阅读说明：本技术 用于制备1,1,3-三氯-4,4,4-三氟丁-1-烯和(e)-1,1,1,4,4,4-六氟丁-2-烯的方法和中间体 (Processes and intermediates for the preparation of 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene and (E) -1,1,1,4,4, 4-hexafluorobut-2-ene ) 是由 彭晟 V.A.彼得罗 于 2018-12-04 设计创作，主要内容包括：本申请提供了用于制备(Z)-1,1,1,4,4,4-六氟-2-丁烯的方法和中间体,以及可在包括制冷剂、高温热泵、有机朗肯循环在内的应用中用作灭火剂/抑燃剂、推进剂、发泡剂、溶剂和/或清洁流体的组合物。(Provided herein are processes and intermediates for the preparation of (Z) -1,1,1,4,4, 4-hexafluoro-2-butene, and compositions useful as fire extinguishing/suppression agents, propellants, blowing agents, solvents, and/or cleaning fluids in applications including refrigerants, high temperature heat pumps, organic rankine cycles.)

1. A process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a metal catalyst to form the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

2. The method of claim 1, wherein the heating is performed in the absence of hydrogen fluoride.

3. The method according to claim 1, comprising the further step of: (ii) substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

4. The method of claim 1, wherein the metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst.

5. The process of claim 4, wherein the transition metal oxide catalyst is selected from the group consisting of chromium oxide, chromium oxide on carbon, chromium chloride, and chromium chloride on carbon.

6. The method of claim 4, wherein the transition metal oxide catalyst is chromium oxide.

7. The process of claim 4, wherein the transition metal oxide catalyst is chromium oxide on carbon.

8. The method of claim 7, wherein the method further comprises:

a) contacting the chromium oxide on carbon with hydrogen fluoride to form an activated chromium catalyst prior to the reaction of step i).

9. The method of claim 8, wherein the contacting of step a) is performed at a temperature of about 280 ℃ to about 320 ℃.

10. The process of claim 8, wherein the reaction of step i) is carried out at a temperature of about 150 ℃ to about 200 ℃.

11. The process of claim 8, wherein the reaction is conducted at a pressure of about 0psig to about 150 psig.

12. The process of claim 8, wherein the process is a gas phase process.

13. The method of claim 4, wherein the metal halide catalyst is an iron halide catalyst.

14. The method of claim 13, wherein the metal halide catalyst is iron (III) chloride.

15. The process of claim 14, wherein the reaction of step i) is carried out at a temperature of about 75 ℃ to about 115 ℃.

16. The process of claim 14, wherein the process is a liquid phase process.

17. The method of claim 14, wherein the method is performed in the absence of an additional solvent component.

18. The process of claim 14, wherein the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is isolated substantially by distillation.

19. The process of claim 18, wherein the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is isolated in a yield greater than about 75%.

20. The method of claim 18, wherein the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is isolated in greater than about 99% purity.

21. The method of claim 1, further comprising:

iii) heating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene in the presence of a second transition metal catalyst to form (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

22. The method of claim 21, wherein the second transition metal oxide catalyst is chromium (III) oxide.

23. The process of claim 1, wherein the passing of the 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane comprises reacting 3, 3, 3-trifluoroprop-1-ene with carbon tetrachloride in a third transition metal catalyst and in tris (C)_1-6Alkyl) phosphates in the presence of a base.

24. The method of claim 23, wherein the third transition metal catalyst is iron powder.

25. The method of claim 23, wherein the tris (C)_1-6Alkyl) phosphate is tributyl phosphate.

26. A liquid phase process for the preparation of 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of an aqueous base to form the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

27. The method of claim 26, further comprising (ii) substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

28. The method of claim 27 wherein the aqueous base is an aqueous hydroxide base.

29. The process of claim 27 wherein the aqueous base is aqueous sodium hydroxide or aqueous potassium hydroxide.

30. The method of claim 27, further comprising:

iii) heating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene in the presence of a transition metal catalyst to form (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

31. The method of claim 30, wherein the transition metal catalyst is a chromium oxide catalyst.

32. The method of claim 30, wherein the transition metal catalyst is chromium (III) oxide.

33. The method of claim 30, wherein the transition metal catalyst is chromium (III) oxide on carbon.

34. The method of claim 33, further comprising contacting the chromium (Hi) oxide on carbon with hydrogen fluoride to form an activated chromium (III) oxide on carbon catalyst prior to the heating of step III).

35. A vapor phase process for the preparation of 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) contacting chromium (III) oxide with hydrogen fluoride at a temperature of about 280 ℃ to about 320 ℃ to form an activated chromium (III) catalyst; and

ii) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of the activated chromium (III) oxide catalyst at a temperature of about 150 ℃ to about 200 ℃ and a pressure of about 0psig to 150psig to form the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

36. The method of claim 35, further comprising substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

37. The method of claim 35, wherein the heating of step ii) is performed in the absence of hydrogen fluoride.

38. A liquid phase process for the preparation of 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of iron (III) chloride at a temperature of about 75 ℃ to about 115 ℃ to form the 1,1, 3-trichloro-4, 4, 4-trifluorobutan-1-ene.

39. The liquid phase process of claim 38, further comprising substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

40. A composition, comprising:

(E) -1,1,1,4,4, 4-hexafluorobut-2-ene;

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene;

the composition is prepared according to a process comprising heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a metal catalyst to form the composition.

41. The composition of claim 40, wherein the heating is carried out in the presence of hydrogen fluoride.

42. The composition of claim 40, wherein the metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst.

43. The composition of claim 40, wherein the metal catalyst is chromium oxide on carbon.

44. The composition of claim 43, wherein the process further comprises contacting the chromium oxide on carbon with the hydrogen fluoride to form an activated chromium catalyst prior to heating the 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane.

45. The composition of claim 44, wherein the process is a gas phase process.

46. A composition, comprising:

(E) -1,1,1,4,4, 4-hexafluorobut-2-ene;

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene;

the composition is prepared according to a process comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a first metal catalyst and hydrogen fluoride to form a first mixture comprising 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene;

ii) heating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene in the presence of a transition metal catalyst and hydrogen fluoride to form the composition.

47. The composition according to claim 46, wherein the process for preparing the composition further comprises substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene prior to the heating of step ii).

48. The composition of claim 46, wherein the method of preparing the composition further comprises substantially isolating the composition.

49. The composition according to claim 46, wherein the composition comprises greater than about 99 mole% of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

50. A composition, comprising:

2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane;

1,1, 1-trichloro-4, 4, 4-trifluorobutane; and

1,1, 1-trichloro-2- (chloromethyl) -3, 3, 3-trifluoropropane;

the composition is prepared according to a process comprising:

i) in the presence of a transition metal catalyst, in the presence of a transition metal catalyst and in the presence of a tri (C)_1-6Alkyl) phosphate ester with carbon tetrachloride to form said composition; and

ii) substantially isolating the composition.

51. The composition of claim 50, wherein the composition comprises greater than about 99 mole% 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane.

Technical Field

The present invention relates to processes and intermediates for the preparation of (E) -1,1,1,4,4, 4-hexafluoro-2-butene, and compositions useful as fire extinguishing/suppression agents, propellants, blowing agents, solvents, and/or cleaning fluids in applications including refrigerants, high temperature heat pumps, organic rankine cycles.

Background

Over the last several decades, various industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermophotonic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particle removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In finding alternatives to these versatile compounds, many industries have turned to the use of Hydrofluorocarbons (HFCs).

Disclosure of Invention

The present application provides, inter alia, a process for the preparation of 1,1, 3-trioxa-4, 4, 4-trifluorobut-1-ene, 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene being a key intermediate in the preparation of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene. A process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprises heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a transition metal catalyst to form 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene and substantially isolating 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

The present application also provides methods of using the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene described herein to prepare (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

The present application also provides compositions prepared according to one or more of the methods described herein.

The present application also provides for the use of the compositions of the present invention in applications including refrigeration (e.g., as refrigerant compositions), high temperature heat pumps, organic rankine cycles, fire extinguishing/suppression agents, propellants, blowing agents, solvents, and/or cleaning fluids.

Unless defined otherwise, 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. Methods and materials for use in the present invention are described herein; in addition, suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and 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 case of conflict, the present specification, including definitions, will control.

Detailed Description

HFCs do not contribute to the destruction of stratospheric ozone, but are of concern because they contribute to the "greenhouse effect," i.e., they contribute to global warming. HFCs have received much attention because of their contribution to global warming, and their wide use may also be limited in the future. Thus, there is a need for compositions that do not contribute to the destruction of stratospheric ozone and also have low Global Warming Potentials (GWPs). Specific hydrofluoroolefins such as 1,1,1,4,4, 4-hexafluoro-2-butene (CF)₃CH＝CHCF₃HFO-1336mzz) meets both objectives. For example, (E) -HFO-1336mzz (i.e., (E) -1,1,1,4,4, 4-hexafluoro-2-butene) is useful in many applications (e.g., foam expansion agents or refrigerants) due to its low GWP, nonflammability, high efficiency and thermal stability. Described herein are key intermediates useful for the preparation of (E) -1,1,1,4,4, 4-hexafluoro-2-butene, processes for the preparation of said intermediates, and integrated processes for the preparation of the intermediates.

Definition of

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" means an inclusive or and not an exclusive or. For example, condition a or B satisfies one of the following conditions: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).

In addition, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. The description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

As used herein, the term "about" is meant to account for variations due to experimental error (e.g., plus or minus about 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein are to be understood as being modified by the term "about", whether or not that term is expressly used.

When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

Global Warming Potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of one kilogram of a specific greenhouse gas, compared to emission of one kilogram of carbon dioxide. GWP can be calculated over different time ranges, showing the effect on atmospheric lifetime for a given gas. For GWP in the 100 year time frame is usually the reference value.

In the whole processIn the meaning, the term "C_n-m"indicates ranges including endpoints, where n and m are integers and indicate carbon number. Examples include C_1-4、C_1-6And the like.

As used herein, the term "C_n-mAlkyl "refers to a saturated hydrocarbon group having n to m carbons that may be straight or branched. Examples of alkyl moieties include, but are not limited to, chemical groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl; higher homologues such as 2-methyl-1-butyl, n-pentyl, 3-pentyl, n-hexyl, 1, 2, 2-trimethylpropyl and the like. In some embodiments, the alkyl group has 1 to 6, 1 to 4, 1 to 3, or 1 to 2 carbon atoms.

As used herein, "halide" refers to fluoride, chloride, bromide, or iodide. In some embodiments, the halide is chloride or bromide.

As used herein, "tris (C)_n-mAlkyl) phosphates "are of the formula P (O) O (C)_n-mAlkyl radical)₃Wherein each C is_n-mAlkyl refers to a saturated hydrocarbon group, which may be straight or branched chain, having n to m carbons, and wherein each C_n-mThe alkyl groups may be the same or different. Exemplary three (C)_n-mAlkyl) phosphates include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl ethyl phosphate, dimethyl butyl phosphate, butyl ethyl methyl phosphate, and the like.

As used herein, "alkali metal hydroxide base" refers to a compound of formula MOH, wherein M is an alkali metal (e.g., sodium, potassium, etc.).

As used herein, the term "substantially isolated" means that a compound or composition is at least partially or substantially separated from the environment in which it was formed or detected. Partial isolation may include, for example, compositions enriched for the compounds provided herein. Substantial separation may include compositions containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of a compound provided herein. Methods for isolating compounds and compositions are conventional in the art.

As used herein, "transition metal oxide" refers to the formula M₂O_yWherein M is a transition metal (e.g., chromium, iron, etc.), and y is the oxidation number of the transition metal. Exemplary transition metal oxides include, but are not limited to, chromium (III) oxide (Cr)₂O₃) Iron (II) oxide (FeO), iron (III) oxide (Fe)₂O₃) And so on. The transition metal oxide may optionally be supported on a substrate such as activated carbon, alumina, and fluorided alumina. Additional transition metal oxide catalysts and support substrates can be found, for example, in U.S. patent No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

As used herein, "transition metal halide" refers to the formula MX_yWherein M is a transition metal (e.g., chromium, iron, etc.), X is a halide (e.g., fluorine, chlorine, etc.), and y is the oxidation number of the transition metal. Exemplary transition metal halides include, but are not limited to, iron (III) chloride (FeCl)₃) Titanium (IV) chloride (TiCl)₄) And so on. Additional transition metal halides can be found, for example, in U.S. patent No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

As used herein, "absence of HF" means that there is no constant flow of HF during the reaction, but does not preclude the use of HF to activate the catalyst prior to the reaction.

The compounds described herein may be asymmetric (e.g., having one or more stereocenters). Unless otherwise indicated, all stereoisomers, such as enantiomers and diastereomers, are contemplated. Cis/trans and/or E/Z geometric isomers of the compounds of the invention are described and may be isolated as a mixture of isomers or as isolated isomeric forms.

Chemicals, abbreviations and acronyms

Method of producing a composite material

The present application provides a process (e.g., a vapor phase process or a liquid phase process) for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene. In some embodiments, the process comprises heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a metal catalyst (e.g., a first metal catalyst) to form 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out in the absence of Hydrogen Fluoride (HF).

In some embodiments, the method further comprises substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene. In some embodiments, the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is isolated substantially by distillation.

Exemplary metal catalysts that can be used in the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene include, but are not limited to, transition metal halides (e.g., group IVb metal halides, group Vb metal halides), transition metal oxides (e.g., chromium oxide), group IIIa metal halides (e.g., aluminum halides such as aluminum chloride or aluminum fluoride), and combinations thereof. In some embodiments, the metal catalyst is selected from antimony halides (e.g., SbCl)₅、SbCl₃、SbF₅) Tin halides (e.g. SnCl)₄) Tantalum halides (e.g., TaCl)₅) Titanium halides (e.g. TiCl)₄) Niobium halides (e.g., NbCl)₅) Molybdenum halides (e.g. M)_oCl₆) Iron halides (e.g., FeCl)₃) A chromium halide (e.g., chromium chloride), chromium oxide, an aluminum halide (e.g., aluminum chloride or aluminum fluoride), an alumina halide (e.g., alumina fluoride), a fluorinated chromium halide, a fluorinated chromium oxide, a fluorinated aluminum halide, a fluorinated aluminum oxide, or any combination thereof. Additional metal catalysts can be found, for example, in U.S. patent No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

In some embodiments, the metal catalyst is a transition metal catalyst. In some embodiments, the transition metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst. In some embodiments, the transition metal catalyst is selected from chromium oxide, chromium chloride, and iron (III) chloride. In some embodiments, the transition metal catalyst is supported on a substrate (e.g., carbon).

In some embodiments, the transition metal catalyst is a transition metal oxide catalyst. In some embodiments, the transition metal oxide catalyst is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium oxide. In some embodiments, the chromium oxide is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium (III) oxide. In some embodiments, the transition metal oxide catalyst is chromium (III) oxide on carbon.

In some embodiments, the transition metal catalyst is a transition metal halide catalyst. In some embodiments, the transition metal halide is supported on a substrate. In some embodiments, the metal halide catalyst is an iron halide catalyst. In some embodiments, the metal halide catalyst is a chromium halide catalyst. In some embodiments, the metal halide catalyst is iron (III) chloride. In some embodiments, the metal halide catalyst is chromium chloride. In some embodiments, the metal halide catalyst is chromium chloride on carbon.

In some embodiments, a method of making 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene includes contacting a metal catalyst with hydrogen fluoride to form an activated metal catalyst (e.g., a partially or fully fluorinated metal catalyst). In some embodiments, the activated metal catalyst is prepared prior to heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of the metal catalyst.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene further comprises contacting the chromium (III) oxide on carbon with hydrogen fluoride to form an activated chromium (III) oxide on carbon catalyst prior to heating the 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of the chromium (III) oxide on carbon catalyst.

In some embodiments, the method of preparing an activated metal catalyst is carried out at a temperature of from about 30 ℃ to about 350 ℃, e.g., from about 30 ℃ to about 300 ℃, from about 30 ℃ to about 250 ℃, from about 30 ℃ to about 200 ℃, from about 30 ℃ to about 100 ℃, from about 100 ℃ to about 350 ℃, from about 100 ℃ to about 300 ℃, from about 100 ℃ to about 250 ℃, from about 100 ℃ to about 200 ℃, from about 200 ℃ to about 350 ℃, from about 200 ℃ to about 300 ℃, from about 200 ℃ to about 250 ℃, from about 250 ℃ to about 350 ℃, from about 250 ℃ to about 300 ℃, or from about 300 ℃ to about 350 ℃. In some embodiments, contacting the metal catalyst with hydrogen fluoride is conducted at a temperature of from about 280 ℃ to about 320 ℃.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a gas phase process. In some embodiments, the vapor phase process for producing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out in the absence of an additional solvent component.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a gas phase process at a temperature of from about 100 ℃ to about 500 ℃, e.g., from about 100 ℃ to about 400 ℃, from about 100 ℃ to about 300 ℃, from about 100 ℃ to about 200 ℃, from about 200 ℃ to about 500 ℃, from about 200 ℃ to about 400 ℃, from about 200 ℃ to about 300 ℃, from about 300 ℃ to about 500 ℃, from about 300 ℃ to about 400 ℃, or from about 400 ℃ to about 500 ℃. In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a gas phase process at a temperature of from about 150 ℃ to about 200 ℃.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a liquid phase process. In some embodiments, the liquid phase process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out in the absence of an additional solvent component.

In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a liquid phase process at a temperature of from about 30 ℃ to about 200 ℃, e.g., from about 30 ℃ to about 150 ℃, from about 30 ℃ to about 120 ℃, from about 30 ℃ to about 75 ℃, from about 75 ℃ to about 200 ℃, from about 75 ℃ to about 150 ℃, from about 75 ℃ to about 120 ℃, from about 120 ℃ to about 200 ℃, from about 120 ℃ to about 150 ℃, or from about 150 ℃ to about 200 ℃. In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out as a liquid phase process at a temperature of from about 75 ℃ to about 115 ℃.

In some embodiments, the process for making 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is conducted at a pressure of from about 0psig to about 200psig, e.g., from about 0psig to about 150psig, from about 0psig to about 100psig, from about 0psig to about 50psig, from about 50psig to about 200psig, from about 50psig to about 150psig, from about 50psig to about 100psig, from about 100psig to about 200psig, from about 100psig to about 150psig, or from about 150psig to about 200 psig. In some embodiments, the process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is carried out at a pressure of from about 0psig to about 150 psig.

The present application also provides a process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a base to form 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene. In some embodiments, the process of heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a base is carried out as a liquid phase process. In some embodiments, the process of heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a base is carried out in an aqueous solvent.

In some embodiments, the method further comprises substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene. In some embodiments, the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is isolated substantially by distillation.

Exemplary bases include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, and sodium bicarbonate, each of which can optionally be prepared in water to form an aqueous base mixture or aqueous base solution. In some embodiments, the base is an aqueous base.

In some embodiments, the aqueous base is an aqueous alkali metal hydroxide base.

In some embodiments, the aqueous base is aqueous sodium hydroxide or aqueous potassium hydroxide.

In some embodiments, the present application provides a vapor phase process for producing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) contacting the chromium (III) oxide on carbon with hydrogen fluoride at a temperature of about 280 ℃ to about 320 ℃ to form an activated chromium (III) oxide on carbon catalyst; and

ii) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of an activated chromium (III) oxide on carbon catalyst at a temperature of about 150 ℃ to about 200 ℃ and a pressure of about 0psig to 150psig to form 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

In some embodiments, the vapor phase process further comprises substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

In some embodiments, the heating of step ii) of the gas phase process is carried out in the absence of hydrogen fluoride.

In some embodiments, the present application provides a liquid phase process for preparing 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of iron (III) chloride at a temperature of about 75 ℃ to about 115 ℃ to form 1,1, 3-trichloro-4, 4, 4-trifluorobutan-1-ene.

In some embodiments, the liquid phase process further comprises substantially isolating the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene.

In some embodiments, 1, 3-trichloro-4, 4, 4-trifluorobut-1-ene prepared according to the methods described herein is substantially isolated in greater than about 75% yield, greater than about 85% yield, greater than about 90% yield, greater than about 95% yield, greater than about 97% yield, greater than about 99% yield, or greater than about 99.5% yield.

In some embodiments, 1, 3-trichloro-4, 4, 4-trifluorobut-1-ene prepared according to the methods described herein is substantially isolated at greater than about 75% purity, greater than about 85% purity, greater than about 90% purity, greater than about 95% purity, greater than about 97% purity, greater than about 99% purity, or greater than about 99.5% purity.

The present application also provides a process comprising heating 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene (e.g., substantially isolated 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene prepared according to the processes described herein) in the presence of a metal catalyst (e.g., a second metal catalyst) to form (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

Exemplary metal catalysts that can be used in the process for preparing (E) -1,1,1,4,4, 4-hexafluorobut-2-ene include, but are not limited to, metal halides, halogenated metal oxides, neutral (or zero oxidation state) metals or metal alloys, or activated carbon in bulk or supported form. Additional exemplary metal catalysts that can be used to prepare (E) -1,1,1,4,4, 4-hexafluorobut-2-ene can be found, for example, in U.S. patent No. 8,461,401 and U.S. patent application No. 15/124,738, the disclosures of each of which are incorporated herein by reference in their entirety.

In some embodiments, the metal catalyst (e.g., the second metal catalyst) useful in the process for preparing (E) -1,1,1,4,4, 4-hexafluorobut-2-ene is a transition metal catalyst (e.g., the second transition metal catalyst). In some embodiments, the transition metal catalyst is a transition metal oxide catalyst. In some embodiments, the transition metal oxide catalyst is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium oxide. In some embodiments, the chromium oxide is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium (III) oxide. In some embodiments, the transition metal oxide catalyst is chromium (III) oxide on carbon.

In some embodiments, the 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane described herein is prepared by a process comprising: in the presence of a metal catalyst (e.g., a third transition metal catalyst) and a tris (C)_1-6Alkyl) phosphate, reacting 3, 3, 3-trifluoroprop-1-ene with carbon tetrachloride.

In some embodiments, the transition metal catalyst useful for preparing 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane is iron powder.

In some embodiments, tris (C)_1-6Alkyl) phosphate is tributyl phosphate.

Additional methods and conditions for preparing 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane can be found, for example, in U.S. patent No. 8,461,401 and U.S. patent application No. 15/124,738, the disclosures of each of which are incorporated herein by reference in their entirety.

The methods and chemical reactions described herein can be monitored according to any suitable method known in the art. For example, product formation can be by spectroscopic means, such as nuclear magnetic resonance spectroscopy (e.g., nuclear magnetic resonance spectroscopy)¹H or¹³C) The compound can be purified by one of skill in the art by a variety of methods, including but not limited to high performance liquid chromatography (HP L C) or distillation.

Composition comprising a metal oxide and a metal oxide

The present application also provides compositions prepared according to one or more of the methods described herein. In some embodiments, the compositions of the present invention are substantially isolated.

In some embodiments, the compositions of the present invention comprise a major component (e.g., (E) -1,1,1,4,4, 4-hexafluorobut-2-ene or 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane) in combination with one or more minor components (i.e., additional compounds or additional components). In some embodiments, the compositions of the present invention are prepared according to one or more of the methods described herein. In some embodiments, the major component of the composition comprises greater than about 50 mole%, greater than about 75 mole%, greater than about 85 mole%, greater than about 90 mole%, greater than about 95 mole%, greater than about 97 mole%, greater than about 99 mole%, or greater than about 99.5 mole% of the composition.

In addition, for refrigerant applications such as for air conditioning, heat pumping, refrigeration, and power cycles (e.g., organic Rankine cycles), the minor component of the composition may provide improved solubility with refrigeration lubricants such as mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly (α) olefins, polyol esters (POEs), polyalkylene glycols (PAGs), polyvinyl ethers (PVEs), or perfluoropolyethers (PFPEs), or mixtures thereof.

Furthermore, the presence of a secondary compound in a sample of a composition of the invention can be used to identify a method of preparing the compound.

In some embodiments, the present application provides a composition comprising:

(E) -1,1,1,4,4, 4-hexafluorobut-2-ene;

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene.

In some embodiments, the compositions comprise a major component that is (E) -1,1,1,4,4, 4-hexafluorobut-2-ene in combination with one or more of the following minor components:

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene.

In some embodiments, the composition comprises a major component that is (E) -1,1,1,4,4, 4-hexafluorobut-2-ene in combination with the following minor components:

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene.

In some embodiments, the composition comprises greater than about 90 mole% of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

In some embodiments, the composition comprises greater than about 97 mole% of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

In some embodiments, the composition comprises greater than about 99 mole% of (E) -1,1,1,4,4, 4-hexafluorobut-2-ene.

In some embodiments, a composition comprising the major component, (E) -1,1,1,4,4, 4-hexafluorobut-2-ene is prepared according to one or more of the methods described herein.

In some embodiments, the present application provides a composition comprising:

(E) -1,1,1,4,4, 4-hexafluorobut-2-ene;

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene.

The composition is prepared according to a process comprising heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a metal catalyst to form a composition, wherein the metal catalyst is defined herein with respect to the definition provided for the process of the invention.

In some embodiments, the compositions comprise a major component that is (E) -1,1,1,4,4, 4-hexafluorobut-2-ene in combination with one or more of the following minor components:

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene;

wherein the composition is prepared according to a process comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a first metal catalyst to form a first mixture comprising 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene; and

ii) heating 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene in the presence of a second metal catalyst to form a composition;

wherein the metal catalyst is defined according to the definitions provided herein for the process of the present invention.

In some embodiments, the composition comprises a major component that is (E) -1,1,1,4,4, 4-hexafluorobut-2-ene in combination with the following minor components:

(Z) -1,1,1,4,4, 4-hexafluorobut-2-ene;

3, 3, 3-trifluoro-2- (trifluoromethyl) prop-1-ene;

2-chloro-1, 1,1,4,4, 4-hexafluorobut-2-ene;

1,1,1,4,4, 4-hexafluorobutane; and

1-chloro-1, 1,4,4, 4-pentafluorobut-2-ene;

wherein the composition is prepared according to a process comprising:

i) heating 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in the presence of a first metal catalyst to form a first mixture comprising 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene; and

ii) heating 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene in the presence of a second metal catalyst to form a composition;

wherein the metal catalyst is defined according to the definitions provided herein for the process of the present invention.

In some embodiments, the 1,1, 3-trichloro-4, 4, 4-trifluorobut-1-ene is substantially separated prior to the heating of step ii).

In some embodiments, compositions comprising the major component, i.e., (E) -1,1,1,4,4, 4-hexafluorobut-2-ene, are substantially isolated.

In some embodiments, the present application provides a composition comprising:

2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane;

1,1, 1-trichloro-4, 4, 4-trifluorobutane; and

1,1, 1-trichloro-2- (chloromethyl) -3, 3, 3-trifluoropropane.

In some embodiments, the composition comprises a major component that is 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in combination with one or more of the following minor components:

1,1, 1-trichloro-4, 4, 4-trifluorobutane; and

1,1, 1-trichloro-2- (chloromethyl) -3, 3, 3-trifluoropropane.

In some embodiments, the composition comprises a major component that is 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in combination with the following minor components:

1,1, 1-trichloro-4, 4, 4-trifluorobutane; and

1,1, 1-trichloro-2- (chloromethyl) -3, 3, 3-trifluoropropane.

In some embodiments, the composition comprises greater than about 90 mole% 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane.

In some embodiments, the composition comprises greater than about 97 mole% 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane.

In some embodiments, the composition comprises greater than about 99 mole% 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane.

In some embodiments, a composition comprising the major component, 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane, is prepared according to one or more of the processes described herein.

In some embodiments, the composition comprises a major component that is 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane in combination with the following minor components:

1,1, 1-trichloro-4, 4, 4-trifluorobutane; and

1,1, 1-trichloro-2- (chloromethyl) -3, 3, 3-trifluoropropane;

wherein the composition is prepared according to a process comprising:

i) in the presence of a transition metal catalyst, in the presence of a metal catalyst and a tri (C)_1-6Alkyl) phosphate ester with carbon tetrachloride to form a composition;

wherein the metal catalyst and tri (C)_1-6Alkyl) phosphates are defined according to the definitions provided herein for the process of the invention.

In some embodiments, compositions comprising the major component, i.e., 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane, are substantially isolated.

Application method

The compositions provided herein (i.e., compositions of the invention) can be used, for example, in a wide range of applications, including their use as refrigerants, in high temperature heat pumps, organic rankine cycles, as fire extinguishing/suppression agents, propellants, blowing agents, solvents, and/or cleaning fluids.

In some embodiments, the minor component of the composition comprising at least one chlorine atom can provide improved solubility for the major component of the composition (e.g., (E) -1,1,1,4,4, 4-hexafluorobut-2-ene or 2, 4,4, 4-tetrachloro-1, 1, 1-trifluorobutane) in the aerosol or in the polymer component of the foam.

For example, unsaturated fluorocarbons such as (E) -1,1,1,4,4, 4-hexafluoro-2-butene exhibit different solubilities than other fluorocarbon propellants. This reduced solubility can make it difficult to produce single phase, aqueous, homogeneous aerosol formulations. The presence of low levels of chlorinated impurities can improve mixing and simplify the use of formulations and aerosol products.

Unsaturated fluorocarbons such as (E) -1,1,1,4,4, 4-hexafluorobut-2-ene also exhibit different solubilities than other commonly used blowing agents. The reduced solubility may help to promote small cell growth during the foaming reaction, but the compounds may be difficult to mix. The presence of low levels of chlorinated impurities can improve mixing and foam handling properties without sacrificing the benefits of lower HFO solubility. In addition, the chlorinated compounds generally have lower vapor thermal conductivity and therefore will impart improved insulation properties to the foamed insulation product.

In addition, for refrigerant applications such as those used in air conditioning, heat pump, refrigeration and power cycles (e.g., organic rankine cycles), the minor component of the inventive composition containing at least one chlorine atom may provide improved solubility with refrigeration lubricants such as mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly (α) olefins, polyol esters (POE), polyalkylene glycols (PAGs), polyvinyl ethers (PVEs) or perfluoropolyethers (PFPEs), or mixtures thereof.

In addition, minor components of the compositions of the present invention may help to improve leak detection capability. Leakage of refrigerant can result in loss of refrigerant from the system, thus increasing operating costs due to the need to replenish refrigerant charge, and even minimal loss of refrigerant from the system can affect normal operation. Finally, leakage of refrigerant may result in excessive environmental pollution. In particular, even low levels of chlorinated compounds may increase the detectability of the refrigerant at the leak point. Thus, the system may be repaired or redesigned to prevent refrigerant leakage.

However, the level of minor components (e.g., chlorinated compound minor components) in the composition must be kept low, as higher levels of minor components can cause compatibility problems with the structural materials. In aerosols, these compatibility issues may be associated with aerosol containers (e.g., canisters) or with plastic valve components. In foam, these compatibility issues can be a problem with device seals and gaskets. Furthermore, in aerosol products, the interaction of higher levels of minor components (e.g., chlorinated compound minor components) can lead to formulation instability. For example, in foam products, higher levels of chlorinated compounds can soften the foam, resulting in dimensional instability and poor strength of the foam.

The compositions described herein may also be used as low Global Warming Potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for polyolefins and polyurethanes, gaseous dielectrics, fire extinguishing agents, and fire suppression agents in liquid or gaseous form. In one embodiment, the compositions provided herein can be used as a working fluid for transporting heat from a heat source to a heat sink. Such heat transfer compositions may also be used as refrigerants in cycles in which the fluid undergoes a phase change (e.g., from liquid to gas, and vice versa).

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

In some embodiments, the compositions provided herein can be used in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices. In some embodiments, the compositions can be used in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or equipment.

As used herein, mobile heat transfer system refers to any refrigeration, air conditioning or heating apparatus incorporated into a road, rail, sea or air transport unit. In addition, mobile refrigeration or air conditioner units include those devices that are independent of any mobile carrier and are referred to as "combined" systems. Such intermodal systems include "containers" (combined sea/land transport) and "dump trucks" (combined road/rail transport).

As used herein, a stationary heat transfer system is a system that is fixed in one position during operation. The stationary heat transfer system may be incorporated into or attached to any kind of building, or may be a stand-alone device located outdoors, such as a soft drink vending machine. These stationary applications may be stationary air conditioners and heat pumps (including, but not limited to, chillers, high temperature heat pumps, including transcritical heat pumps (e.g., where the condenser temperature is greater than 50 ℃, greater than 70 ℃, greater than 80 ℃, greater than 100 ℃, greater than 120 ℃, greater than 140 ℃, greater than 160 ℃, greater than 180 ℃, or greater than 200 ℃), residential, commercial, or industrial air conditioning systems, and including window chillers, tubeless chillers, ducted chillers, integrated end chillers, and those external to, but connected to, a building, such as rooftop systems). In stationary refrigeration applications, the compositions provided herein can be used in high, medium, and/or low temperature refrigeration equipment, including commercial, industrial, or residential refrigerators and freezers, ice makers, stand-alone coolers and freezers, flooded evaporator coolers, direct expansion coolers, walk-in and reach coolers and freezers, and combined systems. In some embodiments, the disclosed compositions can be used in supermarket refrigerator systems.

Thus, in accordance with the present invention, the compositions provided herein can be used in methods of generating cooling, generating heating, and transferring heat.

In some embodiments, the present application provides methods of producing cooling comprising evaporating a composition provided herein in the vicinity of a body to be cooled, and then condensing the composition.

In some embodiments, the present application provides methods for producing heating comprising condensing a composition provided herein in the vicinity of a body to be heated, and then evaporating the composition.

In some embodiments, the present application provides methods of using the compositions provided herein as heat transfer fluid compositions. In some embodiments, the method comprises transferring the composition from a heat source to a heat sink.

The compositions provided herein may be used as low Global Warming Potential (GWP) replacements for currently used refrigerants, including, but not limited to, R-123 (i.e., HFC-123, 2, 2-dichloro-1, 1, 1-trifluoroethane), R-11 (i.e., CFC-11, trichlorofluoromethane), R-245fa (i.e., HFC-245fa, 1,1,1, 3, 3-pentafluoropropane), R-114 (i.e., CFC-114, 1, 2-dichloro-1, 1, 2, 2-tetrafluoroethane), R-236fa (i.e., HFC-236a, 1,1,3, 3, 3-hexafluoropropane), R-236ea (i.e., HFC-236ea, 1,1,1, 2, 3, 3-hexafluoropropane), R-124 (i.e., HCFC-124, 2-chloro-1, 1,1, 2-tetrafluoroethane), and the like.

In some embodiments, the compositions provided herein can be used as refrigerants and provide cooling performance (i.e., cooling capacity and energy efficiency) at least comparable to the refrigerant sought to be replaced. In addition, the compositions of the present invention can provide heating performance (i.e., heating capacity and energy efficiency) comparable to the refrigerant being replaced.

In some embodiments, the present application provides a method for recharging a heat transfer system comprising a refrigerant to be replaced and a lubricant, the method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a majority of the lubricant in the system, and introducing one of the compositions of the present invention into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., POE lubricant is substituted for a portion of the mineral oil lubricant used with HCFC-123).

In some embodiments, the compositions of the present invention can be used to supplement refrigerant charge in a chiller. For example, if a chiller using HCFC-123 degrades due to refrigerant leakage, the compositions provided herein may be added to bring performance to specification.

The present application further provides a heat exchange system comprising any of the compositions provided herein, wherein the system is selected from the group consisting of an air conditioner, a chiller, a refrigerator, a heat pump, a water cooler, a flooded evaporator chiller, a direct expansion chiller, a walk-in chiller, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and a system having a combination thereof. In addition, the compositions of the present invention can be used in secondary loop systems where these compositions are used as the primary refrigerant, thus providing cooling to the secondary heat transfer fluid, thereby cooling a remote location.

A vapor compression refrigeration, air conditioning or heat pump system includes an evaporator, a compressor, a condenser and an expansion device. The vapor compression cycle reuses refrigerant in multiple steps, creating a cooling effect in one step and a heating effect in a different step. The cycle can be described briefly as follows: the liquid refrigerant enters the evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature by extracting heat from the environment to form a vapor and produce cooling. The low pressure vapor enters a compressor where the vapor is compressed to increase its pressure and temperature. The high pressure (compressed) vapor refrigerant then enters a condenser where the refrigerant condenses and rejects its heat to the environment. The refrigerant returns to the expansion device, through which the liquid is expanded from a higher pressure level in the condenser to a lower pressure level in the evaporator, thereby repeating the cycle.

The present application also provides foam expansion agent compositions comprising the compositions of the present invention for preparing foams. In some embodiments, the present application provides foamable compositions, including but not limited to thermoset (e.g., polyurethane, polyisocyanurate, or phenolic resin) foam compositions, thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions, and methods of making foams. In some embodiments, one or more of the compositions of the present invention may be included as a foam expansion agent in a foamable composition, wherein the foamable composition may include one or more additional components capable of reacting and/or mixing and foaming under the appropriate conditions to form a foam or cellular structure.

The present application also provides a method of forming a foam, the method comprising: (a) adding to the foamable composition the composition of the present invention; and (b) treating the foamable composition under conditions effective to form a foam.

The present application also provides for the use of the compositions of the present invention as propellants in sprayable compositions. In addition, the present application provides the sprayable compositions of the present invention. The active ingredients to be sprayed may also be present in the sprayable composition, along with inert ingredients, solvents, and other materials. In some embodiments, the sprayable composition is an aerosol. The compositions of the present invention may also be used to formulate a variety of industrial aerosols or other sprayable compositions, such as contact cleaners, dusters, lubricant sprays, release sprays, insecticides, and the like, as well as consumer aerosols, such as personal care products (e.g., hair sprays, deodorants, and perfumes), household products (e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (e.g., cleaners and polishes), and medicinal materials such as anti-asthma and anti-halitosis medications. Examples include, but are not limited to, for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of drugs to accessible mucous membranes or to intranasal Metered Dose Inhalers (MDIs).

The present invention also provides a process for the preparation of an aerosol product comprising the step of adding a composition of the present invention to the formulation of an aerosol container, wherein the composition of the present invention acts as a propellant. Furthermore, the present invention also provides a method for producing an aerosol product, the method comprising the steps of: the compositions of the present invention are added to a barrier aerosol package (e.g., a bag-in-can or a piston-in-can) wherein the compositions of the present invention are kept separate from the other formulation ingredients in the aerosol container, and wherein the compositions of the present invention are used as a propellant. Further, the present application also provides a method for producing an aerosol product, the method comprising the steps of: the composition of the present invention is added only to an aerosol package, wherein the composition is used as an active ingredient (e.g., a duster, or a cooling or freeze spray).

The present application also provides a method for converting heat from a heat source to mechanical energy, the method comprising heating a working fluid comprising a composition of the present invention and then expanding the heated working fluid. In the method, heating the working fluid uses heat supplied from a heat source; and as the pressure of the working fluid decreases, the expansion of the heated working fluid generates mechanical energy.

The method for converting heat may be a subcritical cycle, a transcritical cycle, or a supercritical cycle. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure before being heated, and then the working fluid pressure is reduced below its critical pressure during expansion. In a supercritical cycle, the working fluid is maintained above its critical pressure throughout the cycle (e.g., compression, heating, expansion, and cooling).

The heat source may include, for example, low pressure steam, industrial waste heat, solar energy, geothermal hot water, low pressure geothermal steam (primary or secondary arrangement) or distributed generation equipment using fuel cells or prime movers such as turbines, microturbines or internal combustion engines. One low pressure steam source may be a process known as a binary geothermal rankine cycle. Large amounts of low pressure steam are found in many places, such as in fossil fuel powered power plants. Other heat sources include waste heat recovered from the exhaust of a mobile internal combustion engine (e.g., a truck or railroad diesel engine or ship), waste heat from the exhaust of a stationary internal combustion engine (e.g., a stationary diesel generator), waste heat from a fuel cell, heat obtained at combined heating, cooling and electrical or district heating and cooling equipment, waste heat from a biomass fuel engine, waste heat from a natural gas or methane gas burner or a boiler burning methane or a methane fuel cell (e.g., a distributed power generation facility) operating with methane from various sources including biogas, landfill gas and coal bed gas, heat from the combustion of bark and lignin at a paper/pulp plant, heat from an incinerator, heat from low pressure steam from a conventional steam power plant (to drive a "bottoming" rankine cycle), and geothermal heat.

In some embodiments, the thermal conversion process is performed using an organic rankine power cycle. The heat obtained at relatively low temperatures, as compared to steam (inorganic) power cycles, can be used to generate mechanical power through a rankine cycle using a working fluid as described herein. In some embodiments, the working fluid is compressed prior to heating. Compression may be provided by a pump pumping a working fluid to a heat transfer unit (e.g., a heat exchanger or evaporator), where heat from a heat source is used to heat the working fluid. The heated working fluid then expands, lowering its pressure. An expander is used to generate mechanical energy during expansion of the working fluid. Examples of expanders include, but are not limited to, turbo or dynamic expanders (such as turbines), and positive displacement expanders (such as helical, scroll and piston expanders). Examples of expanders also include a rotary vane expander.

Mechanical power may be used directly (e.g., to drive a compressor) or converted to electrical power through the use of an electrical generator. The expanded working fluid is cooled in a power cycle that reuses the working fluid. Cooling may be accomplished in a working fluid cooling unit (e.g., a heat exchanger or condenser). The cooled working fluid may then be used for repeated cycles (i.e., compression, heating, expansion, etc.). The same pump used for compression may be used to transfer the working fluid from the cooling stage.

The present application also provides a method for detecting a leak from a container, the method comprising sampling air in the vicinity of the container and detecting at least one additional compound of a composition provided herein with a device for detecting a leak, wherein the composition of the invention is contained within the container. By "near" is meant within 12 inches of the outer surface of the container. Alternatively, the vicinity may be within 6 inches, within 3 inches, or within 1 inch from the outer surface of the container.

The container can be any known container or system or device filled with the inventors' composition. The containers may include, but are not limited to, storage containers, transport containers, aerosol cans, fire suppression systems, cooler equipment, heat pump equipment, heat transfer containers, and power cycle equipment (e.g., organic rankine cycle systems).

The means for detecting a leak may be performed using any known sensor designed to detect a leak. Specifically, means for detecting leaks include, but are not limited to, electrochemical, corona discharge, and mass spectrometer leak detectors.