Stabilized chlorofluoroethylene

Abstract

The present application provides a composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components, which is useful for use, for example, in refrigeration, air conditioning, or heat pump systems and for reducing oxidation by-products of 1,2-dichloro-1,2-difluoroethylene.

Description

Technology Field

[0001] The present application provides a composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components, which is useful for use, for example, in refrigeration, air conditioning, heat pump, or cooling systems and for reducing oxidation by-products of 1,2-dichloro-1,2-difluoroethylene. Background Technology

[0002] 1,2-dichloro-1,2-difluoroethylene ("CFO-1112" or "1112") is a stable molecule under normal refrigerated conditions. However, in the presence of trace amounts of air, it can be oxidized. The oxidation products produce HCl and HF upon contact with moisture. Additionally, metal surfaces can potentially decompose 1112 by activating carbon halogen bonds, resulting in the formation of 1,1-dichloro-2,2-difluoroethene ("CFO-1112a" or "1112a"), which can be further oxidized to produce phosgene.

[0003] The regulatory landscape for refrigerants is continuously evolving to consider characteristics that go beyond merely the Ozone Depletion Potential (ODP) and Global Warming Potential (GWP), which have recently been the focus of attention. More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and a low GWP, but also provide excellent performance in various applications and satisfy evolving regulatory standards.

[0004] The present invention provides a refrigerant containing stabilized 1,2-dichloro-1,2-difluoroethylene that solves certain problems associated with conventional refrigerants and meets evolving regulatory environments.

[0005] The present application provides, in particular, a composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof.

[0006] The present application further provides a method for generating cooling, comprising the steps of condensing a composition provided herein and then evaporating said composition near an object to be cooled.

[0007] The present application further provides a method for generating heat, comprising the steps of evaporating a composition provided herein and then condensing said composition near an object to be heated.

[0008] The present application further provides an air conditioning system, a heat pump system, a cooler system, and a refrigeration system comprising the composition provided in this specification.

[0009] The present application further provides a method for replacing an existing refrigerant in a refrigeration, air conditioning, chiller, or heat pump system with a substitute composition provided in the present invention (e.g., a substitute composition comprising 1,2-dichloro-1,2-difluoroethylene as provided in the present specification), the method comprising the step of providing the composition provided in the present specification as a substitute for said existing refrigerant.

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. Methods and materials for use in the present invention are described herein; other suitable methods and materials known in the art may also be used. Materials, methods, and examples are merely illustrative and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated by reference in their entirety. In the event of a conflict, the present specification, including definitions, shall prevail. Specific details for implementing the invention

[0011] For example, there is a need to provide an alternative composition to reduce decomposition byproducts generated from the oxidation of 1,2-dichloro-1,2-difluoroethylene and / or 1,1-dichloro-2,2-difluoroethene. Accordingly, the present invention provides a composition (e.g., a heat transfer composition and / or a refrigerant composition) comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components. The composition provided in this specification can reduce undesirable decomposition by-products resulting from the decomposition (e.g., oxidation) of 1,2-dichloro-1,2-difluoroethylene, such as chloride (e.g., hydrogen chloride), fluoride (e.g., hydrogen fluoride), and / or phosgene and / or decomposition products resulting from the decomposition (e.g., oxidation) of 1,2-dichloro-1,2-difluoroethylene, such as 1,1-dichloro-2,2-difluoroethene.

[0012] In some embodiments, one or more stabilizer components are each selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof.

[0013] In some embodiments, one or more stabilizer components are present in small amounts relative to the total composition. In some embodiments, the amount of one or more stabilizer components in the disclosed composition is less than about 0.1 weight% to a maximum of about 5 weight% of the total composition. In some embodiments of the invention, an additive is present in the disclosed composition in an amount of about 0.1 weight% to about 5 weight% of the total composition, or in an amount of about 0.1 weight% to about 3.5 weight%. One or more stabilizer components selected for the disclosed composition are selected based on utility and / or individual equipment component or system requirements.

[0014] In some embodiments, each stabilizer component is independently present in the composition at a concentration of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or an extended range between any of the aforementioned concentrations. In some embodiments, each stabilizer component is independently present in the composition at a concentration of about 500 ppm to about 1000 ppm. In some embodiments, each stabilizer component is independently present in the composition at a concentration of about 500 ppm or about 1000 ppm. In some embodiments, each stabilizer component is independently present in the composition at a concentration of about 1000 ppm. For example, thymol may be present in the composition at a concentration of about 100 ppm to about 1000 ppm.

[0015] In some embodiments, 1,2-dichloro-1,2-difluoroethylene is ( E )-1,2-dichloro-1,2-difluoroethylene. In some embodiments, 1,2-dichloro-1,2-difluoroethylene is ( Z )-1,2-dichloro-1,2-difluoroethylene. In some embodiments, 1,2-dichloro-1,2-difluoroethylene is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z It is a mixture of )-1,2-dichloro-1,2-difluoroethylene.

[0016] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene and an antioxidant. In some embodiments, the composition comprises ( ZIt includes )-1,2-dichloro-1,2-difluoroethylene and an antioxidant. In some embodiments, the composition is ( E It includes )-1,2-dichloro-1,2-difluoroethylene and an antioxidant. In some embodiments, the composition is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z It includes a mixture of )-1,2-dichloro-1,2-difluoroethylene and an antioxidant.

[0017] In some embodiments, the antioxidant is a terpene, butylated hydroxytoluene, butylated hydroxyanisole, tert - Butylhydroquinone, propyl 3,4,5-trihydroxybenzoate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, 4-methoxyphenol, bisphenol methane derivative, 2,2'-methylene bis(4-methyl-6-t-butylphenol), and 2-isopropyl-5-methylphenol are selected from. In some embodiments, the antioxidant is selected from meta-xylene, ortho-xylene, para-xylene, thymol, limonene (particularly d-limonene), and pinene.

[0018] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene and an acid scavenger. In some embodiments, the composition comprises ( Z It includes )-1,2-dichloro-1,2-difluoroethylene and an acid scavenger. In some embodiments, the composition is ( E It includes )-1,2-dichloro-1,2-difluoroethylene and an acid scavenger. In some embodiments, the composition is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z It includes a mixture of )-1,2-dichloro-1,2-difluoroethylene and an acid scavenger.

[0019] In some embodiments, the acid scavenger is selected from epoxides and amines. In some embodiments, the acid scavenger is an epoxide. In some embodiments, the acid scavenger is epoxybutane. In some embodiments, the epoxybutane is 1,2-epoxybutane.

[0020] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene and a metal stabilizer. In some embodiments, the composition comprises ( Z It includes )-1,2-dichloro-1,2-difluoroethylene and a metal stabilizer. In some embodiments, the composition is ( E It includes )-1,2-dichloro-1,2-difluoroethylene and a metal stabilizer. In some embodiments, the composition is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z It includes a mixture of )-1,2-dichloro-1,2-difluoroethylene and a metal stabilizer.

[0021] In some embodiments, the metal stabilizer is selected from N,N′-bis(salicylidene)-1,2-propanediamine and benzotriazole. In some embodiments, the metal stabilizer is N,N′-bis(salicylidene)-1,2-propanediamine. In some embodiments, the metal stabilizer is benzotriazole.

[0022] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid scavenger. In some embodiments, the composition comprises ( Z )-1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid scavenger. In some embodiments, the composition is ( E )-1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid scavenger. In some embodiments, the composition is ( E )-1,2-dichloro-1,2-difluoroethylene and ( ZIt includes a mixture of )-1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid scavenger.

[0023] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene.

[0024] In some embodiments, the composition is ( Z )-1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene. In some embodiments, the composition comprises ( E )-1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene. In some embodiments, the composition comprises ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z It includes a mixture of )-1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene.

[0025] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, meta-xylene, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, meta-xylene, and 1,2-epoxybutane.

[0026] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, meta-xylene, and 1,2-epoxybutane comprises meta-xylene in an amount of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or a range extending between any of the aforementioned concentrations. In some embodiments, the composition comprises about 900 ppm to about 1100 ppm of meta-xylene. In some embodiments, the composition comprises about 1000 ppm of meta-xylene.

[0027] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, meta-xylene, and 1,2-epoxybutane comprises 1,2-epoxybutane at a concentration of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, or about 1500 ppm, or 1,2-epoxybutane in a range extending between any of the aforementioned concentrations. Included. In some embodiments, the composition comprises about 900 ppm to about 1100 ppm of 1,2-epoxybutane. In some embodiments, the composition comprises about 1000 ppm of 1,2-epoxybutane. In some embodiments, the composition comprises about 1000 ppm of meta-xylene and about 1000 ppm of 1,2-epoxybutane.

[0028] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, ortho-xylene, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, ortho-xylene, and 1,2-epoxybutane.

[0029] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, ortho-xylene, and 1,2-epoxybutane comprises ortho-xylene in an amount of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or an extended range between any of the aforementioned concentrations. In some embodiments, the composition comprises about 900 ppm to about 1100 ppm of ortho-xylene. In some embodiments, the composition comprises about 1000 ppm of ortho-xylene.

[0030] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, ortho-xylene, and 1,2-epoxybutane comprises 1,2-epoxybutane in an amount of about 500 ppm to about 1500 ppm, for example, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, or about 1500 ppm, or a range extending between any of the aforementioned concentrations. In some embodiments, the composition comprises 1,2-epoxybutane in an amount of about 900 ppm to about 1100 ppm. In some embodiments, the composition contains about 1,000 ppm of 1,2-epoxybutane.

[0031] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, ortho-xylene, and 1,2-epoxybutane comprises about 1000 ppm of ortho-xylene and about 1000 ppm of 1,2-epoxybutane.

[0032] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, para-xylene, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, para-xylene, and 1,2-epoxybutane.

[0033] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, para-xylene, and 1,2-epoxybutane comprises para-xylene in an amount of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or a range of para-xylene extending between any of the aforementioned concentrations. In some embodiments, the composition comprises about 900 ppm to about 1100 ppm of para-xylene. In some embodiments, the composition comprises about 1000 ppm of para-xylene.

[0034] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, para-xylene, and 1,2-epoxybutane comprises about 500 ppm to about 1500 ppm of 1,2-epoxybutane, for example, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, or about 1500 ppm of 1,2-epoxybutane. In some embodiments, the composition comprises about 900 ppm to about 1100 ppm of 1,2-epoxybutane. In some embodiments, the composition contains about 1,000 ppm of 1,2-epoxybutane.

[0035] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, para-xylene, and 1,2-epoxybutane comprises about 1000 ppm of para-xylene and about 1000 ppm of 1,2-epoxybutane.

[0036] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, thymol, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, thymol, and 1,2-epoxybutane.

[0037] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, thymol, and 1,2-epoxybutane comprises about 100 ppm to about 1000 ppm of thymol, for example, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, or about 1000 ppm of thymol. In some embodiments, the composition comprises about 400 ppm to about 600 ppm of thymol. In some embodiments, the composition comprises about 500 ppm of thymol.

[0038] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, thymol, and 1,2-epoxybutane comprises 1,2-epoxybutane at a concentration of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or a range extending between any of the aforementioned concentrations. It contains 1,2-epoxybutane. In some embodiments, the composition contains about 900 ppm to about 1100 ppm of 1,2-epoxybutane. In some embodiments, the composition contains about 1000 ppm of 1,2-epoxybutane.

[0039] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, thymol, and 1,2-epoxybutane comprises about 500 ppm of thymol and about 1,2-epoxybutane.

[0040] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, pinene, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, pinene, and 1,2-epoxybutane.

[0041] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, pinene, and 1,2-epoxybutane comprises about 100 ppm to about 1000 ppm of pinene, for example, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, or about 1000 ppm of pinene. In some embodiments, the composition comprises about 400 ppm to about 600 ppm of pinene. In some embodiments, the composition comprises about 500 ppm of pinene.

[0042] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, pinene, and 1,2-epoxybutane comprises 1,2-epoxybutane at a concentration of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or a range extending between any of the aforementioned concentrations. It contains 1,2-epoxybutane. In some embodiments, the composition contains about 900 ppm to about 1100 ppm of 1,2-epoxybutane. In some embodiments, the composition contains about 1000 ppm of 1,2-epoxybutane.

[0043] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, pinene, and 1,2-epoxybutane comprises about 500 ppm of pinene and about 1,2-epoxybutane.

[0044] In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, d-limonene, and epoxybutane. In some embodiments, the composition comprises 1,2-dichloro-1,2-difluoroethylene, d-limonene, and 1,2-epoxybutane.

[0045] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, d-limonene, and 1,2-epoxybutane comprises about 100 ppm to about 1000 ppm of d-limonene, for example, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, or about 1000 ppm of d-limonene. In some embodiments, the composition comprises about 400 ppm to about 600 ppm of d-limonene. In some embodiments, the composition comprises about 500 ppm of d-limonene.

[0046] In some embodiments, a composition comprising 1,2-dichloro-1,2-difluoroethylene, d-limonene, and 1,2-epoxybutane comprises 1,2-epoxybutane at a concentration of about 0.5 ppm to about 1500 ppm, for example, about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, about 1500 ppm, or a range extending between any of the aforementioned concentrations. It contains 1,2-epoxybutane. In some embodiments, the composition contains about 900 ppm to about 1100 ppm of 1,2-epoxybutane. In some embodiments, the composition contains about 1000 ppm of 1,2-epoxybutane.

[0047] In some embodiments, the composition comprising 1,2-dichloro-1,2-difluoroethylene, d-limonene, and 1,2-epoxybutane comprises about 500 ppm of d-limonene and about 1,2-epoxybutane.

[0048] In some embodiments, the composition provided herein comprises one or more additional compounds selected from the following:

[0049] 1,1-dichloro-2,2-difluoroethene(1112a);

[0050] 1,1,2-trichloro-1,2,2-trifluoroethane (113);

[0051] 1,1,2,2-tetrachloro-1,2-difluoroethane (112);

[0052] 1,1,1,2-tetrachloro-2,2-difluoroethane(112a);

[0053] ( Z )-2,3,3,3-tetrafluoro-1-chloropropene(Z-1224yd);

[0054] ( E )-2,3,3,3-tetrafluoro-1-chloropropene(E-1224yd);

[0055] 2-chloro-1,1-difluoroethylene (1122); and

[0056] 1-chloro-1,2-difluoroethene(1122a).

[0057] In some embodiments, the composition provided herein essentially consists of 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof.

[0058] In some embodiments, the composition provided herein consists of 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof.

[0059] In some embodiments, the composition provided herein essentially consists of 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds.

[0060] In some embodiments, the composition provided herein essentially comprises 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds selected from the following:

[0061] 1,1-dichloro-2,2-difluoroethene(1112a);

[0062] 1,1,2-trichloro-1,2,2-trifluoroethane (113);

[0063] 1,1,2,2-tetrachloro-1,2-difluoroethane (112);

[0064] 1,1,1,2-tetrachloro-2,2-difluoroethane(112a);

[0065] ( Z )-2,3,3,3-tetrafluoro-1-chloropropene(Z-1224yd);

[0066] ( E )-2,3,3,3-tetrafluoro-1-chloropropene(E-1224yd);

[0067] 2-chloro-1,1-difluoroethylene (1122); and

[0068] 1-chloro-1,2-difluoroethene(1122a).

[0069] In some embodiments, the composition provided herein comprises 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds.

[0070] In some embodiments, the composition provided herein comprises 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds selected from the following:

[0071] 1,1-dichloro-2,2-difluoroethene(1112a);

[0072] 1,1,2-trichloro-1,2,2-trifluoroethane (113);

[0073] 1,1,2,2-tetrachloro-1,2-difluoroethane (112);

[0074] 1,1,1,2-tetrachloro-2,2-difluoroethane(112a);

[0075] ( Z )-2,3,3,3-tetrafluoro-1-chloropropene(Z-1224yd);

[0076] ( E )-2,3,3,3-tetrafluoro-1-chloropropene(E-1224yd);

[0077] 2-chloro-1,1-difluoroethylene (1122); and

[0078] 1-chloro-1,2-difluoroethene(1122a).

[0079] In some embodiments, the composition of the present invention is found to be free of or substantially free of Group A fluorinated substances, and the decomposition products of the composition are found to be free of or substantially free of Group A fluorinated substances.

[0080] In one embodiment, as used herein, “Group A fluorinated material” comprises (i) at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto); and (ii) European Union REACH regulations ( https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html accessed as of May 2, 2023 It comprises any material that meets the criteria for soil / sediment and water persistence established in Appendix XIII (Section 1.1.1) of ) and referenced in the Appendix XV limitation report dated March 22, 2023, the disclosure thereof is incorporated herein by reference ( https / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea accessed as of May 2, 2023 ). In one embodiment, the group A fluorinated material includes trifluoroacetic acid (TFA), but is not limited thereto.

[0081] In another embodiment, "Group A fluorinated material" as used herein is 250 Pa*m 3 Henry's Law constant less than or equal to / mol go , comprises any material containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto). In one embodiment, the group A fluorinated material comprises, but is not limited to, TFA.

[0082] Accordingly, according to some embodiments, the compositions of the present invention comprising, consisting of, or essentially consisting of stabilized 1,2-dichloro-1,2-difluoroethylene are free of or substantially free of Group A fluorinated substances such as TFAs. In one embodiment, the phrase “free of” as used herein in relation to the presence of Group A fluorinated substances in the compositions means that the amount of such substances in the compositions is sufficiently low (including, but not limited to, 0%) to be undetectable when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector by analysis of a gas or liquid sample, and / or ion chromatography by analysis of a water sample after bubbling a thermal fluid through water. Such methodologies are well known to those skilled in the art. In one embodiment, the phrase “substantially absent” as used herein in relation to the presence of a Group A fluorinated substance in the composition means that when measured by a gas chromatography (GC) technique, e.g., gas chromatography (GC) with a flame ionization or electron capture detector or GC coupled with a mass detector (gas chromatography / mass spectrum (GC / MS) method), by an ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS) technique, or by a high-performance liquid chromatography (HPLC) or high-performance liquid chromatography-mass spectrometry (HPLC-MS) technique, the amount of such substance in the composition is greater than 0 wt% and less than 5 wt%, or greater than 0 wt% and less than 4 wt%, or greater than 0 wt% and less than 3 wt%, or greater than 0 wt% and less than 2 wt%, or greater than 0 wt% and less than 1 wt%, and all values ​​and ranges between these. TFA analysis standards can be used in gas chromatography or ion chromatography and are available, for example, from Sigma Aldrich.In some embodiments, the stabilized 1,2-dichloro-1,2-difluoroethylene is free of Group A fluorinated substances, which means that these substances are not detectable by the methods and techniques described herein.

[0083] Additionally, in some embodiments, the decomposition products of the composition of the present invention, which comprises, consists of, or is essentially composed of stabilized 1,2-dichloro-1,2-difluoroethylene, are free from or substantially free of Group A fluorinated substances such as TFAs. In one embodiment, the phrase “free from” as used herein in relation to the formation of Group A fluorinated substances by the composition means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric decomposition of the composition is sufficiently low (including, but not limited to, 0%) to be undetectable when measured by GC techniques, e.g., by a GC or GC / MS method having a flame ionization or electron capture detector, by an IC or IC-MS technique, or by an HPLC or HPLC-MS technique. In one embodiment, the phrase “substantially absent” as used herein in relation to the formation of Group A fluorinated substances by the composition means that when measured by GC techniques, e.g., by GC or GC / MS methods having flame ionization or electron capture detectors, by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric decomposition of the composition is greater than 0% and less than 5%, or greater than 0% and less than 4%, or greater than 0% and less than 3%, or greater than 0% and less than 2%, or greater than 0% and less than 1%, and all values ​​and ranges in between. In some embodiments, the decomposition products of the composition of the present invention comprising, consisting of, or essentially consisting of stabilized 1,2-dichloro-1,2-difluoroethylene do not contain group A fluorinated substances such as TFAs, which means that these substances are not detectable by the methods and techniques described herein.

[0084] As used herein, the terms “comprise,” “comprising,” “include,” “including,” “have,” “having,” or any other variation thereof are intended to include non-exclusive inclusions. For example, a process, method, article, or apparatus comprising a list of elements is not necessarily limited to such elements alone and may include other elements not explicitly enumerated or inherent to such process, method, article, or apparatus. Also, unless explicitly stated otherwise, “or” refers to an inclusive “or” and not to an exclusive “or.” For example, condition A or B is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0085] As used herein, the term “essentially consisting of” is used to define a composition or method comprising materials, steps, features, components, or elements in addition to those literally disclosed, provided that such additionally included materials, steps, features, components, or elements do not substantially affect the basic and novel feature(s) of the mode of operation for achieving the desired result of any process of the claimed invention, particularly the present invention. The term “essentially consisting of” occupies an intermediate position between “comprising” and “consisting of”.

[0086] Additionally, the use of the singular form (“a” or “an”) is utilized to describe the elements and components described herein. This is done merely for convenience and to provide a general meaning of the scope of the invention. Such descriptions should be interpreted as including one or at least one, and the singular form also includes the plural form unless it is evident that the number implies something different.

[0087] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., plus or minus about 10% of the indicated value). All measurements reported herein are understood to be modified by the term “about,” whether or not the term is explicitly used, unless otherwise explicitly stated.

[0088] Where a quantity, concentration, or other value or parameter is given as an enumeration of a range, a preferred range, a preferred upper limit, and / or a preferred lower limit, it should be understood that any pair of any range upper limit or preferred value and any range lower limit or preferred value specifically discloses all ranges formed by any pair of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. Where a range of numerical values ​​is mentioned herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range.

[0089] Refrigeration capacity (sometimes referred to as cooling capacity) is a term that defines the enthalpy change of the refrigerant or working fluid in the evaporator per unit mass of the circulating refrigerant or working fluid. Volumetric cooling capacity refers to the amount of heat removed by the refrigerant or working fluid in the evaporator per unit volume of refrigerant vapor exiting the evaporator. Refrigeration capacity is a measure of the ability of the refrigerant, working fluid, or heat transfer composition to generate cooling. Therefore, the higher the volumetric cooling capacity of the working fluid, the greater the cooling rate that can be generated in the evaporator using the maximum volumetric flow rate achievable with a given compressor. Cooling rate refers to the heat removed by the refrigerant within the evaporator per unit time.

[0090] Similarly, volumetric heating capacity is a term that defines the amount of heat supplied by the refrigerant or working fluid in the condenser per unit volume of refrigerant or working fluid vapor entering the compressor. The higher the volumetric heating capacity of the refrigerant or working fluid, the greater the heating rate generated in the condenser using the maximum volumetric flow rate achievable with a given compressor.

[0091] The coefficient of performance (COP) is calculated by dividing the amount of heat removed by the evaporator by the energy required to operate the compressor. A higher COP indicates higher energy efficiency. The COP is directly related to the energy efficiency ratio (EER), which is the efficiency rating for refrigeration or air conditioning equipment at specific internal and external temperature settings.

[0092] As used herein, a heat transfer medium comprises a composition used to transport heat from a heat source to a heat sink. For example, heat from an object to be cooled to a chiller evaporator, or from a chiller condenser to a cooling tower or other configuration where heat can be discharged to the surroundings.

[0093] As used herein, the working fluid or refrigerant comprises a compound or a mixture of compounds (e.g., a composition provided herein) that functions to transfer heat in a cycle in which the working fluid undergoes a phase change from liquid to gas and back to liquid in a repeated cycle.

[0094] Subcooling is the reduction of a liquid's temperature below its saturation point for a given pressure. The saturation point is the temperature at which a vapor composition completely condenses into a liquid (also referred to as the bubble point). However, subcooling continues to cool the liquid to a lower temperature at a given pressure. By cooling the liquid below the saturation temperature, the net refrigeration capacity can be increased. Consequently, subcooling improves the refrigeration capacity and energy efficiency of a system. The subcool amount refers to the amount (in degrees) cooled below the saturation temperature, or how much a liquid composition is cooled below its saturation temperature.

[0095] The term "superheat" defines how much a vapor composition is heated beyond its saturation vapor temperature. The saturation vapor temperature is the temperature at which the first liquid droplet forms when the vapor composition cools, and is also referred to as the "dew point."

[0096] The compositions provided herein may serve as working fluids used to transport heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change, that is, changing from liquid to gas and returning to its original state or vice versa. Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, high-temperature heat pumps, portable refrigerators, portable air conditioning units, immersion cooling systems, data-center cooling systems, and combinations thereof. Accordingly, the present application provides heat transfer systems (e.g., heat transfer devices) as described herein, comprising the compositions provided herein. In some embodiments, the compositions provided herein are useful as working fluids in heat transfer devices (e.g., working fluids for refrigeration or heating applications). In some embodiments, the composition provided herein is useful for an apparatus or system comprising a high-temperature heat pump. In some embodiments, the high-temperature heat pump comprises a centrifugal compressor. In some embodiments, the composition provided herein is useful for an apparatus or system comprising a chiller unit. In some embodiments, the composition provided herein is useful for an apparatus or system comprising a centrifugal chiller unit. In some embodiments, the composition provided herein is useful for an apparatus or system comprising a screw or scroll chiller unit. In some embodiments, the composition provided herein is useful for a centrifugal high-temperature heat pump.

[0097] Mechanical vapor-compression refrigeration, air conditioning, and heat pump systems include an evaporator, a compressor, a condenser, and an expansion unit. The refrigeration cycle reuses the refrigerant in multiple stages to generate a cooling effect in one stage and a heating effect in another. The cycle can be described as follows: Liquid refrigerant enters the evaporator through the expansion unit; at a low temperature, the liquid refrigerant boils within the evaporator by absorbing heat from the surrounding environment, forming a gas and generating cooling. Often, air or a heat transfer fluid flows over or around the evaporator to transfer the cooling effect caused by the evaporation of the refrigerant within the evaporator to the object to be cooled. The low-pressure gas enters the compressor, where it is compressed, raising its pressure and temperature. Subsequently, the high-pressure (compressed) gaseous refrigerant enters the condenser, where it condenses and releases its heat to the external environment. The refrigerant returns to the expansion unit, whereby the liquid expands from the high-pressure level within the condenser to the low-pressure level within the evaporator, thus repeating the cycle.

[0098] An object to be cooled or heated may be defined as any space, location, object, or thing where it is desirable to provide cooling or heating. Examples include (open or enclosed) spaces requiring air conditioning, cooling, or heating, e.g., rooms, apartments, or buildings, e.g., apartment buildings, university dormitories, townhouses, or other row houses or detached houses, hospitals, office buildings, supermarkets, university classrooms, or government buildings, and car or truck cabins. Additionally, an object to be cooled may include electronic devices, particularly computer equipment, central processing units (CPUs), data centers, server banks, and personal computers.

[0099] “Nearby” means that the evaporator of a system containing a refrigerant is positioned within or adjacent to the object to be cooled so that air moving over the evaporator moves into or around the object to be cooled. In a method for generating heat, “nearby” means that the condenser of a system containing a refrigerant is positioned within or adjacent to the object to be heated so that air moving over the evaporator moves into or around the object to be heated. In some embodiments, in the case of heat transfer, “nearby” may mean that the object to be cooled is directly immersed in a heat transfer composition or a tube containing a heat transfer composition flowing around, for example, inside and outside of electronic equipment.

[0100] Exemplary refrigeration systems include, but are not limited to, equipment comprising commercial, industrial, or residential refrigerators and freezers, ice makers, self-contained coolers and freezers, vending machines, flooded evaporative coolers, direct expansion coolers, water coolers, centrifugal coolers, screw coolers, scroll coolers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the compositions provided herein may be used in supermarket refrigeration systems. Additionally, stationary applications may utilize a secondary loop system that uses a primary refrigerant to generate cooling at one location and transfers it to a remote location via a secondary heat transfer fluid.

[0101] In some embodiments, the composition provided herein is useful for mobile heat transfer systems including refrigeration, air conditioning, chillers, or heat pump systems or devices. In some embodiments, the composition is useful for stationary heat transfer systems including refrigeration, air conditioning, chillers, or heat pump systems or devices.

[0102] As used herein, a mobile refrigeration, air conditioning, chiller, or heat pump system refers to any refrigeration, air conditioning, chiller, or heat pump unit included in a transport unit for road, rail, sea, or air transport. A mobile air conditioning or heat pump system may be used in automobiles, trucks, railway vehicles, or other transport systems. Mobile refrigeration may include transport refrigeration in trucks, aircraft, or railway vehicles. Additionally, the invention includes a device intended to provide refrigeration for any system independent of a moving carrier—which is known as an “intermodal” system. Such intermodal transport systems include “containers” (sea / land transport) as well as “swap bodies” (road and rail transport).

[0103] As used herein, a stationary air conditioning or heat pump system is a system that is fixed in place during operation. A stationary air conditioning or heat pump system may be combined or attached within any various building. Such stationary applications may include, but are not limited to, cooling units (including centrifugal, screw, or scroll cooling units), heat pumps including residential and high-temperature heat pumps, residential, commercial, or industrial air conditioning systems, window-type, ductless, ducted, packaged terminals, and external units connected to a building, e.g., rooftop systems.

[0104] Stationary heat transfer may refer to systems for cooling electronic devices, such as immersion cooling systems, submersion cooling systems, phase change cooling systems, data-center cooling systems, or simply liquid cooling systems.

[0105] In some embodiments, a method is provided for using a composition of the present invention as a heat transfer fluid. The method comprises the step of transporting said composition from a heat source to a heat sink.

[0106] In some embodiments, a method for generating cooling is provided, comprising the step of evaporating any of the compounds or compositions of the present invention near an object to be cooled, and then condensing said composition.

[0107] In some embodiments, a method for generating heat is provided, comprising the step of condensing any of the compositions of the present invention near an object to be heated, and then evaporating said composition.

[0108] In some embodiments, the present composition is intended for use in heat transfer where the working fluid is a heat transfer component.

[0109] In some embodiments, the composition of the present invention is intended for use in refrigeration or air conditioning.

[0110] In some embodiments, the composition of the present invention is intended for use in a cooler or a heat pump.

[0111] In some embodiments, the composition of the present invention is intended for use in a method of replacing existing refrigerants.

[0112] In some embodiments, the composition of the present invention may be useful for reducing or eliminating the flammability of a flammable refrigerant provided herein. In some embodiments, the present application provided herein is a method for reducing the flammability of a flammable refrigerant, comprising the step of adding a composition comprising a composition as disclosed herein to a flammable refrigerant.

[0113] The compositions provided herein may be useful as substitutes for currently used (“conventional”) refrigerants. As used herein, the term “conventional refrigerant” will be understood to mean a refrigerant designed to operate a heat transfer system, or a refrigerant inherent in a heat transfer system. In some embodiments, the conventional refrigerant is selected from R-123 (2,2-dichloro-1,1,1-trifluoroethane), R-245fa (1,1,1,3,3-pentafluoropropane), R-514A (a blend of 74.7 wt% HFO-1336mzzZ (Z-1,1,1,4,4,4-hexafluoro-2-butene) and 25.3 wt% trans-1,2-dichloroethylene), R-1233zdE (E-1-chloro-3,3,3-trifluoropropene), and R-1224ydZ (Z-1-chloro-2,3,3,3-tetrafluoropropene). In some embodiments, the conventional refrigerant is R-123. In some embodiments, the conventional refrigerant is R-245fa. In some embodiments, the conventional refrigerant is R-514A. In some embodiments, the conventional refrigerant is R-1233zdE. In some embodiments, the conventional refrigerant is R-1224ydZ.

[0114] Often, a substitute refrigerant is most useful when it can be used in the original refrigeration equipment designed for a different refrigerant, for example, with or without system modifications. In many applications, some embodiments of the disclosed composition are useful as a refrigerant and provide cooling performance (meaning cooling capacity) that is at least comparable to the refrigerant intended to be replaced.

[0115] In some embodiments, a method is provided for operating a heat transfer system designed to operate with a conventional refrigerant or for transferring heat by filling an empty system with the composition of the present invention, or by substantially replacing the conventional refrigerant with the composition of the present invention. In some embodiments, the conventional refrigerant is selected from R-123, R-245fa, R-514A, R-1233zdE, and R-1224ydZ. In some embodiments, the conventional refrigerant is R-123. In some embodiments, the conventional refrigerant is R-245fa. In some embodiments, the conventional refrigerant is R-514A. In some embodiments, the conventional refrigerant is R-1233zdE. In some embodiments, the conventional refrigerant is R-1224ydZ.

[0116] As used herein, the term “substantially replacing” will be understood to mean allowing the existing refrigerant to be discharged from the system, or pumping the existing refrigerant out of the system and then charging the system with the composition of the present invention. The system may be flushed with one or more amounts of replacement refrigerant before being charged. In some embodiments, it will be understood that some small amount of the existing refrigerant may remain in the system after the system has been charged with the composition of the present invention.

[0117] In another embodiment, a method for recharging a heat transfer system containing an existing refrigerant and a lubricant is provided, the method comprising the steps of substantially removing the existing refrigerant from the heat transfer system while retaining a substantial portion of the lubricant in the system, and introducing one of the compositions into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced. In some embodiments, the existing refrigerant is selected from R-123, R-245fa, R-514A, R-1233zdE, and R-1224ydZ. In some embodiments, the existing refrigerant is R-123. In some embodiments, the existing refrigerant is R-245fa. In some embodiments, the existing refrigerant is R-514A. In some embodiments, the existing refrigerant is R-1233zdE. In some embodiments, the existing refrigerant is R-1224ydZ.

[0118] In some embodiments, the composition of the present invention may be used to fully charge a refrigerant in a cooler. For example, if the performance of a cooler using 1,2-dichloro-1,2-difluoroethylene is degraded due to the decomposition (e.g., oxidation) of 1,2-dichloro-1,2-difluoroethylene, leakage of the refrigerant, etc., the performance can be restored to the standard by adding a composition as disclosed herein.

[0119] In some embodiments, a heat exchange system comprising any of the compositions disclosed herein is provided, said system being selected from the group consisting of an air conditioner, a freezer, a refrigerator, a heat pump, a water cooler, a flooded evaporative cooler, a direct expansion cooler, a walk-in cooler, a heat pump, a portable refrigerator, a portable air conditioning unit, and a combination thereof. Additionally, the compositions provided herein may be useful for a secondary loop system, wherein the compositions act as a primary refrigerant to provide cooling to a secondary heat transfer fluid, thereby cooling a remote location.

[0120] Therefore, the system can operate more efficiently when the heat exchanger operates in counter-current mode or cross-current mode with a tendency. A tendency implies that the closer the heat exchanger is to counter-current mode, the more efficient the heat transfer becomes. Therefore, air conditioning heat exchangers, particularly evaporators, are designed to provide some aspect of a tendency.

[0121] Therefore, an air conditioning or heat pump system is provided in this specification, wherein the system comprises one or more heat exchangers (evaporators, condensers, or both) operating in a reverse flow mode or a cross flow mode having a reverse flow trend.

[0122] In some embodiments, a refrigeration system is provided herein, wherein the system comprises one or more heat exchangers (evaporators, condensers, or both) operating in a reverse flow mode or a cross flow mode having a reverse flow trend.

[0123] In some embodiments, the refrigeration, air conditioning, or heat pump system is a stationary refrigeration, air conditioning, or heat pump system. In some embodiments, the refrigeration, air conditioning, or heat pump system is a mobile refrigeration, air conditioning, or heat pump system.

[0124] Additionally, in some embodiments, the disclosed composition may function as a primary refrigerant in a secondary loop system providing cooling to a remote location using a secondary heat transfer fluid that may comprise water, an aqueous salt solution (e.g., calcium chloride), glycol, carbon dioxide, or a fluorinated hydrocarbon fluid (meaning HFC, HCFC, hydrofluoroolefin ("HFO"), hydrochlorofluoroolefin ("HCFO"), chlorofluoroolefin ("CFO"), or perfluorocarbon ("PFC")). In this case, the secondary heat transfer fluid is the object to be cooled because the fluid is adjacent to the evaporator and is cooled before moving to a second remote object to be cooled. In some embodiments, the disclosed composition may function as a secondary heat transfer fluid and thus may transfer or provide cooling (or heating) to a remote location.

[0125] In some embodiments, the composition provided herein further comprises a lubricant.

[0126] In one embodiment, the lubricant is selected from the group consisting of mineral oil, alkylbenzene, polyol ester, polyalkylene glycol, polyvinyl ether, polycarbonate, perfluoropolyether, silicone, silicate ester, phosphate ester, paraffin, naphthene, polyalpha-olefin, and combinations thereof.

[0127] The lubricant disclosed in this specification may be a commercially available lubricant. For example, the lubricants include paraffin mineral oil sold by BVA Oils as BVM 100 N, naphthenic mineral oil sold by Crompton Co. under the trade names Suniso (registered trademark) 1GS, Suniso (registered trademark) 3GS, and Suniso (registered trademark) 5GS, naphthenic mineral oil sold by Pennzoil under the trade name Sontex (registered trademark) 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trade name Calumet (registered trademark) RO-30, and Zerol (registered trademark) 75, Zerol (registered trademark) 150, and Zerol (registered trademark) by Shrieve Chemicals It may be linear alkylbenzene sold as 500 and branched alkylbenzene sold as HAB 22 by Nippon Oil, polyol ester (POE) sold as trade name Castrol (registered trademark) 100 by Castrol, UK, polyalkylene glycol (PAG) such as RL-488A from Dow (Dow Chemical, Midland, Michigan, USA), and mixtures thereof—meaning mixtures of any lubricants disclosed in this paragraph.

[0128] Notwithstanding the weight ratios for the composition disclosed herein, it is understood that in some heat transfer systems, additional lubricant may be obtained from one or more equipment components of such heat transfer systems while the composition is in use. For example, in some refrigeration, air conditioning, and heat pump systems, lubricant may be filled into the compressor and / or compressor lubricant sump. Such lubricant will be present in the refrigerant of such systems in addition to any lubricant additive. During use, the refrigerant may absorb a certain amount of equipment lubricant while inside the compressor, causing the refrigerant-lubricant composition to change from the starting ratio.

[0129] In some embodiments, the composition provided herein further comprises at least one dye. The dye may be at least one ultraviolet (UV) dye. As used herein, a “UV” dye is defined as a UV fluorescent or phosphorescent composition that absorbs light in the ultraviolet or “near” ultraviolet region of the electromagnetic spectrum. Fluorescence produced by a UV fluorescent dye may be detected under illumination by UV light emitting at least some radiation having a wavelength in the range of 10 nanometers to about 775 nanometers.

[0130] UV dyes are useful components for detecting leaks of a composition by enabling the observation of fluorescence of the dye at or near the leak point of a device (e.g., a refrigeration unit, an air conditioner, or a heat pump). UV emission from the dye, for example, fluorescence, can be observed under ultraviolet light. Therefore, if a composition containing such UV dye is leaking from a specific point of the device, fluorescence can be detected at or near the leak point.

[0131] In some embodiments, the UV dye may be a fluorescent dye. In some embodiments, the fluorescent dye is selected from the group consisting of naphthalimide, perylene, coumarin, anthracene, phenanthracene, xanthen, thioxanthen, naphthoxanthen, fluorescein, and derivatives of said dyes, and combinations thereof—meaning a mixture of any of the aforementioned dyes or derivatives disclosed in this paragraph.

[0132] In some embodiments, the composition disclosed herein further comprises at least one stabilizer selected to improve the solubility of one or more dyes in the disclosed composition. In some embodiments, the weight ratio of dye to solubilizer is in the range of about 99:1 to about 1:1. The solubilizer comprises at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, and 1,1,1-trifluoroalkanes, and mixtures thereof—meaning a mixture of any solubilizers disclosed in this paragraph.

[0133] In some embodiments, the composition disclosed herein further comprises at least one compatibilizer to improve compatibility between one or more lubricants and the composition disclosed herein. The compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (e.g., dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (e.g., methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof—meaning a mixture of any compatibilizers disclosed in this paragraph.

[0134] The solubilizers and / or compatibilizers provided in this specification may be selected from the group consisting of hydrocarbon ethers containing only carbon, hydrogen and oxygen, e.g., dimethyl ether (DME) and mixtures thereof—meaning mixtures of any hydrocarbon ethers disclosed in this paragraph.

[0135] The compatibilizers provided herein may be linear or cyclic aliphatic or aromatic hydrocarbon compatibilizers containing 3 to 15 carbon atoms. The compatibilizer may be at least one hydrocarbon selected from the group consisting of propanes, particularly at least propylene and propane; butanes, including n-butane and isobutene; pentanes, including n-pentane, isopentane, neopentane and cyclopentane; hexanes; octanes; nonanes; and decanes. Commercially available hydrocarbon compatibilizers include those sold by Exxon Chemical (USA) under the trade name Isopar (registered trademark) H, and undecane (C 11 ) and dodecane (C 12 A mixture of ) (high-purity C 11 to C 12 Iso-paraffin), Aromatic 150 (C9 to C 11 Aromatic), Aromatic 200 (C9 to C 15 Aromatic) and Naphtha 140 (C5 to C 11 Mixtures of paraffin, naphthene, and aromatic hydrocarbons), and mixtures thereof—meaning mixtures of any hydrocarbons disclosed in this paragraph—are included but not limited thereto.

[0136] The compatibilizer provided herein may alternatively be at least one polymer compatibilizer. The polymer compatibilizer may be a random copolymer of fluorinated and non-fluorinated acrylates, wherein the polymer is of the formula CH2=C(R 1 )CO2R 2 , CH2=C(R 3)C6H4R 4 , and CH2=C(R 5 )C6H4XR 6 It comprises at least one repeating unit of a monomer represented by; wherein, in the above formula, X is oxygen or sulfur; and R 1 , R 3 , and R 5 is independently selected from the group consisting of H and C1-C4 alkyl radicals; R 2 , R 4 , and R 6 is independently selected from the group consisting of carbon-chain-based radicals containing F and C, and may additionally contain H, Cl, ether oxygen, or sulfur in the form of thioethers, sulfoxides, or sulfone groups and mixtures thereof. Examples of such polymer compatibilizers include those available for purchase under the trade name Zonyl (registered trademark) PHS from E. I. DuPont de Nemours and Company (E. I. du Pont de Nemours and Company; Wilmington, Delaware, 19898, USA). Zonyl (registered trademark) PHS contains 40 wt% CH2=C(CH3)CO2CH2CH2(CF2CF2) m F (also referred to as Zonyl (trademark) fluoromethacrylate or ZFM) (wherein m is 1 to 12, mainly 2 to 8) and 60 wt% of lauryl methacrylate (CH2=C(CH3)CO2(CH2) 11 It is a random copolymer produced by polymerizing CH3 (also referred to as LMA).

[0137] In some embodiments, the compatibilizer component provided herein contains about 0.01 to 30 weight percent (based on the total amount of compatibilizer) of an additive that reduces the surface energy of metal copper, aluminum, steel, or other metals and their metal alloys found in heat exchangers in a manner that reduces the adhesion of the lubricant to the metal. Examples of metal surface energy reducing additives include those available from DuPont under the trade names Zonyl (registered trademark) FSA, Zonyl (registered trademark) FSP, and Zonyl (registered trademark) FSJ.

[0138] In some embodiments, the composition provided herein further comprises a metal surface inert. In some embodiments, the metal surface inactivator is areoxalyl bis(benzylidene) hydrazide (CAS No.: 6629-10-3), N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS No.: 32687-78-8), 2,2'-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CAS No.: 70331-94-1), N,N'-(disalicyclidene)-1,2-diaminopropane (CAS No.: 94-91-7) and ethylenediaminetetraacetic acid (CAS No.: 60-00-4) and salts thereof, and mixtures thereof — meaning a mixture of any metal surface inactivator disclosed in this paragraph — It is selected from a group consisting of.

[0139] In some embodiments, the composition provided herein further comprises a tracer. The tracer may be two or more tracer compounds from the same class of compounds or different classes of compounds. In some embodiments, the tracer is present in the composition at a total concentration of about 50 ppm (part per million) to about 1000 ppm based on the weight of the total composition. In some embodiments, the tracer is present at a total concentration of about 50 ppm to about 500 ppm. Alternatively, the tracer is present at a total concentration of about 100 ppm to about 300 ppm.

[0140] The tracer may be selected from the group consisting of hydrofluorocarbons (HFCs), deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes and ketones, nitrous oxide, and combinations thereof. Alternatively, the tracers are trifluoromethane (HFC-23), fluoroethane (HFC-161), 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca), 1,1,1,2,2,3-hexafluoropropane (HFC-236cb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,2-tetrafluoropropane (HFC-254cb), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1-trifluoropropane (HFC-263fb), 2,2-difluoropropane (HFC-272ca), and 2-fluoropropane (HFC-281ea), 1-Fluoropropane (HFC-281fa), 1,1,1,2,2,3,3,4-Nonafluorobutane (HFC-329p), 1,1,1-Trifluoro-2-Methylpropane (HFC-329mmz), 1,1,1,2,2,4,4,4-Octafluorobutane (HFC-338mf), 1,1,2,2,3,3,4,4-Octafluorobutane (HFC-338pcc), 1,1,1,2,2,3,3-Heptafluorobutane (HFC-347s), Hexafluoroethane (Perfluoroethane, PFC-116), Perfluoro-Cyclopropane (PFC-C216), Perfluoropropane (PFC-218), Perfluoro-Cyclobutane (PFC-C318), Perfluorobutane (PFC-31-10mc), Perfluoro-2-methylpropane (CF3CF(CF3)2), perfluoro-1,3-dimethylcyclobutane (PFC-C51-12mym, trans-perfluoro-2,3-dimethylcyclobutane (PFC-C51-12mym, trans), cis-perfluoro-2,3-dimethylcyclobutane (PFC-C51-12mym, cis), perfluoromethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclohexane (ortho, meta, or para),It may be selected from the group consisting of perfluoroethylcyclohexane, perfluoroindane, perfluorotrimethylcyclohexane and isomers thereof, perfluoroisopropylcyclohexane, cis-perfluorodecalin, trans-perfluorodecalin, cis- or trans-perfluoromethyldecalin and mixtures thereof. In some embodiments, the tracer is a blend containing two or more hydrofluorocarbons, or a combination of one hydrofluorocarbon and one or more perfluorocarbons.

[0141] A tracer may be added to the composition in a predetermined amount to enable the detection of any dilution, contamination, or other changes of the composition of the present invention.

[0142] It will be known that some of the additives mentioned above, suitable for non-refrigerant components, have been identified as potential refrigerants. However, according to the present invention, when these additives are used, they are not present in amounts that affect the novel and fundamental characteristics of the refrigerant mixture of the present invention.

[0143] In some embodiments, the refrigerant composition disclosed herein may be prepared by any convenient method for combining desired amounts of individual components, as is standard in the art. A preferred method is to weigh the desired amounts of components and then combine the components in a suitable container. If desired, stirring may be used.

[0144] Examples

[0145] The present invention will be explained in more detail by specific embodiments. The following embodiments are provided for illustrative purposes only and are not intended to limit the invention in any way. Those skilled in the art will readily recognize various insignificant parameters that may be changed or modified to yield essentially the same results.

[0146] Example 1

[0147] A mixture of 1,2-dichloro-1,2-difluoroethylene (CFO-1112 (30 g)), a stabilizer component, 1000 ppm air, and 500 ppm water was heated at 50°C for 2 weeks in a 210 mL shaker tube. Subsequently, the shaker tube was cooled to room temperature. 30 mL of deionized water was added to the container. After phase separation, the water was tested for fluoride and chloride using ion chromatography, and the pH was tested using a pH meter. The results for an exemplary 1,2-dichloro-1,2-difluoroethylene + stabilizer composition are listed in Table 1. N / D = Not detected.

[0148] [Table 1]

[0149]

[0150] In one or more compositions tested in Table 1, the following additional components are also identified: 1,1-dichloro-2,2-difluoroethene (1112a), 1,1,2-trichloro-1,2,2-trifluoroethane (113), 1,1,2,2-tetrachloro-1,2-difluoroethane (112), 1,1,1,2-tetrachloro-2,2-difluoroethane (112a), ( Z )-2,3,3,3-tetrafluoro-1-chloropropene(Z-1224yd), ( E )-2,3,3,3-tetrafluoro-1-chloropropene (E-1224yd), 2-chloro-1,1-difluoroethylene (1122), and 1-chloro-1,2-difluoroethene (1122a).

[0151] Other embodiments

[0152] In some embodiments, the present application provides a composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof.

[0153] 1. In Embodiment 1, 1,2-dichloro-1,2-difluoroethylene is (E A composition comprising )-1,2-dichloro-1,2-difluoroethylene.

[0154] 2. In Embodiment 1, 1,2-dichloro-1,2-difluoroethylene is ( Z A composition comprising )-1,2-dichloro-1,2-difluoroethylene.

[0155] 3. In Embodiment 1, 1,2-dichloro-1,2-difluoroethylene is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z A composition that is a mixture of )-1,2-dichloro-1,2-difluoroethylene.

[0156] 4. A composition comprising 1,2-dichloro-1,2-difluoroethylene and an antioxidant in any one of embodiments 1 to 4.

[0157] 5. In any one of embodiments 1 to 5, the antioxidant is a terpene, butylated hydroxytoluene, butylated hydroxyanisole, tert A composition selected from butylhydroquinone, propyl 3,4,5-trihydroxybenzoate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, 4-methoxyphenol, bisphenol methane derivative, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 2-isopropyl-5-methylphenol.

[0158] 6. A composition comprising 1,2-dichloro-1,2-difluoroethylene and an acid remover in any one of embodiments 1 to 4.

[0159] 7. A composition in any one of embodiments 1 to 4 and embodiment 7, wherein the acid remover is selected from epoxide and amine.

[0160] 8. A composition in which, in any one of embodiments 1 to 4, 7 and 8, the acid remover is epoxybutane.

[0161] 9. A composition comprising 1,2-dichloro-1,2-difluoroethylene and a metal stabilizer in any one of embodiments 1 to 4.

[0162] 10. A composition in any one of embodiments 1 to 4 and embodiment 10, wherein the metal stabilizer is selected from N,N′-bis(salicylidene)-1,2-propanediamine and benzotriazole.

[0163] 11. A composition comprising 1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid remover in any one of embodiments 1 to 4.

[0164] 12. A composition comprising, in any one of embodiments 1 to 4 and embodiment 12, 1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene.

[0165] 13. A composition comprising one or more additional compounds selected from the following in any one of embodiments 1 to 13:

[0166] 1,1-dichloro-2,2-difluoroethene(1112a);

[0167] 1,1,2-trichloro-1,2,2-trifluoroethane (113);

[0168] 1,1,2,2-tetrachloro-1,2-difluoroethane (112);

[0169] 1,1,1,2-tetrachloro-2,2-difluoroethane(112a);

[0170] ( Z )-2,3,3,3-tetrafluoro-1-chloropropene(Z-1224yd);

[0171] ( E )-2,3,3,3-tetrafluoro-1-chloropropene(E-1224yd);

[0172] 2-chloro-1,1-difluoroethylene (1122); and

[0173] 1-chloro-1,2-difluoroethene(1122a).

[0174] 14. A composition essentially comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof, in any one of embodiments 1 to 13.

[0175] 15. A composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from an antioxidant, an acid remover, and a metal stabilizer, or any combination thereof, in any one of embodiments 1 to 13.

[0176] 16. A composition essentially comprising, in any one of embodiments 1 to 14, 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds.

[0177] 17. A composition comprising, in any one of embodiments 1 to 14, 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds.

[0178] 18. A composition in any one of embodiments 1 to 18, wherein one or more stabilizer components are present in the composition at a concentration of 1,2-epoxybutane of about 0.5 ppm to about 1500 ppm.

[0179] 19. In any one of embodiments 1 to 19, the one or more stabilizer components are present in the composition at a concentration of about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, or about 1500 ppm.

[0180] 20. In any one of embodiments 1 to 20, the one or more stabilizer components are present in the composition at a concentration of X to Y ppm, and

[0181] a. X is selected from the group consisting of about 0.5 ppm, about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, and about 1400 ppm;

[0182] b. A composition in which Y is selected from the group consisting of about 30 ppm, about 50 ppm, about 75 ppm, about 100 ppm, about 200 ppm, about 300 ppm, about 400 ppm, about 500 ppm, about 600 ppm, about 700 ppm, about 800 ppm, about 900 ppm, about 1000 ppm, about 1100 ppm, about 1200 ppm, about 1300 ppm, about 1400 ppm, and about 1500 ppm.

[0183] 21. In some embodiments, the present application provides a method for generating cooling comprising the step of condensing a composition of any one of embodiments 1 to 21, and then evaporating said composition near an object to be cooled.

[0184] 22. In some embodiments, the present application provides a method for generating heat comprising the step of evaporating a composition of any one of embodiments 1 to 21, and then condensing said composition near an object to be heated.

[0185] 23. In some embodiments, the present application provides an air conditioning system, a heat pump system, a cooler system, or a refrigeration system comprising a composition of any one of embodiments 1 to 21.

[0186] 24. In embodiment 21, an air conditioning system, heat pump system, cooler system, or refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device.

[0187] 25. In some embodiments, the present application provides a method for replacing an existing refrigerant in an air conditioning system, a heat pump system, a cooler system, or a refrigeration system, and the method comprises the step of providing a composition of any one of embodiments 1 to 21.

[0188] 26. In embodiment 26, the conventional refrigerant is selected from the group consisting of R-123, R-245fa, R-514A, R-1233zdE, and R-1224ydZ.

[0189] 27. A composition in any one of embodiments 1 to 21, wherein the composition has no or substantially no Group A fluorinated substance and the decomposition product of the composition has no or substantially no Group A fluorinated substance.

[0190] Although the present invention has been described in connection with its detailed description, it should be understood that the foregoing description is intended to be illustrative and not to limit the scope of the invention as defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It will be recognized by those skilled in the art that any feature described herein with respect to any specific aspect and / or embodiment of the invention may be combined with one or more other features of any other aspect and / or embodiment of the invention described herein and may be appropriately modified to ensure compatibility of such combination. Such combination is considered to be part of the invention as defined by this disclosure.

Claims

Claim 1 A composition comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof. Claim 2 In paragraph 1, 1,2-dichloro-1,2-difluoroethylene is ( E A composition comprising )-1,2-dichloro-1,2-difluoroethylene. Claim 3 In paragraph 1, 1,2-dichloro-1,2-difluoroethylene is ( Z A composition comprising )-1,2-dichloro-1,2-difluoroethylene. Claim 4 In paragraph 1, 1,2-dichloro-1,2-difluoroethylene is ( E )-1,2-dichloro-1,2-difluoroethylene and ( Z A composition that is a mixture of )-1,2-dichloro-1,2-difluoroethylene. Claim 5 A composition according to claim 1, comprising 1,2-dichloro-1,2-difluoroethylene and an antioxidant. Claim 6 In paragraph 1, the antioxidant is a terpene, butylated hydroxytoluene, butylated hydroxyanisole, tert A composition selected from butylhydroquinone, propyl 3,4,5-trihydroxybenzoate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, 4-methoxyphenol, bisphenol methane derivative, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 2-isopropyl-5-methylphenol. Claim 7 A composition comprising 1,2-dichloro-1,2-difluoroethylene and an acid remover in claim 1. Claim 8 A composition according to claim 1, wherein the acid remover is selected from epoxides and amines. Claim 9 A composition according to claim 1, wherein the acid remover is epoxybutane. Claim 10 A composition comprising 1,2-dichloro-1,2-difluoroethylene and a metal stabilizer in claim 1. Claim 11 A composition according to claim 1, wherein the metal stabilizer is selected from N,N′-bis(salicylidene)-1,2-propanediamine and benzotriazole. Claim 12 A composition according to claim 1, comprising 1,2-dichloro-1,2-difluoroethylene, an antioxidant, and an acid remover. Claim 13 A composition according to claim 1, comprising 1,2-dichloro-1,2-difluoroethylene, 1,2-epoxybutane, and one or more antioxidants selected from meta-xylene, ortho-xylene, para-xylene, thymol, d-limonene, and pinene. Claim 14 The composition of claim 1 further comprising one or more additional compounds selected from the following: 1,1-dichloro-2,2-difluoroethene (1112a); 1,1,2-trichloro-1,2,2-trifluoroethane (113); 1,1,2,2-tetrachloro-1,2-difluoroethane (112); 1,1,1,2-tetrachloro-2,2-difluoroethane (112a); (Z)-2,3,3,3-tetrafluoro-1-chloropropene (Z-1224yd); (E)-2,3,3,3-tetrafluoro-1-chloropropene (E-1224yd); 2-chloro-1,1-difluoroethylene (1122); and 1-chloro-1,2-difluoroethene (1122a). Claim 15 A composition according to claim 1, essentially comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof. Claim 16 A composition according to claim 1, comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof. Claim 17 A composition essentially comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds. Claim 18 A composition according to claim 14 comprising 1,2-dichloro-1,2-difluoroethylene and one or more stabilizer components selected from antioxidants, acid scavengers, and metal stabilizers, or any combination thereof; and one or more additional compounds. Claim 19 A method for generating cooling, comprising the step of condensing the composition of claim 1, and then the step of evaporating the composition near an object to be cooled. Claim 20 A method for generating heat, comprising the step of evaporating the composition of claim 1, and then the step of condensing the composition near an object to be heated. Claim 21 An air conditioning system, heat pump system, cooler system, or refrigeration system comprising the composition of claim 1. Claim 22 In paragraph 21, an air conditioning system, heat pump system, cooler system, or refrigeration system comprising an evaporator, a compressor, a condenser, and an expansion device. Claim 23 A method for replacing an existing refrigerant in an air conditioning system, heat pump system, cooler system, or refrigeration system, comprising the step of providing the composition of claim 1 instead of the existing refrigerant. Claim 24 In paragraph 23, the existing refrigerant is selected from the group consisting of R-123, R-245fa, R-514A, R-1233zdE, and R-1224ydZ. Claim 25 A composition according to claim 1, wherein the composition has no or substantially no Group A fluorinated substance, and the decomposition product of the composition has no or substantially no Group A fluorinated substance.

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