Azeotropic and azeotropic compositions of Z-1233zd

Abstract

This application relates to azeotropic and near-azeotropic compositions of Z-1233zd. This application provides azeotropic and near-azeotropic compositions of Z-1233zd and a second component selected from methyl formate, dimethoxymethane, HFC-43-10-mee, and HFC-245fa. The compositions of this invention can be used as aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastic and thermosetting foams, solvents, heat transfer media, gaseous dielectrics, fire extinguishing and fire suppressing agents, power circulation working fluids, polymerization media, particle removal fluids, carrier fluids, polishing abrasives, and displacement desiccants. The compositions are modeled based on vapor-liquid balance data (such as those shown in the figures).

Description

[0001] This application is a divisional application of an invention patent application, the parent application of which was filed on March 17, 2017, with application number 201780019943.0 (PCT / US2017 / 023001) and invention title "Azeotropic and Azeotropic Compositions of Z-1233zd".

[0002] Background technology. Technical Field

[0003] This invention relates to the discovery of azeotropic or azeotropic compositions comprising Z-1-chloro-3,3,3-trifluoropropylene. These compositions can be used as aerosol propellants, refrigerants, cleaning agents, expanding agents (“foaming agents”) for the preparation of thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, solvents, fire extinguishing and fire suppressing agents, power circulation working fluids, polymerization media, particle removal fluids, carrier fluids, polishing abrasives, and displacement desiccants.

[0004] Related technical descriptions For decades, many industries have been searching for alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs are widely used, including as aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppressing agents, power circulation working fluids, polymerization media, particulate removal fluids, carrier fluids, polishing abrasives, and displacement desiccants. In the search for alternatives to these versatile compounds, many industries have turned to hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrochlorofluoroolefins (HCFOs).

[0005] HFCs do not contribute to stratospheric ozone depletion, but they have attracted attention due to their contribution to the "greenhouse effect," i.e., their contribution to global warming. Therefore, they are subject to rigorous scrutiny, and their widespread use may be restricted in the future. Unlike HFCs, many HFOs and HCFOs do not contribute to the greenhouse effect because they react and decompose relatively quickly in the atmosphere. However, HFOs such as HFO-1234ze and HCFOs such as E-HCFO-1233zd have been found to be too unstable for many applications. Summary of the Invention

[0006] Mixtures of certain hydrocarbons or fluorocarbons containing Z-1-chloro-3,3,3-trifluoropropene (Z-CF3CH=CHCl, Z-1233zd) are considered potential candidates for use as alternatives to CFCs and HCFCs, but do not show a low global warming potential (“GWP”) and do not contribute to the destruction of stratospheric ozone.

[0007] In embodiment 1.0, a composition comprising Z-1233zd and a second component selected from the following is provided: a) Methyl formate; b) Dimethoxymethane; c) HFC-43-10-mee; and, d)HFC-245fa The second component exists in an effective amount to form an azeotropic or azeotropic mixture with Z-1233zd.

[0008] In embodiment 2.0, a composition according to embodiment 1.0 is provided, wherein the second component is methyl formate.

[0009] In embodiment 3.0, a composition according to embodiment 1.0 is provided, wherein the second component is dimethoxymethane.

[0010] In embodiment 4.0, a composition according to embodiment 1.0 is provided, wherein the second component is HFC-43-10-mee.

[0011] In embodiment 5.0, a composition according to embodiment 1.0 is provided, wherein the second component is HFC-245fa.

[0012] In embodiment 6.0, a composition according to embodiment 1.0 is provided, which further comprises additives selected from the following: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

[0013] In embodiment 6.1, a composition according to embodiment 2.0 is provided, which further comprises additives selected from the following: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

[0014] In embodiment 6.2, a composition according to embodiment 3.0 is provided, which further comprises additives selected from the following: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

[0015] In embodiment 6.3, a composition according to embodiment 4.0 is provided, which further comprises additives selected from the following: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

[0016] In embodiment 6.4, a composition according to embodiment 5.0 is provided, which further comprises additives selected from the following: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

[0017] In implementation scheme 7.0, a method for forming foam is provided, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to embodiment 1.0.

[0018] In implementation scheme 7.1, a method for forming foam is provided, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to embodiment 2.0.

[0019] In implementation scheme 7.2, a method for forming foam is provided, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to embodiment 3.0.

[0020] In implementation scheme 7.3, a method for forming foam is provided, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to embodiment 4.0.

[0021] In implementation scheme 7.4, a method for forming foam is provided, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to embodiment 5.0.

[0022] In implementation scheme 8.0, foam is provided formed by the method according to any one of implementation schemes 7.1 to 7.4.

[0023] In embodiment 9.0, a foam is provided comprising a polymer and a composition according to any one of embodiments 2.0 to 5.0.

[0024] In embodiment 10.0, a premixed composition is provided comprising a foamable component and a composition according to any one of embodiments 2.0 to 5.0 as a foaming agent.

[0025] In embodiment 11.0, a method for generating refrigeration is provided, comprising condensing a composition according to any one of embodiments 2.0 to 5.0, and then evaporating the composition near a body to be cooled.

[0026] In embodiment 12.0, a heat transfer system is provided, comprising a composition according to any one of embodiments 2.0 to 5.0 as a heat transfer medium.

[0027] In embodiment 13.0, a method for cleaning a surface is provided, comprising contacting the surface with a composition according to any one of embodiments 2.0 to 5.0.

[0028] In embodiment 14.0, an aerosol product is provided comprising the components to be dispensed and the composition according to any one of embodiments 2.0 to 5.0 as a propellant.

[0029] In embodiment 15.0, a method for extinguishing or suppressing a flame is provided, comprising dispensing a composition according to any one of embodiments 2.0 to 5.0 at the flame.

[0030] In embodiment 16.0, a system for preventing or suppressing flames is provided, comprising a container containing a composition according to any one of embodiments 2.0 to 5.0 and a nozzle for distributing the composition toward a desired or actual location of the flame.

[0031] In embodiment 17.0, a method for dissolving a solute is provided, comprising contacting and mixing the solute with a sufficient amount of the composition according to any one of embodiments 2.0 to 5.0.

[0032] In embodiment 18.0, a method for preventing or rapidly quenching discharges in a space within a high-voltage device is provided, comprising injecting a composition according to any one of embodiments 2.0 to 5.0 as a gaseous dielectric into the space.

[0033] In embodiment 19.0, a high-voltage device is provided, comprising the composition according to any one of embodiments 2.0 to 5.0 as a gaseous dielectric.

[0034] In embodiment 20.0, a high-voltage device according to embodiment 19.0 is provided, which is selected from transformers, circuit breakers, switches and radar waveguides.

[0035] In embodiment 21.0, an azeotropic or near-azeotropic composition for any linear purpose is provided according to any one of Tables 1.2, 1.3, 2.2, 2.3, 2.4, 3.2, 3.3, 4.2 and 4.3.

[0036] In embodiment 22.0, a composition according to any one of embodiments 21.0, 21.1, 21.2, 21.3, 21.4 and 22.0 is provided, further comprising additives selected from: lubricants, pour point regulators, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants and acid traps. Attached Figure Description

[0037] Figure 1 The vapor / liquid equilibrium curves of a mixture of Z-1233zd (cis-1233zd) and methyl formate at 30°C are shown.

[0038] Figure 2 The vapor / liquid equilibrium curves of a mixture of Z-1233zd (cis-1233zd) and dimethoxymethane (methyl acetal) at 29.9 °C are shown.

[0039] Figure 3 The vapor / liquid equilibrium curves of a mixture of Z-1233zd (cis-1233zd) and HFC-43-10-mee (FC4310mee) at 30 °C are shown.

[0040] Figure 4The vapor / liquid equilibrium curves of a mixture of Z-1233zd (cis-1233zd) and HFC-245fa (FC245fa) at 30°C are shown. Detailed Implementation

[0041] The present invention relates to azeotropic and near-azeotropic compositions having each of Z-1233zd and methyl formate, dimethoxymethane, HFC-43-10-mee, and HFC-245fa.

[0042] Alternative names for Z-1233zd include Z-1-chloro-3,3,3-trifluoropropene (Z-CF3CH=CHCl), cis-1-chloro-3,3,3-trifluoropropene, cis-1233zd, Z-HFO-1233zd, and cis-HFO-1233zd. Alternative names for methyl formate (C2H4O2) include MF and methanol formate. Alternative names for dimethoxymethane (CH3OCH2OCH3) include DMM, methylal, and dimethylformal. Alternative names for HFC-43-10-mee include 1,1,1,2,2,3,4,5,5,5-decafluoropentane and FC4310mee. Alternative names for HFC-245fa include 1,1,1,3,3-pentafluoropropane and FC245fa.

[0043] The azeotropic or azeotropic compositions of the present invention can be prepared by any convenient method, including mixing or combining the required amounts. A preferred method is to weigh the required amounts of components and then mix them in a suitable container.

[0044] The compositions of the present invention can be used in a wide range of applications, including their use as aerosol propellants, refrigerants, solvents, cleaning agents, foaming agents (foam expanders) for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing agents and fire suppressants, power circulation working fluids, polymerization media, particle removal fluids, carrier fluids, polishing abrasives, and displacement desiccants.

[0045] As used herein, the terms “composition of the invention” and “composition of the invention” should be understood to refer to an azeotropic and near-azeotropic composition of Z-1233zd and a second component selected from methyl formate, dimethoxymethane, HFC-43-10-mee, and HFC-245fa.

[0046] Uses as a heat transfer medium The disclosed compositions can be used as working fluids for transporting heat from a heat source to a radiator. Such heat transfer compositions can also be used as refrigerants in cycles where the fluid undergoes a phase change; that is, from liquid to gas and back to liquid, or vice versa.

[0047] Examples of heat transfer systems include, but are not limited to, air conditioners, chillers, refrigeration units, heat pumps, water coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, heat pumps, portable refrigeration units, portable air conditioning units, and combinations thereof.

[0048] In one embodiment, the composition comprising Z-1233zd 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.

[0049] As used herein, the term "mobile heat transfer system" should be understood to mean any refrigeration, air conditioning, or heating equipment integrated into a transport unit used for road, rail, sea, or air transport. Furthermore, mobile refrigeration or air conditioning units include those devices independent of any mobile carrier and referred to as "integrated" systems. Such integrated systems include "containers" (sea / land combined transport) and "foldable containers" (road / rail combined transport).

[0050] As used herein, the term "fixed heat transfer system" should be understood to mean a system that is fixed in place during operation. Fixed heat transfer systems may be located within or attached to a building, or may be stand-alone units located outside a door, such as soft drink vending machines. Such fixed applications may be fixed air conditioning units or heat pumps, including but not limited to coolers, high-temperature heat pumps (which may be transcritical heat pumps (heat pumps that operate at condenser temperatures above 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 may be window-mounted, tubeless coolers, ducted coolers, integral terminal coolers, and those located outside the building but connected to it, 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 refrigeration and freezing units, ice makers, independent coolers and freezers, flooded evaporator coolers, direct expansion coolers, walk-in and reach coolers and freezers, and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigeration systems.

[0051] Therefore, according to the present invention, the compositions disclosed herein containing Z-1233zd can be used in methods of generating cooling, generating heat, and heat transfer.

[0052] In one embodiment, a method for generating cooling is provided, the method comprising evaporating any of the inventive compositions containing Z-1233zd near the body to be cooled, and then condensing the composition.

[0053] In another embodiment, a method for generating heat is provided, comprising condensing any of the inventive compositions containing Z-1233zd near the body to be heated, and then evaporating the composition.

[0054] In another embodiment, a method is disclosed for using the composition of the present invention comprising Z-1233zd as a heat transfer fluid composition. The method includes transferring the composition from a heat source to a heat sink.

[0055] Any of the compositions disclosed herein may be used as alternatives to currently used (“existing”) refrigerants, including but not limited to R-123 (or HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R-11 (or CFC-11, trichlorofluoromethane), R-12 (or CFC-12, dichlorodifluoromethane), R-22 (chlorodifluoromethane), R-245fa (or HFC-245fa, 1,1,1,3,3-pentafluoropropane), R-114 (or CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236fa (or HFC-236fa, 1,1,1,3,3,3-hexafluoropropane), R-236ea (or HFC-236ea, 1,1,1,2,3,3-hexafluoropropane), R-124 (or HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane), etc.

[0056] As used herein, the term “existing refrigerant” should be understood to refer to the refrigerant that the heat transfer system is designed to operate with, or the refrigerant that resides in the heat transfer system.

[0057] In another embodiment, a method for operating a heat transfer system or for transferring heat is provided, the method being designed to operate with an existing refrigerant by loading an empty system with the composition of the present invention or by substantially replacing the existing refrigerant with the composition of the present invention.

[0058] As used herein, the term "substantially replace" should be understood to mean removing or pumping existing refrigerant from the system before loading the system with the composition of the present invention. Prior to loading, the system may be purged with one or more amounts of replacement refrigerant. It should be understood that after loading the system with the composition of the present invention, some small amounts of existing refrigerant may remain in the system.

[0059] In another embodiment, a method is provided for reloading a heat transfer system containing existing refrigerant and lubricant, the method comprising substantially removing the existing refrigerant from the heat transfer system while retaining a majority of the lubricant in the system and introducing one of the compositions of the present invention comprising Z-1233zd into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced.

[0060] In another embodiment, the composition of the present invention containing Z-1233zd can be used to replenish the refrigerant in a cooler. For example, if a cooler using HCFC-123 experiences performance degradation due to refrigerant leakage, the composition disclosed herein can be added to restore performance to specifications.

[0061] In another embodiment, a heat exchange system comprising any of the compositions of the present invention containing Z-1233zd is provided, wherein the system is selected from air conditioners, refrigerators, chillers, heat pumps, water coolers, flooded evaporator coolers, direct expansion coolers, walk-in coolers, heat pumps, portable chillers, portable air conditioning units, and systems having combinations thereof. Furthermore, compositions containing Z-1233zd can be used in secondary loop systems, wherein these compositions serve as the primary refrigerant, thus providing cooling for the secondary heat transfer fluid, thereby cooling remote locations.

[0062] Each of the vapor compression refrigeration system, air conditioning system, and heat pump system includes an evaporator, compressor, condenser, and expansion unit as components. The vapor compression cycle reuses the refrigerant in multiple steps, thus producing a cooling effect in one step and a heating effect in different steps. This cycle can be simply described as follows: Liquid refrigerant enters the evaporator through the expansion unit, and the liquid refrigerant boils in the evaporator at a low temperature to form vapor and produce cooling by extracting heat from the environment. The low-pressure vapor enters the compressor, where the vapor is compressed to increase its pressure and temperature. The high-pressure (compressed) vapor refrigerant then enters the condenser, where the refrigerant condenses and releases its heat to the environment. The refrigerant returns to the expansion unit, 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.

[0063] In one embodiment, a heat transfer system comprising any of the compositions of the present invention containing Z-1233zd is provided. In another embodiment, a refrigeration, air conditioning, or heat pump device comprising any of the compositions of the present invention containing Z-1233zd is disclosed. In another embodiment, a stationary refrigeration or air conditioning device comprising any of the compositions of the present invention containing Z-1233zd is disclosed. In yet another embodiment, a mobile refrigeration or air conditioning device comprising the compositions disclosed herein is disclosed.

[0064] Lubricants and additives In one embodiment, a composition of the present invention comprising Z-1233zd and at least one additive is provided. The most common additive is a lubricant. Lubricants and other additives in Fuels and Lubricants Handbook: Technology, Properties, Performance and Testing Ch. 15, “Refrigeration Lubricants - Properties and Applications,” Michels, H. Harvey and Seinel, Tobias H., MNL37WCD-EB, ASTM International, published in mid-June 2003, which is incorporated herein by reference. Lubricants include polyol esters (“POE”), cycloalkane mineral oils (“NMO”), and polyalkylene glycols (“PAG”) and synthetic lubricants. Other additives are selected from the group of chemically active agents that are perceptibly reactive with metals in the system or with contaminants in the lubricant, including dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, and acid traps. The choice of oxidation inhibitors may depend on the choice of lubricant. Alkylphenols (e.g., butylated hydroxytoluene) can be used in polyol ester lubricants. Nitrogen-containing inhibitors (e.g., arylamines and phenols) can be used in mineral oil lubricants. Acid traps can be particularly important in synthetic lubricant systems and include alkanolamines, long-chain amides and imines, carbonates, and epoxides. Other additives are selected from the group that alter physical properties, including pour point modifiers, defoamers, viscosity improvers, and emulsifiers. Defoamers include polydimethylsiloxane, polyalkoxyamine, and polyacrylate.

[0065] Methods of forming foam The present invention also relates to a method for forming foam, comprising: (a) adding a foamable composition to a composition of the present invention; and (b) reacting the foamable composition under conditions that effectively form foam.

[0066] Closed-cell polyisocyanate-based foams are widely used for insulation purposes, such as in building structures and the manufacture of energy-efficient appliances. In the construction industry, polyurethane (polyisocyanurate) sheets are used for insulation and load-bearing capacity in roofing and siding. Cast and sprayed polyurethane foams are widely used in a variety of applications, including insulating roofs, insulating large structures such as storage tanks, insulating equipment such as refrigeration and freezing machines, insulating refrigerated cars and railcars, etc.

[0067] The second type of insulating foam is thermoplastic foam, primarily polystyrene foam. Polyolefin foams (e.g., polystyrene, polyethylene, and polypropylene) are widely used in insulation and packaging applications. These thermoplastic foams are typically made with CFC-12 (dichlorodifluoromethane) as a blowing agent. Recently, HCFC (HCFC-22, dichlorodifluoromethane) or blends of HCFC (HCFC-22 / HCFC-142b) or HFC (HFC-152a) have been used as blowing agents for polystyrene.

[0068] The third important type of insulating foam is phenolic foam. These foams, which have very attractive flammability, are typically made from CFC-11 (trichlorofluoromethane) and CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) blowing agents.

[0069] In addition to closed-cell foams, open-cell foams also have commercial value, for example in the production of fluid-absorbing products.

[0070] U.S. Patent 6,703,431 (Dietzen et al.) describes open-cell foams based on thermoplastic polymers that can be used in fluid-absorbent hygiene products, such as wound contact materials. U.S. Patent 6,071,580 (Bland et al.) describes absorbent extrusion thermoplastic foams that can be used in a variety of absorbent applications. Open-cell foams can also be used in vacuum or evacuated plate technology, such as in the production of vacuum insulation plates described in U.S. Patent 5,977,271 (Malone). Using open-cell foams in vacuum insulation plates yields an R-value of 10 to 15 per inch of thickness, depending on the level of evacuation or vacuum, polymer type, cell size, density, and open-cell content of the foam. These open-cell foams have traditionally been produced using CFCs, HCFCs, or more recently, HFCs as blowing agents.

[0071] Multimodal foams also have commercial value and are described, for example, in U.S. Patents 6,787,580 (Chonde et al.) and 5,332,761 (Paquet et al.). Multimodal foams are foams with a multimodal cell size distribution, and these foams have particular use in insulation articles because they typically have a higher insulation value (R-value) than similar foams with a generally uniform cell size distribution. These foams are produced using CFCs, HCFCs, and more recently, HFCs as blowing agents.

[0072] All these different types of foam require a foaming (expanding) agent to manufacture them. Insulating foams depend on the use of halogenated hydrocarbon foaming agents, not only for foaming the polymer, but primarily for their low vapor thermal conductivity, a very important property for insulation values.

[0073] Other embodiments provide foamable compositions, preferably thermosetting or thermoplastic foam compositions prepared using the compositions of this disclosure. In such foam embodiments, one or more of the compositions of the present invention are included as a blowing agent in or as part of the foamable composition, which preferably contains one or more additional components capable of reacting and / or foaming under suitable conditions to form a foam or honeycomb structure. On the other hand, foams are involved, and closed-cell foams are preferred, prepared from polymeric foam formulations containing a blowing agent comprising the compositions of this disclosure.

[0074] Some embodiments provide methods for preparing foams. In such foam embodiments, a foaming agent comprising a composition of the present disclosure is added to and reacts with a foamable composition, which may contain one or more additional components capable of reacting and / or foaming under suitable conditions to form a foam or honeycomb structure. Any methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, may be used or adapted according to the foam embodiment, and are incorporated herein by reference.

[0075] In some implementations, it is often desirable to use certain additional components in the preparation of foam. These additional components include catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, UV absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, etc.

[0076] Polyurethane foam is typically prepared by mixing isocyanates with polyols and reacting them in the presence of a blowing agent or expanding agent, with the addition of auxiliary chemicals to control and modify the properties of the polyurethane reaction itself and the final polymer. For ease of processing, these materials can be premixed into two non-reactive portions, often referred to as "side A" and "side B".

[0077] The term "A side" is intended to refer to isocyanates or mixtures containing isocyanates. Mixtures containing isocyanates may include isocyanates, foaming agents or expanding agents, and auxiliary chemicals such as catalysts, surfactants, stabilizers, chain extenders, crosslinking agents, water, flame retardants, smoke suppressants, pigments, coloring materials, fillers, etc.

[0078] The term "B side" is intended to refer to polyols or mixtures containing polyols. Mixtures containing polyols typically include polyols, foaming agents or expanding agents, and auxiliary chemicals such as catalysts, surfactants, stabilizers, chain extenders, crosslinking agents, water, flame retardants, smoke suppressants, pigments, coloring materials, fillers, etc.

[0079] To prepare foam, appropriate amounts of side A and side B are then combined to carry out the reaction.

[0080] When preparing foams using the methods disclosed herein, it is generally preferred to use a small amount of surfactant to stabilize the foaming reaction mixture until it solidifies. Such surfactants may comprise liquid or solid organosiloxane compounds. Other less preferred surfactants include polyethylene glycol ethers of long-chain alcohols, tertiary amines or alkanolamine salts of long-chain alkyl acid sulfates, alkyl sulfonates, and alkyl aryl sulfonic acids. The surfactant is used in an amount sufficient to stabilize the foaming reaction mixture to prevent collapse and the formation of large, uneven cells. About 0.2 parts to about 5 parts or even more of surfactant per 100 parts by weight of polyol is generally sufficient.

[0081] One or more catalysts for the reaction of polyols with polyisocyanates may also be used. Any suitable carbamate catalyst, including tertiary amine compounds and organometallic compounds, can be used. Such catalysts are used in amounts that quantify the increase in the reaction rate of the polyisocyanate. Typical amounts are about 0.1 parts to about 5 parts catalyst per 100 parts by weight of polyol.

[0082] Therefore, in one aspect, the present invention relates to closed-cell foam prepared by foaming a foamable composition in the presence of the aforementioned foaming agent.

[0083] On the other hand, there is a foam premix composition, which contains polyols and the aforementioned foaming agent.

[0084] Another aspect is a method for forming foam, including: (a) adding the above-mentioned foaming agent to the foamable composition; and (b) React the foamable composition under conditions that effectively form foam.

[0085] In the context of polyurethane foam, the terms "expandable composition" and "expandable component" shall be understood herein to mean isocyanate or mixtures containing isocyanate. In the context of polystyrene foam, the terms "expandable composition" and "expandable component" shall be understood herein to mean polyolefin or mixtures containing polyolefin.

[0086] Another method is a method for forming polyisocyanate-based foam, which includes reacting at least one organic polyisocyanate with at least one compound containing active hydrogen in the presence of the aforementioned foaming agent. Another method is the production of polyisocyanate foam by said method.

[0087] Propellant Another embodiment of the invention relates to the use of the compositions of the invention as described herein as propellants in aerosol compositions. Additionally, the invention relates to aerosol compositions comprising the compositions of the invention as described herein. The active ingredient to be aerosolized, along with inert components, solvents, and other materials, may also be present in the aerosol composition. Preferably, the aerosol composition is an aerosol. Suitable active materials to be aerosolized include, but are not limited to, cosmetic materials such as deodorants, perfumes, hairsprays, detergents, and polishes, and pharmaceutical materials such as anti-asthma and anti-halitosis medications.

[0088] The present invention also relates to a method for preparing aerosol products, the method comprising the step of adding an active ingredient in an aerosol container as described herein, wherein the composition is used as a propellant.

[0089] Flame retardancy and inertness On the other hand, a method for suppressing flames is provided, the method comprising contacting the flame with a fluid containing the composition of the present invention disclosed herein. Any suitable method for contacting the flame with the composition of the present invention may be used. For example, the composition of the present invention disclosed herein may be sprayed, poured onto the flame, etc., or at least a portion of the flame may be immersed in the flame-suppressing composition. Based on the teachings herein, those skilled in the art will be able to readily adapt various conventional flame-suppressing devices and methods to this disclosure.

[0090] Another embodiment provides a method for extinguishing or suppressing a fire in a total flooding application, the method comprising providing a reagent comprising the composition of the present invention disclosed herein; treating the reagent in a pressurized discharge system; and discharging the reagent into an area to extinguish or suppress a fire in that area.

[0091] Another embodiment provides a method for inertizing a space to prevent fire or explosion, the method comprising providing a reagent comprising the composition of the present invention disclosed herein; treating the reagent in a pressurized discharge system; and discharging the reagent into the space to prevent fire or explosion.

[0092] The term "extinguish" is generally used to mean the complete elimination of a fire; however, "suppress" is generally used to mean the reduction of a fire or explosion, but not necessarily its complete elimination. As used herein, the terms "extinguish" and "suppress" are used interchangeably. There are four general types of fire and explosion protection applications for halogenated hydrocarbons: 1) In total flooding fire extinguishing and / or suppression applications, reagents are released into a space to a concentration sufficient to extinguish or suppress an existing fire. Total flooding applications include protecting enclosed, potentially occupied spaces, such as computer rooms, as well as dedicated, normally unoccupied spaces, such as aircraft engine compartments and engine compartments in vehicles.

[0093] 2) In flow-through applications, the reagent is applied directly to the fire or the fire zone. This is typically accomplished using manually operated wheeled or portable units. A second method of flow-through application is the use of a "localization" system, which directs the reagent from one or more fixed nozzles toward the fire. Localization systems can be activated manually or automatically.

[0094] 3) In explosion suppression, the composition of the present invention disclosed herein is discharged to suppress an explosion that has already begun. The term "suppression" is generally used in this application because explosions are typically self-limiting. However, using this term does not necessarily mean that the explosion will not be extinguished by the reagent. In this application, a detector is typically used to detect the expanding fireball produced by the explosion, and the reagent is rapidly discharged to suppress the explosion. Explosion suppression is primarily, but not exclusively, used in defensive applications.

[0095] 4) In an inertized state, the composition of the present invention disclosed herein is released into the space to prevent the occurrence of an explosion or fire. Typically, a system similar to or the same as that used for total flooding fire extinguishing or suppression is used. Typically, the presence of a hazardous condition (e.g., a dangerous concentration of flammable or explosive gases) is detected, and then the composition of the present invention disclosed herein is released to prevent an explosion or fire until the situation can be remedied.

[0096] Extinguishing methods can be carried out by introducing the composition into an enclosed area surrounding the fire. Any known introduction method can be used, provided that an appropriate amount of the composition is metered into the enclosed area at suitable intervals. For example, the composition can be introduced by, for instance, using a conventional portable (or stationary) fire extinguishing device with a feed stream; by atomization; or by, for instance, by overflowing the composition (using suitable conduits, valves, and control devices) into the enclosed area surrounding the fire. The composition may optionally be combined with an inert propellant (e.g., nitrogen, argon, decomposition products of glycidyl azide polymers, or carbon dioxide) to increase the rate of emission of the composition from the feed stream or overflow device used.

[0097] Preferably, the extinguishing method involves introducing the composition of the present invention disclosed herein into a fire or flame in an amount sufficient to extinguish the fire or flame. Those skilled in the art will recognize that the amount of flame retardant required to extinguish a particular fire will depend on the nature and extent of the hazard. When the flame retardant is introduced via overflow, cup burner test data can be used to determine the amount or concentration of flame retardant required to extinguish a particular type and size of fire.

[0098] When used in combination with fire extinguishing or fire suppression in total flooding applications or fire inertization, laboratory tests for determining the effective concentration range of the compositions of the invention are described, for example, in U.S. Patent 5,759,430.

[0099] gaseous dielectric Dielectric gases, or insulating gases, are gaseous dielectric materials. Their primary purpose is to prevent or rapidly quench discharge. Dielectric gases are used as electrical insulators in high-voltage applications, such as transformers, circuit breakers, switchgear (i.e., high-voltage switchgear), and radar waveguides. As used herein, the term "high voltage" should be understood to mean above 1000V for alternating current and at least 1500V for direct current. The compositions of this invention can be used as gaseous dielectrics in high-voltage applications.

[0100] solvent The compositions of this invention can also be used as inert media for polymerization reactions, as fluids for removing particles from metal surfaces, as carrier fluids for placing fine lubricant films on metal parts, or as polishing abrasives to remove polishing compounds from polished surfaces such as metals. They are also used as displacement desiccants for removing water, such as from jewelry or metal parts, as resist developers in conventional circuit manufacturing techniques including chlorinated developers, or as strippers for photoresists when used with, for example, chlorinated hydrocarbons such as 1,1,1-trichloroethane or trichloroethylene. It is desirable to identify new agents with reduced global warming potential values ​​for these applications.

[0101] Binary azeotropic or azeotropic compositions of essentially azeotropic mixtures can be characterized in a variety of ways depending on the chosen conditions. For example, it is well known to those skilled in the art that the composition of a given azeotropic or azeotropic composition will vary at least to some extent under different pressures, as will the boiling point temperature. Thus, azeotropic or azeotropic compositions of two compounds represent a unique type of relationship but have variable compositions that depend on temperature and / or pressure. Therefore, composition ranges rather than fixed compositions are often used to define azeotropic and azeotropic compositions.

[0102] As used herein, the term "azeotropic composition" should be understood to mean a composition in which, at equilibrium at a given temperature, the boiling point pressure (of the liquid phase) is the same as the dew point pressure (of the vapor phase), i.e., X² = Y². One way to characterize an azeotropic composition is by having the vapor produced by partial evaporation or distillation of a liquid that has the same composition as the evaporated or distilled liquid, i.e., the mixture is distilled / refluxed without a change in composition. Azeotropic compositions are characterized by azeotropy because they exhibit the maximum or minimum boiling point compared to non-azeotropic mixtures of the same components. Azeotropic compositions are also characterized by the minimum or maximum vapor pressure of the mixture relative to the vapor pressure of the pure components at a constant temperature.

[0103] As used herein, the terms “quasi-azeotropic composition” and “near-azeotropic composition” should be understood to mean a composition in which the difference between bubble point pressure (“BP”) and dew point pressure (“DP”) at a given temperature is based on a bubble point pressure less than or equal to 5%, i.e., [(BP-VP) / BP] ×100 ≤ 5. As used herein, the terms “3% quasi-azeotropic composition” and “3% near-azeotropic composition” should be understood to mean a composition in which the difference between bubble point pressure (“BP”) and dew point pressure (“DP”) at a given temperature is based on a bubble point pressure less than or equal to 3%, i.e., [(BP-VP) / BP] ×100 ≤ 3.

[0104] For the purposes of this invention, "effective amount" is defined as the amount of each component of the compositions of this invention that, when combined, results in the formation of an azeotropic or azeotropic-like composition. This definition includes the amount of each component, which can vary depending on the pressure applied to the composition, as long as the azeotropic or azeotropic-like composition persists at different pressures, but may have different boiling points. Therefore, effective amount includes the amount of each component of the compositions of this invention that forms an azeotropic or azeotropic-like composition at temperatures or pressures different from those described herein, and may be expressed as a weight percentage.

[0105] As used herein, the term “molar number” should be understood as the ratio of the number of moles of one component in a binary composition to the sum of the number of moles of each of the two components in the composition (e.g., X2 = m2 / (m1 + m2)).

[0106] To determine the relative volatility of any two compounds, a method known as the PTx method can be used. In this process, for various combinations of the two compounds, the total absolute pressure in a known volume of bubbles is measured at a constant temperature. The use of the PTx method is described in detail in Harold R. Null's "Phase Equilibrium in Process Design," Wiley-Interscience Publisher, 1970, pp. 124–126, which is incorporated herein by reference. The resulting pressure and liquid composition data are alternately referred to as gas-liquid equilibrium data (or "VLE data").

[0107] These measurements can be transformed into equilibrium vapor-liquid compositions in PTx pores to represent liquid-phase nonidealities by using activity coefficient equation models, such as the non-random two-liquid (NRTL) equation. Activity coefficient equations, such as the NRTL equation, are described in detail in *The Properties of Gases and Liquids*, 4th edition, McGraw Hill, by Reid, Prausnitz, and Poling, pp. 241–387, and in *Phase Equilibria in Chemical Engineering*, Butterworth Publishers, by Stanley M. Walas, 1985, pp. 165–244. The collection of VLE data, the determination of interaction parameters by regression, and the use of equations of state to predict the nonideal behavior of the system are discussed in *Double Azeotropy in Binary Mixtures of NH3 and CHF2CF2*, C.-P. Chai Kao, ME Paulaitis, A. Yokozeki. Fluid Phase Equilibria The teachings are found in ,127 (1997), pages 191-203. All the foregoing references are incorporated herein by reference. Without wishing to be bound by any theory or interpretation, it is believed that the NRTL equations, together with PTx pore data, can adequately predict the relative volatility of the Z-1233zd-containing compositions of the present invention, and thus the behavior of these mixtures in multi-stage separation equipment such as distillation columns.

[0108] For the sake of space economy in the table below, "Z-1233zd" can be abbreviated to "Z1233zd".

[0109] Example 1: Z-1233zd / methyl formate The potential azeotropic and near-azeotropic behavior of the Z-1233zd / methyl formate binary system was investigated. The PTx method described above was used to determine the relative volatility of this binary system. For various binary compositions, the pressure in PTx cells of known volume was measured at a constant temperature of 30°C. The collected experimental data are shown in Table 1.1 below.

[0110] Table 1.1: Experimental VLE data for the Z-1233zd / methyl formate system at 30℃. X2 Y2 Pexp(psia) Pcalc(psia) Pcalc - Pexp(psia) 0.000 0.000 13.832 0.025 0.018 13.665 13.724 0.0043 0.055 0.039 13.575 13.597 0.0016 0.087 0.063 13.469 13.464 -0.0003 0.128 0.096 13.312 13.294 -0.0014 0.181 0.139 13.103 13.080 -0.0017 0.229 0.180 12.881 12.893 0.0009 0.285 0.229 12.681 12.684 0.0003 0.446 0.383 12.136 12.115 -0.0017 0.522 0.460 11.861 11.870 0.0007 0.606 0.548 11.598 11.614 0.0013 0.689 0.638 11.363 11.373 0.0009 0.776 0.736 11.133 11.135 0.0002 0.861 0.835 10.928 10.913 -0.0013 0.939 0.926 10.743 10.724 -0.0018 1.000 1.000 10.580 X2 = Z-1233zd, which represents the number of liquid moles. The number of vapor moles of Y2 = Z-1233zd. P exp =The pressure measured in the experiment. P calc =Pressure calculated by the NRTL model.

[0111] Figure 1 The graph shows the relationship between pressure and composition data for Z-1233zd in the range of 0-1 liquid molar parts. The top curve represents the bubble point (“BP”) trajectory, and the bottom curve represents the dew point (“DP”) trajectory.

[0112] Based on these VLE data, interaction coefficients were extracted. These coefficients were then used in the NRTL model to predict the behavior of the Z-1233zd / methyl formate system at various temperatures and pressures. The NRTL model was run in increments of 20°C (and 29.9°C) and 0.002 liquid molars of Z-1233zd over a temperature range of -40°C to 140°C. For brevity, a list of 5511 combinations (501 compositions × 11 temperatures) was compiled to reflect increments of 0.100 liquid molar composition of Z-1233zd, or the boundaries of near-azeotropic behavior. The resulting list of abbreviations for near-azeotropic compounds in the Z-1233zd / methyl formate system is shown in Table 1.2.

[0113] Table 1.2: Predicted near-azeotropic conditions of the Z-1233zd / methyl formate system from -40°C to 140°C. Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fractions (MF) Vapor molar fraction MF Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 -40.0 0.000 0 1 1 0.359 0.359 0.00% -40.0 0.002 0.001 0.998 0.999 0.359 0.359 0.03% -40.0 0.100 0.073 0.9 0.927 0.348 0.344 1.09% -40.0 0.200 0.154 0.8 0.846 0.338 0.332 1.59% -40.0 0.300 0.242 0.7 0.758 0.328 0.322 1.72% -40.0 0.400 0.339 0.6 0.661 0.319 0.313 1.61% -40.0 0.500 0.441 0.5 0.559 0.310 0.306 1.38% -40.0 0.600 0.547 0.4 0.453 0.303 0.300 1.09% -40.0 0.700 0.657 0.3 0.343 0.296 0.294 0.81% -40.0 0.800 0.769 0.2 0.231 0.290 0.289 0.54% -40.0 0.900 0.883 0.1 0.117 0.285 0.284 0.29% -40.0 0.998 0.998 0.002 0.002 0.279 0.279 0.01% -40.0 1 1.000 0 0.000 0.279 0.279 0.00% -20.0 0 0.000 1 1.000 1.299 1.299 0.00% -20.0 0.002 0.001 0.998 0.999 1.298 1.298 0.03% -20.0 0.1 0.073 0.9 0.927 1.260 1.247 1.04% -20.0 0.2 0.154 0.8 0.846 1.222 1.203 1.54% -20.0 0.3 0.243 0.7 0.757 1.187 1.167 1.68% -20.0 0.4 0.339 0.6 0.661 1.154 1.136 1.60% -20.0 0.5 0.440 0.5 0.560 1.124 1.109 1.40% -20.0 0.6 0.546 0.4 0.454 1.097 1.085 1.14% -20.0 0.7 0.656 0.3 0.344 1.073 1.064 0.86% -20.0 0.8 0.768 0.2 0.232 1.050 1.044 0.58% -20.0 0.9 0.882 0.1 0.118 1.029 1.026 0.31% -20.0 0.998 0.998 0.002 0.002 1.009 1.009 0.01% -20.0 1 1.000 0 0.000 1.009 1.009 0.00% 0.0 0.000 0.000 1 1.000 3.773 3.773 0.00% 0.0 0.002 0.001 0.998 0.999 3.770 3.769 0.03% 0.0 0.100 0.074 0.9 0.926 3.659 3.623 1.01% 0.0 0.200 0.155 0.8 0.845 3.552 3.498 1.51% 0.0 0.300 0.244 0.7 0.756 3.450 3.392 1.67% 0.0 0.400 0.339 0.6 0.661 3.355 3.301 1.62% 0.0 0.500 0.440 0.5 0.560 3.268 3.221 1.43% 0.0 0.600 0.545 0.4 0.455 3.188 3.150 1.18% 0.0 0.700 0.655 0.3 0.345 3.115 3.087 0.90% 0.0 0.800 0.767 0.2 0.233 3.048 3.029 0.62% 0.0 0.900 0.882 0.1 0.118 2.984 2.974 0.33% 0.0 0.998 0.998 0.002 0.002 2.924 2.923 0.01% 1 1.000 0 0.000 2.922 2.922 0.00% 20.0 0 0.000 1 1.000 9.243 9.243 0.00% 20.0 0.002 0.001 0.998 0.999 9.237 9.235 0.03% 20.0 0.1 0.074 0.9 0.926 8.967 8.878 0.99% 20.0 0.2 0.155 0.8 0.845 8.703 8.572 1.50% 20.0 0.3 0.244 0.7 0.756 8.453 8.311 1.68% 20.0 0.4 0.339 0.6 0.661 8.220 8.084 1.65% 20.0 0.5 0.439 0.5 0.561 8.003 7.885 1.48% 20.0 0.6 0.545 0.4 0.455 7.804 7.708 1.23% 20.0 0.7 0.654 0.3 0.346 7.620 7.548 0.95% 20.0 0.8 0.766 0.2 0.234 7.450 7.401 0.66% 20.0 0.9 0.881 0.1 0.119 7.290 7.264 0.35% 20.0 0.998 0.998 0.002 0.002 7.137 7.136 0.01% 20.0 1 1.000 0 0.000 7.134 7.134 0.00% 29.9 0 0.000 1 1.000 13.735 13.735 0.00% 29.9 0.002 0.001 0.998 0.999 13.727 13.724 0.03% 29.9 0.1 0.074 0.9 0.926 13.325 13.194 0.99% 29.9 0.2 0.155 0.8 0.845 12.932 12.738 1.50% 29.9 0.3 0.244 0.7 0.756 12.560 12.347 1.69% 29.9 0.4 0.339 0.6 0.661 12.211 12.008 1.66% 29.9 0.5 0.439 0.5 0.561 11.887 11.709 1.50% 29.9 0.6 0.544 0.4 0.456 11.588 11.442 1.25% 29.9 0.7 0.653 0.3 0.347 11.311 11.201 0.97% 29.9 0.8 0.766 0.2 0.234 11.054 10.980 0.67% 29.9 0.9 0.881 0.1 0.119 10.812 10.774 0.36% 29.9 0.998 0.998 0.002 0.002 10.582 10.581 0.01% 29.9 1 1.000 0 0.000 10.577 10.577 40.0 0.000 0.000 1 1.000 19.817 19.817 0.00% 40.0 0.002 0.001 0.998 0.999 19.805 19.800 0.03% 40.0 0.100 0.074 0.9 0.926 19.223 19.034 0.98% 40.0 0.200 0.156 0.8 0.844 18.654 18.374 1.50% 40.0 0.300 0.244 0.7 0.756 18.115 17.807 1.70% 40.0 0.400 0.339 0.6 0.661 17.608 17.313 1.68% 40.0 0.500 0.439 0.5 0.561 17.137 16.877 1.52% 40.0 0.600 0.544 0.4 0.456 16.701 16.488 1.28% 40.0 0.700 0.653 0.3 0.347 16.297 16.135 0.99% 40.0 0.800 0.765 0.2 0.235 15.921 15.812 0.69% 40.0 0.900 0.881 0.1 0.119 15.567 15.510 0.36% 40.0 0.998 0.998 0.002 0.002 15.231 15.230 0.01% 40.0 1.000 1.000 0 0.000 15.224 15.224 0.00% 60.0 0 0.000 1 1.000 38.211 38.211 0.00% 60.0 0.002 0.001 0.998 0.999 38.188 38.178 0.02% 60.0 0.1 0.075 0.9 0.925 37.056 36.695 0.97% 60.0 0.2 0.156 0.8 0.844 35.949 35.409 1.50% 60.0 0.3 0.244 0.7 0.756 34.897 34.300 1.71% 60.0 0.4 0.339 0.6 0.661 33.907 33.331 1.70% 60.0 0.5 0.439 0.5 0.561 32.983 32.473 1.55% 60.0 0.6 0.544 0.4 0.456 32.125 31.705 1.31% 60.0 0.7 0.653 0.3 0.347 31.328 31.009 1.02% 60.0 0.8 0.765 0.2 0.235 30.586 30.370 0.71% 60.0 0.9 0.881 0.1 0.119 29.886 29.775 0.37% 60.0 0.998 0.998 0.002 0.002 29.226 29.223 0.01% 60.0 1 1.000 0 0.000 29.212 29.212 0.00% 80.0 0.000 0.000 1 1.000 67.665 67.665 0.00% 80.0 0.002 0.001 0.998 0.999 67.623 67.607 0.02% 80.0 0.100 0.075 0.9 0.925 65.596 64.967 0.96% 80.0 0.200 0.157 0.8 0.843 63.612 62.667 1.48% 80.0 0.300 0.246 0.7 0.754 61.727 60.678 1.70% 80.0 0.400 0.340 0.6 0.660 59.951 58.933 1.70% 80.0 0.500 0.440 0.5 0.560 58.290 57.387 1.55% 80.0 0.600 0.545 0.4 0.455 56.745 56.000 1.31% 80.0 0.700 0.654 0.3 0.346 55.309 54.743 1.02% 80.0 0.800 0.766 0.2 0.234 53.972 53.590 0.71% 80.0 0.900 0.881 0.1 0.119 52.714 52.518 0.37% 80.0 0.998 0.998 0.002 0.002 51.530 51.526 0.01% 1 1.000 0 0.000 51.507 51.507 100.0 0 0.000 1 1.000 111.844 111.844 0.00% 100.0 0.002 0.001 0.998 0.999 111.773 111.747 0.02% 100.0 0.1 0.076 0.9 0.924 108.378 107.371 0.93% 100.0 0.2 0.159 0.8 0.841 105.060 103.544 1.44% 100.0 0.3 0.248 0.7 0.752 101.909 100.222 1.66% 100.0 0.4 0.342 0.6 0.658 98.943 97.304 1.66% 100.0 0.5 0.442 0.5 0.558 96.169 94.714 1.51% 100.0 0.6 0.547 0.4 0.453 93.589 92.391 1.28% 100.0 0.7 0.656 0.3 0.344 91.194 90.286 1.00% 100.0 0.8 0.767 0.2 0.233 88.967 88.357 0.69% 100.0 0.9 0.882 0.1 0.118 86.878 86.569 0.36% 100.0 0.998 0.998 0.002 0.002 84.925 84.918 0.01% 100.0 1 1.000 0 0.000 84.885 84.885 0.00% 120.0 0 0.000 1 1.000 174.772 174.772 0.00% 120.0 0.002 0.001 0.998 0.999 174.660 174.621 0.02% 120.0 0.1 0.077 0.9 0.923 169.285 167.795 0.88% 120.0 0.2 0.161 0.8 0.839 164.045 161.802 1.37% 120.0 0.3 0.251 0.7 0.749 159.081 156.588 1.57% 120.0 0.4 0.346 0.6 0.654 154.419 152.002 1.56% 120.0 0.5 0.446 0.5 0.554 150.069 147.930 1.43% 120.0 0.6 0.551 0.4 0.449 146.033 144.280 1.20% 120.0 0.7 0.659 0.3 0.341 142.298 140.978 0.93% 120.0 0.8 0.770 0.2 0.230 138.837 137.959 0.63% 120.0 0.9 0.884 0.1 0.116 135.609 135.168 0.33% 120.0 0.998 0.998 0.002 0.002 132.610 132.601 0.01% 1 1.000 0 0.000 132.550 132.550 140.0 0.000 0.000 1 1.000 260.836 260.836 0.00% 140.0 0.002 0.002 0.998 0.998 260.667 260.613 0.02% 140.0 0.100 0.079 0.9 0.921 252.540 250.500 0.81% 140.0 0.200 0.164 0.8 0.836 244.651 241.590 1.25% 140.0 0.300 0.255 0.7 0.745 237.212 233.824 1.43% 140.0 0.400 0.351 0.6 0.649 230.256 226.992 1.42% 140.0 0.500 0.451 0.5 0.549 223.796 220.932 1.28% 140.0 0.600 0.556 0.4 0.444 217.835 215.514 1.07% 140.0 0.700 0.664 0.3 0.336 212.353 210.628 0.81% 140.0 0.800 0.774 0.2 0.226 207.311 206.182 0.54% 140.0 0.900 0.886 0.1 0.114 202.647 202.091 0.27% 140.0 0.998 0.998 0.002 0.002 198.361 198.349 0.01% 1 1.000 0 0.000 198.275 198.275 0.00%

[0114] The NRTL model was run at 1 atm with increments of 0.002 liquid molar components of Z-1233zd. For simplicity, the list has been edited to reflect increments of 0.100 liquid molar composition of Z-1233zd, or the boundaries of near-azeotropic behavior. A list of abbreviations for the near-azeotropic compounds of the resulting Z-1233zd / methyl formate system is shown in Table 1.3.

[0115] Table 1.3: Near-azeotropic reaction of Z-1233zd / MF system predicted at 1 Atm. Pressure (atm) Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fractions (MF) Vapor molar fraction MF Point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP] × 100 1.00 31.787 0.000 0.000 1.000 1.000 14.696 14.696 0.00% 1.00 31.804 0.002 0.001 0.998 0.999 14.696 14.692 0.03% 1.00 32.599 0.100 0.074 0.900 0.926 14.696 14.551 0.98% 1.00 33.404 0.200 0.155 0.800 0.845 14.696 14.475 1.50% 1.00 34.195 0.300 0.244 0.700 0.756 14.696 14.447 1.69% 1.00 34.965 0.400 0.339 0.600 0.661 14.696 14.450 1.67% 1.00 35.705 0.500 0.439 0.500 0.561 14.696 14.474 1.51% 1.00 36.414 0.600 0.544 0.400 0.456 14.696 14.510 1.27% 1.00 37.090 0.700 0.653 0.300 0.347 14.696 14.551 0.99% 1.00 37.739 0.800 0.765 0.200 0.235 14.696 14.596 0.68% 1.00 38.369 0.900 0.881 0.100 0.119 14.696 14.643 0.36% 1.00 38.984 0.998 0.998 0.002 0.002 14.696 14.695 0.01% 1.00 38.996 1.000 1.000 0.000 0.000 14.696 14.696 0.00%

[0116] The detailed data in Tables 1.2 and 1.3 are summarized in Tables 1.4 and 1.5 below. A wide range of azeotropic compositions (based on [(BP-VP) / BP] × 100 ≤ 5) is listed in Table 1.4.

[0117] Table 1.4: Summary of near-azeotropic properties of the Z-1233zd / MF system. Components T（℃） Z-1233zd / Methyl Formate Liquid Mole Percentage Range Z-1233zd / Methyl formate -40 1-99 / 99-1 Z-1233zd / Methyl formate -20 1-99 / 99-1 Z-1233zd / Methyl formate 0 1-99 / 99-1 Z-1233zd / Methyl formate 20 1-99 / 99-1 Z-1233zd / Methyl formate 29.9 1-99 / 99-1 Z-1233zd / Methyl formate 40 1-99 / 99-1 Z-1233zd / Methyl formate 60 1-99 / 99-1 Z-1233zd / Methyl formate 80 1-99 / 99-1 Z-1233zd / Methyl formate 100 1-99 / 99-1 Z-1233zd / Methyl formate 120 1-99 / 99-1 Z-1233zd / Methyl formate 140 1-99 / 99-1

[0118] A wide range of 3% azeotropic compositions (based on [(BP-VP) / BP] × 100 ≤ 3) are listed in Table 1.5.

[0119] Table 1.5: Summary of 3% near-azeotropic content in the Z-1233zd / MF system. Components T（℃） Z-1233zd / Methyl Formate Liquid Mole Percentage Range Z-1233zd / Methyl formate -40 1-99 / 99-1 Z-1233zd / Methyl formate -20 1-99 / 99-1 Z-1233zd / Methyl formate 0 1-99 / 99-1 Z-1233zd / Methyl formate 20 1-99 / 99-1 Z-1233zd / Methyl formate 29.9 1-99 / 99-1 Z-1233zd / Methyl formate 40 1-99 / 99-1 Z-1233zd / Methyl formate 60 1-99 / 99-1 Z-1233zd / Methyl formate 80 1-99 / 99-1 Z-1233zd / Methyl formate 100 1-99 / 99-1 Z-1233zd / Methyl formate 120 1-99 / 99-1 Z-1233zd / Methyl formate 140 1-99 / 99-1

[0120] At atmospheric pressure, all compositions were found to be 3% near-azeotropic.

[0121] Example 2: Z-1233zd / dimethoxymethane The binary system of Z-1233zd / dimethoxymethane was investigated for potential azeotropic and near-azeotropic behavior. The PTx method described above was used to determine the relative volatility of this binary system. For various binary compositions, the pressure in PTx cells of known volume was measured at a constant temperature of 29.9 °C. The collected experimental data are shown in Table 2.1 below.

[0122] Table 2-1: VLE data for the Z-1233zd / dimethoxymethane system. X2 Y2 Pexp psia Pcalc psia Pcalc-Pexp psia 0.000 0.000 9.329 0.038 0.030 9.197 9.241 0.005 0.085 0.069 9.191 9.140 -0.006 0.131 0.110 9.192 9.050 -0.015 0.188 0.165 8.964 8.956 -0.001 0.259 0.240 8.827 8.865 0.004 0.318 0.307 8.790 8.818 0.003 0.384 0.385 8.760 8.799 0.005 0.522 0.552 8.877 8.892 0.002 0.576 0.617 8.970 8.980 0.001 0.642 0.694 9.118 9.128 0.001 0.715 0.772 9.354 9.340 -0.002 0.793 0.848 9.657 9.621 -0.004 0.869 0.913 9.991 9.940 -0.005 0.939 0.963 10.307 10.259 -0.005 1.000 1.000 10.556 X2 = Z-1233zd, which represents the number of liquid moles. The number of vapor moles of Y2 = Z-1233zd. P exp =The pressure measured in the experiment. P calc =Pressure calculated by the NRTL model.

[0123] The above vapor pressure v and liquid molar fraction data (Z-1233zd) are plotted on Figure 2 In the middle. Experimental data points are in Figure 2 The solid lines represent bubble point predictions using the NRTL equation. The dashed lines represent predicted dew points.

[0124] Based on these VLE data, the interaction coefficients were extracted. The NRTL model was run in 10°C increments over a temperature range of -40°C to 140°C, allowing pressure variations to satisfy the azeotropic condition (X2 = Y2). Table 2.2 shows the predicted azeotropic conditions for the Z-1233zd / DMM system.

[0125] Table 2.2: Predicted azeotropic conditions of the Z-1233zd / DMM system from -40℃ to 140℃. Temperature (°C) Pressure (psia) Z1233zd vapor molar fractions DMM vapor molar parts Z1233zd Liquid Molar Parts DMM liquid molar fractions Z1233zd liquid weight parts DMM liquid weight parts -40 0.18 0.394 0.606 0.394 0.606 0.527 0.473 -30 0.38 0.389 0.611 0.389 0.611 0.522 0.478 -20 0.73 0.385 0.615 0.385 0.615 0.518 0.482 -10 1.33 0.382 0.618 0.382 0.618 0.515 0.485 0 2.28 0.381 0.619 0.381 0.619 0.513 0.487 10 3.72 0.380 0.620 0.380 0.620 0.513 0.487 20 5.84 0.382 0.618 0.382 0.618 0.514 0.486 29.9 8.78 0.385 0.615 0.385 0.615 0.517 0.483 30 8.82 0.385 0.615 0.385 0.615 0.517 0.483 40 12.90 0.389 0.611 0.389 0.611 0.522 0.478 50 18.33 0.395 0.605 0.395 0.605 0.529 0.471 60 25.37 0.403 0.597 0.403 0.597 0.536 0.464 70 34.31 0.411 0.589 0.411 0.589 0.545 0.455 80 45.44 0.421 0.579 0.421 0.579 0.555 0.445 90 59.05 0.431 0.569 0.431 0.569 0.565 0.435 100 75.45 0.440 0.560 0.440 0.560 0.574 0.426 110 94.94 0.450 0.550 0.450 0.550 0.583 0.417 120 117.82 0.458 0.542 0.458 0.542 0.592 0.408 130 144.38 0.465 0.535 0.465 0.535 0.599 0.401 140 174.86 0.471 0.529 0.471 0.529 0.605 0.395

[0126] The model was used to predict azeotropes in 1 atm increments over a pressure range of 1 atm to 31 atm, and the results are shown in Table 2.3.

[0127] Table 2.3: Predicted azeotropics of the A-1233zd / DMM system from 1 Atm to 31 Atm. Pressure (atm) Temperature (°C) Z1233zd vapor molar fractions DMM vapor molar parts Z1233zd Liquid Molar Parts DMM liquid molar fractions Z1233zd liquid weight parts DMM liquid weight parts 1 43.6 0.391 0.609 0.391 0.609 0.524 0.476 2 64.8 0.407 0.593 0.407 0.593 0.540 0.460 3 78.9 0.420 0.580 0.420 0.580 0.554 0.446 4 89.8 0.431 0.569 0.431 0.569 0.565 0.435 5 98.9 0.439 0.561 0.439 0.561 0.573 0.427 6 106.7 0.447 0.553 0.447 0.553 0.581 0.419 7 113.6 0.453 0.547 0.453 0.547 0.587 0.413 8 119.9 0.458 0.542 0.458 0.542 0.591 0.409 9 125.6 0.462 0.538 0.462 0.538 0.596 0.404 10 130.9 0.466 0.534 0.466 0.534 0.599 0.401 11 135.8 0.469 0.531 0.469 0.531 0.602 0.398 12 140.5 0.472 0.528 0.472 0.528 0.605 0.395 13 144.8 0.474 0.526 0.474 0.526 0.607 0.393 14 149.0 0.476 0.524 0.476 0.524 0.609 0.391 15 152.9 0.478 0.522 0.478 0.522 0.611 0.389 16 156.7 0.480 0.520 0.480 0.520 0.613 0.387 17 160.4 0.481 0.519 0.481 0.519 0.614 0.386 18 163.9 0.483 0.517 0.483 0.517 0.616 0.384 19 167.3 0.484 0.516 0.484 0.516 0.617 0.383 20 170.6 0.486 0.514 0.486 0.514 0.618 0.382 21 173.8 0.487 0.513 0.487 0.513 0.620 0.380 22 176.9 0.489 0.511 0.489 0.511 0.621 0.379 23 180.0 0.491 0.509 0.491 0.509 0.623 0.377 24 183.0 0.493 0.507 0.493 0.507 0.625 0.375 25 186.0 0.495 0.505 0.495 0.505 0.627 0.373 26 189.0 0.497 0.503 0.497 0.503 0.629 0.371 27 192.0 0.501 0.499 0.501 0.499 0.632 0.368 28 195.1 0.505 0.495 0.505 0.495 0.636 0.364 29 198.5 0.513 0.487 0.513 0.487 0.644 0.356 30 202.0 0.522 0.478 0.522 0.478 0.652 0.348 31 205.8 0.528 0.472 0.528 0.472 0.657 0.343

[0128] To compare with experimental measurements, the model was run in 20°C increments over a temperature range of -40°C to 140°C and at 29.9°C. At each temperature, the model was run in increments of 0.002 across the entire range of Z-1233zd liquid molar compositions from 0 to 1. Therefore, the model was run at a total of 5511 combinations of temperature and Z-1233zd liquid molar compositions (11 temperatures × 501 compositions = 5511). Among these 5511 combinations, some exhibit azeotropic or near-azeotropic properties, which are the combinations claimed by the applicant. For brevity, the list of the 5511 combinations has been edited to reflect increments of 0.10 Z-1233zd liquid molar compositions, or the boundaries of near-azeotropic behavior. The resulting list of abbreviations is shown in Table 2.4.

[0129] Table 2.4: Predicted near-azeotropic properties of the Z-1233zd / DMM system. Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fractions DMM Vapor molar fractions DMM Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 -40.00 0.000 0.000 1.000 1.000 0.211 0.211 0.00% -40.00 0.002 0.001 0.998 0.999 0.211 0.211 0.08% -40.00 0.100 0.063 0.900 0.937 0.202 0.198 2.02% -40.00 0.200 0.151 0.800 0.849 0.193 0.190 1.66% -40.00 0.300 0.264 0.700 0.736 0.187 0.186 0.56% -40.00 0.400 0.403 0.600 0.597 0.185 0.185 0.00% -40.00 0.500 0.555 0.500 0.445 0.188 0.186 1.01% -40.00 0.600 0.702 0.400 0.298 0.198 0.190 3.88% -40.00 0.628 0.740 0.372 0.260 0.202 0.192 4.94% -40.00 0.630 0.742 0.370 0.258 0.202 0.192 5.02% -40.00 0.966 0.990 0.034 0.010 0.272 0.259 5.05% -40.00 0.968 0.990 0.032 0.010 0.273 0.260 4.81% -40.00 0.998 0.999 0.002 0.001 0.279 0.278 0.34% -40.00 1.000 1.000 0.000 0.000 0.279 0.279 0.00% -20.00 0.000 0.000 1.000 1.000 0.813 0.813 0.00% -20.00 0.002 0.001 0.998 0.999 0.813 0.812 0.05% -20.00 0.100 0.070 0.900 0.930 0.783 0.773 1.28% -20.00 0.200 0.161 0.800 0.839 0.757 0.749 1.01% -20.00 0.300 0.274 0.700 0.726 0.739 0.737 0.30% -20.00 0.400 0.406 0.600 0.594 0.734 0.734 0.01% -20.00 0.500 0.547 0.500 0.453 0.745 0.739 0.75% -20.00 0.600 0.683 0.400 0.317 0.774 0.754 2.63% -20.00 0.696 0.797 0.304 0.203 0.819 0.778 5.00% -20.00 0.698 0.799 0.302 0.201 0.820 0.779 5.04% -20.00 0.700 0.801 0.300 0.199 0.821 0.779 5.09% -20.00 0.928 0.969 0.072 0.031 0.964 0.915 5.05% -20.00 0.930 0.970 0.070 0.030 0.965 0.917 4.96% -20.00 0.998 0.999 0.002 0.001 1.007 1.005 0.18% -20.00 1.000 1.000 0.000 0.000 1.009 1.009 0.00% 0.00 0.000 0.000 1.000 1.000 2.470 2.470 0.00% 0.00 0.002 0.001 0.998 0.999 2.469 2.468 0.03% 0.00 0.100 0.075 0.900 0.925 2.392 2.372 0.84% 0.00 0.200 0.169 0.800 0.831 2.328 2.313 0.65% 0.00 0.300 0.280 0.700 0.720 2.287 2.282 0.18% 0.00 0.400 0.406 0.600 0.594 2.276 2.276 0.01% 0.00 0.500 0.538 0.500 0.462 2.303 2.291 0.52% 0.00 0.600 0.667 0.400 0.333 2.371 2.330 1.74% 0.00 0.700 0.781 0.300 0.219 2.479 2.397 3.31% 0.00 0.800 0.875 0.200 0.125 2.617 2.502 4.38% 0.00 0.900 0.946 0.100 0.054 2.769 2.665 3.77% 0.00 0.998 0.999 0.002 0.001 2.919 2.916 0.11% 1.000 1.000 0.000 0.000 2.922 2.922 0.00% 20.00 0.000 0.000 1.000 1.000 6.249 6.249 0.00% 20.00 0.002 0.001 0.998 0.999 6.246 6.244 0.02% 20.00 0.100 0.079 0.900 0.921 6.079 6.044 0.58% 20.00 0.200 0.174 0.800 0.826 5.944 5.918 0.45% 20.00 0.300 0.284 0.700 0.716 5.859 5.851 0.12% 20.00 0.400 0.404 0.600 0.596 5.837 5.836 0.01% 20.00 0.500 0.530 0.500 0.470 5.889 5.869 0.34% 20.00 0.600 0.654 0.400 0.346 6.022 5.953 1.14% 20.00 0.700 0.766 0.300 0.234 6.231 6.096 2.16% 20.00 0.800 0.861 0.200 0.139 6.502 6.316 2.86% 20.00 0.900 0.939 0.100 0.061 6.811 6.645 2.45% 20.00 0.998 0.999 0.002 0.001 7.127 7.122 0.07% 20.00 1.000 1.000 0.000 0.000 7.134 7.134 0.00% 29.93 0.000 0.000 1.000 1.000 9.364 9.364 0.00% 29.93 0.002 0.001 0.998 0.999 9.359 9.357 0.02% 29.93 0.100 0.081 0.900 0.919 9.127 9.081 0.50% 29.93 0.200 0.176 0.800 0.824 8.939 8.904 0.39% 29.93 0.300 0.285 0.700 0.715 8.820 8.810 0.11% 29.93 0.400 0.403 0.600 0.597 8.787 8.786 0.00% 29.93 0.500 0.527 0.500 0.473 8.854 8.830 0.27% 29.93 0.600 0.648 0.400 0.352 9.029 8.946 0.92% 29.93 0.700 0.759 0.300 0.241 9.307 9.143 1.76% 29.93 0.800 0.856 0.200 0.144 9.670 9.443 2.35% 29.93 0.900 0.936 0.100 0.064 10.091 9.887 2.02% 29.93 0.998 0.999 0.002 0.001 10.528 10.522 0.06% 29.93 1.000 1.000 0.000 0.000 10.537 10.537 40.00 0.000 0.000 1.000 1.000 13.703 13.703 0.00% 40.00 0.002 0.002 0.998 0.998 13.696 13.693 0.02% 40.00 0.100 0.082 0.900 0.918 13.375 13.317 0.44% 40.00 0.200 0.177 0.800 0.823 13.118 13.073 0.34% 40.00 0.300 0.285 0.700 0.715 12.953 12.939 0.10% 40.00 0.400 0.402 0.600 0.598 12.903 12.903 0.00% 40.00 0.500 0.523 0.500 0.477 12.986 12.959 0.21% 40.00 0.600 0.643 0.400 0.357 13.210 13.113 0.74% 40.00 0.700 0.754 0.300 0.246 13.572 13.377 1.44% 40.00 0.800 0.851 0.200 0.149 14.051 13.778 1.94% 40.00 0.900 0.933 0.100 0.067 14.615 14.367 1.70% 40.00 0.998 0.999 0.002 0.001 15.212 15.204 0.05% 40.00 1.000 1.000 0.000 0.000 15.224 15.224 0.00% 60.00 0.000 0.000 1.000 1.000 26.837 26.837 0.00% 60.00 0.002 0.002 0.998 0.998 26.824 26.821 0.01% 60.00 0.100 0.084 0.900 0.916 26.251 26.158 0.35% 60.00 0.200 0.179 0.800 0.821 25.788 25.713 0.29% 60.00 0.300 0.285 0.700 0.715 25.484 25.458 0.10% 60.00 0.400 0.400 0.600 0.600 25.373 25.373 0.00% 60.00 0.500 0.517 0.500 0.483 25.480 25.449 0.12% 60.00 0.600 0.634 0.400 0.366 25.821 25.695 0.49% 60.00 0.700 0.744 0.300 0.256 26.395 26.131 1.00% 60.00 0.800 0.843 0.200 0.157 27.182 26.801 1.40% 60.00 0.900 0.929 0.100 0.071 28.139 27.782 1.27% 60.00 0.998 0.999 0.002 0.001 29.190 29.178 0.04% 60.00 1.000 1.000 0.000 0.000 29.212 29.212 0.00% 80.00 0.000 0.000 1.000 1.000 48.031 48.031 0.00% 80.00 0.002 0.002 0.998 0.998 48.009 48.003 0.01% 80.00 0.100 0.085 0.900 0.915 47.027 46.879 0.31% 80.00 0.200 0.180 0.800 0.820 46.227 46.100 0.28% 80.00 0.300 0.285 0.700 0.715 45.683 45.632 0.11% 80.00 0.400 0.397 0.600 0.603 45.443 45.441 0.00% 80.00 0.500 0.512 0.500 0.488 45.549 45.520 0.06% 80.00 0.600 0.627 0.400 0.373 46.030 45.879 0.33% 80.00 0.700 0.737 0.300 0.263 46.897 46.552 0.74% 80.00 0.800 0.838 0.200 0.162 48.134 47.609 1.09% 80.00 0.900 0.926 0.100 0.074 49.696 49.178 1.04% 80.00 0.998 0.999 0.002 0.001 51.468 51.450 0.04% 1.000 1.000 0.000 0.000 51.507 51.507 100.00 0.000 0.000 1.000 1.000 79.955 79.955 0.00% 100.00 0.002 0.002 0.998 0.998 79.919 79.910 0.01% 100.00 0.100 0.085 0.900 0.915 78.280 78.042 0.30% 100.00 0.200 0.181 0.800 0.819 76.930 76.712 0.28% 100.00 0.300 0.284 0.700 0.716 75.977 75.876 0.13% 100.00 0.400 0.395 0.600 0.605 75.495 75.485 0.01% 100.00 0.500 0.509 0.500 0.491 75.552 75.528 0.03% 100.00 0.600 0.623 0.400 0.377 76.203 76.022 0.24% 100.00 0.700 0.733 0.300 0.267 77.483 77.027 0.59% 100.00 0.800 0.834 0.200 0.166 79.394 78.655 0.93% 100.00 0.900 0.924 0.100 0.076 81.894 81.125 0.94% 100.00 0.998 0.999 0.002 0.001 84.822 84.792 0.03% 100.00 1.000 1.000 0.000 0.000 84.885 84.885 0.00% 120.00 0.000 0.000 1.000 1.000 125.531 125.531 0.00% 120.00 0.002 0.002 0.998 0.998 125.471 125.457 0.01% 120.00 0.100 0.086 0.900 0.914 122.767 122.375 0.32% 120.00 0.200 0.180 0.800 0.820 120.514 120.140 0.31% 120.00 0.300 0.283 0.700 0.717 118.878 118.686 0.16% 120.00 0.400 0.393 0.600 0.607 117.972 117.941 0.03% 120.00 0.500 0.506 0.500 0.494 117.906 117.887 0.02% 120.00 0.600 0.620 0.400 0.380 118.781 118.558 0.19% 120.00 0.700 0.730 0.300 0.270 120.678 120.049 0.52% 120.00 0.800 0.832 0.200 0.168 123.637 122.555 0.88% 120.00 0.900 0.923 0.100 0.077 127.636 126.452 0.93% 120.00 0.998 0.999 0.002 0.001 132.444 132.397 0.04% 1.000 1.000 0.000 0.000 132.550 132.550 140.00 0.000 0.000 1.000 1.000 187.944 187.944 0.00% 140.00 0.002 0.002 0.998 0.998 187.845 187.822 0.01% 140.00 0.100 0.086 0.900 0.914 183.369 182.711 0.36% 140.00 0.200 0.180 0.800 0.820 179.618 178.970 0.36% 140.00 0.300 0.282 0.700 0.718 176.846 176.489 0.20% 140.00 0.400 0.391 0.600 0.609 175.222 175.146 0.04% 140.00 0.500 0.504 0.500 0.496 174.924 174.910 0.01% 140.00 0.600 0.618 0.400 0.382 176.130 175.834 0.17% 140.00 0.700 0.728 0.300 0.272 179.002 178.083 0.51% 140.00 0.800 0.832 0.200 0.168 183.659 181.991 0.91% 140.00 0.900 0.923 0.100 0.077 190.128 188.224 1.00% 140.00 0.998 0.999 0.002 0.001 198.098 198.018 0.04% 1.000 1.000 0.000 0.000 198.275 198.275 0.00%

[0130] The data in Table 2.4 are summarized in Tables 2.5 and 2.6 below. Azotropic compositions (based on [(BP-VP) / BP] × 100 ≤ 5) are summarized in Table 2.5, and 3% of near-azeotropic compositions (where [(BP-VP) / BP] × 100 ≤ 3) are listed in Table 2.6.

[0131] Table 2.5: Predicted near-azeotropic properties of the Z-1233zd / DMM system.

[0132] Table 2.6: Predicted 3% near-azeotropic content of the Z-1233zd / DMM system. Components T（℃） Z-1233zd / DMM Liquid Mole Percentage Range Z-1233zd / DMM -40 1-57 / 99-43 Z-1233zd / DMM -20 1-61 / 99-39 Z-1233zd / DMM 0 1-68 / 99-32 Z-1233zd / DMM 20 1-99 / 99-1 Z-1233zd / DMM 29.9 1-99 / 99-1 Z-1233zd / DMM 40 1-99 / 99-1 Z-1233zd / DMM 60 1-99 / 99-1 Z-1233zd / DMM 80 1-99 / 99-1 Z-1233zd / DMM 100 1-99 / 99-1 Z-1233zd / DMM 120 1-99 / 99-1 Z-1233zd / DMM 140 1-99 / 99-1

[0133] At atmospheric pressure, all compositions were found to be 3% near-azeotropic.

[0134] Example 3: Z-1233zd / HFC-43-10-mee The binary system Z-1233zd / HFC-43-10-mee was investigated for potential azeotropic and near-azeotropic behavior. The PTx method described above was used to determine the relative volatility of this binary system. For various binary compositions, the pressure in PTx cells of known volume was measured at a constant temperature of 30°C. The collected experimental data are shown in Table 3.1 below.

[0135] Table 3.1: VLE data of Z-1233zd / HFC-43-10-mee system at 30℃. X2 Y2 Pexp (psia) Pcalc (psia) Pcalc - Pexp (psia) 0.0000 0.0000 5.8500 0.0610 0.1322 6.3480 6.3498 0.0003 0.1381 0.2660 6.9310 6.9332 0.0003 0.2243 0.3849 7.5230 7.5241 0.0001 0.3099 0.4811 8.0510 8.0518 0.0001 0.3924 0.5594 8.5070 8.5089 0.0002 0.4711 0.6247 8.9020 8.9015 -0.0001 0.5326 0.6713 9.1930 9.1809 -0.0013 0.6549 0.7558 9.6750 9.6676 -0.0008 0.7124 0.7936 9.8670 9.8666 0.0000 0.7659 0.8286 10.0380 10.0349 -0.0003 0.8143 0.8605 10.1560 10.1728 0.0017 0.8673 0.8967 10.2940 10.3077 0.0013 0.9172 0.9328 10.4030 10.4173 0.0014 0.9620 0.9677 10.5020 10.4988 -0.0003 1.0000 1.0000 10.5530 99.6% purity X2 = Z-1233zd, which represents the number of liquid moles. The number of vapor moles of Y2 = Z-1233zd. P exp =The pressure measured in the experiment.

[0136] The above vapor pressure v and liquid molar fraction data (Z-1233zd) are plotted on Figure 3 In the middle. Experimental data points are in Figure 3 The solid lines represent bubble point predictions using the NRTL equation (see below). The dashed lines represent predicted dew points.

[0137] The model was operated in increments of 20°C over a temperature range of -40°C to 140°C, and at 29.93°C. At each temperature, the model was operated in increments of 0.002 over the entire range of Z1233zd liquid molar compositions from 0 to 1. Therefore, the model was operated at a total of 5511 combinations of temperature and Z-1233zd liquid molar compositions (11 temperatures × 501 compositions = 5511). Among these 5511 combinations, some exhibit azeotropic or near-azeotropic properties, which are the combinations claimed by the applicant. For brevity, the list of the 5511 combinations has been edited to reflect increments of 0.100 Z-1233zd liquid molar composition, or the boundaries of near-azeotropic behavior. The resulting list of abbreviations is shown in Table 3.2. HFC-43-10mee is abbreviated as "4310mee" in the table headings.

[0138] Table 3.2: Predicted near-azeotropic conditions of the Z-1233zd / HFC-43-10mee system from -40℃ to 140℃. Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fraction 4310 mee Vapor molar fraction 4310 mee Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 -40.00 0.000 0.000 1.000 1.000 0.0680 0.0680 0.00% -40.00 0.002 0.013 0.998 0.987 0.0687 0.0681 0.96% -40.00 0.010 0.063 0.990 0.937 0.0718 0.0685 4.54% -40.00 0.012 0.075 0.988 0.925 0.0726 0.0687 5.37% -40.00 0.100 0.407 0.900 0.593 0.1036 0.0743 28.32% -40.00 0.200 0.587 0.800 0.413 0.1339 0.0819 38.88% -40.00 0.300 0.691 0.700 0.309 0.1599 0.0911 43.02% -40.00 0.400 0.760 0.600 0.240 0.1824 0.1027 43.71% -40.00 0.500 0.811 0.500 0.189 0.2021 0.1174 41.89% -40.00 0.600 0.852 0.400 0.148 0.2196 0.1367 37.72% -40.00 0.700 0.888 0.300 0.112 0.2355 0.1627 30.90% -40.00 0.800 0.922 0.200 0.078 0.2503 0.1977 21.00% -40.00 0.900 0.958 0.100 0.042 0.2647 0.2409 8.97% -40.00 0.936 0.972 0.064 0.028 0.2698 0.2562 5.04% -40.00 0.938 0.973 0.062 0.027 0.2701 0.2570 4.84% -40.00 0.998 0.999 0.002 0.001 0.2788 0.2784 0.11% -40.00 1.000 1.000 0.000 0.000 0.2790 0.2790 0.00% -20.00 0.000 0.000 1.000 1.000 0.3319 0.3319 0.00% -20.00 0.002 0.009 0.998 0.991 0.3343 0.3324 0.57% -20.00 0.018 0.078 0.982 0.922 0.3534 0.3366 4.75% -20.00 0.020 0.086 0.980 0.914 0.3558 0.3372 5.23% -20.00 0.100 0.326 0.900 0.674 0.4447 0.3601 19.01% -20.00 0.200 0.503 0.800 0.497 0.5424 0.3935 27.45% -20.00 0.300 0.616 0.700 0.384 0.6272 0.4333 30.92% -20.00 0.400 0.697 0.600 0.303 0.7012 0.4814 31.34% -20.00 0.500 0.759 0.500 0.241 0.7662 0.5405 29.45% -20.00 0.600 0.811 0.400 0.189 0.8237 0.6136 25.50% -20.00 0.700 0.856 0.300 0.144 0.8754 0.7041 19.58% -20.00 0.800 0.900 0.200 0.100 0.9228 0.8115 12.06% -20.00 0.892 0.942 0.108 0.058 0.9635 0.9142 5.12% -20.00 0.894 0.943 0.106 0.057 0.9644 0.9163 4.98% -20.00 0.998 0.999 0.002 0.001 1.0077 1.0072 0.05% -20.00 1.000 1.000 0.000 0.000 1.0086 1.0086 0.00% 0.00 0.000 0.000 1.000 1.000 1.1959 1.1959 0.00% 0.00 0.002 0.007 0.998 0.993 1.2020 1.1976 0.36% 0.00 0.030 0.097 0.970 0.903 1.2853 1.2223 4.90% 0.00 0.032 0.103 0.968 0.897 1.2912 1.2241 5.19% 0.00 0.100 0.270 0.900 0.730 1.4811 1.2885 13.00% 0.00 0.200 0.439 0.800 0.561 1.7318 1.3957 19.41% 0.00 0.300 0.557 0.700 0.443 1.9520 1.5207 22.10% 0.00 0.400 0.645 0.600 0.355 2.1454 1.6674 22.28% 0.00 0.500 0.716 0.500 0.284 2.3156 1.8404 20.52% 0.00 0.600 0.776 0.400 0.224 2.4660 2.0434 17.14% 0.00 0.700 0.830 0.300 0.170 2.5997 2.2765 12.43% 0.00 0.800 0.882 0.200 0.118 2.7197 2.5269 7.09% 0.00 0.840 0.903 0.160 0.097 2.7642 2.6244 5.06% 0.00 0.842 0.904 0.158 0.096 2.7664 2.6292 4.96% 0.00 0.900 0.937 0.100 0.063 2.8275 2.7578 2.47% 0.00 0.998 0.999 0.002 0.001 2.9205 2.9198 0.03% 1.000 1.000 0.000 0.000 2.9223 2.9223 0.00% 20.00 0.000 0.000 1.000 1.000 3.4438 3.4438 0.00% 20.00 0.002 0.006 0.998 0.994 3.4566 3.4483 0.24% 20.00 0.046 0.118 0.954 0.882 3.7313 3.5510 4.83% 20.00 0.048 0.122 0.952 0.878 3.7435 3.5558 5.01% 20.00 0.100 0.231 0.900 0.769 4.0502 3.6850 9.02% 20.00 0.200 0.390 0.800 0.610 4.5899 3.9589 13.75% 20.00 0.300 0.509 0.700 0.491 5.0685 4.2709 15.74% 20.00 0.400 0.602 0.600 0.398 5.4915 4.6267 15.75% 20.00 0.500 0.679 0.500 0.321 5.8645 5.0306 14.22% 20.00 0.600 0.746 0.400 0.254 6.1930 5.4822 11.48% 20.00 0.700 0.807 0.300 0.193 6.4821 5.9684 7.92% 20.00 0.778 0.853 0.222 0.147 6.6828 6.3483 5.01% 20.00 0.780 0.854 0.220 0.146 6.6877 6.3578 4.93% 20.00 0.800 0.866 0.200 0.134 6.7357 6.4510 4.23% 20.00 0.900 0.929 0.100 0.071 6.9549 6.8612 1.35% 20.00 0.998 0.998 0.002 0.002 7.1306 7.1298 0.01% 20.00 1.000 1.000 0.000 0.000 7.1337 7.1337 0.00% 29.93 0.000 0.000 1.000 1.000 5.4729 5.4729 0.00% 29.93 0.002 0.005 0.998 0.995 5.4906 5.4798 0.20% 29.93 0.058 0.134 0.942 0.866 5.9708 5.6790 4.89% 29.93 0.060 0.138 0.940 0.862 5.9874 5.6863 5.03% 29.93 0.100 0.215 0.900 0.785 6.3123 5.8371 7.53% 29.93 0.200 0.370 0.800 0.630 7.0635 6.2466 11.57% 29.93 0.300 0.488 0.700 0.512 7.7325 6.7078 13.25% 29.93 0.400 0.583 0.600 0.417 8.3253 7.2261 13.20% 29.93 0.500 0.663 0.500 0.337 8.8483 7.8042 11.80% 29.93 0.600 0.732 0.400 0.268 9.3081 8.4359 9.37% 29.93 0.700 0.797 0.300 0.203 9.7105 9.0969 6.32% 29.93 0.740 0.822 0.260 0.178 9.8563 9.3582 5.05% 29.93 0.742 0.823 0.258 0.177 9.8634 9.3711 4.99% 29.93 0.800 0.859 0.200 0.141 10.0595 9.7312 3.26% 29.93 0.900 0.925 0.100 0.075 10.3547 10.2520 0.99% 29.93 0.998 0.998 0.002 0.002 10.5816 10.5808 0.01% 29.93 1.000 1.000 0.000 0.000 10.5854 10.5854 40.00 0.000 0.000 1.000 1.000 8.3654 8.3654 0.00% 40.00 0.002 0.005 0.998 0.995 8.3890 8.3754 0.16% 40.00 0.074 0.155 0.926 0.845 9.2100 8.7510 4.98% 40.00 0.076 0.159 0.924 0.841 9.2319 8.7618 5.09% 40.00 0.100 0.201 0.900 0.799 9.4917 8.8939 6.30% 40.00 0.200 0.352 0.800 0.648 10.5049 9.4827 9.73% 40.00 0.300 0.469 0.700 0.531 11.4106 10.1383 11.15% 40.00 0.400 0.566 0.600 0.434 12.2150 10.8649 11.05% 40.00 0.500 0.647 0.500 0.353 12.9251 11.6613 9.78% 40.00 0.600 0.720 0.400 0.280 13.5479 12.5129 7.64% 40.00 0.700 0.787 0.300 0.213 14.0897 13.3805 5.03% 40.00 0.702 0.788 0.298 0.212 14.0998 13.3976 4.98% 40.00 0.800 0.853 0.200 0.147 14.5541 14.1878 2.52% 40.00 0.900 0.922 0.100 0.078 14.9380 14.8296 0.73% 40.00 0.998 0.998 0.002 0.002 15.2195 15.2187 0.00% 40.00 1.000 1.000 0.000 0.000 15.2240 15.2240 0.00% 60.00 0.000 0.000 1.000 1.000 17.8054 17.8054 0.00% 60.00 0.002 0.004 0.998 0.996 17.8448 17.8248 0.11% 60.00 0.100 0.179 0.900 0.821 19.6882 18.8191 4.41% 60.00 0.118 0.207 0.882 0.793 20.0086 19.0115 4.98% 60.00 0.120 0.210 0.880 0.790 20.0438 19.0330 5.04% 60.00 0.200 0.321 0.800 0.679 21.3967 19.9276 6.87% 60.00 0.300 0.437 0.700 0.563 22.9338 21.1345 7.85% 60.00 0.400 0.535 0.600 0.465 24.3040 22.4363 7.68% 60.00 0.500 0.620 0.500 0.380 25.5135 23.8160 6.65% 60.00 0.600 0.697 0.400 0.303 26.5684 25.2322 5.03% 60.00 0.602 0.699 0.398 0.301 26.5880 25.2604 4.99% 60.00 0.700 0.770 0.300 0.230 27.4736 26.6056 3.16% 60.00 0.800 0.841 0.200 0.159 28.2287 27.8133 1.47% 60.00 0.900 0.916 0.100 0.084 28.8212 28.7136 0.37% 60.00 0.998 0.998 0.002 0.002 29.2069 29.2064 0.00% 60.00 1.000 1.000 0.000 0.000 29.2123 29.2123 0.00% 80.00 0.000 0.000 1.000 1.000 34.1318 34.1318 0.00% 80.00 0.002 0.004 0.998 0.996 34.1923 34.1656 0.08% 80.00 0.100 0.162 0.900 0.838 37.0346 35.8870 3.10% 80.00 0.200 0.296 0.800 0.704 39.6869 37.7715 4.83% 80.00 0.216 0.315 0.784 0.685 40.0877 38.0847 5.00% 80.00 0.218 0.317 0.782 0.683 40.1374 38.1241 5.02% 80.00 0.300 0.409 0.700 0.591 42.0847 39.7786 5.48% 80.00 0.400 0.508 0.600 0.492 44.2265 41.8870 5.29% 80.00 0.442 0.546 0.558 0.454 45.0500 42.7930 5.01% 80.00 0.444 0.548 0.556 0.452 45.0881 42.8363 4.99% 80.00 0.500 0.596 0.500 0.404 46.1135 44.0512 4.47% 80.00 0.600 0.678 0.400 0.322 47.7468 46.1888 3.26% 80.00 0.700 0.755 0.300 0.245 49.1251 48.1693 1.95% 80.00 0.800 0.831 0.200 0.169 50.2384 49.8196 0.83% 80.00 0.900 0.911 0.100 0.089 51.0561 50.9657 0.18% 80.00 0.998 0.998 0.002 0.002 51.5019 51.5017 0.00% 1.000 1.000 0.000 0.000 51.5065 51.5065 100.00 0.000 0.000 1.000 1.000 60.1374 60.1374 0.00% 100.00 0.002 0.003 0.998 0.997 60.2250 60.1921 0.05% 100.00 0.100 0.148 0.900 0.852 64.3551 62.9516 2.18% 100.00 0.200 0.275 0.800 0.725 68.2291 65.9189 3.39% 100.00 0.300 0.386 0.700 0.614 71.7421 69.0116 3.81% 100.00 0.400 0.486 0.600 0.514 74.8807 72.1775 3.61% 100.00 0.500 0.576 0.500 0.424 77.6345 75.3279 2.97% 100.00 0.600 0.661 0.400 0.339 79.9938 78.3264 2.08% 100.00 0.700 0.742 0.300 0.258 81.9440 80.9846 1.17% 100.00 0.800 0.823 0.200 0.177 83.4575 83.0805 0.45% 100.00 0.900 0.907 0.100 0.093 84.4768 84.4146 0.07% 100.00 0.998 0.998 0.002 0.002 84.8843 84.8843 0.00% 100.00 1.000 1.000 0.000 0.000 84.8853 84.8853 0.00% 120.00 0.000 0.000 1.000 1.000 98.8993 98.8993 0.00% 120.00 0.002 0.003 0.998 0.997 99.0215 98.9831 0.04% 120.00 0.100 0.137 0.900 0.863 104.7995 103.1798 1.55% 120.00 0.200 0.258 0.800 0.742 110.2376 107.6130 2.38% 120.00 0.300 0.367 0.700 0.633 115.1747 112.1356 2.64% 120.00 0.400 0.467 0.600 0.533 119.5766 116.6474 2.45% 120.00 0.500 0.559 0.500 0.441 123.4131 121.0009 1.95% 120.00 0.600 0.646 0.400 0.354 126.6546 124.9944 1.31% 120.00 0.700 0.731 0.300 0.269 129.2657 128.3788 0.69% 120.00 0.800 0.816 0.200 0.184 131.1928 130.8897 0.23% 120.00 0.900 0.904 0.100 0.096 132.3437 132.3115 0.02% 120.00 0.998 0.998 0.002 0.002 132.5570 132.5569 0.00% 1.000 1.000 0.000 0.000 132.5503 132.5503 140.00 0.000 0.000 1.000 1.000 153.6232 153.6232 0.00% 140.00 0.002 0.003 0.998 0.997 153.7917 153.7485 0.03% 140.00 0.100 0.128 0.900 0.872 161.7708 159.9762 1.11% 140.00 0.200 0.244 0.800 0.756 169.2911 166.4385 1.69% 140.00 0.300 0.351 0.700 0.649 176.1079 172.8860 1.83% 140.00 0.400 0.450 0.600 0.550 182.1522 179.1450 1.65% 140.00 0.500 0.544 0.500 0.456 187.3617 184.9877 1.27% 140.00 0.600 0.634 0.400 0.366 191.6773 190.1364 0.80% 140.00 0.700 0.722 0.300 0.278 195.0356 194.2849 0.38% 140.00 0.800 0.810 0.200 0.190 197.3537 197.1419 0.11% 140.00 0.900 0.902 0.100 0.098 198.5046 198.4955 0.00% 140.00 0.998 0.998 0.002 0.002 198.2953 198.2947 0.00% 1.000 1.000 0.000 0.000 198.2752 198.2752 0.00%

[0139] The near-azeotropic Z-1233zd / HFC-43-10mee system at atmospheric pressure was also simulated. At each temperature, the model was run in increments of 0.002 across the entire range of 0 to 1 Z-1233zd liquid molar composition. Some of the combinations exhibit azeotropic or near-azeotropic properties, which are the combinations for which the applicant claims protection. For brevity, the list of combinations has been edited to reflect increments of 0.1 Z-1233zd liquid molar composition, or the boundaries of near-azeotropic behavior. The resulting list of abbreviations is shown in Table 3.3.

[0140] Table 3.3: Predicted near-azeotropic reaction of the Z-1233zd / HFC-43-10mee system at 1 Atm. Pressure (atm) Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fraction 4310 mee Vapor molar fraction 4310 mee Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 1.00 54.620 0.000 0.000 1.000 1.000 14.696 14.696 0.00% 1.00 54.555 0.002 0.004 0.998 0.996 14.696 14.678 0.12% 1.00 51.734 0.096 0.181 0.904 0.819 14.696 13.968 4.96% 1.00 51.678 0.098 0.184 0.902 0.816 14.696 13.955 5.04% 1.00 51.623 0.100 0.188 0.900 0.812 14.696 13.943 5.12% 1.00 49.075 0.200 0.337 0.800 0.663 14.696 13.475 8.31% 1.00 46.918 0.300 0.457 0.700 0.543 14.696 13.244 9.88% 1.00 45.096 0.400 0.557 0.600 0.443 14.696 13.214 10.08% 1.00 43.560 0.500 0.642 0.500 0.358 14.696 13.353 9.14% 1.00 42.266 0.600 0.717 0.400 0.283 14.696 13.624 7.29% 1.00 41.239 0.694 0.782 0.306 0.218 14.696 13.954 5.05% 1.00 41.219 0.696 0.783 0.304 0.217 14.696 13.961 5.00% 1.00 41.199 0.698 0.785 0.302 0.215 14.696 13.969 4.95% 1.00 41.179 0.700 0.786 0.300 0.214 14.696 13.976 4.90% 1.00 40.273 0.800 0.853 0.200 0.147 14.696 14.329 2.50% 1.00 39.539 0.900 0.922 0.100 0.078 14.696 14.588 0.74% 1.00 39.005 0.998 0.998 0.002 0.002 14.696 14.695 0.01% 1.00 38.996 1.000 1.000 0.000 0.000 14.696 14.696 0.00%

[0141] The data in Tables 3.2 and 3.3 are summarized in Tables 3.4 and 3.5 below. A wide range of near-azeotropic compositions (based on [(BP-VP) / BP] × 100 ≤ 5) is summarized in Table 3.4, and compositions that meet the 3% near-azeotropic criterion ([(BP-VP) / BP] × 100 ≤ 3) are summarized in Table 3.5.

[0142] Table 3.4: Summary of near-azeotropic properties of the Z-1233zd / HFC-43-10mee system.

[0143] Table 3.5: Summary of 3% near-azeotropic content in the Z-1233zd / HFC-43-10mee system.

[0144] At atmospheric pressure, near-azeotropic compositions with a molar percentage of Z-1233zd / HFC-43-10mee of 1-9 / 99-91 and 70-99 / 30-1 are predicted. Near-azeotropic compositions with a molar percentage of Z-1233zd / HFC-43-10mee of 1-5 / 99-95 and 78-99 / 22-1 are predicted at 3%.

[0145] Example 4: Z-1233zd / HFC-245fa The binary system Z-1233zd / HFC-245fa was investigated for potential azeotropic and near-azeotropic behavior. The PTx method described above was used to determine the relative volatility of this binary system. For various binary compositions, the pressure in PTx cells of known volume was measured at a constant temperature of 30°C. The collected experimental data are shown in Table 4.1 below.

[0146] Table 4.1: Experimental VLE data of the Z-1233zd / HFC-245fa system at 30℃. <![CDATA[X2]]> <![CDATA[Y2]]> Pexp (psia) Pcalc (psia) Pcalc - Pexp (psia) 0.000 0.000 25.8120 0.039 0.022 25.4290 25.3665 -0.0025 0.085 0.049 24.8830 24.8259 -0.0023 0.134 0.076 24.2920 24.2544 -0.0015 0.191 0.108 23.6040 23.5738 -0.0013 0.264 0.149 22.6980 22.6837 -0.0006 0.323 0.184 21.9630 21.9401 -0.0010 0.389 0.223 21.1220 21.0900 -0.0015 0.531 0.319 19.0760 19.1176 0.0022 0.597 0.371 18.1040 18.1387 0.0019 0.662 0.429 17.0830 17.1123 0.0017 0.731 0.501 15.9240 15.9384 0.0009 0.804 0.592 14.6430 14.6393 -0.0003 0.874 0.704 13.2870 13.2640 -0.0017 0.942 0.843 11.8760 11.8452 -0.0026 1.000 1.000 10.5540 X2 = Z-1233zd, which represents the number of liquid moles. The number of vapor moles of Y2 = Z-1233zd. P exp =The pressure measured in the experiment.

[0147] The above vapor pressure v and liquid molar fraction data (Z-1233zd) are plotted on Figure 4 In the middle. Experimental data points are in Figure 4 The solid lines represent bubble point predictions using the NRTL equation (see below). The dashed lines represent predicted dew points.

[0148] Based on these VLE data, the interaction coefficients were extracted. The NRTL model was run in increments of 20°C over a temperature range of -40°C to 140°C, and at 29.93°C. At each temperature, the model was run in increments of 0.002 over the entire range of Z-1233zd liquid molar compositions from 0 to 1. Therefore, the model was run at a total of 5511 combinations of temperature and Z-1233zd liquid molar compositions (11 temperatures × 501 compositions = 5511). Among these 5511 combinations, some exhibit near-azeotropic properties, which are the combinations claimed by the applicant. For brevity, the list of the 5511 combinations has been edited to reflect increments of 0.100 Z-1233zd liquid molar composition, or the boundaries of near-azeotropic behavior. The resulting list of abbreviations is shown in Table 4.2.

[0149] Table 4.2: Predicted near-azeotropic properties of the Z-1233zd / HFC-245fa system. Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fractions HFC-245fa Vapor molar fraction HFC-245fa Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 -40.00 0.000 0.000 1.000 1.000 0.8144 0.8144 0.00% -40.00 0.002 0.001 0.998 0.999 0.8137 0.8131 0.07% -40.00 0.100 0.053 0.900 0.947 0.7783 0.7421 4.65% -40.00 0.104 0.055 0.896 0.945 0.7768 0.7389 4.88% -40.00 0.106 0.056 0.894 0.944 0.7761 0.7373 5.00% -40.00 0.108 0.057 0.892 0.943 0.7753 0.7357 5.12% -40.00 0.200 0.101 0.800 0.899 0.7409 0.6585 11.13% -40.00 0.300 0.149 0.700 0.851 0.7019 0.5775 17.73% -40.00 0.400 0.198 0.600 0.802 0.6605 0.5073 23.19% -40.00 0.500 0.252 0.500 0.748 0.6153 0.4493 26.98% -40.00 0.600 0.316 0.400 0.684 0.5651 0.4017 28.92% -40.00 0.700 0.398 0.300 0.602 0.5084 0.3625 28.69% -40.00 0.800 0.512 0.200 0.488 0.4432 0.3299 25.56% -40.00 0.900 0.686 0.100 0.314 0.3675 0.3024 17.71% -40.00 0.978 0.911 0.022 0.089 0.2997 0.2839 5.29% -40.00 0.980 0.918 0.020 0.082 0.2979 0.2834 4.85% -40.00 0.998 0.991 0.002 0.009 0.2810 0.2795 0.53% -40.00 1.000 1.000 0.000 0.000 0.2790 0.2790 0.00% -20.00 0.000 0.000 1.000 1.000 2.7787 2.7787 0.00% -20.00 0.002 0.001 0.998 0.999 2.7762 2.7744 0.07% -20.00 0.100 0.054 0.900 0.946 2.6548 2.5384 4.39% -20.00 0.110 0.059 0.890 0.941 2.6423 2.5123 4.92% -20.00 0.112 0.060 0.888 0.940 2.6397 2.5070 5.03% -20.00 0.200 0.104 0.800 0.896 2.5271 2.2707 10.14% -20.00 0.300 0.154 0.700 0.846 2.3939 2.0119 15.96% -20.00 0.400 0.207 0.600 0.793 2.2527 1.7840 20.81% -20.00 0.500 0.265 0.500 0.735 2.1002 1.5918 24.21% -20.00 0.600 0.333 0.400 0.667 1.9325 1.4317 25.92% -20.00 0.700 0.419 0.300 0.581 1.7450 1.2980 25.61% -20.00 0.800 0.535 0.200 0.465 1.5325 1.1857 22.63% -20.00 0.900 0.707 0.100 0.293 1.2892 1.0903 15.43% -20.00 0.974 0.905 0.026 0.095 1.0855 1.0286 5.24% -20.00 0.976 0.912 0.024 0.088 1.0797 1.0271 4.87% -20.00 0.998 0.992 0.002 0.008 1.0146 1.0101 0.44% -20.00 1.000 1.000 0.000 0.000 1.0086 1.0086 0.00% 0.00 0.000 0.000 1.000 1.000 7.6333 7.6333 0.00% 0.00 0.100 0.055 0.900 0.945 7.2931 6.9946 4.09% 0.00 0.118 0.065 0.882 0.935 7.2309 6.8717 4.97% 0.00 0.120 0.066 0.880 0.934 7.2239 6.8579 5.07% 0.00 0.200 0.108 0.800 0.892 6.9425 6.3028 9.21% 0.00 0.300 0.160 0.700 0.840 6.5774 5.6344 14.34% 0.00 0.400 0.216 0.600 0.784 6.1920 5.0379 18.64% 0.00 0.500 0.278 0.500 0.722 5.7784 4.5261 21.67% 0.00 0.600 0.350 0.400 0.650 5.3276 4.0934 23.17% 0.00 0.700 0.439 0.300 0.561 4.8291 3.7277 22.81% 0.00 0.800 0.557 0.200 0.443 4.2712 3.4172 19.99% 0.00 0.900 0.727 0.100 0.273 3.6405 3.1515 13.43% 0.00 0.970 0.901 0.030 0.099 3.1479 2.9876 5.09% 0.00 0.972 0.907 0.028 0.093 3.1331 2.9832 4.79% 0.00 0.998 0.993 0.002 0.007 2.9376 2.9266 0.38% 1.000 1.000 0.000 0.000 2.9223 2.9223 0.00% 20.00 0.000 0.000 1.000 1.000 17.7440 17.7440 0.00% 20.00 0.002 0.001 0.998 0.999 17.7284 17.7172 0.06% 20.00 0.100 0.057 0.900 0.943 16.9549 16.3154 3.77% 20.00 0.200 0.112 0.800 0.888 16.1417 14.7991 8.32% 20.00 0.300 0.167 0.700 0.833 15.2965 13.3341 12.83% 20.00 0.400 0.226 0.600 0.774 14.4073 12.0106 16.64% 20.00 0.500 0.291 0.500 0.709 13.4592 10.8580 19.33% 20.00 0.600 0.367 0.400 0.633 12.4347 9.8696 20.63% 20.00 0.700 0.459 0.300 0.541 11.3136 9.0247 20.23% 20.00 0.800 0.578 0.200 0.422 10.0734 8.3003 17.60% 20.00 0.900 0.744 0.100 0.256 8.6893 7.6758 11.66% 20.00 0.964 0.893 0.036 0.107 7.7153 7.3203 5.12% 20.00 0.966 0.899 0.034 0.101 7.6836 7.3097 4.87% 20.00 0.998 0.994 0.002 0.006 7.1667 7.1438 0.32% 20.00 1.000 1.000 0.000 0.000 7.1337 7.1337 0.00% 29.93 0.000 0.000 1.000 1.000 25.7347 25.7347 0.00% 29.93 0.002 0.001 0.998 0.999 25.7122 25.6964 0.06% 29.93 0.100 0.058 0.900 0.942 24.5914 23.7058 3.60% 29.93 0.132 0.076 0.868 0.924 24.2187 23.0247 4.93% 29.93 0.134 0.077 0.866 0.923 24.1952 22.9819 5.01% 29.93 0.200 0.114 0.800 0.886 23.4135 21.5692 7.88% 29.93 0.300 0.171 0.700 0.829 22.1903 19.5038 12.11% 29.93 0.400 0.231 0.600 0.769 20.9059 17.6272 15.68% 29.93 0.500 0.298 0.500 0.702 19.5407 15.9815 18.21% 29.93 0.600 0.375 0.400 0.625 18.0715 14.5608 19.43% 29.93 0.700 0.469 0.300 0.531 16.4722 13.3397 19.02% 29.93 0.800 0.589 0.200 0.411 14.7134 12.2880 16.48% 29.93 0.900 0.753 0.100 0.247 12.7629 11.3779 10.85% 29.93 0.960 0.887 0.040 0.113 11.4861 10.8896 5.19% 29.93 0.962 0.892 0.038 0.108 11.4420 10.8740 4.96% 29.93 0.998 0.994 0.002 0.006 10.6315 10.6003 0.29% 29.93 1.000 1.000 0.000 0.000 10.5854 10.5854 40.00 0.000 0.000 1.000 1.000 36.2187 36.2187 0.00% 40.00 0.002 0.001 0.998 0.999 36.1870 36.1656 0.06% 40.00 0.100 0.059 0.900 0.941 34.6109 33.4249 3.43% 40.00 0.140 0.082 0.860 0.918 33.9549 32.2577 5.00% 40.00 0.142 0.083 0.858 0.917 33.9218 32.1991 5.08% 40.00 0.200 0.116 0.800 0.884 32.9548 30.5018 7.44% 40.00 0.300 0.175 0.700 0.825 31.2365 27.6736 11.41% 40.00 0.400 0.237 0.600 0.763 29.4360 25.0900 14.76% 40.00 0.500 0.305 0.500 0.695 27.5282 22.8091 17.14% 40.00 0.600 0.384 0.400 0.616 25.4838 20.8277 18.27% 40.00 0.700 0.479 0.300 0.521 23.2696 19.1153 17.85% 40.00 0.800 0.599 0.200 0.401 20.8490 17.6340 15.42% 40.00 0.900 0.761 0.100 0.239 18.1816 16.3474 10.09% 40.00 0.958 0.887 0.042 0.113 16.5045 15.6778 5.01% 40.00 0.960 0.892 0.040 0.108 16.4448 15.6556 4.80% 40.00 0.998 0.994 0.002 0.006 15.2863 15.2450 0.27% 40.00 1.000 1.000 0.000 0.000 15.2240 15.2240 0.00% 60.00 0.000 0.000 1.000 1.000 66.7688 66.7688 0.00% 60.00 0.002 0.001 0.998 0.999 66.7103 66.6745 0.05% 60.00 0.100 0.061 0.900 0.939 63.8046 61.8505 3.06% 60.00 0.154 0.094 0.846 0.906 62.1686 59.0973 4.94% 60.00 0.156 0.095 0.844 0.905 62.1075 58.9951 5.01% 60.00 0.200 0.122 0.800 0.878 60.7530 56.7525 6.58% 60.00 0.300 0.183 0.700 0.817 57.5940 51.8058 10.05% 60.00 0.400 0.249 0.600 0.751 54.2984 47.2405 13.00% 60.00 0.500 0.321 0.500 0.679 50.8292 43.1587 15.09% 60.00 0.600 0.402 0.400 0.598 47.1437 39.5701 16.07% 60.00 0.700 0.499 0.300 0.501 43.1938 36.4366 15.64% 60.00 0.800 0.619 0.200 0.381 38.9270 33.7028 13.42% 60.00 0.900 0.777 0.100 0.223 34.2865 31.3120 8.68% 60.00 0.948 0.874 0.052 0.126 31.9089 30.2707 5.13% 60.00 0.950 0.878 0.050 0.122 31.8075 30.2287 4.96% 60.00 0.998 0.995 0.002 0.005 29.3184 29.2517 0.23% 60.00 1.000 1.000 0.000 0.000 29.2123 29.2123 0.00% 80.00 0.000 0.000 1.000 1.000 113.6113 113.6113 0.00% 80.00 0.002 0.001 0.998 0.999 113.5114 113.4575 0.05% 80.00 0.100 0.064 0.900 0.936 108.5492 105.6388 2.68% 80.00 0.176 0.113 0.824 0.887 104.6058 99.3861 4.99% 80.00 0.178 0.114 0.822 0.886 104.5008 99.2215 5.05% 80.00 0.200 0.128 0.800 0.872 103.3418 97.4158 5.73% 80.00 0.300 0.193 0.700 0.807 97.9667 89.4034 8.74% 80.00 0.400 0.262 0.600 0.738 92.3874 81.9355 11.31% 80.00 0.500 0.337 0.500 0.663 86.5569 75.1801 13.14% 80.00 0.600 0.422 0.400 0.578 80.4199 69.1746 13.98% 80.00 0.700 0.520 0.300 0.480 73.9150 63.8800 13.58% 80.00 0.800 0.640 0.200 0.360 66.9753 59.2239 11.57% 80.00 0.900 0.793 0.100 0.207 59.5304 55.1252 7.40% 80.00 0.938 0.864 0.062 0.136 56.5536 53.6975 5.05% 80.00 0.940 0.868 0.060 0.132 56.3946 53.6242 4.91% 80.00 0.998 0.995 0.002 0.005 51.6732 51.5747 0.19% 1.000 1.000 0.000 0.000 51.5065 51.5065 100.00 0.000 0.000 1.000 1.000 181.5097 181.5097 0.00% 100.00 0.002 0.001 0.998 0.999 181.3487 181.2754 0.04% 100.00 0.100 0.068 0.900 0.932 173.3471 169.3983 2.28% 100.00 0.200 0.136 0.800 0.864 164.9587 156.9132 4.88% 100.00 0.204 0.138 0.796 0.862 164.6184 156.4152 4.98% 100.00 0.206 0.140 0.794 0.860 164.4481 156.1664 5.04% 100.00 0.300 0.205 0.700 0.795 156.3322 144.6793 7.45% 100.00 0.400 0.277 0.600 0.723 147.4334 133.1677 9.68% 100.00 0.500 0.355 0.500 0.645 138.2123 122.6421 11.27% 100.00 0.600 0.442 0.400 0.558 128.6074 113.1890 11.99% 100.00 0.700 0.542 0.300 0.458 118.5491 104.7811 11.61% 100.00 0.800 0.661 0.200 0.339 107.9624 97.3327 9.85% 100.00 0.900 0.808 0.100 0.192 96.7681 90.7369 6.23% 100.00 0.924 0.849 0.076 0.151 93.9821 89.2685 5.02% 100.00 0.926 0.853 0.074 0.147 93.7481 89.1481 4.91% 100.00 0.998 0.996 0.002 0.004 85.1302 84.9957 0.16% 100.00 1.000 1.000 0.000 0.000 84.8853 84.8853 0.00% 120.00 0.000 0.000 1.000 1.000 276.0074 276.0074 0.00% 120.00 0.002 0.001 0.998 0.999 275.7583 275.6697 0.03% 120.00 0.100 0.073 0.900 0.927 263.3647 258.5244 1.84% 120.00 0.200 0.145 0.800 0.855 250.3842 240.4131 3.98% 120.00 0.246 0.179 0.754 0.821 244.3120 232.1144 4.99% 120.00 0.248 0.180 0.752 0.820 244.0466 231.7560 5.04% 120.00 0.300 0.218 0.700 0.782 237.1040 222.5367 6.14% 120.00 0.400 0.294 0.600 0.706 223.5188 205.5642 8.03% 120.00 0.500 0.376 0.500 0.624 209.5934 189.8986 9.40% 120.00 0.600 0.465 0.400 0.535 195.2721 175.7050 10.02% 120.00 0.700 0.565 0.300 0.435 180.4862 162.9836 9.70% 120.00 0.800 0.682 0.200 0.318 165.1587 151.6417 8.18% 120.00 0.900 0.823 0.100 0.177 149.2079 141.5453 5.14% 120.00 0.902 0.826 0.098 0.174 148.8820 141.3551 5.06% 120.00 0.904 0.829 0.096 0.171 148.5557 141.1653 4.97% 120.00 0.998 0.996 0.002 0.004 132.8909 132.7203 0.13% 1.000 1.000 0.000 0.000 132.5503 132.5503 140.00 0.000 0.000 1.000 1.000 403.8797 403.8797 0.00% 140.00 0.002 0.002 0.998 0.998 403.5025 403.4156 0.02% 140.00 0.100 0.080 0.900 0.920 384.6271 379.5635 1.32% 140.00 0.200 0.158 0.800 0.842 364.8595 354.0001 2.98% 140.00 0.300 0.236 0.700 0.764 344.8410 328.5830 4.71% 140.00 0.316 0.248 0.684 0.752 341.6231 324.6035 4.98% 140.00 0.318 0.250 0.682 0.750 341.2206 324.1083 5.02% 140.00 0.400 0.316 0.600 0.684 324.6726 304.3234 6.27% 140.00 0.500 0.400 0.500 0.600 304.3601 281.8149 7.41% 140.00 0.600 0.491 0.400 0.509 283.8567 261.3120 7.94% 140.00 0.700 0.591 0.300 0.409 263.0876 242.8404 7.70% 140.00 0.800 0.705 0.200 0.295 241.9640 226.2934 6.48% 140.00 0.866 0.791 0.134 0.209 227.7826 216.3456 5.02% 140.00 0.868 0.793 0.132 0.207 227.3495 216.0555 4.97% 140.00 0.900 0.839 0.100 0.161 220.3917 211.5016 4.03% 140.00 0.998 0.996 0.002 0.004 198.7235 198.5256 0.10% 1.000 1.000 0.000 0.000 198.2752 198.2752 0.00%

[0150] For the Z-1233zd / HFC-245fa system, the model was run at atmospheric pressure in increments of 0.002 for the liquid molar percentage range of Z = 1233zd from 0 to 1. Abbreviated results are listed in Table 4.3, showing compositions that meet the near-azeotropic criterion ([(BP-VP) / BP] × 100 ≤ 5). Results are given in liquid molar increments of 0.100, up to the point where the criterion is not met.

[0151] Table 4.3: Near azeotropic properties of the Z-1233zd / HFC245fa system at 1 Atm. Pressure (atm) Temperature (°C) Liquid molar fraction Z-1233zd Vapor molar fraction Z-1233zd Liquid molar fractions HFC-245fa Vapor molar fraction HFC-245fa Bubble point pressure (psia) Dew point pressure (psia) [(BP-DP) / BP]× 100 1.00 15.222 0.000 0.000 1.000 1.000 14.6960 14.6960 0.00% 1.00 15.244 0.002 0.001 0.998 0.999 14.6960 14.6865 0.06% 1.00 16.358 0.100 0.056 0.900 0.944 14.6960 14.1328 3.83% 1.00 16.670 0.126 0.071 0.874 0.929 14.6960 13.9630 4.99% 1.00 16.694 0.128 0.072 0.872 0.928 14.6960 13.9496 5.08% 1.00 17.598 0.200 0.111 0.800 0.889 14.6960 13.4580 8.42% 1.00 18.969 0.300 0.167 0.700 0.833 14.6960 12.7996 12.90% 1.00 20.514 0.400 0.226 0.600 0.774 14.6960 12.2585 16.59% 1.00 22.289 0.500 0.293 0.500 0.707 14.6960 11.8936 19.07% 1.00 24.377 0.600 0.370 0.400 0.630 14.6960 11.7423 20.10% 1.00 26.890 0.700 0.466 0.300 0.534 14.6960 11.8462 19.39% 1.00 29.987 0.800 0.588 0.200 0.412 14.6960 12.2729 16.49% 1.00 33.905 0.900 0.756 0.100 0.244 14.6960 13.1456 10.55% 1.00 36.686 0.958 0.885 0.042 0.115 14.6960 13.9403 5.14% 1.00 36.790 0.960 0.890 0.040 0.110 14.6960 13.9725 4.92% 1.00 38.880 0.998 0.994 0.002 0.006 14.6960 14.6559 0.27% 1.00 38.996 1.000 1.000 0.000 0.000 14.6960 14.6960 0.00%

[0152] The data in Tables 4.2 and 4.3 are summarized in Tables 4.4 and 4.5 below. A wide range of near-azeotropic compositions (based on [(BP-VP) / BP] × 100 ≤ 5) is summarized in Table 4.4, and compositions that meet the 3% near-azeotropic criterion ([(BP-VP) / BP] × 100 ≤ 3) are summarized in Table 4.5.

[0153] Table 4.4: Summary of near-azeotropic properties of the Z-1233zd / HFC-245fa system.

[0154] Table 4.5: Summary of 3% near-azeotropic content in the Z-1233zd / HFC-245fa system.

[0155] Near-azeotropic compositions with a predicted liquid molar percentage of Z-1233zd at atmospheric pressure of 1-12 / 99-88 and 96-99 / 4-1 are predicted. Near-azeotropic compositions with a predicted liquid molar percentage of 3% are also predicted at 1-8 / 99-92 and 98-99 / 2-1.

[0156] All references cited in this article are included in their entirety.

[0157] Those skilled in the art will understand that the invention is not limited to the specific embodiments described herein, but extends to all its equivalents, variations and extensions.

Claims

1. An azeotropic composition comprising 39.5 mol% to 42.1 mol% of Z-1233zd and 57.9 mol% to 60.5 mol% of dimethoxymethane, wherein Z-1233zd and dimethoxymethane form an azeotropic mixture at a vapor pressure of 18.33 psia to 45.44 psia and a temperature of 50°C to 80°C.

2. The azeotropic composition according to claim 1, comprising: 39.5 mol% Z-1233zd and 60.5 mol% dimethoxymethane form an azeotropic mixture at a vapor pressure of 18.33 psia and a temperature of 50 °C. 40.3 mol% Z-1233zd and 59.7 mol% dimethoxymethane form an azeotropic mixture at a vapor pressure of 25.37 psia and a temperature of 60 °C. 41.1 mol% Z-1233zd and 58.9 mol% dimethoxymethane form an azeotropic mixture at a vapor pressure of 34.31 psia and a temperature of 70 °C, or 42.1 mol% Z-1233zd and 57.9 mol% dimethoxymethane form an azeotropic mixture at a vapor pressure of 45.44 psia and a temperature of 80 °C.

3. A near-azeotropic composition comprising 40 liquid mol% Z-1233zd and 60 liquid mol% dimethoxymethane at a temperature of 40°C to 140°C.

4. The composition according to any one of claims 1 to 3, further comprising additives selected from the group consisting of: lubricants, pour point modifiers, defoamers, viscosity modifiers, emulsifiers, dispersants, oxidation inhibitors, extreme pressure agents, corrosion inhibitors, detergents, catalysts, surfactants, flame retardants, preservatives, colorants, antioxidants, reinforcing agents, fillers, antistatic agents, solubilizers, IR attenuators, nucleating agents, cell control agents, extrusion aids, stabilizers, heat insulation agents, plasticizers, viscosity modifiers, impact modifiers, gas barrier resins, polymer modifiers, rheology modifiers, antibacterial agents, vapor pressure regulators, ultraviolet absorbers, crosslinking agents, permeability regulators, bittering agents, propellants, and acid traps.

5. A method for forming foam, comprising: (a) Adding a foamable composition to a foaming agent; and, (b) Reacting the foamable composition under conditions that effectively form foam. The foaming agent comprises the composition according to any one of claims 1 to 3.

6. A foam formed by the method according to claim 5.

7. A foam comprising a polymer and the composition according to any one of claims 1 to 3.

8. A premixed composition comprising a foamable component and a foaming agent, wherein the foaming agent comprises the composition according to any one of claims 1 to 3.

9. A method for generating refrigeration, comprising: (a) Condensing the composition according to any one of claims 1 to 3; as well as, (b) Evaporate the composition near the body to be cooled.

10. A heat transfer system comprising a heat transfer medium, wherein the heat transfer medium comprises the composition according to any one of claims 1 to 3.

11. A method of cleaning a surface, comprising contacting the surface with the composition according to any one of claims 1 to 3.

12. An aerosol product comprising a component to be dispensed and a propellant, wherein the propellant comprises a composition according to any one of claims 1 to 3.

13. A method for extinguishing or suppressing a flame, comprising dispensing the composition according to any one of claims 1 to 3 at the flame.

14. A system for preventing or suppressing flames, comprising a container containing a composition according to any one of claims 1 to 3 and a nozzle for distributing the composition toward a desired or actual location of the flame.

15. A method for dissolving a solute, comprising contacting and mixing the solute with a sufficient amount of the composition according to any one of claims 1 to 3.

16. A method for preventing or rapidly quenching discharges in a space within a high-voltage device, comprising injecting a gaseous dielectric into the space, wherein the gaseous dielectric comprises a composition according to any one of claims 1 to 3.

17. A high-voltage device comprising a gaseous dielectric, wherein the gaseous dielectric comprises the composition according to any one of claims 1 to 3.

18. The high-voltage device according to claim 17, wherein the device is selected from transformers, circuit breakers, switches and radar waveguides.

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