Patent Application
20210017106
This invention relates to processes and intermediates for preparing (Z)-1,1,1,4,4,4-hexafluoro-2-butene and compositions which may be useful in applications including refrigerants, high-temperature heat pumps, organic Rankine cycles, as fire extinguishing/fire suppression agents, propellants, foam blowing agents, solvents, and/or cleaning fluids.
Many industries have been working for the past few decades to find replacements for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The CFCs and HCFCs have been employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. In the search for replacements for these versatile compounds, many industries have turned to the use of hydrofluorocarbons (HFCs).
The present application provides, inter alia, processes of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising reacting hexachlorobutadiene with hydrofluoric acid in the presence of a transition metal catalyst, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides processes comprising reacting 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with a base in the presence of an alkali metal halide and a quaternary (C4-12 alkyl)ammonium salt to form perfluorobut-2-yne.
The present application further provides processes comprising reacting perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides compositions prepared according to one or more processes described herein.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Methods and materials are described herein for use in the present invention; other, 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.
Antimony (V) catalysts have been used in anhydrous the HF fluorination of halo(hydro)carbons since the 1890s. However, there are notable issues associated with antimony catalysts including water toxicity. For example, water regulations for antimony are limited to approximately 6 ppb. Meeting these regulations requires significant consideration in the work-up of reaction mixtures involving antimony catalysts and subsequent waste handling. In addition, reduction of Sb(V) to Sb(III) is a highly favorable process which leads to rapid catalyst deactivation. For example, the use of SbCl5 requires a chlorine co-feed into the reaction to provide catalyst regeneration. Furthermore, antimony (V) pentafluoride catalyst is highly volatile, and high temperature operations are not suitable as the catalyst easily vaporizes and can plug reactor lines. Accordingly, the present application provides alternative transition metal catalysts useful in the HF fluorination of halo(hydro)carbons, particularly fluorination of hexachlorobutadiene (HCBD) to stereoselectively produce (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (i.e., (Z)-1326mxz), a key intermediate in the preparation of (Z)-1,1,1,4,4,4-hexafluoro-2-butene which is useful in various applications (e.g., as a foam expansion agent or refrigerant) due to its low GWP, non-flammability, high efficiency, and thermal stability.
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” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: 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).
Also, use of “a” or “an” are 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. This 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 approximately 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 explicitly stated otherwise.
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 a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the value referenced.
Throughout the definitions, the term “Cn-m” indicates a range which includes the endpoints, wherein n and m are integers and indicate the number of carbons. Examples include C1-4, C1-6, and the like.
As used herein, the term “Cn-m alkyl” refers to a saturated hydrocarbon group that may be straight-chain or branched, having n to m carbons. Examples of alkyl moieties include, but are not limited to, chemical groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl; higher homologs 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 20, 1 to 10, 1 to 6, 4 to 20, 4 to 12, or 4 to 8 carbon atoms.
As used herein, “halide” refers to fluoride, chloride, bromide, or iodide. In some embodiments, the halo is chloride or bromide.
As used herein, the term “alkali metal” refers to lithium, sodium, potassium, or rubidium.
As used herein, the term “quaternary (Cn-m alkyl)ammonium salt” refers to a salt of formula (Cn-m alkyl)4N+X−, wherein X− is an anionic group (e.g., halide, hydrogen sulfate, and the like), and each Cn-m alkyl refers to a saturated hydrocarbon group that may be straight-chain or branched, having n to m carbons, wherein each Cn-m alkyl group may be the same or different. Exemplary quaternary (Cn-m alkyl)ammonium salt include, but are not limited to, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.
As used herein the term, “hydrogenation catalyst” refers to a metal (e.g., palladium, nickel, or rhodium) catalyst suitable to catalyze a hydrogenation reaction (i.e., reaction of a compound with hydrogen gas). Exemplary hydrogenation catalysts include, but are not limited to, palladium on carbon, Lindlar's catalyst, Wilkinson's catalyst, HRuCl(PPh3)3, RhCl(PPh3)3, [Rh(COD)Cl]2, [Ir(COD)(PMePh2)2]+, [Rh(1,5-cyclooctadiene)(PPh3)2]+, PtO2 (Adam's catalyst), palladium on carbon, palladium black, a palladium catalyst, a palladium catalyst dispersed on aluminum oxide or titanium silicate doped with silver and/or a lanthanide, and the like. In some embodiments, the hydrogenation catalyst is a palladium catalyst. In some embodiments, the hydrogenation catalyst is a Lindlar's catalyst. In some embodiments, the hydrogenation catalyst is a the catalyst is a palladium catalyst dispersed on aluminum oxide or titanium silicate, doped with silver and/or a lanthanide.
The present application provides, inter alia, a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising reacting hexachlorobutadiene with hydrofluoric acid in the presence of a transition metal catalyst.
In some embodiments, greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 99.5 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 99.7 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 99.9 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 90 mole percent (e.g., greater than about 95, greater than about 97, greater than about 99, greater than about 99.5, or greater than about 99.9 mole percent) of the hexachlorobutadiene is converted to the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 90 mole percent (e.g., greater than about 95, greater than about 97, greater than about 99, greater than about 99.5, or greater than about 99.9 mole percent) of the hexachlorobutadiene is converted to the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene in less than about 10 hours of reacting (e.g., less than about 8 hours, less than about 6 hours, less than about 5 hours of reacting).
In some embodiments, the transition metal catalyst is a Group V transition metal catalyst. In some embodiments, the Group V transition metal is niobium or tantalum. In some embodiments, the transition metal catalyst is selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.
In some embodiments, the transition metal catalyst is a tantalum catalyst. In some embodiments, the transition metal catalyst is a tantalum halide catalyst. In some embodiments, the transition metal catalyst is tantalum (V) chloride.
In some embodiments, the transition metal catalyst is a niobium catalyst. In some embodiments, the transition metal catalyst is a niobium halide catalyst. In some embodiments, the transition metal catalyst is selected from niobium (IV) chloride, niobium (V) chloride, or a mixture thereof.
In some embodiments, the transition metal catalyst is tantalum (V) chloride, niobium (IV) chloride, niobium (V) chloride, or any mixture thereof.
In some embodiments, the transition metal catalyst is a mixture of a tantalum catalyst and a niobium catalyst. In some embodiments, the transition metal catalyst is a mixture of a tantalum halide catalyst and a niobium halide catalyst.
In some embodiments, the transition metal catalyst is a mixture of tantalum chloride and niobium chloride.
In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (IV) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride and niobium (V) chloride. In some embodiments, the transition metal catalyst is a mixture of tantalum (V) chloride, niobium (IV) chloride, and niobium (V) chloride.
In some embodiments, a molar excess of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene, for example, greater than 1 molar equivalent, greater than 2 molar equivalents, greater than 5 molar equivalents, greater than 10 molar equivalents, greater than 20 molar equivalents, greater than 50 molar equivalents, or greater than 100 molar equivalents of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
In some embodiments, about 10 to about 50 molar equivalents of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene, for example about 10 to about 40, about 10 to about 30, about 10 to about 20, about 20 to about 50, about 20 to about 40, about 20 to about 30, about 30 to about 50, about 30 to about 40, or about 40 to about 50 molar equivalents of hydrofluoric acid. In some embodiments, about 20 to about 30 molar equivalents of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
In some embodiments, a catalytic amount of the catalyst is used based on 1 molar equivalent of hexachlorobutadiene, for example, less than 1 molar equivalent, less than 2 molar equivalents, less than 5 molar equivalents, less than 10 molar equivalents, less than 20 molar equivalents, less than 50 molar equivalents, or less than 100 molar equivalents of transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene.
In some embodiments, about 0.05 to about 0.5 molar equivalents of the transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene, for example, about 0.05 to about 0.3, about 0.05 to about 0.2, about 0.05 to about 0.1, about 0.1 to about 0.5, about 0.1 to about 0.3, about 0.1 to about 0.2, about 0.2 to about 0.5, about 0.2 to about 0.3, or about 0.3 to about 0.5 molar equivalents of transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene. In some embodiments, about 0.1 to about 0.3 molar equivalents of the transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene.
In some embodiments, the process is performed a temperature of from about 100° C. to about 150° C., for example, about 100° C. to about 140° C., about 100° C. to about 130° C., about 120° C. to about 140° C., about 100° C. to about 110° C., about 110° C. to about 150° C., about 110° C. to about 140° C., about 110° C. to about 130° C., about 110° C. to about 140° C., about 120° C. to about 150° C., about 120° C. to about 140° C., about 120° C. to about 130° C., about 130° C. to about 150° C., about 130° C. to about 140° C., or about 140° C. to about 150° C. In some embodiments, the process is performed a temperature of from about 110° C. to about 135° C.
In some embodiments, the process comprises:
i) adding the transition metal catalyst to the hydrofluoric acid to form a first mixture; and
ii) adding the hexachlorobutadiene to the first mixture to form a second mixture.
In some embodiments, the first mixture is heated to a temperature of from about 100° C. to about 150° C., for example, about 100° C. to about 140° C., about 100° C. to about 130° C., about 120° C. to about 140° C., about 100° C. to about 110° C., about 110° C. to about 150° C., about 110° C. to about 140° C., about 110° C. to about 130° C., about 110° C. to about 140° C., about 120° C. to about 150° C., about 120° C. to about 140° C., about 120° C. to about 130° C., about 130° C. to about 150° C., about 130° C. to about 140° C., or about 140° C. to about 150° C. In some embodiments, the first mixture is heated to a temperature of from about 110° C. to about 140° C.
In some embodiments, the process further comprises cooling the first mixture to a temperature of from about −25° C. to about 25° C. prior to performing step ii), for example, about −25° C. to about 10° C., about −25° C. to about 0° C., about −25° C. to about −10° C., about −10° C. to about 25° C., about −10° C. to about 10° C., about −10° C. to about 0° C., about 0° C. to about 25° C., about 0° C. to about 10° C., or about 10° C. to about 25° C. In some embodiments, the process further comprises cooling the first mixture to a temperature of from about −10° C. to about 10° C. prior to performing step ii).
In some embodiments, the hexachlorobutadiene is added to the first mixture at a temperature of from about −25° C. to about 25° C. to form the second mixture, for example, about −25° C. to about 10° C., about −25° C. to about 0° C., about −25° C. to about −10° C., about −10° C. to about 25° C., about −10° C. to about 10° C., about −10° C. to about 0° C., about 0° C. to about 25° C., about 0° C. to about 10° C., or about 10° C. to about 25° C. In some embodiments, the hexachlorobutadiene is added to the first mixture at a temperature of from about −10° C. to about 10° C. to form the second mixture.
In some embodiments, the process further comprises heating the second mixture to a temperature of from about 100° C. to about 150° C., for example, about 100° C. to about 140° C., about 100° C. to about 130° C., about 120° C. to about 140° C., about 100° C. to about 110° C., about 110° C. to about 150° C., about 110° C. to about 140° C., about 110° C. to about 130° C., about 110° C. to about 140° C., about 120° C. to about 150° C., about 120° C. to about 140° C., about 120° C. to about 130° C., about 130° C. to about 150° C., about 130° C. to about 140° C., or about 140° C. to about 150° C. In some embodiments, the process further comprises heating the second mixture to a temperature of from about 110° C. to about 140° C.
The present application further provides a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) adding tantalum (V) chloride to hydrofluoric acid to form a first mixture;
ii) heating the first mixture to a temperature of from about 110° C. to about 120° C.;
iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;
iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and
v) heating the second mixture to a temperature of from about 110° C. to about 120° C.
The present application further provides a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) adding niobium (V) chloride to hydrofluoric acid to form a first mixture;
ii) heating the first mixture to a temperature of from about 125° C. to about 135° C.;
iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;
iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and
v) heating the second mixture to a temperature of from about 125° C. to about 135° C.
In some embodiments, the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene provided herein is performed as a liquid phase process. In some embodiments, the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene (e.g., the liquid phase process) is performed in the absence of an additional solvent component.
In some embodiments, greater than about 99.5 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 99.7 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, greater than about 99.9 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced by the processes provided herein is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene further comprises reacting the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with a base in the presence of an alkali metal halide and a quaternary (C4-12 alkyl)ammonium salt to form perfluorobut-2-yne. In some embodiments, the process of preparing the perfluorobut-2-yne from the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is performed according to the procedures described in U.S. Pat. No. 9,328,042 and International Publication No. WO 2014/052695 the disclosure of each which is incorporated herein by reference in its entirety.
Exemplary bases include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof. Some example strong bases include, but are not limited to, hydroxides, alkoxides, metal amides, metal hydrides, metal dialkylamides and arylamines, wherein; alkoxides include lithium, sodium and potassium salts of methyl, ethyl and t-butyl oxides; metal amides include sodium amide, potassium amide and lithium amide; metal hydrides include sodium hydride, potassium hydride and lithium hydride; and metal dialkylamides include lithium, sodium, and potassium salts of methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, trimethylsilyl and cyclohexyl substituted amides.
In some embodiments, the base is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof.
In some embodiments, the base is an aqueous basic solution. As used herein, the “basic aqueous solution” is a liquid (e.g., a solution, dispersion, emulsion, or suspension, and the like) that is primarily an aqueous liquid having a pH of over 7.
In some embodiments, the basic aqueous solution contains small amounts of organic liquids which may be miscible or immiscible with water. In some embodiments, the liquid medium in the basic aqueous solution is at least 90% water, for example, at least 95%, at least 97%, at least 98%, at least 99%, at least 99.5%, or at least 99.9%. In some embodiments, the water used in the aqueous basic solution is tap water. In some embodiments, the water is used in the aqueous basic solution deionized water or distilled water.
In some embodiments, the alkali metal halide is selected from the group consisting of lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, and mixtures thereof. In some embodiments, the alkali metal halide is sodium chloride.
In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.
In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is a tetrabutylammonium salt. In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium hydrogen sulfate. In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium halide. In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is tetrabutylammonium chloride. In some embodiments, the quaternary (C4-12 alkyl)ammonium salt is trioctylmethylammonium chloride.
In some embodiments, about 1 to about 5 molar equivalents of base is used based on one molar equivalent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, for example, about 1 to about 3, about 1 to about 2, about 1 to about 1.5, about 1.5 to about 5, about 1.5 to about 3, about 1.5 to about 2, about 2 to about 5, about 2 to about 3, or about 3 to about 5 molar equivalents. In some embodiments, about 1 to about 1.5 molar equivalents of base is used based on one molar equivalent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, a molar excess of base is used based on one molar equivalent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the process of preparing the perfluorobut-2-yne is performed at a temperature of from about 30° C. to about 60° C., for example, about 30° to about 50° C., about 30° to about 40° C., about 40° to about 60° C., about 40° to about 50° C., or about 50° C. to about 60° C.
In some embodiments, the process of preparing the perfluorobut-2-yne is performed as a liquid phase process. In some embodiments, the process of preparing the perfluorobut-2-yne is performed in the absence of an additional solvent component.
In some embodiments, the process of preparing perfluorobut-2-yne further comprises reacting the perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form 1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the hydrogen is hydrogen gas. In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene from the perfluorobut-2-yne is performed according to the procedures described in U.S. Pat. No. 9,328,042 and International Publication No. WO 2014/052695 the disclosure of each which is incorporated herein by reference in its entirety.
In some embodiments, about 1 molar equivalent of hydrogen is used based on 1 molar equivalent of the perfluorobut-2-yne.
In some embodiments, about 0.5 to about 1 molar equivalents of hydrogen is used based on 1 molar equivalent of the perfluorobut-2-yne.
In some embodiments, about 0.67 to about 1 molar equivalents of hydrogen is used based on 1 molar equivalent of the perfluorobut-2-yne.
In some embodiments, the hydrogenation catalyst is a palladium catalyst. In some embodiments, the hydrogenation catalyst is Lindlar's catalyst. As used herein, the term “Lindlar's catalyst” refers to a heterogeneous palladium catalyst on a calcium carbonate support, which has been deactivated or conditioned with a lead compound. The lead compound can be, for example, lead acetate, lead oxide, or any other suitable lead compound. In some embodiments, the Lindlar's catalyst is prepared by reduction of a palladium salt in the presence of a slurry of calcium carbonate, followed by the addition of the lead compound. In some embodiments, the palladium salt is palladium chloride. In some embodiments, the catalyst is deactivated or conditioned with quinoline.
In some embodiments, the hydrogenation catalyst is a palladium catalyst dispersed on aluminum oxide or titanium silicate, doped with silver and/or a lanthanide. In some embodiments, the palladium loading on the aluminum oxide or titanium silicate is from 100 ppm to 5000 ppm. In some embodiments, the palladium loading on the aluminum oxide or titanium silicate is from 200 ppm to 5000 ppm.
In some embodiments, the hydrogenation catalyst is doped with at least one of silver, cerium, or lanthanum.
In some embodiments, the hydrogenation catalyst is doped with silver. In some embodiments the molar ratio of silver to palladium is about 0.5:1.0.
In some embodiments, the hydrogenation catalyst is doped with cerium or lanthanum. In some embodiments, the molar ratio of cerium or lanthanum to palladium is from about 2:1 to about 3:1.
In some embodiments, a catalytic amount (i.e., less than 1 molar equivalent) of the hydrogenation catalyst is used based on 1 molar equivalent of the perfluorobut-2-yne.
In some embodiments, about 0.5 to about 4 percent by weight of the hydrogenation catalyst is used based on the weight of perfluorobut-2-yne.
In some embodiments, about 1 to about 3 percent by weight of the hydrogenation catalyst is used based on the weight of perfluorobut-2-yne.
In some embodiments, about 1 to about 2 percent by weight of the hydrogenation catalyst is used based on the weight of perfluorobut-2-yne.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at about room temperature.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature greater than room temperature.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature of from about 40° C. to about 90° C.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature of from about 60° C. to about 90° C.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature less than room temperature.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature less than about 0° C.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed at a temperature of from about −70° C. to about −80° C.
In some embodiments, greater than about 95 mole percent of the 1,1,1,4,4,4-hexafluoro-2-butene produced by the process provided herein is (Z)-1,1,1,4,4,4-hexafluoro-2-butene, for example, greater than about 97 mole percent, greater than about 98 mole percent, greater than about 99 mole percent, greater than about 99.5 mole percent, greater than about 99.9 mole percent. In some embodiments, greater than about 99 mole percent of the 1,1,1,4,4,4-hexafluoro-2-butene produced by the process provided herein is (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed as a liquid phase process. In some embodiments, the process of preparing the 1,1,1,4,4,4-hexafluoro-2-butene is performed in the absence of an additional solvent component.
The present application further provides a process of preparing (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of tantalum (V) chloride to form 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with sodium hydroxide in the presence of sodium chloride and tetabutylammonium chloride to form perfluorobut-2-yne; and
iii) reacting the perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form the (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides a process of preparing (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of niobium (V) chloride to form 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium salt to form perfluorobut-2-yne; and
iii) reacting the perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form the (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides a process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of tantalum (V) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium salt to form a second composition comprising perfluorobut-2-yne; and
iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides a process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of niobium (V) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium salt to form a second composition comprising perfluorobut-2-yne; and
iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the first composition comprises greater than about 95 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the first composition comprises greater than about 97 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the first composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the first composition comprises greater than about 99 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the first composition comprises greater than about 99.5 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the first composition comprises greater than about 99.9 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the second composition comprises greater than about 95 mole percent perfluorobut-2-yne. In some embodiments, the second composition comprises greater than about 97 mole percent perfluorobut-2-yne. In some embodiments, the second composition comprises greater than about 98 mole percent perfluorobut-2-yne. In some embodiments, the second composition comprises greater than about 99 mole percent perfluorobut-2-yne. In some embodiments, the second composition comprises greater than about 99.5 mole percent perfluorobut-2-yne. In some embodiments, the second composition comprises greater than about 99.9 mole percent perfluorobut-2-yne.
In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 95 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 97 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 98 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 99.5 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene comprises greater than about 99.9 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
The present application further provides compositions comprising a major component (e.g., (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, or perfluorobut-2-yne, or (Z)-1,1,1,4,4,4-hexafluoro-2-butene) in combination with one or more additional compounds. In some embodiments, the compositions are prepared according to one or more of the processes described herein.
The additional compounds of the compositions described herein may provide improved solubility for active ingredients in an aerosol or polymer constituents of a foam. Additionally, for refrigerant applications, such as use in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), the additional compounds may provide improved solubility with refrigeration lubricants, such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly(alpha)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE), or perfluoropolyethers (PFPE), or mixtures thereof.
Further, the presence of the additional compounds in a sample of (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, or perfluorobut-2-yne, or (Z)-1,1,1,4,4,4-hexafluoro-2-butene may be used to identify the process by which the compound was manufactured.
The present application further provides a composition, comprising:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 95 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and one of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like).
In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and each of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to twenty-five of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to twenty of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to ten of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to five of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to four of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to three of the additional compounds. In some embodiments, the composition comprises (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and from one to two of the additional compounds. In some embodiments, the composition comprises:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 95 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition comprises greater than about 97 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99.5 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99.9 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition consists essentially of the (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene and the one or more additional compounds.
The present application further provides a composition, comprising:
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 95 mole percent perfluorobut-2-yne.
In some embodiments, the composition comprises perfluorobut-2-yne and one of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like).
In some embodiments, the composition comprises perfluorobut-2-yne and each of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to twenty-five of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to twenty of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to ten of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to five of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to four of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to three of the additional compounds. In some embodiments, the composition comprises perfluorobut-2-yne and from one to two of the additional compounds.
In some embodiments, the composition comprises
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 95 mole percent perfluorobut-2-yne.
In some embodiments, the composition comprises greater than about 97 mole percent perfluorobut-2-yne. In some embodiments, the composition comprises greater than about 98 mole percent perfluorobut-2-yne. In some embodiments, the composition comprises greater than about 99 mole percent perfluorobut-2-yne. In some embodiments, the composition comprises greater than about 99.5 mole percent perfluorobut-2-yne. In some embodiments, the composition comprises greater than about 99.9 mole percent perfluorobut-2-yne.
In some embodiments, the composition consists essentially of the perfluorobut-2-yne and the one or more additional compounds.
The present application further provides a composition, comprising:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and one of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and more than one of the additional compounds (e.g., two or more; three or more; five or more; ten or more; and the like).
In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and each of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and from one to ten of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and from one to five of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and from one to four of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and from one to three of the additional compounds. In some embodiments, the composition comprises (Z)-1,1,1,4,4,4-hexafluoro-2-butene and from one to two of the additional compounds.
In some embodiments, the composition comprises:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition comprises greater than about 97 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 98 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99.5 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene. In some embodiments, the composition comprises greater than about 99.9 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
In some embodiments, the composition consists essentially of the (Z)-1,1,1,4,4,4-hexafluoro-2-butene and the one or more additional compounds.
The composition provided herein (i.e., the compositions of the invention) may be useful, for example, in a wide range of applications, including their use as refrigerants, uses in high-temperature heat pumps, organic Rankine cycles, as fire extinguishing/fire suppression agents, propellants, foam blowing agents, solvents, and/or cleaning fluids.
In some embodiments, the additional compounds of the compositions containing at least one chlorine atom may provide improved solubility for the major component of the composition (e.g., (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, or perfluorobut-2-yne, or (Z)-1,1,1,4,4,4-hexafluoro-2-butene) in an aerosol or polymer constituents of a foam.
For example, unsaturated fluorocarbons, such as (Z)-1,1,1,4,4,4-hexafluoro-2-butene, exhibit different solubility than other fluorocarbon propellants. This reduced solubility can make it difficult to prepare single phase aqueous homogenous aerosol formulations. The presence of low level chlorinated impurities can improve mixing and ease formulations and use of aerosol products.
Unsaturated fluorocarbons, such as (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, also exhibit different solubility than other common blowing agents. The reduced solubility can assist in seeding small cell growth during a foaming reaction but the compounds can be difficult to mix. The presence of low level chlorinated impurities can improve mixing and foam processing performance without sacrificing the benefits from the lower HFO solubility. Also, the chlorinated compounds typically have lower vapor thermal conductivities and so will impart improved insulating performance to a foam insulation product.
Additionally, for refrigerant applications, such as use in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), additional compounds containing at least one chlorine atom may provide improved solubility with refrigeration lubricants, such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly(alpha)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE), or perfluoropolyethers (PFPE) or mixtures thereof.
Further, the additional compounds of the compositions provided herein may assist in improving leak detection ability. Leakage of refrigerants may lead to loss of refrigerant from a system, thus increasing cost of operation due to the need to top-off refrigerant charge, and even minor loss of refrigerant from a system may impact proper operation. Finally, leakage of refrigerant may lead to excessive environmental contamination. In particular, chlorinated compounds, even at low levels can increase the detectability of refrigerant at the point of a leak. Thus, the system may be repaired or redesigned to prevent refrigerant leakage.
The levels of additional compounds (e.g., additional chlorinated compounds) must be kept low, however, because higher levels of the additional compounds may create compatibility problems with materials of construction. In aerosols, these compatibility problems may be with the aerosol container (e.g., cans) or with plastic valve parts. In foams, these compatibility problems may be with equipment seals and gaskets. Additionally, in aerosol products interaction of higher levels of additional compounds (e.g., chlorinated compounds) may cause instability of the formulation. For example, in foam products, higher levels of chlorinated compounds may soften the foam resulting in dimensional instability and poor strength of the foam.
The compositions described herein may also useful as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for poly-olefins and polyurethane, gaseous dielectrics, fire extinguishing agents, and fire suppression agents, in liquid or gaseous form. In some embodiments, the compositions provided herein may be useful as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change (e.g., from a liquid to a gas and back 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, heat pumps, mobile refrigerators, mobile air conditioning units and combinations thereof.
In some embodiments, the compositions provided herein may be useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus. In some embodiments, the compositions may be useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus.
As used herein, mobile heat transfer systems refers to any refrigeration, air conditioner, or heating apparatus incorporated into a transportation unit for the road, rail, sea or air. In addition, mobile refrigeration or air conditioner units, include those apparatus that are independent of any moving carrier and are known as “intermodal” systems. Such intermodal systems include “containers' (combined sea/land transport) as well as “swap bodies” (combined road/rail transport).
As used herein, stationary heat transfer systems are systems that are fixed in place during operation. A stationary heat transfer system may be associated within or attached to buildings of any variety or may be stand-alone devices located out of doors, such as a soft drink vending machine. These stationary applications may be stationary air conditioning and heat pumps (including but not limited to chillers, high temperature heat pumps, including trans-critical heat pumps (e.g., with condenser temperatures above 50° C., above 70° C., above 80° C., above 100° C., above 120° C., above 140° C., above 160° C., above 180° C., or above 200° C.), residential, commercial or industrial air conditioning systems, and including window, ductless, ducted, packaged terminal, chillers, and those exterior but connected to the building such as rooftop systems). In stationary refrigeration applications, the compositions provided herein may be useful in high temperature, medium temperature, and/or low temperature refrigeration equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed compositions may be used in supermarket refrigerator systems.
Therefore, in accordance with the present invention, the compositions provided herein may be useful in methods for producing cooling, producing heating, and transferring heat.
In some embodiments, the present application provides a method for producing cooling comprising evaporating a composition provided herein in the vicinity of a body to be cooled, and thereafter condensing said composition.
In some embodiments, the present application provides a method for producing heating comprising condensing a composition provided herein in the vicinity of a body to be heated, and thereafter evaporating said compositions.
In some embodiments, the present application provides a method of using compositions provided herein as heat transfer fluid compositions. In some embodiments, the method comprises transporting said composition from a heat source to a heat sink.
The compositions provided herein may also be useful 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, 1,1,1,3,3,3-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), among others.
In some embodiments, the composition provided herein may be useful as refrigerants and provide at least comparable cooling performance (i.e., cooling capacity and energy efficiency) as the refrigerant for which a replacement is being sought. Additionally, the compositions of the present invention may provide heating performance (i.e., heating capacity and energy efficiency) comparable to a refrigerant being replaced.
In some embodiments the present application provides a method for recharging a heat transfer system that contains a refrigerant to be replaced and a lubricant, said method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant in said system and introducing one of compositions of the present invention to the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., replace a portion of the mineral oil lubricant used with HCFC-123 with a POE lubricant).
In some embodiments, the compositions of the present invention may be used to top-off a refrigerant charge in a chiller. For example, if a chiller using HCFC-123 has diminished performance due to leakage of refrigerant, the compositions provided herein may be added to bring performance back up to specification.
The present application further provides a heat exchange system containing any of the compositions provided herein, wherein said system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof. Additionally, the compositions of the invention may be useful in secondary loop systems wherein these compositions serve as the primary refrigerant thus providing cooling to a secondary heat transfer fluid that thereby cools a remote location.
Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows: Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, by withdrawing heat from the environment, at a low temperature to form a vapor and produce cooling. The low-pressure vapor enters a compressor where the vapor is compressed to raise its pressure and temperature. The higher-pressure (compressed) vapor refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.
The present application further provides foam expansion agent compositions comprising a composition of the invention for use in preparing foams. In some embodiments, the present application provides foamable compositions, including but not limited to, thermoset (e.g., polyurethane, polyisocyanurate, or phenolic) foam compositions, thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions and methods of preparing foams. In some embodiments, one or more of the present compositions may be included as a foam expansion agent in the foamable compositions, wherein foamable composition may include one or more additional components capable of reacting and/or mixing and foaming under the proper conditions to form a foam or cellular structure.
The present application further provides a method of forming a foam comprising: (a) adding to a foamable composition a composition of the present invention; and (b) processing the foamable composition under conditions effective to form a foam.
The present application further provides the use of the compositions of the present invention as propellants in sprayable compositions. Additionally, the present application provides sprayable compositions of the invention. The active ingredient to be sprayed together with inert ingredients, solvents, and other materials may also be present in a sprayable composition. In some embodiments, the sprayable composition is an aerosol. The compositions of the invention can also be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, mold release sprays, insecticides, and the like, and 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 polishers), as well as medicinal materials such as anti-asthma and anti-halitosis medications. Examples include, but are not limited to, metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intra-nasally.
The present invention further provides a process for producing aerosol products comprising the step of adding a composition of the invention to a formulation to an aerosol container, wherein said composition of the invention functions as a propellant. Additionally, the present application further provides a process for producing aerosol products comprising the step of adding a composition of the invention to a barrier type aerosol package (e.g., a bag-in-a-can or piston can) wherein said composition of the invention is kept separated from other formulation ingredients in an aerosol container, and wherein said composition of the invention functions as a propellant. Additionally, the present application further provides a process for producing aerosol products comprising the step of adding only a composition of the invention to an aerosol package, wherein said composition functions as the active ingredient (e.g., a duster, or a cooling or freezing spray).
The present application further provides a process for converting heat from a heat source to mechanical energy, comprising heating a working fluid comprising a composition of the invention and thereafter expanding the heated working fluid. In the process, heating of the working fluid uses heat supplied from the heat source; and expanding of the heated working fluid generates mechanical energy as the pressure of the working fluid is lowered.
The process for converting heat may be a subcritical cycle, a trans-critical cycle, or a supercritical cycle. In a transcritical cycle, the working fluid is compressed to a pressure above its critical pressure prior to being heated, and then during expansion the working fluid pressure is reduced to below its critical pressure. In a super critical cycle, the working fluid remains above its critical pressure for the complete cycle (e.g., compression, heating, expansion and cooling).
Heat sources may include, for example, low pressure steam, industrial waste heat, solar energy, geothermal hot water, low-pressure geothermal steam (primary or secondary arrangements), or distributed power generation equipment utilizing fuel cells or prime movers such as turbines, microturbines, or internal combustion engines. One source of low-pressure steam could be the process known as a binary geothermal Rankine cycle. Large quantities of low-pressure steam can be found in numerous locations, such as in fossil fuel powered electrical generating power plants. Other sources of heat include waste heat recovered from gases exhausted from mobile internal combustion engines (e.g., truck or rail diesel engines or ships), waste heat from exhaust gases from stationary internal combustion engines (e.g., stationary diesel engine power generators), waste heat from fuel cells, heat available at combined heating, cooling and power or district heating and cooling plants, waste heat from biomass fueled engines, heat from natural gas or methane gas burners or methane-fired boilers or methane fuel cells (e.g., at distributed power generation facilities) operated with methane from various sources including biogas, landfill gas and coal-bed methane, heat from combustion of bark and lignin at paper/pulp mills, heat from incinerators, heat from low pressure steam at conventional steam power plants (to drive “bottoming” Rankine cycles), and geothermal heat.
In some embodiments, the process of converting heat is performed using an organic Rankine power cycle. Heat available at relatively low temperatures compared to steam (inorganic) power cycles can be used to generate mechanical power through Rankine cycles using working fluids as described herein. In some embodiments, the working fluid is compressed prior to being heated. Compression may be provided by a pump which pumps working fluid to a heat transfer unit (e.g., a heat exchanger or an evaporator) where heat from the heat source is used to heat the working fluid. The heated working fluid is then expanded, lowering its pressure. Mechanical energy is generated during the working fluid expansion using an expander. Examples of expanders include, but are not limited to, turbo or dynamic expanders, such as turbines, and positive displacement expanders, such as screw expanders, scroll expanders, and piston expanders. Examples of expanders also include rotary vane expanders.
Mechanical power can be used directly (e.g., to drive a compressor) or be converted to electrical power through the use of electrical power generators. In a power cycle where the working fluid is re-used, the expanded working fluid is cooled. Cooling may be accomplished in a working fluid cooling unit (e.g., a heat exchanger or a condenser). The cooled working fluid can then be used for repeated cycles (i.e., compression, heating, expansion, etc.). The same pump used for compression may be used for transferring the working fluid from the cooling stage.
The present application further provides a method for detecting a leak from a container comprising sampling the air in the vicinity of the container and detecting at least one additional compound of a composition provided herein with means for detecting the leak, wherein a composition of the present invention is contained inside the container. The term “in the vicinity of” refers to within 12 inches of the outside surface of the container. Alternatively, in the vicinity may be within 6 inches, within 3 inches or within one inch of the outside surface of the container.
A container may be any known container or system or apparatus that is filled with a composition of the inventor. A container may include, but is not limited to, a storage container, a transport container, an aerosol can, a fire extinguishing system, a chiller apparatus, a heat pump apparatus, heat transfer container, and a power cycle apparatus (e.g., an organic Rankine cycle system).
Means for detecting a leak may be performed using any known sensor designed to detect leaks. In particular, means for detecting the leak includes, but is not limited to, electrochemical, corona discharge, and mass spectroscopic leak detectors.
The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes, and are not intended to limit the invention in any manner.
SbCl5 (10.5 g) was added to a 210 mL Hastelloy C reactor, followed by HF (49 g). The reaction mixture was heated at 100° C. for 1 hour and then cooled to 0° C. Hexachlorobutadiene (30 g) was added to the reactor and the reaction mixture was heated to 100° C. The reaction rate was indicated by pressure increase and stabilization of the pressure indicated completion of the reaction. Similar reactions were also performed using TaCl5 catalyst or NbCl4 catalyst. Results of the comparative processes are provided in Table 1. The reactions performed using TaCl5 and NbCl4 were found to stereoselectively produce (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene in a ratio of greater than about 99:1 (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene:(E)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
1. In some embodiments, the present application provides a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising reacting hexachlorobutadiene with hydrofluoric acid in the presence of a transition metal catalyst, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
2. The process of embodiment 1, wherein the transition metal catalyst is a Group V transition metal catalyst.
3. The process of embodiment 1 or 2, wherein the transition metal catalyst is selected from a tantalum catalyst, a niobium catalyst, or a tantalum-niobium catalyst.
4. The process of embodiment 1 or 2, wherein the transition metal catalyst is a tantalum catalyst.
5. The process of embodiment 1 or 2, wherein the transition metal catalyst is a tantalum halide catalyst.
6. The process of embodiment 1 or 2, wherein the transition metal catalyst is tantalum (V) chloride.
7. The process of embodiment 1 or 2, wherein the transition metal catalyst is a niobium catalyst.
8. The process of embodiment 1 or 2, wherein the transition metal catalyst is a niobium halide catalyst.
9. The process of embodiment 1 or 2, wherein the transition metal catalyst is niobium (V) chloride or niobium (IV) chloride.
10. The process of embodiment 1 or 2, wherein the transition metal catalyst is a mixture of a tantalum catalyst and a niobium catalyst.
11. The process of any one of embodiments 1 to 10, wherein a molar excess of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
12. The process of any one of embodiments 1 to 10, wherein about 20 to about 30 molar equivalents of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
13. The process of any one of embodiments 1 to 12, wherein about 0.1 to about 0.3 molar equivalents of the transition metal catalyst is used based on 1 molar equivalent of hexachlorobutadiene.
14. The process of any one of embodiments 1 to 13, wherein the process is performed a temperature of from about 110° C. to about 135° C.
15. The process of embodiment 1, wherein the process comprises:
i) adding the transition metal catalyst to the hydrofluoric acid to form a first mixture; and
ii) adding the hexachlorobutadiene to the first mixture to form a second mixture.
16. The process of embodiment 15, wherein the first mixture is heated to a temperature of from about 110° C. to about 140° C.
17. The process of embodiment 16, further comprising cooling the first mixture to a temperature of from about −10° C. to about 10° C. prior to performing step ii).
18. The process of embodiment 17, wherein the hexachlorobutadiene is added to the first mixture at the temperature of from about −10° C. to about 10° C. to form the second mixture.
19. The process of embodiment 18, further comprising heating the second mixture to a temperature of from about 110° C. to about 140° C.
20. In some embodiments, the present application further provides a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) adding tantalum (V) chloride to hydrofluoric acid to form a first mixture;
ii) heating the first mixture to a temperature of from about 110° C. to about 120° C.;
iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;
iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and
v) heating the second mixture to a temperature of from about 110° C. to about 120° C.
21. In some embodiments, the present application further provides a process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) adding niobium (V) chloride to hydrofluoric acid to form a first mixture;
ii) heating the first mixture to a temperature of from about 125° C. to about 135° C.;
iii) cooling the first mixture to a temperature of from about −10° C. to about 10° C.;
iv) adding hexachlorobutadiene to the first mixture to form a second mixture; and
v) heating the second mixture to a temperature of from about 125° C. to about 135° C.
22. The process of embodiment 20 or 21, wherein a molar excess of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
23. The process of any one of embodiments 20 to 22, wherein about 20 to about 30 molar equivalents of hydrofluoric acid is used based on 1 molar equivalent of hexachlorobutadiene.
24. The process of any one of embodiments 20 to 23, wherein about 0.1 to about 0.3 molar equivalents of the catalyst is used based on 1 molar equivalent of hexachlorobutadiene.
25. The process of any one of embodiments 1 to 24, wherein the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is performed as a liquid phase process.
26. The process of any one of embodiments 1 to 25, wherein the process of preparing 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene is performed in the absence of an additional solvent component.
27. The process of any one of embodiments 1 to 26, further comprising reacting the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene with a base in the presence of an alkali metal halide and a quaternary (C4-12 alkyl)ammonium salt to form perfluorobut-2-yne.
28. The process of embodiment 27, wherein the base is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof.
29. The process of embodiment 27, wherein the base is an aqueous basic solution.
30. The process of embodiment 27, wherein the alkali metal halide is sodium chloride.
31. The process of any one of embodiments 27 to 30, wherein the quaternary (C4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraoctylammonium chloride, tetraoctylammonium bromide, tetraoctylammonium hydrogen sulfate, trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.
32. The process of any one of embodiments 27 to 30, wherein the quaternary (C4-12 alkyl)ammonium salt is a trioctylmethylammonium salt.
33. The process of any one of embodiments 27 to 30, wherein the quaternary (C4-12 alkyl)ammonium salt is selected from the group consisting of tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium hydrogen sulfate.
34. The process of any one of embodiments 27 to 33, wherein about 1 to about 1.5 molar equivalents of base is used based on one molar equivalent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
35. The process of any one of embodiments 27 to 34, wherein the reaction is performed at a temperature of from about 30° C. to about 60° C.
36. The process of any one of embodiments 27 to 35, further comprising reacting the perfluorobut-2-yne with hydrogen in the presence of a hydrogenation catalyst to form 1,1,1,4,4,4-hexafluoro-2-butene.
37. The process of embodiment 36, wherein the hydrogenation catalyst is Lindlar's catalyst.
38. The process of embodiment 36 or 37, wherein about 0.5 to about 4 percent by weight of the hydrogenation catalyst is used based on the weight of perfluorobut-2-yne.
39. The process of any one of embodiments 36 to 38, wherein the reacting is performed at about room temperature.
40. The process of any one of embodiments 36 to 39, wherein greater than about 95% of the 1,1,1,4,4,4-hexafluoro-2-butene is (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
41. The process of any one of embodiments 36 to 39, wherein the process of preparing 1,1,1,4,4,4-hexafluoro-2-butene is performed as a liquid phase process.
42. The process of any one of embodiments 36 to 41, wherein the process of preparing 1,1,1,4,4,4-hexafluoro-2-butene is performed in the absence of an additional solvent component.
43. The process of any one of embodiments 1 to 42, wherein greater than about 99.5 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
44. The process of any one of embodiments 1 to 42, wherein greater than about 99.9 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
45. In some embodiments, the present application further provides a process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of tantalum (V) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium chloride to form a second composition comprising perfluorobut-2-yne; and
iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
46. In some embodiments, the present application further provides a process of preparing a composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene, comprising:
i) reacting hexachlorobutadiene with hydrofluoric acid in the presence of niobium (IV) chloride to form a first composition comprising 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, wherein greater than about 99 mole percent of the 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene produced is (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene;
ii) reacting the first composition with sodium hydroxide in the presence of sodium chloride and trioctylmethylammonium salt chloride to form a second composition comprising perfluorobut-2-yne; and
iii) reacting the second composition in the presence of a hydrogenation catalyst to form the composition comprising (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
47. The process of any one of embodiments 1 to 46, wherein the process is performed as a one-pot process.
48. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
49. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
1,1,1,2,2,4,4,4-octafluorobutane;
wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
wherein the composition is prepared according to the process of any one of embodiments 1 to 47.
50. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene.
51. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 98 mole percent (Z)-2-chloro-1,1,1,4,4,4-hexafluoro-2-butene; and
wherein the composition is prepared according to the process of any one of embodiments 1 to 47.
52. In some embodiments, the present application further provides a composition, comprising:
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne.
53. In some embodiments, the present application further provides a composition, comprising:
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne; and
wherein the composition is prepared according to the process of any one of embodiments 27 to 47.
54. In some embodiments, the present application further provides a composition, comprising:
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne.
55. In some embodiments, the present application further provides a composition, comprising:
i) perfluorobut-2-yne; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent perfluorobut-2-yne; and
wherein the composition is prepared according to the process of any one of embodiments 27 to 47.
56. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
57. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
wherein the composition is prepared according to the process of any one of embodiments 36 to 47.
58. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene.
59. In some embodiments, the present application further provides a composition, comprising:
i) (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
ii) one or more additional compounds selected from the group consisting of:
wherein the composition comprises greater than about 99 mole percent (Z)-1,1,1,4,4,4-hexafluoro-2-butene; and
wherein the composition is prepared according to the process of any one of embodiments 36 to 47.
It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be appreciated by those persons having ordinary skill in the art(s) to which the present invention relates that any of the features described herein in respect of any particular aspect and/or embodiment of the present invention can be combined with one or more of any of the other features of any other aspects and/or embodiments of the present invention described herein, with modifications as appropriate to ensure compatibility of the combinations. Such combinations are considered to be part of the present invention contemplated by this disclosure.
This application claims the benefit of U.S. Provisional Application Ser. No. 62/537,784, filed Jul. 27, 2017, the disclosure of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62537784 | Jul 2017 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 16047515 | Jul 2018 | US |
| Child | 17034472 | US |
