Compositions and uses of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene

Abstract

To provide compositions having utility in numerous applications, and uses thereof.SOLUTION: Disclosed herein are: mixtures of the compound Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene, HFO, HFC, HFE, CFC, CO2, olefin, organic acid, alcohol, hydrocarbon, ether, aldehyde, ketone, and others such as methyl formate, formic acid, trans-1,2 dichloroethylene, carbon dioxide and cis-HFO-1234ze+HFO-1225yez, and water; mixtures of these and CO2; mixtures of these trans 1,2-dichloroethylene (DCE); mixtures of these and methyl formate; mixtures with cis-HFO-1234ze+CO2; mixtures with cis-HFO-1234ze+HFO-1225yez+CO2; mixtures with cis-HFO-1234ze+HFC-245fa; and mixtures including at least one compound selected from the group consisting of azeotropes and azeotrope-like compositions. Also disclosed are methods of using the compositions as blowing agents, solvents, heat transfer compositions, aerosol propellant compositions, and fire extinguishing and suppressant compositions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 547,518, filed August 18, 2017, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present disclosure relates to compositions, methods, and systems that have utility in many applications, specifically the use of compositions containing the compound Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd). [Background technology]

[0003] Over the past several decades, many industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide variety of applications, including as aerosol propellants, refrigerants, cleaning agents, blowing agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and displacement drying agents. In the search for alternatives to these versatile compounds, many industries have focused on the use of hydrofluorocarbons (HFCs). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Provisional Patent Application No. 62 / 547,518 Summary of the Invention [Problem to be solved by the invention]

[0005] HFCs are of concern because, while they do not contribute to stratospheric ozone depletion, they do contribute to the "greenhouse effect," i.e., global warming. As a result, HFCs have come under scrutiny and their widespread use may be restricted in the future. Therefore, there is a need for compositions that do not contribute to stratospheric ozone depletion and also have a low global warming potential (GWP). [Means for solving the problem]

[0006] Provided herein are compositions, methods, and systems that have utility in many applications, specifically the use of compositions containing the compound Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) having the following structure:

[0007] [ka]

[0008] Embodiments of the present invention include the compound Z-HCFO-1224yd, alone or in combination with one or more other compounds described in detail herein below. Mixtures containing the compound Z-HCFO-1224yd can be azeotropic, azeotrope-like, or non-azeotropic (non-azeotropic).

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be limiting. [Brief explanation of the drawings]

[0010] [Figure 1] Figure 1 shows the vapor pressure measured for the binary system Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) and Z-1-chloro-2,3,3,3-tetrafluoropropene (Z-HCFO-1224yd) in a PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 2] Figure 1 shows the vapor pressure measured for the binary system of Z-HCFO-1224yd and methyl formate versus composition in a PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 3] Figure 1 shows the vapor pressure measured for the binary system E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd) and Z-HCFO-1224yd in a PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 4] Figure 1 shows the vapor pressure measured for the binary system E-HFO-1336mzz and Z-HCFO-1224yd versus composition in the PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 5] Figure 1 shows the vapor pressure measured for the binary system E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) and Z-HCFO-1224yd versus composition in a PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the data calculated using the NRTL equation. [Figure 6] 1 shows the vapor pressure measured for the binary system of Z-HCFO-1224yd and HFC-245eb versus composition in a PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 7]Figure 1 shows the vapor pressure measured for the binary system Z-HCFO-1224yd and HCFO-1233xf versus composition in the PTx sample cell. Experimental data points are shown as black dots, and the solid line is drawn from the calculated data using the NRTL equation. [Figure 8] 1 shows the K coefficient at 75° F. as a function of time for mixtures prepared according to the procedure described in Example 15. [Figure 9] 1 shows the K coefficient at 50° F. as a function of time for mixtures prepared according to the procedure described in Example 15. [Figure 10] 1 shows the K coefficient at 35° F. as a function of time for mixtures prepared according to the procedure described in Example 15. [Figure 11] 1 shows the K coefficient at 25° F. as a function of time for mixtures prepared according to the procedure described in Example 15. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hydrochlorofluoroolefins have low global warming potential and are not believed to contribute to stratospheric ozone depletion. One such hydrochlorofluoroolefin is 1-chloro-2,3,3,3-tetrafluoroprop-1-ene. 1-Chloro-2,3,3,3-tetrafluoroprop-1-ene exists as two different stereoisomers, each with a different boiling point, which may perform differently in different applications.

[0012] Provided herein are compositions comprising the hydrochlorofluoroolefin 1-chloro-2,3,3,3-tetrafluoroprop-1-ene (CFCF=CHCl, HCFO-1224yd), specifically compositions comprising the Z isomer Z-HCFO-1224yd.

[0013] In some embodiments, the composition comprises the compound Z-HCFO-1224yd and at least one additional fluoroalkene, such as a fluoroalkene containing 2 to 6, e.g., 3 to 5, or 3 to 4 carbon atoms. In some embodiments, the fluoroalkene comprises at least one carbon-carbon double bond. In some embodiments, the fluoroalkene comprises 3 carbon atoms and at least one carbon-carbon double bond. The fluoroalkene compounds described herein, when they contain at least one hydrogen, may be referred to herein as hydrofluoroolefins or "HFOs."

[0014] In some embodiments, the composition includes Z-HCFO-1224yd and at least one additional compound, such as an HFO, HFC, hydrofluoroether (HFE), hydrocarbon, ether, aldehyde, ketone, or the like, such as methyl formate, formic acid, trans-1,2-dichloroethylene (DCE), carbon dioxide (CO), cis-HFO-1234ze and HFO-1225yez, mixtures thereof with water, mixtures thereof with CO, mixtures thereof with DCE, mixtures thereof with methyl formate, mixtures of cis-HFO-1234ze and CO, mixtures of cis-HFO-1234ze and HFO-1225yez and CO, and mixtures of cis-HFO-1234ze and HFC-245fa. In such compositions, the amount of the compound Z-HCFO-1224yd can vary, including in all cases where it constitutes the remainder of the composition after taking into account all other components in the composition.

[0015] In some embodiments, Z-HCFO-1224yd comprises about 1% to about 99% by weight, about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight of the composition.

[0016] The compositions provided herein are environmentally acceptable and do not contribute to the depletion of the Earth's stratospheric ozone layer. In some embodiments, the compounds and compositions provided herein have no substantial ozone depletion potential (ODP), e.g., an ODP of about 0.5 or less, e.g., an ODP of about 0.25 or less, or an ODP of about 0.1 or less. In some embodiments, the compounds and compositions provided herein have a global warming potential (GWP) of about 150 or less, e.g., a GWP of about 50 or less.

[0017] As used herein, ODP is defined in the World Meteorological association report "Scientific Assessment of Ozone Depletion, 2002," which is incorporated herein by reference. As used herein, GWP is defined for the global warming of carbon dioxide over a 100-year period and is defined in the same document as ODP.

[0018] In some embodiments, Z-HCFO-1224yd is mixed with one or more compounds to form a blend composition. In some embodiments, Z-HCFO-1224yd forms a blend composition with one or more of HFOs, HFEs, hydrocarbons, alcohols, ethers, aldehydes, ketones, or other compounds, such as water, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene, CO, and others. In some embodiments, the other compounds comprise from about 1% to about 99% by weight of the composition. For example, about 1% by weight to about 90% by weight, about 1% by weight to about 80% by weight, about 1% by weight to about 70% by weight, about 1% by weight to about 60% by weight, about 1% by weight to about 50% by weight, about 1% by weight to about 40% by weight, about 1% by weight to about 30% by weight, about 1% by weight to about 20% by weight, about 1% by weight to about 10% by weight, about 1% by weight to about 5% by weight, about 5% by weight to about 99% by weight, about 5% by weight to about 95% by weight, about 5% by weight to about 75% by weight, about 5% by weight to about 50% by weight, about 5% by weight to about 25% by weight, about 10% by weight to about 99% by weight , about 10% by weight to about 90% by weight, about 10% by weight to about 75% by weight, about 10% by weight to about 50% by weight, about 10% by weight to about 25% by weight, about 25% by weight to about 99% by weight, about 25% by weight to about 90% by weight, about 25% by weight to about 75% by weight, about 25% by weight to about 50% by weight, about 40% by weight to about 60% by weight, about 45% by weight to about 55% by weight, about 50% by weight to about 99% by weight, about 50% by weight to about 75% by weight, about 60% by weight to about 99% by weight, about 60% by weight to about 75% by weight, or about 75% by weight to about 99% by weight.

[0019] In some embodiments, Z-HCFO-1224yd forms a blend composition with the compounds shown in Table 1 below (all percentages are weight percent and are understood to be preceded by the word "about").

[0020] [Table 1-1]

[0021] [Table 1-2]

[0022] [Table 1-3]

[0023] [Table 1-4]

[0024] [Table 1-5]

[0025] [Table 1-6]

[0026] foaming agent Also provided herein are methods and systems that include Z-HCFO-1224yd as a blowing agent, optionally in conjunction with one or more additional compounds, including, but not limited to, other compounds that also act as blowing agents (hereinafter, for convenience and not by way of limitation, referred to as co-blowing agents), surfactants, polyols, catalysts, flame retardants, polymer modifiers, colorants, dyes, solubility enhancers, rheology modifiers, plasticizers, fillers, nucleating agents, viscosity reducers, vapor pressure modifiers, stabilizers, etc. In some embodiments, the blowing agent used in foams, such as spray foams and panel foams, includes a blend of Z-HCFO-1224yd with hydrocarbons (e.g., pentanes, including cyclopentane), and one or more of HFC-245fa, HFC-365mfc, and HCFO-1233zd.

[0027] In some embodiments, when used as a blowing agent, Z-HCFO-1224yd comprises about 1 wt% to about 99 wt%, about 30 wt% to about 99 wt%, about 50 wt% to about 99 wt%, about 75 wt% to about 99 wt%, about 85 wt% to about 99 wt%, about 20 wt% to about 80 wt%, about 90 wt% to about 99 wt%, about 95 wt% to about 99 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 40 wt%, about 1 wt% to about 50 wt%, about 5 wt% to about 20 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 60 wt%, about 10 wt% to about 80 wt%, about 10 wt% to about 90 wt%, about 20 wt% to about 80 wt%, or about 20 wt% to about 90 wt% of the blowing agent composition. Other amount ranges are shown in Table 1 and described above, and these amounts are equally applicable to this use of the compositions of the present invention.

[0028] In some embodiments, dispersants, cell stabilizers, surfactants, and other additives are also incorporated into the blowing agent composition. Certain surfactants are optional but may be added to function as cell stabilizers. Suitable stabilizers include polysiloxane polyoxyalkylene block copolymers, such as those disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, each of which is incorporated herein by reference. Representative materials, typically polysiloxane polyoxyalkylene block copolymers, are sold under the names DC-193, B-8404, and L-5340. Other optional additives for the blowing agent mixture include flame retardants such as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, alumina trihydrate, polyvinyl chloride, etc. With regard to nucleating agents, all known compounds and materials with nucleating functionality, including talc, are available for use in the present invention.

[0029] In some embodiments, other compounds and / or ingredients are included in the composition that modify certain properties of the composition (e.g., cost, etc.), and the presence of such compounds and ingredients is within the broad scope of the present invention.

[0030] In some embodiments, co-blowing agents according to the present invention include physical blowing agents, chemical blowing agents (which in some embodiments include water), or blowing agents having a combination of properties of physical and chemical blowing agents.

[0031] A wide variety of co-blowing agents can be used in accordance with the present invention. In some embodiments, the blowing agent compositions of the present invention comprise one or more HFCs as co-blowing agents, such as one or more C1-C4 HFCs, and / or one or more hydrocarbons, such as C4-C6 hydrocarbons. In some embodiments, the blowing agent compositions comprise an HFC selected from one or more of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and all isomers of all such HFCs.

[0032] In some embodiments, the blowing agent composition includes one or more hydrocarbons, such as iso-, normal-, and / or cyclopentane for thermoset foams, and butane or isobutane for thermoplastic foams. Other materials may be included, such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such as dichloroethylene (e.g., dichloroethylene (e.g., trans-1,2-dichloroethylene), ethyl chloride, and chloropropane), HCFCs, C1-C5 alcohols (e.g., ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including dimethyl ether and diethyl ether), diethers (e.g., dimethoxymethane and diethoxymethane), and methyl formate (including any combination thereof). In some embodiments, such components are not included due to their negative environmental impact.

[0033] In some embodiments, one or more of the following HFC isomers are used as co-blowing agents in the compositions of the present invention: 1,1,1,2,2-Pentafluoroethane (HFC-125) 1,1,2,2-Tetrafluoroethane (HFC-134) 1,1,1,2-Tetrafluoroethane (HFC-134a) 1,1-difluoroethane (HFC-152a) 1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea) 1,1,1,3,3,3-Hexafluoropropane (HFC-236fa) 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-Pentafluorobutane (HFC-365mfc).

[0034] In some embodiments, the relative amounts of any of the above additional co-blowing agents, as well as any additional components that may be included in the present compositions, may vary widely within the general broad scope of the present invention according to the particular application of the composition, and all such relative amounts are considered to be within the scope of the present invention.

[0035] In some embodiments, the blowing agent composition comprises at least one co-blowing agent and Z-HCFO-1224yd in an amount sufficient to produce a blowing agent composition that is generally non-flammable.

[0036] In some embodiments, the blowing agent composition includes Z-HCFO-1224yd in a wide range of amounts, hi some embodiments, the Z-HCFO-1224yd is present in an amount of at least about 1% by weight of the composition, e.g., at least about 5% by weight, or about 15% by weight.

[0037] In some embodiments, the blowing agent composition comprises at least about 50% by weight of Z-HCFO-1224yd. In some embodiments, the blowing agent consists essentially of Z-HCFO-1224yd. In some embodiments, one or more co-blowing agents may be used. In some embodiments, water is used either as a co-blowing agent or in combination with other co-blowing agents (e.g., pentane, especially cyclopentane).

[0038] In some embodiments, the blowing agent composition comprises about 30% to about 95% by weight of Z-HCFO-1224yd and about 5% to about 90% by weight, e.g., about 5% to about 65% by weight, of a co-blowing agent. In some embodiments, the co-blowing agent comprises HO, HFCs, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof. In some embodiments, the co-blowing agent consists essentially of HO, HFCs, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof.

[0039] In some embodiments, the co-blowing agent comprises HO. In some embodiments, the composition comprises HO in an amount of from about 5% to about 50% by weight of the total blowing agent composition, e.g., from about 10% to about 40% by weight, or from about 10% to about 20% by weight of the total blowing agent.

[0040] In some embodiments, the co-blowing agent comprises CO. In some embodiments, the composition comprises CO in an amount of from about 5% to about 60% by weight of the total blowing agent composition, e.g., from about 20% to about 50% by weight, or from about 40% to about 50% by weight of the total blowing agent.

[0041] In some embodiments, the co-blowing agent comprises an alcohol, such as a C2, C3, and / or C4 alcohol. In some embodiments, the composition comprises the alcohol in an amount of from about 5% to about 40% by weight of the total blowing agent composition, e.g., from about 10% to about 40% by weight, or from about 15% to about 25% by weight of the total blowing agent.

[0042] In some embodiments, the composition includes one or more HFC co-blowing agents, such as a C2, C3, C4, or C5 HFC. In some embodiments, the composition includes a difluoroethane, such as HFC-152a, for example, in an extruded thermoplastic material. In some embodiments, the composition includes a pentafluoropropane, such as HFC-245. In some embodiments, the HFC co-blowing agent is present in the composition in an amount of from about 5% to about 80% by weight of the total blowing agent composition, e.g., from about 10% to about 75% by weight, or from about 25% to about 75% by weight of the total blowing agent. In some embodiments, the HFC is a C2-C4 HFC. In some embodiments, the HFC is a C3 HFC. In some embodiments, the HFC is a pentafluorinated C3 HFC, e.g., HFC-245fa.

[0043] In some embodiments, the composition includes an HC co-blowing agent. In some embodiments, the HC co-blowing agent is a C3, C4, or C5HC. In some embodiments, the HC is present in the composition in an amount of from about 5% to about 80% by weight of the total blowing agent composition, for example, from about 20% to about 60% by weight of the total blowing agent.

[0044] Foamable composition Foamable compositions are provided herein. As known to those skilled in the art, foamable compositions generally include one or more components capable of forming a foam. As used herein, the term "foam foaming agent" refers to a component or combination of components capable of forming a foam structure, e.g., a generally cellular foam structure. The foamable compositions provided herein include such a component and a blowing agent compound. In some embodiments, the blowing agent compound is Z-HCFO-1224yd.

[0045] In some embodiments, the foamable composition comprises Z-HCFO-1224yd and one or more components, such as HFO-1234ye-E, Z-HFO-1234ye, HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1336mcyf, E-HFO-1336mzz, Z-HFO-1336mzz, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-14 38ezy, Z-HFO-1438ezy, E-HFO-1438mzz, Z-HFO-1438mzz, E-HCFO-1233zd, Z-HCFO-1233zd, HFC-32, HFC- 134, HFC-134a, HFC-152a, HFC-227ea, HFC-236ea, HFC-245ca, HFC-245cb, HFC-245ea, HFC-245fa, HFC-3 and one or more components selected from among 65MFC, HFC-43-10MEE, 2-methylbutane, 2-methylpentane, 3-methylpentane, butane, cyclobutane, cyclohexane, cyclopentane, cyclopropane, diethyl ether, dimethoxyethane, dimethoxymethane, dimethyl ether (DME), ethanol, isohexane (2-methylpentane), isobutane, isopentane (2-methylbutane), isopropanol, methanol, methylcyclopentane, methyl ethyl ether (methoxyethane), neohexane (2,2-dimethylbutane), neopentane, n-hexane, pentane, propane, CO2, ethyl formate, methyl acetate, methyl formate, methylal, trans-1,2-dichloroethylene, and cis-1,2 dichloroethylene.In some embodiments, the foamable composition comprises Z-HCFO-1224yd and one or more components selected from HFO-1234yf, E-HFO-234ze, E-HFO-1336mzz, Z-HFO-1336mzz, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, E-HFO-1438mzz, HFC-134, HFC-134a, HFC-152a, butane, cyclobutane, cyclopentane, cyclopropane, dimethyl ether (DME), ethanol, isobutane, isopentane (2-methylbutane), pentane, propane, CO2, methyl acetate, and methyl formate. In some embodiments, the composition is used as a blowing agent for expanding thermoplastic foam. In some embodiments, the foam is polystyrene foam.

[0046] In some embodiments, the amount of Z-HCFO-1224yd in the foamable composition is about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1, and these amounts are equally applicable to the foamable compositions provided herein.

[0047] In some embodiments, the one or more components capable of forming a foam include a thermosetting composition capable of forming a foam and / or a foamable composition. Examples of thermosetting compositions also include polyurethane and polyisocyanurate foam compositions, as well as phenolic foam compositions. In some embodiments, this reaction and foaming process is enhanced by the use of various additives, such as catalysts and surfactant materials that function to control and adjust cell size and stabilize the foam structure during formation. In some embodiments, any one or more of the additional components described above with respect to the blowing agent compositions described herein are incorporated into the foamable compositions described herein. In such thermosetting foam embodiments, one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as part of a two- or more-part foamable composition, which may include one or more components that can react and / or foam under appropriate conditions to form a foam or cell structure.

[0048] In some embodiments, the one or more foamable components comprise a thermoplastic material, such as a thermoplastic polymer and / or resin. Examples of thermoplastic foam components include polyolefins, such as monovinyl aromatic compounds of the formula Ar--CH=CH2, where Ar is a benzene-based aromatic hydrocarbon group, such as polystyrene (PS). Other examples of suitable polyolefin resins include various ethylene resins, including ethylene homopolymers and copolymers, such as polyethylene, polypropylene (PP), and polyethylene terephthalate (PET). In some embodiments, the thermoplastic foamable composition is an extrudable composition.

[0049] Any currently known and available methods and systems for forming foams can be readily adapted for use in connection with the present invention. For example, in some embodiments, the methods of the present invention involve incorporating a blowing agent according to the present invention into a foamable or foam-forming composition and then foaming the composition. In some embodiments, the methods include a step or series of steps, including causing a volumetric expansion of the blowing agent according to the present invention.

[0050] In some embodiments, systems and equipment currently used for incorporating and foaming blowing agents can be readily adapted for use in accordance with the present invention. One advantage of the present invention is that it provides an improved blowing agent that is generally compatible with existing foaming methods and systems.

[0051] Thus, those skilled in the art will appreciate that the present invention encompasses methods and systems for foaming all types of foams, including thermoset foams, thermoplastic foams, and formed-in-place foams. In some embodiments, the blowing agents are used in conjunction with conventional foaming equipment, such as polyurethane foaming equipment, under conventional processing conditions. Thus, the methods of the present invention include polyol premix-type operations, blend-type operations, third-stream blowing agent addition, and foam head blowing agent addition.

[0052] With respect to thermoplastic foams, in some embodiments, the method comprises introducing a blowing agent according to the present invention into a thermoplastic material, e.g., a thermoplastic polymer such as a polyolefin, and then subjecting the thermoplastic material to conditions effective to foam it. In some embodiments, the step of introducing the blowing agent into the thermoplastic material comprises introducing the blowing agent into a screw extruder containing the thermoplastic material. In some embodiments, the foaming step comprises reducing pressure on the thermoplastic material, thereby allowing the blowing agent to expand and contribute to foaming the material.

[0053] Those skilled in the art will understand, particularly in light of the disclosure contained herein, that the order and manner in which the blowing agents of the present invention are formed and / or added to the foamable composition generally does not affect the operability of the present invention. For example, in the case of extrudable foams, in some embodiments, the various components of the blowing agent, as well as the components of the foamable composition, are not mixed prior to introduction into the extrusion equipment. In some embodiments, the components are not added at the same location within the extrusion equipment. In some embodiments, the blowing agent is introduced either directly or as part of a premix, and then further added to other portions of the foamable composition.

[0054] In some embodiments, one or more components of the blowing agent are introduced at a first location in the extruder that is upstream of where one or more other components of the blowing agent are added, with the expectation that the components will combine in the extruder and / or function more effectively in this manner. In some embodiments, two or more components of the blowing agent are precombined and introduced together into the foamable composition, either directly or as part of a premix, and then further added to other portions of the foamable composition.

[0055] Azeotropes and Azeotrope-Like Compositions Also provided herein are azeotropic and azeotrope-like compositions comprising Z-1-chloro-2,3,3,3-tetrafluoropropene (Z-HCFO-1224yd) and additional compounds. These compositions have near-zero ozone depletion potential (ODP) and low global warming potential. These compositions are useful as aerosol propellants, refrigerants, cleaning agents, blowing agents ("blowing agents") for making thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, solvents, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and displacement drying agents.

[0056] Binary azeotropic or azeotrope-like compositions of substantially constant-boiling mixtures can be characterized in a number of ways, depending on selected conditions. For example, it is well known to those skilled in the art that at different pressures, the composition of a given azeotrope or azeotrope-like composition will vary, at least to some extent, as will the boiling point temperature. Thus, an azeotropic or azeotrope-like composition of two compounds represents a unique type of relationship, but with a composition that varies with temperature and / or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes and azeotrope-like compositions.

[0057] An "azeotropic" composition refers to a constant-boiling liquid mixture of two or more substances that behaves as a single substance. In some embodiments, an azeotropic composition is characterized in that the vapor generated by partial evaporation or distillation of a liquid has the same composition as the liquid from which the vapor was evaporated or distilled, i.e., the mixture distills / refluxes without a change in composition. In some embodiments, a constant-boiling composition is characterized as azeotropic because it exhibits either a maximum or minimum boiling point compared to a non-azeotropic mixture of the same components. In some embodiments, an azeotropic composition is characterized in that the vapor pressure of the mixture is either minimum or maximum relative to the vapor pressure of the undiluted components at a constant temperature.

[0058] An "azeotrope-like" composition refers to a constant-boiling or substantially constant-boiling liquid mixture of two or more substances that behaves as a single substance. In some embodiments, an azeotrope-like composition may be characterized in that the vapor generated by partial evaporation or distillation of a liquid has substantially the same composition as the liquid from which the vapor was evaporated or distilled, i.e., the mixture distills / refluxes without a substantial change in composition. In some embodiments, an azeotrope-like composition may be characterized in that the bubble point vapor pressure and dew point vapor pressure of the composition at a particular temperature are substantially the same. In some embodiments, an azeotrope-like composition may be characterized by the area adjacent to the maximum or minimum vapor pressure in a plot of the vapor pressure of the composition at a given temperature as a function of the mole fraction of the components in the composition.

[0059] In one embodiment, a composition is recognized in the art as azeotrope-like if, after removal of 50 percent by weight of the composition, such as by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after removal of 50 percent by weight of the original composition is less than about 10 percent, as measured in absolute units. Absolute units refer to measurements of pressure, such as psia, atmospheres, bar, torr, dynes per square centimeter, millimeters of mercury, inches of water, and other equivalent terms known in the art. When an azeotrope exists, there is no difference in vapor pressure between the original composition and the composition remaining after removal of 50 percent by weight of the original composition.

[0060] For azeotropic compositions, in some embodiments, there exists a range of compositions around the azeotropic point, with the highest boiling point azeotrope having a higher boiling point at a particular pressure than the pure components of the composition at that pressure and a lower vapor pressure at a particular temperature than the pure components of the composition at that temperature, and the lowest boiling point azeotrope having a lower boiling point at a particular pressure than the pure components of the composition at that pressure and a higher vapor pressure at a particular temperature than the pure components of the composition at that temperature. Boiling points and vapor pressures above or below the pure components are caused by unexpected intermolecular forces between the molecules of the composition, which can be a combination of repulsive and attractive forces such as van der Waals forces and hydrogen bonding.

[0061] In some embodiments, the range of compositions having the highest or lowest boiling points at a particular pressure, or the highest or lowest vapor pressure at a particular temperature, may or may not be coextensive with the range of compositions whose vapor pressure changes by less than about 10% when 50 weight percent of the composition evaporates. If the range of compositions having the highest or lowest boiling points at a particular pressure, or the highest or lowest vapor pressure at a particular temperature, is broader than the range of compositions whose vapor pressure changes by less than about 10% when 50 weight percent of the composition evaporates, the unexpected intermolecular forces are nevertheless considered important in that refrigerant compositions having intermolecular forces that are not substantially constant boiling may exhibit unexpected increases in capacity or efficiency relative to the components of the refrigerant composition.

[0062] It is recognized in the art that when an azeotropic liquid composition is subjected to boiling at various pressures, both the boiling point and the amount of each component of the azeotropic composition can change. Thus, in some embodiments, an azeotropic composition can be defined in terms of a unique relationship that exists between the components, or in terms of the exact amount of each component that results in a composition characterized by a constant boiling point at a particular pressure. In some embodiments, an azeotrope or azeotrope-like composition of two compounds can be characterized by defining the composition as characterized by its boiling point at a given pressure, thereby providing a distinguishing feature without unduly limiting the scope of the invention with a specific numerical composition, which is limited, but only as accurate, by available analytical equipment.

[0063] It is recognized in the art that a system is defined as forming an azeotrope-like composition when its relative volatility approaches 1.0. Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The ratio of the mole fraction of a component in the vapor to the mole fraction of the component in the liquid is the volatility of the component.

[0064] To determine the relative volatility of any two compounds, a method known as the PTx method can be used. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for different compositions of the two compounds. The use of the PTx method is described in detail in "Phase Equilibrium in Process Design," Wiley-Interscience Publishers, 1970, by Harold R. Null, pp. 124-126, which is incorporated herein by reference.

[0065] These measurements can be converted to equilibrium vapor and liquid compositions in a PTx cell using an activity coefficient equation model, such as the non-random two-liquid (NRTL) equation, to describe a liquid-phase nonideal system. The use of activity coefficient equations, such as the NRTL equation, is described in detail in "The Properties of Gases and Liquids," 4th Edition, McGraw Hill, by Reid, Prausnitz, and Poling, pp. 241-387, and "Phase Equilibria in Chemical Engineering," Butterworth Publishers, 1985, by Stanley M. Walas, pp. 165-244, both of which are incorporated herein by reference. Without wishing to be bound by any theory or explanation, it is believed that the NRTL equation, in conjunction with PTx cell data, is capable of adequately predicting the relative volatility of the Z-HFO-1224yd-containing compositions of the present invention and, therefore, the behavior of these mixtures in multistage separation equipment, such as distillation columns.

[0066] As used herein, an "effective amount" is the amount of each component of the compositions provided herein that, when combined, forms an azeotropic or azeotrope-like composition. This definition includes the amounts of each component, which may vary depending on the pressure applied to the composition, so long as the azeotropic or azeotrope-like composition continues to exist at different pressures (although the boiling points may differ). Thus, an effective amount includes the amount (which may be expressed, for example, by weight) of each component of the compositions of the present invention that forms an azeotropic or azeotrope-like composition at temperatures or pressures other than those described herein.

[0067] In some embodiments, the azeotrope or azeotrope-like composition is a mixture of Z-HCFO-1224yd and methyl formate, methyl ethyl ether, diethyl ether, cyclobutane, isopentane (2-methylbutane), ethylene oxide, Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), E ... Butene (E-HFO-1336mzz), Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd), E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd), Z-1,1,1,4,4,5,5,5-octafluoro-2-pentene (Z-HFO-1439mzz), E-1,1,1,4,4,5,5,5-octafluoro -2-Pentene (E-HFO-1439mzz), 1,1,1,2,3-Pentafluoropropane (HFC-245eb), E-HFO-1234ye, Z-HFO-1234ye, Z-HFO-1234ze, HFO-1243yf, HFO-1336mcyf, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, Z-HFO1438ezy, and one or more components selected from E-HFO-1438mzz, HCFO-1233xf, HFC-236ea, HFC-245fa, HFC-356mff, HFC-245ca, HFC-245ea, HCFC-123, CFC-11, HFE-236eaEbg, HFE-E347mmyl, and HFE-1-methoxyheptafluoropropane (hfe-7000).

[0068] In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and methyl formate. In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1,1,1,4,4,5,5,5-octafluoro-2-pentene (Z-HFO-1439mzz). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1439mzz). In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HCFO-1224yd and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0069] In some embodiments, Z-HCFO-1224yd is from about 1 mol % to about 99 mol % of the azeotrope or azeotrope-like composition, e.g., from about 1 mol % to about 2 mol %, 1 mol % to about 3 mol %, 1 mol % to about 4 mol %, 1 mol % to about 6 mol %, 1 mol % to about 8 mol %, 1 mol % to about 10 mol %, 1 mol % to about 11 mol %, 1 mol % to about 12 mol %, 1 mol % to about 15 mol %, 1 mol % to about 20 mol %, 1 mol % to about 15 mol %, 1 mol % to about 16 mol %, 1 mol % to about 18 mol %, 1 mol % to about 29 mol %, 1 mol % to about 30 mol %, 1 mol % to about 31 mol %, 1 mol % to about 32 mol %, 1 mol % to about 35 mol %, 1 mol % to about 36 mol %, 1 mol % to about 37 mol %, 1 mol % to about 38 mol %, 1 mol % to about 39 mol %, 1 mol % to about 40 mol %, 1 mol % to about 42 mol %, 1 mol % to about 45 mol %, 1 mol % to about 46 mol %, 1 mol % to about 48 mol %, 1 mol % to about 49 mol %, 1 mol % to about 50 mol %, 1 mol % to about 51 mol %, 1 mol % to about mol% to about 22 mol%, 5 mol% to about 6 mol%, 5 mol% to about 8 mol%, 5 mol% to about 10 mol%, 5 mol% to about 11 mol%, 5 mol% to about 12 mol%, 5 mol% to about 15 mol%, 5 mol% to about 20 mol%, 5 mol% to about 22 mol%, 5 mol% to about 95 mol%, 38 mol% to about 95 mol%, 38 mol% to about 99 mol%, 49 mol% to about 95 mol%, 49 mol% to about 99 mol%, 50 mol% to about 95 mol%, 50 mol% to about 99 mol%, 53 mol% % to about 95 mol%, 53 mol% to about 99 mol%, 55 mol% to about 95 mol%, 55 mol% to about 99 mol%, 58 mol% to about 95 mol%, 58 mol% to about 99 mol%, 60 mol% to about 95 mol%, 60 mol% to about 99 mol%, 62 mol% to about 95 mol%, 62 mol% to about 99 mol%, 69 mol% to about 95 mol%, 69 mol% to about 99 mol%, 70 mol% to about 95 mol%, 70 mol% to about 99 mol%, 74 mol% to about 95 mol%, 74 mol% to about 99 mol%, 76 mol% to about 95 mol%, 76 mol% to about 99 mol%, 80 mol% to about 95 mol%, 80 mol% to about 99 mol%, 81 mol% to about 95 mol%, 81 mol% to about 99 mol%, 84 mol% to about 95 mol%, 84 mol% to about 99 mol%, 86 mol% to about 95 mol%, 86 mol% to about 99 mol%, 88 mol% to about 95 mol%, 88 mol% to about 99 mol%, 89 mol% to about 95 mol%, or 89 mol% to about 99 mol%.In some embodiments, Z-HCFO-1224yd constitutes about 66 mol%, 67 mol%, 68 mol%, 69 mol%, 70 mol%, 71 mol%, 72 mol%, 73 mol%, 74 mol%, 75 mol%, 76 mol%, 77 mol%, 78 mol%, 79 mol%, 80 mol%, 81 mol%, 82 mol%, 83 mol%, 84 mol%, 85 mol%, 86 mol%, 87 mol%, 88 mol%, 89 mol%, 90 mol%, 91 mol%, 92 mol%, 93 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, or 99 mol% of the azeotrope or azeotrope-like composition.

[0070] In some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed in a temperature range of about −40° C. to about 130° C. In some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed at temperatures of about −40° C., −30° C., −20° C., −10° C., 0° C., 10° C., 20° C., 30° C., 31.7° C., 31.75° C., 31.8° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., or about 130° C.

[0071] In some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed at pressures of about 0.98 psia (130 kPa) to about 333 psia (2296 kPa). In some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed at pressures of about 0.98 psia, 1.84 psia, 3.23 psia, 5.37 psia, 8.48 psia, 12.87 psia, 18.84 psia, 26.75 psia, 28.37 psia, 37.02 psia, 50.09 psia, 66.46 psia, 86.71 psia, 111.45 psia, 141.40 psia, 177.37 psia, 220.34 psia, 271.53 psia, or 332.68 psia. In some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed at pressures of about 1 atm to about 31 atm, hi some embodiments, azeotropes or azeotrope-like compositions comprising Z-HCFO-1224yd are formed at pressures of about 1 atm, 2 atm, 3 atm, 4 atm, 5 atm, 6 atm, 7 atm, 8 atm, 9 atm, 10 atm, 11 atm, 12 atm, 13 atm, 14 atm, 15 atm, 16 atm, 17 atm, 18 atm, 19 atm, 20 atm, 21 atm, 22 atm, 23 atm, 24 atm, 25 atm, 26 atm, 27 atm, 28 atm, 29 atm, 30 atm, or 31 atm.

[0072] In some embodiments, the azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) methyl formate. In some embodiments, the azeotrope-like composition consists essentially of (i) 5 to 95 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 5 to 95 mole % methyl formate at a temperature of −40° C. to about 140° C. In some embodiments, the azeotrope-like composition consists essentially of (i) 85 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 15% methyl formate at 20° C. In some embodiments, the azeotrope-like composition is as shown in Table 12A or 12B.

[0073] In some embodiments, the azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1-chloro-3,3,3-trifluoropropene (E-1233yd). In some embodiments, the azeotrope-like composition consists essentially of (i) 5 to 95 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 5 to 95 mole % E-1-chloro-3,3,3-trifluoropropene (E-1233yd) at a temperature of −40° C. to about 140° C. In some embodiments, the azeotrope-like composition is as shown in Table 13.

[0074] In some embodiments, the azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz). In some embodiments, the azeotrope-like composition consists essentially of (i) 5 to 95 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 5 to 95 mole % E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) at a temperature of −40° C. to about 140° C. In some embodiments, the azeotrope-like composition is as shown in Table 14A or 14B.

[0075] In some embodiments, the azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz). In some embodiments, the azeotrope-like composition consists essentially of (i) 1 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) at −40 to about 140° C. In some embodiments, (i) 1 to 12 mol % and 89 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 11 mol % and 88 to 99 mol % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) at a temperature of 20° C. In some embodiments, the azeotrope-like compositions are as shown in Table 15A or 15B.

[0076] In some embodiments, the azeotrope composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). In some embodiments, the azeotrope composition consists essentially of 16 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and 84 mole % 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) at a temperature of 31.8° C.

[0077] The azeotrope or azeotrope-like compositions provided herein can be prepared by any convenient method. In some embodiments, the azeotrope or azeotrope-like compositions are prepared by mixing or combining the desired amounts. In some embodiments, the azeotrope or azeotrope-like compositions are prepared by weighing the desired amounts of the components and then combining them in a suitable container.

[0078] Specific examples illustrating the present invention are set forth below in the Examples. Unless otherwise specified herein, all percentages are by weight. It should be understood that these examples are merely illustrative and should not be construed as limiting the scope of the present invention in any way.

[0079] Use of the composition The compositions provided herein can be used in a wide variety of applications as replacements for compositions containing CFCs and less desirable HCFCs. In some embodiments, the compositions are useful as blowing agents, refrigerants, heating agents, power cycle agents, cleaning agents, aerosol propellants, sterilants, lubricants, flavoring and fragrance extracts, flammability reducing agents, and flame suppressants. Each of these uses is described in more detail below.

[0080] Method for forming foam Provided herein are methods for forming foams, such as panel foams and spray foams. In some embodiments, the foams are made from polyurethanes and polyisocyanurates. In some embodiments, the methods include providing a blowing agent composition described herein, adding the blowing agent composition (directly or indirectly) to a foamable composition, and reacting the foamable composition under conditions effective to form a foam or cellular structure, as is well known in the art. Any of the methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Vols. I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, incorporated herein by reference, can be used or adapted for use in accordance with foam embodiments of the present invention.

[0081] In some embodiments of the method, the amount of Z-HCFO-1224yd in the composition is about 1% by weight to about 99% by weight, e.g., about 30% by weight to about 99% by weight, about 50% by weight to about 99% by weight, about 75% by weight to about 99% by weight, about 85% by weight to about 99% by weight, about 20% by weight to about 80% by weight, about 90% by weight to about 99% by weight, about 95% by weight to about 99% by weight, about 1% by weight to about 20% by weight, about 1% by weight to about 40% by weight, about 1% by weight to about 50% by weight, about 5% by weight to about 20% by weight, about 5% by weight to about 40% by weight, about 5% by weight to about 60% by weight, about 10% by weight to about 80% by weight, about 10% by weight to about 90% by weight, about 20% by weight to about 80% by weight, or about 20% by weight to about 90% by weight. Other amount ranges are shown in Table 1, and these amounts are equally applicable to the methods provided herein.

[0082] In some embodiments, the blowing agent compositions provided herein comprise Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and one or more compounds selected from Z-1,1,1,4,4,4-hexafluoro-2-butene, E-1,1,1,4,4,4-hexafluoro-2-butene, and E-1-chloro-3,3,3-trifluoropropene.

[0083] In some embodiments, the blowing agent compositions provided herein comprise Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0084] In some embodiments, the blowing agent compositions provided herein comprise Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0085] In some embodiments, the blowing agent compositions provided herein comprise Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene.

[0086] In some embodiments, the blowing agent compositions provided herein further comprise water.

[0087] In some embodiments, the method includes preparing a polyurethane or polyisocyanurate foam by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents comprising one or more of the compositions of the present invention, and other ingredients, such as a catalyst, a surfactant, and optionally, a flame retardant, a colorant, or other additives.

[0088] In some embodiments, the components of polyurethane or polyisocyanurate foams are provided in a pre-blended formulation. In some embodiments, the foam formulation is pre-blended into two components. In some embodiments, the isocyanate, and optionally certain surfactants and blowing agents, comprise a first component, commonly referred to as the "A" component. In some embodiments, the polyol or polyol mixture, surfactants, catalysts, blowing agents, flame retardants, and other isocyanate-reactive components comprise a second component, commonly referred to as the "B" component. In some embodiments, polyurethane or polyisocyanurate foams are readily prepared by combining the A and B components by hand mixing in small batches and by mechanical mixing techniques to form blocks, slabs, laminates, pour-in-place panels and other articles, spray-applied foams, foams, and the like. In some embodiments, other components, such as flame retardants, colorants, auxiliary blowing agents, and even other polyols, are added as one or more additional streams to the mix head or reaction site. In some embodiments, these are all incorporated into a single B component as described above.

[0089] In some embodiments, the present application provides a composition that is a blend of an A-side composition provided herein and a B-side composition provided herein.

[0090] In some embodiments, the composition that is a blend of A-side and B-side comprises a blowing agent component that is a blend of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0091] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0092] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0093] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0094] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0095] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0096] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0097] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0098] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0099] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0100] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0101] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0102] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0103] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0104] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0105] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0106] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0107] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0108] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0109] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.113 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.158 Btu·in / ft 2 Indicates the K factor in °F.

[0110] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.113 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.119 Btu·in / ft 2 Indicates the K factor in °F.

[0111] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.137 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.143 Btu·in / ft 2In some embodiments, the foam exhibits a K-factor of about 0.137 Btu·in / ft at a temperature of about 20° F. for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.143 Btu·in / ft 2 Indicates the K factor in °F.

[0112] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.143 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.149 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.143 Btu·in / ft at a temperature of about 20° F. for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.149 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.143 Btu·in / ft at a temperature of about 20° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.149 Btu·in / ft 2 Indicates the K factor in °F.

[0113] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.150 Btu in / ft at a temperature of about 20°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.150 Btu·in / ft at a temperature of about 20° F. for up to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.150 Btu·in / ft at a temperature of about 20° F. for about 60 days to about 120 days after the foam is formed.2 ·h·°F ~ approx. 0.156Btu·in / ft 2 Indicates the K factor in °F.

[0114] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.116 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.122 Btu·in / ft 2 Indicates the K factor in °F.

[0115] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.116 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.119 Btu·in / ft 2 Indicates the K factor in °F.

[0116] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.137 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.143 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.137 Btu·in / ft at a temperature of about 35° F for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.143 Btu·in / ft 2 Indicates the K factor in °F.

[0117] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.145 Btu in / ft at a temperature of about 35°F.2 ·h·°F~approx. 0.151 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.145 Btu·in / ft at a temperature of about 35° F. for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.151 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.145 Btu·in / ft at a temperature of about 35° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.151 Btu·in / ft 2 Indicates the K factor in °F.

[0118] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.152 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.159 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.152 Btu·in / ft at a temperature of about 35° F. for up to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.159 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.152 Btu·in / ft at a temperature of about 35° F. for about 60 days to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.159 Btu·in / ft 2 Indicates the K factor in °F.

[0119] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.122 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.165 Btu·in / ft 2 Indicates the K factor in °F.

[0120] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.122 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.126 Btu·in / ft 2 Indicates the K factor in °F.

[0121] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.144 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 50°F for up to about 30 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 Indicates the K factor in °F.

[0122] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.150 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.155 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.150 Btu·in / ft at a temperature of about 50° F. for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.155 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.150 Btu·in / ft at a temperature of about 50° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.155 Btu·in / ft 2Indicates the K factor in °F.

[0123] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.158 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.158 Btu·in / ft at a temperature of about 50° F. for up to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.158 Btu·in / ft at a temperature of about 50° F. for about 60 days to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 Indicates the K factor in °F.

[0124] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.132 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.175 Btu·in / ft 2 Indicates the K factor in °F.

[0125] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.132 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.137 Btu·in / ft 2 Indicates the K factor in °F.

[0126] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.155 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.161 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.155 Btu·in / ft at a temperature of about 75°F for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.161 Btu·in / ft 2 Indicates the K factor in °F.

[0127] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.164 Btu in / ft at a temperature of about 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.164 Btu·in / ft at a temperature of about 75°F for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.164 Btu·in / ft at a temperature of about 75°F for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 Indicates the K factor in °F.

[0128] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.168 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.172 Btu·in / ft 2In some embodiments, the foam exhibits a K-factor of about 0.168 Btu·in / ft at a temperature of about 75°F for up to about 90 days after the foam is formed. 2 ·h·°F~approx. 0.172 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.168 Btu·in / ft at a temperature of about 75°F for about 60 days to about 90 days after the foam is formed. 2 ·h·°F~approx. 0.172 Btu·in / ft 2 Indicates the K factor in °F.

[0129] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.170 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.175 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.170 Btu·in / ft at a temperature of about 75°F for up to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.175 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.170 Btu·in / ft at a temperature of about 75°F for about 90 days to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.175 Btu·in / ft 2 Indicates the K factor in °F.

[0130] In some embodiments, the composition that is a blend of A-side and B-side comprises a blowing agent component that is a blend of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0131] In some embodiments, the composition that is a blend of A-side and B-side comprises a blowing agent component that is a blend of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0132] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0133] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0134] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0135] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0136] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0137] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0138] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0139] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0140] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0141] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0142] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0143] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0144] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0145] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0146] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0147] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0148] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0149] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1,1,1,4,4,4-hexafluoro-2-butene.

[0150] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.111 Btu in / ft at a temperature of about 20° F. 2 ·h·°F ~ approx. 0.144Btu·in / ft 2 Indicates the K factor in °F.

[0151] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.110 Btu in / ft at a temperature of about 20°F. 2 ·h·°F ~ approx. 0.114Btu·in / ft 2 Indicates the K factor in °F.

[0152] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.127 Btu in / ft at a temperature of about 20°F. 2 ·h·°F ~ approx. 0.131Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.127 Btu·in / ft at a temperature of about 20° F. for up to about 30 days after the foam is formed. 2 ·h·°F ~ approx. 0.131Btu·in / ft 2 Indicates the K factor in °F.

[0153] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.138 Btu in / ft at a temperature of about 20°F. 2 ·h·°F ~ approx. 0.134Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.138 Btu·in / ft at a temperature of about 20° F. for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.134Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.138 Btu·in / ft at a temperature of about 20° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.134Btu·in / ft 2 Indicates the K factor in °F.

[0154] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.140 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.145 Btu·in / ft 2In some embodiments, the foam exhibits a K-factor of about 0.140 Btu·in / ft at a temperature of about 20° F. for up to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.140 Btu·in / ft at a temperature of about 20° F. for about 60 days to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 Indicates the K factor in °F.

[0155] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.115 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.150 Btu·in / ft 2 Indicates the K factor in °F.

[0156] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.115 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.119 Btu·in / ft 2 Indicates the K factor in °F.

[0157] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.131 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.135 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.131 Btu·in / ft at a temperature of about 35° F for up to about 30 days after the foam is formed. 2·h·°F~approx. 0.135 Btu·in / ft 2 Indicates the K factor in °F.

[0158] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.138 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.142 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.138 Btu·in / ft at a temperature of about 35° F. for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.142 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.138 Btu·in / ft at a temperature of about 20° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.142 Btu·in / ft 2 Indicates the K factor in °F.

[0159] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.146 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.152 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.146 Btu·in / ft at a temperature of about 35° F. for up to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.152 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.146 Btu·in / ft at a temperature of about 35° F. for about 60 days to about 120 days after the foam is formed. 2 ·h·°F~approx. 0.152 Btu·in / ft 2 Indicates the K factor in °F.

[0160] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.120 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 Indicates the K factor in °F.

[0161] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.120 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.124 Btu·in / ft 2 Indicates the K factor in °F.

[0162] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.137 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.141 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.137 Btu·in / ft at a temperature of about 50°F for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.141 Btu·in / ft 2 Indicates the K factor in °F.

[0163] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.144 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 50° F. for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 50° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 Indicates the K factor in °F.

[0164] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.152 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.152 Btu·in / ft at a temperature of about 50° F for up to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.152 Btu·in / ft at a temperature of about 50° F. for about 60 days to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 Indicates the K factor in °F.

[0165] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.130 Btu in / ft at a temperature of about 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 Indicates the K factor in °F.

[0166] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a viscosity of about 0.130 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.135 Btu·in / ft 2 Indicates the K factor in °F.

[0167] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.148 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.153 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.148 Btu·in / ft at a temperature of about 75°F for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.153 Btu·in / ft 2 Indicates the K factor in °F.

[0168] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.155 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.161 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.155 Btu·in / ft at a temperature of about 75°F for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.161 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.155 Btu·in / ft at a temperature of about 75°F for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.161 Btu·in / ft 2 Indicates the K factor in °F.

[0169] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene, has a foam yield of about 0.164 Btu in / ft at a temperature of about 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.164 Btu·in / ft at a temperature of about 75°F for up to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.164 Btu·in / ft at a temperature of about 75°F for about 60 days to about 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 Indicates the K factor in °F.

[0170] In some embodiments, the composition that is a blend of A-side and B-side comprises a blowing agent component that is a blend of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene.

[0171] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0172] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0173] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0174] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0175] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0176] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0177] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0178] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0179] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0180] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0181] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0182] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0183] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0184] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 10 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0185] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 5 weight percent to about 7 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0186] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 10 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0187] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 11 weight percent to about 13 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0188] In some embodiments, the composition that is a blend of A-side and B-side comprises from about 13 weight percent to about 15 weight percent Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 6 weight percent to about 8 weight percent E-1-chloro-3,3,3-trifluoropropene.

[0189] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.109 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 Indicates the K factor in °F.

[0190] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.109 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.113 Btu·in / ft 2 Indicates the K factor in °F.

[0191] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.132 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.136 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.132 Btu·in / ft at a temperature of about 20° F. for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.136 Btu·in / ft 2 Indicates the K factor in °F.

[0192] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.140 Btu in / ft at a temperature of about 20°F. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.140 Btu·in / ft at a temperature of about 20° F. for up to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.140 Btu·in / ft at a temperature of about 20° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F~approx. 0.145 Btu·in / ft 2 Indicates the K factor in °F.

[0193] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.112 Btu in / ft at a temperature of about 35°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 Indicates the K factor in °F.

[0194] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.112 Btu in / ft at a temperature of about 35°F. 2 ·h·°F ~ approx. 0.116Btu·in / ft 2 Indicates the K factor in °F.

[0195] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.135 Btu in / ft at a temperature of about 35°F. 2 ·h·°F~approx. 0.139 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.135 Btu·in / ft at a temperature of about 35° F. for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.139 Btu·in / ft 2 Indicates the K factor in °F.

[0196] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.144 Btu in / ft at a temperature of about 35°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 35° F. for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 35° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 Indicates the K factor in °F.

[0197] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.116 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.155 Btu·in / ft 2 Indicates the K factor in °F.

[0198] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.116 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.118 Btu·in / ft 2 Indicates the K factor in °F.

[0199] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.135 Btu in / ft at a temperature of about 50°F. 2 ·h·°F~approx. 0.139 Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.135 Btu·in / ft at a temperature of about 50° F. for up to about 30 days after the foam is formed. 2 ·h·°F~approx. 0.139 Btu·in / ft 2 Indicates the K factor in °F.

[0200] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.144 Btu in / ft at a temperature of about 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 50° F. for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.144 Btu·in / ft at a temperature of about 50° F. for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 Indicates the K factor in °F.

[0201] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.128 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.166 Btu·in / ft 2 Indicates the K factor in °F.

[0202] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.128 Btu in / ft at a temperature of about 75°F. 2 ·h·°F~approx. 0.132 Btu·in / ft 2 Indicates the K factor in °F.

[0203] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.152 Btu in / ft at a temperature of about 75°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.152 Btu·in / ft at a temperature of about 75°F for up to about 30 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 Indicates the K factor in °F.

[0204] In some embodiments, a foam prepared from the blowing agent composition described herein, Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1-chloro-3,3,3-trifluoropropene, has a foam density of about 0.162 Btu in / ft at a temperature of about 75°F. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2In some embodiments, the foam exhibits a K-factor of about 0.162 Btu·in / ft at a temperature of about 75°F for up to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2 In some embodiments, the foam exhibits a K-factor of about 0.162 Btu·in / ft at a temperature of about 75°F for about 30 days to about 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2 Indicates the K factor in °F.

[0205] In some embodiments, the composition that is a blend of the A-side and the B-side further comprises water.

[0206] In some embodiments, the composition that is a blend of the A-side and the B-side further comprises from about 1 weight percent to about 5 weight percent water.

[0207] In some embodiments, the composition that is a blend of the A-side and the B-side further comprises from about 1 weight percent to about 3 weight percent water.

[0208] In some embodiments, the composition that is a blend of the A-side and the B-side further comprises from about 1 weight percent to about 2 weight percent water.

[0209] In some embodiments of the methods and systems provided herein, a one-component foam containing a blowing agent according to the present invention is formed. In some embodiments, the foam is a polyurethane foam containing a blowing agent according to the present invention. In some embodiments, a portion of the blowing agent is contained in the foam-forming agent, for example, by dissolving it in the foam-forming agent, which is liquid at the pressure in the vessel, and a second portion of the blowing agent exists as a separate gas phase. In such systems, the contained / dissolved blowing agent acts primarily to cause the expansion of the foam, and the separate gas phase acts to provide a driving force for the foam-forming agent.

[0210] In some embodiments, the one-component system is packaged in a container such as an aerosol can. In some embodiments, a blowing agent described herein provides foam expansion. In some embodiments, a blowing agent described herein provides energy for transporting the foam / foamable material from the package. In some embodiments, a blowing agent described herein provides energy for foam expansion and for transporting the foam / foamable material from the package. In some embodiments, such systems and methods include filling a package with a fully formulated system (e.g., an isocyanate / polyol system) and incorporating a gaseous blowing agent according to the present invention into the package, e.g., an aerosol can.

[0211] In some embodiments, it is desirable to utilize the present compositions when in the supercritical or near supercritical state as blowing agents.

[0212] Also provided herein are foams, including, but not limited to, closed-cell foams, open-cell foams, spray foams, panel foams, rigid foams, flexible foams, integral skins, and the like, prepared from polymeric foam formulations containing a blowing agent comprising or consisting essentially of Z-HCFO-1224yd, alone or in combination with one or more other compounds.

[0213] One advantage of foams according to the present invention, e.g., thermoset foams such as polyurethane foams, is their ability to achieve excellent thermal performance. In some embodiments, thermal performance is measured, for example, by K-factor or lambda under low temperature conditions. The foams provided herein, such as the thermoset foams provided herein, can be used in a wide variety of applications. In some embodiments, the foams include appliance foams, including refrigerator foams, freezer foams, freezer / freezer foams, panel foams, and other low-temperature or cryogenic manufacturing applications.

[0214] In some embodiments, the foams provide one or more advantageous features, characteristics, and / or properties, including thermal insulation efficiency (particularly for thermoset foams), dimensional stability, compressive strength, and thermal insulation aging, in addition to the low ozone depletion potential and low global warming potential associated with many of the blowing agents described herein. In some embodiments, thermoset foams are provided that include such foams formed into foam articles, which exhibit improved thermal conductivity when compared to foams made with the same amount of the same blowing agent (or a commonly used blowing agent such as HFC-245fa) but without Z-HCFO-1224yd.

[0215] In some embodiments, the foams exhibit improved mechanical properties compared to foams made using blowing agents outside the scope of the present invention. In some embodiments, utilizing a blowing agent comprising cyclopentane provides foams and foam articles having compressive strengths that are at least about 10 relative percent or at least about 15 relative percent higher than foams made under substantially the same conditions.

[0216] In some embodiments, foams made according to the methods provided herein have compressive strengths comparable to those produced commercially by making foams under substantially the same conditions except that the blowing agent consists of HFC-245fa. In some embodiments, the foams provided herein exhibit compressive strengths of at least about 12.5% ​​yield (parallel and perpendicular directions) or at least about 13% yield in each of such directions.

[0217] Methods and systems Table 1 above lists compositions comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the compositions are useful in connection with many methods and systems, including heat transfer fluids in heat transfer methods and systems, such as refrigeration, air conditioning, including vehicle air conditioning systems, and refrigerants used in heat pump systems. In some embodiments, the compositions are useful in aerosol-generating systems and methods, such as those that comprise or consist of aerosol propellants in such systems and methods. In some embodiments, methods for forming foams and methods for fire extinguishing and suppression are also provided. In some embodiments, methods for removing residue from articles in which the present compositions are used as solvent compositions in such methods and systems are provided.

[0218] Heat Transfer Method Provided herein are methods of transferring heat using the compositions provided herein. In some embodiments, the heat transfer method includes providing a composition comprising or consisting essentially of Z-HCFO-1224yd and transferring heat to or from the composition to change the phase of the composition. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is a blend set forth in Table 1. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is a blend set forth in Table 2 below. In some embodiments, the method provides cooling by absorbing heat from a fluid or item, such as by evaporating the refrigerant composition in the vicinity of the body or fluid to be cooled to produce a vapor comprising or consisting essentially of Z-HCFO-1224yd.

[0219] In some embodiments of the heat transfer method, the composition is a blend of Z-HCFO-1224yd and one or more additional compounds. In some embodiments of the heat transfer method, Z-HCFO-1224yd forms a blend composition with one or more of HFOs, HFEs, hydrocarbons, alcohols, ethers, aldehydes, ketones, or other compounds, such as water, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene, CO, and others. In some embodiments of the heat transfer method, the other compounds comprise from about 1% to about 99% by weight of the composition. For example, about 1% by weight to about 90% by weight, about 1% by weight to about 80% by weight, about 1% by weight to about 70% by weight, about 1% by weight to about 60% by weight, about 1% by weight to about 50% by weight, about 1% by weight to about 40% by weight, about 1% by weight to about 30% by weight, about 1% by weight to about 20% by weight, about 1% by weight to about 10% by weight, about 1% by weight to about 5% by weight, about 5% by weight to about 99% by weight, about 5% by weight to about 95% by weight, about 5% by weight to about 75% by weight, about 5% by weight to about 50% by weight, about 5% by weight to about 25% by weight, about 10% by weight to about 99% by weight , about 10% by weight to about 90% by weight, about 10% by weight to about 75% by weight, about 10% by weight to about 50% by weight, about 10% by weight to about 25% by weight, about 25% by weight to about 99% by weight, about 25% by weight to about 90% by weight, about 25% by weight to about 75% by weight, about 25% by weight to about 50% by weight, about 40% by weight to about 60% by weight, about 45% by weight to about 55% by weight, about 50% by weight to about 99% by weight, about 50% by weight to about 75% by weight, about 60% by weight to about 99% by weight, about 60% by weight to about 75% by weight, or about 75% by weight to about 99% by weight.

[0220] In some embodiments of the heat transfer method, the composition comprising Z-HCFO-1224yd is a blend composition with the compounds set forth in Table 2 below (all percentages are weight percent and are understood to be preceded by the word "about").

[0221] [Table 2-1]

[0222] [Table 2-2]

[0223] [Table 2-3]

[0224] [Table 2-4]

[0225] [Table 2-5]

[0226] [Table 2-6]

[0227] [Table 2-7]

[0228] In some embodiments, the method further includes compressing the refrigerant vapor, for example, in a compressor or similar equipment, to produce a vapor of the composition at a relatively high pressure. In some embodiments, the compressing step results in the addition of heat to the vapor, thereby increasing the temperature of the relatively high-pressure vapor. In some embodiments, the method includes removing from this relatively high-temperature, high-pressure vapor at least a portion of the heat added by the evaporation and compression steps. In some embodiments, the heat removal step includes condensing the high-temperature, high-pressure vapor while the vapor is still at a relatively high pressure to produce a relatively high-pressure liquid comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, this relatively high-pressure liquid then undergoes a nominally isenthalpic pressure reduction to produce a relatively low-temperature, low-pressure liquid. In some embodiments, it is this reduced-temperature refrigerant liquid that is then vaporized by heat transferred from the body or fluid being cooled.

[0229] In some embodiments, the compositions provided herein are used in a method of producing refrigeration comprising evaporating a refrigerant comprising or consisting essentially of Z-HCFO-1224yd in the vicinity of a liquid or body to be cooled. In some embodiments, the refrigerant comprising or consisting essentially of Z-HCFO-1224yd is a blend set forth in Table 2.

[0230] In some embodiments, the compositions provided herein are used in a method for producing heating, comprising condensing a refrigerant comprising or consisting essentially of Z-HCFO-1224yd in the vicinity of a liquid or body to be heated. In some embodiments, the refrigerant comprising or consisting essentially of Z-HCFO-1224yd is a blend set forth in Table 2. In some embodiments, the method is similar to the refrigeration cycle described above, except that the primary objective is to release heat in a condenser instead of recovering heat in an evaporator.

[0231] In some embodiments of the heat transfer method, Z-HCFO-1224yd constitutes about 1% to about 99% by weight of the composition, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 2 and are equally applicable to this use of the compositions of the present invention.

[0232] Refrigerant compositions and systems In some embodiments, the methods, systems, and compositions comprising or consisting essentially of Z-HCFO-1224yd are suitable for use in connection with air conditioning systems and devices, including automotive air conditioning systems, commercial refrigeration systems and devices (including medium- and low-temperature refrigeration systems and transport refrigeration), chillers, residential refrigerators and freezers, residential and window air conditioners, chillers, and general air conditioning systems, including heat pumps. In some embodiments, the composition is a blend as set forth in Table 2. In some embodiments, the condenser temperature ranges from about 20°C to about 55°C. In some embodiments, the evaporator temperature ranges from >0°C to 15°C for air conditioners, about -15°C to 0°C for heat pumps, about -20°C to 5°C for medium-temperature refrigeration, and about -45°C to -20°C for low-temperature refrigeration. This includes high-temperature heat pumps (condenser temperatures greater than about 55°C, 70°C, or 100°C), etc.

[0233] Many existing refrigeration systems are currently adapted for use with existing refrigerants, and the compositions of the present invention are believed to be adaptable for use in many such systems, with or without system modifications. In some embodiments, the compositions of the present invention offer advantages as replacements in systems currently based on refrigerants with relatively high capacities. In some embodiments, such compositions offer potential advantages when it is desirable to use the low-capacity refrigerant compositions of the present invention to replace higher-capacity refrigerants for efficiency reasons, for example. Thus, in some embodiments, compositions comprising or consisting essentially of Z-HCFO-1224yd are used as replacements for existing refrigerants such as CFC-11, CFC-12, CFC-113, CFC-114 or CFC-114a, HCFC-123, HCFC-22, HFC-134a, HFC-236fa, HFC-245fa, R-404A, R-407C, R-407A, R-407F, R-407H, R410A, and R507, among others. In some embodiments, the compositions comprising or consisting essentially of Z-HCFO-1224yd are blends set forth in Table 2. In some embodiments, the refrigerants of the present invention potentially enable the beneficial use of larger positive displacement compressors, thereby providing greater energy efficiency than other refrigerants, such as HCFC-123 or HFC-134a. Thus, the refrigerant compositions of the present invention, particularly those comprising or consisting essentially of Z-HCFO-1224yd, offer the potential to achieve competitive advantages on an energy basis for refrigerant replacement applications.

[0234] In some embodiments, the refrigerant composition is an azeotrope of azeotrope-like compositions comprising Z-HCFO-1224yd and one or more additional components. In some embodiments, the refrigerant composition is an azeotrope of azeotrope-like compositions comprising Z-HCFO-1224yd and one or more additional components selected from E-HFO-1234ye, Z-HFO-1234ye, Z-HFO-1234ze, HFO-1336mcyf, E-HFO-1336mzz, Z-HFO-1336mzz, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, E-HFO-1438mzz, E-HCFO-1233zd, HFC-236ea, HFC-245fa, HFC-245ca, HFC-245ea, HCFC-123, and CFC-11. In some embodiments, the refrigerant composition is an azeotrope of an azeotrope-like composition comprising Z-HCFO-1224yd and one or more additional components selected from among Z-HFO-1234ye, E-HFO-1336mzz, Z-HFO-1336mzz, HFC-236ea, HFC-245fa, HFC-245ca, HFC-245ea, HCFC-123, and CFC-11. In some embodiments, the azeotrope or azeotrope-like composition is used as a refrigerant for a centrifugal or positive displacement chiller. In some embodiments, the azeotrope or azeotrope-like composition is used as a refrigerant in a flooded evaporator.

[0235] In some embodiments, the azeotrope or azeotrope-like composition is used as a replacement refrigerant. In some embodiments, the azeotrope or azeotrope-like composition is used as a replacement refrigerant in chillers designed for CFC-114 or HFC-236fa. In some embodiments, the azeotrope or azeotrope-like composition comprises Z-HFO-1224yd and one or more additional components selected from E-HFO-1234ye, Z-HFO-1234ze, HFO-1243yf, HFO-1336mcyf, E-HFO-1336mzz, E-HFO-1336ze, HFC-236ea, HFC-236fa, and CFC-114.

[0236] In some embodiments, the refrigerant compositions provided herein comprise Z-HCFO-1224yd in an amount of at least about 50% by weight of the composition, such as at least about 70% by weight.

[0237] In some embodiments, the compositions provided herein include other components to enhance or provide specific functionality to the composition, or in some cases to reduce the cost of the composition. In some embodiments, the refrigerant compositions provided herein, e.g., those used in vapor compression systems, include a lubricant. In some embodiments, the lubricant is present in an amount of about 5 to about 50% by weight of the composition, e.g., about 30 to about 50% by weight of the composition. In some embodiments, the composition also includes a compatibilizer, such as propane, to aid in the compatibility and / or solubility of the lubricant. In some embodiments, compatibilizers, including propane, butane, and pentane, are present in an amount of about 0.5 to about 5% by weight of the composition.

[0238] In some embodiments, a combination of surfactants and solubilizers is added to the composition to aid oil solubility, as disclosed, for example, in U.S. Patent No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants, such as polyol esters (POE) and polyalkylene glycols (PAG), polyvinyl ethers (PVE), fluorinated and perfluorinated oils (e.g., perfluoropolyethers, PFPE), polycarbonates, silicone oils, mineral oils, alkylbenzenes (AB), and poly(alpha-olefins) (PAO), used in refrigerators with hydrofluorocarbon (HFC) refrigerants, can be used with the refrigerant compositions provided herein.

[0239] In some embodiments, compositions comprising or consisting essentially of Z-HCFO-1224yd have advantages in chillers typically used in connection with commercial air conditioning systems (either in the original system or when used as a replacement for refrigerants such as R-12 and R-500). In some embodiments, the compositions comprising or consisting essentially of Z-HCFO-1224yd are blends set forth in Table 2. In some embodiments, compositions comprising Z-HCFO-1224yd include from about 0.5% to about 5% of a fire suppressant. In some embodiments, the fire suppressant is CF3I.

[0240] In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd further comprises a lubricant. Any of a variety of conventional lubricants may be used in the composition comprising or consisting essentially of Z-HCFO-1224yd. A key requirement for a lubricant is that, when used in a refrigeration system, it must provide sufficient lubrication back to the system's compressor so that the compressor is lubricated. Therefore, in some embodiments, the suitability of a lubricant for any given system is determined in part by the refrigerant / lubricant properties and in part by the characteristics of the system in which it is intended to be used. Examples of suitable lubricants include, but are not limited to, mineral oil, polyol esters containing alkylbenzenes and polyalkylene glycols, PAG oils, and the like. Mineral oils containing paraffinic or naphthenic oils are commercially available. Commercially available mineral oils include Witco LP 250® from Witco, Zerol 300® from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet. Commercially available alkylbenzene lubricants include Zerol 150®. Commercially available esters include neopentyl glycol dipelargonate, available as Emery 2917® and Hatcol 2370®. Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.

[0241] In some embodiments, perfluoropolyethers (PFPEs), such as Krytox®, Galden®, and Fomblin®, function as refrigerant lubricants or performance enhancing additives.

[0242] In some embodiments, the lubricant comprises a polyalkylene glycol and a polyol ester. In some embodiments, the lubricant comprises a polyalkylene glycol. In some embodiments, the lubricant comprises a polyol ether.

[0243] The present invention can employ any of a wide variety of methods for introducing the refrigerant composition of the present invention into a refrigeration system. In some embodiments, the method includes attaching a refrigerant container to the low-pressure side of the refrigeration system and operating a compressor of the refrigeration system to draw refrigerant into the system. In some embodiments, the refrigerant container is scaled so that the amount of refrigerant composition entering the system can be monitored. In some embodiments, dosing is stopped when a desired amount of refrigerant composition has been introduced into the system. In some embodiments, a wide variety of dosing tools known to those skilled in the art are commercially available. Thus, in light of the above disclosure, one skilled in the art will be readily able to introduce the refrigerant composition of the present invention into a refrigeration system according to the present invention without undue experimentation.

[0244] Power cycle applications Rankine cycle systems are known to be a simple and reliable means for converting thermal energy into mechanical shaft power. Organic working fluids are useful alternatives to water / steam when low-grade thermal energy is encountered. Water / steam systems operating at low-grade thermal energy (typically below 400°F) have associated high volumes and low pressures. To keep system size small and efficiency high, organic working fluids with boiling points near room temperature are used. Such fluids will have higher gas densities, resulting in higher capacity and favorable transport, and heat transfer properties, resulting in higher efficiency compared to water at low operating temperatures. In industrial environments, flammable working fluids such as toluene and pentane are more common, especially when the industrial environment already has large amounts of flammable materials on-site in the process or storage area. When the risks associated with using flammable working fluids are unacceptable, such as for power generation in densely populated areas or near buildings, other fluids such as CFC-113 and CFC-11 can be used. While these materials are non-flammable, they pose environmental risks due to their ozone depletion potential. Ideally, organic working fluids should be environmentally acceptable, non-flammable, have low toxicity, and operate at pressures above atmospheric pressure.

[0245] Organic Rankine cycle (ORC) systems are often used to recover waste heat from industrial processes. In cogeneration applications, waste heat from the combustion of fuel used to drive a prime mover in a power generation facility is recovered and used, for example, to generate heat or to produce hot water to operate an absorption chiller that supplies heat and provides cooling. In some cases, the demand for hot water is small or nonexistent. The most challenging case occurs when thermal requirements are variable, making load matching difficult and compromising the efficient operation of the cogeneration system. In such cases, it is more useful to use an organic Rankine cycle system to convert the waste heat into shaft power. The shaft power can be used, for example, to operate a pump or to generate electricity. This approach results in higher overall system efficiency and higher fuel utilization. More electricity can be generated for the same amount of fuel input, thereby reducing air emissions from fuel combustion.

[0246] In some embodiments, the process that produces waste heat is selected from the group consisting of fuel cells, internal combustion engines, internal combustion engines, external combustion engines, and gas turbines. Other sources of waste heat can be found in association with refineries, petrochemical plants, oil and gas pipelines, chemical industries, commercial buildings, hotels, shopping malls, supermarkets, bakeries, food processing industries, restaurants, paint curing ovens, furniture manufacturing, plastic molders, cement kilns, lumber kilns (drying), baking operations, steel industries, glass industries, foundries, smelting, air conditioning, refrigeration, and central heating operations. See U.S. Patent No. 7,428,816, the disclosure of which is incorporated herein by reference.

[0247] Provided herein are compositions comprising Z-HCFO-1224yd for ORC power cycle applications. In some embodiments, the compositions are those set forth in Table 3 below (all percentages are weight percent and are understood to be preceded by the word "about").

[0248] [Table 3-1]

[0249] Table 3-2

[0250] Table 3-3

[0251] Table 3-4

[0252] In some embodiments, the composition comprises Z-HCFO-1224yd, E-HFO-1234ye, Z-HFO-1234ye, HFO-1234yf, E-HFO-1234ze, Z-HFO-1234ze, HFO-1243zf, HFO-1336mcyf, E-HFO-1336mzz, Z-HFO-1336mzz, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, Z-HFO-1438ezy, E-HFO-1438mzz, Z-HFO-1438mzz, E-HCFO-1233zd, Z-HC and one or more compounds selected from FO-1233zd, HFC-134, HFC-134a, HFC-152a, HFC-227ea, HFC-236ea, HFC-245ca, HFC-245cb, HFC-245ea, HFC-245fa, HFC-365mfc, HFC-43-10mee, butane, cyclobutane, isobutene, isopentane (2-methylbutane), HFE-1-methoxyheptafluoropropane (HFE-7000), and HFE-methoxy-nonafluorobutane (C4F9OCH3; HFE7100). In some embodiments, the composition comprises Z-HCFO-1224yd and one or more compounds selected from HFO-1234yf, E-HFO-1234ze, E-HFO-1336mzz, Z-HFO-1336mzz, HFC-134, HFC-134a, HFC-152a, HFC-236ea, HFC-245cb, HFC-245fa, HFC-365mfc, and HFC-43-10mee. In some embodiments, the composition is used as a working fluid for high temperature heat pumps and organic Rankine cycles.

[0253] In some embodiments, the composition comprises Z-HCFO-1224yd and one or more compounds selected from among E-HFO-1234ye, Z-HFO-1234ye, Z-HFO-1234ze, HFO-1336mcyf, E-HFO-1336mzz, Z-HFO-1336mzz, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, E-HFO-1438mzz, E-HCFO-1233zd, HFC-236ea, HFC-245ca, HFC-245ea, HFC-245fa, cyclobutane, and isopentane (2-methylbutane). In some embodiments, the composition comprises Z-HCFO-1224yd and one or more compounds selected from E-HFO-1336mzz, Z-HFO-1336mzz, HFC-236ea, and HFC-245fa. In some embodiments, the composition is used as a replacement fluid in high temperature heat pumps and organic Rankine cycles designed for HFC-235fa.

[0254] In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd is used in a power cycle. In some embodiments, the process includes recovering waste heat in an organic Rankine cycle system, where the working fluid is a composition comprising or consisting essentially of Z-HCFO-1224yd, and optionally one or more additional compounds. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is a composition set forth in Table 3.

[0255] Cleaning and decontamination Provided herein are methods for removing contaminants from products, parts, components, substrates, or any other article or portion thereof by applying to the article a composition comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is a blend described in Table 1 above. The term "article," as used herein, refers to all such products, parts, components, substrates, etc., and is further intended to refer to any surface or portion thereof. As used herein, the term "contaminant" refers to any undesirable material or substances present on an article, even if the substance was intentionally placed on the article. For example, in the manufacture of semiconductor devices, it is common to deposit a photoresist material on a substrate to form a mask for an etching operation, and then remove the photoresist material from the substrate. The term "contaminant," as used herein, is intended to encompass and include such photoresist materials.

[0256] In some embodiments of the cleaning and contaminant removal methods, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 above, and these amounts are equally applicable to this use of the compositions of the present invention.

[0257] In some embodiments, the method includes applying a composition comprising or consisting essentially of Z-HCFO-1224yd to an article. Many and varied cleaning techniques can utilize the compositions of the present invention to good advantage. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is used in conjunction with supercritical cleaning techniques. Supercritical cleaning is disclosed in U.S. Patent No. 6,589,355, which is incorporated herein by reference.

[0258] In some embodiments for supercritical cleaning applications, the cleaning composition includes Z-HCFO-1224yd and another component. In some embodiments, the additional component is CO. In some embodiments, the additional component is known for use in connection with supercritical cleaning applications.

[0259] In some embodiments, cleaning compositions containing Z-HCFO-1224yd are used in conjunction with certain subcritical vapor degreasing and solvent cleaning methods. In some solvent-based embodiments, compositions containing the compound Z-HCFO-1224yd are blended with one or more of cis-1234ze, cis-1233zd, HFC-245fa, methylal (dimethoxymethane), methyl ethyl ketone, methyl isobutyl ketone, or HFC-134a. In some embodiments, the blend includes Z-HCFO-1224yd blended with one or more of pentane, hexane, HFC-365, C4F9OCH3, C4F9OC2H5, propane, butane, isobutane, or dimethyl ether. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of trans-1,2-dichloroethylene, trans-HFO-1234ze, trans-HCFO-1233zd, trans-1336, HFC-43-10, HFC-152a, methanol, ethanol, isopropanol, and / or acetone.

[0260] In some embodiments, cleaning includes removing contaminants from vapor compression systems and their auxiliary components as the systems are manufactured and repaired. As used herein, the term "contaminants" refers to process fluids, lubricants, particulates, sludge, and / or other materials used in the manufacture of these systems or generated during their use. Generally, these contaminants include compounds such as alkylbenzenes, mineral oils, esters, polyalkylene glycols, polyvinyl ethers, and other compounds composed primarily of carbon, hydrogen, and oxygen. In some embodiments, compositions comprising or consisting essentially of Z-HCFO-1224yd are useful for this purpose.

[0261] Sprayable Compositions and Uses In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd is used as a propellant in a sprayable composition, either alone or in combination with a propellant, hi some embodiments, the composition is a blend described in Table 1 above. In some embodiments, Z-HCFO-1224yd is present in the sprayable composition in an amount of about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 and are equally applicable to this use of the compositions of the present invention.

[0262] In some embodiments, the sprayable composition comprises a material to be sprayed and a propellant comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the sprayable composition comprises a blend as set forth in Table 1. In some embodiments, inactive ingredients, solvents, and other materials are also present in the sprayable mixture. In some embodiments, the sprayable composition is an aerosol. Materials suitable for spraying include, but are not limited to, cosmetic materials such as deodorants, fragrances, hairsprays, cleaners, and polishes, and pharmaceuticals such as anti-asthma medications and breath fresheners.

[0263] In some embodiments for aerosol applications, compositions containing Z-HCFO-1224yd are blended with one or more of cis-HFO-1234ze, cis-HCFO-1233zd, HFC-245fa, methylal (dimethoxymethane), methyl ethyl ketone, methyl isobutyl ketone, or HFC-134a. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of pentane, hexane, HFC-365, C4F9OCH3, or C4F9OC2H5. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of trans-1,2-dichloroethylene, trans-HFO-1234ze, trans-HCFO-1233zd, cis-HFO-1336mzz, HFC-43-10, HFC-152a, methanol, ethanol, isopropanol, propane, butane, isobutane, dimethyl ether, or acetone.

[0264] In some embodiments of aerosol applications, the active ingredient to be sprayed is mixed with inert ingredients, solvents, and the like. In some embodiments, the sprayable composition is an aerosol. Suitable active substances to be sprayed include, but are not limited to, lubricants, insecticides, cleaning agents, cosmetic materials such as deodorants, fragrances, and hairsprays, abrasives, and medicinal materials such as skin coolants (tanning agents), topical anesthetics, and anti-asthma medications.

[0265] In some embodiments, provided herein are propellants comprising or consisting essentially of Z-HCFO-1224yd, alone or in combination with one or more other compounds. In some embodiments, the propellant comprises or consists essentially of a blend described in Table 1 above. In some embodiments, the propellant composition is a sprayable composition. In some embodiments, the propellant composition comprises a material to be sprayed and a propellant comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, inert ingredients, solvents, and other materials are also present in the sprayable mixture. In some embodiments, the sprayable composition is an aerosol. Suitable sprayable materials include, but are not limited to, lubricants, insecticides, detergents, deodorants, fragrances, and cosmetic materials such as hairsprays, abrasives, medicinal materials such as anti-asthma ingredients, and any other pharmaceuticals, including any other pharmaceuticals or agents intended for inhalation. In some embodiments, the pharmaceutical or other therapeutic agent is present in the composition in a therapeutic amount, with a substantial portion of the remainder of the composition comprising or consisting essentially of Z-HCFO-1224yd.

[0266] In some embodiments, the aerosol product is for industrial, consumer, or medical use. Aerosol products for industrial, consumer, or medical use typically contain one or more propellants along with one or more active ingredients, inactive ingredients, or solvents. The propellant provides the force that expels the product in aerosolized form. While some aerosol products are propelled with compressed gases such as carbon dioxide, nitrogen, nitrous oxide, and even air, most commercially available aerosols use liquefied gas propellants. The most commonly used liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used alone or in blends with hydrocarbon propellants. Unfortunately, all of these liquefied gas propellants are highly flammable, and their incorporation into aerosol formulations often results in flammable aerosol products.

[0267] In some embodiments, the aerosol products described herein comprise a non-flammable liquefied gas propellant. In some embodiments, the aerosol products described herein comprise or consist essentially of Z-HCFO-1224yd. In some embodiments, the aerosol products described herein comprise or consist essentially of a blend described in Table 1 above. In some embodiments, the aerosol products are for use in certain industrial aerosol products, including, for example, spray cleaners, lubricants, and the like, and in medical aerosols, including, for example, for delivering medications to the lungs or mucous membranes. Examples of these include metered-dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases, and for the delivery of medications to accessible mucous membranes or intranasal passages. In some embodiments, methods are provided for treating illnesses, diseases, and similar health-related problems in an organism (e.g., a human or animal) in need of treatment, comprising administering to the organism a composition comprising or consisting essentially of Z-HCFO-1224yd and a medication or other therapeutic component. In some embodiments, the step of applying the composition comprising or consisting essentially of Z-HCFO-1224yd comprises providing an MDI containing the composition comprising or consisting essentially of Z-HCFO-1224yd (e.g., incorporating the composition into an MDI) and then releasing the composition comprising or consisting essentially of Z-HCFO-1224yd from the MDI.

[0268] As used herein, the term "non-flammable" refers to compounds and compositions of the present invention that do not exhibit a flash point as measured by one of the standard flash point methods, for example, ASTM-1310-86 "Flash point of liquids by tag Open-cup apparatus."

[0269] In some embodiments, compositions comprising or consisting essentially of Z-HCFO-1224yd are used to formulate various industrial aerosols or other sprayable compositions, such as contact cleaners, dusters, and lubricant sprays, as well as consumer aerosols, such as personal care products, household products, and automotive products. In some embodiments, the aerosol or sprayable composition is a medical aerosol, such as a metered-dose inhaler. In some embodiments, the medical aerosol and / or propellant and / or sprayable composition comprises, in addition to Z-HCFO-1224yd, a pharmaceutical, such as a beta-agonist, corticosteroid, or other pharmaceutical, and optionally other ingredients, such as surfactants, solvents, other propellants, flavorings, and other excipients.

[0270] sterile Many articles, devices, and materials, particularly for use in the medical field, need to be sterilized before use for health and safety reasons, such as the health and safety of patients and hospital staff. Provided herein are methods of sterilization comprising contacting the article, device, or material to be sterilized with a composition comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the composition is a blend as defined in Table 1 above. In some embodiments, the composition is optionally combined with one or more additional sterilants.

[0271] In some embodiments of the sterilization method, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 and are equally applicable to this use of the compositions of the present invention.

[0272] While many sterilants are known in the art and are contemplated as being suitable for use in connection with the present invention, in some embodiments, the sterilant includes ethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone, and combinations thereof. In some embodiments, the sterilant is ethylene oxide. One skilled in the art would be readily able to determine the relative proportions of sterilant and other compounds, including Z-HCFO-1224yd, to be used in connection with the present sterilization compositions and methods.

[0273] As known to those skilled in the art, certain sterilants, such as ethylene oxide, are highly flammable components, and the compounds of the present invention, along with other components present in the compositions, are included in the compositions in effective amounts to reduce the flammability of the sterilized compositions to an acceptable level. In some embodiments, the sterilization method is either high-temperature or low-temperature sterilization. In some embodiments, sterilization involves using a compound or composition comprising Z-HCFO-1224yd at a temperature of about 250°F to about 270°F. In some embodiments, sterilization is performed in a substantially sealed chamber. In some embodiments, the sterilization process is completed in less than about two hours. In some embodiments, some items, such as plastic items and electrical components, cannot withstand such high temperatures and require low-temperature sterilization.

[0274] In some embodiments, the sterilization method is a low-temperature sterilization method. In some embodiments of a low-temperature sterilization method, the article to be sterilized is exposed to a fluid comprising or consisting essentially of Z-HCFO-1224yd at a temperature of about room temperature to about 200°F, for example, at a temperature of about room temperature to about 100°F.

[0275] In some embodiments, low-temperature sterilization is at least a two-step process carried out in a substantially sealed chamber. In some embodiments, the chamber is airtight. In some embodiments, the first step (sterilization step) involves placing cleaned, gas-permeable bagged articles into the chamber. In some embodiments, the chamber is evacuated by drawing a vacuum. In some embodiments, the chamber is evacuated by replacing the air with steam. In some embodiments, the chamber is evacuated by drawing a vacuum and replacing the air with steam. In some embodiments, steam is injected into the chamber to achieve a relative humidity in the range of about 30% to about 70%. In some embodiments, such humidity maximizes the sterilizing effect of a sterilant introduced into the chamber after the desired relative humidity has been achieved. In some embodiments, the sterilant and steam are evacuated from the chamber after sufficient time has passed for the sterilant to penetrate the packaging and reach the interstices of the articles.

[0276] In some embodiments, the second step of the process (the aeration step) involves aerating the article to remove sterilant residue. In some embodiments, the residue is a toxic sterilant. In some embodiments, aeration is optional, for example, when a substantially non-toxic compound is used. In some embodiments, the substantially non-toxic compound is a composition comprising Z-HCFO-1224yd. In some embodiments, the aeration process includes air purging, continuous aeration, and combinations of the two. The air purging is a batch process, and in some embodiments, includes evacuating the chamber for a relatively short period of time, e.g., 12 minutes, and then introducing air at atmospheric pressure or above into the chamber.

[0277] As used herein, the term "non-toxic" refers to compounds and compositions that have acute toxicity levels substantially lower than the toxicity level of HFO-1223xd, preferably at least about 30 relative percent lower, as measured by the methods published in Anesthesiology, Vol. 14, pp. 466-472, 1953, which is incorporated herein by reference.

[0278] In some embodiments, this cycle is repeated any number of times until the desired removal of sterilant is achieved. In some embodiments, continuous aeration involves introducing air through an inlet on one side of the chamber and then drawing the air through an outlet on the other side of the chamber by applying a slight vacuum to the outlet. In some embodiments, the two approaches are combined. In some embodiments, the method includes air purging and then performing an aeration cycle.

[0279] Extraction of flavorings and fragrances In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd is used to transport, extract, or separate desirable materials from biomass. In some embodiments, the composition is a blend as set forth in Table 1 above. In some embodiments, the materials include, but are not limited to, essential oils such as flavors and fragrances, oils that can be used as fuels, medicines, dietary supplements, and the like. Thus, provided herein are methods for transporting, extracting, or separating desirable materials from biomass.

[0280] In some embodiments of the extraction method, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 and are equally applicable to this use of the compositions of the present invention.

[0281] In some embodiments, compositions comprising Z-HCFO-1224yd are used as extractants, carriers, or part of delivery systems for flavor and fragrance formulations. In some embodiments, the formulations are aerosol formulations. In some embodiments, compositions comprising Z-HCFO-1224yd are used as extractants for flavor and fragrance agents. In some embodiments, the flavor and fragrance agents are extracted from plant materials.

[0282] Flammability reduction methods Provided herein are methods for reducing the flammability of a fluid, the method comprising adding a composition comprising Z-HCFO-1224yd to the fluid. In some embodiments, the composition comprising Z-HCFO-1224yd is a blend as defined in Table 1. In some embodiments, the method reduces the flammability associated with any of a wide range of other flammable fluids. In some embodiments, the method reduces the flammability associated with fluids such as ethylene oxide, flammable hydrofluorocarbons, and hydrocarbons, including HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, octane, and the like. For purposes of this invention, a flammable fluid is any fluid that exhibits a range of flammability in air as measured via any standard conventional test method, such as ASTM E-681.

[0283] In some embodiments of the method for reducing flammability, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 and are equally applicable to this use of the compositions of the present invention.

[0284] Any suitable amount of the present compounds or compositions can be added to reduce the flammability of a fluid in accordance with the present invention. As will be recognized by those skilled in the art, the amount added will depend, at least in part, on the degree of flammability of the fluid in question and the degree to which it is desired to reduce that flammability. In some embodiments, the amount of the compound or composition comprising Z-HCFO-1224yd added to a flammable fluid is effective to render the resulting fluid substantially non-flammable.

[0285] Flame suppression method The present invention further provides a method for suppressing a flame, comprising contacting the flame with a Z-HCFO-1224yd-containing composition. In some embodiments, the Z-HCFO-1224yd-containing composition is a blend described in Table 1 above. In some embodiments, an additional flame suppression agent is used with the Z-HCFO-1224yd-containing composition, either in a mixture or as a secondary flame suppression agent. In some embodiments, the compound is a fluoroketone. In some embodiments, the fluoroketone is dodecafluoro-2-methylpentan-3-one, which is sold under the trade name Novec 1230 by 3M Company.

[0286] In some embodiments of the flame suppression method, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, e.g., about 30% to about 99% by weight, about 50% to about 99% by weight, about 75% to about 99% by weight, about 85% to about 99% by weight, about 20% to about 80% by weight, about 90% to about 99% by weight, about 95% to about 99% by weight, about 1% to about 20% by weight, about 1% to about 40% by weight, about 1% to about 50% by weight, about 5% to about 20% by weight, about 5% to about 40% by weight, about 5% to about 60% by weight, about 10% to about 80% by weight, about 10% to about 90% by weight, about 20% to about 80% by weight, or about 20% to about 90% by weight. Other amount ranges are shown in Table 1 and are equally applicable to this use of the compositions of the present invention.

[0287] Any suitable method of contacting the flame with the composition may be used, and in some embodiments, the composition comprising Z-HCFO-1224yd may be sprayed, poured, etc. onto the flame, or the composition may be placed into at least a portion of the flame.

[0288] Etching Method Etching gases used in the semiconductor industry are used to etch deposits from surfaces. Chemical vapor deposition (CVD) and plasma-enhanced chemical vapor deposition (PECVD) chambers must be periodically cleaned to remove deposits from the chamber walls and platens. This cleaning process reduces the chamber's production capacity because the chamber cannot be used during the cleaning cycle. The cleaning process may include, for example, venting a reactive gas and replacing it with a cleaning gas, activating the cleaning gas, and then flushing the chamber using an inert carrier gas to remove the cleaning gas. Cleaning gases typically work by etching accumulated contaminants from interior surfaces. Therefore, the etch rate of a cleaning gas is an important parameter in the gas's usefulness and commercial application, and some cleaning gases can also be used as etching gases. These gases can produce relatively large amounts of toxic exhaust gases, which can cause additional GWP or environmental, health, and safety (EHS) issues separate from the GWP of the cleaning or etching gas itself.

[0289] Therefore, there is a need to reduce the global warming harm caused by cleaning and operating CVD reactors using effective, inexpensive cleaning / etching gases that have high etch rates and lower GWP and ESH impacts than current gases. In some embodiments, clean gas mixtures are provided that have low EHS and GWP, thereby reducing the environmental impact of unreacted gases, even if they are released. In some embodiments, methods are provided for using these gases, including activating the gases, either in a remote chamber or in situ in the process chamber, where the gas mixture comprises an oxygen source and a hydrofluoroolefin, and contacting the activated gas with surface deposits for a time sufficient to remove the surface deposits. In some embodiments, the gas mixture is activated by a radio frequency (RF) source using sufficient power for a sufficient time such that the gas mixture reaches a neutral temperature of about 1000-3000 K to form an activated gas mixture. In some embodiments, the gases are activated using a glow discharge. In some embodiments, the activated gas mixture is contacted with the surface deposits, thereby removing at least a portion of the surface deposits. In some embodiments, the gas mixture includes Z-HCFO-1224yd. In some embodiments, the gas mixture includes Z-HCFO-1224yd alone. In some embodiments, the gas mixture includes Z-HCFO-1224yd in admixture with one or more of the compounds listed in Table 1.

[0290] In some embodiments, the surface deposits to be removed include materials typically deposited by chemical vapor deposition (CVD) or plasma enhanced chemical vapor deposition (PECVD) or similar processes. Such materials include, but are not limited to, nitrogen-containing deposits such as silicon nitride, silicon oxynitride, silicon carbonitride (SiCN), silicon boronitride (SiBN), and metal nitrides such as tungsten nitride, titanium nitride, or tantalum nitride. In some embodiments, the surface deposit is silicon nitride.

[0291] In some embodiments, surface deposits are removed from the interior of a process chamber used in the manufacture of electronic devices. In some embodiments, the process chamber is a CVD chamber or a PECVD chamber. In some embodiments, the gas mixture is used to remove surface deposits from metals. In some embodiments, the gas mixture is used to clean a plasma etch chamber. In some embodiments, the gas mixture is used to remove N-containing films from wafers. In some embodiments, the gas is used in etching applications.

[0292] In some embodiments, the process involves an activation step in which the cleaning gas mixture is activated in a remote chamber. Activation can be achieved by any means capable of dissociating a large portion of the feed gas, such as radio frequency (RF) energy, direct current (DC) energy, laser radiation, and microwave energy. In some embodiments, the plasma has a torroidal configuration and uses a transformer inductively coupled to a low-frequency RF power source, acting as the secondary of the transformer. In some embodiments, the use of low-frequency RF power allows the use of a magnetic core that enhances inductive coupling over capacitive coupling, thereby allowing for more efficient energy transfer to the plasma without excessive ion bombardment, which can limit the lifetime of the remote plasma source chamber. In some embodiments, the RF power has a frequency less than 1000 kHz. In some embodiments, the power source is a remote microwave inductively coupled or capacitively coupled plasma source. In some embodiments, a glow discharge is used to activate the gas.

[0293] Dielectric Method In some embodiments, Z-HCFO-1224yd is used as a dielectric in electrical devices. In some embodiments, Z-HCFO-1224yd is used alone. In some embodiments, Z-HCFO-1224yd is used in a mixture with one or more of the compounds listed in Table 1. In medium- or high-voltage electrical devices, the functions of electrical insulation and electric arc quenching are typically performed by an insulating gas confined within the device. In the generally accepted meaning of the terms, "medium-voltage" refers to voltages greater than 1,000 volts AC and strictly greater than 1,500 volts DC, but not greater than 52,000 volts AC or 75,000 volts DC, while the term "high-voltage" refers to voltages strictly greater than 52,000 volts AC and 75,000 volts DC.

[0294] In some embodiments, the insulating gas used within these devices contains Z-HCFO-1224yd. In some embodiments, the insulating gas used within these devices is a mixture of Z-HCFO-1224yd and one or more of the compounds listed in Table 1.

[0295] While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the invention. It is intended that the claims be construed to cover the above-described disclosed embodiments, alternatives thereof, and all equivalents thereof.

[0296] It should be noted that not all of the operations or embodiments described above in the general description are required, that some of the specific operations may not be required, and that one or more additional operations may be performed in addition to the operations described above. Furthermore, the order in which the operations are listed is not necessarily the order in which they are performed.

[0297] In the foregoing specification, the concepts of the present invention have been described with reference to specific embodiments. However, those skilled in the art will recognize that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

[0298] Benefits, other advantages, and solutions to problems have been described above with reference to specific embodiments. However, these benefits, advantages, solutions to problems, and any features that may produce or make more apparent any benefit, advantage, or solution are not to be construed as essential, required, or essential features in any or all of the claims.

[0299] It should be understood that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, references to values ​​stated in ranges include each and every value within that range. [Example]

[0300] The present disclosure is further defined in the following examples. It should be understood that these examples, while showing preferred embodiments, are provided for illustrative purposes only. From the above description and these examples, those skilled in the art can ascertain preferred features and make various changes and modifications to adapt to various uses and conditions without departing from the spirit and scope thereof.

[0301] Example 1: Cooling and Heating Performance Data The cooling and heating performance of pure fluids and compositions containing Z-HCFO-1224yd were measured. Measurements included evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and average evaporator and condenser temperature gradient (Avg Temp Glide). The relative energy efficiency (COP) and capacity (CAP) of blends containing Z-HCFO-1224yd (1224ydZ) were measured compared to Z-HCFO-1224yd and pure fluids HFC-245fa, HCFC-123, and HCFO-1233zdE. The results are shown in Table 4 below.

[0302] The data was based on the following conditions: Evaporator temperature 4.44℃ Condenser temperature 37.78℃ Supercooling amount 0K Return gas temperature 25℃ Compressor efficiency 75%

[0303] [Table 4-1]

[0304] [Table 4-2]

[0305] The results showed that Z-HCFO-1224yd (1224ydZ) is a good replacement for HFC-245fa, HCFC-123, and 1233zdE. It is particularly closely matched in capacity to 1233zdE. The mixtures shown were also good replacements for pure fluids shown to have similar capacities and efficiencies. Mixtures with low temperature gradients (<~1K) are particularly suitable for use in centrifugal chillers. Mixtures with high gradients are suitable for use in counter- or counter-flow heat exchangers.

[0306] The compressor discharge temperatures of the mixture and the pure fluid were also similar.

[0307] Example 2: Cooling and Heating Performance Data The cooling and heating performance of compositions containing Z-HCFO-1224yd was measured. Measurements included evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and average evaporator and condenser temperature gradient (Avg Temp Glide). The relative energy efficiency (COP) and capacity (CAP) of blends containing Z-HCFO-1224yd (1224ydZ) were measured in comparison with HFC-236fa and HCFC-124. The results are shown in Table 5 below.

[0308] The data was based on the following conditions: Evaporator temperature 4.44℃ Condenser temperature 37.78℃ Supercooling amount 0K Return gas temperature 25℃ Compressor efficiency 75%

[0309] [Table 5]

[0310] The results showed that the blends containing Z-HCFO-1224yd closely matched both HFC-236fa and HCFC-124. The blends exhibited similar cooling and heating capacities and efficiencies. The blends also had similar compressor discharge temperatures.

[0311] Example 3: Cooling and Heating Performance Data The cooling and heating performance of compositions containing Z-HCFO-1224yd was measured. Measurements included evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and average evaporator and condenser temperature gradient (Avg Temp Glide). The relative energy efficiency (COP) and capacity (CAP) of mixtures containing Z-HCFO-1224yd (1224ydZ) were measured compared to HFO-1234yf, HFC-134a, and HFO-t-1234ze. The results are shown in Table 6 below.

[0312] The data was based on the following conditions: Evaporator temperature 4.44℃ Condenser temperature 37.78℃ Supercooling amount 0K Return gas temperature 25℃ Compressor efficiency is 75%

[0313] [Table 6]

[0314] The results showed that the blends containing Z-HCFO-1224yd closely matched HFO-1234yf, HFC-134a, and HFO-t-1234ze. The blends shown had similar cooling and heating capacities and efficiencies. The blends also had similar compressor discharge temperatures.

[0315] Example 4: Cooling and Heating Performance Data The cooling and heating performance of compositions containing Z-HCFO-1224yd was measured. Measurements included evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and average evaporator and condenser temperature gradient (Avg Temp Glide). The relative energy efficiency (COP) and capacity (CAP) of blends containing Z-HCFO-1224yd (1224ydZ) were measured compared to R-407C, HCFC-22, and R-410A. The results are shown in Table 7 below.

[0316] The data is based on the following conditions: Evaporator temperature 4.44℃ Condenser temperature 37.78℃ Supercooling amount 0K Return gas temperature 25℃ Compressor efficiency is 75%

[0317] [Table 7]

[0318] The results showed that the blends containing HCFO-1224yd closely matched R-407C, R-22, and R-410A. The blends shown had similar cooling and heating capacities and efficiencies. The blends also had similar compressor discharge temperatures.

[0319] Example 5: Power cycle using Z-HCFO-1224yd as working fluid The cycle efficiency of an ORC system using HFC-245fa as the working fluid was compared with that of an ORC system using Z-HCFO-1224yd as the working fluid. It was assumed that the maximum achievable operating pressure of the ORC system was approximately 2.5 MPa, and that a heat source capable of maintaining the temperature of one of the working fluids at the expander inlet at 160°C was available.

[0320] Table 8 is a comparison table showing HFC-245fa and Z-HCFO-1224yd utilized as working fluids in a subcritical Rankine power cycle. Operating parameters for an ORC system using HFC-245fa as the working fluid are listed under the column labeled "HFC-245fa." Operating parameters for an ORC system using HCFO-1224yd (Z) as the working fluid are listed under the column labeled "Z-HCFO-1224yd."

[0321] [Table 8]

[0322] To ensure that the pressure in the evaporator remained below the maximum allowable design operating pressure of commonly available commercial equipment components (e.g., heat exchangers) for ORC systems, the evaporation temperature using HFC-245fa was limited to 133.5°C.

[0323] The above example shows that Z-HCFO-1224yd, when used in an ORC system designed to use HFC-245fa as the working fluid, achieves 8.97% higher cycle efficiency than HFC-245fa and reduces the GWP of the working fluid by more than 99.88%. This demonstrates that it is possible to replace a working fluid containing HFC-245fa in an existing ORC system by draining the working fluid, flushing the ORC system with a lubricant or working fluid containing Z-HCFO-1224yd, and then filling the ORC system with the working fluid containing Z-HCFO-1224yd.

[0324] Example 6: High temperature heat pump performance using Z-HCFO-1224yd to raise the temperature from 80°C to 126°C Heat pumps operating with either Z-HCFO-1224yd or HFC-245fa as the working fluid were used to increase the temperature from 80° C. to 126° C. Performance data is shown in Table 9 below.

[0325] [Table 9]

[0326] As shown in Table 9, Z-HCFO-1224yd has a COP of 1.2 times that of HFC-245fa. h , but results in a working fluid GWP that is greater than 99.88% lower than the GWP of HFC-245fa.

[0327] Example 7: Flame Suppression A composition containing Z-HCFO-1224yd was used as the fire suppression composition. An NFPA 2001 cup burner was used to evaluate full-immersion fire suppression applications. A small heptane fire was positioned in a chimney with airflow around the flame to provide the necessary oxygen. Z-HCFO-1224yd was added to this airflow until the flame was extinguished. Table 10 below shows the extinguishing concentrations of heptane using Z-HCFO-1224yd as the extinguishing agent.

[0328] [Table 10]

[0329] Example 8: Azeotropic Composition of Z-HCFO-1224yd and 1,1,1,4,4,4-Hexafluoro-2-butene (Z-HFO-1336mzz) The existence of azeotrope-like compositions between the binary pair Z-1,1,1,4,4,4-hexafluoro-2-butene and Z-1-chloro-2,3,3,3-tetrafluoropropene was tested. The PTx method was used to determine the relative volatility of each binary pair. In this procedure, the total absolute pressure in a sample cell with a volume of 85 mL was measured at a constant temperature for various binary compositions. These measurements were then converted to equilibrium vapor and liquid compositions using the nonrandom two-liquid model (NRTL) equation. The vapor pressures measured for the compositions in the PTx sample cell for this binary system are shown in Figure 1.

[0330] At 31.8°C, azeotrope-like compositions of Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) and Z-1-chloro-2,3,3,3-tetrafluoropropene (Z-HCFO-1224yd) were formed, as indicated by a mixture of about 1-22 mol% Z-1,1,1,4,4,4-hexafluoro-2-butene and about 78-99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene, and a mixture of about 93-99 mol% Z-1,1,1,4,4,4-hexafluoro-2-butene and about 1-7 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene (see Figure 1).

[0331] The substantially constant boiling azeotrope-like composition comprised a mixture of Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) and Z-1-chloro-2,3,3,3-tetrafluoropropene (Z-HCFO-1224yd) shown below in Table 11A. (Over this temperature range, the difference between the dew point pressure and bubble point pressure of the composition at a particular temperature is 0.05 (based on the bubble point pressure).) ) 5 percent or less. Azeotrope-like compositions of 1 to 24 mol % and 62 to 99 mol % Z-HCFO-1224yd with 1 to 38 mol % and 76 to 99 mol % Z-HFO-1336mzz were formed at temperatures ranging from about −40° C. to about 140° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 3 percent or less (based on the bubble point pressure)) (Table 11B).

[0332] [Table 11]

[0333] [Table 12]

[0334] Example 9: Azeotrope Composition of Z-HCFO-1224yd and Methyl Formate The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and methyl formate. The pressure inside a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then converted to the equilibrium vapor and liquid compositions inside the cell using the NRTL equation.

[0335] The measured pressure versus composition in the PTx cell for Z-HCFO-1224yd / methyl formate mixtures is shown in FIG. 2, which graphically illustrates the formation of azeotrope-like compositions of 1-3 mol % Z-HCFO-1224yd and 97-99 mol % methyl formate at 31.8° C. and a pressure of about 15 psia, and also illustrates the formation of azeotrope-like compositions of 64-99 mol % Z-HCFO-1224yd and 1-36 mol % methyl formate at 31.8° C. and a pressure range of about 25-28 psia.

[0336] Azeotrope-like compositions of 1 to 99 mole percent Z-HCFO-1224yd and 1 to 99 mole percent methyl formate were formed at temperatures ranging from about −40° C. to about 140° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 5 percent or less (based on bubble point pressure)) (Table 12A). Azeotrope-like compositions of 1 to 99 mole percent Z-HCFO-1224yd and 1 to 99 mole percent methyl formate were formed at temperatures ranging from about −40° C. to about 140° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 3 percent or less (based on bubble point pressure)). At 20° C., an azeotrope-like composition of 85 to 99 mole percent Z-HCFO-1224yd and 1 to 15 mole percent methyl formate was formed. Azeotrope-like compositions are listed below in Tables 12A-12B.

[0337] [Table 13]

[0338] [Table 14]

[0339] Example 10: Azeotrope Composition of Z-HCFO-1224yd and E-HCFO-1233zd The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and E-HCFO-1233zd. Pressures in a PTx cell of known volume were measured at constant temperature for various binary compositions. These measurements were then converted to equilibrium vapor and liquid compositions in the cell using the NRTL equation.

[0340] The measured pressure versus composition in the PTx cell for E-1-chloro-3,3,3-trifluoropropene / Z-1-chloro-2,3,3,3-tetrafluoropropene mixtures is shown in Figure 3, which graphically illustrates the formation of azeotrope-like compositions of 1 to 99 mole % E-1-chloro-3,3,3-trifluoropropene and 1 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from about 24 to 38 psia.

[0341] Azeotrope-like compositions of 1 to 99 mole % E-1-chloro-3,3,3-trifluoropropene and 1 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoropropene are formed at temperatures ranging from about −40° C. to about 140° C. (Over this temperature range, the difference between the dew point pressure and bubble point pressure of the composition at a particular temperature is 3 percent or less (based on bubble point pressure)) (Table 13).

[0342] [Table 15]

[0343] Example 11: Azeotrope Composition of Z-HCFO-1224yd and E-HFO-1336mzz The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and E-HFO-1336mzz. The pressure inside a PTx cell of known volume was measured at constant temperature for various binary compositions. These measurements were then converted to the equilibrium vapor and liquid compositions inside the cell using the NRTL equation.

[0344] The pressure measured versus composition in the PTx cell for E-HFO-1336mzz / Z-HCFO-1224yd mixtures is shown in Figure 4, which graphically illustrates the formation of azeotrope-like compositions of 1-99 mol% E-HFO-1336mzz and 1-99 mol% E-HCFO-1224yd at 31.7°C and pressures ranging from about 28-36 psia.

[0345] Azeotrope-like compositions of 1 to 99 mole percent E-HFO-1336mzz and 1 to 99 mole percent Z-HCFO-1224yd are formed at temperatures ranging from about −40° C. to about 120° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at the specified temperature is 5 percent or less (based on bubble point pressure)) (Table 14A). Azeotrope-like compositions of 5 to 95 mole percent E-HFO-1336mzz and 5 to 95 mole percent Z-HCFO-1224yd are formed at temperatures ranging from about −40° C. to about 120° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at the specified temperature is 3 percent or less (based on bubble point pressure)) (Table 14B).

[0346] [Table 16]

[0347] [Table 17]

[0348] Example 12: Azeotropic Composition of Z-HCFO-1224yd and E-1,1,1,4,4,5,5,5-Octafluoro-2-pentene (E-HFO-1438mzz) The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz). Pressures in a PTx cell of known volume were measured at constant temperature for various binary compositions. These measurements were then converted to equilibrium vapor and liquid compositions in the cell using the NRTL equation.

[0349] The measured pressure versus composition in the PTx cell for E-1,1,1,4,4,5,5,5-octafluoro-2-pentene / Z-1-chloro-2,3,3,3-tetrafluoropropene mixtures is shown in Figure 5, which graphically illustrates the formation of azeotrope-like compositions of 1 to 33 mole % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 67 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from about 25 to 28 psia, and also illustrates the formation of azeotrope-like compositions of 84 to 99 mole % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 1 to 16 mole % Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from about 16 to 19 psia.

[0350] Azeotrope-like compositions of 1 to 99 mole % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 1 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoropropene are formed at temperatures ranging from about −40° C. to about 140° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 5 percent or less (based on bubble point pressure) (Table 15A). ... Azeotrope-like compositions of 1,3,3,3-tetrafluoropropene are formed at temperatures ranging from about -40°C to about 140°C (over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 3 percent or less (based on bubble point pressure)) (Table 15B). At 20°C, azeotrope-like compositions of 1-12 mol% and 89-99 mol% Z-HCFO-1224yd and 1-11 mol% and 88-99 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene are formed.

[0351] [Table 18]

[0352] [Table 19]

[0353] Example 13: Azeotrope and Azeotrope-Like Mixtures of Z-HCFO-1224yd and HFC-245eb The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and HFC-245eb. The temperature inside a PTx cell of known volume was measured at constant pressure for various binary compositions. These measurements were then converted to the equilibrium vapor and liquid compositions inside the cell using the NRTL equation.

[0354] The pressure measured versus composition in the PTx cell for Z-HCFO-1224yd / HFC-245eb mixtures is shown in Figure 6, which graphically illustrates the formation of an azeotropic composition of Z-HCFO-1224yd and HFC-245eb, as indicated by a mixture of about 78.8 mol% Z-HCFO-1224yd and 21.2 mol% HFC-245eb having the highest pressure across the range of compositions at about 31.7°C.

[0355] Azeotropic compositions of Z-HCFO-1224yd and HFC-245eb are formed in the range of about 65.6 mole percent to about 86.7 mole percent Z-HCFO-1224yd and about 34.4 mole percent to about 13.3 mole percent HFC-245eb (forming azeotropic compositions boiling at temperatures from about -40°C to about 130°C and pressures from about 0.98 psia (6.76 kPa) to about 333 psia (2296 kPa)).

[0356] At 20.0°C and 18.8 psia (130 kPa), the azeotropic composition was 81.4 mol% Z-HCFO-1224yd and 18.6 mol% HFC-245eb. At 13.4°C and atmospheric pressure (14.7 psia, 101 kPa), the azeotropic composition was 82.7 mol% Z-HCFO-1224yd and 17.3 mol% HFC-245eb. The azeotropic compositions are listed in Tables 16 and 17 below.

[0357] [Table 20]

[0358] [Table 21]

[0359] Additionally, azeotrope-like compositions containing Z-HCF0-1224yd and HFC-245eb are also formed. Azeotrope-like compositions of 1 to 99 mole percent Z-HCF0-1224yd and 99 to 1 mole percent HFC-245eb are formed at temperatures ranging from about −40° C. to about 120° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 5 percent or less (based on bubble point pressure)) (Table 18A). Azeotrope-like compositions of 1 to 99 mole percent Z-HCF0-1224yd and 99 to 1 mole percent HFC-245eb are formed at temperatures ranging from about −40° C. to about 120° C. (Over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a particular temperature is 3 percent or less (based on bubble point pressure)) (Table 18B). At 20°C, azeotrope-like compositions were formed with 1-9 mol% and 58-99 mol% Z-HCFO-1224yd and 1-42 mol% and 91-99 mol% HFC-245eb. These azeotrope-like compositions exist near the azeotropic composition.

[0360] [Table 22]

[0361] [Table 23]

[0362] Example 14: Azeotrope and Azeotrope-Like Mixtures of Z-HCFO-1224yd and HCFO-1233xf The PTx method described above in Example 8 was used to determine the relative volatility of the binary pair Z-HCFO-1224yd and HCFO-1233xf. The temperature inside a PTx cell of known volume was measured at constant pressure for various binary compositions. These measurements were then converted to the equilibrium vapor and liquid compositions inside the cell using the NRTL equation.

[0363] The pressure measured versus composition in the PTx cell for Z-HCFO-1224yd / HFC-1233xf mixtures is shown in Figure 7, which graphically illustrates the formation of an azeotropic composition of Z-HCFO-1224yd and HCFO-1233xf, as indicated by the mixture of about 16 mol% Z-HCFO-1224yd and 84 mol% HCFO-1233xf having the highest pressure across the range of compositions at about 31.8°C.

[0364] Example 15: Aging R-values ​​reinforced with HCFO-1224yd and HFO-1336mzz-E blends Foam samples were produced in an 8" x 8" x 2.5" mold using a manual mixing method. The foams were allowed to cure overnight, cut into 6" x 6" x 1.5", and analyzed with a calibrated heat flow meter. Sample analysis was performed, and the values ​​at each set point were considered the baseline k-factor values. An exemplary manual mixing method consisted of adding the appropriate amount of HCFO or HFO and water (a typical polyurethane B-side mix) to the B-side and mixing. The appropriate amount of A-side (a typical polyurethane A-side mix) was then mixed using a high-speed Arroad mixer at 4000 rpm for 1.5 seconds, and the mixture was poured into the mold. The weight percentages of each blowing agent component used to prepare the foams are presented in Table 19 (weight percentages based on the total amount of A-side and B-side combined), and samples were produced using a 100:123 ratio of B-side:A-side. The results of the thermal analysis experiments are shown in Tables 20-24 and Figures 8-11.

[0365] [Table 24]

[0366] [Table 25] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0367] [Table 26] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0368] [Table 27] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0369] [Table 28] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0370] [Table 29] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0371] [Table 30] NA = Data not applicable K factor is Btu·in / ft 2 Expressed in h°F

[0372] As shown by the data in Tables 20-25, combining HFO-1336mzz-E with HCFO-1224yd formed a synergistic combination that resulted in improved thermal insulation performance over a wide range of temperatures. Furthermore, the effect was long-lasting, continuing to provide improved thermal insulation. At higher temperatures, the combination of HFO-1336mzz-Z with HCFO-1224yd also showed favorable results compared to the control and a blend of HCFO-1233zd and HCFO-1224yd.

[0373] Other embodiments 1. In some embodiments, the present application provides a method for producing a fluororesin-based fluoropolymer of the compound Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene in a solvent containing an HFO, HCFO, HFC, HFE, HCFC, CFC, CO, olefins, hydrochloroolefins, chlorinated hydrocarbons, organic acids, alcohols, hydrocarbons, ethers, aldehydes, ketones, water, and others, such as methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene (DCE), carbon dioxide, 3,3,3-trifluoropropane, and one or more compounds selected from the group consisting of cis-HFO-1234ze and HFO-1225yez, a mixture thereof with water; a mixture thereof with CO2, a mixture thereof with trans-1,2-dichloroethylene; a mixture thereof with methyl formate; a mixture of cis-HFO-1234ze and CO2, a mixture of cis-HFO-1234ze and HFO-1225yez and CO2, and a mixture of cis-HFO-1234ze and HFC-245fa.

[0374] 2. The composition of embodiment 1, wherein the additional compound comprises one or more compounds selected from the group consisting of trans-1,2-dichloroethylene, carbon dioxide; cis-HFO-1234ze; HFO-1225yez; low molecular weight alcohols; low global warming potential olefins; chlorofluorocarbons; ketones; aldehydes; organic acids, and alkanes.

[0375] 3. Additional compounds include cis-HFO-1234ze, trans-HFO-1234ze; HFO-1234yf; Z-HFO-1225ye, E-HFO-1225ye, HFO-1225yc; E-HFO-1233zd, Z-HFO-1233zd, HFC-1233xf; E-HFO-1336ze, Z-HFO-1336ze, E-HCFO-1224y 3. The composition of claim 1 or 2, comprising one or more compounds selected from the group consisting of: CF3, Z-HCFO-1224yd, E-(CF3)2CFCH=CHF, Z-(CF3)2CFCH=CHF, (CF3)2CFCH=CF2, E-CF3CHFC=CHF, Z-CF3CHFC=CHF, HFO-1354myc, and (C2F5)(CF3)C=CH2.

[0376] 4. The composition of any one of embodiments 1-3, wherein the additional compound comprises one or more compounds selected from the group consisting of HFC-245eb, HFC-245ca; HFC-227ea; HFC-236ea; HFC-236fa; HFC-134a; HFC-134; HFC-152a; HFC-32; HFC-125; HFC-143a; HFC-365mfc; HFC-161, and HFC-43-10mee.

[0377] 5. Additional compounds are CHF2-O-CHF2, CHF2-O-CH2F, CH2F-O-CH2F, CH2F-O-CH3, cyclo-CF2-CH2-CF2-O, cyclo-CF2-CF2-CH2-O, CHF2-O-CF2-CHF2, CF3-CF2-O-CH2F, CHF2-O-CHF-CF3, CHF2-O-CF2-CHF2, CH2F-O-CF2-CHF2, CF3-O-CF2-CH3, CHF2-CHF-O-CHF2, CF3-O-CHF-CH2F, CF3-CHF-O-CH2F, CF3-O-CH2-CHF2, CH 5. The composition of any one of embodiments 1-4, comprising one or more compounds selected from the group consisting of F2-O-CH2-CF3, CH2F-CF2-O-CH2F, CHF2-O-CF2-CH3, CHF2-CF2-O-CH3, CH2F-O-CHF-CH2F, CHF2-CHF-O-CH2F, CF3-O-CHF-CH3, CF3-CHF-O-CH3, CHF2-O-CH2-CHF2, CF3-O-CH2-CH2F, CF3-CH2-O-CH2F, HFE-7000, HFE-7100, and CF2H-CF2-CF2-O-CH3.

[0378] 6. The composition of any one of embodiments 1-5, wherein the additional compound comprises one or more compounds selected from the group consisting of propane, butane; isobutane; neopentane; isopentane; cyclopentane, n-hexane; isohexane, and heptane.

[0379] 7. The composition of any one of embodiments 1 to 6, wherein the additional compound comprises one or more compounds selected from the group consisting of dimethyl ether, methyl ethyl ether; diethyl ether; methyl propyl ether; methyl isopropyl ether; ethyl propyl ether; ethyl isopropyl ether; dipropyl ether; diisopropyl ether; dimethyloxymethane; diethoxymethane; dipropoxymethane, and dibutoxymethane.

[0380] 8. The composition of any one of embodiments 1-7, wherein the additional compound comprises one or more compounds selected from the group consisting of formaldehyde, acetaldehyde; propanal; butanal, and isobutanal.

[0381] 9. The composition of any one of embodiments 1-8, wherein the additional compound comprises one or more compounds selected from the group consisting of acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0382] 10. In some embodiments, the present application provides a method for producing a fluororesin comprising the steps of: (a) reacting Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene with methyl formate, methyl ethyl ether, diethyl ether, cyclobutane, isopentane (2-methylbutane), ethylene oxide, Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz), E-1,1,1,4,4,4-hexafluoro-2-butene (E- HFO-1336mzz), Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd), E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd), Z-1,1,1,4,4,5,5,5-octafluoro-2-pentene (Z-HFO-1439mzz), E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1439mzz) zz), 1,1,1,2,3-pentafluoropropane (HFC-245eb), E-HFO-1234ye, Z-HFO-1234ye, Z-HFO-1234ze, HFO-1243yf, HFO-1336mcyf, E-HFO-1336ze, Z-HFO-1336ze, E-HFO-1438ezy, Z-HFO1438ezy, E-HFO-1438mzz, HCFO-1233xf, HFC-23 and one or more compounds selected from the group consisting of HFC-6ea, HFC-236fa, HFC-245fa, HFC-356mff, HFC-245ca, HFC-245ea, HCFC-123, CFC-11, CFC-114, HFE-236eaEbg, HFE-E347mmyl, and HFE-1-methoxyheptafluoropropane (hfe-7000).

[0383] 11. The azeotrope or azeotrope-like composition of embodiment 10 formed at a pressure of from about 0.98 psia (130 kPa) to about 333 psia (2296 kPa), or at a pressure of about 1 atm, 2 atm, 3 atm, 4 atm, 5 atm, 6 atm, 7 atm, 8 atm, 9 atm, 10 atm, 11 atm, 12 atm, 13 atm, 14 atm, 15 atm, 16 atm, 17 atm, 18 atm, 19 atm, 20 atm, 21 atm, 22 atm, 23 atm, 24 atm, 25 atm, 26 atm, 27 atm, 28 atm, 29 atm, 30 atm, or 31 atm.

[0384] 12. The azeotrope or azeotrope-like composition of embodiment 10 or 11, formed at a temperature of from about -40°C to about 130°C.

[0385] 13. The azeotrope-like composition of any one of embodiments 10-12, consisting essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) methyl formate.

[0386] 14. The azeotrope-like composition of any one of embodiments 10-13, consisting essentially of (i) 1 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol % methyl formate at a temperature from −40° C. to about 140° C.

[0387] 15. The azeotrope-like composition of any one of embodiments 10-14, consisting essentially of (i) 85-99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1-15 mol % methyl formate at 20°C.

[0388] 16. The azeotrope-like composition of any one of embodiments 10-12, consisting essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1-chloro-3,3,3-trifluoropropene (E-1233zd).

[0389] 17. The azeotrope-like composition of any one of embodiments 10-12 and 16, consisting essentially of (i) 1 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol % E-1-chloro-3,3,3-trifluoropropene (E-1233zd) at a temperature from −40° C. to about 140° C.

[0390] 18. The azeotrope-like composition of any one of embodiments 10-12, consisting essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz).

[0391] 19. The azeotrope-like composition of any one of embodiments 10-12 and 18, consisting essentially of (i) 1 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol % E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) at a temperature from −40° C. to about 140° C.

[0392] 20. The azeotrope-like composition of any one of embodiments 10-12, consisting essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz).

[0393] 21. The azeotrope-like composition of any one of embodiments 10-12 and 20, consisting essentially of (i) 1 to 99 mol % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol % E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) at a temperature from −40° C. to about 140° C.

[0394] 22. The azeotrope-like composition of any one of embodiments 10-12, 20, and 21, consisting essentially of (i) 1 to 12 mol % and 89 to 99 mol % of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 11 mol % and 88 to 99 mol % of E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) at a temperature of 20°C.

[0395] 23. The azeotrope-like composition of any one of embodiments 10-12, consisting essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0396] 24. The azeotrope composition of any one of embodiments 10-12 and 23, consisting essentially of 16 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and 84 mole % 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) at a temperature of 31.8°C.

[0397] 25. In some embodiments, the present application provides a process for forming a foam, comprising: (a) adding a foamable composition to a blowing agent; (b) reacting the foamable composition under conditions effective to form a foam; Including, The blowing agent comprises the composition of any one of embodiments 1 to 24.

[0398] 26. In some embodiments, the present application further provides a process for forming a foam, comprising: (a) adding a foamable composition comprising one or more thermoplastic polymers to a blowing agent; (b) processing the foamable composition under conditions effective to form a foam; Including, The blowing agent comprises the composition of any one of embodiments 1 to 24.

[0399] 27. The process of embodiment 26, comprising extruding a mixture of the foamable composition and a blowing agent.

[0400] 28. The process of embodiment 26 or 27, wherein the blowing agent comprises Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0401] 29. The process of embodiment 28, wherein the blowing agent further comprises water.

[0402] 30. The process of embodiment 26 or 27, wherein the blowing agent comprises Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0403] 31. The process of embodiment 30, wherein the blowing agent further comprises water.

[0404] 32. In some embodiments, the present application provides a foam formed by the process of any one of embodiments 25-31.

[0405] 33. In some embodiments, the present application provides a foam comprising a polymer and the composition of any one of embodiments 1-24.

[0406] 34. The foam of embodiment 32 or 33, wherein the blowing agent comprises Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0407] 35. The foam of any one of embodiments 32-34, wherein the blowing agent further comprises water.

[0408] 36. At a temperature of about 20°F, it is about 0.113 Btu·in / ft 2 ·h·°F~approx. 0.158 Btu·in / ft 2 36. The foam of any one of embodiments 32-35, exhibiting a K-factor of .lambda.·h·°F.

[0409] 37. At a temperature of about 35°F, it is about 0.116 Btu·in / ft 2 ·h·°F~approx. 0.122 Btu·in / ft 2 37. The foam of any one of embodiments 32-36, exhibiting a K-factor of .lambda.·h·°F.

[0410] 38. At a temperature of about 50°F, it is about 0.122 Btu·in / ft 2 ·h·°F~approx. 0.165 Btu·in / ft 2 38. The foam of any one of embodiments 32-37, exhibiting a K-factor of ·h·°F.

[0411] 39. At a temperature of about 75°F, it is about 0.132 Btu·in / ft 2 ·h·°F~approx. 0.175 Btu·in / ft 2 39. The foam of any one of embodiments 32-38, exhibiting a K-factor of .lambda.·h·°F.

[0412] 40. The foam of embodiment 32 or 33, wherein the blowing agent comprises Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0413] 41. The foam of any one of embodiments 32, 33, and 40, wherein the blowing agent further comprises water.

[0414] 42. At a temperature of about 20°F, it is about 0.111 Btu·in / ft 2 ·h·°F ~ approx. 0.144Btu·in / ft 2 42. The foam of any one of embodiments 32, 33, 40, and 41, exhibiting a K-factor of .lambda.h.degree.F.

[0415] 43. At a temperature of about 35°F, it is about 0.115 Btu·in / ft 2 ·h·°F~approx. 0.150 Btu·in / ft 2 43. The foam of any one of embodiments 32, 33, and 40-42, exhibiting a K-factor of .lambda.·h·°F.

[0416] 44. At a temperature of about 50°F, it is about 0.120 Btu·in / ft 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 44. The foam of any one of embodiments 32, 33, and 40-43, exhibiting a K coefficient of .lambda.·h·°F.

[0417] 45. At a temperature of about 75°F, it is about 0.130 Btu·in / ft 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 45. The foam of any one of embodiments 32, 33, and 40-44, exhibiting a K-factor of .lambda.·h·°F.

[0418] 46. ​​In some embodiments, the present application provides a process for producing cooling, comprising: (a) condensing the composition according to any one of embodiments 1 to 24; (b) evaporating the composition in the vicinity of the object to be cooled; The present invention provides a process including:

[0419] 47. In some embodiments, the present application provides a process for producing heat, comprising: (a) condensing the composition of any one of embodiments 1 to 24 in the vicinity of an object to be heated; (b) then evaporating the composition; The present invention provides a process including:

[0420] 48. In some embodiments, the present application provides a heat transfer system comprising a heat transfer medium, wherein the heat transfer medium comprises the composition of any one of embodiments 1-24.

[0421] 49. In some embodiments, the present application provides a high temperature heat pump comprising a working fluid comprising the composition of any one of embodiments 1-24.

[0422] 50. In some embodiments, the present application provides an aerosol product comprising a component to be dispensed and a propellant, wherein the propellant comprises a composition described in any one of embodiments 1 to 24.

[0423] 51. In some embodiments, the present application provides a method of extinguishing or suppressing a flame, comprising dispensing a composition of any one of embodiments 1-24 into the flame.

[0424] 52. In some embodiments, the present application provides a system for preventing or suppressing a flame, the system comprising: a container containing a composition of any one of embodiments 1-24; and a nozzle for dispensing the composition toward the location of the anticipated or actual flame.

[0425] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, but not limit, the scope of the invention as defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art that the present invention may be combined with any of the features described herein with respect to any particular aspect and / or embodiment of the invention, with one or more of the other features of any other aspect and / or embodiment of the invention described herein, modified as appropriate to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. An azeotrope-like composition consisting essentially of (i) 1 to 99 mole % Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mole % E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) at a temperature from −40° C. to about 140° C.

2. 1. A process for forming a foam, comprising: (a) adding a foamable composition to a blowing agent; (b) reacting the foamable composition under conditions effective to form a foam; Including, The process wherein the blowing agent comprises the composition of claim 1.

3. A process for producing cooling, comprising: (a) concentrating the composition of claim 1; (b) evaporating the composition in the vicinity of the object to be cooled; The process includes:

4. A process for producing heat, comprising: (a) condensing the composition of claim 1 in the vicinity of a body to be heated; (b) then evaporating the composition; The process includes:

5. 10. A heat transfer system comprising a heat transfer medium, wherein the heat transfer medium comprises the composition of claim 1.

6. 10. A high temperature heat pump comprising a working fluid comprising the composition of claim 1.

7. 10. An aerosol product comprising a component to be dispensed and a propellant, wherein the propellant comprises the composition of claim 1.

8. 10. A method of extinguishing or suppressing a flame, comprising the step of dispensing the composition of claim 1 into said flame.

9. 10. A system for preventing or suppressing a flame, comprising: a container containing the composition of claim 1; and a nozzle for dispensing the composition toward the location of the expected or actual flame.

10. A foam comprising a polymer and the composition described in claim 1.

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