Composition and use of Z-1-chloro-2,3,3,3-tetrafluoropropane

Abstract

The present invention aims to provide a composition that does not contribute to stratospheric ozone depletion and also has a low global warming index (GWP). [Solution] The present invention is an azeotropic mixture or azeotropic mixture-like composition comprising Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd).

Description

[Technical Field]

[0001] (Cross-reference of 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 Invention) This disclosure relates to compositions, methods, and systems that are useful in many applications, specifically to the use of compositions containing the compound Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd). [Background technology]

[0003] For 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 range of applications, including aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastic and thermosetting foams, heat transfer fluids, gaseous dielectrics, fire extinguishing and suppressing agents, power cycle working fluids, polymerization media, particulate control fluids, carrier fluids, buffing abrasives, and displacement drying agents. In the search for alternatives to these versatile compounds, many industries have turned their attention to the use of hydrofluorocarbons (HFCs). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent Provisional Application No. 62 / 547,518 [Overview of the project] [Problems that the invention aims to solve]

[0005] HFCs are a cause for 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 are 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 have a low global warming index (GWP). [Means for solving the problem]

[0006] This specification provides for the use of compositions, methods, and systems useful in many applications, specifically compositions containing the compound Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd), which has the following structure:

[0007] [ka]

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

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods and materials are described below. All publications, patent applications, patents, and other references referred herein are incorporated herein by reference in their entirety unless a specific section is cited. In the event of any inconsistency, including definitions, this specification shall prevail. Furthermore, materials, methods, and examples are merely illustrative and not intended to limit the scope of the invention. [Brief explanation of the drawing]

[0010] [Figure 1] The vapor pressures measured for the binary system 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) in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 2] The vapor pressures measured for the binary system of Z-HCFO-1224yd and methyl formate in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 3] The vapor pressures measured for the binary system of E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd) and Z-HCFO-1224yd in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 4] The vapor pressures measured for the E-HFO-1336mzz and Z-HCFO-1224yd binary systems for compositions in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 5] The vapor pressures measured for the binary system of E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) and Z-HCFO-1224yd in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 6] The vapor pressures measured for the Z-HCFO-1224yd and HFC-245eb binary systems in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 7]The vapor pressures measured for the Z-HCFO-1224yd and HCFO-1233xf binary systems in a PTx sample cell are shown. Experimental data points are shown as black dots, and solid lines are drawn from data calculated using the NRTL formula. [Figure 8] The K coefficient at 75°F as a function of time is shown for the mixture prepared according to the procedure described in Example 15. [Figure 9] The K coefficient at 50°F as a function of time is shown for the mixture prepared according to the procedure described in Example 15. [Figure 10] The K coefficient at 35°F as a function of time is shown for the mixture prepared according to the procedure described in Example 15. [Figure 11] The K coefficient at 25°F as a function of time is shown for the mixture prepared according to the procedure described in Example 15. [Modes for carrying out the invention]

[0011] Hydrochlorofluoroolefins have a low global warming potential and are not thought to contribute to stratospheric ozone depletion. One such hydrochlorofluoroolefin is 1-chloro-2,3,3,3-tetrafluoropropa-1-ene. 1-chloro-2,3,3,3-tetrafluoropropa-1-ene exists as two different stereoisomers, each with a different boiling point, and therefore can exhibit different functions in different applications.

[0012] Compositions comprising hydrochlorofluoroolefin 1-chloro-2,3,3,3-tetrafluoropropa-1-ene (CF3CF=CHCl, HCFO-1224yd), specifically compositions comprising the Z isomer Z-HCFO-1224yd, are provided herein.

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

[0014] In some embodiments, the composition comprises Z-HCFO-1224yd and at least one additional compound, such as HFO, HFC, hydrofluoroether (HFE), hydrocarbon, ether, aldehyde, ketone, and others, such as methyl formate, formic acid, trans-1,2-dichloroethylene (DCE), carbon dioxide (CO2), cis-HFO-1234ze+HFO-1225yez, mixtures of these with water; mixtures of these with CO2, mixtures of these with DCE; mixtures of these with methyl formate; mixtures of cis-HFO-1234ze+CO2, mixtures of cis-HFO-1234ze+HFO-1225yez+CO2, and mixtures of cis-HFO-1234ze+HFC-245fa. In such compositions, the amount of compound Z-HCFO-1224yd can vary, including in all cases that constitute the remainder of the composition after considering all other components in the composition.

[0015] In some embodiments, Z-HCFO-1224yd constitutes 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 virtually no ozone depletion potential (ODP), for example, an ODP of about 0.5 or less, for example, 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, for example, 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 global warming over a 100-year period due to carbon dioxide and is defined in the same literature as ODP.

[0018] In some embodiments, Z-HCFO-1224yd is mixed with one or more compounds to form a blended composition. In some embodiments, Z-HCFO-1224yd forms a blended 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, CO2, and others. In some embodiments, the other compounds constitute about 1% to about 99% by weight of the composition. For example, approximately 1% to 90% by weight of the composition, approximately 1% to 80% by weight, approximately 1% to 70% by weight, approximately 1% to 60% by weight, approximately 1% to 50% by weight, approximately 1% to 40% by weight, approximately 1% to 30% by weight, approximately 1% to 20% by weight, approximately 1% to 10% by weight, approximately 1% to 5% by weight, approximately 5% to 99% by weight, approximately 5% to 95% by weight, approximately 5% to 75% by weight, approximately 5% to 50% by weight, approximately 5% to 25% by weight, approximately 10% to 99% by weight These are approximately 10% to 90% by weight, 10% to 75% by weight, 10% to 50% by weight, 10% to 25% by weight, 25% to 99% by weight, 25% to 90% by weight, 25% to 75% by weight, 25% to 50% by weight, 40% to 60% by weight, 45% to 55% by weight, 50% to 99% by weight, 50% to 75% by weight, 60% to 99% by weight, 60% to 75% by weight, or 75% to 99% by weight.

[0019] In some embodiments, Z-HCFO-1224yd forms blended compositions with the compounds shown in Table 1 below (all percentages are by weight and should be understood as being preceded by the word "approximately").

[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 Furthermore, methods and systems are provided herein that include Z-HCFO-1224yd as a blowing agent, optionally together with one or more additional compounds that also act as blowing agents (hereinafter referred to as co-blowing agents for convenience, not for the purpose of limitation), surfactants, polyols, catalysts, flame retardants, polymer modifiers, colorants, dyes, solubility improvers, rheology modifiers, plasticizers, fillers, nucleating agents, viscosity reducers, vapor pressure regulators, stabilizers, etc. In some embodiments, the blowing agent is used in foams such as spray foams and panel foams and comprises a blend of Z-HCFO-1224yd with hydrocarbons (e.g., pentane containing 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 constitutes 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 blowing agent composition. Other ranges of quantities are shown in Table 1 and described above, and these quantities are also applicable to this use of the composition of the present invention.

[0028] In some embodiments, dispersants, foam stabilizers, surfactants, and other additives are also incorporated into the foaming agent composition. Certain surfactants are optional but may be added to function as foam stabilizers. Suitable stabilizers include polysiloxane polyoxyalkylene block copolymers, such as those disclosed in U.S. Patents 2,834,748, 2,917,480, and 2,846,458, which are incorporated herein by reference. Representative materials, typically examples of polysiloxane polyoxyalkylene block copolymers, are marketed under the names DC-193, B-8404, and L-5340. Other optional additives for the foaming agent mixture include 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, and flame retardants such as polyvinyl chloride. Regarding nucleating agents, all known compounds and materials with nucleating properties, including talc, are available for use in the present invention.

[0029] In some embodiments, the composition contains other compounds and / or components that modulate specific properties of the composition (e.g., cost), and the presence of such compounds and components is within the broad scope of the present invention.

[0030] In some embodiments, the co-foaming agent according to the present invention includes a physical foaming agent, a chemical foaming agent (including water in some embodiments), or a foaming agent having a combination of the properties of a physical and a chemical foaming agent.

[0031] A wide range of co-foaming agents can be used in accordance with the present invention. In some embodiments, the foaming agent composition of the present invention comprises one or more HFCs as co-foaming agents, such as one or more C1-C4 HFCs, and / or one or more hydrocarbons, such as C4-C6 hydrocarbons. In some embodiments, the foaming agent composition comprises 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 one or more HFCs selected from all isomers of all such HFCs.

[0032] In some embodiments, the foaming agent composition includes one or more hydrocarbons, for example, iso, n, and / or cyclopentane for thermosetting foams, and butane or isobutane for thermoplastic foams. Other materials may also be included, for example, water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such as dichloroethylene (e.g., dichloroethylene (trans-1,2-dichloroethylene, etc.), ethyl chloride, and chloropropane), HCFCs, C1-C5 alcohols (e.g., ethanol and / or propanol and / or butanol, etc.), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including dimethyl ether and diethyl ether), diethers (such as dimethoxymethane and diethoxymethane), and methyl formate (including any combination thereof). In some embodiments, such components are omitted due to their negative impact on the environment.

[0033] In some embodiments, one or more of the following HFC isomers are used as a co-foaming agent in the composition 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 the additional co-foaming agents described above, as well as any additional components that may be included in the composition, can vary widely within the broad overall scope of the present invention according to the specific use 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 a sufficient amount of Z-HCFO-1224yd to produce a blowing agent composition that is non-flammable overall.

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

[0037] In some embodiments, the blowing agent composition contains at least about 50% by weight of Z-HCFO-1224yd. In some embodiments, the blowing agent is essentially made up 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, particularly 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, for example, about 5% to about 65% by weight of a co-blowing agent. In some embodiments, the co-blowing agent comprises H2O, HFCs, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof. In some embodiments, the co-blowing agent essentially consists of H2O, HFCs, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof.

[0039] In some embodiments, the co-foaming agent contains H2O. In some embodiments, the composition contains H2O in an amount of about 5% to about 50% by weight of the total foaming agent composition, for example, about 10% to about 40% by weight, or about 10% to about 20% by weight of the total foaming agent.

[0040] In some embodiments, the co-foaming agent contains CO2. In some embodiments, the composition contains CO2 in an amount of about 5% to about 60% by weight of the total foaming agent composition, for example, about 20% to about 50% by weight of the total foaming agent, or about 40% to about 50% by weight of the total foaming agent.

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

[0042] In some embodiments, the composition comprises one or more HFC co-foaming agents, such as C2, C3, C4, or C5HFCs. In some embodiments, the composition comprises difluoroethane, such as HFC-152a, in an extruded thermoplastic material, for example. In some embodiments, the composition comprises pentafluoropropane, such as HFC-245. In some embodiments, the HFC co-foaming agent is present in the composition in an amount of about 5% to about 80% by weight of the total foaming agent composition, for example, about 10% to about 75% by weight of the total foaming agent, or about 25% to about 75% by weight. In some embodiments, the HFC is C2 to C4HFC. In some embodiments, the HFC is C3HFC. In some embodiments, the HFC is C3HFC, such as pentafluorinated C3HFC, for example, HFC-245fa.

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

[0044] Foaming composition Foaming compositions are provided herein. As is known to those skilled in the art, foaming compositions generally comprise one or more components capable of forming a foam. As used herein, the term “foaming agent” is used to refer to a component or combination of components capable of forming a foam structure, for example, a generally foamy foam structure. The foaming compositions provided herein comprise such components and foaming agent compounds. In some embodiments, the foaming agent compound is Z-HCFO-1224yd.

[0045] In some embodiments, the foaming composition comprises Z-HCFO-1224yd and one or more components. In some embodiments, the foaming composition comprises Z-HCFO-1224yd and 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 It contains one or more components selected from 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 foaming 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 foaming agent to expand a thermoplastic foam. In some embodiments, the foam is a polystyrene foam.

[0046] In some embodiments, the amount of Z-HCFO-1224yd in the foaming composition is about 1% by weight to about 99% by weight, for example, 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to the foaming compositions provided herein.

[0047] In some embodiments, one or more components capable of forming a foam include a thermosetting composition capable of forming a foam and / or foaming composition. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, as well as phenol 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 have the function of controlling and adjusting bubble size and stabilizing the foam structure during formation. In some embodiments, any one or more of the additional components described above with respect to the foaming agent compositions described herein are incorporated into the foaming compositions described herein. In such embodiments of thermosetting foams, one or more of the compositions are included in the foaming composition as a foaming agent or as part thereof, or as part of two or more foaming compositions, and the compositions may include one or more components capable of reacting and / or foaming under appropriate conditions to form a foam or foam structure.

[0048] In some embodiments, one or more foamable components include thermoplastic materials, such as thermoplastic polymers and / or resins. Examples of thermoplastic foam components include polyolefins such as monovinyl aromatic compounds of the formula Ar--CH=CH2 (wherein Ar is a benzene-based aromatic hydrocarbon group such as polystyrene (PS)). Other examples of suitable polyolefin resins include various ethylene resins, such as ethylene homopolymers and ethylene copolymers such as polyethylene, polypropylene (PP), and polyethylene terephthalate (PET). In some embodiments, the thermoplastic foam composition is an extrudeable 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 method of the present invention requires the step of incorporating the blowing agent according to the present invention into a foaming or foam-forming composition, and then foaming the composition. In some embodiments, the method includes a step or series of steps, which includes the step of causing volume expansion of the blowing agent according to the present invention.

[0050] In some embodiments, existing systems and apparatus for incorporating and foaming foaming agents are readily adaptable to use according to the present invention. One advantage of the present invention is to provide an improved foaming agent that is generally compatible with existing foaming methods and systems.

[0051] Therefore, those skilled in the art will understand that the present invention includes methods and systems for foaming all types of foams, such as thermosetting foams, thermoplastic foams, and in-situ formed foams. In some embodiments, the foaming agent is used in conjunction with conventional foaming equipment, such as polyurethane foaming equipment, under conventional processing conditions. Accordingly, the method of the present invention includes a polyol premix type operation, a blend type operation, foaming agent addition in a third flow, and foaming agent addition in a foaming head.

[0052] With respect to thermoplastic foams, in some embodiments, the method includes the steps of introducing a blowing agent according to the present invention into a thermoplastic material, such as a thermoplastic polymer such as a polyolefin, and then subjecting the thermoplastic material to conditions effective for foaming. In some embodiments, the step of introducing the blowing agent into the thermoplastic material includes introducing the blowing agent into a screw extrusion molding machine containing the thermoplastic material. In some embodiments, the foaming step includes reducing the pressure on the thermoplastic material, thereby causing the blowing agent to expand and contributing to the foaming of the material.

[0053] Those skilled in the art will understand, particularly in consideration of the disclosures contained herein, that the order and method by which the blowing agent of the present invention is formed and / or added to the foaming composition generally does not affect the operability of the present invention. For example, in the case of extrudeable foams, in some embodiments, the various components of the blowing agent, and even the components of the foaming composition, are not mixed before 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 parts of the foaming composition.

[0054] In some embodiments, one or more components of the blowing agent are introduced at a first position in the extruder, upstream of the location where one or more other components of the blowing agent are added, anticipating that the components will integrate within the extruder and / or function more effectively in this manner. In some embodiments, two or more components of the blowing agent are pre-combined and introduced together into the foaming composition, either directly or as part of a premix, and then further added to other parts of the foaming composition.

[0055] Azeotropic mixtures and azeotropic mixture-like compositions Also provided herein are azeotropic compositions and azeotropic mixture-like compositions comprising Z-1-chloro-2,3,3,3-tetrafluoropropene (Z-HCFO-1224yd) and additional compounds. These compositions have a near-zero ozone depletion potential (ODP) and a low global warming potential. These compositions are useful as aerosol propellants, refrigerants, cleaning agents, expanding agents ("foaming agents") for producing thermoplastic and thermosetting foams, heat transfer fluids, gaseous dielectrics, solvents, fire extinguishing and fire suppressing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and displacement drying agents.

[0056] A two-component azeotropic composition or azeotropic-like composition of a mixture with substantially constant boiling points can be characterized in many 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 azeotropic mixture or azeotropic-like composition changes, at least to some extent, as does its boiling point temperature. Thus, an azeotropic composition or azeotropic-like composition of two compounds exhibits a unique kind of relationship, but with a composition that changes depending on temperature and / or pressure. Therefore, to define azeotropic mixtures and azeotropic-like compositions, a range of compositions, rather than a fixed composition, is often used.

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

[0058] An "azeotropic mixture-like" composition means a mixture of two or more liquids with constant or substantially constant boiling points that behave as a single substance. In some embodiments, an azeotropic mixture-like composition may be characterized in that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the evaporated or distilled liquid, i.e., the mixture is distilled / refluxed without substantially changing its composition. In some embodiments, an azeotropic mixture-like composition may be characterized in that the bubble point vapor pressure and dew point vapor pressure of the composition are substantially the same at a particular temperature. In some embodiments, an azeotropic mixture-like composition may be characterized by a region adjacent to the highest or lowest 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 an azeotropic mixture if, after removing 50 weight percent of the composition by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after the removal of 50 weight percent of the original composition is less than about 10 percent when measured in absolute units. Absolute units mean pressure measurements, such as psia, atmospheric pressure, bar, toll, dyne / cm², millimeters of mercury, inches of water, and other equivalent terms well known in the art. If an azeotropic mixture is present, there is no difference in vapor pressure between the original composition and the composition remaining after the removal of 50 weight percent of the original composition.

[0060] In the case of azeotropic compositions, in some embodiments, there exist compositions in a range around the azeotropic point where the highest boiling point azeotropic mixture has a boiling point at a certain pressure that is higher than that of the pure components of the composition, and a vapor pressure at a certain temperature that is lower than that of the pure components of the composition, and where the lowest boiling point azeotropic mixture has a boiling point at a certain pressure that is lower than that of the pure components of the composition, and a vapor pressure at a certain temperature that is higher than that of the pure components of the composition. Boiling points and vapor pressures higher or lower than those of 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 bonds.

[0061] In some embodiments, the range of compositions having a highest or lowest boiling point at a particular pressure, or a highest or lowest vapor pressure at a particular temperature, may or may not be the same as the range of compositions in which the change in vapor pressure is less than about 10% when 50 weight percent of the composition evaporates. If the range of compositions having a highest or lowest boiling point at a particular pressure, or a highest or lowest vapor pressure at a particular temperature, is wider than the range of compositions in which the change in vapor pressure is less than about 10% when 50 weight percent of the composition evaporates, then unexpected intermolecular forces are considered important, in that refrigerant compositions having substantially non-constant boiling point intermolecular forces may exhibit an unexpected increase in volume or efficiency relative to the components of the refrigerant composition.

[0062] It is recognized in the art that when an azeotropic mixture 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. Therefore, in some embodiments, an azeotropic composition can be defined in terms of the specific relationships that exist between its components, or in terms of the precise amounts of each component of a composition characterized by a constant boiling point at a particular pressure. In some embodiments, an azeotropic mixture or azeotropic mixture-like composition of two compounds can be characterized by defining a composition characterized by its boiling point at a given pressure, thereby providing distinguishing features without overly limiting the scope of the invention by a specific numerical composition, which is limited, but only to a similar degree, by the available analytical instruments.

[0063] It is recognized in this field that a system is defined as forming an azeotropic mixture-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 volatility of a component is the ratio of the mole fraction of the component in vapor to the mole fraction of the component in liquid.

[0064] A method known as the PTx method can be used to determine the relative volatility of any two compounds. This procedure measures the total absolute pressure in a cell of known volume at a constant temperature for two different compositions of 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 within a PTx cell using activity coefficient models such as the non-random two-liquid (NRTL) equation, thereby representing a non-ideal liquid-phase 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, published by McGraw Hill, by Reid, Prausnitz, and Poling, pp. 241-387, and "Phase Equilibria in Chemical Engineering," published by Butterworth Publishers, 1985, by Stanley M. Walas, pp. 165-244, both incorporated herein by reference. While not bound by any theory or explanation, the NRTL equation, in conjunction with PTx cell data, is considered capable of adequately predicting the relative volatility of the Z-HFO-1224yd-containing composition of the present invention, and therefore, predicting the behavior of these mixtures in multi-stage separation equipment such as distillation columns.

[0066] As used herein, “effective amount” means the amount of each component of the composition provided herein that, when combined, forms an azeotropic composition or an azeotropic mixture-like composition. This definition includes the amount of each component, which may vary depending on the pressure applied to the composition, as long as the azeotropic composition or azeotropic mixture-like composition remains at different pressures (though the boiling points may differ). Thus, the effective amount includes the amount of each component of the composition of the present invention that forms an azeotropic composition or an azeotropic mixture-like composition at temperatures or pressures other than those described herein (for example, it may be expressed in weight percent).

[0067] In some embodiments, the azeotropic mixture or azeotropic mixture-like composition is 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-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), 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, It contains 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 azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and methyl formate. In some embodiments, the azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). In some embodiments, the azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz). In some embodiments, the azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd). In some embodiments, the azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd). In some embodiments, the azeotropic mixture or azeotropic mixture-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 azeotropic mixture or azeotropic mixture-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 azeotropic mixture or azeotropic mixture-like composition comprises Z-HCFO-1224yd and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0069] In some embodiments, Z-HCFO-1224yd is present in an azeotropic mixture or azeotropic mixture-like composition in amounts of about 1 mol% to about 99 mol%, for example, 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%, and 1 mol%. 0%~approx. 22 mol%, 5 mol%~approx. 6 mol%, 5 mol%~approx. 8 mol%, 5 mol%~approx. 10 mol%, 5 mol%~approx. 11 mol%, 5 mol%~approx. 12 mol%, 5 mol%~approx. 15 mol%, 5 mol%~approx. 20 mol%, 5 mol%~approx. 22 mol%, 5 mol%~approx. 95 mol%, 38 mol%~approx. 95 mol%, 38 mol%~approx. 99 mol%, 49 mol%~approx. 95 mol%, 49 mol%~approx. 99 mol%, 50 mol%~approx. 95 mol%, 50 mol%~approx. 99 mol%, 53 mol 0%~approximately 95 mol%, 53 mol%~approximately 99 mol%, 55 mol%~approximately 95 mol%, 55 mol%~approximately 99 mol%, 58 mol%~approximately 95 mol%, 58 mol%~approximately 99 mol%, 60 mol%~approximately 95 mol%, 60 mol%~approximately 99 mol%, 62 mol%~approximately 95 mol%, 62 mol%~approximately 99 mol%, 69 mol%~approximately 95 mol%, 69 mol%~approximately 99 mol%, 70 mol%~approximately 95 mol%, 70 mol%~approximately 99 mol%, 74 mol%~approximately 95 mol%, 74 mol% It constitutes approximately 99 mol%, 76 mol% to approximately 95 mol%, 76 mol% to approximately 99 mol%, 80 mol% to approximately 95 mol%, 80 mol% to approximately 99 mol%, 81 mol% to approximately 95 mol%, 81 mol% to approximately 99 mol%, 84 mol% to approximately 95 mol%, 84 mol% to approximately 99 mol%, 86 mol% to approximately 95 mol%, 86 mol% to approximately 99 mol%, 88 mol% to approximately 95 mol%, 88 mol% to approximately 99 mol%, 89 mol% to approximately 95 mol%, or 89 mol% to approximately 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 azeotropic mixture or azeotropic mixture-like composition.

[0070] In some embodiments, the azeotrope or azeotrope-like composition containing Z-HCFO-1224yd is formed in a temperature range of about -40°C to about 130°C.

[0071] In some embodiments, an azeotropic mixture or azeotropic mixture-like composition containing Z-HCFO-1224yd is formed at pressures ranging from approximately 0.98 psia (130 kPa) to approximately 333 psia (2296 kPa). In some embodiments, an azeotropic mixture or azeotropic mixture-like composition containing Z-HCFO-1224yd is formed at pressures ranging from approximately 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, the azeotropic mixture or azeotropic mixture-like composition containing Z-HCFO-1224yd is formed at a pressure of about 1 atm to about 31 atm. In some embodiments, the azeotropic mixture or azeotropic mixture-like composition containing Z-HCFO-1224yd is formed 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.

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

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

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

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

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

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

[0078] Specific examples illustrating the present invention are shown below in the examples. Unless otherwise specified herein, all percentages are by weight. It should be understood that these examples are for illustrative purposes only and should not be construed as limiting the scope of the present invention.

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

[0080] Method for forming foam Methods for forming foams, such as panel foams and spray foams, are provided herein. In some embodiments, the foams are made from polyurethane and polyisocyanurate. In some embodiments, the method includes the steps of providing a blowing agent composition described herein, adding the blowing agent composition (directly or indirectly) to a foaming composition, and reacting the foaming composition under conditions effective for forming a foam or buoyant structure, as is well known in the art. Any method well known in the art, such as those described in "Polyurethanes Chemistry and Technology," Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, NY, which is incorporated herein by reference, can be used or adapted for use in accordance with embodiments of the foams 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, for example, 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, and about 20% by weight to about 90% by weight. Other ranges of quantities are shown in Table 1, and these quantities are similarly applicable to the methods provided herein.

[0082] In some embodiments, the foaming agent compositions provided herein include Z-1-chloro-2,3,3,3-tetrafluoropropane-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 foaming agent compositions provided herein include Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

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

[0085] In some embodiments, the foaming agent compositions provided herein include Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene.

[0086] In some embodiments, the foaming agent composition provided herein further comprises water.

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

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

[0089] In some embodiments, this application provides a composition that is a blend of composition A provided herein and composition B provided herein.

[0090] In some embodiments, the composition, which is a blend of side A and side B, contains a foaming agent component which is a blend of Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0109] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.113 Btu·in / ft at a temperature of approximately 20°F. 2 h°F ~ approximately 0.158 Btu·in / ft 2 This shows the K coefficient for h°F.

[0110] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.113 Btu·in / ft at a temperature of approximately 20°F. 2 h°F ~ approximately 0.119 Btu·in / ft 2 This shows the K coefficient for h°F.

[0111] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.137 Btu·in / ft at a temperature of approximately 20°F. 2 h°F ~ approximately 0.143 Btu·in / ft 2·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.137 Btu·in / ft 2 ·h·°F to about 0.143 Btu·in / ft 2 ·h·°F shows the K coefficient.

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

[0113] In some embodiments, the foam prepared from the blowing agent composition Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a K coefficient of about 0.150 Btu·in / ft 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.150 Btu·in / ft at a temperature of about 20°F for up to about 120 days after the formation of the foam 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.150 Btu·in / ft at a temperature of about 20°F for about 60 days to about 120 days after the formation of the foam2 ·h·°F ~ approx. 0.156Btu·in / ft 2 This shows the K coefficient for h°F.

[0114] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.116 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.122 Btu·in / ft 2 This shows the K coefficient for h°F.

[0115] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.116 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.119 Btu·in / ft 2 This shows the K coefficient for h°F.

[0116] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.137 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.143 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.137 Btu·in / ft at a temperature of approximately 35°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.143 Btu·in / ft 2 This shows the K coefficient for h°F.

[0117] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.145 Btu·in / ft at a temperature of approximately 35°F.2 h°F ~ approximately 0.151 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.145 Btu·in / ft at a temperature of approximately 35°F for up to approximately 60 days after the foam is formed. 2 h°F ~ approximately 0.151 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.145 Btu·in / ft at a temperature of approximately 35°F for approximately 30 to 60 days after the foam is formed. 2 h°F ~ approximately 0.151 Btu·in / ft 2 This shows the K coefficient for h°F.

[0118] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.152 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.159 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is maintained at a temperature of approximately 35°F for up to approximately 120 days after the foam is formed, yielding approximately 0.152 Btu·in / ft 2 h°F ~ approximately 0.159 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.152 Btu·in / ft at a temperature of approximately 35°F for approximately 60 to 120 days after the foam is formed. 2 h°F ~ approximately 0.159 Btu·in / ft 2 This shows the K coefficient for h°F.

[0119] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.122 Btu·in / ft at a temperature of approximately 50°F. 2 • h°F ~ approximately 0.165 Btu·in / ft 2 This shows the K coefficient for h°F.

[0120] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.122 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.126 Btu·in / ft 2 This shows the K coefficient for h°F.

[0121] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.144 Btu·in / ft at a temperature of approximately 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 50°F for up to approximately 30 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 This shows the K coefficient for h°F.

[0122] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein has a yield of approximately 0.150 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.155 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.150 Btu·in / ft at a temperature of approximately 50°F for up to approximately 60 days after the foam is formed. 2 h°F ~ approximately 0.155 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.150 Btu·in / ft at a temperature of approximately 50°F for approximately 30 to 60 days after the foam is formed. 2 h°F ~ approximately 0.155 Btu·in / ft 2This shows the K coefficient for h°F.

[0123] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.158 Btu·in / ft at a temperature of approximately 50°F. 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is maintained at a temperature of about 50°F for up to about 120 days after the foam is formed, yielding about 0.158 Btu·in / ft 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.158 Btu·in / ft at a temperature of approximately 50°F for approximately 60 to 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.164Btu·in / ft 2 This shows the K coefficient for h°F.

[0124] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.132 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.175 Btu·in / ft 2 This shows the K coefficient for h°F.

[0125] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.132 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.137 Btu·in / ft 2 This shows the K coefficient for h°F.

[0126] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.155 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.161 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.155 Btu·in / ft at a temperature of approximately 75°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.161 Btu·in / ft 2 This shows the K coefficient for h°F.

[0127] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.164 Btu·in / ft at a temperature of approximately 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.164 Btu·in / ft at a temperature of approximately 75°F for up to approximately 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.164 Btu·in / ft at a temperature of approximately 75°F for approximately 30 to 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 This shows the K coefficient for h°F.

[0128] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.168 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.172 Btu·in / ft 2The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.168 Btu·in / ft at a temperature of approximately 75°F for up to approximately 90 days after the foam is formed. 2 h°F ~ approximately 0.172 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.168 Btu·in / ft at a temperature of approximately 75°F for approximately 60 to 90 days after the foam is formed. 2 h°F ~ approximately 0.172 Btu·in / ft 2 This shows the K coefficient for h°F.

[0129] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.170 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.175 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is maintained at a temperature of about 75°F for up to about 120 days after the foam is formed, yielding about 0.170 Btu·in / ft 2 h°F ~ approximately 0.175 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.170 Btu·in / ft at a temperature of approximately 75°F for approximately 90 to 120 days after the foam is formed. 2 h°F ~ approximately 0.175 Btu·in / ft 2 This shows the K coefficient for h°F.

[0130] In some embodiments, the composition, which is a blend of side A and side B, contains a foaming agent component which is a blend of Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0131] In some embodiments, the composition, which is a blend of side A and side B, contains a foaming agent component which is a blend of Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0152] In some embodiments, the foam prepared from the blowing agent composition Z-1-chloro-2,3,3,3-tetrafluoropropene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein has a K-factor of about 0.127 Btu·in / ft 2 ·h·°F to about 0.131 Btu·in / ft 2 ·h·°F at a temperature of about 20°F. In some embodiments, the foam has a K-factor of about 0.127 Btu·in / ft<000009�>·h·°F to about 0.131 Btu·in / ft 2 ·h·°F at a temperature of about 20°F for up to about 30 days after formation of the foam.

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

[0154] In some embodiments, the foam prepared from the blowing agent composition Z-1-chloro-2,3,3,3-tetrafluoropropene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein has a K-factor of about 0.140 Btu·in / ft[[ID=@9]] 2 ·h·°F to about 0.145 Btu·in / ft 2The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.140 Btu·in / ft at a temperature of approximately 20°F for up to approximately 120 days after the foam is formed. 2 h°F ~ approximately 0.145 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.140 Btu·in / ft at a temperature of approximately 20°F for approximately 60 to 120 days after the foam is formed. 2 h°F ~ approximately 0.145 Btu·in / ft 2 This shows the K coefficient for h°F.

[0155] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.115 Btu·in / ft at a temperature of approximately 35°F. 2 • h°F ~ approximately 0.150 Btu·in / ft 2 This shows the K coefficient for h°F.

[0156] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.115 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.119 Btu·in / ft 2 This shows the K coefficient for h°F.

[0157] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.131 Btu·in / ft at a temperature of approximately 35°F. 2 • h°F ~ approximately 0.135 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.131 Btu·in / ft at a temperature of approximately 35°F for up to approximately 30 days after the foam is formed. 2• h°F ~ approximately 0.135 Btu·in / ft 2 This shows the K coefficient for h°F.

[0158] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.138 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.142 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.138 Btu·in / ft at a temperature of approximately 35°F for up to approximately 60 days after the foam is formed. 2 h°F ~ approximately 0.142 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.138 Btu·in / ft at a temperature of approximately 20°F for approximately 30 to 60 days after the foam is formed. 2 h°F ~ approximately 0.142 Btu·in / ft 2 This shows the K coefficient for h°F.

[0159] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.146 Btu·in / ft at a temperature of approximately 35°F. 2 • h°F ~ approximately 0.152 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.146 Btu·in / ft at a temperature of approximately 35°F for up to approximately 120 days after the foam is formed. 2 • h°F ~ approximately 0.152 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam yields approximately 0.146 Btu·in / ft at a temperature of approximately 35°F for approximately 60 to 120 days after the foam is formed. 2 • h°F ~ approximately 0.152 Btu·in / ft 2 This shows the K coefficient for h°F.

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

[0161] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein has a yield of about 0.120 Btu·in / ft at a temperature of about 50°F. 2 h°F ~ approximately 0.124 Btu·in / ft 2 This shows the K coefficient for h°F.

[0162] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.137 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.141 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.137 Btu·in / ft at a temperature of approximately 50°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.141 Btu·in / ft 2 This shows the K coefficient for h°F.

[0163] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein has a foam yield of approximately 0.144 Btu·in / ft at a temperature of approximately 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 50°F for up to approximately 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 50°F for approximately 30 to 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 This shows the K coefficient for h°F.

[0164] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.152 Btu·in / ft at a temperature of approximately 50°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is maintained at a temperature of about 50°F for up to about 120 days after the foam is formed, yielding about 0.152 Btu·in / ft 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.152 Btu·in / ft at a temperature of approximately 50°F for approximately 60 to 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 This shows the K coefficient for h°F.

[0165] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.130 Btu·in / ft at a temperature of approximately 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 This shows the K coefficient for h°F.

[0166] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.130 Btu·in / ft at a temperature of approximately 75°F. 2 • h°F ~ approximately 0.135 Btu·in / ft 2 This shows the K coefficient for h°F.

[0167] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.148 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.153 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.148 Btu·in / ft at a temperature of approximately 75°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.153 Btu·in / ft 2 This shows the K coefficient for h°F.

[0168] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.155 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.161 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.155 Btu·in / ft at a temperature of approximately 75°F for up to approximately 60 days after the foam is formed. 2 h°F ~ approximately 0.161 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.155 Btu·in / ft at a temperature of approximately 75°F for approximately 30 to 60 days after the foam is formed. 2 h°F ~ approximately 0.161 Btu·in / ft 2 This shows the K coefficient for h°F.

[0169] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene described herein yields approximately 0.164 Btu·in / ft at a temperature of approximately 75°F. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is maintained at a temperature of about 75°F for up to about 120 days after the foam is formed, yielding about 0.164 Btu·in / ft 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.164 Btu·in / ft at a temperature of approximately 75°F for approximately 60 to 120 days after the foam is formed. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 This shows the K coefficient for h°F.

[0170] In some embodiments, the composition, which is a blend of side A and side B, includes a foaming agent component which is a blend of Z-1-chloro-2,3,3,3-tetrafluoropropane and E-1-chloro-3,3,3-trifluoropropene.

[0171] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 15% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0172] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 10% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 15% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0173] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 7% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 15% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0174] In some embodiments, the composition, which is a blend of side A and side B, comprises about 10% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 15% by weight of E-1-chloro-3,3,3-trifluoropropene.

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

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

[0177] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 10% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0178] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 10% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 10% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0179] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 7% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 10% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0180] In some embodiments, the composition, which is a blend of side A and side B, comprises about 10% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 5% to about 10% by weight of E-1-chloro-3,3,3-trifluoropropene.

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

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

[0183] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 6% to about 8% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0184] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 10% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 6% to about 8% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0185] In some embodiments, the composition, which is a blend of side A and side B, comprises about 5% to about 7% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 6% to about 8% by weight of E-1-chloro-3,3,3-trifluoropropene.

[0186] In some embodiments, the composition, which is a blend of side A and side B, comprises about 10% to about 15% by weight of Z-1-chloro-2,3,3,3-tetrafluoropropane and about 6% to about 8% by weight of E-1-chloro-3,3,3-trifluoropropene.

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

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

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

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

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

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

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

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

[0195] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.135 Btu·in / ft at a temperature of approximately 35°F. 2 h°F ~ approximately 0.139 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.135 Btu·in / ft at a temperature of approximately 35°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.139 Btu·in / ft 2 This shows the K coefficient for h°F.

[0196] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.144 Btu·in / ft at a temperature of approximately 35°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 35°F for up to approximately 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 35°F for approximately 30 to 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 This shows the K coefficient for h°F.

[0197] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.116 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.155 Btu·in / ft 2 This shows the K coefficient for h°F.

[0198] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.116 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.118 Btu·in / ft 2 This shows the K coefficient for h°F.

[0199] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.135 Btu·in / ft at a temperature of approximately 50°F. 2 h°F ~ approximately 0.139 Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.135 Btu·in / ft at a temperature of approximately 50°F for up to approximately 30 days after the foam is formed. 2 h°F ~ approximately 0.139 Btu·in / ft 2 This shows the K coefficient for h°F.

[0200] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.144 Btu·in / ft at a temperature of approximately 50°F. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 50°F for up to approximately 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.144 Btu·in / ft at a temperature of approximately 50°F for approximately 30 to 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.148Btu·in / ft 2 This shows the K coefficient for h°F.

[0201] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.128 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.166 Btu·in / ft 2 This shows the K coefficient for h°F.

[0202] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.128 Btu·in / ft at a temperature of approximately 75°F. 2 h°F ~ approximately 0.132 Btu·in / ft 2 This shows the K coefficient for h°F.

[0203] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.152 Btu·in / ft at a temperature of approximately 75°F. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.152 Btu·in / ft at a temperature of approximately 75°F for up to approximately 30 days after the foam is formed. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 This shows the K coefficient for h°F.

[0204] In some embodiments, the foam prepared from the foaming agent compositions Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1-chloro-3,3,3-trifluoropropene described herein yields approximately 0.162 Btu·in / ft at a temperature of approximately 75°F. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.162 Btu·in / ft at a temperature of approximately 75°F for up to approximately 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2 The K coefficient is given as h·°F. In some embodiments, the foam is heated to approximately 0.162 Btu·in / ft at a temperature of approximately 75°F for approximately 30 to 60 days after the foam is formed. 2 ·h·°F ~ approx. 0.167Btu·in / ft 2 This shows the K coefficient for h°F.

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

[0206] In some embodiments, the composition, which is a blend of side A and side B, further contains about 1% to about 5% by weight of water.

[0207] In some embodiments, the composition, which is a blend of side A and side B, further contains about 1% to about 3% by weight of water.

[0208] In some embodiments, the composition, which is a blend of side A and side B, further contains about 1% to about 2% by weight of 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 container, and a second portion of the blowing agent exists as a separate gas phase. In such a system, the contained / dissolved blowing agent acts mostly to cause the foam to expand, and the separate gas phase acts to impart propulsion to the foam-forming agent.

[0210] In some embodiments, the one-component system is packaged within a container such as an aerosol can. In some embodiments, the blowing agents described herein result in the expansion of the foam. In some embodiments, the blowing agents described herein provide the energy for transferring the foam / foamable material from the package. In some embodiments, the blowing agents described herein provide the energy for the expansion of the foam and for transferring the foam / foamable material from the package. In some embodiments, such systems and methods include the steps of 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, such as an aerosol can.

[0211] In some embodiments, it is desirable to utilize the present composition when the blowing agent is in a supercritical or near-supercritical state.

[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, etc., prepared from a polymeric foam formulation 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 the foams according to the present invention, such as thermosetting foams such as polyurethane foams, is the ability to achieve excellent thermal performance. In some embodiments, the thermal performance is measured, for example, by the coefficient of thermal conductivity or lambda under low temperature conditions. The foams provided herein, such as the thermosetting foams provided herein, can be used in a wide variety of applications. In some embodiments, examples of the foam include foams for household appliances including refrigerator foams, freezer foams, refrigerator / freezer foams, panel foams, and other low temperature or cryogenic manufacturing applications.

[0214] In some embodiments, the foam provides one or more excellent features, characteristics, and / or properties, including low ozone depletion potential and low global warming potential, all associated with many of the blowing agents described herein, as well as thermal insulation efficiency (especially in the case of thermosetting foams), dimensional stability, compressive strength, and changes in thermal insulation over time. In some embodiments, thermosetting foams are provided, including such foams molded into foam articles, which exhibit improved thermal conductivity compared to foams produced using the same amount of the same blowing agent (or commonly used blowing agents such as HFC-245fa) but without using Z-HCFO-1224yd.

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

[0216] In some embodiments, foams produced according to the methods provided herein have a compressive strength comparable to that obtained by producing foams under substantially the same conditions, except that the blowing agent is HFC-245fa, on a commercial basis. In some embodiments, foams provided herein exhibit a compressive strength of at least about 12.5% ​​yield point (parallel and perpendicular directions) or at least about 13% yield point in each of those directions.

[0217] Methods and Systems Table 1 above lists compositions containing or essentially comprising Z-HCFO-1224yd. In some embodiments, the composition is useful in relation to many methods and systems, including heat transfer methods and heat transfer fluids in systems, such as refrigeration, air conditioning including vehicle air conditioning systems, and refrigerants used in heat pump systems. In some embodiments, the composition is useful in systems and methods for generating aerosols, for example, those systems and methods that contain or consist of an aerosol propellant. In some embodiments, methods for forming foams, as well as methods for extinguishing and suppressing fires, are also provided. In some embodiments, methods for removing residues from articles in which the composition is used as a solvent composition in such methods and systems are provided.

[0218] Heat transfer method A heat transfer method using the compositions provided herein is provided herein. In some embodiments, the heat transfer method comprises the steps of providing a composition comprising or essentially comprising Z-HCFO-1224yd, and causing a phase change of the composition by transferring heat to or from the composition. In some embodiments, the composition comprising or essentially comprising Z-HCFO-1224yd is the blends listed in Table 1. In some embodiments, the composition comprising or essentially comprising Z-HCFO-1224yd is the blends listed in Table 2 below. In some embodiments, the method brings about cooling by absorbing heat from a fluid or article, such as by evaporating the refrigerant composition in the vicinity of the object or fluid to be cooled in order to generate a vapor comprising or essentially comprising Z-HCFO-1224yd.

[0219] In some embodiments of the heat transfer method, the composition is a blend of Z-HCFO-1224yd with one or more additional compounds. In some embodiments of the heat transfer method, Z-HCFO-1224yd is blended with one or more of HFO, HFE, hydrocarbons, alcohols, ethers, aldehydes, ketones, or other compounds, such as water, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene, CO2, and others to form a blended composition. In some embodiments of the heat transfer method, the other compounds constitute about 1% to about 99% by weight of the composition. For example, approximately 1% to 90% by weight of the composition, approximately 1% to 80% by weight, approximately 1% to 70% by weight, approximately 1% to 60% by weight, approximately 1% to 50% by weight, approximately 1% to 40% by weight, approximately 1% to 30% by weight, approximately 1% to 20% by weight, approximately 1% to 10% by weight, approximately 1% to 5% by weight, approximately 5% to 99% by weight, approximately 5% to 95% by weight, approximately 5% to 75% by weight, approximately 5% to 50% by weight, approximately 5% to 25% by weight, approximately 10% to 99% by weight These are approximately 10% to 90% by weight, 10% to 75% by weight, 10% to 50% by weight, 10% to 25% by weight, 25% to 99% by weight, 25% to 90% by weight, 25% to 75% by weight, 25% to 50% by weight, 40% to 60% by weight, 45% to 55% by weight, 50% to 99% by weight, 50% to 75% by weight, 60% to 99% by weight, 60% to 75% by weight, or 75% to 99% by weight.

[0220] In some embodiments of the heat transfer method, the composition containing Z-HCFO-1224yd is a blend composition with the compounds shown in Table 2 below (all percentages are by weight and should be understood as being preceded by the word "approximately").

[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 the step of compressing a refrigerant vapor in, for example, a compressor or similar equipment to produce a vapor of the composition at a relatively high pressure. In some embodiments, as a result of the step of compressing the vapor, heat is added to the vapor, so that the temperature of the relatively high-pressure vapor rises. In some embodiments, the method includes the step of removing at least a portion of the heat added by the evaporation and compression steps from this relatively high-temperature, high-pressure vapor. In some embodiments, the heat removal step includes condensing the high-temperature, high-pressure vapor while the vapor is in a relatively high-pressure state to produce a relatively high-pressure liquid containing or essentially consisting of Z-HCFO-1224yd. In some embodiments, this relatively high-pressure liquid then undergoes an apparent isenthalpic pressure drop to produce a relatively low-temperature, low-pressure liquid. In some embodiments, this is the reduced-temperature refrigerant liquid, which is then vaporized by heat transferred from the object or fluid being cooled.

[0229] In some embodiments, the compositions provided herein are used in a method for producing cooling, which includes the step of evaporating a refrigerant containing or essentially derived from Z-HCFO-1224yd in the vicinity of a liquid or object to be cooled. In some embodiments, the refrigerant containing or essentially derived from Z-HCFO-1224yd is the blends listed in Table 2.

[0230] In some embodiments, the compositions provided herein are used in a method for generating heating, which includes the step of condensing a refrigerant containing or essentially derived from Z-HCFO-1224yd in the vicinity of a liquid or object to be heated. In some embodiments, the refrigerant containing or essentially derived from Z-HCFO-1224yd is the blends listed in Table 2. In some embodiments, the method is similar to the refrigeration cycle described above, except that its 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, for example, 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 ranges of quantities are shown in Table 2, and these quantities are also applicable to this use of the composition of the present invention.

[0232] Refrigerant composition and system In some embodiments, the method, system, and compositions comprising or essentially derived from Z-HCFO-1224yd are adaptable for use in connection with air conditioning systems and equipment, including automotive air conditioning systems, commercial refrigeration systems and equipment (including medium-temperature and low-temperature refrigeration systems and transport refrigeration), coolers, residential refrigerators and freezers, residential and window air conditioners, coolers, and heat pumps, as well as general air conditioning systems. In some embodiments, the compositions are the blends listed in Table 2. In some embodiments, the condenser temperature is in the range of about 20°C to about 55°C. In some embodiments, the evaporator temperature is in the range of >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 also includes high-temperature heat pumps (condenser temperatures exceeding about 55°C, 70°C, or 100°C), etc.

[0233] Many existing refrigeration systems are now adapted for use with existing refrigerants, and the compositions of the present invention are considered adaptable for use in many such systems, with or without system modifications. In some embodiments, the compositions of the present invention offer advantages as substitutes in systems currently based on refrigerants with relatively high capacities. In some embodiments, such embodiments of the compositions offer promising advantages when it is desirable to use the low-capacity refrigerant compositions of the present invention to replace higher-capacity refrigerants, for example, for efficiency reasons. Accordingly, in some embodiments, compositions comprising or essentially consisting of Z-HCFO-1224yd are used as substitutes 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. In some embodiments, compositions containing or essentially derived from Z-HCFO-1224yd are the blends listed in Table 2. In some embodiments, the refrigerants of the present invention potentially enable the beneficial use of larger positive displacement compressors, thereby resulting in better energy efficiency than other refrigerants such as HCFC-123 or HFC-134a. Thus, the refrigerant compositions of the present invention, specifically compositions containing or essentially derived from Z-HCFO-1224yd, offer the potential to achieve energy-based competitive advantages for refrigerant replacement applications.

[0234] In some embodiments, the refrigerant composition is an azeotropic mixture of an azeotropic mixture-like composition comprising Z-HCFO-1224yd and one or more additional components. In some embodiments, the refrigerant composition is an azeotropic mixture of an azeotropic mixture-like composition 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 azeotropic mixture of an azeotropic mixture-like composition comprising Z-HCFO-1224yd and one or more additional components selected from 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 azeotropic mixture or azeotropic mixture-like composition is used as a refrigerant for centrifugal or positive displacement coolers. In some embodiments, the azeotropic mixture or azeotropic mixture-like composition is used as a refrigerant in a liquid-filled evaporator.

[0235] In some embodiments, the azeotrope mixture or azeotrope-like composition is used as an alternative refrigerant. In some embodiments, the azeotrope mixture or azeotrope-like composition is used as an alternative refrigerant for a cooler designed for CFC-114 or HFC-236fa. In some embodiments, the azeotrope mixture 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 include at least about 50% by weight, for example, at least about 70% by weight, of Z-HCFO-1224yd.

[0237] In some embodiments, the compositions provided herein include other components for the purpose of enhancing or providing specific functionality to the composition, or, optionally, reducing the cost of the composition. In some embodiments, the refrigerant compositions provided herein, for example, 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, for example, about 30 to about 50% by weight of the composition. In some embodiments, the composition also includes a compatibilizer, such as propane, for the purpose of assisting the compatibility and / or solubility of the lubricant. In some embodiments, the compatibilizer, including propane, butane, and pentane, is present in an amount of about 0.5 to about 5% by weight of the composition.

[0238] In some embodiments, a combination of a surfactant and a solubilizer, for example, disclosed by U.S. Patent No. 6,516,837, whose disclosure is incorporated by reference, is added to the composition to support oil solubility. 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 refrigeration units with hydrofluorocarbon (HFC) refrigerants, can be used with the refrigerant compositions provided herein.

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

[0240] In some embodiments, compositions containing or essentially comprising Z-HCFO-1224yd further comprise a lubricant. Any of a variety of conventional lubricants may be used in compositions containing or essentially comprising Z-HCFO-1224yd. A key requirement of the lubricant is that, when used in a refrigerant system, it must have sufficient lubricity to return to the compressor of the system so that the compressor is lubricated. Therefore, in some embodiments, the suitability of the lubricant for any given system is determined partly by the refrigerant / lubricant properties and partly 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 oils, alkylbenzenes, polyol esters containing polyalkylene glycols, and PAG oils. Mineral oils containing paraffin or naphthenic oils are commercially available. Examples of commercially available mineral oils include Witco LP 250® from Witco, Zerol 300® from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet. Examples of commercially available alkylbenzene lubricants include Zerol 150®. Examples of commercially available esters include neopentyl glycol diperargonate, 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 polyalkylene glycol and polyol ester. In some embodiments, the lubricant comprises polyalkylene glycol. In some embodiments, the lubricant comprises polyol ether.

[0243] In the present invention, any of the wide range of methods for introducing the refrigerant composition of the present invention into a refrigeration system can be used. In some embodiments, the method includes the steps of: attaching a refrigerant container to the low-pressure side of the refrigeration system; and operating the compressor of the refrigeration system to draw the refrigerant into the system. In some embodiments, the refrigerant container is positioned on a scale that allows monitoring of the amount of refrigerant composition entering the system. In some embodiments, the introduction is stopped when the desired amount of refrigerant composition has been introduced into the system. In some embodiments, a wide range of introduction tools known to those skilled in the art are commercially available. Therefore, in light of the above disclosure, it will be readily possible for those skilled in the art to introduce the refrigerant composition of the present invention into a refrigeration system according to the present invention without excessive experimentation.

[0244] Power cycle applications The Rankine cycle system is known to be a simple and reliable means of converting thermal energy into mechanical shaft power. Organic working fluids are useful as an alternative to water / steam when encountering lower thermal energy. Water / steam systems operating with lower thermal energy (typically below 400°F) have associated high volume and low pressure. 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 preferred transport, and heat transfer properties that provide higher efficiency compared to water at lower operating temperatures. In industrial environments, there are more opportunities to use flammable working fluids such as toluene and pentane, especially when the industrial environment already has large amounts of flammable material in the process or storage area. Other fluids such as CFC-113 and CFC-11 can be used when the risks associated with the use of flammable working fluids are unacceptable, for example, in power generation in densely populated areas or near buildings. Although these materials are non-flammable, they posed an environmental risk due to their ozone depletion potential. Ideally, organic working fluids should be environmentally acceptable, non-flammable, low in 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 combined heat and power (combined heat and power) applications, waste heat from the combustion of fuel used to drive prime movers in power generation equipment is recovered and used, for example, for generating heat or to produce hot water to operate absorption coolers that supply heat and provide cooling. In some cases, the demand for hot water is small or nonexistent. The most challenging cases are when thermal requirements are variable and load matching becomes difficult, degrading the efficient operation of the combined heat and power system. In such cases, it is more useful to convert the waste heat into shaft power by using an organic Rankine cycle system. The shaft power may be used, for example, to operate pumps or to generate electricity. This method increases overall system efficiency and fuel utilization. Since more electricity can be generated for the same amount of fuel input, atmospheric emissions from fuel combustion can be reduced.

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

[0247] Compositions comprising Z-HCFO-1224yd for ORC power cycle applications are provided herein. In some embodiments, the compositions are as shown in Table 3 below (all percentages are by weight and should be understood as being preceded by the word "approximately").

[0248] [Table 3-1]

[0249] Table 3-2

[0250] Table 3-3

[0251] Table 3-4

[0252] In some embodiments, the composition is Z-HCFO-1224yd and 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 It comprises 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 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 an alternative fluid for high-temperature heat pumps and organic Rankine cycles designed for HFC-235fa.

[0254] In some embodiments, compositions comprising or essentially derived from Z-HCFO-1224yd are used in power cycles. In some embodiments, the process includes a step of recovering waste heat in an organic Rankine cycle system, wherein the working fluid is a composition comprising or essentially derived from Z-HCFO-1224yd and optionally one or more additional compounds. In some embodiments, compositions comprising or essentially derived from Z-HCFO-1224yd are the compositions listed in Table 3.

[0255] Cleaning and contaminant removal A method for removing contaminants from a product, part, component, substrate, or any other article or part thereof by applying a composition containing or essentially comprising Z-HCFO-1224yd to the article is provided herein. In some embodiments, the composition containing or essentially comprising Z-HCFO-1224yd is the blend listed in Table 1 above. The term “article” as used herein means all such products, parts, components, substrates, etc., and is intended to mean any surface or part thereof. The term “contaminant” as used herein means any undesirable material or such material present on the article, even if the material has been intentionally placed on the article. For example, in the manufacture of semiconductor devices, it is common to deposit a photoresist material onto a substrate to form a mask for etching operations, 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 method, the amount of Z-HCFO-1224yd in the composition is about 1% to about 99% by weight, for example, 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 ranges of quantities are shown in Table 1 above, and these quantities are also applicable to this use of the composition of the present invention.

[0257] In some embodiments, the method includes the step of applying an article to a composition comprising or essentially comprising Z-HCFO-1224yd. Many and various cleaning techniques can take advantage of the compositions of the present invention. In some embodiments, compositions comprising or essentially comprising Z-HCFO-1224yd are used in connection 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 comprises Z-HCFO-1224yd and another component. In some embodiments, the additional component is CO2. In some embodiments, the additional component is known to be used in connection with supercritical cleaning applications.

[0259] In some embodiments, cleaning compositions containing Z-HCFO-1224yd are used in connection with specific subcritical vapor degreasing and solvent cleaning methods. In some embodiments of solvent use, compositions containing compound Z-HCFO-1224yd are blended with one or more of the following: cis-1234ze, cis-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 the following: 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 the following: 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 the step of removing contaminants from the vapor compression system and its auxiliary components when the system is manufactured and repaired. As used herein, the term “contaminants” refers to processing fluids, lubricants, particulate matter, 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 mainly composed of carbon, hydrogen, and oxygen. In some embodiments, compositions containing or essentially derived from Z-HCFO-1224yd are useful for this purpose.

[0261] Aerosolable compositions and uses In some embodiments, compositions containing or essentially derived from Z-HCFO-1224yd are used alone or in combination with a propellant in sprayable compositions. In some embodiments, the compositions are the blends listed in Table 1 above. In some embodiments, Z-HCFO-1224yd is present in a sprayable composition in an amount of about 1% to about 99% by weight, for example, 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to this use of the composition of the present invention.

[0262] In some embodiments, the sprayable composition comprises a material to be sprayed and a propellant containing or essentially derived from Z-HCFO-1224yd. In some embodiments, the sprayable composition comprises the blends listed in Table 1. In some embodiments, inert components, solvents, and other materials are also present in the sprayable mixture. In some embodiments, the sprayable composition is an aerosol. Suitable materials for spraying include, but are not limited to, cosmetic materials such as deodorants, fragrances, hairsprays, detergents, and abrasives, as well as pharmaceuticals such as antiasthma drugs and breath fresheners.

[0263] In some embodiments for aerosol applications, compositions containing Z-HCFO-1224yd are blended with one or more of the following: 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 the following: pentane, hexane, HFC-365, C4F9OCH3, or C4F9OC2H5. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of the following: 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 an inert component, a solvent, and other components. In some embodiments, the sprayable composition is an aerosol. Suitable active substances to be sprayed include, but are not limited to, lubricants, insecticides, detergents, deodorizers, cosmetic materials such as fragrances and hairsprays, abrasives, and pharmaceutical materials such as skin coolants (sunscreens), topical anesthetics, and anti-asthma drugs.

[0265] In some embodiments, propellants comprising or essentially comprising Z-HCFO-1224yd, either alone or in combination with one or more other compounds, are provided herein. In some embodiments, the propellant comprises or essentially comprising the blends listed 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 essentially comprising Z-HCFO-1224yd. In some embodiments, inert components, solvents, and other materials are also present in the sprayable mixture. In some embodiments, the sprayable composition is an aerosol. Suitable materials to be sprayed include, but are not limited to, lubricants, insecticides, cleaning agents, deodorizers, cosmetic materials such as fragrances and hairsprays, abrasives, pharmaceutical materials such as anti-asthma components, and any other pharmaceuticals comprising any other pharmaceutical or agent intended for inhalation. In some embodiments, a pharmaceutical or other therapeutic agent is present in the composition in a therapeutic amount, and the substantial remainder of the composition comprises or essentially comprises Z-HCFO-1224yd.

[0266] In some embodiments, aerosol products are intended 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, inactive, or solvent components. The propellants provide the force to eject the product in an 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 incorporating them into aerosol formulations often results in flammable aerosol products.

[0267] In some embodiments, the aerosol products described herein include a non-flammable liquefied gas propellant. In some embodiments, the aerosol products described herein include or are essentially derived from Z-HCFO-1224yd. In some embodiments, the aerosol products described herein include or are essentially derived from the blends listed in Table 1 above. In some embodiments, the aerosol products are for use in certain industrial aerosol products, including, for example, spray cleaners and lubricants, and medical aerosols, including, for example, for delivering pharmaceuticals 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 pharmaceuticals into accessible mucous membranes or nasal cavities. In some embodiments, a method is provided for treating diseases, disorders, and similar health-related problems of an organism (such as a human or animal) requiring treatment, comprising the step of applying to the organism a composition containing or essentially derived from Z-HCFO-1224yd and a pharmaceutical or other therapeutic component. In some embodiments, the step of applying a composition comprising or essentially comprising Z-HCFO-1224yd includes providing an MDI containing a composition comprising or essentially comprising Z-HCFO-1224yd (e.g., introducing the composition into the MDI), and then releasing the composition comprising or essentially comprising Z-HCFO-1224yd from the MDI.

[0268] As used herein, the term “non-flammable” refers to the 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 essentially derived from 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, pharmaceuticals such as beta-agonists, corticosteroids, or other pharmaceuticals, and optionally other components such as surfactants, solvents, other propellants, flavorings, and other excipients.

[0270] sterile Many articles, devices, and materials, particularly those used 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. A sterilization method is provided herein, comprising the step of bringing the article, device, or material to be sterilized into contact with a composition containing or essentially consisting of Z-HCFO-1224yd. In some embodiments, the composition is a blend defined in Table 1 above. In some embodiments, the composition is optionally combined with one or more additional sterilizing agents.

[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, for example, 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to this use of the composition of the present invention.

[0272] Many sterilizing agents are known in the art and are considered suitable for use in connection with the present invention, but in some embodiments, the sterilizing agent includes ethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozone, and combinations thereof. In some embodiments, the sterilizing agent is ethylene oxide. Those skilled in the art will be able to easily determine the relative ratio of the sterilizing agent to other compounds containing Z-HCFO-1224yd used in connection with the present sterilization composition and method.

[0273] As is known to those skilled in the art, certain sterilizing agents, such as ethylene oxide, are highly flammable components, and the compounds according to the present invention are included in the composition in effective amounts together with other components present in the composition to reduce the flammability of the sterilizing composition 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 containing Z-HCFO-1224yd at a temperature of about 250°F to about 270°F. In some embodiments, sterilization is carried out in a substantially sealed chamber. In some embodiments, the sterilization process is completed in less than about two hours. In some embodiments, certain articles, such as plastic articles 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 the low-temperature sterilization method, the articles to be sterilized are exposed to a fluid containing or essentially consisting of Z-HCFO-1224yd at a temperature of around room temperature to about 200°F, for example, around room temperature to about 100°F.

[0275] In some embodiments, cryogenic sterilization is a two-step process carried out in a substantially sealed chamber. In some embodiments, the chamber is an airtight chamber. In some embodiments, the first step (sterilization step) includes placing articles, which have been cleaned and packaged in gas-permeable bags, into the chamber. In some embodiments, the chamber is evacuated by vacuuming. In some embodiments, the chamber is evacuated by replacing the air with steam. In some embodiments, the chamber is evacuated by vacuuming 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 the sterilizing agent introduced into the chamber after the desired relative humidity has been achieved. In some embodiments, the sterilizing agent and steam are evacuated from the chamber after sufficient time has passed for the sterilizing agent to penetrate the packaging and reach the crevices of the articles.

[0276] In some embodiments, a second step of the process (aeration step) includes a step of aerating the articles to remove sterilizer residue. In some embodiments, the residue is a toxic sterilizer. 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 containing Z-HCFO-1224yd. In some embodiments, the aeration process includes air cleaning, continuous aeration, and a combination of the two. Air cleaning is a batch process and, in some embodiments, includes a step of evacuating the chamber for a relatively short time, for example, 12 minutes, and then introducing air at or above atmospheric pressure into the chamber.

[0277] As used herein, the term “non-toxic” means compounds and compositions having an acute toxicity level substantially lower than the toxicity level of HFO-1223xd, preferably at least about 30 relative percent lower, as measured by the method 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 the sterilizing agent is achieved. In some embodiments, continuous ventilation involves the steps of introducing air through an inlet on one side of the chamber and then drawing the air out through an outlet on the other side of the chamber by applying a slight depressurization to the outlet. In some embodiments, the two approaches are combined. In some embodiments, the method includes the steps of air purifying and then carrying out the ventilation cycle.

[0279] Extraction of fragrances and air fresheners In some embodiments, compositions containing or essentially consisting of Z-HCFO-1224yd are used to transport, extract, or separate desired materials from biomass. In some embodiments, the compositions are the blends listed in Table 1 above. In some embodiments, the materials include, but are not limited to, essential oils such as flavorings and fragrances, oils that can be used as fuels, pharmaceuticals, or nutritional supplements. Thus, a method for transporting, extracting, or separating desired materials from biomass is provided herein.

[0280] In some embodiments of the extraction method, the amount of Z-HCFO-1224yd in the composition is about 1% by weight to about 99% by weight, for example, 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to this use of the composition of the present invention.

[0281] In some embodiments, compositions containing Z-HCFO-1224yd are used as extractants, carriers, or part of a delivery system for fragrance and aromatic formulations. In some embodiments, the formulations are aerosol formulations. In some embodiments, compositions containing Z-HCFO-1224yd are used as extractants for fragrances and aromatics. In some embodiments, fragrances and aromatics are extracted from plant materials.

[0282] Flammability reduction method A method for reducing the flammability of a fluid is provided herein, comprising the step of adding a composition containing Z-HCFO-1224yd to the fluid. In some embodiments, the composition containing Z-HCFO-1224yd is a blend defined in Table 1. In some embodiments, the method reduces flammability associated with any of the broad range of other flammable fluids. In some embodiments, it reduces flammability with respect to 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 the purposes of the present invention, a flammable fluid is any fluid that exhibits a range of flammability in air when 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to this use of the composition of the present invention.

[0284] In accordance with the present invention, any suitable amount of the compound or composition may be added to reduce the flammability of a fluid. As will be recognized by those skilled in the art, the amount added depends at least in part on the degree of flammability of the fluid in question and the extent to which the reduction of its flammability is desired. In some embodiments, the amount of the compound or composition containing Z-HCFO-1224yd added to a flammable fluid is effective in making the resulting fluid substantially nonflammable.

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

[0286] In some embodiments of the flame suppression method, the amount of Z-HCFO-1224yd in the composition is about 1% by weight to about 99% by weight, for example, 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 ranges of quantities are shown in Table 1, and these quantities are also applicable to this use of the composition of the present invention.

[0287] Any preferred method of bringing the flame into contact with the composition may be used. In some embodiments, the composition containing Z-HCFO-1224yd may be sprayed or poured onto the flame, or the composition may be placed in at least a portion of the flame.

[0288] Etching method Etching gases used in the semiconductor industry are employed to etch deposits from surfaces. Chemical vapor deposition (CVD) chambers and plasma chemical vapor deposition (PECVD) chambers require periodic cleaning to remove deposits from the chamber walls and platens. Since the chamber cannot be used during the cleaning cycle, this cleaning process reduces the chamber's production capacity. The cleaning process may include, for example, the discharge of reaction gases and their replacement with cleaning gases, activation of the cleaning gases, and subsequent flushing steps to remove the cleaning gases from the chamber using an inert carrier gas. Cleaning gases typically work by etching contaminants accumulated from the interior, and therefore the etching rate of the cleaning gas is an important parameter in the gas's usefulness and commercial application; some cleaning gases can also be used as etching gases. These gases can generate relatively large amounts of toxic exhaust gases, which can cause further GWP, or environmental, health, and safety (EHS) problems separate from the GWP of the cleaning gas or etching gas itself.

[0289] Therefore, there is a need to reduce the global warming harm caused by cleaning and operating CVD reactors by using effective and inexpensive cleaning / etching gases that have a high etching rate and less impact on GWP and ESH than current gases. In some embodiments, clean gas mixtures having low EHS and GWP are provided, resulting in reduced environmental impact even if unreacted gases are released. In some embodiments, methods are provided for using these gases, comprising the steps of activating the gases in situ, either in a remote chamber or in a process chamber, wherein the gas mixture comprises an oxygen source and a hydrofluoroolefin, and contacting the activated gases with the surface deposits for a sufficient time 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 to reach a neutral temperature of about 1000–3000 K to form an activated gas mixture. In some embodiments, a glow discharge is used to activate the gases. 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 contains Z-HCFO-1224yd. In some embodiments, the gas mixture contains Z-HCFO-1224yd alone. In some embodiments, the gas mixture contains Z-HCFO-1224yd in a mixture with one or more of the compounds listed in Table 1.

[0290] In some embodiments, the surface deposits to be removed include materials commonly deposited by chemical vapor deposition (CVD), plasma 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 inside a process chamber used in the manufacture of electronic equipment. In some embodiments, the process chamber is a CVD chamber or a PECVD chamber. In some embodiments, a gas mixture is used to remove surface deposits from a metal. In some embodiments, a gas mixture is used to clean a plasma etching chamber. In some embodiments, a gas mixture is used to remove N-containing thin films from a wafer. In some embodiments, the gas is used for etching purposes.

[0292] In some embodiments, the process involves an activation step in which the cleaning gas mixture is activated within a remote chamber. Activation can be achieved by any means capable of dissociating a large portion of the supply gas, such as radio frequency (RF) energy, direct current (DC) energy, laser irradiation, and microwave energy. In some embodiments, a transformer inductively coupled to a low-frequency RF power supply is used, with the plasma having a torroidal configuration and acting as the secondary side of the transformer. In some embodiments, the use of low-frequency RF power allows for the use of a magnetic core that enhances inductive coupling over capacitive coupling, thereby enabling more efficient energy transfer to the plasma without excessive ion bombardments that limit the lifetime inside the remote plasma source chamber. In some embodiments, the RF power has a frequency of less than 1000 kHz. In some embodiments, the power supply 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 equipment. In some embodiments, Z-HCFO-1224yd is used alone. In some embodiments, Z-HCFO-1224yd is used in mixtures with one or more of the compounds listed in Table 1. In medium-voltage or high-voltage electrical equipment, the functions of electrical insulation and electric arc extinguishing are typically performed by an insulating gas confined within the equipment. In the generally accepted sense of the term, “medium voltage” means voltages greater than 1,000 volts AC and strictly greater than 1,500 volts DC, but not exceeding 52,000 volts AC or 75,000 volts DC, while the term “high voltage” means voltages greater than 52,000 volts AC and greater than 75,000 DC.

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

[0295] While the present invention has been specifically 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 without departing from the scope of the invention. The claims are intended to encompass the disclosed embodiments described above, their substitutes, and all their equivalents.

[0296] Note that not all of the tasks or examples described above are necessary in the general description, and some parts of certain tasks may not be required. Furthermore, one or more additional tasks may be performed in addition to those described above. Also, the order in which the tasks are described is not necessarily the order in which they are performed.

[0297] The concept of the present invention is described in the above specification with reference to specific embodiments. However, it will be understood by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention as set forth in the claims below. Accordingly, this specification and the figures are to be considered illustrative rather than restrictive, and all such modifications are intended to fall within the scope of the invention.

[0298] Benefits, other advantages, and solutions to problems are described above in relation to specific embodiments. However, these benefits, advantages, solutions to problems, and any features that may give rise to or make more apparent any benefits, advantages, or solutions are not to be construed as essential, necessary, or indispensable features in any part or all of the claims.

[0299] For clarity, it should be understood that certain features described herein in the context of separate embodiments may be provided in combination within a single embodiment. Conversely, various features described in the context of a single embodiment for the sake of brevity may also be provided separately or in any subcombination. Furthermore, references to values ​​given in ranges include each and all values ​​within that range. [Examples]

[0300] The present disclosure is further defined in the following embodiments. These embodiments illustrate preferred embodiments, but should be understood to be provided for illustrative purposes only. Those skilled in the art will be able to identify preferred features from the above description and these embodiments, and various changes and modifications can be made to suit 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 was measured. Measurements included evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and average temperature gradient (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of mixtures 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°C Compressor efficiency 75%

[0303] [Table 4-1]

[0304] [Table 4-2]

[0305] The results showed that Z-HCFO-1224yd(1224ydZ) is a good substitute for HFC-245fa, HCFC-123, and 1233zdE. Its capacity is particularly closely matched to that of 1233zdE. Furthermore, the mixtures shown were good substitutes for the pure fluids, demonstrating similar capacity and efficiency. Mixtures with low-temperature gradients (<~1K) are particularly suitable for use in centrifugal coolers. Mixtures with high gradients are suitable for use in heat exchangers with counterflow or backflow.

[0306] The compressor discharge temperatures for both the mixture and the pure fluid were 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 the average temperature gradient (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of mixtures 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°C Compressor efficiency 75%

[0309] [Table 5]

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

[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 temperature gradient (Avg Temp Glide) of the evaporator and condenser. 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°C The compressor efficiency is 75%.

[0313] [Table 6]

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

[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 temperature gradient (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of mixtures 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°C The compressor efficiency is 75%.

[0317] [Table 7]

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

[0319] Example 5: Power cycle using Z-HCFO-1224yd as the 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. The maximum achievable operating pressure of the ORC system was assumed to be approximately 2.5 MPa, and it was assumed that a heat source capable of maintaining the temperature of any 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 used as working fluids in a subcritical Rankine power cycle. The operating parameters of the ORC system using HFC-245fa as the working fluid are shown under the column labeled "HFC-245fa". The operating parameters of the ORC system using HCFO-1224yd(Z) as the working fluid are shown under the column labeled "Z-HCFO-1224yd".

[0321] [Table 8]

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

[0323] The above examples demonstrate that using Z-HCFO-1224yd in an ORC system designed to use HFC-245fa as the working fluid achieves an 8.97% higher cycle efficiency compared to HFC-245fa, while also reducing the working fluid's GWP by more than 99.88%. This indicates that the working fluid containing HFC-245fa in existing ORC systems can be replaced by draining the working fluid, flushing the ORC system with a lubricant or working fluid containing Z-HCFO-1224yd, and refilling the ORC system with working fluid containing Z-HCFO-1224yd.

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

[0325] [Table 9]

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

[0327] Example 7: Flame suppression A composition containing Z-HCFO-1224yd was used as a flame suppression composition. To evaluate its use in suppressing total flood fires, an NFPA 2001 cup burner was used. In this case, a small heptane flame was located inside a chimney with an airflow around the flame to supply 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 an extinguishing agent.

[0328] [Table 10]

[0329] Example 8: Azeotropic mixture composition of Z-HCFO-1224yd and 1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz) The presence of azeotropic mixture-like compositions between the binary pairs Z-1,1,1,4,4,4-hexafluoro-2-butene and Z-1-chloro-2,3,3,3-tetrafluoropropene was investigated. 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 each binary composition. These measurements were then converted to equilibrium vapor and liquid compositions using a non-random two-liquid model (NRTL) equation. Figure 1 shows the vapor pressures measured for the compositions in the PTx sample cell for this binary system.

[0330] As shown by a mixture of approximately 1-22 mol% of Z-1,1,1,4,4,4-hexafluoro-2-butene and approximately 78-99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropene, and a mixture of approximately 93-99 mol% of Z-1,1,1,4,4,4-hexafluoro-2-butene and approximately 1-7 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropene, an azeotrope-like composition 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) was formed at 31.8°C (see Figure 1).

[0331] The substantially constant boiling azeotropic mixture-like composition contained 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) as shown in Table 11A below. (Across this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a given temperature was (based on the foaming point pressure). ) is 5 percent or less. Azeotropic mixture-like compositions of 1-24 mol% and 62-99 mol% Z-HCFO-1224yd and 1-38 mol% and 76-99 mol% Z-HFO-1336mzz were formed at temperatures in the range of approximately -40°C to approximately 140°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a given temperature is 3 percent or less (based on the foaming point pressure)) (Table 11B).

[0332] [Table 11]

[0333] [Table 12]

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

[0335] Figure 2 shows the pressures measured for the Z-HCFO-1224yd / methyl formate mixture in a PTx cell. This graph illustrates the formation of an azeotropic mixture-like composition of 1-3 mol% Z-HCFO-1224yd and 97-99 mol% methyl formate at 31.8°C and a pressure of approximately 15 psia, and also shows the formation of an azeotropic mixture-like composition of 64-99 mol% Z-HCFO-1224yd and 1-36 mol% methyl formate at a pressure in the range of 31.8°C and approximately 25-28 psia.

[0336] Azeotropic mixture-like compositions of 1 to 99 mol% Z-HCFO-1224yd and 1 to 99 mol% methyl formate were formed at temperatures ranging from approximately -40°C to approximately 140°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a specific temperature was 5 percent or less (based on the foaming point pressure)) (Table 12A). Azeotropic mixture-like compositions of 1 to 99 mol% Z-HCFO-1224yd and 1 to 99 mol% methyl formate were formed at temperatures ranging from approximately -40°C to approximately 140°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a specific temperature was 3 percent or less (based on the foaming point pressure)). At 20°C, azeotropic mixture-like compositions of 85 to 99 mol% Z-HCFO-1224yd and 1 to 15 mol% methyl formate were formed. Azeotropic mixture-like compositions are listed in Tables 12A to 12B below.

[0337] [Table 13]

[0338] [Table 14]

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

[0340] Figure 3 shows the pressures measured for the E-1-chloro-3,3,3-trifluoropropene / Z-1-chloro-2,3,3,3-tetrafluoropropene mixture in a PTx cell, which graphically illustrates the formation of an azeotrope-like composition of 1-99 mol% E-1-chloro-3,3,3-trifluoropropene and 1-99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from approximately 24 to 38 psia.

[0341] An azeotropic mixture-like composition of 1 to 99 mol% E-1-chloro-3,3,3-trifluoropropene and 1 to 99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene is formed at temperatures ranging from approximately -40°C to approximately 140°C (within this temperature range, the difference between the dew point pressure and the foaming point pressure of the composition at a given temperature is 3 percent or less (based on the foaming point pressure)) (Table 13).

[0342] [Table 15]

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

[0344] Figure 4 shows the pressures measured for the E-HFO-1336mzz / Z-HCFO-1224yd mixture in a PTx cell, which graphically illustrates the formation of an azeotrope-like composition of 1-99 mol% E-HFO-1336mzz and 1-99 mol% E-HCFO-1224yd at 31.7°C and pressures in the range of approximately 28-36 psia.

[0345] Azeotropic mixture-like compositions of 1 to 99 mol percent E-HFO-1336mzz and 1 to 99 mol percent Z-HCFO-1224yd are formed at temperatures in the range of approximately -40°C to approximately 120°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a particular temperature is 5 percent or less (based on the foaming point pressure)) (Table 14A). Azeotropic mixture-like compositions of 5 to 95 mol percent E-HFO-1336mzz and 5 to 95 mol percent Z-HCFO-1224yd are formed at temperatures in the range of approximately -40°C to approximately 120°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a particular temperature is 3 percent or less (based on the foaming point pressure)) (Table 14B).

[0346] [Table 16]

[0347] [Table 17]

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

[0349] Figure 5 shows the pressures measured for the E-1,1,1,4,4,5,5,5-octafluoro-2-pentene / Z-1-chloro-2,3,3,3-tetrafluoropropene mixture in a PTx cell. This graph illustrates the formation of an azeotropic mixture-like composition of 1-33 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 67-99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from approximately 25 to 28 psia. It also shows the formation of an azeotropic mixture-like composition of 84-99 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 1-16 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene at 31.8°C and pressures ranging from 16 to 19 psia.

[0350] An azeotropic mixture-like composition of 1-99 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 1-99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene is formed at temperatures ranging from approximately -40°C to approximately 140°C (over this temperature range, the difference between the dew point pressure and the foaming point pressure of the composition at a given temperature is 5 percent or less (based on the foaming point pressure) (Table 15A). Azeotropic mixture-like compositions of lol-2,3,3,3-tetrafluoropropene were formed at temperatures ranging from approximately -40°C to approximately 140°C (over this temperature range, the difference between the dew point pressure and the foaming point pressure of the composition at a given temperature was 3 percent or less (based on the foaming point pressure)) (Table 15B). At 20°C, azeotropic mixture-like compositions of 1-12 mol% and 89-99 mol% of Z-HCFO-1224yd and 1-11 mol% and 88-99 mol% of E-1,1,1,4,4,5,5,5-octafluoro-2-pentene were formed.

[0351] [Table 18]

[0352] [Table 19]

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

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

[0355] An azeotropic composition of Z-HCFO-1224yd and HFC-245eb is formed, ranging from approximately 65.6 mole percent to approximately 86.7 mole percent of Z-HCFO-1224yd and approximately 34.4 mole percent to approximately 13.3 mole percent of HFC-245eb, (forming an azeotropic composition that boils at temperatures of approximately -40°C to approximately 130°C and pressures of approximately 0.98 psia (6.76 kPa) to approximately 333 psia (2296 kPa)).

[0356] At 20.0°C and 18.8 psia (130 kPa), the azeotropic composition consisted of 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 consisted of 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] Furthermore, azeotropic mixture-like compositions containing Z-HCF0-1224yd and HFC-245eb are also formed. Azeotropic mixture-like compositions of 1 to 99 mol percent of Z-HCF0-1224yd and 99 to 1 mol percent of HFC-245eb are formed at temperatures in the range of approximately -40°C to approximately 120°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a particular temperature is 5 percent or less (based on the foaming point pressure)) (Table 18A). Azeotropic mixture-like compositions of 1 to 99 mol percent of Z-HCF0-1224yd and 99 to 1 mol percent of HFC-245eb are formed at temperatures in the range of approximately -40°C to approximately 120°C (over this temperature range, the difference between the dew point pressure and foaming point pressure of the composition at a particular temperature is 3 percent or less (based on the foaming point pressure)) (Table 18B). At 20°C, azeotropic mixture-like compositions were formed of 1-9 mol% and 58-99 mol% of Z-HCFO-1224yd and 1-42 mol% and 91-99 mol% of HFC-245eb. Such azeotropic mixture-like compositions exist around the azeotropic composition.

[0360] [Table 22]

[0361] [Table 23]

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

[0363] Figure 7 shows the pressure measured against the composition in a PTx cell for the Z-HCFO-1224yd / HFC-1233xf mixture, and graphically illustrates the formation of azeotropic compositions of Z-HCFO-1224yd and HCFO-1233xf, as shown by the mixture of approximately 16 mol% Z-HCFO-1224yd and 84 mol% HCFO-1233xf, which has the highest pressure across the range of compositions at approximately 31.8°C.

[0364] Example 15: R-value over time enhanced by HCFO-1224yd and HFO-1336mzz-E blend Foam samples were prepared in an 8"×8"×2.5" mold using a manual mixing method. The foam was cured overnight, cut into 6"×6"×1.5" sections, and analyzed using a calibrated heat flow meter. The sample analysis was performed, and the values ​​at each setpoint were considered the baseline k-coefficient values. An exemplary manual mixing method consisted of adding an appropriate amount of HCFO or HFO and water (a typical polyurethane B-side mixture) to side B, and then mixing. Next, an appropriate amount of side A (a typical polyurethane A-side mixture) was 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 foaming agent component used to prepare the foam are shown in Table 19 (weight percentages based on the combined total amount of side A and side B), and samples were prepared using a side B:side A ratio of 100:123. The results of the thermal analysis experiments are shown in Tables 20 to 24 and Figures 8 to 11.

[0365] [Table 24]

[0366] [Table 25] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0367] [Table 26] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0368] [Table 27] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0369] [Table 28] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0370] [Table 29] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0371] [Table 30] NA = No data found. The K coefficient is Btu·in / ft 2 Expressed in h·°F

[0372] As shown in the data in Tables 20-25, combining HFO-1336mzz-E with HCFO-1224yd created a synergistic combination, resulting in improved thermal insulation performance across a wide temperature range. Furthermore, the effect was long-lasting, providing continued improved thermal insulation. At higher temperatures, the combination of HFO-1336mzz-Z and HCFO-1224yd also showed good results compared to the control and the blend of HCFO-1233zd and HCFO-1224yd.

[0373] Other Embodiments 1. In some embodiments, this application relates to the compound Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and HFO, HCFO, HFC, HFE, HCFC, CFC, CO2, 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-trifluoropropyl The present invention provides a composition comprising: cis-HFO-1234ze+HFO-1225yez, a mixture of these with water; a mixture of these with CO2; a mixture of these with trans-1,2-dichloroethylene; a mixture of these with methyl formate; a mixture of cis-HFO-1234ze+CO2, a mixture of cis-HFO-1234ze+HFO-1225yez+CO2, and a mixture of cis-HFO-1234ze+HFC-245fa; and one or more compounds selected from the group.

[0374] 2. The composition according to 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 The composition according to Embodiment 1 or 2, comprising one or more compounds selected from the group consisting of d, 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 according to any one of Embodiments 1 to 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 A composition according to any one of Embodiments 1 to 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 according to any one of Embodiments 1 to 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 according to 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; dimethyl oxymethane; diethoxymethane; dipropoxymethane; and dibutoxymethane.

[0380] 8. The composition according to any one of Embodiments 1 to 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 according to any one of Embodiments 1 to 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, this application uses Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene 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-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-1439m 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 The present invention provides an azeotropic mixture or azeotropic mixture-like composition comprising one or more compounds selected from the group consisting of 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. An azeotropic mixture or azeotropic mixture-like composition according to Embodiment 10, formed at a pressure of approximately 0.98 psia (130 kPa) to approximately 333 psia (2296 kPa), or at a pressure of approximately 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. An azeotropic mixture or azeotropic mixture-like composition according to Embodiment 10 or 11, formed at a temperature of approximately -40°C to approximately 130°C.

[0385] 13. An azeotropic mixture-like composition according to any one of Embodiments 10 to 12, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) methyl formate.

[0386] 14. An azeotropic mixture-like composition according to any one of Embodiments 10 to 13, comprising essentially (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol% of methyl formate at a temperature of -40°C to approximately 140°C.

[0387] An azeotropic mixture-like composition according to any one of Embodiments 10 to 14, comprising essentially (i) 85 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 1 to 15 mol% of methyl formate at 15.20°C.

[0388] 16. An azeotropic mixture-like composition according to any one of Embodiments 10 to 12, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) E-1-chloro-3,3,3-trifluoropropene (E-1233zd).

[0389] 17. An azeotropic mixture-like composition according to any one of embodiments 10 to 12 and 16, comprising essentially (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol% of E-1-chloro-3,3,3-trifluoropropene (E-1233zd) at a temperature of -40°C to approximately 140°C.

[0390] 18. An azeotropic mixture-like composition according to any one of Embodiments 10 to 12, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz).

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

[0392] 20. An azeotrope-like composition according to any one of Embodiments 10 to 12, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz).

[0393] 21. An azeotropic mixture-like composition according to any one of Embodiments 10 to 12 and 20, comprising essentially (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol% of E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz) at a temperature of -40°C to approximately 140°C.

[0394] An azeotropic mixture-like composition according to any one of embodiments 10 to 12, 20, and 21, essentially consisting of (i) 1 to 12 mol% and 89 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-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 22.20°C.

[0395] 23. An azeotrope-like composition according to any one of Embodiments 10 to 12, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf).

[0396] An azeotropic mixture composition according to any one of embodiments 10 to 12 and 23, essentially consisting of 16 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and 84 mol% of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) at a temperature of 24.31.8°C.

[0397] 25. In some embodiments, the present application relates to a process for forming a foam, (a) A step of adding a foaming composition to a foaming agent, (b) A step of reacting the foaming composition under conditions effective for forming a foam, Includes, The present invention provides a process in which the foaming agent comprises the composition described in any one of Embodiments 1 to 24.

[0398] 26. In some embodiments, the present application further relates to a process for forming a foam, (a) A step of adding a foaming composition containing one or more thermoplastic polymers to a foaming agent, (b) A step of processing the foaming composition under conditions effective for forming a foam, Includes, The present invention provides a process in which the foaming agent comprises the composition described in any one of Embodiments 1 to 24.

[0399] 27. The process according to Embodiment 26, comprising the step of extruding a mixture of the foaming composition and a foaming agent.

[0400] 28. The process according to Embodiment 26 or 27, wherein the blowing agent comprises Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0401] 29. The process according to Embodiment 28, wherein the foaming agent further contains water.

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

[0403] 31. The process according to Embodiment 30, wherein the foaming agent further contains water.

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

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

[0406] 34. The foam according to Embodiment 32 or 33, wherein the foaming agent comprises Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0407] 35. The foam according to any one of embodiments 32 to 34, wherein the foaming agent further contains water.

[0408] 36. At a temperature of approximately 20°F, the pressure is approximately 0.113 Btu·in / ft. 2 h°F ~ approximately 0.158 Btu·in / ft 2 A foam according to any one of embodiments 32 to 35, exhibiting a K coefficient of h·°F.

[0409] 37. At a temperature of approximately 35°F, the flow rate is approximately 0.116 Btu·in / ft. 2 h°F ~ approximately 0.122 Btu·in / ft 2 A foam according to any one of embodiments 32 to 36, exhibiting a K coefficient of h·°F.

[0410] 38. At a temperature of approximately 50°F, the flow rate is approximately 0.122 Btu·in / ft. 2 • h°F ~ approximately 0.165 Btu·in / ft 2 A foam according to any one of embodiments 32 to 37, exhibiting a K coefficient of h·°F.

[0411] 39. At a temperature of approximately 75°F, the flow rate is approximately 0.132 Btu·in / ft. 2 h°F ~ approximately 0.175 Btu·in / ft 2 A foam according to any one of embodiments 32 to 38, exhibiting a K coefficient of h·°F.

[0412] 40. The foam according to Embodiment 32 or 33, wherein the foaming agent comprises Z-1-chloro-2,3,3,3-tetrafluoropropane-1-ene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0413] 41. The foam according to any one of embodiments 32, 33, and 40, wherein the foaming agent further contains water.

[0414] 42. At a temperature of approximately 20°F, approximately 0.111 Btu·in / ft 2 ·h·°F ~ approx. 0.144Btu·in / ft 2 A foam according to any one of embodiments 32, 33, 40, and 41, exhibiting a K coefficient of h·°F.

[0415] 43. At a temperature of approximately 35°F, the pressure is approximately 0.115 Btu·in / ft. 2 • h°F ~ approximately 0.150 Btu·in / ft 2 A foam according to any one of embodiments 32, 33, and 40-42, exhibiting a K coefficient of h·°F.

[0416] 44. At a temperature of approximately 50°F, the pressure is approximately 0.120 Btu·in / ft. 2 ·h·°F ~ approx. 0.156Btu·in / ft 2 A foam according to any one of embodiments 32, 33, and 40-43, exhibiting a K coefficient of h·°F.

[0417] 45. At a temperature of approximately 75°F, the pressure is approximately 0.130 Btu·in / ft. 2 ·h·°F ~ approx. 0.168Btu·in / ft 2 A foam according to any one of embodiments 32, 33, and 40-44, exhibiting a K coefficient of h·°F.

[0418] 46. ​​In some embodiments, the present application relates to a process for causing cooling, (a) A step of condensing the composition described in any one of Embodiments 1 to 24, (b) A step of evaporating the composition in the vicinity of the object to be cooled, It provides a process that includes this.

[0419] 47. In some embodiments, the present application relates to a process for generating heating, (a) A step of condensing the composition described in any one of Embodiments 1 to 24 in the vicinity of an object to be heated, (b) The process of evaporating the composition thereafter, It provides a process that includes this.

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

[0421] 49. In some embodiments, the present application provides a high-temperature heat pump comprising a working fluid comprising the composition described in any one of Embodiments 1 to 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 for extinguishing or suppressing a flame, comprising the step of distributing a composition described in any one of Embodiments 1 to 24 to the flame.

[0424] 52. In some embodiments, the present application provides a system for preventing or suppressing a flame, comprising a container containing a composition described in any one of Embodiments 1 to 24, and a nozzle for distributing the composition toward the expected or actual location of the 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, and 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 any feature described herein with respect to any particular aspect and / or embodiment of the invention can be combined with one or more other features of any other aspect and / or embodiment of the invention described herein, and can be modified as appropriate to ensure the suitability of the combination. Such combinations are considered to be part of the invention as contemplated by this disclosure.

Claims

1. An azeotropic mixture or azeotropic mixture-like composition comprising Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene and E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd).

2. The azeotropic mixture-like composition according to claim 1, comprising essentially (i) Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) E-1-chloro-3,3,3-trifluoropropene (E-1233zd).

3. An azeotropic mixture-like composition according to claim 1, comprising essentially (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropa-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol% of E-1-chloro-3,3,3-trifluoropropene (E-1233zd) at a temperature of -40°C to about 140°C.

4. A process for forming a foam, (a) A step of adding a foaming composition to a foaming agent, (b) A step of reacting the foaming composition under conditions effective for forming a foam, Includes, A process wherein the foaming agent comprises the composition described in claim 1.

5. A process for forming a foam, (a) A step of adding a foaming composition containing one or more thermoplastic polymers to a foaming agent, (b) A step of processing the foaming composition under conditions effective for forming a foam, Includes, A process wherein the foaming agent comprises the composition described in claim 1.

6. The process according to claim 5, comprising the step of extruding a mixture of the foaming composition and a foaming agent.

7. The process according to claim 6, wherein the foaming agent further contains water.

8. A foam formed by the process described in claim 5.

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

10. A process that produces cooling, (a) A step of condensing the composition described in claim 1, (b) A step of evaporating the composition in the vicinity of the object to be cooled, A process that includes this.

11. A process that generates heating, (a) A step of condensing the composition according to claim 1 in the vicinity of an object to be heated, (b) The process thereafter involves evaporating the composition, A process that includes this.

12. A heat transfer system comprising a heat transfer medium, wherein the heat transfer medium comprises the composition described in claim 1.

13. A high-temperature heat pump comprising a working fluid containing the composition described in claim 1.

14. An aerosol product comprising a component to be dispensed and a propellant, wherein the propellant comprises the composition described in claim 1.

15. A method for extinguishing or suppressing a flame, comprising the step of distributing the composition according to claim 1 to the flame.

16. A system for preventing or suppressing flames, comprising a container containing the composition described in claim 1, and a nozzle for distributing the composition toward the expected or actual location of the flames.

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