Compositions and Uses of Z-1-Chloro-2,3,3,3-Tetrafluoroprop-1-ene

Abstract

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

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 547,518, filed Aug. 18, 2017, the entire disclosure of which is incorporated herein by reference.

[0002] (Field of the Invention) The present disclosure relates to compositions, methods, and systems that are useful in many applications, specifically to the use of compositions containing the compound Z - 1 - chloro - 2,3,3,3 - tetrafluoroprop - 1 - ene (Z - HCFO - 1224yd).

Background Art

[0003] Over the past few decades, efforts have been made in many industries to find alternatives to ozone - depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including as aerosol propellants, refrigerants, cleaning agents, blowing agents for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and fire - suppressing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasives, and replacement desiccants. In the search for alternatives to these multi - purpose compounds, the use of hydrofluorocarbons (HFCs) has been noted in many industries.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] HFCs do not contribute to stratospheric ozone depletion but are a concern because they 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 potential (GWP).

Means for Solving the Problems

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

[0007]

Chemical

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

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

Brief Description of the Drawings

[0010]

Figure 1

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Figure 11

Mode for Carrying Out the Invention

[0011] Hydrochlorofluorocarbons are thought to have a low global warming potential and not contribute to stratospheric ozone depletion. One such hydrochlorofluorocarbon is 1-chloro-2,3,3,3-tetrafluoroprop-1-ene. 1-Chloro-2,3,3,3-tetrafluoroprop-1-ene exists as two different stereoisomers, each having a different boiling point, and thus can exhibit different functions in different applications.

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

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

[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 with cis-HFO-1234ze + CO2, mixtures with cis-HFO-1234ze + HFO-1225yez + CO2, and mixtures with cis-HFO-1234ze + HFC-245fa. In such compositions, the amount of the compound Z-HCFO-1224yd can vary, including in all cases that make up the remainder of the composition after considering all other components in the composition.

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

[0016] The compositions provided herein are environmentally acceptable and do not contribute to the destruction of the earth's stratospheric ozone layer. In some embodiments, the compounds and compositions provided herein have a substantially zero ozone depletion potential (ODP), e.g., an ODP of about 0.5 or less, e.g., an ODP of about 0.25 or less, or an ODP of about 0.1 or less. In some embodiments, the compounds and compositions provided herein have a global warming potential (GWP) of about 150 or less, e.g., a GWP of about 50 or less.

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

[0018] In some embodiments, Z-HCFO-1224yd is mixed with one or more compounds to form a blend composition. In some embodiments, Z-HCFO-1224yd forms a blend composition with an HFO, an HFE, a hydrocarbon, an alcohol, an ether, an aldehyde, a ketone, or other compounds, such as water, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene, CO2, and one or more of the others. In some embodiments, the other compounds constitute from about 1 wt% to about 99% of the composition. For example, from about 1 wt% to about 90 wt%, from about 1 wt% to about 80 wt%, from about 1 wt% to about 70 wt%, from about 1 wt% to about 60 wt%, from about 1 wt% to about 50 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 5 wt%, from about 5 wt% to about 99 wt%, from about 5 wt% to about 95 wt%, from about 5 wt% to about 75 wt%, from about 5 wt% to about 50 wt%, from about 5 wt% to about 25 wt%, from about 10 wt% to about 99 wt%, from about 10 wt% to about 90 wt%, from about 10 wt% to about 75 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 25 wt%, from about 25 wt% to about 99 wt%, from about 25 wt% to about 90 wt%, from about 25 wt% to about 75 wt%, from about 25 wt% to about 50 wt%, from about 40 wt% to about 60 wt%, from about 45 wt% to about 55 wt%, from about 50 wt% to about 99 wt%, from about 50 wt% to about 75 wt%, from about 60 wt% to about 99 wt%, from about 60 wt% to about 75 wt%, or from about 75 wt% to about 99 wt% of the composition.

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

[0020]

Table 1-1

[0021]

Table 1-2

[0022]

Table 1-3

[0023]

Table 1-4

[0024]

Table 1-5

[0025]

Table 1-6

[0026] Blowing agent Also provided herein are methods and systems that include, optionally, Z-HCFO-1224yd as a blowing agent, together with one or more additional compounds including, but not limited to, other compounds that also act as blowing agents (hereinafter referred to as co-blowing agents for convenience and not for purposes of limitation), surfactants, polyols, catalysts, flame retardants, polymer modifiers, colorants, dyes, solubility enhancers, 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 includes a blend of Z-HCFO-1224yd with a hydrocarbon (e.g., pentane including cyclopentane) and one or more of HFC-245fa, HFC-365mfc, and HCFO-1233zd.

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

[0028] In some embodiments, dispersants, foam stabilizers, surfactants, and other additives are also incorporated into the blowing agent composition. Specific 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. Patent Nos. 2,834,748, 2,917,480, and 2,846,458, which are hereby incorporated by reference in their entirety. Examples of representative materials, typically polysiloxane polyoxyalkylene block copolymers, are those sold under the names DC-193, B-8404, and L-5340. Other optional additives for the blowing agent mixture include flame retardants such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-dibromopropyl)-phosphate, tris(1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, alumina trihydrate, and polyvinyl chloride. With respect to nucleating agents, all known compounds and materials having a nucleating function, including talc, are available for use in the present invention.

[0029] In some embodiments, other compounds and / or components that modulate certain properties of the composition (such as cost, etc.) are included in the composition, 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 physical and chemical foaming agents.

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

[0032] In some embodiments, the blowing agent composition includes one or more hydrocarbons, for example, for thermosetting foams, iso, normal, and / or cyclopentane, and for thermoplastic foams, butane or isobutane. Other materials, such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (dichloroethylene (such as trans-1,2-dichloroethylene), ethyl chloride, and HCCs such as chloropropane), HCFCs, C1-C5 alcohols (such as ethanol and / or propanol and / or butanol), 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) may be included. In some embodiments, such components are not included because they have a negative impact on the environment.

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

[0034] In some embodiments, the relative amounts of any of the above additional co - blowing agents and any additional components that may be included in the present composition can vary widely within the broad general scope of the present invention according to the particular 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 an amount of Z - HCFO - 1224yd sufficient to produce a blowing agent composition that is overall non - flammable.

[0036] In some embodiments, the blowing agent composition comprises 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, such as at least about 5% by weight, or about 15% by weight.

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

[0038] In some embodiments, the blowing agent composition comprises from about 30% to about 95% by weight of Z - HCFO - 1224yd and from about 5% to about 90% by weight, such as from about 5% to about 65% by weight, of a co - blowing agent. In some embodiments, the co - blowing agent comprises H2O, HFC, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof. In some embodiments, the co - blowing agent consists essentially of H2O, HFC, hydrocarbons, alcohols (such as C2, C3, and / or C4 alcohols), CO2, and combinations thereof.

[0039] In some embodiments, the co - blowing agent includes H2O. In some embodiments, the composition includes H2O in an amount of about 5 wt% to about 50 wt% of the total blowing agent composition, such as about 10 wt% to about 40 wt% of the total blowing agent, or about 10 wt% to about 20 wt% of the total blowing agent.

[0040] In some embodiments, the co - blowing agent includes CO2. In some embodiments, the composition includes CO2 in an amount of about 5 wt% to about 60 wt% of the total blowing agent composition, such as about 20 wt% to about 50 wt% of the total blowing agent, or about 40 wt% to about 50 wt% of the total blowing agent.

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

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

[0043] In some embodiments, the composition comprises an HC co - blowing agent. In some embodiments, the HC co - blowing agent is a C3, C4, or C5 HC. In some embodiments, the HC is present in the composition in an amount of about 5 wt% to about 80 wt% of the total blowing agent composition, for example, about 20 wt% to about 60 wt% of the total blowing agent.

[0044] Foamable composition A foamable composition is provided herein. As is known to those skilled in the art, a foamable composition generally comprises one or more components capable of forming a foam. As used herein, the term "foam blowing agent" is used to refer to a component or combination of components capable of forming a foam structure, e.g., a generally cellular foam structure. The foamable compositions provided herein include such components and blowing agent compounds. In some embodiments, the blowing 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 one or more components selected from 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-1438ezy, 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-365mfc, 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, methylethyl ether (methoxyethane), neohexane (2,2-dimethylbutane), neopentane, n-hexane, pentane, propane, CO2, ethyl formate, methyl acetate, methyl formate, methylal, trans-1,2-dichloro-ethylene, and cis-1,2-dichloro-ethylene.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 blowing agent for expanding 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 from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to the foaming compositions provided herein.

[0047] In some embodiments, the one or more components capable of forming a foam include a thermosetting composition capable of forming a foam and / or a foamable composition. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, as well as phenolic foam compositions. In some embodiments, this reaction and foaming process is enhanced by using various additives such as catalysts and surfactant materials that have the function of controlling and adjusting the cell 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 composition described herein are incorporated into the foamable composition described herein. In such embodiments of the thermosetting foam, one or more of the compositions are included as a blowing agent or part thereof in the foamable composition, or as part of two or more portions of the foamable composition, and the composition may include one or more of the components capable of reacting and / or foaming under appropriate conditions to form a foam or a cellular structure.

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

[0049] Any currently known and available method and system for forming a foam can be readily adapted for use in connection with the present invention. For example, in some embodiments, the method of the present invention requires incorporating a blowing agent according to the present invention into a foamable or foam-forming composition and then foaming the composition. In some embodiments, the method includes a step or series of steps that cause the volume expansion of the blowing agent according to the present invention.

[0050] In some embodiments, the systems and apparatuses currently used for incorporation and foaming of blowing agents can be readily adapted for use according to the present invention. One advantage of the present invention is to provide an improved blowing agent that is generally compatible with existing foaming methods and systems.

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

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

[0053] Those skilled in the art will understand that, particularly in view of the disclosure contained herein, the order and manner in which the blowing agents of the present invention are formed and / or added to the foamable composition will generally have no effect on the operability of the present invention. For example, in the case of an extrudable foam, in some embodiments, the various components of the blowing agent, and indeed the components of the foamable composition, are not mixed prior to introduction into the extrusion equipment. In some embodiments, the components are not added at the same location within the extrusion equipment. In some embodiments, the blowing agent is introduced either directly or as part of a premix and is then further added to other portions of the foamable composition.

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

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

[0056] A binary azeotropic composition or an azeotrope-like composition of a substantially constant-boiling mixture can be characterized in many ways according to the selected conditions. For example, it is well known to those skilled in the art that at different pressures, the composition of a given azeotrope or azeotrope-like composition varies at least to some extent, like the boiling point temperature. Thereby, the azeotropic composition or azeotrope-like composition of two compounds represents a unique kind of relationship, but has a composition that varies according to temperature and / or pressure. Therefore, to define azeotropes and azeotrope-like compositions, a range of compositions rather than a fixed composition is often used.

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

[0058] An "azeotrope-like" composition means a liquid mixture of two or more substances that behaves as a single substance and has a constant boiling point or a substantially constant boiling point. In some embodiments, an azeotrope-like composition is characterized in that the vapor generated by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which the vapor is evaporated or distilled, i.e., the mixture distills / refluxes without substantial change in composition. In some embodiments, an azeotrope-like composition may be characterized in that the bubble point vapor pressure and the dew point vapor pressure of the composition are substantially the same at a specific temperature. In some embodiments, an azeotrope-like composition can 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, if after removing 50 weight percent of the composition by evaporation or boiling, etc., the difference in vapor pressure between the original composition and the composition remaining after removing 50 weight percent of the original composition is less than about 10 percent when measured in absolute units, the composition is recognized in the art as being azeotrope-like. Absolute units mean a measured value of pressure, e.g., psia, atmospheric pressure, bar, torr, dyne / square centimeter, millimeter of mercury, inch of water, and other equivalent terms well known in the art. If an azeotrope is present, there is no difference in vapor pressure between the original composition and the composition remaining after removing 50 weight percent of the original composition.

[0060] In the case of an azeotropic composition, in some embodiments, for a maximum-boiling azeotrope, it has a boiling point at a particular pressure that is higher than the pure components of the composition at that pressure, and a vapor pressure at a particular temperature that is lower than the pure components of the composition at that temperature. For a minimum-boiling azeotrope, it has a boiling point at a particular pressure that is lower than the pure components of the composition at that pressure, and a vapor pressure at a particular temperature that is higher than the pure components of the composition at that temperature. There exists a composition within some range around the azeotropic point having these characteristics. The boiling point and vapor pressure that are higher or lower than 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 the highest or lowest boiling point at a particular pressure, or the highest or lowest vapor pressure at a particular temperature, may or may not have the same spread as the range of compositions for which the change in vapor pressure is less than about 10% when 50 weight percent of the composition has evaporated. When the range of compositions having the highest or lowest boiling point at a particular pressure, or the highest or lowest vapor pressure at a particular temperature, is wider than the range of compositions for which the change in vapor pressure is less than about 10% when 50 weight percent of the composition has evaporated, nonetheless, unexpected intermolecular forces are considered important in that refrigerant compositions having intermolecular forces that are not substantially constant-boiling can exhibit an unexpected increase in volume or efficiency with respect 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 points and amounts of the components of the azeotropic composition can change. Thus, in some embodiments, the azeotropic composition can be defined from the perspective of the specific relationships existing between the components or from the perspective of the exact amounts of the components of a composition characterized by having a constant boiling point at a specific pressure. In some embodiments, an azeotropic mixture or azeotrope-like composition of two compounds can be characterized by defining a composition characterized by its boiling point at a given pressure, thereby providing a distinguishing feature without unduly limiting the scope of the invention by a specific numerical composition, which is limited by the available analytical equipment, although not as accurate as that.

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

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

[0065] These measurements can be converted to the equilibrium vapor and liquid compositions in the PTx cell by using an activity coefficient model such as the non-random two-liquid (NRTL) equation, and can represent a liquid-phase non-ideal system. Regarding the use of activity coefficient equations such as the NRTL equation, all are incorporated herein by reference in "The Properties of Gases and Liquids", 4th Edition, published by McGraw Hill, written by Reid, Prausnitz, and Poling, pages 241 - 387 and "Phase Equilibria in Chemical Engineering", published by Butterworth Publishers, 1985, written by Stanley M. Walas, pages 165 - 244, which are described in detail. Without being bound by any theory or explanation, the NRTL equation, together with the PTx cell data, can adequately predict the relative volatility of the Z-HFO-1224yd-containing compositions of the present invention, and thus it is considered that the behavior of these mixtures in a multi-stage separation facility such as a distillation column can be predicted.

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

[0067] In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and one or more components selected from 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, 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 azeotrope-like composition comprises Z-HCFO-1224yd and methyl formate. In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-HFO-1336mzz). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and Z-1,1,1,4,4,5,5,5-octafluoro-2-pentene (Z-HFO-1439mzz). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1439mzz). In some embodiments, the azeotropic mixture or azeotrope-like composition comprises Z-HCFO-1224yd and 1,1,1,2,3-pentafluoropropane (HFC-245eb).

[0069] In some embodiments, Z-HCFO-1224yd comprises from about 1 mol% to about 99 mol% of an azeotrope or azeotrope-like composition, such as from about 1 mol% to about 2 mol%, 1 mol% to about 3 mol%, 1 mol% to about 4 mol%, 1 mol% to about 6 mol%, 1 mol% to about 8 mol%, 1 mol% to about 10 mol%, 1 mol% to about 11 mol%, 1 mol% to about 12 mol%, 1 mol% to about 15 mol%, 1 mol% to about 20 mol%, 1 mol% to about 22 mol%, 5 mol% to about 6 mol%, 5 mol% to about 8 mol%, 5 mol% to about 10 mol%, 5 mol% to about 11 mol%, 5 mol% to about 12 mol%, 5 mol% to about 15 mol%, 5 mol% to about 20 mol%, 5 mol% to about 22 mol%, 5 mol% to about 95 mol%, 38 mol% to about 95 mol%, 38 mol% to about 99 mol%, 49 mol% to about 95 mol%, 49 mol% to about 99 mol%, 50 mol% to about 95 mol%, 50 mol% to about 99 mol%, 53 mol% to about 95 mol%, 53 mol% to about 99 mol%, 55 mol% to about 95 mol%, 55 mol% to about 99 mol%, 58 mol% to about 95 mol%, 58 mol% to about 99 mol%, 60 mol% to about 95 mol%, 60 mol% to about 99 mol%, 62 mol% to about 95 mol%, 62 mol% to about 99 mol%, 69 mol% to about 95 mol%, 69 mol% to about 99 mol%, 70 mol% to about 95 mol%, 70 mol% to about 99 mol%, 74 mol% to about 95 mol%, 74 mol% to about 99 mol%, 76 mol% to about 95 mol%, 76 mol% to about 99 mol%, 80 mol% to about 95 mol%, 80 mol% to about 99 mol%, 81 mol% to about 95 mol%, 81 mol% to about 99 mol%, 84 mol% to about 95 mol%, 84 mol% to about 99 mol%, 86 mol% to about 95 mol%, 86 mol% to about 99 mol%, 88 mol% to about 95 mol%, 88 mol% to about 99 mol%, 89 mol% to about 95 mol%, or 89 mol% to about 99 mol% of the azeotrope or azeotrope-like composition.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 an azeotropic mixture or an azeotrope-like composition.

[0070] In some embodiments, an azeotropic mixture or an azeotrope-like composition containing Z-HCFO-1224yd is formed in a temperature range of about -40°C to about 130°C. In some embodiments, an azeotropic mixture or an azeotrope-like composition containing Z-HCFO-1224yd is formed at a temperature of about -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 31.7°C, 31.75°C, 31.8°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, or about 130°C.

[0071] In some embodiments, an azeotropic mixture or azeotrope-like composition comprising Z-HCFO-1224yd is formed at a pressure of from about 0.98 psia (130 kPa) to about 333 psia (2296 kPa). In some embodiments, an azeotropic mixture or azeotrope-like composition comprising Z-HCFO-1224yd is formed at a pressure of about 0.98 psia, 1.84 psia, 3.23 psia, 5.37 psia, 8.48 psia, 12.87 psia, 18.84 psia, 26.75 psia, 28.37 psia, 37.02 psia, 50.09 psia, 66.46 psia, 86.71 psia, 111.45 psia, 141.40 psia, 177.37 psia, 220.34 psia, 271.53 psia, or 332.68 psia. In some embodiments, an azeotropic mixture or azeotrope-like composition comprising Z-HCFO-1224yd is formed at a pressure of from about 1 atm to about 31 atm. In some embodiments, an azeotropic mixture or azeotrope-like composition comprising 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 azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) methyl formate. In some embodiments, the azeotrope-like composition consists essentially of (i) 5 to 95 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 5 to 95 mol% of methyl formate at a temperature from -40 °C to about 140 °C. In some embodiments, the azeotrope-like composition consists essentially of (i) 85 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 15% of methyl formate at 20 °C. In some embodiments, the azeotrope-like composition is as shown in Table 12A or 12B.

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

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

[0075] In some embodiments, the azeotrope-like composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz). In some embodiments, the azeotrope-like composition consists essentially of (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-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-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 11 mol% and 88 to 99 mol% of E-1,1,1,4,4,5,5,5-octafluoro-2-pentene (E-HFO-1438mzz). In some embodiments, the azeotrope-like composition is as shown in Table 15A or 15B.

[0076] In some embodiments, the azeotropic mixture composition consists essentially of (i) Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). In some embodiments, the azeotropic mixture composition consists essentially of 16 mol% Z-1-chloro-2,3,3,3-tetrafluoroprop-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 or azeotrope-like mixture provided herein can be prepared by any convenient method. In some embodiments, the azeotropic or azeotrope-like mixture is prepared by mixing or combining the desired amounts. In some embodiments, the azeotropic or azeotrope-like mixture is prepared by weighing the desired amounts of the components and then combining them in a suitable container.

[0078] Specific examples illustrating the invention are set forth below in the examples. Unless otherwise specified herein, all percentages are by weight. It should be understood that these examples are merely illustrative and should in no way be construed as limiting the scope of the invention.

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

[0080] Method of Forming a Foam Methods for forming foams such as panel foams and spray foams are provided herein. In some embodiments, the foam is made from polyurethane and polyisocyanurate. In some embodiments, the method comprises providing a blowing agent composition as described herein, adding the blowing agent composition (directly or indirectly) to a foamable composition, and reacting the foamable composition under conditions effective to form a foam or cellular structure, as is well known in the art. Any methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology", Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., 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 from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to the methods provided herein.

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

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

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

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

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

[0087] In some embodiments, the method comprises 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 comprising one or more of the compositions of the present invention, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.

[0088] In some embodiments, the components of the polyurethane or polyisocyanurate foam are provided as a pre-blended formulation. In some embodiments, the foam formulation is pre-blended into two components. In some embodiments, the isocyanate, and optionally certain surfactants and blowing agents, together comprise a first component commonly referred to as the "A" component. In some embodiments, the polyol or polyol mixture, surfactants, catalysts, blowing agents, flame retardants, and other isocyanate-reactive components together comprise a second component commonly referred to as the "B" component. In some embodiments, the polyurethane or polyisocyanurate foam is easily prepared by manually mixing when preparing in small amounts and by combining the components on the A and B sides by mechanical mixing techniques to form blocks, slabs, laminates, on-site 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 streams. In some embodiments, all of these are incorporated into one type of B component as described above.

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

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

[0091] In some embodiments, the composition that is a blend of the A side and the B side comprises from about 5 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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 from about 5 weight percent to about 10 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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 from about 5 weight percent to about 7 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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 from about 10 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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 from about 11 weight percent to about 13 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent 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 from about 13 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent 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 from about 5 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent 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 from about 5 weight percent to about 10 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent 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 from about 5 weight percent to about 7 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent 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 from about 10 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 10 weight percent 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 from about 11 weight percent to about 13 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent 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 from about 13 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent 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 from about 5 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 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 from about 5 weight percent to about 10 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 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 from about 5 weight percent to about 7 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 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 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 Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0107] 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 Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0108] 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 Z-1,1,1,4,4,4-hexafluoro-2-butene.

[0109] 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-factor of from about 0.113 Btu·in / ft 2 ·h·°F to about 0.158 Btu·in / ft 2 ·h·°F at a temperature of about 20°F.

[0110] 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-factor of from about 0.113 Btu·in / ft 2 ·h·°F to about 0.119 Btu·in / ft 2 ·h·°F at a temperature of about 20°F.

[0111] 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-factor of from about 0.137 Btu·in / ft 2 ·h·°F to about 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 to approximately 0.156 Btu·in / ft² 2 Indicates the K coefficient of ·h·°F.

[0114] 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 approximately 0.116 Btu·in / ft² 2 ·h·°F to approximately 0.122 Btu·in / ft² 2 Indicates the K coefficient of ·h·°F.

[0115] 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 approximately 0.116 Btu·in / ft² 2 ·h·°F to approximately 0.119 Btu·in / ft² 2 Indicates the K coefficient of ·h·°F.

[0116] 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 approximately 0.137 Btu·in / ft² 2 ·h·°F to approximately 0.143 Btu·in / ft² 2 Indicates the K coefficient of ·h·°F. In some embodiments, the foam has a K coefficient of approximately 0.137 Btu·in / ft² to approximately 0.143 Btu·in / ft² at a temperature of about 35°F for up to about 30 days after formation of the foam. 2 ·h·°F to approximately 0.143 Btu·in / ft² 2 Indicates the K coefficient of ·h·°F.

[0117] 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 approximately 0.145 Btu·in / ft²2 ·h·°F ~ approximately 0.151 Btu·in / ft 2 The K coefficient of ·h·°F is shown. In some embodiments, the foam has a K coefficient of approximately 0.145 Btu·in / ft at a temperature of about 35°F for up to about 60 days after the formation of the foam 2 ·h·°F ~ approximately 0.151 Btu·in / ft 2 The K coefficient of ·h·°F is shown. In some embodiments, the foam has a K coefficient of approximately 0.145 Btu·in / ft at a temperature of about 35°F for about 30 days to about 60 days after the formation of the foam 2 ·h·°F ~ approximately 0.151 Btu·in / ft 2 The K coefficient of ·h·°F is shown.

[0118] 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 approximately 0.152 Btu·in / ft at a temperature of about 35°F 2 ·h·°F ~ approximately 0.159 Btu·in / ft 2 The K coefficient of ·h·°F is shown. In some embodiments, the foam has a K coefficient of approximately 0.152 Btu·in / ft at a temperature of about 35°F for up to about 120 days after the formation of the foam 2 ·h·°F ~ approximately 0.159 Btu·in / ft 2 The K coefficient of ·h·°F is shown. In some embodiments, the foam has a K coefficient of approximately 0.152 Btu·in / ft at a temperature of about 35°F for about 60 days to about 120 days after the formation of the foam 2 ·h·°F ~ approximately 0.159 Btu·in / ft 2 The K coefficient of ·h·°F is shown.

[0119] 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 approximately 0.122 Btu·in / ft at a temperature of about 50°F 2 ·h·°F ~ approximately 0.165 Btu·in / ft 2 The K coefficient of ·h·°F is shown.

[0120] 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-factor of about 0.122 Btu·in / ft 2 ·h·°F to about 0.126 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0121] 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-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 50°F. In some embodiments, the foam has a K-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for up to about 30 days after the formation of the foam.

[0122] 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-factor of about 0.150 Btu·in / ft 2 ·h·°F to about 0.155 Btu·in / ft 2 ·h·°F at a temperature of about 50°F. In some embodiments, the foam has a K-factor of about 0.150 Btu·in / ft 2 ·h·°F to about 0.155 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for up to about 60 days after the formation of the foam. In some embodiments, the foam has a K-factor of about 0.150 Btu·in / ft 2 ·h·°F to about 0.155 Btu·in / ft 2Indicates the K coefficient at ·h·°F.

[0123] 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 0.158 Btu·in / ft at a temperature of about 50°F 2 ·h·°F to about 0.164 Btu·in / ft 2 Indicates the K coefficient at ·h·°F. In some embodiments, the foam has a K coefficient of about 0.158 Btu·in / ft at a temperature of about 50°F for up to about 120 days after the formation of the foam 2 ·h·°F to about 0.164 Btu·in / ft 2 Indicates the K coefficient at ·h·°F. In some embodiments, the foam has a K coefficient of about 0.158 Btu·in / ft at a temperature of about 50°F for about 60 days to about 120 days after the formation of the foam 2 ·h·°F to about 0.164 Btu·in / ft 2 Indicates the K coefficient at ·h·°F.

[0124] 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 0.132 Btu·in / ft at a temperature of about 75°F 2 ·h·°F to about 0.175 Btu·in / ft 2 Indicates the K coefficient at ·h·°F.

[0125] 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 0.132 Btu·in / ft at a temperature of about 75°F 2 ·h·°F to about 0.137 Btu·in / ft 2 Indicates the K coefficient at ·h·°F.

[0126] 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-factor of about 0.155 Btu·in / ft 2 ·h·°F to about 0.161 Btu·in / ft 2 ·h·°F at a temperature of about 75°F. In some embodiments, the foam has a K-factor of about 0.155 Btu·in / ft 2 ·h·°F to about 0.161 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for up to about 30 days after formation of the foam.

[0127] 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-factor of about 0.164 Btu·in / ft 2 ·h·°F to about 0.168 Btu·in / ft 2 ·h·°F at a temperature of about 75°F. In some embodiments, the foam has a K-factor of about 0.164 Btu·in / ft 2 ·h·°F to about 0.168 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for up to about 60 days after formation of the foam. In some embodiments, the foam has a K-factor of about 0.164 Btu·in / ft 2 ·h·°F to about 0.168 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for about 30 days to about 60 days after formation of the foam.

[0128] 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-factor of about 0.168 Btu·in / ft 2 ·h·°F to about 0.172 Btu·in / ft 2·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.168 Btu·in / ft 2 ·h·°F to about 0.172 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.168 Btu·in / ft at a temperature of about 75°F for about 60 days to about 90 days after the formation of the foam 2 ·h·°F to about 0.172 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0129] 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 0.170 Btu·in / ft 2 ·h·°F to about 0.175 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.170 Btu·in / ft at a temperature of about 75°F for up to about 120 days after the formation of the foam 2 ·h·°F to about 0.175 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.170 Btu·in / ft at a temperature of about 75°F for about 90 days to about 120 days after the formation of the foam 2 ·h·°F to about 0.175 Btu·in / ft 2 ·h·°F shows the K coefficient.

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

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

[0132] In some embodiments, the composition, which is a blend of side A and side B, contains from about 5 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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, contains from about 5 weight percent to about 10 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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, contains from about 5 weight percent to about 7 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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, contains from about 10 weight percent to about 15 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent 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, contains from about 11 weight percent to about 13 weight percent of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and from about 5 weight percent to about 15 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0137] 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 5 weight percent to about 15 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

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

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

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

[0141] 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 5 weight percent to about 10 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0142] 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 5 weight percent to about 10 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0143] 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 5 weight percent to about 10 weight percent of E-1,1,1,4,4,4-hexafluoro-2-butene.

[0144] In some embodiments, the composition that is a blend of side A and side B comprises from about 5 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.

[0145] In some embodiments, the composition that is a blend of side A and side B comprises from about 5 weight percent to about 10 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.

[0146] In some embodiments, the composition that is a blend of side A and side B comprises from about 5 weight percent to about 7 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.

[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-tetrafluoroprop-1-ene 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 2 ·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 the formation of the foam.

[0153] 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 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 the 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 the formation of the foam.

[0154] 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 about 0.140 Btu·in / ft 2 ·h·°F to about 0.145 Btu·in / ft 2·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.140 Btu·in / ft 2 ·h·°F to about 0.145 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.140 Btu·in / ft at a temperature of about 20°F for about 60 days to about 120 days after the formation of the foam 2 ·h·°F to about 0.145 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0155] 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 coefficient of about 0.115 Btu·in / ft at a temperature of about 35°F 2 ·h·°F to about 0.150 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0156] 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 coefficient of about 0.115 Btu·in / ft at a temperature of about 35°F 2 ·h·°F to about 0.119 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0157] 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 coefficient of about 0.131 Btu·in / ft at a temperature of about 35°F 2 ·h·°F to about 0.135 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.131 Btu·in / ft at a temperature of about 35°F for up to about 30 days after the formation of the foam 2·h·°F to approximately 0.135 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F.

[0158] 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 coefficient of approximately 0.138 Btu·in / ft²·h·°F at a temperature of about 35°F. 2 ·h·°F to approximately 0.142 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F. In some embodiments, the foam has a K coefficient of approximately 0.138 Btu·in / ft²·h·°F at a temperature of about 35°F for up to about 60 days after the formation of the foam. 2 ·h·°F to approximately 0.142 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F. In some embodiments, the foam has a K coefficient of approximately 0.138 Btu·in / ft²·h·°F 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 approximately 0.142 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F.

[0159] 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 coefficient of approximately 0.146 Btu·in / ft²·h·°F at a temperature of about 35°F. 2 ·h·°F to approximately 0.152 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F. In some embodiments, the foam has a K coefficient of approximately 0.146 Btu·in / ft²·h·°F at a temperature of about 35°F for up to about 120 days after the formation of the foam. 2 ·h·°F to approximately 0.152 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F. In some embodiments, the foam has a K coefficient of approximately 0.146 Btu·in / ft²·h·°F at a temperature of about 35°F for about 60 days to about 120 days after the formation of the foam. 2 ·h·°F to approximately 0.152 Btu·in / ft²·h·°F 2 Indicates the K coefficient of ·h·°F.

[0160] 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 about 0.120 Btu·in / ft 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0161] 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 about 0.120 Btu·in / ft 2 ·h·°F to about 0.124 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0162] 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 about 0.137 Btu·in / ft 2 ·h·°F to about 0.141 Btu·in / ft 2 ·h·°F at a temperature of about 50°F. In some embodiments, the foam has a K factor of about 0.137 Btu·in / ft 2 ·h·°F to about 0.141 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for up to about 30 days after formation of the foam.

[0163] 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 about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.144 Btu·in / ft at a temperature of about 50°F for about 30 days to about 60 days after the formation of the foam 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0164] 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 coefficient of about 0.152 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 0.152 Btu·in / ft at a temperature of about 50°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 0.152 Btu·in / ft at a temperature of about 50°F for about 60 days 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.

[0165] 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 coefficient of about 0.130 Btu·in / ft 2 ·h·°F to about 0.168 Btu·in / ft 2 ·h·°F shows the K coefficient.

[0166] 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 about 0.130 Btu·in / ft 2 ·h·°F to about 0.135 Btu·in / ft 2 ·h·°F at a temperature of about 75°F.

[0167] 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 about 0.148 Btu·in / ft 2 ·h·°F to about 0.153 Btu·in / ft 2 ·h·°F at a temperature of about 75°F. In some embodiments, the foam has a K-factor of about 0.148 Btu·in / ft 2 ·h·°F to about 0.153 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for up to about 30 days after the formation of the foam.

[0168] 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 about 0.155 Btu·in / ft 2 ·h·°F to about 0.161 Btu·in / ft 2 ·h·°F at a temperature of about 75°F. In some embodiments, the foam has a K-factor of about 0.155 Btu·in / ft 2 ·h·°F to about 0.161 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for up to about 60 days after the formation of the foam. In some embodiments, the foam has a K-factor of about 0.155 Btu·in / ft 2 ·h·°F to about 0.161 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for about 30 days to about 60 days after the formation of the foam.

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

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

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

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

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

[0174] 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 5 weight percent to about 15 weight percent of E-1-chloro-3,3,3-trifluoropropene.

[0175] 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 5 weight percent to about 15 weight percent of E-1-chloro-3,3,3-trifluoropropene.

[0176] 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 5 weight percent to about 15 weight percent of E-1-chloro-3,3,3-trifluoropropene.

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

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

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

[0180] 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 5 weight percent to about 10 weight percent of E-1-chloro-3,3,3-trifluoropropene.

[0181] 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 5 weight percent to about 10 weight percent of E-1-chloro-3,3,3-trifluoropropene.

[0182] 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 5 weight percent 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 from about 5 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.

[0184] In some embodiments, the composition, which is a blend of side A and side B, comprises from about 5 weight percent to about 10 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.

[0185] In some embodiments, the composition, which is a blend of side A and side B, comprises from about 5 weight percent to about 7 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.

[0186] In some embodiments, the composition, which 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-chloro-3,3,3-trifluoropropene.

[0187] In some embodiments, the composition, which 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-chloro-3,3,3-trifluoropropene.

[0188] In some embodiments, the composition, which 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 the formation of the foam.

[0192] 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 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-tetrafluoroprop-1-ene 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-tetrafluoroprop-1-ene 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 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 0.135 Btu·in / ft 2 ·h·°F to about 0.139 Btu·in / ft 2 ·h·°F at a temperature of about 35°F. In some embodiments, the foam has a K-factor of about 0.135 Btu·in / ft 2 ·h·°F to about 0.139 Btu·in / ft 2 ·h·°F at a temperature of about 35°F for up to about 30 days after the formation of the foam.

[0196] 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 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 35°F. In some embodiments, the foam has a K-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 35°F for up to about 60 days after the formation of the foam. In some embodiments, the foam has a K-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 35°F for about 30 days to about 60 days after the formation of the foam.

[0197] 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 0.116 Btu·in / ft 2 ·h·°F to about 0.155 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0198] 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 about 0.116 Btu·in / ft 2 ·h·°F to about 0.118 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0199] 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 about 0.135 Btu·in / ft 2 ·h·°F to about 0.139 Btu·in / ft 2 ·h·°F at a temperature of about 50°F. In some embodiments, the foam has a K-factor of about 0.135 Btu·in / ft 2 ·h·°F to about 0.139 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for up to about 30 days after the formation of the foam.

[0200] 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 about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 50°F. In some embodiments, the foam has a K-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for up to about 60 days after the formation of the foam. In some embodiments, the foam has a K-factor of about 0.144 Btu·in / ft 2 ·h·°F to about 0.148 Btu·in / ft 2 ·h·°F at a temperature of about 50°F for about 30 days to about 60 days after the formation of the foam.

[0201] 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 about 0.128 Btu·in / ft 2 ·h·°F to about 0.166 Btu·in / ft 2 ·h·°F at a temperature of about 75°F.

[0202] 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 about 0.128 Btu·in / ft 2 ·h·°F to about 0.132 Btu·in / ft 2 ·h·°F at a temperature of about 75°F.

[0203] 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 about 0.152 Btu·in / ft 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F at a temperature of about 75°F. In some embodiments, the foam has a K factor of about 0.152 Btu·in / ft 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F at a temperature of about 75°F for up to about 30 days after formation of the foam.

[0204] 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 about 0.162 Btu·in / ft 2 ·h·°F to about 0.167 Btu·in / ft 2·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.162 Btu·in / ft 2 ·h·°F to about 0.167 Btu·in / ft 2 ·h·°F shows the K coefficient. In some embodiments, the foam has a K coefficient of about 0.162 Btu·in / ft 2 ·h·°F to about 0.167 Btu·in / ft 2 ·h·°F shows the K coefficient.

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

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

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

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

[0209] In some embodiments of the methods and systems provided herein, a one-component foam containing a blowing agent according to the present invention is formed. In some embodiments, the foam is a polyurethane foam containing a blowing agent according to the present invention. In some embodiments, a portion of the blowing agent is contained in a foam-forming agent that is liquid, for example, at the pressure within 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 expansion of the foam, and the separate gas phase acts to impart a propulsive force 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 expanding the foam and 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 polymer 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 thermoset 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 thermoset foams provided herein, can be used in a wide variety of applications. In some embodiments, the foams include foams for electrical 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 heat insulation efficiency (especially in the case of thermosetting foams), dimensional stability, compression strength, and change in heat insulation properties over time, in addition to a low ozone depletion potential and a low global warming potential associated with many of the blowing agents described herein. In some embodiments, a thermosetting foam is provided that includes such a foam formed into a foam article, which exhibits improved thermal conductivity compared to a foam made using the same amount of the same blowing agent (or a commonly used blowing agent such as HFC-245fa) but without using Z-HCFO-1224yd.

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

[0216] In some embodiments, the foam made according to the methods provided herein has a compression strength comparable to the compression strength resulting from making the foam under substantially the same conditions on a commercial basis, except that the blowing agent consists of HFC-245fa. In some embodiments, the foam provided herein exhibits a compression strength at the yield point of at least about 12.5% (parallel and perpendicular directions) or at least about 13% at the yield point in each of those directions.

[0217] Methods and Systems Table 1 above describes a composition comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the composition is useful in 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 heat pump systems. In some embodiments, the composition is useful in systems and methods for generating aerosols, for example, in systems and methods that include or consist of aerosol propellants. In some embodiments, methods for forming foams, as well as methods for fire extinguishing and fire suppression are also provided. In some embodiments, a method for removing residues from articles in which the present composition is used as a solvent composition in such methods and systems is provided.

[0218] Heat transfer method A heat transfer method using the composition provided herein is provided herein. In some embodiments, the heat transfer method includes providing a composition comprising or consisting essentially of Z-HCFO-1224yd and transferring heat to or from the composition to change the phase of the composition. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is the blend described in Table 1. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is the blend described in Table 2 below. In some embodiments, the method provides 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 to generate a vapor comprising or consisting essentially of Z-HCFO-1224yd.

[0219] In some embodiments of the heat transfer method, the composition is a blend of Z-HCFO-1224yd and one or more additional compounds. In some embodiments of the heat transfer method, Z-HCFO-1224yd forms a blend composition with an HFO, an HFE, a hydrocarbon, an alcohol, an ether, an aldehyde, a ketone, or other compounds, such as water, methyl formate, ethyl formate, formic acid, trans-1,2-dichloroethylene, CO2, and one or more of the others. In some embodiments of the heat transfer method, the other compounds constitute from about 1 wt% to about 99 wt% of the composition. For example, from about 1 wt% to about 90 wt%, from about 1 wt% to about 80 wt%, from about 1 wt% to about 70 wt%, from about 1 wt% to about 60 wt%, from about 1 wt% to about 50 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 5 wt%, from about 5 wt% to about 99 wt%, from about 5 wt% to about 95 wt%, from about 5 wt% to about 75 wt%, from about 5 wt% to about 50 wt%, from about 5 wt% to about 25 wt%, from about 10 wt% to about 99 wt%, from about 10 wt% to about 90 wt%, from about 10 wt% to about 75 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 25 wt%, from about 25 wt% to about 99 wt%, from about 25 wt% to about 90 wt%, from about 25 wt% to about 75 wt%, from about 25 wt% to about 50 wt%, from about 40 wt% to about 60 wt%, from about 45 wt% to about 55 wt%, from about 50 wt% to about 99 wt%, from about 50 wt% to about 75 wt%, from about 60 wt% to about 99 wt%, from about 60 wt% to about 75 wt%, or from about 75 wt% to about 99 wt% of the composition.

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

[0221]

Table 2-1

[0222]

Table 2-2

[0223]

Table 2-3

[0224]

Table 2-4

[0225]

Table 2-5

[0226]

Table 2-6

[0227]

Table 2-7

[0228] In some embodiments, the method further includes, for example, compressing the refrigerant vapor with a compressor or similar equipment to generate vapor of the present 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 increases. In some embodiments, the method includes removing at least a portion of the heat added by the evaporation and compression steps from this relatively high-temperature and high-pressure vapor. In some embodiments, the heat removal step includes condensing the high-temperature and high-pressure vapor while the vapor is in a relatively high-pressure state to produce a relatively high-pressure liquid containing or consisting essentially 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 and low-pressure liquid. In some embodiments, it is this refrigerant liquid with reduced temperature, which is then vaporized by the heat transferred from the object or fluid to be cooled.

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

[0230] In some embodiments, the compositions provided herein are used in a method of producing heating that includes the step of condensing a refrigerant comprising or consisting essentially of Z-HCFO-1224yd in the vicinity of a liquid or object to be heated. In some embodiments, the refrigerant comprising or consisting essentially of Z-HCFO-1224yd is a blend as set forth in Table 2. In some embodiments, the method is similar to the refrigeration cycle described above except that its primary purpose is to reject heat in a condenser rather than recover heat in an evaporator.

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

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

[0233] Many existing refrigeration systems are currently adapted for use with existing refrigerants, and the compositions of the present invention are believed to be adaptable for use in many such systems, with or without system modification. In some embodiments, the compositions of the present invention offer advantages as replacements in systems currently based on refrigerants having relatively high capacities. In some embodiments, for reasons of efficiency, it may be desirable to use the low-capacity refrigerant compositions of the present invention, for example, to replace higher-capacity refrigerants, and such embodiments of the compositions offer promising advantages. Thus, in some embodiments, compositions comprising or consisting essentially of Z-HCFO-1224yd are used as replacements for existing refrigerants such as, inter alia, 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 comprising or consisting essentially of Z-HCFO-1224yd are blends as set forth in Table 2. In some embodiments, the refrigerants of the present invention potentially enable the beneficial use of larger positive displacement compressors, thereby providing better energy efficiency than other refrigerants such as HCFC-123 or HFC-134a. Thus, the refrigerant compositions of the present invention, specifically compositions comprising or consisting essentially of 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 a centrifugal or positive displacement chiller. In some embodiments, the azeotropic mixture or azeotropic mixture-like composition is used as a refrigerant in a flooded evaporator.

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

[0237] In some embodiments, the compositions provided herein include other components for the purpose of enhancing or providing certain functionality to the composition, or in some cases, for reducing the cost of the composition. In some embodiments, the refrigerant compositions provided herein, such as 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, such as about 30% to about 50% by weight of the composition. In some embodiments, the composition also includes a solubilizer such as propane for the purpose of assisting the compatibility and / or solubility of the lubricant. In some embodiments, the solubilizer 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, for example, a combination of a surfactant and a solubilizer, as disclosed in U.S. Patent No. 6,516,837, the disclosure of which is incorporated herein by reference, is added to the composition to assist with oil solubility. Commonly used refrigeration lubricants, such as polyol esters (POE), 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), which are used in refrigerators with hydrofluorocarbon (HFC) refrigerants, can be used with the refrigerant compositions provided herein.

[0239] In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd has advantages in chillers typically used in commercial air conditioning systems (in the original system or when used as a replacement for refrigerants such as R-12 and R-500). In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd is the blend described in Table 2. In some embodiments, a composition comprising Z-HCFO-1224yd comprises from about 0.5% to about 5% of a fire suppressant. In some embodiments, the fire suppressant is CF3I.

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

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

[0242] In some embodiments, the lubricant includes polyalkylene glycols and polyol esters. In some embodiments, the lubricant includes polyalkylene glycols. In some embodiments, the lubricant includes polyol ethers.

[0243] In the present invention, any of a 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 attaching a refrigerant container to the low-pressure side of the refrigeration system and operating a compressor of the refrigeration system to draw the refrigerant into the system. In some embodiments, the refrigerant container is sized such that it can monitor the amount of refrigerant composition entering the system. In some embodiments, the charging is stopped when a desired amount of the refrigerant composition has been introduced into the system. In some embodiments, a wide range of charging tools known to those skilled in the art are commercially available. Thus, in light of the above disclosure, those skilled in the art will be able to easily introduce the refrigerant composition of the present invention into a refrigeration system according to the present invention without undue experimentation.

[0244] Power cycle applications The Rankine cycle system is known to be a simple and reliable means for converting thermal energy into mechanical shaft power. Organic working fluids are useful in place of water / steam when encountering lower levels of thermal energy. Water / steam systems operating at lower levels of thermal energy (typically below 400°F) have associated high volumes and low pressures. To reduce system size and maintain high efficiency, organic working fluids with boiling points near room temperature are used. Such fluids will have higher gas densities resulting in higher volumes and favorable transport, and heat transfer characteristics that result in higher efficiency compared to water at lower operating temperatures. In industrial environments, there is more opportunity to use flammable working fluids such as toluene and pentane, especially when the industrial environment already has large amounts of combustible substances at the site within the process or storage location. For example, when the risks associated with the use of flammable working fluids are unacceptable, such as in power generation in populated areas or near buildings, other fluids such as CFC-113 and CFC-11 can be used. Although these materials are nonflammable, there were environmental risks due to their ozone depletion coefficients. Ideally, an organic working fluid needs to be environmentally acceptable, nonflammable, of low toxicity, and operate at pressures above atmospheric pressure.

[0245] Organic Rankine Cycle (ORC) systems are often used to recover waste heat from industrial processes. In cogeneration applications, waste heat from the combustion of fuel used to drive the prime mover of a power generation facility is recovered and used, for example, for heating, or for producing hot water to operate an absorption chiller that provides heat and cooling. In some cases, the demand for hot water is low or non-existent. The most difficult cases are those where the thermal requirements are variable and load matching becomes difficult, deteriorating the efficient operation of the cogeneration system. In such cases, using an organic Rankine cycle system to convert waste heat into shaft power can be more useful. The shaft power may be used, for example, to operate a pump or for power generation. By using this approach, the overall system efficiency and fuel utilization rate are increased. Since more electricity can be generated for the same fuel input, the atmospheric emissions from fuel combustion can be reduced.

[0246] In some embodiments, the process that generates 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 work in 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, plastic molding, cement kilns, timber kilns (drying), firing operations, the steel industry, the glass industry, foundries, smelting, air conditioning, refrigeration, and central heating. See U.S. Patent No. 7,428,816, the disclosure of which is incorporated herein by reference.

[0247] Compositions containing Z-HCFO-1224yd are provided herein for use in ORC power cycle applications. In some embodiments, the composition is as set forth in Table 3 below (all percentages are by weight and are understood to be preceded by the word "about").

[0248] [Table 3-1]

[0249]

Table 3-2

[0250]

Table 3-3

[0251]

Table 3-4

[0252] In some embodiments, the composition comprises Z-HCFO-1224yd and one or more compounds selected from 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-HCFO-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, a composition comprising or consisting essentially of Z-HCFO-1224yd is used in a power cycle. In some embodiments, the process comprises recovering waste heat in an organic Rankine cycle system wherein the working fluid is a composition comprising or consisting essentially of Z-HCFO-1224yd and optionally one or more additional compounds. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is the composition described in Table 3.

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

[0256] In some embodiments of the method of cleaning and removing contaminants, the amount of Z-HCFO-1224yd in the composition is from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1 above, and these amounts are equally applicable to this use of the compositions of the present invention.

[0257] In some embodiments, the method includes applying to an article a composition comprising or consisting essentially of Z-HCFO-1224yd. Many and various cleaning techniques can utilize the compositions of the present invention to good advantage. In some embodiments, the composition comprising or consisting essentially of Z-HCFO-1224yd is used in 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 of 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, the cleaning composition comprising Z-HCFO-1224yd is used in connection with certain subcritical vapor degreasing and solvent cleaning methods. In some embodiments of solvent use, the composition containing the compound Z-HCFO-1224yd is blended with one or more of cis-1234ze, cis-1233zd, HFC-245fa, methylal (dimethoxymethane), methyl ethyl ketone, methyl isobutyl ketone, or HFC-134a. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of pentane, hexane, HFC-365, C4F9OCH3, C4F9OC2H5, propane, butane, isobutane, or dimethyl ether. In some embodiments, the blend comprises Z-HCFO-1224yd blended with one or more of trans-1,2-dichloroethylene, trans-HFO-1234ze, trans-HCFO-1233zd, trans-1336, HFC-43-10, HFC-152a, methanol, ethanol, isopropanol, and / or acetone.

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

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

[0262] In some embodiments, the sprayable composition comprises a material to be sprayed and a propellant comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the sprayable composition comprises the blends described in Table 1. In some embodiments, inert ingredients, solvents, and other materials are also present in the sprayable mixture. In some embodiments, the sprayable composition is an aerosol. Suitable materials for spraying include, but are not limited to, cosmetic materials such as deodorants, fragrances, hairsprays, detergents, and abrasives, and pharmaceutical products such as anti-asthma drugs and antihalitosis drugs.

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

[0264] In some embodiments for aerosol applications, the active ingredient to be sprayed is mixed with inert ingredients, solvents, and others. In some embodiments, the sprayable composition is an aerosol. Suitable active substances to be sprayed include, but are not limited to, cosmetic materials such as lubricants, insecticides, detergents, deodorants, fragrances, and hairsprays, abrasives, and pharmaceutical materials such as skin coolants (sunburn treatment agents), local anesthetics, and anti-asthma drugs.

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

[0266] In some embodiments, aerosol products are for industrial, consumer, or medical use. Aerosol products for industrial, consumer, or medical use typically contain one or more propellants together with one or more active ingredients, inert ingredients, or solvents. The propellant provides the force to expel the product in aerosolized form. Some aerosol products are propelled by compressed gases such as carbon dioxide, nitrogen, nitrous oxide, and even air, but 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 when incorporated into aerosol formulations, they often result in flammable aerosol products.

[0267] In some embodiments, the aerosol products described herein include a nonflammable liquefied gas propellant. In some embodiments, the aerosol products described herein include or consist essentially of Z-HCFO-1224yd. In some embodiments, the aerosol products described herein include or consist essentially of the blends described in Table 1 above. In some embodiments, the aerosol products are for use in specific industrial aerosol products, such as spray cleaners, lubricants, etc., and in medical aerosols, such as 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 to accessible mucous membranes or nasal cavities. In some embodiments, there is provided a method of treating a disease, disorder, and similar health-related problems of an organism, the method comprising the step of applying to the organism in need of treatment a composition comprising or consisting essentially of Z-HCFO-1224yd and a pharmaceutical or other therapeutic ingredient. In some embodiments, the step of applying the composition comprising or consisting essentially of Z-HCFO-1224yd comprises providing (e.g., introducing the composition into) an MDI containing the composition comprising or consisting essentially of Z-HCFO-1224yd and then releasing the composition comprising or consisting essentially of Z-HCFO-1224yd from the MDI.

[0268] As used herein, the term "nonflammable" 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, e.g., ASTM-1310-86 "Flash point of liquids by tag Open-cup apparatus".

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

[0270] Sterilization In particular, many articles, devices, and materials for use in the medical field need to be sterilized prior to use for health and safety reasons, such as the health and safety of patients and hospital staff. Provided herein is a sterilization method comprising the step of contacting an article, device, or material to be sterilized with a composition comprising or consisting essentially of Z-HCFO-1224yd. In some embodiments, the composition is the 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 from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to this use of the compositions of the present invention.

[0272] Many sterilizing agents are known in the art and would be considered adaptable for use in connection with the present invention. However, 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. One of ordinary skill in the art would be able to readily determine the relative ratios of the sterilizing agent used in connection with the present sterilizing composition and method to other compounds including Z-HCFO-1224yd.

[0273] As is known to those of ordinary skill 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 an effective amount 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, the 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, the sterilization is carried out in a substantially sealed chamber. In some embodiments, the sterilization process is completed in less than about 2 hours. In some embodiments, some 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 article to be sterilized is exposed to a fluid containing or consisting essentially of Z-HCFO-1224yd at a temperature from near room temperature to about 200°F, for example, from near room temperature to about 100°F.

[0275] In some embodiments, pasteurization is a multi-stage process, at least two stages, 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 an article, which has been cleaned and packaged in a gas permeable bag, into the chamber. In some embodiments, it is evacuated from the chamber by vacuuming. In some embodiments, it is evacuated by replacing the air with steam. In some embodiments, it is evacuated from the chamber 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 sterilization effect of the sterilant introduced into the chamber after the desired relative humidity has been achieved. In some embodiments, after sufficient time for the sterilant to penetrate the packaging material and reach the gaps in the article, the sterilant and steam are evacuated from the chamber.

[0276] In some embodiments, the second step (venting step) of the process includes venting the article to remove sterilant residues. In some embodiments, the residues are toxic sterilants. In some embodiments, venting 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 venting process includes air scrubbing, continuous venting, and combinations of these two. Air scrubbing is a batch process and in some embodiments includes evacuating the chamber for a relatively short time, for example 12 minutes, and then introducing air into the chamber at a pressure above atmospheric pressure.

[0277] As used herein, the term "non-toxic" refers to compounds and compositions having an acute toxicity level that is substantially lower than the toxicity level of HFO-1223xd, preferably at least about 30 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 sterilant is achieved. In some embodiments, continuous aeration involves introducing air through an inlet on one side of the chamber and then withdrawing the air through an outlet on the other side of the chamber by applying a slight vacuum to the outlet. In some embodiments, two approaches are combined. In some embodiments, the method includes an air cleaning step and then a ventilation cycle step.

[0279] Extraction of flavoring agents and fragrances In some embodiments, a composition comprising or consisting essentially of Z-HCFO-1224yd is used to convey, extract, or separate desired materials from biomass. In some embodiments, the composition is the blend described in Table 1 above. In some embodiments, materials include, but are not limited to, essential oils such as flavoring agents and fragrances, fuels, pharmaceuticals, oils that can be used as dietary supplements, etc. Accordingly, a method for conveying, 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 from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to this use of the compositions of the present invention.

[0281] In some embodiments, a composition comprising Z-HCFO-1224yd is used as part of an extractant, carrier, or delivery system for perfumes and fragrance formulations. In some embodiments, the formulation is an aerosol formulation. In some embodiments, a composition comprising Z-HCFO-1224yd is used as an extractant for perfumes and fragrances. In some embodiments, the perfumes and fragrances are extracted from plant material.

[0282] Method for reducing flammability Provided herein is a method for reducing the flammability of a fluid, the method comprising adding a composition comprising Z-HCFO-1224yd to the fluid. In some embodiments, the composition comprising Z-HCFO-1224yd is a blend as defined in Table 1. In some embodiments, the method reduces the flammability associated with any of a wide range of other flammable fluids. In some embodiments, the method reduces the flammability of fluids such as hydrocarbons, including ethylene oxide, flammable hydrofluorocarbons, and HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane (HFC-32), propane, hexane, octane, etc. For the purposes of the present invention, a flammable fluid is any fluid that exhibits a flammable range 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 from about 1 wt% to about 99 wt%, from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to this use of the compositions of the present invention.

[0284] In accordance with the present invention, any suitable amount of the present compound or composition can be added to reduce the flammability of a fluid. As will be appreciated by those skilled in the art, the amount added depends at least in part on the degree of flammability of the target fluid and the degree to which its flammability is desired to be reduced. In some embodiments, the amount of the compound or composition comprising Z-HCFO-1224yd added to a flammable fluid is effective to render the resulting fluid substantially non-flammable.

[0285] Flame suppression method The present invention further provides a method of 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 blend described in Table 1 above. In some embodiments, an additional flame suppressant is used in combination with the composition containing Z-HCFO-1224yd, either in the mixture or as a secondary flame suppressant. In some embodiments, the compound is a fluoroketone. In some embodiments, the fluoroketone is dodecafluoro-2-methylpentan-3-one, which is sold 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 from about 1 wt% to about 99 wt%, such as from about 30 wt% to about 99 wt%, from about 50 wt% to about 99 wt%, from about 75 wt% to about 99 wt%, from about 85 wt% to about 99 wt%, from about 20 wt% to about 80 wt%, from about 90 wt% to about 99 wt%, from about 95 wt% to about 99 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 50 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 60 wt%, from about 10 wt% to about 80 wt%, from about 10 wt% to about 90 wt%, from about 20 wt% to about 80 wt%, or from about 20 wt% to about 90 wt%. Other ranges of amounts are shown in Table 1, and these amounts are equally applicable to this use of the compositions of the present invention.

[0287] Any suitable method of bringing the flame into contact with the present composition may be used. In some embodiments, the composition containing Z-HCFO-1224yd is sprayed onto the flame, poured, etc., 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 used to etch deposits from the surface. Chemical vapor deposition (CVD) chambers and plasma-enhanced chemical vapor deposition (PECVD) chambers need to be cleaned regularly 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, exhausting the reaction gas and replacing it with the cleaning gas, activating the cleaning gas, and then a flushing step using an inert carrier gas to remove the cleaning gas from the chamber. Cleaning gases typically act by etching contaminants accumulated from the inner surface, and thus the etching rate of the cleaning gas is an important parameter in the usefulness and commercial utilization of the gas, and some cleaning gases can also be used as etching gases. These gases can generate relatively large amounts of toxic exhaust gases, which can cause additional environmental, health, and safety (EHS) problems separate from the GWP of the cleaning gas or the etching gas itself, or from the GWP of the additional GWP.

[0289] Therefore, it is necessary to use an effective and inexpensive cleaning / etching gas with a high etching rate and a smaller impact on GWP and ESH than the current gas to reduce the harm of global warming caused by the cleaning and operation of the CVD reactor. In some embodiments, a clean gas mixture with low EHS and GWP is provided, so that even if unreacted gas is released, its impact on the environment is reduced. In some embodiments, a method of using these gases is provided, which includes a step of activating the gas either in a remote chamber or in situ in a process chamber, where the gas mixture includes an oxygen source and a hydrofluoroolefin; and a step of contacting the activated gas with the surface deposits for a time sufficient to remove the surface deposits. In some embodiments, the gas mixture is activated by a radio frequency (RF) source using sufficient power for a sufficient time so that the gas mixture reaches a neutral temperature of about 1000 - 3,000K to form an activated gas mixture. In some embodiments, a glow discharge is used to activate the gas. In some embodiments, the activated gas mixture is contacted with the surface deposits, thereby removing at least a portion of the surface deposits. In some embodiments, the gas mixture includes Z-HCFO-1224yd. In some embodiments, the gas mixture includes Z-HCFO-1224yd alone. In some embodiments, the gas mixture includes Z-HCFO-1224yd in 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 generally deposited by chemical vapor deposition (CVD) method, plasma enhanced chemical vapor deposition (PECVD) method, or similar processes. Such materials include, but are not limited to, nitrogen-containing deposits such as silicon nitride, silicon oxynitride, silicon carbonitride (SiCN), silicon boron nitride (SiBN), and metal nitrides such as tungsten nitride, titanium nitride, or tantalum nitride. In some embodiments, the surface deposits are silicon nitride.

[0291] In some embodiments, surface deposits are removed from the interior of a process chamber used in the manufacture of electronic devices. In some embodiments, the process chamber is a CVD chamber or a PECVD chamber. In some embodiments, 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 an N-containing thin film from a wafer. In some embodiments, the gas is used for etching applications.

[0292] In some embodiments, the process involves an activation step of activating a cleaning gas mixture within a remote chamber. The activation can be achieved by any means capable of dissociating most of the feed gas, such as high-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 source, where the plasma has a torroidal configuration and acts as the secondary side of the transformer, is used. In some embodiments, the use of low-frequency RF power allows for the use of a magnetic core that enhances inductive coupling relative to capacitive coupling, thereby enabling more efficient energy transfer to a plasma without excessive ion bombardment that limits 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 source is a remote microwave inductively coupled or capacitively coupled plasma source. In some embodiments, a glow discharge is used to activate the gas.

[0293] Dielectric method In some embodiments, Z-HCFO-1224yd is used as a dielectric in an electrical device. In some embodiments, Z-HCFO-1224yd is used alone. In some embodiments, Z-HCFO-1224yd is used as a mixture with one or more of the compounds listed in Table 1. In medium-voltage or high-voltage electrical devices, the functions of electrical insulation and electrical arc extinction are typically performed by an insulating gas confined within the device. In the generally accepted meaning of the terms, "medium voltage" means a voltage that exceeds 1,000 volts AC and strictly exceeds 1,500 volts DC, but is 52,000 volts AC or less, or 75,000 volts DC or less, while the term "high voltage" means a voltage that strictly exceeds 52,000 volts AC and exceeds 75,000 volts 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 of the compounds listed in Table 1.

[0295] Although the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the present invention. The claims are intended to be construed to cover the disclosed embodiments described above, their alternatives, and all their equivalents.

[0296] Note that not all of the operations or examples described in the general description are necessary, and some parts of a particular operation may not be necessary, and one or more additional operations may be performed in addition to the operations described above. Further, the order in which the operations are described is not necessarily the order in which they are performed.

[0297] In the above specification, the concept of the present invention is described 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 present invention as set forth in the following claims. Accordingly, the present specification and drawings are to be regarded in an illustrative rather than a limiting sense, and all such modifications are intended to be included within the scope of the present invention.

[0298] Benefits, other advantages, and solutions to problems have been described above in the context of specific embodiments. However, none of these benefits, advantages, problem solutions, and any features that may give rise to or make more apparent any benefit, advantage, or solution are to be construed as essential, necessary, or indispensable features in part or all of the claims.

[0299] For clarity, it should be understood that the specific features described herein in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, various features described in the context of a single embodiment for brevity may also be provided separately or in any sub-combination. Further, references to values described in ranges include each and every value within that range.

Examples

[0300] The present disclosure is further defined in the following examples. It is to be understood that these examples illustrate preferred embodiments but are provided for illustrative purposes only. From the above description and these examples, those skilled in the art can identify the preferred features and make various changes and modifications to adapt to various applications 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. The measured values included the evaporator (Evap) and condenser (Cond), the discharge temperature (Disch T), and the average temperature glide of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of mixtures containing Z-HCFO-1224yd (1224ydZ) were measured and compared to 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 °C Condenser temperature 37.78 °C Subcooling 0 K 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 alternative to HFC-245fa, HCFC-123, and 1233zdE. This is particularly closely matched in capacity to 1233zdE. Also, the mixtures shown were good alternatives to pure fluids shown to have similar capacity and efficiency. Mixtures with low temperature glides (< ~1 K) are particularly suitable for use in centrifugal chillers. Mixtures with high glides are suitable for use in heat exchangers with co-current or counter-current flow.

[0306] The compressor discharge temperatures of the mixtures and pure fluids were also similar.

[0307] Example 2: Cooling and Heating Performance Data The cooling and heating performance of a composition containing Z-HCFO-1224yd was measured. The measured values included the evaporator (Evap) and condenser (Cond), the discharge temperature (Disch T), and the average temperature glide (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of the mixture containing Z-HCFO-1224yd (1224ydZ) were measured and compared 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 °C Condenser temperature 37.78 °C Subcooling amount 0 K 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 shown had 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 a composition containing Z-HCFO-1224yd was measured. The measured values included the evaporator (Evap) and condenser (Cond), the discharge temperature (Disch T), and the average temperature glide (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of the mixture containing Z-HCFO-1224yd (1224ydZ) were measured and compared with 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 °C Condenser temperature 37.78 °C Subcooling amount 0 K Return gas temperature 25 °C The compressor efficiency was 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 shown had 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 the composition containing Z-HCFO-1224yd was measured. The measured values included the evaporator (Evap) and condenser (Cond), discharge temperature (Disch T), and the average temperature glide (Avg Temp Glide) of the evaporator and condenser. The relative energy efficiency (COP) and capacity (Cap) of the mixture containing Z-HCFO-1224yd (1224ydZ) were measured and compared with 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 °C Condenser temperature 37.78 °C Subcooling amount 0 K Return gas temperature 25 °C The compressor efficiency was 75%.

[0317] [Table 7]

[0318] The results showed that the mixtures containing HCFO-1224yd closely matched R-407C, R-22, and R-410A. The mixtures shown had 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 the cycle efficiency of an ORC system using Z-HCFO-1224yd as the working fluid. The maximum achievable operating pressure of the ORC system was about 2.5 MPa, and it was assumed that a heat source capable of maintaining the temperature of either working fluid at the inlet of the expander 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 in the evaporator remains below the maximum allowable design operating pressure of the components (e.g., heat exchangers) of commercially available equipment generally available for ORC systems, the evaporation temperature using HFC-245fa was limited to 133.5 °C.

[0323] As described in the above embodiments, when using Z-HCFO-1224yd, when used in an ORC system designed to use HFC-245fa as the working fluid, it achieves a cycle efficiency 8.97% higher than that of HFC-245fa, and shows a 99.88% ultra-low reduction in the GWP of the working fluid. This indicates that by discharging the working fluid, flushing the ORC system with a lubricant or working fluid containing Z-HCFO-1224yd, and filling the ORC system with a working fluid containing Z-HCFO-1224yd, the working fluid containing HFC-245fa in the existing ORC system can be replaced.

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

[0325]

Table 9

[0326] As shown in Table 9, Z-HCFO-1224yd has a COP h substantially identical to that of HFC-245fa, but results in a working fluid GWP that is 99.88% ultra-low compared to the GWP of HFC-245fa.

[0327] Example 7: Flame suppression A composition containing Z-HCFO-1224yd was used as a flame suppression composition. To evaluate total immersion water fire suppression applications, an NFPA 2001 cup burner was used. At this time, a small fire of heptane was located in a chimney with an air flow around the flame to supply the necessary oxygen. To this air flow, Z-HCFO-1224yd was added until the flame was extinguished. Table 10 below shows the extinguishing concentration of heptane using Z-HCFO-1224yd as the fire 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 existence of an azeotrope-like composition between the binary pair of Z-1,1,1,4,4,4-hexafluoro-2-butene and Z-1-chloro-2,3,3,3-tetrafluoropropene was tested. To determine the relative volatility of each binary pair, the PTx method was used. In this procedure, for each binary pair, the total absolute pressure in a sample cell having a volume of 85 mL was measured at a constant temperature for various binary compositions. Then, using the non-random two-liquid model (NRTL) equation, these measured values were converted into equilibrium vapor and liquid compositions. The vapor pressures measured for the compositions in the PTx sample cell for this binary system are shown in Figure 1.

[0330] As shown by a mixture of about 1 to 22 mol% of Z-1,1,1,4,4,4-hexafluoro-2-butene and about 78 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoropropene and a mixture of about 93 to 99 mol% of Z-1,1,1,4,4,4-hexafluoro-2-butene and about 1 to 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] A substantially constant boiling azeotrope-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 (over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a specific temperature was 5 percent or less (based on the bubble point pressure)). An azeotrope-like composition of 1 to 24 mol% and 62 to 99 mol% of Z-HCFO-1224yd and 1 to 38 mol% and 76 to 99 mol% of Z-HFO-1336mzz was formed at temperatures in the range of about -40°C to about 140°C (over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a specific temperature was 3 percent or less (based on the bubble point pressure)) (Table 11B).

[0332] [Table 11]

[0333] [Table 12]

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

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

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

[0337] [Table 13]

[0338] [Table 14]

[0339] Example 10: Azeotrope Composition of Z-HCFO-1224yd and E-HCFO-1233zd To determine the relative volatility of the binary pair of Z-HCFO-1224yd and E-HCFO-1233zd, the PTx method described in Example 8 was used. 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 the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

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

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

[0342] [Table 15]

[0343] Example 11: Azeotrope Composition of Z-HCFO-1224yd and E-HFO-1336mzz To determine the relative volatility of the binary pair of Z-HCFO-1224yd and E-HFO-1336mzz, the PTx method described in Example 8 was used. 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 the equilibrium vapor and liquid compositions in the cell using the NRTL equation.

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

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

[0346] [Table 16]

[0347] [Table 17]

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

[0349] Figure 5 shows the pressures measured for the composition in the P-T-x cell for the E-1,1,1,4,4,5,5,5-octafluoro-2-pentene / Z-1-chloro-2,3,3,3-tetrafluoropropene mixture, which graphically shows the formation of an azeotrope-like composition of 1 to 33 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 67 to 99 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene at pressures in the range of 31.8 °C and about 25 - 28 psia, and also shows the formation of an azeotrope-like composition of 84 to 99 mol% E-1,1,1,4,4,5,5,5-octafluoro-2-pentene and 1 to 16 mol% Z-1-chloro-2,3,3,3-tetrafluoropropene at pressures in the range of 31.8 °C and 16 - 19 psia.

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

[0351]

Table 18

[0352]

Table 19

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

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

[0355] (An azeotropic composition is formed that boils at a temperature of about -40 °C to about 130 °C and a pressure of about 0.98 psia (6.76 kPa) to about 333 psia (2296 kPa)) An azeotropic composition of Z-HCFO-1224yd and HFC-245eb is formed in the range of about 65.6 mole percent to about 86.7 mole percent of Z-HCFO-1224yd and about 34.4 mole percent to about 13.3 mole percent of HFC-245eb.

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

[0357]

Table 20

[0358]

Table 21

[0359] Furthermore, an azeotrope-like composition containing Z-HCF0-1224yd and HFC-245eb is also formed. An azeotrope-like composition of 1 to 99 mole percent of Z-HCF0-1224yd and 99 to 1 mole % of HFC-245eb is formed at a temperature in the range of about -40°C to about 120°C (over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a specific temperature is 5 percent or less (based on the bubble point pressure)) (Table 18A). An azeotrope-like composition of 1 to 99 mole percent of Z-HCF0-1224yd and 99 to 1 mole % of HFC-245eb is formed at a temperature in the range of about -40°C to about 120°C (over this temperature range, the difference between the dew point pressure and the bubble point pressure of the composition at a specific temperature is 3 percent or less (based on the bubble point pressure)) (Table 18B). At 20°C, an azeotrope-like composition of 1 to 9 mole % and 58 to 99 mole % of Z-HCFO-1224yd and 1 to 42 mole % and 91 to 99 mole % of HFC-245eb was formed. Such an azeotrope-like composition exists around the azeotropic composition.

[0360]

Table 22

[0361]

Table 23

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

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

[0364] Example 15: R-value of aged degradation enhanced by HCFO-1224yd and HFO-1336mzz-E blend Using the manual mixing method, foam samples were made in an 8”×8”×2.5” mold. The foam was cured overnight, cut to 6”×6”×1.5”, and analyzed with a calibrated heat flow meter. The samples were analyzed and the values at each set point were considered baseline k-factor values. An exemplary manual mixing method consisted of adding an appropriate amount of HCFO or HFO and water (typical polyurethane B-side mixture) to side B, and mixing. Then, an appropriate amount of side A (typical polyurethane A-side mixture) was mixed at 4000 rpm for 1.5 seconds using a high-speed Arroad mixer, and the mixture was poured into the mold. The weight percentages of each blowing agent component used to prepare the foam are presented in Table 19 (weight percentages based on the combined total amount of sides A and B), and samples were made using a B-side:A-side 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 applicable The k-factor is shown in Btu·in / ft 2 ·h·°F

[0367] [Table 26] NA = No corresponding data The K coefficient is in Btu·in / ft 2 and is expressed in ·h·°F

[0368]

Table 27

[0369]

Table 28

[0370]

Table 29

[0371]

Table 30

[0372] As shown in the data of Tables 20 to 25, a synergistic combination was formed by combining HFO - 1336mzz - E with HCFO - 1224yd, which brought about improved thermal insulation performance over a wide range of temperatures. Furthermore, the effect lasted and continued to provide 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, the present application provides a composition comprising the compound Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and one or more compounds selected from the group consisting of HFO, HCFO, HFC, HFE, HCFC, CFC, CO2, olefins, hydrochlorofluoroolefins, 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-trifluoropropyne, cis-HFO-1234ze + HFO-1225yez, mixtures of these with water; mixtures of these with CO2; mixtures of these with trans-1,2-dichloroethylene; mixtures of these with methyl formate; mixtures with cis-HFO-1234ze + CO2, mixtures with cis-HFO-1234ze + HFO-1225yez + CO2, and mixtures with cis-HFO-1234ze + HFC-245fa.

[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. The composition according to embodiment 1 or 2, wherein the additional compound comprises one or more compounds selected from the group consisting of 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-1224yd, 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. The composition according to any one of Embodiments 1 to 4, wherein the additional compound comprises one or more compounds selected from the group consisting of 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, CHF2-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; dimethyloxymethane; 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, the present application provides an azeotropic mixture or an azeotrope-like composition comprising Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene and one or more compounds selected from the group consisting of 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, E-HFO-1438mzz, HCFO-1233xf, HFC-236ea, 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 azeotrope-like composition according to Embodiment 10, formed at a pressure of about 0.98 psia (130 kPa) to about 333 psia (2296 kPa), or at a pressure of about 1 atm, 2 atm, 3 atm, 4 atm, 5 atm, 6 atm, 7 atm, 8 atm, 9 atm, 10 atm, 11 atm, 12 atm, 13 atm, 14 atm, 15 atm, 16 atm, 17 atm, 18 atm, 19 atm, 20 atm, 21 atm, 22 atm, 23 atm, 24 atm, 25 atm, 26 atm, 27 atm, 28 atm, 29 atm, 30 atm, or 31 atm.

[0384] 12. An azeotropic mixture or azeotrope-like composition according to Embodiment 10 or 11, formed at a temperature of about -40 °C to about 130 °C.

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

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

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

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

[0389] 17. An azeotrope-like composition according to any one of embodiments 10 to 12 and 16, consisting essentially of (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-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.

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

[0391] 19. An azeotrope-like composition according to any one of embodiments 10 to 12 and 18, consisting essentially of (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-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 about 140°C.

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

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

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

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

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

[0397] 25. In some embodiments, the present application is a process for forming a foam, (a) adding a foamable composition to a blowing agent, (b) reacting the foamable composition under conditions effective to form a foam, comprising, Provided is a process in which the blowing agent comprises the composition according to any one of Embodiments 1 to 24.

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

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

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

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

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

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

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

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

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

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

[0408] 36. The foam according to any one of embodiments 32 to 35, having a K value of about 0.113 Btu·in / ft 2 ·h·°F to about 0.158 Btu·in / ft 2 ·h·°F at a temperature of about 20°F.

[0409] 37. The foam according to any one of embodiments 32 to 36, having a K value of about 0.116 Btu·in / ft 2 ·h·°F to about 0.122 Btu·in / ft 2 ·h·°F at a temperature of about 35°F.

[0410] 38. The foam according to any one of embodiments 32 to 37, having a K value of about 0.122 Btu·in / ft 2 ·h·°F to about 0.165 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0411] 39. The foam according to any one of embodiments 32 to 38, having a K value of about 0.132 Btu·in / ft 2 ·h·°F to about 0.175 Btu·in / ft 2 ·h·°F at a temperature of about 75°F.

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

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

[0414] 42. The foam according to any one of Embodiments 32, 33, 40, and 41, having a K value of 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.

[0415] 43. The foam according to any one of Embodiments 32, 33, and 40 to 42, having a K value of about 0.115 Btu·in / ft 2 ·h·°F to about 0.150 Btu·in / ft 2 ·h·°F at a temperature of about 35°F.

[0416] 44. The foam according to any one of Embodiments 32, 33, and 40 to 43, having a K value of about 0.120 Btu·in / ft 2 ·h·°F to about 0.156 Btu·in / ft 2 ·h·°F at a temperature of about 50°F.

[0417] 45. The foam according to any one of Embodiments 32, 33, and 40 to 44, having a K value of about 0.130 Btu·in / ft 2 ·h·°F to about 0.168 Btu·in / ft 2 ·h·°F at a temperature of about 75°F.

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

[0419] 47. In some embodiments, the present application provides a process for causing heating, the process comprising: (a) A step of condensing the composition according to any one of Embodiments 1 to 24 in the vicinity of an object to be heated; (b) Thereafter, a step of evaporating the composition; A process is provided that includes:

[0420] 48. In some embodiments, the present application provides a heat transfer system including a heat transfer medium, wherein the heat transfer medium includes the composition according to any one of Embodiments 1 to 24.

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

[0422] 50. In some embodiments, the present application provides an aerosol product including a component to be dispensed and a propellant, wherein the propellant includes the composition according to any one of Embodiments 1 to 24.

[0423] 51. In some embodiments, the present application provides a method for extinguishing or suppressing a flame, the method including a step of dispensing the composition according to any one of Embodiments 1 to 24 onto the flame.

[0424] 52. In some embodiments, the present application provides a system for preventing or suppressing a flame, the system including a container including the composition according to any one of Embodiments 1 to 24 and a nozzle for dispensing the composition toward a predicted or actual position of the flame.

[0425] Although 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 of the features described herein with respect to any particular aspect and / or embodiment of the present invention can be combined with one or more of any other features described herein with respect to any other aspect and / or embodiment of the present invention, and can be appropriately modified to ensure the compatibility of the combination. Such combinations are considered to be a part of the invention contemplated by this disclosure.

Claims

1. An azeotrope-like composition consisting essentially of (i) 1 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 99 mol% of methyl formate at a temperature of -40°C to about 140°C.

2. The azeotrope-like composition according to claim 1, consisting essentially of (i) 85 to 99 mol% of Z-1-chloro-2,3,3,3-tetrafluoroprop-1-ene (Z-HCFO-1224yd) and (ii) 1 to 15 mol% of methyl formate at 20°C.

3. A process for forming a foam, comprising: (a) adding a foamable composition to a blowing agent; and (b) reacting the foamable composition under conditions effective to form a foam, wherein the blowing agent comprises the azeotrope-like composition according to claim 1 or 2.

4. A process for forming a foam, comprising: (a) adding a foamable composition comprising one or more thermoplastic polymers to a blowing agent; and processing the foamable composition under conditions effective to form a foam, wherein the blowing agent comprises the azeotrope-like composition according to claim 1 or 2.

5. The process according to claim 4, further comprising extruding a mixture of the foamable composition and the blowing agent.

6. The process according to claim 4, wherein the blowing agent further comprises water.

7. A foam comprising a polymer and the azeotrope-like composition according to claim 1 or 2.

8. A process for causing cooling, comprising: condensing the azeotrope-like composition according to claim 1 or 2; and evaporating the composition in the vicinity of an object to be cooled.

9. A process for causing heating, comprising: condensing the azeotrope-like composition according to claim 1 or 2 in the vicinity of an object to be heated; and subsequently evaporating the composition. ​ ​ ​ ​

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