Chloro-1,1,1-trifluoroethane, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 2-chloro-3,3,3-trifluoropropene, or E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or E-1-chloro-3,3,3-trifluoropropene, Z-1-chloro-3,3,3-trifluoropropene and 1,1,1,2,4,4,4-heptafluoro-2-butene, or E-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or Z-1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene and 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, or Z-1-chloro-3,3,3-trifluoropropene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene and 1,1,1,2,4,4,4-heptafluoro-2-butene.

18. The fluorobutene composition of any one of claims 1 to 17, further comprising a lubricant selected from the group consisting of mineral oils such as paraffins, cycloalkanes and aromatics, alkyl aromatics such as linear and branched alkyl alkyl benzenes, synthetic paraffins, synthetic cycloalkanes, poly(alpha olefins), polyol esters, polyalkylene glycols and polyethylene ethers.

19. A method for forming foam, the method include: (a) adding a composition according to any one of claims 1 to 17 to a foamable composition; and (b) processing the foamable composition under conditions effective to form foam.

20. A method for preparing a thermoplastic foam, the method comprising providing a foamable composition comprising a thermoplastic polymer and a blowing agent, wherein the blowing agent comprises the composition of any one of claims 1 to 17.

21. A method for preparing a polyurethane or polyisocyanurate foam, the method comprising reacting a polyisocyanate with an active hydrogen-containing compound in the presence of a blowing agent to obtain the foamed reaction product, the blowing agent comprising the composition according to any one of claims 1 to 17.

22. A method for producing an aerosol product, the method The following steps are involved: The composition according to any one of claims 1 to 17 is added to a formulation comprising an active ingredient in an aerosol container, wherein the composition acts as a propellant.

23. A method for treating a surface, the method include: providing a surface; and contacting the surface with a treatment composition; wherein the surface comprises a treatable material deposited thereon; and wherein the treatment composition comprises the fluorobutylene composition according to any one of claims 1 to 17.

24. The method of claim 23, wherein the treating composition substantially dissolves the treatable material.

25. A method for forming a composition, the method include: providing a solute; and contacting the solute with a solvent; wherein the solvent comprises the fluorobutene composition according to any one of claims 1 to 17.

26. A method for producing cooling, the method comprising evaporating a composition according to any one of claims 1 to 18 in the vicinity of a body to be cooled, and then condensing the composition.

27. A method for generating heat, the method comprising condensing a composition according to any one of claims 1 to 18 in the vicinity of a body to be heated, and then evaporating the composition.

28. A method for transferring heat, the method include: Provide finished products; and contacting the article with a heat transfer medium; wherein the heat transfer medium comprises the fluorobutene composition according to any one of claims 1 to 18.

29. A method for converting heat into mechanical energy, the method comprising heating a working fluid comprising a composition according to any one of claims 1 to 18, and then expanding the heated working fluid.

30. A refrigeration system, the refrigeration system include: Evaporator; Condenser; compressor; Expansion device; and a heat transfer medium; wherein the heat transfer medium comprises the fluorobutene composition according to any one of claims 1 to 18.

31. A chiller apparatus comprising the fluorobutene composition according to any one of claims 1 to 18.

32. The fluorobutene composition of any one of claims 1 to 18 for use in a chiller apparatus, preferably a medium temperature chiller apparatus.

33. Use of a fluorobutene composition according to any one of claims 1 to 18 in a cooler apparatus, preferably in a medium temperature cooler apparatus.

34. A method of producing cooling, the method include: The composition according to any one of claims 1 to 18 is evaporated in the vicinity of a body to be cooled and then condensed.

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