HK1135465B - Method of detecting leaks of fluoroolefin compositions and sensors used therefor - Google Patents

Description

Method for detecting leakage of fluoroolefin composition and sensor used therefor

Technical Field

The present disclosure relates to a method of detecting leaks in fluoroolefin compositions and sensors used therein. In particular, the present disclosure relates to detecting leaks of fluoroolefin refrigerant compositions from vapor compression systems. Such refrigerant compositions can be used in cooling systems as a replacement for existing refrigerants having a higher global warming potential.

Background

New environmental regulations on refrigerants have driven the refrigeration and air conditioning industry to look for new refrigerants with low Global Warming Potentials (GWPs).

Alternative refrigerants having low GWP, non-toxicity, non-flammability, reasonable cost, and excellent refrigeration performance are being sought.

Fluoroolefins have been proposed as refrigerants, either alone or in mixtures. When used in a vapor compression system, any refrigerant has a tendency to leak from the system over time due to the creation of holes in the system. However, leakage of refrigerant is sometimes difficult to detect, especially when the holes in the system are small. A solution to this problem is to add a dye to the refrigerant and pass the dye through the system. However, there are costs associated with adding the dye, both in terms of material and time. Furthermore, typically the dye must pass through the system for a period of time before a leak can be detected, which requires tracking (follow-up).

Summary of The Invention

The method of the present invention does not require the use of dyes to detect leaks in the fluid system. Which provides nearly instantaneous feedback of the location of the leak in the system and eliminates the expense and time of adding dye to the system. Which is therefore more cost effective than the known methods of detecting leaks.

The process of the present invention is based on an understanding of the unique double bond structure of fluoroolefins. This double bond structure allows the use of sensing technologies that have not heretofore been used to detect leaks.

Thus, in accordance with the present invention, a method of detecting a leak of a fluoroolefin composition in a fluid system is provided. The method includes testing the components of the system with a sensing tool for detecting leaks in the fluoroolefin composition. In particular, the sensing means is capable of detecting the double bond structure in the fluoroolefin composition.

Also in accordance with the present invention, there is provided a method of detecting a leak in a refrigerant fluid in a refrigeration or air conditioning system, wherein the refrigerant fluid comprises carbon dioxide, said method comprising adding a fluoroolefin to said refrigerant fluid.

Also in accordance with the present invention, a detection system for detecting a double bond structure in a fluoroolefin composition is provided. Such detection systems include means for sensing the double bond structure of the fluoroolefin composition. The sensing means may comprise a sensor for use in situ in the system, a wand tip (wand tip) for use close to a component of the system or an extraction device for use remote from a component of the system.

The sensor used in the sensing tool of any of the embodiments may use any of the following technologies: infrared sensors, ultraviolet sensors, NIR sensors, ion mobility or plasma chromatography, gas chromatography, refractometry, mass spectrometry, high temperature thick film sensors, thin film field effect sensors, pellistor sensors, Taguchi sensors and quartz microbalance sensors.

Brief Description of Drawings

Fig. 1 is a schematic view of a refrigeration or air-conditioning apparatus comprising an extraction device for use in the method according to the invention.

FIG. 1A is a schematic view of one example of a tip for use in the method and detection system according to the present invention.

FIG. 2 shows raw NIR spectral data for a sample of 1, 2, 3, 3, 3-pentafluoropropene (HFC-1225 ye).

Figure 3 shows a background NIR spectrum collected for an evacuated sample chamber as blank data.

Figure 4 shows the background subtracted NIR spectrum of HFC-1225 ye.

Description of the invention

In accordance with the present invention, a method of detecting a leakage of a fluoroolefin composition from a fluid system is provided. Fluoroolefin compositions tested with the present invention have a variety of uses, including use as blowing agents, fire extinguishing agents, heat transfer media (e.g., heat transfer fluids and refrigerants for use in refrigeration systems, refrigerators, air conditioning systems, heat pumps, chillers, and the like), to name a few. The type of fluid system in which a leak is detected depends on the use of the composition. For example, when the composition is a refrigerant, the fluid system being tested for leaks may be a cooling system.

The invention is exemplified, for example, with reference to a cooling system of a motor vehicle. Such a system is shown generally at 10 in fig. 1. Such a cooling system may be a vapor compression system. A vapor compression system is a closed loop system that reuses refrigerant in multiple steps, producing cooling in one step and heating in a different step. Such systems typically include an evaporator, a compressor, a condenser, and an expander as described in detail below with reference to fig. 1. The vapor compression system may be used in stationary or mobile refrigeration or air conditioning applications.

Referring to fig. 1, gaseous refrigerant from the evaporator 42 flows through a hose 63 to an inlet of the compressor 12 and is then discharged. The present invention may employ various types of compressors depending on the mechanical means used to compress the fluid, including reciprocating, rotary, injection, centrifugal, scroll, screw or axial flow types, or as positive displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or injection) types.

Compressed refrigerant gas from the compressor flows through the compressor outlet and hose 61 to the condenser 41. The pressure regulating valve 51 may be used in the hose 61. The valve allows the refrigerant flow to be recirculated back to the compressor via hose 63, thereby enabling control of the pressure of the refrigerant reaching the condenser 41 and, if necessary, preventing compressor surge. The compressed refrigerant is condensed in the condenser, thereby releasing heat. The liquid refrigerant flows via hose 62 through the expander 52 to the evaporator 42, which is located, for example, in the vehicle cabin or near another location to be cooled. In the evaporator, the liquid refrigerant is vaporized to provide cooling, and the cycle is then repeated. The expander 52 may be an expansion valve, a capillary tube, or an orifice tube.

Further in accordance with the present invention, there is provided a detection system for detecting a double bond structure in a fluoroolefin composition. Such detection systems include means for sensing the double bond structure of the fluoroolefin composition. The sensing means may comprise a sensor for use in situ in the system. Alternatively, the sensing means may comprise an extraction device shown generally at 70 in figure 1. The sensor 72 is placed within the extraction device. Line 74 carries the fluid to be sensed to the extraction device. Alternatively, in another embodiment, the sensing means may comprise a tip as shown at 70' in FIG. 1A. A sensor 72' is included in the handheld device. The tip is typically a hand-held device that can be placed in proximity to the fluid to detect leaks. An advantage of this type of detector is a rapid response, so the operator detects the leak immediately when the "rod" tip passes the leak point. The particular apparatus shown in FIG. 1A is a hand-held refractometer for viewing a liquid sample at atmospheric pressure. However, it should be understood that the present invention is not limited to viewing liquid samples, but may also include hand-held devices for detecting gases, such as hand-held gas chromatographs.

The sensor used in the sensing tool of any of the embodiments may use any of the following technologies: infrared sensors, ultraviolet sensors, NIR sensors, ion mobility or plasma chromatography, gas chromatography, refractometry, mass spectrometry, high temperature thick film sensors, thin film field effect sensors, pellistor sensors, Taguchi sensors and quartz microbalance sensors. Such techniques are known in the art.

The infrared sensor of the present invention uses a unique spectral absorbance in the infrared region for all polyatomic gases. By measuring the spectral intensity in a region specifically selected for the target analyte gas, the concentration of that gas can be determined. Many techniques are available for selecting the spectral region to be detected, including filters, spectrometers, transform techniques such as fourier and Hadamard, emission sources with limited emission range, detectors with specific sensitivities, including microphones surrounded by the gas to be analyzed. The use of infrared spectroscopy for gas detection and concentration determination is well known to spectrographers.

As used herein, UV/vis refers to the "ultraviolet and visible regions of the spectrum". The UV/vis spectrophotometer measures the intensity of light transmitted through the sample (I) and compares it with the intensity of light before transmission through the sample (I)_o) A comparison is made. Ratio I/I_oIs called transmittance and is usually expressed as a percentage (% T). Absorbance a is based on transmittance:

A＝-log(％T)

the basic components of a spectrophotometer are a light source (typically an incandescent bulb for visible wavelengths or a deuterium arc lamp for ultraviolet), a sample holder, a diffraction grating or monochromator to separate the different wavelengths of light, and a detector. The detector is typically a photodiode or a charge coupled device, also referred to as a CCD, which can store a charge profile. Photodiodes are used with monochromators that filter light so that only a single wavelength of light reaches the detector. Diffraction gratings are used with CCDs, which collect light with different wavelengths on different pixels.

As used herein, NIR refers to "near infrared spectroscopy". Near infrared spectrometers (NIRS) are spectroscopy methods that use the near infrared region of the electromagnetic spectrum (approximately 800 nm to 2500 nm). NIRS is based on molecular harmonics (molecular overone) and combined vibrations. The molar absorption coefficient in the near infrared region is usually rather small.

Instrumentation of near infrared spectroscopy is similar to instrumentation for the visible and mid infrared ranges. There are power supplies, detectors and dispersive elements (such as prisms or more commonly diffraction gratings) to record the intensities of the different wavelengths. Fourier transform instruments using interferometers are also available, especially for wavelengths above-1000 nm. Depending on the sample, the spectrum can be measured in transmission or reflection.

Common incandescent bulbs or quartz halogen bulbs are most commonly used as broadband sources of near-infrared radiation for analysis. Light Emitting Diodes (LEDs) are also used. The type of detector used depends mainly on the wavelength range to be measured. Silicon-based CCD, InGaAs and PbS devices are suitable.

Ion mobility spectrometry is based on two principles: (1) sample molecules are ionized via gas phase chemical reactions by electron or proton transfer, and (2) these ions are characterized based on gas phase mobility in a weak electric field. The mass, size and shape of these ions control mobility through a voltage gradient, and this can be measured in the time required to traverse a fixed distance. Thus, the IMS detector generates drift time or mobility values that are characteristic of certain ions (i.e., chemicals) and provides response specificity (e.g., peak detection). The initial step of ion formation is common to all ion mobility spectrometers. To achieve this, sample molecules must be transported from the suspect article to the IMS instrument in some way. This is typically accomplished using an air pump to sample the air for suspected leaks. Leak detection can be performed relatively remotely from the instrument using a hose (stainless steel or various plastics or rubbers) in combination with an air sampling pump. The simultaneous detection of multiple gases has been demonstrated at ppm to ppb levels. Ambient air contains specific reactant ion peaks and hydrofluoric acid (HF). The detection by drift time difference is shown on the collector current vs. drift time diagram. This is a very powerful technique for quickly and unambiguously detecting the amount and composition of ambient air.

GC as used herein refers to "gas chromatograph or gas chromatography analysis techniques". Fluids, particularly refrigerants, can be identified by Micro GC detectors (which are ion detectors) using various ionization methods of components eluted from the GC column. The ion detector is similar to a capacitor or a vacuum tube. It can be thought of as two metal gates (grid) separated by air, over which opposite charges are placed. A potential difference (voltage) exists between the two gates. After the components are ionized in the detector, they enter the region between the two gates, causing current to pass from one gate to the other. The current is amplified and is the signal generated by the detector. The higher the concentration of the component, the more ions are produced and the higher the current.

Flame Ionization Detectors (FIDs) use an air-hydrogen flame to generate ions. As the components elute from the GC column, they pass through the flame and burn, thereby generating ions. The ions generate a current, which is the signal output of the detector.

The Thermal Conductivity Detector (TCD) is composed of an electric heating wire or a thermistor. The temperature of the sensing element depends on the thermal conductivity of the gas flowing around it. A change in thermal conductivity, such as when organic molecules displace some of the carrier gas, causes a temperature rise in the element, which is sensed as a change in resistance.

An Electron Capture Detector (ECD) uses a radioactive beta particle (electron) emitter-a typical source contains a metal foil with 10 millicurie nickel-63. The electrons formed are attracted to the positively charged anode, thereby generating a steady state current. As the nitrogen flow or 5% methane/95% argon mixture flow carries the sample into the detector, the analyte molecules capture electrons and reduce the current between the current collecting anode and cathode. The analyte concentration is thus proportional to the degree of electron capture, and such detectors are particularly sensitive to halogens, organometallic compounds, nitriles or nitro compounds.

The ECD is sensitive with a detection limit of 5 nanograms per second (fg/s), and the detector typically exhibits a 10,000 fold linear range. This allows the detection of even only 1 part per trillion (ppt) of a particular halide.

Photoionization detectors (PIDs) are ion detectors that generate ions using high energy photons, typically in the UV range. As components elute from the GC column, they are bombarded with high energy photons and ionized. The ions generate a current, which is the signal output of the detector. The greater the concentration of the component, the more ions are produced and the greater the current.

The refractometry uses a fluid in a liquid state, such as a refrigerant whose refractive index identifies the leak condition or measures the composition in the blend to adjust to the desired composition. Refractive index refers to the angular change of a beam of light passing through the interface of two different substances. This technique makes use of the following facts: each refrigerant has a different atomic composition and thus a different refractive index at a given temperature. Since the refractive index is nearly linear for any two components in the mixture, a two or three component mixture can be evaluated quite accurately.

The refractive index of a substance or some physical property of a substance that is directly related to its refractive index is determined using a refractometer. A fluid sample is introduced into the sample chamber and a light source is passed through the interface of the fluid and a window in the chamber. The refractometer sensor measures the angle of light emanating from the refrigerant fluid. The fluids are identified with reference to known predetermined relationship data for a plurality of different fluids. In more advanced sensors, the temperature may be varied to obtain data, identify the composition of a multi-component mixture of certain fluids, and measure the percentage of the mixture. Gases and liquids may be measured using some type of refractometer.

Conventional hand-held refractometers operate on the critical angle principle. They employ lenses and prisms to project the shadow line onto a small optical cross within the instrument, which is then viewed by the user through a magnifying eyepiece. In use, the sample is sandwiched between the measurement prism and the small cover sheet. Light passing through the sample is transmitted to the cross-hair or is totally internally reflected. The net effect is that a shadow line is formed between the illuminated area and the shaded area. The hatching now spans the scale where the readings are taken. Since the refractive index is very temperature dependent, it is important to use a refractometer with automatic temperature compensation. Compensation is achieved using a small bi-metal strip that moves the lens or prism in response to temperature changes.

A mass spectrometer is a device that measures the mass/charge ratio of ions. This is achieved as follows: the sample is ionized, ions of different masses are separated, and their relative abundance is recorded by measuring the intensity of the ion stream. A typical mass spectrometer comprises three components: an ion source, a mass analyzer, and a detector system. Each gas mixture exhibits a unique mass spectrum that can be directly related to the composition and concentration of the refrigerant mixture.

In fluids such as other refrigerants and most other ambient gases, the fragmentation pattern of fluoroolefins is unique, which allows it to be specifically identified and its concentration determined relative to the other gases present. The fragmentation pattern should be sufficiently different from other gases present in the vicinity of the internal combustion engine, such as an automotive engine, that it is easily distinguished by the method. Furthermore, sensing techniques such as mass spectrometry offer the option of measuring the concentration of other gases that may also be present.

In another embodiment, a high temperature thick film sensor may serve as the sensor of the method of the present invention. Many semiconductor materials become significantly conductive at higher temperatures, for example, temperatures above 400 ℃. These materials become conductive because the valence electrons are excited to the conduction band due to their thermal energy. A gas that can give electrons or accept electrons from the valence band changes the number of electrons in the conduction band and thus the material conductivity.

The chemical selectivity of the high-temperature thick-film sensor is realized by changing the main components and doping the thin film. To impart selectivity to the technique, arrays of sensors containing different principal components and/or dopants are used, and the concentration of any given gas is empirically determined as a function of the output of each array of sensor elements.

In another embodiment, a thin film field effect sensor can serve as the sensor of the method of the present invention. Field effect sensors are based on the field effect generated by gases in Metal Oxide Semiconductor Field Effect Transistor (MOSFET) devices containing catalytic metals. Charging of the gate contact by gas molecules causes a voltage change in the sensor signal. The operating temperature, the selection of the gate metal and the gate metal structure determine the selectivity of the gas response. For devices based on silicon (Si) as the semiconductor, Si-MOSFETs, the operating temperature is 150-. For devices based on silicon carbide as the semiconductor, SiC-MOSFETs, the operating temperature was 200-600 ℃.

The selectivity and sensitivity of a MOSFET sensor is achieved by changes in the semiconductor, its doping, and the device operating temperature.

In another embodiment, a pellistor catalytic gas sensor may be used as a sensor in the method of the invention. Pellistor is a small calorimeter used to measure the energy released upon oxidation of a gas. It consists of a small diameter platinum coil supported in refractory particles. The coil was used to electrically heat the beads to their operating temperature (approximately 500 ℃) and to detect temperature changes caused by gas oxidation. The selectivity of the pellistor sensor is achieved by a change in the composition of the refractory beads.

In another embodiment, a Taguchi sensor may be used as a sensor in the method of the invention. The Taguchi sensor is composed of a powder made of a semiconducting metal oxide. In the formation of metal oxide crystals, e.g. SnO₂When heated at a certain high temperature in air, oxygen is adsorbed on the crystal surface having a negative charge. The donor electrons in the crystal surface are then transferred to the adsorbed oxygen, leaving a positive charge in the space charge layer. Thereby, a surface potential is formed to act as a barrier to electron flow. In the sensor, a current flows through SnO₂Connected portions of crystallites (grain boundaries). At the grain boundaries, the adsorbed oxygen forms a barrier that prevents carriers from moving freely. The resistance of the sensor is due to this potential barrier.

In the presence of a gas capable of removing oxygen from the surface at high temperatures, the surface density of negatively charged oxygen decreases, and therefore the barrier height in the grain boundary decreases. The reduced barrier height reduces the sensor resistance.

The selectivity and sensitivity of the Taguchi sensor can be varied by the choice of metal oxides, metal doping and other modifications of the oxide surface, and operating temperature.

In another embodimentIn embodiments, a quartz microbalance sensor may be used as the sensor in the method of the present invention. The quartz microbalance sensor technology is based on measuring the frequency of a quartz crystal coated with a polymer. The bulk absorption of analyte molecules imbibed into the polymer matrix affects this frequency. The sensitivity and selectivity of the microbalance sensor can be varied by selecting different polymer coatings with different functional groups in the side chains. Bulk absorption of analyte molecules absorbed into the polymer layer increases the mass of the quartz crystal, thereby lowering the resonant frequency. The absorption method is completely reversible. Using resins, e.g. E.I.du Pont DE Nemours and Company of Wilmington, DE, PTFE under the trade mark PTFEThose sold, and polystyrene sulfonate, modulate the response of the sensor to specific analytes, including refrigerant gases.

These sensing techniques have been found to be particularly useful for determining the composition of fluoroolefin compositions having double bonds. Representative fluoroolefins include, but are not limited to, all of the compounds listed in tables 1 and 2. As can be seen from these tables, the fluoroolefins have at least one double bond. Fluoroolefins, as used herein, include compounds having from 2 to 12 carbon atoms, in another embodiment from 3 to 10 carbon atoms, and in yet another embodiment from 3 to 7 carbon atoms.

In one embodiment of the invention, the fluoroolefin may be of the formula E-or Z-R¹CH＝CHR²(formula I) (and mixtures of such compounds) wherein R¹And R²Independently is C₁To C₆A perfluoroalkyl group. R¹And R²Examples of groups include, but are not limited to, CF₃、C₂F₅CF₂CF₂CF₃、CF(CF₃)₂、CF₂CF₂CF₂CF₃、CF(CF₃)CF₂CF₃、CF₂CF(CF₃)₂、C(CF₃)₃、CF₂CF₂CF₂CF₂CF₃、CF₂CF₂CF(CF₃)₂、C(CF₃)₂C₂F₅、CF₂CF₂CF₂CF₂CF₂CF₃、CF(CF₃)CF₂CF₂C₂F₅And C (CF)₃)₂CF₂C₂F₅. Exemplary, non-limiting compounds of formula I are listed in table 1.

TABLE 1

Code	Structure of the product	Chemical name
			F11E	CF3CH＝CHCF3	1, 1, 1, 4, 4, 4-hexafluorobut-2-ene
F12E	CF3CH＝CHC2F5	1, 1, 1, 4, 4, 5, 5, 5-octafluoropent-2-ene
			F13E	CF3CH＝CHCF2C2F5	1, 1, 1, 4, 4, 5, 5, 6, 6, 6-decafluorohex-2-ene
F13iE	CF3CH＝CHCF(CF3)2	1, 1, 1, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene
			F22E	C2F5CH＝CHC2F5	1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluorohex-3-ene
F14E	CF3CH＝CH(CF2)3CF3	1, 1, 1, 4, 4, 5, 5, 6, 6,7, 7, 7-dodecafluorohept-2-ene
			F14iE	CF3CH＝CHCF2CF-(CF3)2	1, 1, 1, 4, 4, 5, 6, 6, 6-nonafluoro-5- (trifluoromethyl) hex-2-ene
F14sE	CF3CH＝CHCF(CF3)-C2F5	1, 1, 1, 4, 5, 5, 6, 6, 6-nonafluoro-4- (trifluoromethyl) hex-2-ene
			F14tE	CF3CH＝CHC(CF3)3	1, 1, 1, 5, 5, 5-hexafluoro-4, 4-bis (trifluoromethyl) pent-2-ene
F23E	C2F5CH＝CHCF2C2F5	1, 1, 1, 2, 2, 5, 5, 6, 6,7, 7, 7-dodecafluorohept-3-ene
			F23iE	C2F5CH＝CHCF(CF3)2	1, 1, 1, 2, 2, 5, 6, 6, 6-nonafluoro-5- (trifluoromethyl) hex-3-ene
F15E	CF3CH＝CH(CF2)4CF3	1, 1, 1, 4, 4, 5, 5, 6, 6,7, 7, 8, 8, 8-decatetrafluorooct-2-ene
			F15iE	CF3CH＝CH-CF2CF2CF(CF3)2	1, 1, 1, 4, 4, 5, 5, 6,7, 7, 7-undecafluoro-6- (trifluoromethyl) hept-2-ene
F15tE	CF3CH＝CH-C(CF3)2C2F5	1, 1, 1, 5, 5, 6, 6, 6-octafluoro-4, 4-bis (trifluoromethyl) hex-2-ene
			F24E	C2F5CH＝CH(CF2)3CF3	1, 1, 1, 2, 2, 5, 5, 6, 6,7, 7, 8, 8, 8-decatetrafluorooct-3-ene
F24iE	C2F5CH＝CHCF2CF-(CF3)2	1, 1, 1, 2, 2, 5, 5, 6,7, 7, 7-undecafluoro-6- (trifluoromethyl) hept-3-ene
			F24sE	C2F5CH＝CHCF(CF3)-C2F5	1, 1, 1, 2, 2, 5, 6, 6,7, 7, 7-undecafluoro-5- (trifluoromethyl) hept-3-ene
F24tE	C2F5CH＝CHC(CF3)3	1, 1, 1, 2, 2, 6, 6, 6-octafluoro-5, 5-bis (trifluoromethyl) hex-3-ene
			F33E	C2F5CF2CH＝CH-CF2C2F5	1, 1, 1, 2, 2, 3, 3, 6, 6,7, 7, 8, 8, 8-decatetrafluorooct-4-ene
F3i3iE	(CF3)2CFCH＝CH-CF(CF3)2	1, 1, 1, 2, 5, 6, 6, 6-octafluoro-2, 5-bis (trifluoromethyl) hex-3-ene
			F33iE	C2F5CF2CH＝CH-CF(CF3)2	1, 1, 1, 2, 5, 5, 6, 6,7, 7, 7-undecafluoro-2- (trifluoromethyl) hept-3-ene

F16E	CF3CH＝CH(CF2)5CF3	1, 1, 1, 4, 4, 5, 5, 6, 6,7, 7, 8, 8, 9, 9, 9-decahexafluoronon-2-ene
			F16sE	CF3CH＝CHCF(CF3)(CF2)2C2F5	1, 1, 1, 4, 5, 5, 6, 6,7, 7, 8, 8, 8-tridecafluoro-4- (trifluoromethyl) hept-2-ene
F16tE	CF3CH＝CHC(CF3)2CF2C2F5	1, 1, 1, 6, 6, 6-octafluoro-4, 4-bis (trifluoromethyl) hept-2-ene
			F25E	C2F5CH＝CH(CF2)4CF3	1, 1, 1, 2, 2, 5, 5, 6, 6,7, 7, 8, 8, 9, 9, 9-decahexafluoronon-3-ene
F25iE	C2F5CH＝CH-CF2CF2CF(CF3)2	1, 1, 1, 2, 2, 5, 5, 6, 6,7, 8, 8, 8-tridecafluoro-7- (trifluoromethyl) oct-3-ene
			F25tE	C2F5CH＝CH-C(CF3)2C2F5	1, 1, 1, 2, 2, 6, 6,7, 7, 7-decafluoro-5, 5-bis (trifluoromethyl) hept-3-ene
F34E	C2F5CF2CH＝CH-(CF2)3CF3	1, 1, 1, 2, 2, 3, 3, 6, 6,7, 7, 8, 8, 9, 9, 9-decahexafluoronon-4-ene
			F34iE	C2F5CF2CH＝CH-CF2CF(CF3)2	1, 1, 1, 2, 2, 3, 3, 6, 6,7, 8, 8, 8-tridecafluoro-7- (trifluoromethyl) oct-4-ene
F34sE	C2F5CF2CH＝CH-CF(CF3)C2F5	1, 1, 1, 2, 2, 3, 3, 6,7, 7, 8, 8, 8-tridecafluoro-6- (trifluoromethyl) oct-4-ene
			F34tE	C2F5CF2CH＝CH-C(CF3)3	1, 1, 1, 5, 5, 6, 6,7, 7, 7-decafluoro-2, 2-bis (trifluoromethyl) hept-3-ene
F3i4E	(CF3)2CFCH＝CH-(CF2)3CF3	1, 1, 1, 2, 5, 5, 6, 6,7, 7, 8, 8, 8-tridecafluoro-2 (trifluoromethyl) oct-3-ene
			F3i4iE	(CF3)2CFCH＝CH-CF2CF(CF3)2	1, 1, 1, 2, 5, 5, 6,7, 7, 7-decafluoro-2, 6-bis (trifluoromethyl) hept-3-ene
F3i4sE	(CF3)2CFCH＝CH-CF(CF3)C2F5	1, 1, 1, 2, 5, 6, 6,7, 7, 7-decafluoro-2, 5-bis (trifluoromethyl) hept-3-ene
			F3i4tE	(CF3)2CFCH＝CH-C(CF3)3	1, 1, 1, 2, 6, 6, 6-heptafluoro-2, 5, 5-tris (trifluoromethyl) hex-3-ene
F26E	C2F5CH＝CH(CF2)5CF3	1，1，1，2，2，5，5，6，6,7, 7, 8, 8, 9, 9, 10, 10, 10-octadecafluorodec-3-ene
			F26sE	C2F5CH＝CHCF(CF3)(CF2)2C2F5	1, 1, 1, 2, 2, 5, 6, 6,7, 7, 8, 8, 9, 9, 9-pentadecafluoro-5- (trifluoromethyl) non-3-ene

F26tE	C2F5CH＝CHC(CF3)2CF2C2F5	1, 1, 1, 2, 2, 6, 6,7, 7, 8, 8, 8-dodecafluoro-5, 5-bis (trifluoromethyl) oct-3-ene
			F35E	C2F5CF2CH＝CH-(CF2)4CF3	1, 1, 1, 2, 2, 3, 3, 6, 6,7, 7, 8, 8, 9, 9, 10, 10, 10-octadecafluorodec-4-ene
F35iE	C2F5CF2CH＝CH-CF2CF2CF(CF3)2	1，1，1，22, 3, 3, 6, 6,7, 7, 8, 9, 9, 9-pentadecafluoro-8- (trifluoromethyl) non-4-ene
			F35tE	C2F5CF2CH＝CH-C(CF3)2C2F5	1, 1, 1, 2, 2, 3, 3, 7, 7, 8, 8, 8-dodecafluoro-6, 6-bis (trifluoromethyl) oct-4-ene
F3i5E	(CF3)2CFCH＝CH-(CF2)4CF3	1, 1, 1, 2, 5, 5, 6, 6,7, 7, 8, 8, 9, 9, 9-pentadecafluoro-2- (trifluoromethyl) non-3-ene
			F3i5iE	(CF3)2CFCH＝CH-CF2CF2CF(CF3)2	1, 1, 1, 2, 5, 5, 6, 6,7, 8, 8, 8-dodecafluoro-2, 7-bis (trifluoromethyl) oct-3-ene
F3i5tE	(CF3)2CFCH＝CH-C(CF3)2C2F5	1, 1, 1, 2, 6, 6,7, 7, 7-nonafluoro-2, 5, 5-tris (trifluoromethyl) hept-3-ene
			F44E	CF3(CF2)3CH＝CH-(CF2)3CF3	1, 1, 1, 2, 2, 3, 3, 4, 4, 7, 7, 8, 8, 9, 9, 10, 10, 10-eighteenFluorodec-5-ene
F44iE	CF3(CF2)3CH＝CH-CF2CF(CF3)2	1, 1, 1, 2, 3, 3, 6, 6,7, 7, 8, 8, 9, 9, 9-pentadecafluoro-2- (trifluoromethyl) non-4-ene
			F44sE	CF3(CF2)3CH＝CH-CF(CF3)C2F5	1, 1, 1, 2, 2, 3, 6, 6,7, 7, 8, 8, 9, 9, 9-pentadecafluoro-3- (trifluoromethyl) non-4-ene
F44tE	CF3(CF2)3CH＝CH-C(CF3)3	1, 1, 1, 5, 5, 6, 6,7, 7, 8, 8, 8-dodecafluoro-2, 2-bis (trifluoromethyl) oct-3-ene
			F4i4iE	(CF3)2CFCF2CH＝CH-CF2CF(CF3)2	1, 1, 1, 2, 3, 3, 6, 6,7, 8, 8, 8-dodecafluoro-2, 7-bis (trifluoromethyl) oct-4-ene
F4i4sE	(CF3)2CFCF2CH＝CH-CF(CF3)C2F5	1, 1, 1, 2, 3, 3, 6,7, 7, 8, 8, 8-dodecafluoro-2, 6-bis (trifluoromethyl) oct-4-ene
			F4i4tE	(CF3)2CFCF2CH＝CH-C(CF3)3	1, 1, 1, 5, 5, 6,7, 7, 7-nonafluoro-2, 2, 6-tris (trifluoromethyl) hept-3-ene
F4s4sE	C2F5CF(CF3)CH＝CH-CF(CF3)C2F5	1, 1, 1, 2, 2, 3, 6,7, 7, 8, 8, 8-dodecafluoro-3, 6-bis (trifluoromethyl) oct-4-ene

F4s4tE	C2F5CF(CF3)CH＝CH-C(CF3)3	1, 1, 1, 5, 6, 6,7, 7, 7-nonafluoro-2, 2, 5-tris (trifluoromethyl) hept-3-ene
			F4t4tE	(CF3)3CCH＝CH-C(CF3)3	1, 1, 1, 6, 6, 6-hexafluoro-2, 2, 5, 5-tetrakis (trifluoromethyl) hex-3-ene

Compounds of formula I may be prepared by reacting a compound of formula R¹Perfluoroalkyl iodides of formula I and R²CH＝CH₂To form a perfluoroalkyl trihydroalkene of the formula R¹CH₂CHIR²Is prepared from the trihydroiodoperfluoroalkane. Such trihydroiodoperfluoroalkanes can be subsequently dehydroiodinated to form R¹CH＝CHR². Or, the olefin R¹CH＝CHR²Can be prepared by the formula R¹CHICH₂R²Is prepared by dehydroiodination of trihydroiodoperfluoroalkanes of the formula R²Perfluoroalkyl iodides of formula I and R¹CH＝CH₂Is reacted with a perfluoroalkyl trihydroalkene of (a). This contacting of the perfluoroalkyl iodide with the perfluoroalkyl trihydroalkene can be carried out in a batch mode by combining the reactants in a suitable reaction vessel capable of operating at the reaction temperature at the autogenous pressures of the reactants and product. Suitable reaction vessels include those made from stainless steel, particularly austenitic stainless steel, and well known high nickel alloys, such as those sold under the trademark "NikelSold nickel-copper alloy, nickel base alloyAnd by trade markCommercially available nickel-chromium alloys.

Alternatively, the reaction may be carried out in a semi-batch mode wherein the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant at the reaction temperature by means of a suitable feeding device, such as a pump. The ratio of perfluoroalkyl iodide to perfluoroalkyl trihydroalkene should be from about 1: 1 to about 4: 1, preferably from about 1.5: 1 to 2.5: 1. Such as Jeanneaux et alJournal of Fluorine ChemistryA ratio of less than 1.5: 1, reported in Vol.4, pp.261-270 (1974), tends to produce a large amount of the 2: 1 adduct.

In some embodiments, the temperature at which the perfluoroalkyl iodide and perfluoroalkyl trihydroolefin are contacted is preferably from about 150 ℃ to 300 ℃, preferably from about 170 ℃ to about 250 ℃, and most preferably from about 180 ℃ to about 230 ℃. Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyl trihydroalkene are from about 0.5 hours to 18 hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkanes produced by the reaction of perfluoroalkyl iodides with perfluoroalkyl trihydroolefins may be used directly in the dehydroiodination step or, in some embodiments, recovered and purified by distillation prior to the dehydroiodination step.

In some embodiments, the dehydroiodination step is performed by contacting the trihydroiodoperfluoroalkane with a basic material. Suitable basic materials include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxides (e.g., sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic materials, such as soda lime. Preferred alkaline substances are sodium hydroxide and potassium hydroxide. Said contacting of the trihydroiodoperfluoroalkane with the basic material may be carried out in the liquid phase, preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Suitable solvents for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, and t-butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease with which traces of solvent are separated from the product during purification. Typically, ethanol or isopropanol is a good solvent for the reaction.

In some embodiments, the dehydroiodination reaction can be carried out by adding one of the reactants (the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. The reactor may be made of glass, ceramic or metal and is preferably agitated with an impeller or stirring device.

In certain embodiments, suitable temperatures for the dehydroiodination reaction range from about 10 ℃ to about 100 ℃, preferably from about 20 ℃ to about 70 ℃. In other embodiments, the dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. In certain embodiments, the dehydroiodination reaction is a reaction in which the compound of formula I is distilled off from the reaction vessel as it is formed.

In an alternative embodiment, the dehydroiodination reaction can be carried out by contacting an aqueous solution of the basic substance with a solution of trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity, such as an alkane (e.g., hexane, heptane, or octane), an aromatic hydrocarbon (e.g., toluene), a halogenated hydrocarbon (e.g., dichloromethane, chloroform, carbon tetrachloride, or perchloroethylene), or an ether (e.g., diethyl ether, methyl t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and trioctylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), or cyclic polyether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

According to an alternative embodiment of the present invention, the dehydroiodination reaction can be carried out by adding trihydroiodoperfluoroalkanes to a solid or liquid basic substance in the absence of a solvent.

In some embodiments, suitable reaction times for the dehydroiodination reaction range from about 15 minutes to about 6 hours or more, depending on the solubility of the reactants. In some embodiments, the dehydroiodination reaction is rapid and takes about 30 minutes to about 3 hours to complete.

The compound of formula I can be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.

The composition in some embodiments may comprise a single compound of formula I, for example one of the compounds in table 1, or may comprise a combination of compounds of formula I.

In another embodiment, the fluoroolefin may be a compound (including mixtures thereof) as listed in table 2. The composition in some embodiments may comprise a single compound of table 2, or may comprise a combination of compounds of table 2, i.e., mixtures thereof.

TABLE 2

Code	Structure of the product	Chemical name
			HFC-1225ye	CF3CF＝CHF	1, 2, 3, 3, 3-pentafluoro-1-propene
HFC-1225zc	CF3CH＝CF2	1, 1, 3, 3, 3-pentafluoro-1-propene
			HFC-1225yc	CHF2CF＝CF2	1, 1, 2, 3, 3-pentaFluoro-1-propene
HFC-1234ye	CHF2CF＝CHF	1, 2, 3, 3-tetrafluoro-1-propene
			HFC-1234yf	CF3CF＝CH2	2, 3, 3, 3-tetrafluoro-1-propene
HFC-1234ze	CF3CH＝CHF	1, 3, 3, 3-tetrafluoro-1-propene
			HFC-1234yc	CH2FCF＝CF2	1, 1, 2, 3-tetrafluoro-1-propene
HFC-1234zc	CHF2CH＝CF2	1, 1, 3, 3-tetrafluoro-1-propene
			HFC-1234ye	CHF2CF＝CHF	1, 2, 3, 3-tetrafluoro-1-propene
HFC-1243yf	CHF2CF＝CH2	2, 3, 3-trifluoro-1-propene
			HFC-1243zf	CF3CH＝CH2	3, 3, 3-trifluoro-1-propene
HFC-1243yc	CH3CF＝CF2	1, 1, 2-trifluoro-1-propene
			HFC-1243zc	CH2FCH＝CF2	1, 1, 3-trifluoro-1-propene
HFC-1243ye	CHF2CF＝CHF	1, 2, 3-trifluoro-1-propene
			HFC-1243ze	CHF2CH＝CHF	1, 3, 3-trifluoro-1-propene
FC-1318my	CF3CF＝CFCF3	1, 1, 1, 2, 3, 4, 4, 4-octafluoro-2-butene
			FC-1318cy	CF3CF2CF＝CF2	1, 1, 2, 3, 3, 4, 4, 4-octafluoro-1-butene
HFC-1327my	CF3CF＝CHCF3	1, 1, 1, 2, 4, 4, 4-heptafluoro-2-butene

HFC-1327ye	CHF＝CFCF2CF3	1, 2, 3, 3, 4, 4, 4-heptafluoro-1-butene
			HFC-1327py	CHF2CF＝CFCF3	1, 1, 1, 2, 3, 4, 4-heptafluoro-2-butene
HFC-1327et	(CF3)2C＝CHF	1, 3, 3, 3-tetrafluoro-2- (trifluoromethyl) -1-propene
			HFC-1327cz	CF2＝CHCF2CF3	1, 1, 3, 3, 4, 4, 4-heptafluoro-1-butene
HFC-1327cye	CF2＝CFCHFCF3	1，1，2，3，4，4，4-heptafluoro-1-butene
			HFC-1327cyc	CF2＝CFCF2CHF2	1, 1, 2, 3, 3, 4, 4-heptafluoro-1-butene
HFC-1336yf	CF3CF2CF＝CH2	2, 3, 3, 4, 4, 4-hexafluoro-1-butene
			HFC-1336mzz	CF3CH＝CHCF3	1, 1, 1, 4, 4, 4-hexafluoro-2-butene
HFC-1336ze	CHF＝CHCF2CF3	1, 3, 3, 4, 4, 4-hexafluoro-1-butene
			HFC-1336eye	CHF＝CFCHFCF3	1, 2, 3, 4, 4, 4-hexafluoro-1-butene
HFC-1336eyc	CHF＝CFCF2CHF2	1, 2, 3, 3, 4, 4-hexafluoro-1-butene
			HFC-1336pyy	CHF2CF＝CFCHF2	1, 1, 2, 3, 4, 4-hexafluoro-2-butene
HFC-1336qy	CH2FCF＝CFCF3	1, 1, 1, 2, 3, 4-hexafluoro-2-butene
			HFC-1336pz	CHF2CH＝CFCF3	1, 1, 1, 2, 4, 4-hexafluoro-2-butene
HFC-1336mzy	CF3CH＝CFCHF2	1, 1, 1, 3, 4, 4-hexafluoro-2-butene
			HFC-1336qc	CF2＝CFCF2CH2F	1, 1, 2, 3, 3, 4-hexafluoro-1-butene
HFC-1336pe	CF2＝CFCHFCHF2	1, 1, 2, 3, 4, 4-hexafluoro-1-butene
			HFC-1336ft	CH2＝C(CF3)2	3, 3, 3-trifluoro-2- (trifluoromethyl) -1-propene
HFC-1345qz	CH2FCH＝CFCF3	1, 1, 1, 2, 4-pentafluoro-2-butene
			HFC-1345mzy	CF3CH＝CFCH2F	1, 1, 1, 3, 4-pentafluoro-2-butene
HFC-1345fz	CF3CF2CH＝CH2	3, 3, 4, 4, 4-pentafluoro-1-butene
			HFC-1345mzz	CHF2CH＝CHCF3	1, 1, 1, 4, 4-pentafluoro-2-butene
HFC-1345sy	CH3CF＝CFCF3	1, 1, 1, 2, 3-pentafluoro-2-butene
			HFC-1345fyc	CH2＝CFCF2CHF2	2, 3, 3, 4, 4-pentafluoro-1-butene
HFC-1345pyz	CHF2CF＝CHCHF2	1, 1, 2, 4, 4-pentafluoro-2-butene
			HFC-1345cyc	CH3CF2CF＝CF2	1, 1, 2, 3, 3-pentafluoro-1-butene
HFC-1345pyy	CH2FCF＝CFCHF2	1, 1, 2, 3, 4-pentafluoro-2-butene
			HFC-1345eyc	CH2FCF2CF＝CF2	1, 2, 3, 3, 4-pentafluoro-1-butene
HFC-1345ctm	CF2＝C(CF3)(CH3)	1, 1, 3, 3, 3-pentafluoro-2-methyl-1-propene
			HFC-1345ftp	CH2＝C(CHF2)(CF3)	2- (difluoromethyl) -3, 3, 3-trifluoro-1-propene
HFC-1354fzc	CH2＝CHCF2CHF2	3, 3, 4, 4-tetrafluoro-1-butene

HFC-1354ctp	CF2＝C(CHF2)(CH3)	1, 1, 3, 3-tetrafluoro-2-methyl-1-propene
			HFC-1354etm	CHF＝C(CF3)(CH3)	1, 3, 3, 3-tetrafluoro-2-methyl-1-propene
HFC-1354tfp	CH2＝C(CHF2)2	2- (difluoromethyl) -3, 3-difluoro-1-propene
			HFC-1354my	CF3CF＝CFCH3	1, 1, 1, 2-tetrafluoro-2-butene
HFC-1354mzy	CH3CF＝CHCF3	1, 1, 1, 3-tetrafluoro-2-butene
			FC-141-10myy	CF3CF＝CFCF2CF3	1, 1, 1, 2, 3, 4, 4, 5, 5, 5-decafluoro-2-pentene
FC-141-10cy	CF2＝CFCF2CF2CF3	1, 1, 2, 3, 3, 4, 4, 5, 5, 5-decafluoro-1-pentene
			HFC-1429mzt	(CF3)2C＝CHCF3	1, 1, 1, 4, 4, 4-hexafluoro-2- (trifluoromethyl) -2-butene
HFC-1429myz	CF3CF＝CHCF2CF3	1, 1, 1, 2, 4, 4, 5, 5, 5-nonafluoro-2-pentene
			HFC-1429mzy	CF3CH＝CFCF2CF3	1, 1, 1, 3, 4, 4, 5, 5, 5-nonafluoro-2-pentene
HFC-1429eyc	CHF＝CFCF2CF2CF3	1, 2, 3, 3, 4, 4, 5, 5, 5-nonafluoro-1-pentene
			HFC-1429czc	CF2＝CHCF2CF2CF3	1, 1, 3, 3, 4, 4, 5, 5, 5-nonafluoro-1-pentene
HFC-1429cycc	CF2＝CFCF2CF2CHF2	1，1，2，3，3, 4, 4, 5, 5-nonafluoro-1-pentene
			HFC-1429pyy	CHF2CF＝CFCF2CF3	1, 1, 2, 3, 4, 4, 5, 5, 5-nonafluoro-2-pentene
HFC-1429myyc	CF3CF＝CFCF2CHF2	1, 1, 1, 2, 3, 4, 4, 5, 5-nonafluoro-2-pentene
			HFC-1429myye	CF3CF＝CFCHFCF3	1, 1, 1, 2, 3, 4, 5, 5, 5-nonafluoro-2-pentene
HFC-1429eyym	CHF＝CFCF(CF3)2	1, 2, 3, 4, 4, 4-hexafluoro-3- (trifluoromethyl) -butene
			HFC-1429cyzm	CF2＝CFCH(CF3)2	1, 1, 2, 4, 4, 4-hexafluoro-3- (trifluoromethyl) -1-butene
HFC-1429mzt	CF3CH＝C(CF3)2	1, 1, 1, 4, 4, 4-hexafluoro-3- (trifluoromethyl) -2-butene
			HFC-1429czym	CF2＝CHCF(CF3)2	1, 1, 3, 4, 4, 4-hexafluoro-3- (trifluoromethyl) -1-butene
HFC-1438fy	CH2＝CFCF2CF2CF3	2, 3, 3, 4, 4, 5, 5, 5-octafluoro-1-pentene
			HFC-1438eycc	CHF＝CFCF2CF2CHF2	1, 2, 3, 3, 4, 4, 5, 5-octafluoro-1-pentene
HFC-1438ftmc	CH2＝C(CF3)CF2CF3	3, 3, 4, 4, 4-Pentafluoro-2- (trifluoromethyl) -1-butene
			HFC-1438czzm	CF2＝CHCH(CF3)2	1, 1, 4, 4, 4-pentafluoro-3- (trifluoromethyl) -1-butene
HFC-1438ezym	CHF＝CHCF(CF3)2	1, 3, 4, 4, 4-pentafluoro-3- (trifluoromethyl) -1-butene
			HFC-1438ctmf	CF2＝C(CF3)CH2CF3	1, 1, 4, 4, 4-pentafluoro-2- (trifluoromethyl) -1-butene
HFC-1438mzz	CF3CH＝CHCF2CF3	1, 1, 1, 4, 4, 5, 5, 5-octafluoro-2-pentene
			HFC-1447fzy	(CF3)2CFCH＝CH2	3, 4, 4, 4-tetrafluoro-3- (trifluoromethyl) -1-butene
HFC-1447fz	CF3CF2CF2CH＝CH2	3, 3, 4, 4, 5, 5, 5-heptafluoro-1-pentene
			HFC-1447fycc	CH2＝CFCF2CF2CHF2	2, 3, 3, 4, 4, 5, 5-heptafluoro-1-pentene
HFC-1447czcf	CF2＝CHCF2CH2CF3	1, 1, 3, 3, 5, 5, 5-heptafluoro-1-pentene

HFC-1447mytm	CF3CF＝C(CF3)(CH3)	1, 1, 1, 2, 4, 4, 4-heptafluoro-3-methyl-2-butene
			HFC-1447fyz	CH2＝CFCH(CF3)2	2, 4, 4, 4-tetrafluoro-3- (trifluoromethyl) -1-butene
HFC-1447ezz	CHF＝CHCH(CF3)2	1, 4, 4, 4-tetrafluoro-3- (trifluoromethyl) -1-butene
			HFC-1447qzt	CH2FCH＝C(CF3)2	1, 4, 4, 4-tetrafluoro-3- (trifluoromethyl) -2-butene
HFC-1447syt	CH3CF＝C(CF3)2	2, 4, 4, 4-tetrafluoro-3- (trifluoromethyl) -2-butene
			HFC-1456szt	(CF3)2C＝CHCH3	3- (trifluoromethyl) -4, 4, 4-trifluoro-2-butene
HFC-1456szy	CF3CF2CF＝CHCH3	3, 4, 4, 5, 5, 5-hexafluoro-2-pentene
			HFC-1456mstz	CF3C(CH3)＝CHCF3	1, 1, 1, 4, 4, 4-hexafluoro-2-methyl-2-butene
HFC-1456fzce	CH2＝CHCF2CHFCF3	3, 3, 4, 5, 5, 5-hexafluoro-1-pentene
			HFC-1456ftmf	CH2＝C(CF3)CH2CF3	4, 4, 4-trifluoro-2- (trifluoromethyl) -1-butene
FC-151-12c	CF3(CF2)3CF＝CF2	1, 1, 2, 3, 3, 4, 4, 5, 5, 6, 6, 6-dodecafluoro-1-hexene (or perfluoro-1-hexene)
			FC-151-12mcy	CF3CF2CF＝CFCF2CF3	1, 1, 1, 2, 2, 3, 4, 5, 5, 6, 6, 6-dodecafluoro-3-hexene (or perfluoro-3-hexene)
FC-151-12mmtt	(CF3)2C＝C(CF3)2	1, 1, 1, 4, 4, 4-hexafluoro-2, 3-bis (trifluoromethyl) -2-butene
			FC-151-12mmzz	(CF3)2CFCF＝CFCF3	1, 1, 1, 2, 3, 4, 5, 5, 5-nonafluoro-4- (trifluoromethyl) pentene-2
HFC-152-11mmtz	(CF3)2C＝CHC2F5	1, 1, 1, 4, 4, 5, 5, 5-octafluoro-2- (trifluoromethyl) pentene-2
			HFC-152-11mmyyz	(CF3)2CFCF＝CHCF3	1, 1, 1, 3, 4, 5, 5, 5-octafluoro-4- (trifluoromethyl) -2-pentene
HFC-153-10mmyzz	CF3CH＝CHCF(CF3)2	1, 1, 1, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) -2-pentene
			HFC-153-10mzz	CF3CH＝CHCF2CF2CF3	1, 1, 1, 4, 4, 5, 5, 6, 6, 6-decafluoro-2-hexene
HFC-153-10mczz	CF3CF2CH＝CHCF2CF3	1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene
			PFBE (or HFC-1549fz)	CF3CF2CF2CF2CH＝CH2	3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro-1-hexene (or perfluorobutylethylene)
HFC-1549fztmm	CH2＝CHC(CF3)3	4, 4, 4-trifluoro-3, 3-bis (trifluoromethyl) -1-butene
			HFC-1549mmtts	(CF3)2C＝C(CH3)(CF3)	1, 1, 1, 4, 4, 4-hexafluoro-3-methyl-2- (trifluoromethyl) -2-butene

HFC-1549fycz	CH2＝CFCF2CH(CF3)2	2, 3, 3, 5, 5, 5-hexafluoro-4- (trifluoromethyl) -1-pentene
			HFC-1549myts	CF3CF＝C(CH3)CF2CF3	1, 1, 1, 2, 4, 4, 5, 5, 5-nonafluoro-3-methyl-2-pentene
HFC-1549mzzz	CF3CH＝CHCH(CF3)2	1, 1, 1, 5, 5, 5-hexafluoro-4- (trifluoromethyl) -2-pentene
			HFC-1558szy	CF3CF2CF2CF＝CHCH3	3, 4, 4, 5, 5, 6, 6, 6-octafluoro-2-hexene
HFC-1558fzccc	CH2＝CHCF2CF2CF2CHF2	3, 3, 4, 4, 5, 5, 6, 6-octafluoro-2-hexene
			HFC-1558mmtzc	(CF3)2C＝CHCF2CH3	1, 1, 1, 4, 4-pentafluoro-2- (trifluoromethyl) -2-pentene
HFC-1558ftmf	CH2＝C(CF3)CH2C2F5	4, 4, 5, 5, 5-pentafluoro-2- (trifluoromethyl) -1-pentene
			HFC-1567fts	CF3CF2CF2C(CH3)＝CH2	3, 3, 4, 4, 5, 5, 5-heptafluoro-2-methyl-1-pentene
HFC-1567szz	CF3CF2CF2CH＝CHCH3	4, 4, 5, 5, 6, 6, 6-heptafluoro-2-hexene
			HFC-1567fzfc	CH2＝CHCH2CF2C2F5	4, 4, 5, 5, 6, 6, 6-heptafluoro-1-hexene
HFC-1567sfyy	CF3CF2CF＝CFC2H5	1, 1, 1, 2, 2, 3, 4-heptafluoro-3-hexene
			HFC-1567fzfy	CH2＝CHCH2CF(CF3)2	4, 5, 5, 5-tetrafluoro-4- (trifluoromethyl) -1-pentene
HFC-1567myzzm	CF3CF＝CHCH(CF3)(CH3)	1, 1, 1, 2, 5, 5, 5-heptafluoro-4-methyl-2-pentene
			HFC-1567mmtyf	(CF3)2C＝CFC2H5	1, 1, 1, 3-tetrafluoro-2- (trifluoromethyl) -2-pentene
FC-161-14myy	CF3CF＝CFCF2CF2C2F5	1, 1, 1, 2, 3, 4, 4, 5, 5, 6, 6,7, 7, 7-tetradecafluoro-2-heptene
			FC-161-14mcyy	CF3CF2CF＝CFCF2C2F5	1, 1, 1, 2, 2, 3, 4, 5, 5, 6, 6,7, 7, 7-tetradecafluoro-2-heptene
HFC-162-13mzy	CF3CH＝CFCF2CF2C2F5	1, 1, 1, 3, 4, 4, 5, 5, 6, 6,7, 7, 7-tridecafluoro-2-heptene
			HFC162-13myz	CF3CF＝CHCF2CF2C2F5	1, 1, 1, 2, 4, 4, 5, 5, 6, 6,7, 7, 7-tridecafluoro-2-heptene
HFC-162-13mczy	CF3CF2CH＝CFCF2C2F5	1, 1, 1, 2, 2, 4, 5, 5, 6, 6,7, 7, 7-thirteenFluoro-3-heptene
			HFC-162-13mcyz	CF3CF2CF＝CHCF2C2F5	1, 1, 1, 2, 2, 3, 5, 5, 6, 6,7, 7, 7-tridecafluoro-3-heptene
HFC-C1316cc	Ring-CF2CF2CF＝CF-	1, 2, 3, 3, 4, 4-hexafluorocyclobutene
			HFC-C1334cc	Ring-CF2CF2CH＝CH-	3, 3, 4, 4-tetrafluorocyclobutene
HFC-C1436	Ring-CF2CF2CF2CH＝CH-	3, 3, 4, 4, 5, 5, -hexafluorocyclopentene
			HFC-C1418y	Ring-CF2CF＝CFCF2CF2-	1, 2, 3, 3, 4, 4, 5, 5-octafluorocyclopentene
FC-C151-10y	Ring-CF2CF＝CFCF2CF2CF2-	1, 2, 3, 3, 4, 4, 5, 5, 6, 6-decafluorocyclohexene

The compounds listed in table 2 are commercially available or can be prepared by methods known in the art or as described herein.

The 1, 1, 1, 4, 4-pentafluoro-2-butene may be prepared from 1, 1, 1, 2, 4, 4-hexafluorobutane (CHF)₂CH₂CHFCF₃) Prepared by dehydrofluorination in the gas phase at room temperature over solid KOH. The synthesis of 1, 1, 1, 2, 4, 4-hexafluorobutane is described in US 6,066,768, which is incorporated herein by reference.

The 1, 1, 1, 4, 4, 4-hexafluoro-2-butene may be prepared from 1, 1, 1, 4, 4, 4-hexafluoro-2-iodobutane (CF)₃CHICH₂CF₃) Prepared by reaction with KOH at about 60 c using a phase transfer catalyst. Synthesis of 1, 1, 1, 4, 4, 4-hexafluoro-2-iodobutane can be carried out by perfluoromethyl iodide (CF)₃I) And 3, 3, 3-trifluoropropene (CF)₃CH＝CH₂) The reaction was carried out at about 200 ℃ under autogenous pressure for about 8 hours.

The 3, 4, 4, 5, 5, 5-hexafluoro-2-pentene may be produced by using solid KOH or 1, 1, 1, 2, 2, 3, 3-heptafluoropentane (CF) over a carbon catalyst at 200-₃CF₂CF₂CH₂CH₃) By dehydrofluorination. The 1, 1, 1, 2, 2, 3, 3-heptafluoropentane can be prepared by reacting 3, 3, 4, 4, 5, 5, 5-heptafluoro-1-pentene (CF)₃CF₂CF₂CH＝CH₂) Hydrogenation preparation of (2).

1, 1, 1, 2, 3, 4-hexafluoro-2-butene can be obtained by 1, 1, 1, 2, 3, 3, 4-heptafluorobutane (CH) using solid KOH₂FCF₂CHFCF₃) By dehydrofluorination.

1, 1, 1, 2, 4, 4-hexafluoro-2-butene can be obtained by 1, 1, 1, 2, 2, 4, 4-heptafluorobutane (CHF) using solid KOH₂CH₂CF₂CF₃) By dehydrofluorination.

1，1，1，The 3, 4, 4-hexafluoro-2-butene can be obtained by 1, 1, 1, 3, 3, 4, 4-heptafluorobutane (CF) using solid KOH₃CH₂CF₂CHF₂) By dehydrofluorination.

1, 1, 1, 2, 4-Pentafluoro-2-butene can be obtained by 1, 1, 1, 2, 2, 3-hexafluorobutane (CH) using solid KOH₂FCH₂CF₂CF₃) By dehydrofluorination.

1, 1, 1, 3, 4-Pentafluoro-2-butene can be obtained by 1, 1, 1, 3, 3, 4-hexafluorobutane (CF) using solid KOH₃CH₂CF₂CH₂F) By dehydrofluorination.

1, 1, 1, 3-tetrafluoro-2-butene can be obtained by reacting 1, 1, 1, 3, 3-pentafluorobutane (CF)₃CH₂CF₂CH₃) Reacting with KOH aqueous solution at 120 ℃.

The 1, 1, 1, 4, 4, 5, 5, 5-octafluoro-2-pentene may be substituted with (CF)₃CHICH₂CF₂CF₃) Prepared by reaction with KOH at about 60 c using a phase transfer catalyst. The synthesis of 4-iodo-1, 1, 1, 2, 2, 5, 5, 5-octafluoropentane can be carried out by perfluoroethyl iodide (CF)₃CF₂I) And 3, 3, 3-trifluoropropene at about 200 ℃ under autogenous pressure for about 8 hours.

The 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-hexene may be replaced by 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-iodohexane (CF)₃CF₂CHICH₂CF₂CF₃) Prepared by reaction with KOH at about 60 c using a phase transfer catalyst. Synthesis of 1, 1, 1, 2, 2, 5, 5, 6, 6, 6-decafluoro-3-iodohexane can be carried out by perfluoroethyl iodide (CF)₃CF₂I) And 3, 3, 4, 4, 4-pentafluoro-1-butene (CF)₃CF₂CH＝CH₂) The reaction was carried out at about 200 ℃ under autogenous pressure for about 8 hours.

1, 1, 1, 4, 5, 5, 5-heptafluoro-4- (trifluoromethyl) -2-pentene may be prepared by reaction in isopropanolIn the presence of KOH, 1, 1, 1, 2, 5, 5, 5-heptafluoro-4-iodo-2- (trifluoromethyl) -pentane (CF)₃CHICH₂CF(CF₃)₂) Dehydrofluorination. CF (compact flash)₃CHICH₂CF(CF₃)₂From (CF)₃)₂CFI and CF₃CH＝CH₂Reaction at elevated temperatures, for example about 200 ℃.

1, 1, 1, 4, 4, 5, 5, 6, 6, 6-decafluoro-2-hexene can be produced by 1, 1, 1, 4, 4, 4-hexafluoro-2-butene (CF)₃CH＝CHCF₃) With tetrafluoroethylene (CF)₂＝CF₂) And antimony pentafluoride (SbF)₅) The reaction of (1).

2, 3, 3, 4, 4-pentafluoro-1-butene may be prepared by dehydrofluorination of 1, 1, 2, 2, 3, 3-hexafluorobutane over fluorinated alumina at elevated temperature.

2, 3, 3, 4, 4, 5, 5, 5-octafluoro-1-pentene may be prepared by dehydrofluorination of 2, 2, 3, 3, 4, 4, 5, 5, 5-nonafluoropentane over solid KOH.

1, 2, 3, 3, 4, 4, 5, 5-octafluoro-1-pentene may be prepared by dehydrofluorination of 2, 2, 3, 3, 4, 4, 5, 5, 5-nonafluoropentane over fluorided alumina at elevated temperature.

Many of the compounds of formula I, table 1 and table 2 exist as different configurational isomers or stereoisomers. Where no particular isomer is specified, the present invention is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For example, F11E is intended to represent the E-isomer, the Z-isomer, or any combination or mixture of these two isomers in any ratio. As another example, HFC-1225ye is intended to represent the E-isomer, the Z-isomer, or any combination or mixture of any ratio of the two isomers.

The heat transfer fluid compositions of the present invention are generally useful when the fluoroolefin is present in about 1 wt.% to about 99 wt.%, preferably about 20 wt.% to about 99 wt.%, more preferably about 40 wt.% to about 99 wt.%, and even more preferably about 50 wt.% to about 99 wt.%.

The invention further provides a composition as set forth in table 3.

TABLE 3

The most preferred compositions of the present invention listed in Table 3 are generally expected to maintain the desired properties and functionality when the components are present at concentrations of +/-2 weight percent of the values listed. Containing CO₂In CO₂The desired properties and functionality are expected to be maintained when present at the listed concentrations +/-0.2 wt%.

The compositions of the present invention may be azeotropic or near-azeotropic compositions. By azeotropic composition is meant a constant boiling mixture of two or more substances that behaves as if they were a single substance. One way of characterizing an azeotropic composition is that the vapor produced by partial evaporation or distillation of a liquid has the same composition as the liquid from which it was evaporated or distilled, i.e., the mixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic because they exhibit a maximum or minimum boiling point as compared to a non-azeotropic mixture of the same compounds. Azeotropic compositions do not fractionate during operation within a refrigeration or air conditioning system, which can reduce the efficiency of the system. In addition, azeotropic compositions do not fractionate upon leakage from refrigeration or air conditioning systems. In the case where one component of the mixture is flammable, fractional distillation during a leak can produce a flammable composition either within the system or outside the system.

Near-azeotropic compositions (also commonly referred to as "azeotrope-like compositions") are liquid mixtures of two or more substances that behave essentially as if the substances were substantially constant boiling as a single substance. One way of characterizing a near-azeotropic composition is that the vapor produced by the partial evaporation or distillation of a liquid has substantially the same composition as the liquid from which it was evaporated or distilled, i.e., the mixture distills/refluxes with substantially no change in composition. Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is near-azeotropic if, after 50 weight percent of the composition is removed, for example, by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition is removed is less than about 10 percent.

The azeotropic compositions of the present invention at the indicated temperatures are shown in table 4.

TABLE 4

Component A	Component B	Wt％A	Wt％B	Psia	kPa	T(C)
							HFC-1234yf	HFC-32	7.4	92.6	49.2	339	-25
HFC-1234yf	HFC-125	10.9	89.1	40.7	281	-25
							HFC-1234yf	HFC-134a	70.4	29.6	18.4	127	-25
HFC-1234yf	HFC-152a	91.0	9.0	17.9	123	-25
							HFC-1234yf	HFC-143a	17.3	82.7	39.5	272	-25
HFC-1234yf	HFC-227ea	84.6	15.4	18.0	124	-25
							HFC-1234yf	Propane	51.5	48.5	33.5	231	-25
HFC-1234yf	N-butane	98.1	1.9	17.9	123	-25
							HFC-1234yf	Isobutane	88.1	11.9	19.0	131	-25
HFC-1234yf	DME	53.5	46.5	13.1	90	-25
							HFC-1225ye	Trans-HFC-1234 ze	63.0	37.0	11.7	81	-25
HFC-1225ye	HFC-1243zf	40.0	60.0	13.6	94	-25
							HFC-1225ye	HFC-134	52.2	47.8	12.8	88	-25
HFC-1225ye	HFC-152a	7.3	92.7	14.5	100	-25
							HFC-1225ye	Propane	29.7	70.3	30.3	209	-25
HFC-1225ye	N-butane	89.5	10.5	12.3	85	-25
							HFC-1225ye	Isobutane	79.3	20.7	13.9	96	-25
HFC-1225ye	DME	82.1	17.9	10.8	74	-25

HFC-1225ye	CF3SCF3	37.0	63.0	12.4	85	-25
							Trans-HFC-1234 ze	HFC-1243zf	17.0	83.0	13.0	90	-25
Trans-HFC-1234 ze	HFC-134	45.7	54.3	12.5	86	-25
							Trans-HFC-1234 ze	HFC-134a	9.5	90.5	15.5	107	-25
Trans-HFC-1234 ze	HFC-152a	21.6	78.4	14.6	101	-25
							Trans-HFC-1234 ze	HFC-227ea	59.2	40.8	11.7	81	-25
Trans-HFC-1234 ze	Propane	28.5	71.5	30.3	209	-25
							Trans-HFC-1234 ze	N-butane	88.6	11.4	11.9	82	-25
Trans-HFC-1234 ze	Isobutane	77.9	22.1	12.9	89	-25
							Trans-HFC-1234 ze	DME	84.1	15.9	10.8	74	-25
Trans-HFC-1234 ze	CF3SCF3	34.3	65.7	12.7	88	-25
							HFC-1243zf	HFC-134	63.0	37.0	13.5	93	-25
HFC-1243zf	HFC-134A	25.1	74.9	15.9	110	-25
							HFC-1243zf	HFC-152A	40.7	59.3	15.2	104	-25
HFC-1243zf	HFC-227ea	78.5	21.5	13.1	90	-25
							HFC-1243zf	Propane	32.8	67.2	31.0	213	-25
HFC-1243zf	N-butane	90.3	9.7	13.5	93	-25
							HFC-1243zf	Isobutane	80.7	19.3	14.3	98	-25
HFC-1243zf	DME	72.7	27.3	12.0	83	-25
							cis-HFC-1234 ze	HFC-236ea	20.9	79.1	30.3	209	25
cis-HFC-1234 ze	HFC-245fa	76.2	23.8	26.1	180	25
							cis-HFC-1234 ze	N-butane	51.4	48.6	6.08	42	-25
cis-HFC-1234 ze	Isobutane	26.2	73.8	8.74	60	-25
							cis-HFC-1234 ze	2-methylbutane	86.6	13.4	27.2	188	25
cis-HFC-1234 ze	N-pentane	92.9	7.1	26.2	181	25
							HFC-1234ye	HFC-236ea	24.0	76.0	3.35	23.1	-25
HFC-1234ye	HFC-245fa	42.5	57.5	22.8	157	25
							HFC-1234ye	N-butane	41.2	58.8	38.0	262	25
HFC-1234ye	Isobutane	16.4	83.6	50.9	351	25
							HFC-1234ye	2-methylbutane	80.3	19.7	23.1	159	25
HFC-1234ye	N-pentane	87.7	12.3	21.8	150	25

In addition, the ternary azeotrope compositions were found to be as listed in table 5.

TABLE 5

Component A	Component B	Component C	Wt％A	Wt％B	Wt％C	Pressure (psi)	Pressure (kPa)	Temperature (. degree.C.)
									HFC-1234yf	HFC-32	HFC-143A	3.9	74.3	21.8	50.02	345	-25
HFC-1234yf	HFC-32	Isobutane	1.1	92.1	6.8	50.05	345	-25
									HFC-1234yf	HFC-125	HFC-143A	14.4	43.5	42.1	38.62	266	-25
HFC-1234yf	HFC-125	Isobutane	9.7	89.1	1.2	40.81	281	-25
									HFC-1234yf	HFC-134	Propane	4.3	39.1	56.7	34.30	236	-25
HFC-1234yf	HFC-134	DME	15.2	67.0	17.8	10.38	71.6	-25
									HFC-1234yf	HFC-134a	Propane	24.5	31.1	44.5	34.01	234	-25
HFC-1234yf	HFC-134a	N-butane	60.3	35.2	4.5	18.58	128	-25
									HFC-1234yf	HFC-134a	Isobutane	48.6	37.2	14.3	19.86	137	-25
HFC-1234yf	HFC-134a	DME	24.0	67.9	8.1	17.21	119	-25
									HFC-1234yf	HFC-143a	Propane	17.7	71.0	11.3	40.42	279	-25
HFC-1234yf	HFC-143a	DME	5.7	93.0	1.3	39.08	269	-25
									HFC-1234yf	HFC-152a	N-butane	86.6	10.8	2.7	17.97	124	-25
HFC-1234yf	HFC-152a	Isobutane	75.3	11.8	12.9	19.12	132	-25
									HFC-1234yf	HFC-152a	DME	24.6	43.3	32.1	11.78	81.2	-25
HFC-1234yf	HFC-227ea	Propane	35.6	17.8	46.7	33.84	233	-25
									HFC-1234yf	HFC-227ea	N-butane	81.9	16.0	2.1	18.07	125	-25
HFC-1234yf	HFC-227ea	Isobutane	70.2	18.2	11.6	19.27	133	-25
									HFC-1234yf	HFC-227ea	DME	28.3	55.6	16.1	15.02	104	-25
HFC-1234yf	N-butane	DME	48.9	4.6	46.4	13.15	90.7	-25
									HFC-1234yf	Isobutane	DME	31.2	26.2	42.6	14.19	97.8	-25
HFC-1234yf	DME	CF3I	16.3	10.0	73.7	15.65	108	-25
									HFC-1234yf	DME	CF3SCF3	34.3	10.5	55.2	14.57	100	-25
HFC-1225ye	Trans-HFC-1234 ze	HFC-134	47.4	5.6	47.0	12.77	88.0	-25

Trans-HFC-1234 ze	HFC-1243zf	DME	2.6	70.0	27.4	12.03	82.9	-25
									Trans-HFC-1234 ze	HFC-134	HFC-152a	52.0	42.9	5.1	12.37	85.3	-25
Trans-HFC-1234 ze	HFC-134	HFC-227ea	30.0	43.2	26.8	12.61	86.9	-25
									Trans-HFC-1234 ze	HFC-134	DME	27.7	54.7	17.7	9.76	67.3	-25
Trans-HFC-1234 ze	HFC-134a	HFC-152a	14.4	34.7	51.0	14.42	99.4	-25
									Trans-HFC-1234 ze	HFC-152a	N-butane	5.4	80.5	14.1	15.41	106	-25
Trans-HFC-1234ze	HFC-152a	DME	59.1	16.4	24.5	10.80	74.5	-25
									Trans-HFC-1234 ze	HFC-227ea	N-butane	40.1	48.5	11.3	12.61	86.9	-25
Trans-HFC-1234 ze	N-butane	DME	68.1	13.0	18.9	11.29	77.8	-25
									Trans-HFC-1234 ze	N-butane	CF3I	81.2	9.7	9.1	11.87	81.8	-25
Trans-HFC-1234 ze	Isobutane	DME	55.5	28.7	15.8	12.38	85.4	-25
									Trans-HFC-1234 ze	Isobutane	CF3I	34.9	6.1	59.0	12.57	86.7	-25
Trans-HFC-1234 ze	Isobutane	CF3SCF3	37.7	1.1	61.7	12.66	87.3	-25
									HFC-1243zf	HFC-134	HFC-227ea	58.6	34.1	7.3	13.54	93.4	-25
HFC-1243zf	HFC-134	N-butane	27.5	58.7	13.9	14.72	101	-25
									HFC-1243zf	HFC-134	DME	18.7	63.5	17.8	10.11	69.7	-25
HFC-1243zf	HFC-134	CF3I	11.4	23.9	64.7	14.45	99.6	-25
									HFC-1243zf	HFC-134a	HFC-152a	41.5	21.5	37.1	14.95	103	-25

HFC-1243zf	HFC-134A	N-butane	7.0	81.4	11.6	17.03	117	-25
									HFC-1243zf	HFC-152a	Propane	2.9	34.0	63.0	31.73	219	-25
HFC-1243zf	HFC-152a	N-butane	28.8	60.3	11.0	15.71	108	-25
									HFC-1243zf	HFC-152a	Isobutane	6.2	68.5	25.3	17.05	118	-25
HFC-1243zf	HFC-152a	DME	33.1	36.8	30.1	11.41	78.7	-25
									HFC-1243zf	HFC-227ea	N-butane	62.0	28.4	9.6	13.67	94.3	-25
HFC-1243zf	HFC-227ea	Isobutane	27.9	51.0	21.1	15.00	103	-25
									HFC-1243zf	HFC-227ea	DME	48.1	44.8	7.2	12.78	88.1	-25
HFC-1243zf	N-butane	DME	60.3	10.1	29.6	12.28	84.7	-25
									HFC-1243zf	Isobutane	DME	47.1	26.9	25.9	13.16	90.7	-25
HFC-1243zf	Isobutane	CF3I	32.8	1.1	66.1	13.97	96.3	-25
									HFC-1243zf	DME	CF3SCF3	41.1	2.3	56.6	13.60	93.8	-25

The near azeotrope compositions of the present invention at the indicated temperatures are listed in table 6.

TABLE 6

Component A	Component B	(wt％A/wt％B)	T(C)
				HFC-1234yf	HFC-32	1-57/99-43	-25
HFC-1234yf	HFC-125	1-51/99-49	-25
				HFC-1234yf	HFC-134	1-99/99-1	-25
HFC-1234yf	HFC-134a	1-99/99-1	-25
				HFC-1234yf	HFC-152a	1-99/99-1	-25
HFC-1234yf	HFC-161	1-99/99-1	-25
				HFC-1234yf	HFC-143a	1-60/99-40	-25
HFC-1234yf	HFC-227ea	29-99/71-1	-25
				HFC-1234yf	HFC-236fa	66-99/34-1	-25
HFC-1234yf	HFC-1225ye	1-99/99-1	-25
				HFC-1234yf	Trans-HFC-1234 ze	1-99/99-1	-25
HFC-1234yf	HFC-1243zf	1-99/99-1	-25
				HFC-1234yf	Propane	1-80/99-20	-25
HFC-1234yf	N-butane	71-99/29-1	-25

HFC-1234yf	Isobutane	60-99/40-1	-25
				HFC-1234yf	DME	1-99/99-1	-25
HFC-1225ye	Trans-HFC-1234 ze	1-99/99-1	-25
				HFC-1225ye	HFC-1243zf	1-99/99-1	-25
HFC-1225ye	HFC-134	1-99/99-1	-25
				HFC-1225ye	HFC-134a	1-99/99-1	-25
HFC-1225ye	HFC-152a	1-99/99-1	-25
				HFC-1225ye	HFC-161	1-84/99-16，90-99/10-1	-25
HFC-1225ye	HFC-227ea	1-99/99-1	-25
				HFC-1225ye	HFC-236ea	57-99/43-1	-25
HFC-1225ye	HFC-236fa	48-99/52-1	-25
				HFC-1225ye	HFC-245fa	70-99/30-1	-25
HFC-1225ye	Propane	1-72/99-28	-25
				HFC-1225ye	N-butane	65-99/35-1	-25
HFC-1225ye	Isobutane	50-99/50-1	-25
				HFC-1225ye	DME	1-99/99-1	-25
HFC-1225ye	CF3I	1-99/99-1	-25
				HFC-1225ye	CF3SCF3	1-99/99-1	-25
Trans-HFC-1234 ze	cis-HFC-1234 ze	73-99/27-1	-25
				Trans-HFC-1234 ze	HFC-1243zf	1-99/99-1	-25
Trans-HFC-1234 ze	HFC-134	1-99/99-1	-25
				Trans-HFC-1234 ze	HFC-134a	1-99/99-1	-25
Trans-HFC-1234 ze	HFC-152a	1-99/99-1	-25
				Trans-HFC-1234 ze	HFC-161	1-52/99-48，87-99/13-1	-25
Trans-HFC-1234 ze	HFC-227ea	1-99/99-1	-25
				Trans-HFC-1234 ze	HFC-236ea	54-99/46-1	-25
Trans-HFC-1234 ze	HFC-236fa	44-99/56-1	-25
				Trans-HFC-1234 ze	HFC-245fa	67-99/33-1	-25
Trans-HFC-1234 ze	Propane	1-71/99-29	-25
				Trans-HFC-1234 ze	N-butane	62-99/38-1	-25
Trans-HFC-1234 ze	Isobutane	39-99/61-1	-25
				Trans-HFC-1234 ze	DME	1-99/99-1	-25

Trans-HFC-1234 ze	CF3SCF3	1-99/99-1	-25
				Trans-HFC-1234 ze	CF3I	1-99/99-1	-25
HFC-1243zf	HFC-134	1-99/99-1	-25
				HFC-1243zf	HFC-134a	1-99/99-1	-25
HFC-1243zf	HFC-152a	1-99/99-1	-25
				HFC-1243zf	HFC-161	1-99/99-1	-25
HFC-1243zf	HFC-227ea	1-99/99-1	-25
				HFC-1243zf	HFC-236ea	53-99/47-1	-25
HFC-1243zf	HFC-236fa	49-99/51-1	-25
				HFC-1243zf	HFC-245fa	66-99/34-1	-25
HFC-1243zf	Propane	1-71/99-29	-25
				HFC-1243zf	N-butane	62-99/38-1	-25
HFC-1243zf	Isobutane	45-99/55-1	-25
				HFC-1243zf	DME	1-99/99-1	-25
cis-HFC-1234 ze	HFC-236ea	1-99/99-1	25
				cis-HFC-1234 ze	HFC-236fa	1-99/99-1	25
cis-HFC-1234 ze	HFC-245fa	1-99/99-1	25
				cis-HFC-1234 ze	N-butane	1-80/99-20	-25
cis-HFC-1234 ze	Isobutane	1-69/99-31	-25
				cis-HFC-1234 ze	2-methylbutane	60-99/40-1	25
cis-HFC-1234 ze	N-pentane	63-99/37-1	25
				HFC-1234ye	HFC-134	38-99/62-1	25
HFC-1234ye	HFC-236ea	1-99/99-1	-25
				HFC-1234ye	HFC-236fa	1-99/99-1	25
HFC-1234ye	HFC-245fa	1-99/99-1	25
				HFC-1234ye	cis-HFC-1234 ze	1-99/99-1	25
HFC-1234ye	N-butane	1-78/99-22	25
				HFC-1234ye	Cyclopentane	70-99/30-1	25
HFC-1234ye	Isobutane	1-68/99-32	25
				HFC-1234ye	2-methylbutane	47-99/53-1	25
HFC-1234ye	N-pentane	57-99/43-1	25

Ternary and higher near azeotrope compositions comprising fluoroolefins are also listed in table 7.

TABLE 7

Components	Near azeotrope Range (% by weight)	Temperature (. degree.C.)
			HFC-1225ye/HFC-134a/HFC-152a	1-98/1-98/1-98	25
HFC-1225ye/HFC-134a/HFC-161	1-98/1-98/1-98	25
			HFC-1225ye/HFC-134 a/isobutane	1-98/1-98/1-40	25
HFC-1225ye/HFC-134a/DME	1-98/1-98/1-20	25
			HFC-1225ye/HFC-152 a/isobutane	1-98/1-98/1-50	25
HFC-1225ye/HFC-152a/DME	1-98/1-98/1-98	25
			HFC-1225ye/HFC-1234yf/HFC-134a	1-98/1-98/1-98	25
HFC-1225ye/HFC-1234yf/HFC-152a	1-98/1-98/1-98	25
			HFC-1225ye/HFC-1234yf/HFC-125	1-98/1-98/1-20	25
HFC-1225ye/HFC-1234yf/CF3I	1-98/1-98/1-98	25
			HFC-1225ye/HFC-134a/HFC-152a/HFC-32	1-97/1-97/1-97/1-10	25
HFC-125/HFC-1225 ye/isobutane	80-98/1-19/1-10	25
			HFC-125/trans-HFC-1234 ze/isobutane	80-98/1-19/1-10	25
HFC-125/HFC-1234 yf/isobutane	80-98/1-19/1-10	25
			HFC-32/HFC-125/HFC-1225ye	1-98/1-98/1-4	25
HFC-32/HFC-125/trans-HFC-1234 ze	1-98/1-98/1-50	25
			HFC-32/HFC-125/HFC-1234yf	1-98/1-98/1-55	25
HFC-125/trans-HFC-1234 ze/n-butane	80-98/1-19/1-10	25
			HFC-125/HFC-1234 yf/n-butane	80-98/1-19/1-10	25
HFC-1234yf/HFC-32/HFC-143a	1-50/1-98/1-98	-25
			HFC-1234 yf/HFC-32/isobutane	1-40/59-98/1-30	-25
HFC-1234yf/HFC-125/HFC-143a	1-60/1-98/1-98	-25
			HFC-1234 yf/HFC-125/isobutane	1-40/59-98/1-20	-25
HFC-1234 yf/HFC-134/propane	1-80/1-70/19-90	-25
			HFC-1234yf/HFC-134/DME	1-70/1-98/29-98	-25

HFC-1234yf/HFC-134 a/propane	1-80/1-80/19-98	-25
			HFC-1234yf/HFC-134 a/n-butane	1-98/1-98/1-30	-25
HFC-1234yf/HFC-134 a/isobutane	1-98/1-98/1-30	-25
			HFC-1234yf/HFC-134a/DME	1-98/1-98/1-40	-25
HFC-1234yf/HFC-143 a/propane	1-80/1-98/1-98	-25
			HFC-1234yf/HFC-143a/DME	1-40/59-98/1-20	-25
HFC-1234yf/HFC-152 a/n-butane	1-98/1-98/1-30	-25
			HFC-1234yf/HFC-152 a/isobutane	1-98/1-90/1-40	-25
HFC-1234yf/HFC-152a/DME	1-70/1-98/1-98	-25
			HFC-1234yf/HFC-227 ea/propane	1-80/1-70/29-98	-25
HFC-1234yf/HFC-227 ea/n-butane	40-98/1-59/1-20	-25
			HFC-1234yf/HFC-227 ea/isobutane	30-98/1-69/1-30	-25
HFC-1234yf/HFC-227ea/DME	1-98/1-80/1-98	-25
			HFC-1234 yf/n-butane/DME	1-98/1-40/1-98	-25
HFC-1234 yf/isobutane/DME	1-98/1-50/1-98	-25
			HFC-1234yf/DME/CF3I	1-98/1-98/1-98	-25
HFC-1234yf/DME/CF3SCF3	1-98/1-40/1-80	-25
			HFC-1225 ye/trans-HFC-1234 ze/HFC-134	1-98/1-98/1-98	-25
HFC-1225 ye/trans-HFC-1234 ze/HFC-227ea	1-98/1-98/1-98	-25
			HFC-1225 ye/trans-HFC-1234 ze/propane	1-60/1-60/1-98	-25
HFC-1225 ye/trans-HFC-1234 ze/n-butane	1-98/1-98/1-30	-25
			HFC-1225 ye/trans-HFC-1234 ze/DME	1-98/1-98/1-98	-25
HFC-1225 ye/trans-HFC-1234 ze/CF3SCF3	1-98/1-98/1-98	-25
			HFC-1225ye/HFC-1243zf/HFC-134	1-98/1-98/1-98	-25
HFC-1225ye/HFC-1243 zf/n-butane	1-98/1-98/1-30	-25
			HFC-1225ye/HFC-1243 zf/isobutane	1-98/1-98/1-40	-25
HFC-1225ye/HFC-1243zf/DME	1-98/1-98/1-98	-25
			HFC-1225ye/HFC-1243zf/CF3I	1-98/1-98/1-98	-25
HFC-1225ye/HFC-134/HFC-152a	1-98/1-98/1-98	-25
			HFC-1225ye/HFC-134/HFC-227ea	1-98/1-98/1-98	-25
HFC-1225 ye/HFC-134/n-butane	1-98/1-90/1-40	-25

HFC-1225 ye/HFC-134/isobutane	1-98/1-90/1-40	-25
			HFC-1225ye/HFC-134/DME	1-98/1-98/1-40	-25
HFC-1225ye/HFC-227ea/DME	40-98/1-59/1-30	-25
			HFC-1225 ye/n-butane/DME	1-98/1-30/1-98	-25
HFC-1225 ye/n-butane/CF3SCF3	1-98/1-20/1-98	-25
			HFC-1225 ye/isobutane/DME	1-98/1-60/1-98	-25
HFC-1225 ye/isobutane/CF3I	1-98/1-40/1-98	-25
			Trans-HFC-1234 ze/HFC-1243zf/HFC-227ea	1-98/1-98/1-98	-25
trans-HFC-1234 ze/HFC-1243 zf/n-butane	1-98/1-98/1-30	-25
			Trans-HFC-1234 ze/HFC-1243 zf/isobutane	1-98/1-98/1-40	-25
Trans-HFC-1234 ze/HFC-1243zf/DME	1-98/1-98/1-98	-25
			Trans-HFC-1234 ze/HFC-134/HFC-152a	1-98/1-98/1-98	-25
Trans-HFC-1234 ze/HFC-134/HFC-227ea	1-98/1-98/1-98	-25
			Trans-HFC-1234 ze/HFC-134/DME	1-98/1-98/1-40	-25
Trans-HFC-1234 ze/HFC-134a/HFC-152a	1-98/1-98/1-98	-25
			Trans-HFC-1234 ze/HFC-152 a/n-butane	1-98/1-98/1-50	-25
Trans-HFC-1234 ze/HFC-152a/DME	1-98/1-98/1-98	-25
			Trans-HFC-1234 ze/HFC-227 ea/n-butane	1-98/1-98/1-40	-25
Trans-HFC-1234 ze/n-butane/DME	1-98/1-40/1-98	-25
			Trans-HFC-1234 ze/n-butane/CF3I	1-98/1-30/1-98	-25
Trans-HFC-1234 ze/isobutane/DME	1-98/1-60/1-98	-25
			Trans-HFC-1234 ze/isobutane/CF3I	1-98/1-40/1-98	-25
Trans-HFC-1234 ze/isobutane/CF3SCF3	1-98/1-40/1-98	-25
			HFC-1243zf/HFC-134/HFC-227ea	1-98/1-98/1-98	-25
HFC-1243 zf/HFC-134/n-butane	1-98/1-98/1-40	-25
			HFC-1243zf/HFC-134/DME	1-98/1-98/1-98	-25
HFC-1243zf/HFC-134/CF3I	1-98/1-98/1-98	-25
			HFC-1243zf/HFC-134a/HFC-152a	1-98/1-98/1-98	-25
HFC-1243zf/HFC134 a/n-butane	1-98/1-98/1-40	-25
			HFC-1243zf/HFC-152 a/propane	1-70/1-70/29-98	-25
HFC-1243zf/HFC-152 a/n-butane	1-98/1-98/1-30	-25

HFC-1243zf/HFC-152 a/isobutane	1-98/1-98/1-40	-25
			HFC-1243zf/HFC-152a/DME	1-98/1-98/1-98	-25
HFC-1243zf/HFC-227 ea/n-butane	1-98/1-98/1-40	-25
			HFC-1243zf/HFC-227 ea/isobutane	1-98/1-90/1-50	-25
HFC-1243zf/HFC-227ea/DME	1-98/1-80/1-90	-25
			HFC-1243 zf/n-butane/DME	1-98/1-40/1-98	-25
HFC-1243 zf/isobutane/DME	1-98/1-60/1-98	-25
			HFC-1243 zf/isobutane/CF3I	1-98/1-40/1-98	-25
HFC-1243zf/DME/CF3SCF3	1-98/1-40/1-90	-25

U.S. patent application No.11/369,227 filed on 3/2/2006; U.S. patent application No.11/393,109 filed on 30/3/2006; and other fluoroolefin-containing compositions disclosed in U.S. patent application No.11/486,791 filed on 13.7.2006 are intended to be included within the scope of the present invention.

Certain compositions of the present invention are non-azeotropic compositions. Those compositions of the invention within the preferred ranges of table 3 but outside the near azeotrope ranges of tables 6 and 7 may be considered to be non-azeotropic.

Non-azeotropic compositions may have certain advantages over azeotropic or near-azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than as a single substance. One way of characterizing a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of a liquid has a significantly different composition than the liquid from which it was evaporated or distilled, i.e., distillation/reflux of the mixture is accompanied by a significant compositional change. Another way to characterize a non-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are significantly different. Herein, a composition is non-azeotropic if, after removal of 50 weight percent of the composition, for example by evaporation or boiling, the difference in vapor pressure between the original composition and the composition remaining after removal of 50 weight percent of the original composition is greater than about 10%.

The compositions of the present invention may be prepared by any convenient method for combining the components in the desired amounts. A preferred method is to weigh out the desired amounts of the components and thereafter combine the components in a suitable container. Stirring may be used if desired.

An alternative way of making the compositions of the present invention can be a method of making a refrigerant blend composition, wherein the refrigerant blend composition comprises a composition disclosed herein, the method comprising (i) recovering a volume of one or more components of a refrigerant composition from at least one refrigerant vessel, (ii) removing impurities sufficiently to enable reuse of the one or more recovered components, (iii) and, optionally, combining all or a portion of the recovered volume of components with at least one additional refrigerant composition or component.

The refrigerant container may be any container that stores a refrigerant blend composition that has been used in a refrigeration unit, air conditioning unit, or heat pump unit. The refrigerant container may be a refrigeration device, an air conditioning device or a heat pump device in which the refrigerant blend is used. Additionally, the refrigerant container may be a storage container for collecting the recovered refrigerant blend components, including but not limited to a pressurized gas cylinder.

Residual refrigerant refers to any amount of refrigerant blend or refrigerant blend components that can be removed from the refrigerant vessel by any method known for transferring refrigerant blends or refrigerant blend components.

The impurities may be any component present in the refrigerant blend or refrigerant blend components as a result of their use in a refrigeration, air conditioning or heat pump apparatus. Such impurities include, but are not limited to, refrigeration lubricants as described above, particulates that may come from refrigeration, air conditioning or heat pump devices, including but not limited to metal, metal salt or elastomer particles, and any other contaminants that may adversely affect the performance of the refrigerant blend composition.

Such impurities can be removed sufficiently to allow the refrigerant blend or refrigerant blend components to be reused without adversely affecting the equipment or performance in which they are used.

In addition to the residual refrigerant blend or refrigerant blend components, it may be necessary to provide additional refrigerant blend or refrigerant blend components to produce a composition that meets the desired specifications for a given product. For example, if a refrigerant blend has 3 components in a particular weight percent range, it may be necessary to add one or more of the components in a given amount to bring the composition back within specification limits.

The heat transfer fluid compositions of the present invention have a Global Warming Potential (GWP) that is less than many hydrofluorocarbon refrigerants in use today. Preferably, such compositions also have an ozone depletion potential of 0 or less. One aspect of the present invention is to provide refrigerants having a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the invention is to reduce the net GWP of the refrigerant mixture by adding a fluoroolefin to the mixture.

The compositions of the present invention may be used as low Global Warming Potential (GWP) replacements for currently used refrigerants, including, but not limited to, R134a (or HFC-134a, 1, 1, 1, 2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2, 2-dichloro-1, 1, 1-trifluoroethane), R11(CFC-11, fluorotrichloromethane), R12(CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1, 1, 3, 3-pentafluoropropane), R114 (or CFC-114, 1, 2-dichloro-1, 1, 2, 2-tetrafluoroethane), R236fa (or HFC-236fa, 1, 1, 3, 3, 3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1, 1, 1, 2-tetrafluoroethane), R407C (ASHRAE name of a blend of 52 wt% R134a, 25 wt% R125 (pentafluoroethane) and 23 wt% R32 (difluoromethane), R410A (ASHRAE name of a blend of 50 wt% R125 and 50 wt% R32), R417A (ASHRAE name of a blend of 46.6 wt% R125, 50.0 wt% R134a and 3.4 wt% n-butane), R422A, R422B, R422C and R422D (ASHRAE name of a blend of 85.1 wt% R125, 11.5 wt% R134a and 3.4 wt% isobutane), R404A (ASHRAE name of a blend of 44 wt% R125, 52 wt% R143a (1, 1, 1-tetrafluoroethane) and 4.0 wt% R134 a), and R125 and 50 wt% R36507 (ASHRAE name of a blend of R A, R143R 507 and 50 wt% R36507). In addition, the compositions of the present invention may be used as a replacement for R12(CFC-12, dichlorodifluoromethane) or R502 (ASHRAE name for blends of 51.2 wt% CFC-115 (chloropentafluoroethane) and 48.8 wt% HCFC-22).

In general, replacement refrigerants are most useful if they can be used in original refrigeration equipment designed for different refrigerants. The compositions of the present invention can be used in original equipment as a replacement for the refrigerants described above. Additionally, the compositions of the present invention may be used as a replacement for the above-described refrigerants in equipment designed to use the above-described refrigerants.

The composition of the present invention may further comprise a lubricant. The lubricants of the present invention comprise refrigeration lubricants, i.e. those suitable for use with refrigeration, air conditioning or heat pump apparatus. These lubricants include those conventionally used in compression refrigeration units employing chlorofluorocarbon refrigerants. In 1990 ASHRAESuch Lubricants and their properties are discussed in Handbook, refining Systems and Applications, chapter 8, entitled "Lubricants in refining Systems", pages 8.1 to 8.21. The lubricants of the present invention may comprise those commonly referred to as "mineral oils" in the field of compression refrigeration lubrication. Mineral oils comprise paraffinic hydrocarbons (i.e., saturated hydrocarbons with straight and branched carbon chains), naphthenic hydrocarbons (i.e., cycloparaffins), and aromatic hydrocarbons (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention further comprise those commonly referred to as "synthetic oils" in the field of compression refrigeration lubrication. Synthetic oils comprise alkylaryl (i.e., straight and branched alkyl alkylbenzenes), synthetic alkanes and cycloalkanes, and poly (alpha-olefins). Representative conventional lubricants of the present invention are commercially available BVM 100N (paraffinic mineral oil sold by BVA Oils),3GS and5GS (commercially available naphthenic mineral oil from Crompton Co.),372LT (naphthenic mineral oil sold by Pennzoil),RO-30 (naphthenic mineral oil sold by Calumet Lubricants),75、150 and500 (straight alkylbenzene sold by Shrieve Chemicals) and HAB 22 (branched alkylbenzene sold by Nippon Oil).

The lubricants of the present invention further comprise lubricants that have been designed to produce with hydrofluorocarbonsRefrigerants that are used together and are miscible with the refrigerants of the present invention under compression refrigeration, air conditioning or heat pump apparatus operating conditions. Such Lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", R.L. Shunkin, ed., Marcel Dekker, 1993. Such lubricants include, but are not limited to, polyol esters (POEs), for example100(Castrol, United kingdom), polyalkylene glycols (PAG), such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVE). These lubricants are readily available from various commercial sources.

The lubricant of the present invention is selected by considering the requirements of a given compressor and the environment to which the lubricant is exposed. The lubricants of the present invention preferably have a kinematic viscosity of at least about 5cs (centistokes) at 40 ℃.

Conventional refrigeration system additives may optionally be added to the compositions of the present invention as needed to enhance lubricity and system stability. These additives are generally known in the art of refrigeration compressor lubrication and include antiwear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface passivators, free radical scavengers, foaming and antifoam control agents, leak detection agents, and the like. Typically, these additives are present in only small amounts relative to the total lubricant composition. They are generally used at concentrations of less than about 0.1% up to about 3% of each additive. These additives are selected based on the respective system requirements. Some representative examples of such additives may include, but are not limited to, lubricity enhancing additives such as alkyl or aryl esters of phosphoric and thiophosphoric acids. Additionally, metal salts of dialkyldithiophosphoric acids (e.g., zinc dialkyldithiophosphate or ZDDP, Lubrizol 1375) and other members of the chemical family may be used in the compositions of the present invention. Other antiwear additives include natural product oils and asymmetric polyhydroxy lubricant additives such as Synergol TMS (International lubricants). Similarly, stabilizers such as antioxidants, radical scavengers, and water scavengers may be used. Compounds within this class may include, but are not limited to, Butylated Hydroxytoluene (BHT) and epoxides.

The compositions of the present invention may further comprise from about 0.01% to about 5% by weight of additives such as stabilizers, free radical scavengers, and/or antioxidants. Such additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites or lactones. Single additives or combinations may be used.

The compositions of the present invention may further comprise from about 0.01% to about 5% by weight of a water scavenger (dry compound). Such water scavengers may comprise orthoesters, such as trimethyl-, triethyl-, or tripropylorthoformate.

In one embodiment, the present compositions comprising fluoroolefins may further comprise at least one compound selected from HFC-1225ye, HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3, CO2, ammonia, and CF 3I. These additional components are commercially available.

With the double bond, the fluoroolefin compositions of the present invention are more readily detectable at low levels than more traditional saturated fluorocarbon working fluids. Thus, with the present invention, tracer compounds, such as dyes, are not required to detect leaks, even at low concentration levels, such as would occur with small leaks.

In another embodiment, the present invention provides a method of detecting a leak in a refrigeration or air conditioning system in which the fluid is a refrigerant composition comprising carbon dioxide, said method comprising adding a minor amount of a fluoroolefin to said refrigerant composition. The method of the present invention allows for the detection of carbon dioxide or leaks from the system even in the presence of ambient carbon dioxide in the air. The sensor of the present invention responds to fluoroolefins, thereby signaling the presence of a leak. For the addition of fluoroolefins to effectively detect carbon dioxide leaks in the present process, the fluoroolefins may be present at less than about 1 weight percent. In another embodiment, the fluoroolefin may be present in a range of from about 0.1 weight percent (or 1000 weight ppm) to about 0.01 weight percent (or 100 weight ppm).

Examples

Near infrared spectroscopy of fluoroolefins

This example shows that NIR spectra can be obtained for the fluoroolefins described herein. Samples of 1, 2, 3, 3, 3-pentafluoropropene (HFC-1225ye) were analyzed at room temperature using a Variancary 500 UV/Vis/NIR spectrophotometer. The 10 mm sample chamber was charged with HFC-1225ye to a pressure of 748torr on the previously evacuated vacuum tube. The background spectrum of the same evacuated (< 1mTorr) chamber was collected and subtracted from the sample spectrum. For samples and background, the spots were collected at a resolution of 1 nanometer (nm) and averaged to 0.2 seconds/spot with a spectral bandwidth of 4 nanometers; detector and grating conversion occurs at 800 nanometers and the UV source is activated at 350 nanometers; and the spectra were scanned from 2600 to 190 nm. Figure 2 shows raw NIR spectral data of HFC-1225ye samples. Figure 3 shows a background NIR spectrum collected from an evacuated sample chamber. And figure 4 shows the background subtracted NIR spectrum of HFC-1225 ye. These data demonstrate that NIR spectra of fluoroolefins can be obtained, which provide a unique blot (fingerprint) for the detection of such compounds.

Claims (18)

1. A method for detecting a leak of a fluoroolefin composition in a fluid system, comprising sensing a component of the system with a sensing means for detecting a leak of said fluoroolefin composition, wherein said sensing means senses the double bond structure of said fluoroolefin composition, wherein said sensing means comprises a sensor selected from the group consisting of an infrared sensor, an ultraviolet sensor, a near infrared spectroscopy sensor, an ion mobility or plasma chromatography sensor, a gas chromatography sensor, a refractometer, a mass spectrometry sensor, a high temperature thick film sensor, a thin film field effect sensor, a pellistor sensor, a Taguchi sensor, and a quartz microbalance sensor.

2. The method of claim 1, wherein the sensing means is a near infrared spectroscopy sensor.

3. The method of claim 1, wherein the sensing tool comprises a tip.

4. The method of claim 1, wherein the sensing means comprises an extraction device.

5. The method of claim 1, wherein the sensing means comprises a sensor installed in situ in the system.

6. The process of claim 1 wherein said fluoroolefin comprises a compound having the formula E-or Z-R¹CH＝CHR²Wherein R is¹And R²Independently is C₁To C₆A perfluoroalkyl group.

7. The method of claim 6, wherein R¹And R²The radical being CF₃、C₂F₅、CF₂CF₂CF₃、CF(CF₃)₂、CF₂CF₂CF₂CF₃、CF(CF₃)CF₂CF₃、CF₂CF(CF₃)₂、C(CF₃)₃、CF₂CF₂CF₂CF₂CF₃、CF₂CF₂CF(CF₃)₂、C(CF₃)₂C₂F₅、CF₂CF₂CF₂CF₂CF₂CF₃、CF(CF₃)CF₂CF₂C₂F₅And C (CF)₃)₂CF₂C₂F₅。

8. The process of claim 1, wherein the fluoroolefin comprises a compound selected from the group consisting of: CF (compact flash)₃CF＝CHF，CF₃CH＝CF₂，CHF₂CF＝CF₂，CHF₂CF＝CHF，CF₃CF＝CH₂，CF₃CH＝CHF，CH₂FCF＝CF₂，CHF₂CH＝CF₂，CHF₂CF＝CHF，CHF₂CF＝CH₂，CF₃CH＝CH₂，CH₃CF＝CF₂，CH₂FCH＝CF₂，CH₂FCF＝CHF，CHF₂CH＝CHF，CF₃CF＝CFCF₃，CF₃CF₂CF＝CF₂，CF₃CF＝CHCF₃，CHF＝CFCF₂CF₃，CHF₂CF＝CFCF₃，(CF₃)₂C＝CHF，CF₂＝CHCF₂CF₃，CF₂＝CFCHFCF₃，CF₂＝CFCF₂CHF₂，CF₃CF₂CF＝CH₂，CF₃CH＝CHCF₃，CHF＝CHCF₂CF₃，CHF＝CFCHFCF₃，CHF＝CFCF₂CHF₂，CHF₂CF＝CFCHF₂，CH₂FCF＝CFCF₃，CHF₂CH＝CFCF₃，CF₃CH＝CFCHF₂，CF₂＝CFCF₂CH₂F，CF₂＝CFCHFCHF₂，CH₂＝C(CF₃)₂，CH₂FCH＝CFCF₃，CF₃CH＝CFCH₂F，CF₃CF₂CH＝CH₂，CHF₂CH＝CHCF₃，CF₃CF＝CFCH₃，CH₂＝CFCF₂CHF₂，CHF₂CF＝CHCHF₂，CH₃CF₂CF＝CF₂，CH₂FCF＝CFCHF₂，CH₂FCF₂CF＝CF₂，CF₂＝C(CF₃)(CH₃)，CH₂＝C(CHF₂)(CF₃)，CH₂＝CHCF₂CHF₂，CF₂＝C(CHF₂)(CH₃)，CHF＝C(CF₃)(CH₃)，CH₂＝C(CHF₂)₂，CF₃CF＝CHCH₃，CH₂＝CFCHFCF₃，CHF＝CFCH₂CF₃，CHF＝CHCHFCF₃，CHF＝CHCF₂CHF₂，CHF＝CFCHFCHF₂，CH₃CF＝CHCF₃，CF₃CF＝CFC₂F₅，CF₂＝CFCF₂CF₂CF₃，(CF₃)₂C＝CHCF₃，CF₃CF＝CHCF₂CF₃，CF₃CH＝CFCF₂CF₃，CHF＝CFCF₂CF₂CF₃，CF₂＝CHCF₂CF₂CF₃，CF₂＝CFCF₂CF₂CHF₂，CHF₂CF＝CFCF₂CF₃，CF₃CF＝CFCF₂CHF₂，CF₃CF＝CFCHFCF₃，CHF＝CFCF(CF₃)₂，CF₂＝CFCH(CF₃)₂，CF₃CH＝C(CF₃)₂，CF₂＝CHCF(CF₃)₂，CH₂＝CFCF₂CF₂CF₃，CHF＝CFCF₂CF₂CHF₂，CH₂＝C(CF₃)CF₂CF₃，CF₂＝CHCH(CF₃)₂，CHF＝CHCF(CF₃)₂，CF₂＝C(CF₃)CH₂CF₃，CF₃CH＝CHCF₂CF₃，(CF₃)₂CFCH＝CH₂，CF₃CF₂CF₂CH＝CH₂，CH₂＝CFCF₂CF₂CHF₂，CF₂＝CHCF₂CH₂CF₃，CF₃CF＝C(CF₃)(CH₃)，CH₂＝CFCH(CF₃)₂，CHF＝CHCH(CF₃)₂，CH₂FCH＝C(CF₃)₂，CH₃CF＝C(CF₃)₂，(CF₃)₂C＝CHCH₃，C₂F₅CF＝CHCH₃，CF₃C(CH₃)＝CHCF₃，CH₂＝CHCF₂CHFCF₃，CH₂＝C(CF₃)CH₂CF₃，CF₃(CF₂)₃CF＝CF₂，CF₃CF₂CF＝CFCF₂CF₃，(CF₃)₂C＝C(CF₃)₂，(CF₃)₂CFCF＝CFCF₃，(CF₃)₂C＝CHC₂F₅，(CF₃)₂CFCF＝CHCF₃，CF₃CH＝CHCF(CF₃)₂，CF₃CH＝CHCF₂CF₂CF₃，CF₂CF₂CH＝CHCF₂CF₃，CF₃CF₂CF₂CF₂CH＝CH₂，CH₂＝CHC(CF₃)₃，(CF₃)₂C＝C(CH₃)(CF₃)，H₂＝CFCF₂CH(CF₃)₂，CF₃CF＝C(CH₃)CF₂CF₃，CF₃CH＝CHCH(CF₃)₂，C₂F₅CF₂CF＝CHCH₃，CH₂＝CHCF₂CF₂CF₂CHF₂，(CF₃)₂C＝CHCF₂CH₃，CH₂＝C(CF₃)CH₂C₂F₅，CF₃CF₂CF₂C(CH₃)＝CH₂，CF₃CF₂CF₂CH＝CHCH₃，CH₂＝CHCH₂CF₂C₂F₅，CF₃CF₂CF＝CFC₂H₅，CH₂＝CHCH₂CF(CF₃)₂，CF₃CF＝CHCH(CF₃)(CH₃)，(CF₃)₂C＝CFC₂H₅，CF₃CF＝CFCF₂CF₂C₂F₅，CF₃CF₂CF＝CFCF₂C₂F₅，CF₃CH＝CFCF₂CF₂C₂F₅，CF₃CF＝CHCF₂CF₂C₂F₅，CF₃CF₂CH＝CFCF₂C₂F₅，CF₃CF₂CF＝CHCF₂C₂F₅cyclo-CF₂CF₂CF ═ CF-, cyclo-CF₂CF₂CH-, cyclo-CF₂CF₂CF₂CH-, cyclo-CF₂CF＝CFCF₂CF₂-and ring-CF₂CF＝CFCF₂CF₂CF₂。

9. The process of claim 1 wherein said composition comprising fluoroolefins further comprises at least one member selected from the group consisting of HFC-1225ye, HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF, and mixtures thereof₃SCF₃、CO₂Ammonia and CF₃A compound of formula I.

10. The process of claim 1 or 2, wherein the composition comprising a fluoroolefin comprises HFC-1234 yf.

11. A method of detecting a refrigerant fluid leak in a refrigeration or air conditioning system, wherein the refrigerant fluid comprises carbon dioxide, said method comprising adding a fluoroolefin to said refrigerant fluid, wherein the double bond structure of said added fluoroolefin in the resulting fluoroolefin-containing refrigerant fluid is sensed using a sensing means, wherein said sensing means comprises a sensor selected from the group consisting of an infrared sensor, an ultraviolet sensor, a near infrared spectroscopy sensor, an ion mobility or plasma chromatography sensor, a gas chromatography sensor, a refractometer, a mass spectrometry sensor, a high temperature thick film sensor, a thin film field effect sensor, a pellistor sensor, a Taguchi sensor and a quartz microbalance sensor.

12. The method of claim 11, wherein the sensing means is a near infrared spectroscopy sensor.

13. The process of claim 11 or 12 wherein the fluoroolefin added to the refrigerant fluid comprises HFC-1234 yf.

14. A detection system for sensing a leak in a fluoroolefin composition, comprising a sensing means for sensing the double bond structure of said fluoroolefin composition, wherein said sensing means comprises a sensor selected from the group consisting of an infrared sensor, an ultraviolet sensor, a near infrared spectroscopy sensor, an ion mobility or plasma chromatography sensor, a gas chromatography sensor, a refractometer, a mass spectrometry sensor, a high temperature thick film sensor, a thin film field effect sensor, a pellistor sensor, a Taguchi sensor, and a quartz microbalance sensor.

15. The detection system of claim 14, wherein the sensing means comprises a tip.

16. The detection system of claim 14, wherein the sensing means comprises an extraction device.

17. The detection system of claim 14, wherein the sensing means comprises a sensor mounted in situ on a component in the system.

18. The detection system according to claim 14, wherein said sensing means is a near infrared spectroscopy sensor.