Hydrofluoroolefins and methods for using same

Abstract

The following general formula (II): R f (CFH) n CF=CHX (II) [In the formula, R f is a straight, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen, n is 0 or 1, and X is Cl or Br, with the proviso that R f When is CF3, n is 1.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to brominated or chlorinated hydrofluoroolefins and methods for making and using same, and to working fluids containing them. [Background technology]

[0002] Various hydrofluoroolefin compounds are described, for example, in Md. J. Alam et al., International Journal of Refrigeration 2018, 90, 174-180, as well as in U.S. Patent Application Publication No. 2017 / 0369668 and U.S. Patent No. 8,642,819. Summary of the Invention

[0003] In some embodiments, a composition is provided, the composition comprising: The following structural formula (I): (H) n -R f -(CFH) m -CF=CHX (I) [In the formula, R f is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen, n is 0 or 1, m is 0 or 1, m+n=0 or 1, and X is Cl or Br; provided that X is Cl and R f is CF3, m is 1, X is Br, and R f is CF3, m is 1, and R f When m is cyclic, m+n=0. The composition further comprises a contaminant. The hydrofluoroolefin is present in the composition in an amount of at least 25 wt.%, based on the total weight of the composition.

[0004] In some embodiments, a hydrofluoroolefin compound is provided. The composition has the following general formula (II): R f (CFH) n CF=CHX (II) [In the formula, R f is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen, n is 0 or 1, and X is Cl or Br, with the proviso that R f When is CF3, n is 1.

[0005] In some embodiments, a method for removing contaminants from a substrate is provided. The method comprises: (H) n -R f -(CFH) m -CF=CHX (I) [R f is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen, n is 0 or 1, m is 0 or 1, m+n=0 or 1, and X is Cl or Br, with the proviso that X is Cl and R f is CF3, m is 1, X is Br, and R f is CF3, m is 1, and R f where m+n=0 when n is cyclic. The contaminant comprises a long chain hydrocarbon alkane.

[0006] The above summary of the present disclosure is not intended to describe each embodiment of the present disclosure. The details of one or more embodiments of the present disclosure are also set forth in the following description. Other features, objects, and advantages of the present disclosure will become apparent from the specification and claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The ever-increasing demand for reliability, continued miniaturization, and the increasing number of failures in electronic components manufactured using unclean methods have all combined to drive increased attention to the use of cleaning solvents in electronics manufacturing. The rapid increase in demand for industrial and consumer electronic products has led to a boom in the electronics industry. Cleaning solvents are a type of solvent that is used in the production of such industrial and consumer electronic products, such as the common manufacturing greases and oils (e.g., those of formula C n H 2n+2 Fluorinated cleaning solvents are specifically designed to reliably dissolve hydrocarbons (hydrocarbons having a molecular weight of 100 or less). Fluorinated cleaning solvents exhibit high levels of hydrocarbon solubility and are well suited for such applications due in part to their low flammability, high density, low viscosity, low surface tension, and high vapor pressure which results in rapid evaporation from the parts after use. Furthermore, in sharp contrast to hydrocarbon solvents, fluorinated cleaning solvents minimize the amount of residue left on the parts after cleaning.

[0008] Currently, fluids used to dissolve and remove such greases and oils (i.e., long chain hydrocarbons) or other organics from surfaces contain fluid blends including, for example, trans-di-chloro-ethylene, 1,1,1-trichloroethane (TCA), trichloroethylene, and dichloromethane. With respect to such fluid blends, one drawback to this approach is the tendency for the composition ratios to change over the life of the cleaning fluid. This change in composition ratio in turn creates safety concerns and also impairs the performance of the cleaning fluid. Therefore, a single composition cleaning fluid that is non-toxic, non-flammable, and has high hydrocarbon solubility would be of significant benefit to the electronics cleaning industry. Furthermore, some of the materials currently used are regulated by the Montreal Protocol as ozone depleting substances or have toxicity concerns.

[0009] In view of the increasing demand for environmentally friendly and less toxic chemical compounds, there is a need for new long chain hydrocarbon alkane cleaning fluids that have low environmental impact and low toxicity in addition to strong cleaning capabilities. Furthermore, such cleaning fluids should ideally behave as single molecules (as opposed to blends) and have a wide boiling range. Finally, such cleaning fluids should be capable of being manufactured using cost-effective methods.

[0010] Generally, the present disclosure provides a new class of compounds useful as cleaning fluids (or components of cleaning fluids). The compounds are brominated or chlorinated hydrofluoroolefins (HFOs) that provide similar or better cleaning and physical properties to existing cleaning fluids, but generally have lower atmospheric lifetimes and global warming potentials, resulting in a more acceptable environmental profile. Furthermore, the brominated or chlorinated hydrofluoroolefins of the present disclosure can function as single molecules (as opposed to blends), have a wide boiling range (e.g., 30-150 degrees Celsius), and can be produced cost-effectively.

[0011] As used herein, "linked heteroatom" means an atom other than carbon (e.g., oxygen, nitrogen, or sulfur) that is bonded to at least two carbon atoms in a carbon chain (straight or branched or in a ring) to form a carbon-heteroatom-carbon linkage.

[0012] As used herein, "halogenated" (with respect to a compound or molecule, such as in "halogenated HFO") means that there is a halogen atom bonded to at least one carbon.

[0013] As used herein, "fluoro" (with respect to a group or moiety, such as in "fluoroalkylene" or "fluoroalkyl" or "fluorocarbon") or "fluorinated" means (i) partially fluorinated, having at least one hydrogen atom bonded to a carbon, or (ii) perfluorinated.

[0014] As used herein, "perfluoro" (e.g., with respect to a group or moiety, such as in "perfluoroalkylene" or "perfluoroalkyl" or "perfluorocarbon") or "perfluorinated" means fully fluorinated, and unless otherwise indicated, there are no carbon-bonded hydrogen atoms available for replacement with fluorine.

[0015] As used herein, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the accompanying embodiments, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0016] As used herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0017] Unless otherwise indicated, all numbers expressing quantities or ingredients, measurements of properties, and the like used in the specification and embodiments are to be understood in all instances as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and accompanying list of embodiments may vary depending upon the desired properties one of ordinary skill in the art would obtain utilizing the teachings of the present disclosure. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques, which is not intended to limit the application of the doctrine of equivalents to the scope of the claimed embodiments.

[0018] In some embodiments, the present disclosure provides a compound of formula (I): (H) n -R f -(CFH) m -CF=CHX (I) [In the formula, R fis a linear, branched, or cyclic perfluoroalkyl group having 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1, m is 0 or 1; m+n=0 or 1; X is Cl or Br; however, X is Cl and R f When is CF3, m is 1; X is Br and R f When is CF3, m is 1; R f When is cyclic, m+n=0.

[0019] In some embodiments, the particular hydrofluoroolefin of structural formula (I) has the following structural formula: CF2HCF2CF2CF=CHCl (IA) or CF2H(CF2) n CF=CHBr (IB) In one embodiment, the compound may include a hydrofluoroolefin having the formula:

[0020] In some embodiments, the present disclosure provides a compound having the following structural formula (II): R f (CFH) n CF=CHX (II) [In the formula, R f is a straight-chain, branched-chain, or cyclic perfluoroalkyl group having 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1, X is Cl or Br; however, R fWhen is CF3, n is 1.

[0021] In some embodiments, the particular hydrofluoroolefin of structural formula (II) has the following structural formula: R f CF=CHCl (IIA) [In the formula, R f is a straight-chain, branched-chain, or cyclic perfluoroalkyl group having 2-6, 2-5, 2-4, or 2-3 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen. R f CF=CHCl (IIB) [In the formula, R f is a perfluoroalkyl group having 2 to 3 carbon atoms. R f CF=CHBr (IIC) [In the formula, R f is a straight-chain, branched-chain, or cyclic perfluoroalkyl group having 2 to 6, 2 to 5, 2 to 4, or 2 to 3 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; or R f CF=CHBr(IID) [In the formula, R f is a perfluoroalkyl group having 2 to 3 carbon atoms.

[0022] For purposes of this disclosure, it is understood that any of the hydrofluoroolefin compounds, regardless of what is shown in either the general formula or chemical structure, may include E isomers, Z isomers, or mixtures of E and Z isomers.

[0023] In some embodiments, any of the above linked heteroatoms may be a secondary O heteroatom, where O is bonded to two carbon atoms. In some embodiments, any of the above linked heteroatoms may be a tertiary N heteroatom, where N is bonded to three perfluorinated carbon atoms.

[0024] In some embodiments, any of the above hydrofluoroolefins may have excellent hydrocarbon solubility, making them highly suitable for use as cleaning solvents. In this regard, in some embodiments, any of the above hydrofluoroolefins may have a solubility coefficient defined as follows: Solubility Factor (SF) = ((LSH / 14)-1)-3.5((T-70) / 70) 2 +0.643 where LSH is determined according to the Maximum Soluble Hydrocarbon Test of the Examples of the present disclosure, and T is the normal boiling point of the fluid (in degrees Celsius). In some embodiments, the LSH of the hydrofluoroolefins increases in non-negative integer increments and can be 14 to 25, 17 to 23, or 17 to 21. In some embodiments, any of the above hydrofluoroolefins can have a solubility factor (SF) greater than 0, greater than 0.1, 0.2, 0.5, 1.0, 1.1, or greater than 1.2.

[0025] In some embodiments, the fluorine content of the hydrofluoroolefin compounds of the present disclosure may be sufficient to render the compounds non-flammable according to the ASTM D-3278-96 e-1 test method ("Flash Point of Liquids by Small Scale Closed Cup Apparatus").

[0026] In various embodiments, representative examples of compounds of general formula (I) include: [ka] [ka]

[0027] In various embodiments, representative examples of compounds of general formula (II) include: [ka] [ka]

[0028] In some embodiments, the hydrofluoroolefins of the present disclosure may be useful over a wide operating temperature range. In this regard, in some embodiments, the hydrofluoroolefins of the present disclosure may have a boiling point of 30, 40, or 50 degrees Celsius or more and 150, 140, 130, 120, 110, 100, 90, or 80 degrees Celsius or less.

[0029] In some embodiments, the hydrofluoroolefins of the present disclosure may be hydrophobic, relatively unreactive chemically, and thermally stable. Hydrofluoroolefin compounds may have low environmental impact. In this regard, the hydrofluoroolefin compounds of the present disclosure may have a global warming potential (GWP) of less than 200, 150, 100, 50, or less than 10. As used herein, GWP is a relative measure of the global warming potential of a compound based on the structure of the compound. The GWP of a compound was defined by the Intergovernmental Panel on Climate Change (IPCC) in 1990 and revised in 2007, and is calculated as the warming caused by the release of 1 kilogram of the compound relative to the warming caused by the release of 1 kilogram of CO2 over a specific integration time horizon (ITH).

number

[0030] In this formula, a iis the radiative forcing (change in radiation flux through the atmosphere due to the IR absorbance of that compound) per unit mass increase of the compound in the atmosphere, C is the atmospheric concentration of the compound, τ is the atmospheric lifetime of the compound, t is time, and i is the compound of interest. A commonly accepted ITH is 100 years, which represents a compromise between short-term effects (20 years) and long-term effects (500 years or more). The concentration of organic compound i in the atmosphere is assumed to follow pseudo-first-order kinetics (i.e., exponential decay). The concentration of CO2 over the same time interval incorporates a more complex model of exchange and removal of CO2 from the atmosphere (the Bern carbon cycle model).

[0031] In some embodiments, the brominated or chlorinated hydrofluoroolefin compounds of the present disclosure can be synthesized by first reducing a perfluorinated acid fluoride with a suitable reducing agent, such as NaBH4 or LiAlH4, to give an alcohol. The alcohol can also be prepared by the addition of methanol to a perfluorinated olefin in the presence of a radical initiator (an example of such an initiator is tert-amylperoxy-2-ethylhexanoate (TAPEH, available from Arkema, Crosby, TX) or LUPEROX (TAPEH, available from Arkema, Crosby, TX). 575), lauryl peroxide, tert-butyl peroxide, tert-amylperoxy-2-ethylhexyl carbonate, and mixtures thereof. Subsequent conversion to triflates or nonaflates occurs by reaction with CF3SO2F or CF3CF2CF2CF2SO2F in the presence of a base (e.g., NaOH, KOH, Na2CO3, or K2CO3). The resulting triflates or nonaflates can then be converted to their respective chlorides or bromides by displacement with LiCl or LiBr, respectively, in a polar aprotic solvent (e.g., DMF, NMP, diethyl ether, THF, dioxane, diglyme, or tetraglyme). The resulting chlorides or bromides are then subjected to aqueous base (e.g., 50% KOH or NaOH) with a catalytic amount of a phase transfer catalyst, such as tetrabutylammonium chloride, to facilitate dehydrofluorination to give the desired hydrochloro(bromo)fluoroolefins.

[0032] In some embodiments, the present disclosure is also directed to a working fluid comprising the hydrofluoroolefin compound as a major component. For example, the working fluid may comprise at least 25% by weight, at least 50% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or at least 99% by weight of the hydrofluoroolefin compound, based on the total weight of the working fluid. In addition to the hydrofluoroolefin compound, the working fluid may comprise one or more of the following components: alcohols, ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, oxiranes, aromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrochloroolefins, hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof, in a total amount of up to 75% by weight, up to 50% by weight, up to 30% by weight, up to 20% by weight, up to 10% by weight, or up to 5% by weight, based on the total weight of the working fluid. Such additional components may be selected to modify or enhance the properties of the composition for a particular application.

[0033] In some embodiments, the present disclosure relates to a cleaning composition comprising one or more of the hydrofluoroolefin compounds of the present disclosure. When used, the cleaning composition can function to remove (e.g., dissolve) contaminants from the surface of a substrate. For example, it can remove materials such as light hydrocarbon contaminants; high molecular weight hydrocarbon contaminants such as mineral oil and grease; fluorocarbon contaminants such as perfluoropolyethers, bromotrifluoroethylene oligomers (gyroscope fluids), and chlorotrifluoroethylene oligomers (hydraulic oils, lubricants); silicone oils and greases; solder flux; particulates; water; and other contaminants encountered in cleaning precision, electronic, metal, and medical equipment. In some embodiments, the hydrofluoroolefin compounds of the present disclosure can be particularly suitable for removing long-chain hydrocarbon alkane contaminants.

[0034] In some embodiments, the cleaning composition of the present disclosure may include one or more co-solvents. In some embodiments, the hydrofluoroolefin compound may be present in the cleaning composition in an amount greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, greater than 90 wt%, or greater than 95 wt%, based on the total weight of the hydrofluoroolefin compound and the co-solvent.

[0035] In exemplary embodiments, the co-solvent may include an alcohol, an ether, an alkane, an alkene, a haloalkene, a perfluorocarbon, a perfluorinated tertiary amine, a perfluoroether, a cycloalkane, an ester, a ketone, an oxirane, an aromatic, a haloaromatic, a siloxane, a hydrochlorocarbon, a hydrochlorofluorocarbon, a hydrofluorocarbon, a hydrofluoroolefin, a hydrochloroolefin, a hydrochlorofluoroolefin, a hydrofluoroether, or a mixture thereof. Representative examples of co-solvents that can be used in the cleaning compositions include methanol, ethanol, isopropanol, t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether, 1,2-dimethoxyethane, cyclohexane, 2,2,4-trimethylpentane, n-decane, terpenes (e.g., a-pinene, camphene, and limonene), trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone, naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene, bis(trifluoromethyl)benzene, hexamethyldisiloxane, octamethyltrisiloxane, perfluorohexane ... Fluoroheptane, perfluorooctane, perfluorotributylamine, perfluoro-N-methylmorpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane, 1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane, 1,1,1,2,2,4-hexafluorobutane, 1-trifluoromethyl-1,2,2-trifluorocyclobutane, 3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane, or mixtures thereof.Such co-solvents can be selected, for example, to modify or enhance the solubility characteristics of the cleaning composition for a particular application and can be utilized in a ratio (co-solvent to hydrofluoroolefin compound) such that the resulting composition has no flash point.

[0036] In various embodiments, the cleaning composition may include one or more surfactants. Suitable surfactants include those that are sufficiently soluble in the fluorinated olefin to promote the removal of contaminants by dissolving, dispersing or eliminating the contaminants. One useful class of surfactants is nonionic surfactants having a hydrophilic-lipophilic balance (HLB) value of less than about 14. Examples include ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, alkylary sulfonates, glycerol esters, ethoxylated fluoroalcohols, and fluorinated sulfonamides. A mixture of surfactants with complementary properties may be used, where one surfactant is added to the cleaning composition to promote the removal of oily contaminants and another surfactant is added to promote the removal of water-soluble contaminants. The surfactant, if used, may be added in an amount sufficient to promote the removal of contaminants. Typically, the surfactant is added in an amount of 0.1 to 5.0 weight percent, or about 0.2 to 2.0 weight percent, based on the total weight of the surfactant and the hydrofluoroolefin compound.

[0037] In some embodiments, if desired for a particular application, the cleaning composition may further include one or more dissolved or dispersed gas, liquid, or solid additives (e.g., carbon dioxide gas, stabilizers, antioxidants, or activated carbon).

[0038] In some embodiments, the disclosure is further directed to the above cleaning compositions in a post-wash state. In this regard, the disclosure is directed to any of the above cleaning compositions that contain one or more dissolved or dispersed (or otherwise contained) contaminants, such as any of the contaminants described above. In various embodiments, the dissolved or dispersed contaminants may include one or more long-chain hydrocarbon alkanes. The dissolved or dispersed contaminants may be present in the post-wash cleaning composition in an amount of 0.0001% to 0.1% by weight, 0.1 to 10% by weight, or 10 to 20% by weight, or at least 5% by weight, at least 10% by weight, or at least 20% by weight, based on the total weight of the hydrofluoroolefin compound and the contaminants.

[0039] In some embodiments, the cleaning compositions of the present disclosure can be used in either gas or liquid state (or both), and can utilize any known or future technique for "contacting" with the substrate. For example, liquid cleaning compositions can be sprayed or brushed onto the substrate, gas cleaning compositions can be sprayed onto the substrate, or the substrate can be exposed to either the gas or liquid composition. High temperature, ultrasonic energy, and / or agitation can be used to promote cleaning. A variety of different solvent cleaning techniques are described by BN Ellis in Cleaning and Contamination of Electronics Components and Assemblies, Electrochemical Publications Limited, Ayr, Scotland, 182-94 (1986), which is incorporated herein by reference in its entirety.

[0040] Both organic and inorganic substrates can be cleaned by the method of the present disclosure. Representative examples of substrates include metals, ceramics, glass, polycarbonates, polystyrene, acrylonitrile-butadiene-styrene copolymers, natural fibers (and fabrics derived from natural fibers), such as cotton, silk, fur, suede, leather, linen and wool, synthetic fibers (and fabrics), such as polyester, rayon, acrylic, nylon or blends thereof, fabrics including blends of natural and synthetic fibers, and composites of the aforementioned materials. In some embodiments, the method can be used for precision cleaning of electronic components (e.g., circuit boards), optical or magnetic media, or medical devices.

[0041] In some embodiments, the present disclosure relates to a method for cleaning a substrate. The cleaning method can be carried out by contacting a contaminated substrate with the cleaning composition described above.

[0042] LIST OF EMBODIMENTS 1. A composition comprising: The following structural formula (I): (H) n -R f -(CFH) m -CF=CHX (I) [In the formula, R f is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1, m is 0 or 1; m+n=0 or 1; X is Cl or Br; however, X is Cl and R f When is CF3, m is 1; X is Br and R f When is CF3, m is 1; R f is cyclic, m+n=0; and contaminants, A composition, wherein the hydrofluoroolefin is present in the composition in an amount of at least 25% by weight, based on the total weight of the composition. 2. The composition of embodiment 1, wherein the contaminant comprises a long chain hydrocarbon alkane. 3. The hydrofluoroolefin compound is represented by the following general formula (IA): CF2HCF2CF2CF=CHCl (IA) 3. The composition of embodiment 1 or 2, having the following structure: 4. The hydrofluoroolefin compound is represented by the following general formula (IB): CF2H(CF2) n CF=CHBr (IB)

[0024] wherein n is 0 or 2. 5. The composition of any one of embodiments 1 to 4, wherein the hydrofluoroolefin compound has a solubility coefficient greater than 0. EXAMPLES

[0043] Objects and advantages of the present disclosure are further illustrated by the following illustrative examples. Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and the rest of the specification are by weight, and all reagents used in the examples were obtained or are available from common chemical suppliers, such as Sigma-Aldrich Corp. (Saint Louis, MO, US), or can be synthesized by conventional methods.

[0044] The following abbreviations are used herein: mL = milliliter, L = liter, mol = mole, mmol = millimole, min = minute, hr = hour, d = day, g = gram, Å = angstrom, μm = micrometer (10 -6 m), °C = degrees Celsius, bp = boiling point, mp = melting point. "RT" or "room temperature" refers to ambient temperature of approximately 20 to 25 °C, with an average of 23 °C.

[0045] [Table 1]

[0046] Test Method Largest Soluble Hydrocarbon (LSH): The LSH of each hydrofluoroolefin compound is calculated by solubility in various molecular weight hydrocarbons (C n H 2n+2 , where n=9-24) in a weight ratio of about 1:1 to 1:2 hydrofluoroolefin:hydrocarbon. The LSH value is calculated using the formula C for the largest hydrocarbon that was compatible with the hydrofluoroolefin without exhibiting haze to the naked eye. n H 2n+2 The cleaning ability of the hydrofluoroolefin is reported as the value of n in the formula (I) above. A higher value of n is interpreted herein as indicating a higher ability of the hydrofluoroolefin to clean hydrocarbons.

[0047] Atmospheric lifetime: The atmospheric lifetime of the hydrobromofluoroolefins of Examples 1-3 was determined from the reaction rate with hydroxyl groups. The pseudo-first-order reaction rate of gaseous hydrobromofluoroolefins with hydroxyl groups against reference compounds such as chloromethane and ethane was measured in a series of experiments. The measurements were carried out in a 5.7 L heated FTIR gas cell with polished semiconductor grade quartz windows. Hydroxyl groups were generated by photolysis of ozone in the presence of water vapor using an Oriel Instruments UV Lamp, Model 66921 with a 480 W mercury-xenon bulb. The concentrations of hydrobromofluoroolefins and reference compounds were measured as a function of reaction time using an I-Series FTIR from Midac Corporation. The atmospheric lifetime was calculated from the reaction rate of hydrobromofluoroolefins with the reference compounds and the reported lifetime of the reference compounds as shown below:

number

[0048] Sample preparation Example 1: 1-Bromo-2,3,3,3-tetrafluoroprop-1-ene [ka] A 2 L three-necked round flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and dropping funnel was charged with pentafluoro-1-propanol (175 g, 1.17 mol), PBSF (360 g, 1.19 mol), and water (400 mL). No temperature increase was observed during the addition of the reagents. The dropping funnel was then charged with sodium hydroxide (200 g of a 50% solution in water). The 50% sodium hydroxide solution was then added dropwise to the stirred mixture at a rate that kept the internal reaction temperature below 50° C. Once all of the sodium hydroxide had been added, a white cloudy mixture was observed. After stirring for 16 hours without heating, the resulting reaction mixture was diluted by the addition of water (300 mL). Two layers were observed with a white solid at the interface. The bottom layer was filtered with the solid to give a filtrate that contained some aqueous layer but consisted mostly of the fluorochemical layer. The filtrate was then washed with water (300 mL) and the fluorochemical phase was collected to give 2,2,3,3,3-pentafluoropropyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (299 g, 57% yield). GC-FID analysis confirmed it to be 99% pure. The product was stored over 4 Å molecular sieves and used in the next step without further purification.

[0049] A 500 mL three-neck round bottom flask equipped with a magnetic stir bar, temperature probe, cold water condenser, and dropping funnel was charged with diglyme (200 mL). Lithium bromide (75.2 g, 866 mmol) was then added in portions and a temperature increase to 54° C. was observed. Once the temperature had decreased to 35° C., 2,2,3,3,3-pentafluoropropyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (200.1 g, 440 mmol) was added via the dropping funnel at a rate that avoided a reaction temperature exceeding 40° C. After the addition was complete, the resulting reaction mixture was heated to 60° C. and subsequently stirred for 2 days. The reaction mixture was then cooled to room temperature with stirring, followed by the addition of water (200 mL). The fluorous layer was collected and washed again with water (2×100 mL) to give the desired 3-bromo-1,1,1,2,2-pentafluoro-propane (75.5 g, 75% by weight, 60% yield). The isolated material was used in the next step without further purification.

[0050] Powdered potassium hydroxide (37.6 g of 85 wt% KOH powder, 570 mmol) and water (70 mL) were added to a two-necked round bottom flask equipped with a water-cooled reflux condenser, a magnetic stirring bar, and a rubber septum. After the addition of water, the temperature reached 65° C. The solution was allowed to cool to 35° C. with stirring, followed by the addition of tetrabutylammonium chloride (5.0 g, 18.0 mmol). 3-Bromo-1,1,1,2,2-pentafluoropropane (95.1 g at 78 wt% purity, 348 mmol) was then added dropwise via syringe over 15 minutes to the stirred mixture at 35° C. The resulting amber mixture was then stirred for 1 hour at the same temperature. GC-FID analysis of the fluorochemical phase indicated that approximately 92% of the starting material was converted. The reaction was stirred overnight at 35° C. The resulting reaction mixture was then allowed to cool to room temperature, followed by the addition of 100 mL of water. The fluorous phase was separated and analyzed by GC-FID, which showed that the mixture contained 98% of the desired 1-bromo-2,3,3,3-tetrafluoroprop-1-ene. Concentric tube distillation (34° C., 740 mm / Hg) afforded the desired 1-bromo-2,3,3,3-tetrafluoroprop-1-ene (42.4 g, 62% yield) as a colorless liquid. GC-MS analysis confirmed the identity of the purified composition.

[0051] Example 2: 1-Bromo-2,3,3,4,4,4-hexafluorobut-1-ene [ka] A 2 L 3-neck round flask equipped with a magnetic stir bar, temperature probe, cold water condenser, and dropping funnel was charged with heptafluoro-1-butanol (198.7 g, 993.4 mmol), PBSF (300.1 g, 993.4 mmol), and water (400 mL). No temperature increase was observed during the addition of the reagents. The dropping funnel was then charged with potassium hydroxide (167.2 g of a 50% solution in water). The potassium hydroxide solution was then added dropwise to the stirred mixture at a rate that kept the internal reaction temperature below 43° C. Once all of the potassium hydroxide had been added, a white cloudy mixture was observed. After stirring for 16 hours without heating, the resulting reaction mixture was diluted by the addition of water (300 mL). Two layers were observed with a white solid at the interface. The bottom layer was filtered with the solid to give a filtrate that contained some aqueous layer but consisted mostly of the fluorochemical layer. The filtrate was then washed with water (300 mL) and the fluorochemical phase was collected to give 2,2,3,3,4,4,4-heptafluorobutyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (415 g, 93 wt %, 81% yield). The wt % purity of the desired product was determined by GC-FID analysis. The product was stored over 4 Å molecular sieves and used in the next step without further purification.

[0052] A 500 mL three-neck round bottom flask equipped with a magnetic stir bar, temperature probe, cold water condenser, and dropping funnel was charged with diglyme (200 mL). Lithium bromide (70.2 g, 808 mmol) was then added in portions and a temperature increase to 50° C. was observed. Once the temperature had dropped to 35° C., 2,2,3,3,4,4,4-heptafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (197.1 g, 415 mmol) was added via the dropping funnel at a rate that avoided a reaction temperature exceeding 40° C. After the addition was complete, the resulting reaction mixture was heated to 60° C. with stirring. After 16 hours, the reaction mixture was then cooled to room temperature with stirring, followed by the addition of water (200 mL). The fluorous layer was collected and washed again with water (2×100 mL) to give the desired 4-bromo-1,1,1,2,2,3,3-heptafluorobutane (93.7 g, 81% by weight, 71% yield). The isolated material was used in the next step without further purification.

[0053] Powdered potassium hydroxide (54.6 g of 85 wt% KOH powder, 827 mmol) and water (70 mL) were added to a two-necked round-bottom flask equipped with a water-cooled reflux condenser, a magnetic stirring bar, and a rubber septum. After the addition of water, the temperature reached above 65° C. The solution was allowed to cool to 30° C. with stirring, after which tetrabutylammonium chloride (5.0 g, 18 mmol) was added. The resulting mixture was then slowly heated to 35° C., followed by the dropwise addition of 4-bromo-1,1,1,2,2,3,3-heptafluoro-butane (134.3 g at 81 wt% purity, 414 mmol) via syringe over 15 minutes. The resulting amber mixture was then stirred at the same temperature for 1 hour. GC-FID analysis of the fluorochemical phase showed that approximately 92% of the starting material was converted. After stirring overnight at 35° C., the resulting reaction mixture was allowed to cool to room temperature, followed by the addition of 100 mL of water. The fluorous phase was separated and analyzed by GC-FID, which showed that the mixture contained 88% of the desired 1-bromo-2,3,3,4,4,4-hexafluorobut-1-ene. Concentric tube distillation (57° C., 740 mm / Hg) afforded the desired 1-bromo-2,3,3,4,4,4-hexafluorobut-1-ene (85.1 g, 85% yield) as a colorless liquid. GC-MS analysis confirmed the identity of the purified composition.

[0054] Example 3: 1-Bromo-2,3,3-trifluoroprop-1-ene [ka] A 2 L three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and dropping funnel was charged with 2,2,3,3-tetrafluoropropan-1-ol (200 g, 1.51 mol), PBSF (457.2 g, 1.51 mol), and water (400 mL). No temperature increase was observed during the addition of the reagents. The dropping funnel was then charged with potassium hydroxide (238 g of a 50% solution in water, 2.12 mol). The 50% potassium hydroxide solution was then added dropwise to the stirred mixture at a rate that kept the internal reaction temperature below 43° C. Once all of the potassium hydroxide had been added, a white cloudy mixture was observed. After stirring for 16 hours without heating, the resulting reaction mixture was diluted by the addition of water (300 mL). Two layers were observed with a white solid at the interface. The bottom layer was filtered with the solid to give a filtrate that contained some aqueous layer but consisted mostly of the fluorochemical layer. The filtrate was then washed with water (300 mL) and the fluorochemical phase was collected to give 2,2,3,3-tetrafluoropropyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (446 g, 87% by weight, 62% yield). The mass% purity of the product was confirmed by GC-FID analysis. The product was stored over 4 Å molecular sieves and used in the next step without further purification.

[0055] A 500 mL three-neck round bottom flask equipped with a magnetic stir bar, temperature probe, cold water condenser, and dropping funnel was charged with diglyme (200 mL). Lithium bromide (76.3 g, 879 mmol) was then added in portions and a temperature increase to 54° C. was observed. Once the temperature had dropped to 35° C., 2,2,3,3-tetrafluoropropyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (190 g, 86% by weight, 395 mmol) was added via the dropping funnel at a rate that avoided a reaction temperature exceeding 40° C. After the addition was complete, the resulting reaction mixture was heated to 60° C. with stirring. After 16 hours, the reaction mixture was then cooled to room temperature with stirring, followed by the addition of water (200 mL). The fluorous layer was collected and washed again with water (2×100 mL) to give the desired 3-bromo-1,1,2,2-tetrafluoropropane (72.4 g, 71% by weight, 69% yield). The isolated material was used in the next step without further purification.

[0056] To a two-necked round bottom flask equipped with a water-cooled reflux condenser, a magnetic stirring bar, and a rubber septum was added powdered potassium hydroxide (22.2 g of 85 wt % KOH powder, 336 mmol) and water (55 mL). After the addition of water, the temperature reached above 65° C. The solution was allowed to cool to 26° C. with stirring, followed by the addition of tetrabutylammonium chloride (2.1 g, 7.6 mmol). The resulting mixture was then slowly heated to 35° C., followed by the dropwise addition of 3-bromo-1,1,2,2-tetrafluoropropane (54 g at 65 wt % purity, 180 mmol) via syringe over a period of 5 minutes. The resulting amber mixture was then stirred at the same temperature for 16 hours. The resulting reaction mixture was then allowed to cool to room temperature, followed by the addition of 100 mL of water. The fluorochemical phase was separated and analyzed by GC-FID, which showed that the mixture contained 54% of the desired 1-bromo-2,3,3-trifluoroprop-1-ene. Concentric tube distillation (75° C., 740 mm / Hg) afforded the desired 1-bromo-2,3,3-trifluoroprop-1-ene (25.1 g, 58% yield) as a colorless liquid. GC-MS analysis confirmed the identity of the purified composition.

[0057] Example 4: 1-Bromo-2,3,3,4,4,5,5-heptafluoropent-1-ene [ka] A 2 L three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and dropping funnel was charged with 2,2,3,3,4,4,5,5-octafluoropentan-1-ol (200 g, 862 mmol), PBSF (270 g, 894 mmol), and water (400 mL). No temperature increase was observed during the addition of the reagents. The dropping funnel was then charged with sodium hydroxide (94.2 g of a 50% solution in water, 1.18 mol). The 50% sodium hydroxide solution was then added dropwise to the stirred mixture at a rate that kept the internal reaction temperature below 50° C. Once all the sodium hydroxide had been added, a white cloudy mixture was observed. After stirring for 16 hours without heating, the resulting reaction mixture was diluted by the addition of water (300 mL). Two layers were observed with a white solid at the interface. The bottom layer was filtered along with the solids to give a filtrate that contained some aqueous phase but consisted mostly of the fluorochemical phase. The filtrate was then washed with water (300 mL) and the fluorochemical phase was collected to give 2,2,3,3,4,4,5,5-octafluoropentyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (304.9 g, 85 wt %, 58% yield). The wt % purity of the product was confirmed by GC-FID analysis. The product was stored over 4 Å molecular sieves and used in the next step without further purification.

[0058] A 500 mL three-neck round bottom flask equipped with a magnetic stir bar, temperature probe, cold water condenser, and dropping funnel was charged with diglyme (150 mL). Lithium bromide (60.5 g, 697 mmol) was then added in portions and a temperature increase to 55° C. was observed. Once the temperature had dropped to 35° C., 2,2,3,3,4,4,5,5-octafluoropentyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (188 g, 366 mmol) was added via the dropping funnel at a rate that avoided a reaction temperature exceeding 40° C. After the addition was complete, the resulting reaction mixture was heated to 58° C. with stirring. After 16 hours, the reaction mixture was then cooled to room temperature with stirring followed by the addition of water (200 mL). The fluorous layer was collected and washed again with water (2×100 mL) to give the desired 5-bromo-1,1,2,2,3,3,4,4-octafluoropentane (105 g, 80% by weight, 78% yield). The isolated material was used in the next step without further purification.

[0059] To a two-necked round bottom flask equipped with a water-cooled reflux condenser, a magnetic stir bar, and a rubber septum was added powdered potassium hydroxide (45.0 g of 85 wt % KOH powder, 682 mmol) and water (50 mL). After the addition of water, the temperature reached above 65° C. The solution was allowed to cool to 30° C. with stirring, followed by the addition of tetrabutylammonium chloride (4.5 g, 16 mmol). The resulting mixture was then slowly heated to 35° C., followed by the dropwise addition of 5-bromo-1,1,2,2,3,3,4,4-octafluoropentane (100 g at 80 wt % purity, 271 mmol) via syringe over a period of 5 minutes. The resulting amber mixture was then heated to 60° C. and stirred at the same temperature for 16 hours. The resulting reaction mixture was then allowed to cool to room temperature, followed by the addition of 100 mL of water. The fluorochemical phase was separated and analyzed by GC-FID, which showed that greater than 99% of the 5-bromo-1,1,2,2,3,3,4,4-octafluoropentane starting material was converted and the mixture contained 95% of the desired 1-bromo-2,3,3,4,4,5,5-heptafluoropent-1-ene. Concentric tube distillation (110° C., 740 mm / Hg) afforded the desired 1-bromo-2,3,3,4,4,5,5-heptafluoropent-1-ene (41.4 g, 70% yield) as a colorless liquid. GC-MS analysis confirmed the identity of the purified composition.

[0060] Example 5: 1-Chloro-2,3,3,4,4,5,5,5-pent-1-ene [ka] A 5 L three-neck round bottom flask equipped with mechanical stirring, thermocouple, cold water condenser, and dropping funnel was charged with 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol (500 g, 2.0 mol), PBSF (604 g, 2.0 mol), and 2500 g water. 337 g of 50% KOH was added slowly via the dropping funnel at a rate that kept the temperature below 35° C. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered and the filtrate was added to a separatory funnel. The lower phase still contained 13.3% unreacted 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol and 4.0% PBSF. The reaction mixture was charged to a 2 L round bottom flask equipped with the above and 500 mL of water, 110 g of PBSF, and 81 g of 50% KOH were added. The mixture was stirred for 2 hours, filtered, phase separated and washed with water to give 625 g of 2,2,3,3,4,4,5,5,5-nonafluoropentyl 1,1,2,2,3,3,4,4,5-nonafluoropentane-1-sulfonate with a purity of 99% by gas chromatography.

[0061] A 1 L round bottom flask equipped with a magnetic stirrer, water condenser, N2 bubbler, thermocouple, and dropping funnel was charged with 1600 g of dimethylformamide and lithium chloride (25.7 g, 0.61 mol). An exotherm was observed. The flask was cooled to room temperature and 2,2,3,3,4,4,5,5,5-nonafluoropentyl 1,1,2,2,3,3,4,4,5-nonafluoropentane-1-sulfonate (215 g, 0.40 mol) was added and the flask was stirred at room temperature for 48 h. 1 L of water was added and the mixture was steam distilled to give 105.2 g of 5-chloro-1,1,1,2,2,3,3,4,4-nonafluoro-pentane with a purity of 98.8% by gas chromatography. The structure was confirmed by GC-MS.

[0062] A 200 mL round bottom flask equipped with a magnetic stirrer, water condenser, N2 bubbler, thermocouple, and heating mantle was charged with 23.2 g of 90% KOH and 25 g of water. The flask was cooled to room temperature. 2.5 g of tetrabutylammonium chloride and 5-chloro-1,1,1,2,2,3,3,4,4-nonafluoro-pentane (50 g, 0.19 mol) were added and the temperature was kept below 35° C. by an ice bath surrounding the flask. The mixture was stirred for 1 hour and allowed to phase separate to give 41 g of 1-chloro-2,3,3,4,4,5,5,5-pent-1-ene with a purity of 96.8%. The 1-chloro-2,3,3,4,4,5,5,5-pent-1-ene was combined with another batch prepared as above and fractionated to a purity of 99.9% as determined by F-NMR. The boiling point was about 64°C.

[0063] Example 6: 1-Chloro-2,3,3,4,4,4-but-1-ene [ka] A 3 L three-neck round bottom flask equipped with mechanical stirring, thermocouple, cold water condenser, and dropping funnel was charged with 2,2,3,3,4,4,4-heptafluorobutan-1-ol (350 g, 1.75 mol), PBSF (528 g, 1.75 mol), and 700 g water. 300 g of 50% KOH was added slowly via the dropping funnel at a rate that kept the temperature below 35° C. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered and the filtrate was added to a separatory funnel. The lower phase was washed with water to give 2,2,3,3,4,4,4-heptafluorobutyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (502 g, 69% pure by GC). The material was re-treated with 200 ml water and 50 g of 50% KOH and stirred for 2 hours. Phase separation and water washing gave 461 g of 2,2,3,3,4,4,4-heptafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate with a purity of 95.5% by gas chromatography.

[0064] A 3 L round bottom flask equipped with an overhead stirrer, water condenser, N2 bubbler, thermocouple, and addition funnel was charged with 1800 mL of dimethylformamide and lithium chloride (126.6 g, 2.98 mol). An exotherm was observed. The flask was cooled to room temperature and 2,2,3,3,4,4,4-heptafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (430 g, 0.89 mol) was added and the flask was heated to 50° C. and held for 16 hours. 1 L of water was added and the mixture was steam distilled to give 174.6 g of 4-chloro-1,1,1,2,2,3,3-heptafluoro-butane at 99.0% purity by gas chromatography. The structure was confirmed by GC-MS.

[0065] A 1 L round bottom flask equipped with a magnetic stirrer, water condenser, N2 bubbler, thermocouple, and dropping funnel was charged with sodium methoxide (50.4 g, 0.93 mol) dissolved in methanol (198 g, 6.2 mol). 4-Chloro-1,1,1,2,2,3,3-heptafluoro-butane (170 g, 0.78 mol) was added and the mixture was heated to 50° C. After 24 h, 38% of the starting material remained. An additional charge of sodium methoxide in the same methanol was added and held at 50° C. for an additional 2 h. The flask was cooled to room temperature and water was added. The lower phase was separated and fractionated to give 27.4 g of 1-chloro-2,3,3,4,4,4-hexafluoro-but-1-ene with a purity of >98.5% and a boiling point of about 37° C. The structure was confirmed by GC / MS and F-NMR.

[0066] Example 7: 1-Chloro-2,3,3-trifluoro-3-(trifluoromethoxy)prop-1-ene [ka] A 500 mL round bottom flask equipped with a dry ice bath, nitrogen bubbler, PFTE tubing with SWAGELOK fittings, condenser connected to a condenser, magnetic stir bar, and thermocouple was charged with sodium borohydride (37 g, 977.993 mmol) and diethylene glycol dimethyl ether (187.4 g, 1397 mmol). The flask was then cooled to -40°C, the condenser was set to -15°C, and perfluoromethoxypropionyl fluoride (214.9 g, 907.7 mmol) was fed slowly over 4 hours from an inverted cylinder using PTFE tubing with SWAGELOK fittings. The reaction was kept below -15°C during the addition. Upon completion of the addition, the dry ice bath was removed and the reaction was stirred for 16 hours. The reaction was quenched with methanol (98 g, 3058.52 mmol) over 2 hours. The reactor was stirred for an additional 30 minutes until off-gassing ceased. The reaction material was then transferred to a 1000 mL round bottom flask equipped with an overhead stirrer. While stirring the reaction, 200 mL of water was added to the flask followed by phosphoric acid (260 g, 928.631 mmol, 35 wt%) from the addition funnel over 45 minutes. The reaction was heated to 50° C. and stirred for 30 minutes, then cooled with dry ice, the phases were separated, and the lower phase was washed three times with water. 216 g of material, 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propan-1-ol, was recovered at 48 GC-FID area %. The recovered material was washed four more times. 124 g of 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propan-1-ol (124 g, 573.94 mmol, 63.23% yield) was recovered at 76 GC-FID area %.

[0067] A 500 mL round bottom flask equipped with a Claisen adapter, water condenser, dropping funnel, thermocouple, and overhead stirring apparatus was charged with 2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propan-1-ol (50 g, 175.89 mmol, 76 wt %), nonafluorobutanesulfonyl (1.05 equiv, 184.68 mmol), and water (70.2 g, 3900 mmol). An approximately 50 wt % KOH solution was prepared by dissolving potassium hydroxide (29 g, 516.889 mmol) in 30.2 g of water. The resulting solution was added dropwise via the dropping funnel. The reaction temperature was kept below 35° C. during the addition using a dry ice water bath. After the addition, the reaction was stirred at room temperature for 16 h. A sample of the reaction was washed with water and GC analysis revealed 12 GC-FID area % unconverted alcohol. An additional 15.8 g of PBSF was added and the reaction was stirred for 2 h. Final GC analysis showed 2 GC-FID area % unconverted alcohol. After removing solids by filtration through diatomaceous earth, [2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (42 g, 69.137 mmol, 39.308% yield) was recovered with a purity of 82% by GC. The recovered material was dried over molecular sieves.

[0068] A 250 mL round bottom flask equipped with a magnetic stir plate, water condenser, thermocouple, and addition funnel was charged with lithium chloride (9.62 g, 227 mmol) and N,N-dimethylformamide (24.1 g, 330 mmol) and stirred until a suspension formed. An additional 20 mL of dimethyl formamide (DMF) was added to aid in the decomposition of the lithium chloride. [2,2,3,3-tetrafluoro-3-(trifluoromethoxy)propyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (34.5 g, 56.8 mmol, 82%) was charged via the addition funnel. The addition proceeded slowly at first, but the rate of addition was increased as no exothermic reaction occurred. The reaction was allowed to stir and after 4 hours a small sample was washed with water, filtered, and analyzed by GC. The reaction was stirred for an additional 16 h since all reactants except for nonaflate, 7 GC-FID area %, had been converted. The reaction was quenched with water, transferred to a separatory funnel, and the lower phase was collected. A total of 10 g of 3-chloro-1,1,2,2-tetrafluoro-1-(trifluoromethoxy)propane (10 g, 35.394 mmol) was recovered, 83 GC-FID area %.

[0069] A 50 mL round bottom flask equipped with a thermocouple, magnetic stirring apparatus, water condenser, and addition funnel was charged with 3-chloro-1,1,2,2-tetrafluoro-1-(trifluoromethoxy)propane (10.5 g, 44.8 mmol, 100 wt%) and tetrabutylammonium chloride (0.5 g, 2 mmol, 100 wt%). Using the addition funnel, potassium hydroxide (12.11 g, 107.9 mmol, 50 wt%) was slowly charged to the reaction over 20 minutes, during which time the reaction turned yellow / orange. After the addition was complete, a slight exotherm was observed (33.3° C.). A sample was taken at 40 minutes and analyzed by GC. The results showed partial conversion to the olefin. The reaction was stirred for 16 hours, after which the reaction was quenched with water, phase separated, and washed with water. The material was passed through a 0.2 μm syringe filter and analyzed by GC. GC showed complete conversion of the starting material and 83 GC-FID area % of the desired material. The material was then purified by distillation and analyzed by GC, resulting in 99.6 GC-FID area % of the desired material in some cases. GC-MS data for 4.6 g of crude material confirmed the formation of 1-chloro-2,3,3-trifluoro-3-(trifluoromethoxy)prop-1-ene (2.6 g, 12 mmol).

[0070] Example 8: 4-(2-chloro-1-fluoro-vinyl)-2,2,3,3,5,5,6,6-octafluoro-morpholine [ka] A 3 L, three-necked round bottom flask equipped with an overhead stirrer, thermocouple, cold water condenser, dry N2 line, and addition funnel was charged with tetraethylene glycol dimethyl ether (800 g, 3.60 mol) and sodium borohydride (87.0 g, 2.30 mol). The mixture was stirred for 30 minutes to dissolve most of the sodium borohydride. A dry ice-water bath was added to cool the reaction mixture. When the reaction temperature had dropped to 10° C., 2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)acetyl fluoride (699.4 g, 2.14 mol), prepared by electrochemical fluorination of 4-morpholineethanol via a Simmons ECF cell of the type essentially described in U.S. Pat. No. 2,713,593 and REBanks, Preparation, Properties and Industrial Applications of Organofluorine Compounds, pages 19-43, Halsted Press, New York (1982), was added via a dropping funnel at a rate that kept the reaction temperature below 65° C. Upon complete addition of 2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)acetyl fluoride, the reaction mixture was heated to 80° C. and stirred overnight. The reaction mixture was cooled to room temperature and quenched by slow addition of methanol (155.8 g, 4.86 mol). The reaction mixture was then heated to 50° C. until off-gassing ceased. Then 1000 mL of 35% H3PO4 was added. The reaction mixture was heated to 50° C. to dissolve the salts formed. The reaction mixture was separated in a separatory funnel and the lower fluorochemical phase was washed with water. 697 g of crude product was obtained. GC-MS data shows that the crude product contained 74% of the desired 2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)ethanol. The resulting crude product was distilled from polyphosphoric acid.

[0071] A 3 L three-necked round flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and dropping funnel was charged with 2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)ethanol (434.0 g, 1.40 mol), 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (442.3 g, 1.46 mol), and water (560 g, 31.09 mol), with no apparent exotherm being observed. 50% aqueous KOH (300.3 g, 2.68 mol) was then added via the dropping funnel at a rate to keep the internal reaction temperature below 35° C. Once all the KOH had been added, the reaction mixture was stirred at 35° C. for 3 days. The reaction mixture was transferred to a separatory funnel and the resulting fluorochemical phase was separated and washed twice with water to give 779 g of crude product. GC-MS data showed 96% of the desired [2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)ethyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0072] Lithium chloride (55.6 g, 1.31 mol) and DMF (600 g, 8.21 mol) were mixed in a 2000 mL three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water bath, cold water condenser, dry N2 line, and dropping funnel. Once the exotherm had subsided, [2,2-difluoro-2-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)ethyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (738 g, 1.24 mol) was added via the dropping funnel while maintaining the reaction temperature below 40°C. Once the addition was complete, the mixture was stirred at 60°C overnight. The reaction mixture was cooled to room temperature and distilled. 406 g of crude product was obtained. GC / MS data showed it contained 97% of the desired 4-(2-chloro-1,1-difluoro-ethyl)-2,2,3,3,5,5,6,6-octafluoro-morpholine.

[0073] To a 1000 mL three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and addition funnel was added KOH (85%, 314 g, 4.76 mol) and water (318 g, 17.65 mol). Once the exotherm had subsided, tetrabutylammonium chloride (7.4 g, 0.03 mol) was added. 4-(2-chloro-1,1-difluoro-ethyl)-2,2,3,3,5,5,6,6-octafluoro-morpholine (278 g, 0.84 mol) was then added via the addition funnel while maintaining the reaction temperature below 20° C. After the addition of 4-(2-chloro-1,1-difluoro-ethyl)-2,2,3,3,5,5,6,6-octafluoro-morpholine was completed, the reaction mixture was heated to 60° C. for 2 days. The crude product was steam distilled to give 74 g of product, GC-MS data showed that the product contained 93% of the desired 4-[(E / Z)-2-chloro-1-fluoro-vinyl]-2,2,3,3,5,5,6,6-octafluoro-morpholine.

[0074] Example 9: 3-Chloro-1,1,2-trifluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-2-en-1-amine [ka] A 3 L, 3-neck round bottom flask equipped with an overhead stirrer, thermocouple, cold water condenser, dry N2 line, and addition funnel was charged with tetraethylene glycol dimethyl ether (201 g, 0.90 mol) and sodium borohydride (33 g, 0.87 mol). An exotherm was observed. The mixture was stirred for 30 minutes to dissolve most of the sodium borohydride. A dry ice-water bath was added to cool the reaction mixture. When the reaction temperature had dropped to 10° C., 2,2,3,3-tetrafluoro-3-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]propanoyl fluoride (290 g, 0.83 mol), prepared by electrochemical fluorination of methyl 3-[ethyl(methyl)amino]propanoate via a Simmons ECF cell of the type essentially described in U.S. Pat. No. 2,713,593 and REBanks, Preparation, Properties and Industrial Applications of Organofluorine Compounds, pages 19-43, Halsted Press, New York (1982), was added via a dropping funnel at a rate to keep the reaction temperature below 65° C. Upon complete addition of 2,2,3,3-tetrafluoro-3-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]propanoyl fluoride, the reaction mixture was heated to 80° C. and stirred overnight. The reaction mixture was quenched by slow addition of methanol (61.96 g, 1.93 mol). The reaction mixture was heated to 50° C. until no more off-gassing was observed. 450 ml of 35% H3PO4 was added and the reaction mixture was heated to 50° C. to dissolve the salts formed. The reaction mixture was transferred to a separatory funnel and the lower phase was separated and washed with water. 183 g of crude product was obtained, confirmed by GC-MS.

[0075] In a 1000 mL three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and addition funnel, 2,2,3,3-tetrafluoro-3-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]propan-1-ol (150 g, 0.45 mol), 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (138 g, 0.46 mmol), and water (300 g, 16.65 mol) were combined. KOH (55.5 g, 0.50 mol, 50 wt%) was added dropwise through the addition funnel at a rate that maintained the temperature in the flask below 35° C. After stirring for 16 h, the reaction mixture was filtered and transferred to a separatory funnel. Gas chromatography indicated approximately 50% conversion. The fluorochemical phase was transferred to a 600 mL Parr reactor, charged with additional KOH, and stirred at room temperature for 16 hours to achieve complete conversion. The reaction mixture was phase separated and filtered. 161 g of crude product was obtained. GC-MS data of the crude product showed that it contained 89% of the desired [2,2,3,3-tetrafluoro-3-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]propyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0076] Lithium chloride (66 g, 1.56 mol) and DMF (825 ml) were mixed in a 2 L three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and dropping funnel. [2,2,3,3-tetrafluoro-3-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]propyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (161 g, 0.26 mol) was added and the mixture was stirred at 57° C. for 2 days. The crude product was distilled through a Dean-Stark trap. 40 g of crude product was obtained. GC data showed that the crude product contained 80% of the desired 3-chloro-1,1,2,2-tetrafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)propan-1-amine.

[0077] In a 100 mL three-neck round bottom flask equipped with a magnetic stirrer, thermocouple, cold water condenser, and addition funnel, KOH (85%, 12.7 g, 0.19 mol) and water (12.7 g, 0.71 mol) were mixed. An exotherm was observed. Once the exotherm subsided, tetrabutylammonium chloride (0.9 g, 0.004 mol) was added. 3-Chloro-1,1,2,2-tetrafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)propan-1-amine (33.7 g, 0.096 mol) was then added slowly to the reaction flask via the addition funnel while maintaining the reaction temperature below 20° C. Once the addition of 3-chloro-1,1,2,2-tetrafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)propan-1-amine was completed. The reaction mixture was heated to 60° C. and held for 16 hours. 19 g of crude product was obtained by steam distillation. GC-GC data showed that the crude product contained 92% of the desired (E / Z)-3-chloro-1,1,2-trifluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-2-en-1-amine.

[0078] Example 10: 1-Chloro-2,3,4,4,4-pentafluoro-but-1-ene [ka] A 5 L three-neck round bottom flask equipped with mechanical stirring, thermocouple, cold water condenser, and dropping funnel was charged with 2,2,3,4,4,4-hexafluorobutan-1-ol (469 g, 2.58 mol), PBSF (783 g, 2.59 mol), and 2500 g water. 475 g of 50% KOH was added slowly via the dropping funnel at a rate that kept the temperature below 35° C. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered and the filtrate was added to a separatory funnel. The lower phase was washed with water and phase separated to give 911 g of 2,2,3,4,4,4-hexafluorobutyl-1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate with a GC purity of 93.5%. The low boiling materials were then removed by rotary evaporation at 50° C. and 20 torr, giving a purity of 97.0%.

[0079] A 5 L round bottom flask equipped with an overhead stirrer, water condenser, N2 bubbler, thermocouple, and addition funnel was charged with 2325 g of dimethylformamide and lithium chloride (186.3 g, 4.4 mol). An exotherm was observed. The flask was cooled to room temperature and 2,2,3,4,4,4-hexafluorobutyl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (816 g, 1.76 mol) was added. The flask was then heated to 50° C. and held at that temperature for 16 hours. Water was added to the flask and the contents were steam distilled. The lower fluorochemical phase was phase separated and washed with water. The batch was repeated and the fluorochemical phases were combined to give 611 g of 4-chloro-1,1,1,2,3,3-hexafluoro-butane. The structure was confirmed by GC-MS.

[0080] A 1 L round bottom flask equipped with a magnetic stirrer, water condenser, N2 bubbler, thermocouple, and heating mantle was charged with 323 g of 25 wt% sodium methoxide in methanol. 4-Chloro-1,1,1,2,3,3-hexafluoro-butane (200 g, 1.0 mol) was added and the temperature increased to 64° C. The flask was cooled to 50° C. and held for 1 h, then cooled to room temperature and held for 16 h. Gas chromatography showed that there was about 20% unconverted starting material. An additional 0.5 equivalents of 25 wt% sodium methoxide in methanol was added and the mixture was heated to 50° C. About 4% unconverted starting material remained. 250 mL of water was added to the flask and the mixture was steam distilled to provide 134 g of 1-chloro-2,3,4,4,4-pentafluoro-but-1-ene with a purity of 53.6% by gas chromatography. The material was fractionated to give 26.1 g with a purity of >95.0%. The structure and purity were determined by GC-MS and F-NMR. The boiling point was approximately 63° C.

[0081] Example 11: 1-Chloro-2,3-difluoro-3-(trifluoromethoxy)prop-1-ene [ka] A 600 mL Parr reactor was charged with methanol (162 g, 5055.93 mmol) and tert-butyl peroxy-2-ethylhexanoate (6.7 g, 31 mmol). The reactor was then sealed and heated to 70° C. Trifluoromethyl trifluorovinyl ether (190 g, 1.14 mol) was added slowly from a cylinder. After 124 g of trifluoromethyl trifluorovinyl ether had been added, the addition was stopped and the reactor was held at 70° C. for 16 hours. The reactor was cooled in a dry ice-acetone bath and a fresh 7.5 g of initiator was added. The reactor was then heated to 75° C. and charged with an additional 66 g of trifluoromethyl trifluorovinyl ether. The reactor was held at 75° C. for 16 hours, cooled to room temperature and the residual pressure was vented. The reactor contents were washed with water and the lower phase was separated to give 230 g of material. GC-MS confirmed that the main peak was 2,2,3-trifluoro-3-(trifluoromethoxy)propan-1-ol.

[0082] A 1000 mL round bottom flask equipped with a water condenser, magnetic stirring apparatus, dry ice bath, and dropping funnel was charged with 2,2,3-trifluoro-3-(trifluoromethoxy)propan-1-ol (228 g, 1151.2 mmol), nonafluorobutanesulfonyl fluoride (384 g, 1271.15 mmol), and water (233 g, 12933.8 mmol). The flask was then placed in a dry ice bath and 260 g of 50% potassium hydroxide was added dropwise to the reaction flask using the dropping funnel. The rate was adjusted to keep the reaction temperature below 35° C. After the addition was complete, the dry ice bath was removed and a heating mantle was added. The reaction was stirred at 30° C. for 16 hours. The flask was then cooled and the contents were vacuum filtered into a 1000 mL round bottom flask on dry ice. The recovered material was then washed with water and 337 g of material was recovered. GC analysis showed 90% [2,2,3-tetrafluoro-3-(trifluoromethoxy)propyl] 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0083] A 1000 mL round bottom flask equipped with a Claisen adapter, thermocouple, magnetic stir plate, water condenser, and addition funnel was charged with lithium chloride (77.7 g, 1830 mmol) and N,N-dimethylformamide (256.3 g, 3506 mmol). The reaction flask was cooled to room temperature. After an initial exotherm, [2,2,3-tetrafluoro-3-(trifluoromethoxy)propyl]1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (298 g, 620.83 mmol) was added to the addition funnel and added dropwise to the reaction flask while maintaining the temperature below 45° C. The reaction was cooled to room temperature and stirred for 16 hours. The reaction was quenched with water and GC analysis of the lower phase showed 75% 3-chloro-1,2,2-trifluoro-1-(trifluoromethoxy)propane. The material was steam distilled to give 120 g of 3-chloro-1,2,2-trifluoro-1-(trifluoromethoxy)propane with a purity of 94.0%.

[0084] A 250 mL round bottom flask was charged with water (30 g, 1665.30 mmol) and potassium hydroxide (30 g, 534.713 mmol). After the KOH was dissolved and the flask was cooled to 60° C., tetrabutylammonium chloride (0.8 g, 3 mmol, 100 wt %) was added. 3-Chloro-1,2,2-trifluoro-1-(trifluoromethoxy)propane (53 g, 244.79 mmol) was added while maintaining the pot temperature at 50° C. After the addition, heat was removed from the reaction and the flask was cooled to room temperature. The reaction was quenched with water and the product was recovered by steam distillation to give 45 g of 3-chloro-1,2-trifluoro-1-(trifluoromethoxy)prop-3-ene in 94.6% purity. The product is a mixture of E and Z isomers. The structure and purity were determined by GC-MS and F-NMR.

[0085] result Table 2 summarizes the results of the maximum soluble hydrocarbon (LSH) tests for Examples 1-11. The largest hydrocarbon used was C-23 (C 23 H 48), so the LSH of “>23” is C without the hydrofluoroolefin exhibiting haze. 23 H 48 The results presented in Table 2 show that the hydrofluoroolefins of the present invention are highly suitable fluids for cleaning applications.

[0086] [Table 2]

[0087] The atmospheric lifetimes of Examples 1-3 were determined from the reaction rates with hydroxyl groups as described above and are reported in Table 3.

[0088] [Table 3]

[0089] Various modifications and alterations to this disclosure will become apparent to those skilled in the art without departing from the scope and spirit of the disclosure. It is to be understood that this disclosure is not intended to be unduly limited by the exemplary embodiments and examples described herein, and that such examples and embodiments are presented only as examples within the scope of this disclosure, which is intended to be limited only by the claims set forth herein as follows. All references cited in this disclosure are incorporated herein by reference in their entirety.

Claims

1. The following general formula (II): R ｆ (CFH) ｎ CF=CHX (II) [In the formula, R ｆ is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1; X is Cl or Br; However, R ｆ is CF ３ where n is 1. A hydrofluoroolefin compound represented by the formula: In the general formula (II), when X is Cl and n=0, the hydrofluoroolefin compound has the general formula (IIA): R ｆ CF=CHCl (IIA) [In the formula, R ｆ is a straight, branched, or cyclic perfluoroalkyl group having 2 to 6 carbon atoms and containing at least one linked heteroatom selected from nitrogen or oxygen.

2. The following general formula (IIC): R ｆ CF=CHBr (IIC) [In the formula, R ｆ is a straight-chain, branched-chain, or cyclic perfluoroalkyl group having 2 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen. The hydrofluoroolefin compound according to claim 1, having the formula:

3. The following general formula (IIID): R ｆ CF=CHBr (IID) [In the formula, R ｆ is a perfluoroalkyl group having 2 to 3 carbon atoms. The hydrofluoroolefin compound according to claim 1, having the formula:

4. 1. A composition comprising: The following general formula (I): (H) ｎ -R ｆ -(CFH) ｍ -CF=CHX (I) [In the formula, R ｆ is a straight, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1; m is 0 or 1; m+n=0 or 1; X is Cl or Br; however, X is Cl and R ｆ is CF ３ then m is 1; X is Br and R ｆ is CF ３ then m is 1; R ｆ is cyclic, then m+n=0. A hydrofluoroolefin represented by the formula: In the general formula (I), when n=1 and m=0, X=Br, and the hydrofluoroolefin compound has the general formula (IB): CF ２ H-CF=CHBr (IB) A hydrofluoroolefin compound having the formula: and contaminants, A composition, wherein said hydrofluoroolefin is present in said composition in an amount of at least 25 weight percent, based on the total weight of said composition.

5. The composition of claim 4 , wherein the contaminant comprises a long chain hydrocarbon alkane.

6. 1. A method for removing contaminants from a substrate, comprising: The substrate is represented by the following general formula (I): (H) ｎ -R ｆ -(CFH) ｍ -CF=CHX (I) [In the formula, R ｆ is a linear, branched, or cyclic perfluoroalkyl group having 1 to 6 carbon atoms, optionally containing at least one linked heteroatom selected from nitrogen or oxygen; n is 0 or 1; m is 0 or 1; m+n=0 or 1; X is Cl or Br; however, X is Cl and R ｆ is CF ３ then m is 1; X is Br and R ｆ is CF ３ then m is 1; R ｆ is cyclic, then m+n=0. A hydrofluoroolefin represented by the formula: In the general formula (I), when n=1 and m=0, X=Br, and the hydrofluoroolefin compound has the general formula (IB): CF ２ H-CF=CHBr (IB) with a hydrofluoroolefin compound having The method, wherein the contaminants comprise long chain hydrocarbon alkanes.

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