USO08070355B2

(12) United States Patent (10) Patent No.: US 8,070,355 B2

Minor et al. (45) Date of Patent: Dec. 6, 2011

(54) METHOD OF DETECTING LEAKS OF 200,865. R : 3. Willian

Omura etetl . . . . . . . . . . . . . 29.
al. .................
FLUOROOLEFIN COMPOSITIONS AND 2005/0194560 A1* 9, 2005 Minor et al. .................... 252,67
SENSORS USED THEREFOR 2006/0069223 A1 3/2006 Lee et al.
2006, O130511 A1 6/2006 Brown et al.
(75) Inventors: Barbara Haviland Minor, Elkton, MD 2008/0295580 A1 12/2008 Minor et al.
(US); Nandini C. Mouli, Reisterstown, 2008/0314073 A1* 12/2008 Minor ............................. 62/498
MD (US); Daniel B. Laubacher, FOREIGN PATENT DOCUMENTS
Wilmington, DE (US); John Carl WO 00,24843 A 5, 2000
Steichen, Landenberg, PA (US) WO 2005,105.947 A 1 1/2005
WO 2006/083022 A 8, 2006
(73) Assignee: E. I. du Pont de Nemours and WO 2006/094303 A 9, 2006
Company, Wilmington, DE (US) WO 2007/053697 A 5/2007

(*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS
past lSE"listed under 35 Orkin V L et al., Rate constants for the reactions of OH with
M YW- y yS. HFC245cb(CH3CF2CF3) and some fluoroalkenes (CH2CHCF3,
(21) Appl. No.: 11/855,621 CH2CFCF3, CF2CFCF3, and CF2CF2), Journal of Physical Chem
istry A Molecules, Spectroscopy, Kinetics, Environment and General
(22) Filed: Sep. 14, 2007 Theory, Washingtion, DC, US, vol. 101, 1997, pp. 9118-9124.*
(65) Prior Publication Data (Continued)
US 2008/OO69.177 A1 Mar. 20, 2008
Primary Examiner — Christine T Mui
Related U.S. Application Data
(60) Pygal application No. 60/844,869, filed on Sep. (57) ABSTRACT
51) Int. C Disclosed are a method of detecting a leak of fluoroolefin
(51) oiN 25/00 (2006.01) compositions and sensors used therefor. In particular, the
GOIN 25/72 (2006,015 method is particularly useful for detecting a leak of a fluo
roolefin refrigerant composition from a cooling system of an
(52) U.S. Cl. ....... 374/4; 436/2:436/3; 75,233A2; automotive vehicle. Such fluoroolefin refrigerant composi
(58) Field of Classification S h 43 673. 2: tions have double bond structures which make them particu
OSSCO s4: 73,232.40 740 larly well Suited with sensing technologies, including: infra
See application file for com lete search histo s ws red sensors, UV sensors, NIR sensors, ion mobility or plasma
pp p ry. chromatographs, gas chromatography, refractometry, mass
(56) References Cited spectroscopy, high temperature thick film sensors, thin film
field effect sensors, pellistor sensors, Taguchi sensors and
U.S. PATENT DOCUMENTS quartz microbalance sensors.
5,496,901 A * 3/1996 DeSimone ...................... 526/89
5.996,358 A 12/1999 Sumida et al.
6,170,320 B1 1/2001 Scaringe et al. 15 Claims, 5 Drawing Sheets

Condenser

42

Evaporator
No
 US 8,070,355 B2
Page 2

OTHER PUBLICATIONS Atkins P W: “Physical Chemistry, Passage” Physical Chemistry,

Orkin V L et al: “Rate Constants for the Reactions of OH with
1990, pp. 458-497, XP002324574, table 16.3.
Non-Final Office Action mailed Mar. 31, 2010, in co-pending U.S.
HFC-245cb (CH3CF2CF3) and Some Fluoroalkenes (CH2CHCF3, Appl. No. 1 1/855,655.
CH2CFCF3, CF2CFCF3, and CF2CF2)” Journal of Physical Chem Final Office Action mailed Sep. 10, 2010, in co-pending U.S. Appl.
istry. A. Molecules, Spectroscopy, Kinetics, Environment and Gen No. 1 1/855,655.
eral Theory, Washington, DC, US, vol. 101, 1997, pp. 9118-9124, XP PCT International Search Report and Written Opinion, mailed Mar.
13, 2008.
002429691, ISSN: 1089-5639, p.9122, right hand column; figures 3,
6. * cited by examiner
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1. 2
METHOD OF DETECTING LEAKS OF Further in accordance with the present invention, there is
FLUOROOLEFIN COMPOSITIONS AND provided a detection system for detecting the double bond
SENSORS USED THEREFOR structure in a fluoroolefin composition. Such detection sys
tem comprises means for sensing the double bond structure of
CROSS REFERENCE(S) TO RELATED the fluoroolefin composition. The sensing means may com
APPLICATION(S) prise either a sensor which is used in-situ in the system, a
wand tip which may be used proximate the components of the
This application claims the benefit of priority of U.S. Pro system, or an extraction device, which may be used remote
visional Application 60/844,869, filed Sep. 15, 2006. 10
from the components of the system.
The sensor used in the sensing means of either embodiment
FIELD OF THE INVENTION may employ any of the following technologies: infrared sen
sors, UV sensors. NIR sensors, ion mobility or plasma chro
This disclosure relates to a method of detecting a leak of matographs, gas chromatography, refractometry, mass spec
fluoroolefin compositions and sensors used therefor. In par 15 troscopy, high temperature thick film sensors, thin film field
ticular, the disclosure relates to detecting a leak of a fluoroole effect sensors, pellistor sensors, Taguchi sensors and quartz
fin refrigerant composition from a vapor compression system. microbalance sensors.
Such refrigerant compositions may be useful in cooling sys
tems as replacements for existing refrigerants with higher BRIEF DESCRIPTION OF THE DRAWINGS
global warming potential.
FIG. 1 is a schematic diagram of a refrigeration or air
BACKGROUND OF THE INVENTION conditioning apparatus, including an extraction device which
is used in accordance with the method of the present inven
New environmental regulations on refrigerants have forced tion.
the refrigeration and air-conditioning industry to look for new 25 FIG. 1A is a schematic diagram of an example of a wand tip
refrigerants with low global warming potential (GWP). which is used in accordance with the method and the detec
Replacement refrigerants are being sought that have low tion system of the present invention.
GWP no toxicity, non-flammability, reasonable cost and FIG. 2 shows the raw NIR spectral data for a sample of
excellent refrigeration performance. 1,2,3,3,3-pentafluoropropene (HFC-1225ye).
Fluoroolefins have been proposed as refrigerants alone or 30 FIG. 3 shows the background NIR spectrum acquired for
in mixtures. When used in a vapor compression system, any the evacuated sample cell as a blank.
refrigerant has a tendency to leak from the system over time, FIG. 4 shows the background subtracted NIR spectrum for
as holes develop in the system. However, the leakage of HFC-1225ye.
refrigerant is at times difficult to detect, especially where the
holes in the system are small. A solution to this problem has 35 DESCRIPTION OF THE INVENTION
been to add a dye to the refrigerant and let the dye run through
the system. However, there is a cost associated with the addi Provided in accordance with the present invention is a
tion of the dye interms of both materials and time. In addition, method of detecting a leak of a fluoroolefin composition from
often the dye must be run through the system for a period of a fluid system. The fluoroolefin compositions detected with
time before the leak can be detected, which requires follow 40 the present invention have a variety of utilities, which include
up. use as foaming agents, blowing agents, fire extinguishing
agents, heat transfer mediums (such as heat transfer fluids and
SUMMARY OF THE INVENTION refrigerants for use in refrigeration systems, refrigerators, air
conditioning systems, heat pumps, chillers, and the like), to
The method of the present invention eliminates the need for 45 name a few. The type of fluid system from which a leak is
the use of a dye to detect leaks in fluid systems. It provides detected will depend on the utility of the composition. For
nearly instantaneous feedback for the location of a leak in the instance, when the composition is a refrigerant, the fluid
system, and eliminates the to expense and time of adding a system from which a leak is detected may be a cooling sys
dye to the system. It is therefore more cost effective than tem.
known methods for detecting leaks. 50 For exemplification, the present invention is illustrated
The method of the present invention is based on the under with respect to cooling system of an automotive vehicle. Such
standing of the unique double bond structure of fluoroolefins. a system is shown generally at 10 in FIG. 1. Such a cooling
Such double bond structure allows the use of sensing tech system may be a vapor-compression system. A vapor com
nologies which have heretofore not been available for detect pression system is a closed loop system which re-uses refrig
ing leaks. 55 erant in multiple steps producing a cooling effect in one step
Thus, in accordance with the present invention, there is and a heating effect in a different step. Such a system gener
provided a method of detecting leaks of a fluoroolefin com ally includes an evaporator, a compressor, a condenser and an
position in a fluid system. The method comprises sensing the expansion device, as will be described below in detail with
components of the system with sensing means for detecting respect to FIG.1. The vapor compression system may be used
leaks of a fluoroolefin composition. In particular, the sensing 60 in either stationary or mobile refrigeration or air-conditioning
means is capable of detecting the double bond structure in the applications.
fluoroolefin composition. With reference to FIG. 1, gaseous refrigerant from an
Also in accordance with the present invention, there is evaporator 42 flows through a hose 63 to the inlet of a com
provided a method for detecting a leak of a refrigerant fluid in pressor 12, and is then discharged. Various types of compres
a refrigeration or air-conditioning system wherein the refrig 65 sors may be used with the present invention, including recip
erant fluid comprises carbon dioxide, said method compris rocating, rotary jet, centrifugal, Scroll, Screw or axial-flow,
ing adding a fluoroolefin to said refrigerant fluid. depending on the mechanical means to compress the fluid, or
 US 8,070,355 B2
3 4
as positive-displacement (e.g., reciprocating, scroll or screw) tance, and is usually expressed as a percentage (% T). The
or dynamic (e.g., centrifugal or jet). absorbance, A, is based on the transmittance:
The compressed refrigerant gas from the compressor flows
through the compressor outlet and through a hose 61 to a
condenser 41. A pressure regulating valve 51 in hose 61 may The basic parts of a spectrophotometer are a light source
be used. This valve allows recycle of the refrigerant flow back (often an incandescent bulb for the visible wavelengths, or a
to the compressor via a hose 63, thereby providing the ability deuterium arc lamp in the ultraviolet), a holder for the sample,
to control the pressure of the refrigerant reaching the con a diffraction grating or monochromator to separate the differ
denser 41 and if necessary to prevent compressor Surge. The ent wavelengths of light, and a detector. The detector is typi
compressed refrigerant is condensed in the condenser, thus 10 cally a photodiode or a charge-coupled device which can
giving offheat. The liquid refrigerant flows through an expan store patterns of charge, also known as a CCD. Photodiodes
sion device 52 via a hose 62 to the evaporator 42, which is are used with monochromators, which filter the light so that
located in for instance, the passenger compartment of an only light of a single wavelength reaches the detector. Dif
fraction gratings are used with CCDs, which collect light of
automobile, or in the vicinity of another location to be cooled. 15 different wavelengths on different pixels.
In the evaporator, the liquid refrigerant is vaporized, provid As used herein, NIR means “near infrared light spectrum”.
ing cooling and the cycle then repeats. The expansion device Near infrared spectrometer (NIRS) is a spectroscopic method
52 may be an expansion valve, a capillary tube or an orifice utilizing the near infra-red region of the electromagnetic
tube. spectrum (from about 800 nm to 2500 nm). NIRS is based on
Further in accordance with the present invention, there is molecular overtone and combination vibrations. The molar
provided a detection system for detecting the double bond absorptivity in the near IR region is typically quite Small.
structure in a fluoroolefin composition. Such detection sys Instrumentation for near-IR spectroscopy is similar to
tem comprises means for sensing the double bond structure of instruments for the visible and mid-IR ranges. There is a
the fluoroolefin composition. The sensing means may include Source, a detector, and a dispersive element (such as a prism,
a sensor which is used in-situ in the system. Alternatively, the 25 or more commonly a diffraction grating) to allow the intensity
sensing means may include an extraction device, shown gen at different wavelengths to be recorded. Fourier transform
erally at 70 in FIG.1. A sensor 72 is placed inside the extrac instruments using an interferometer are also useful, espe
tion device. A line 74 brings the fluid to be sensed to the cially for wavelengths above -1000 nm. Depending on the
extraction device. Alternatively, in another embodiment, the sample, the spectrum can be measured in transmission or in
sensing means may comprise a wand tip, as shown at 70' in 30 reflection.
FIG. 1A. A sensor 72 is included in this hand-held device. Common incandescent or quartz halogen light bulbs are
This wand tip is generally a hand held device, which may be most often used as broadband sources of near infrared radia
placed near the fluid in order to detect the leak. An advantage tion for analytical applications. Light-emitting diodes
of this type of detector is rapid response so the operator (LEDs) are also used. The type of detector used depends
immediately detects a leak as a “wand tip passes over a 35 primarily on the range of wavelengths to be measured. Sili
leakage site. The particular device as shown in FIG. 1A is a con-based CCDs, InGaAs and PbS devices are suitable.
handheld refractometer for observing liquid samples at atmo Ion mobility spectrometry is based upon two principles: (1)
spheric pressure. However, it should be understood that the the ionization of sample molecules through gas phase chemi
present invention is not limited to observing liquid samples, cal reactions by the transfer of an electron or a proton, and (2)
but may also include hand held devices for detecting gases, 40 the characterization of these ions based upon gas phase
Such as, for example, a hand held gas chromatograph. mobility in a weak electric field. The mass, size, and shape of
The sensor used in the sensing means of either embodiment these ions will govern the mobility through a Voltage gradient,
may employ any of the following technologies: infrared sen and this can be measured as time required to traverse a fixed
sors, UV sensors, NIR sensors, ion mobility or plasma chro distance. Thus IMS detectors yield a drift time or mobility
matographs, gas chromatography, refractometry, mass spec 45 value which is characteristic of certain ions (i.e., chemicals)
troscopy, high temperature thick film sensors, thin film field and provide specificity of response (for example leak detec
effect sensors, pellistor sensors, Taguchi sensors and quartz tion). The initial step of ion formation is common to all ion
microbalance sensors. Such technologies are known in the mobility spectrometers. In order to achieve this, Sample mol
art. ecules must in some way be transported from a suspected item
Infrared sensors of the present invention make use of 50 into the IMS instrument. This is usually accomplished by
unique spectral absorbance in the infrared region for all poly using a gas pump to sample the air for the Suspected leak.
atomic gases. By measurement of the spectral intensities in Leak detection can be relatively remote from the instrument
regions specifically selected for a target analyte gas, the con using a hose (stainless steel or various plastics or rubber)
centration of that gas can be determined. combined with the air-sampling pump. Simultaneous detec
There are many techniques available for selecting the spec 55 tion of multiple gasses has been demonstrated at the ppm to
tral region detected including optical filters, spectrographs, ppb levels. The ambient air contains a particular reactantion
transform techniques such as Fourier and Hadamard, emis peak and hydrofluoric acid (HF). The detection by drift time
sion sources with restricted emission ranges, detectors with discrimination is shown on the plot of collector current versus
specific sensitivities including microphones enclosed with drift time. This is a very powerful technique to quickly and
the analyte gas. The application of infrared spectroscopy to 60 unambiguously detect both amounts and composition of the
gas detection and concentration determination is well known ambient air.
to spectroscopists. As used herein, GC means is a 'gas chromatograph or gas
As used herein, UV/vis means “ultraviolet and visible chromatographic analytical technique'. Fluids, and refriger
regions of the light spectrum. A UV/vis spectrophotometer ants in particular, can be identified by Micro GC detectors that
measures the intensity of light passing through a sample (I), 65 are ion detectors with varying methods of ionizing the com
and compares it to the intensity of light before it passes ponents eluting from the GC's column. An ion detector is
through the sample (I). The ratio I/I is called the transmit analogous to a capacitor or vacuum tube. It can be envisioned
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5 6
as two metal grids separated by air with inverse charges A traditional handheld refractometer works on the critical
placed on them. An electric potential difference (voltage) angle principle. They utilize lenses and prisms to project a
exists between the two grids. After components are ionized in shadow line onto a small glass reticle inside the instrument,
the detector, they enter the region between the two grids, which is then viewed by the user through a magnifying eye
causing current to pass from one to the other. This current is 5 piece. In use, a sample is sandwiched between a measuring
amplified and is the signal generated by the detector, The prism and a small cover plate. Light traveling through the
higher the concentration of the component, the more ions are sample is either passed through to the reticle or totally inter
generated, and the greater the current. nally reflected. The net effect is that a shadow line is formed
A flame ionization detector (FID) uses an air-hydrogen between the illuminated area and the dark area. It is at the
flame to produce ions. As components elute from the GC’s 10 point that this shadow line crosses the scale that a reading is
column they pass through the flame and are burned, produc taken. Because refractive index is very temperature to depen
ing ions. The ions produce an electric current, which is the dent, it is important to use a refractometer with automatic
signal output of the detector.
A Thermal Conductivity Detector (TCD) consists of an temperature compensation. Compensation is accomplished
electrically-heated wire or thermistor. The temperature of the 15 through the use of a small bi-metal strip that moves a lens or
sensing element depends on the thermal conductivity of the prism in response to temperature changes.
gas flowing around it. Changes in thermal conductivity, Such A mass spectrometer is a device that measures the mass
as when organic molecules displace Some of the carrier gas, to-charge ratio of ions. This is achieved by ionizing the
cause a temperature rise in the element, which is sensed as a sample and separating ions of differing masses and recording
change in resistance. their relative abundance by measuring intensities of ion flux.
The Electron Capture Detector (ECD) uses a radioactive A typical mass spectrometer comprises three parts: an ion
Beta particle (electrons) emitter—a typical source contains a Source, a mass analyzer, and a detector system. Each gas
metal foil holding 10 millicuries of Nickel-63. The electrons mixture will display a unique spectrum that can be directly
formed are attracted to a positively charged anode, generating related to the composition and concentration of the refriger
a steady current. As the sample is carried into the detector by 25 ant mixture.
a stream of nitrogen or a 5% methane, 95% argon mixture, The fragmentation patterns of fluoroolefins are unique
analyte molecules capture the electrons and reduce the cur among fluids, such as other refrigerants and most other envi
rent between the collector anode and a cathode. The analyte ronmental gases allowing it to be specifically identified and
concentration is thus proportional to the degree of electron its concentration determined relative to other gases present.
capture, and this detector is particularly sensitive to halogens, 30 The fragmentation pattern should be different enough from
organometallic compounds, nitriles, or nitro compounds. other gases present near an internal combustion engine Such
The ECD is sensitive with the detection limit of 5 femto as an automobile engine that it will be easily differentiated by
grams per second (fg/s), and the detector commonly exhibits this method. Furthermore, sensing techniques such as mass
a 10,000-fold linear range. This makes it possible to detect the spectroscopy provide the option of measuring the concentra
specific halogenated compounds even at levels of only one 35 tion of other gases that might be present as well.
part per trillion (ppt). In another embodiment high temperature, thick film sen
A Photo-Ionization Detector (PID) is anion detector which sors may function as sensors for the present inventive method.
uses high-energy photons, typically in the UV range, to pro Many semi-conducting materials become significantly con
duce ions. As components elute from the GC's column they ductive at higher temperatures, e.g., at temperatures above
are bombarded by high-energy photons and are ionized. The 40 400°C. These materials become conductive because valence
ions produce an electric current, which is the signal output of electrons are excited to conduction bands due to their thermal
the detector. The greater the concentration of the component, energy. Gases that can either donate or receive electrons from
the more ions are produced, and the greater the current. the Valence bands change the population of electrons in the
Refractometry uses the Refractive Index of fluids, such as conduction bands and thereby the materials conductivity.
refrigerants, in the liquid state to identify refrigerants in a leak 45 Chemical selectivity of high temperature, thick film, sen
scenario or to determine the composition in a blend so as to sors is achieved by changing the primary constituent itself
adjust to a desired composition. Refractive Index is defined as and doping the film. In order to impart selectivity to this
the angular change in a beam of light passing through the technique, arrays of sensors containing different primary con
interface of two different substances. The technique uses the stituents and/or dopants are employed, and the relationship of
fact that each refrigerant has a different atomic composition 50 the concentration of any given gas to the output of each
and therefore a different Refractive Index at a given tempera array-sensing element is determined empirically.
ture. Since the Refractive Index is nearly linear with respect In another embodiment, thin film, field effect sensors may
of any two components in the mixture, fairly accurate esti function as sensors for the present inventive method. Field
mates of two or three component mixtures can be made. effect sensors are based on the field effect generated by gases
A refractometer is used to determine the refractive index of 55 in metal oxide semiconductor field-effect transistor (MOS
a Substance or some physical property of a Substance that is FET) devices with catalytic metals. The charging of the gate
directly related to its refractive index. A sample of fluid is contact by the gas molecules results in a Voltage change in the
introduced into a sample chamber and a source of light is sensor signal. The choice of operation temperature, gate
passed through the interface of the fluid and a window in the metal, and structure of the gate metal determine the selectiv
chamber. The refractometer sensor determines the angle of 60 ity of the gas response. For devices based on silicon (Si) as the
light emerging from the refrigerant fluid. The fluid is identi semiconductor, Si-MOSFET, the operation temperature is
fied by reference to known, pre-determined relationship data 150-200° C. For devices based on silicon carbideas the semi
for a plurality of different fluids. In a more advanced sensor, conductor, SiC-MOSFET, the operation temperature is 200
the temperature can be varied to obtain data, to identify the 600° C.
constituents of multi-part mixtures of certain fluids and mea- 65 The selectivity and sensitivity of MOSFET sensors is
Sure the percentage of the mixtures. Certain types of refrac achieved by modification of the semiconductor, its doping,
tometers can be used for measuring gases and liquids. and the temperature at which the device is operated.
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In another embodiment, pellistor catalytic gas sensors may In another embodiment, Quartz, Microbalance Sensors
be used as sensors in the present inventive method. The pel may be used as sensors in the present inventive method.
listor is a miniature calorimeter used to measure the energy Quartz microbalance sensor technology is based on measur
liberated on oxidation of a gas. It consists of a coil of Small frequencyfrequency
ing the
is
of polymer-coated quartz crystals. The
influenced by bulk absorption of analyte mol
diameter platinum wire supported in a refractory bead. The 5 ecules into the polymer matrix.
coil is used to heat the bead electrically to its operating tem of the microbalance sensors canThe be
sensitivity and selectivity
varied through the selec
perature (about 500° C.) and to detect changes in temperature tion of different polymer coatings, having different functional
produced by the oxidation of the gas. Selectivity of pellistor groups in the side chains. Bulk absorption of analyte mol
sensors is achieved by modification of the composition of the ecules into the polymer layer increases the mass of the quartz
refractory bead. 10 crystal, resulting in a decrease of the resonance frequency.
In another embodiment, Taguchi sensors may be used as The absorption process is fully reversible. Resins such as
sensors in the present inventive method. Taguchi sensors are those sold under the trademark Nafion(R) by E. I. du Pont de
composed of powders made of semiconducting metal oxides. Nemours and Company of Wilmington, Del. PTFE, and
When a metal oxide crystal such as SnO, is heated at a certain is polystyrene Sulfonates are used to tailor the sensor response
high temperature in air, oxygen is adsorbed on the crystal to These specific analytes including refrigerant gases.
sensing technologies have been found to be particu
Surface with a negative charge. Then donor electrons in the larly useful in determining the components of fluoroolefin
crystal Surface are transferred to the adsorbed oxygen, result compositions, which have double bonds. Representative fluo
ing in leaving positive charges in a space charge layer. Thus, roolefins includebut are not limited to all compounds as listed
Surface potential is formed to serve as a potential barrier 20 in Table 1 and Table 2. As can be seen from these Tables, the
against electron flow. Inside the sensor, electric current flows fluoroolefins have at least one double bond. Fluoroolefins, as
through the conjunction parts (grainboundary) of SnO micro used herein, comprise compounds with 2 to 12 carbonatoms,
crystals. At grain boundaries, adsorbed oxygen forms a in another embodiment 3 to 10 carbon atoms, and in yet
potential barrier that prevents carriers from moving freely. another embodiment 3 to 7 carbon atoms.
The electrical resistance of the sensor is attributed to this 25 In one embodiment of the invention fluoroolefins may be
potential barrier. compounds (and mixtures of Such compounds) having the
In the presence of gases capable of removing oxygen from formula E- or Z R'CH=CHR (Formula I), wherein R'
the Surface at high temperature, the Surface density of the and Rare, independently, C, to Ce perfluoroalkyl groups.
negatively charged oxygen decreases, so the barrier height in Examples of RandR groups include, but are not limited to,
the grain boundary is reduced. The reduced barrier height 30 CF, CF, CFCFCF, CF(CF), CFCFCFCF,
decreases sensor resistance. CF(CF)CFCF CFCF (CF), C(CF).
The selectivity and sensitivity of Taguchi sensors can be CFCFCFCFCF, CFCFCF (CF), C(CF),CFs,
modified through selection of the metal oxides, oxide doping, CFCFCFCFCFCF, CF(CF)CFCFCF, and
and other modifications of the oxide surface along with the C(CF). CFCFs. Exemplary, non-limiting Formula I com
temperature of operation. pounds are presented in Table 1.
TABLE 1
Code Structure Chemical Name

F11E CFCH=CHCF, 4.4.4-hexafluorobut-2-ene

F12E CFCH=CHC-Fs 4,4,5,5,5-octafluoropent-2-ene
F13E CFCH=CHCFCF 445,5,6,6,6-decafluorohex-2-ene
F13iE CFCH=CHCF(CF), 4.55.5-heptafluoro-4-(trifluoromethyl)pent-2-ene
F22E CFCH=CHC-Fs 2.25,5,6,6,6-decafluorohex-3-ene
F14E CFCH=CH(CF)CF, 4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene
F14iE CFCH=CHCFCF (CF), 4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene
F14sE CFCH=CHCF(CF) CFs 4.5,5,6,6,6-nonfluoro-4-(trifluoromethyl) hex-2-ene
F14tF, CFCH=CHC(CF). 5,55-hexafluoro-44-bis(trifluoromethyl)pent-2-ene
F23E CFCH=CHCFC-Fs ,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene
F23i E.CFCH=CHCF(CF), ,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene
F15E CFCH=CH(CF)CF, 445,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene
F15iE CFCH=CH-CFCF-CF (CF), 4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene
F15tE CFCH=CH-C(CF)CFs 5,5,6,6,6-octafluoro-44-bis(trifluoromethyl)hex-2-ene
F24E CFCH=CH(CF)CF, 2.25,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene
F24iE CFCH=CHCFCF (CF), ,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene
F24sE CFCH=CHCF(CF) CFs ,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene
F24tF, CFCH=CHC(CF). .2.2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene
F33E CFCF-CH=CH-CFCFs 2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene
F3i3iE (CF)CFCH=CH-CF (CF), ,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene
F33iE CFCF-CH=CH-CF(CF), ,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene
F16E CFCH=CH(CF)CF 445,5,6,6,7,7,8,8,9,9.9-hexadecafluoronon-2-ene
F16sE CFCH=CHCF(CF)(CF)2C2Fs 4.5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethy
F16tE CFCH=CHC(CF)CFCFs ,6,6,6-octafluoro-44-bis(trifluoromethyl)hept-2-ene
F25E CFCH=CH(CF)CF 2.25,5,6,6,7,7,8,8,9,9.9-hexadecafluoronon-3-ene
F25iE CFCH=CH-CFCFCF (CF), ,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-
F25tE CFCH=CH-C(CF)2C2Fs .2.2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene
F34E CFCF-CH=CH-(CF)CF, 2,2,3,3,6,6,7,7,8,8,9,9.9-hexadecafluoronon-4-ene
F34iE CFCF-CH=CH-CFCF (CF), ,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethy
 US 8,070,355 B2
10
TABLE 1-continued
Code Structure Chemical Name

F34sE CFCF-CH=CH-CF (CF)CFs sks ,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-

tle
F34tF, CFCF-CH=CH-C(CF). sks 5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene
F3I4E (CF)CFCH=CH (CF)CF sks ,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-
tle
F314iE (CF). CFCH=CH-CFCF (CF), sks ,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene
F3I4SE (CF)CFCH=CH-CF (CF)CFs sks ,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene
F314tF (CF)CFCH=CH-C(CF). ,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluorome hyl)hex-3-ene
F26E CFCH=CH(CF).5CF ,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10, 0-octadecafluorodec-3-ene
F26sE CFCH=CHCF (CF)(CF),CFs ,1,1,2,2,5,6,6,7,7,8,8,9,9.9-penta ecafluoro-5-
(trifluoromethyl)non-3-ene
F26tE CFCH=CHC(CF). CFC-Fs sks ,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct
3-ene
F35E CFCF-CH=CH-(CF). CF ,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10, 0-octadecafluorodec-4-ene
F35iE CFCF-CH=CH-CFCF-CF (CF), ,1,1,2,2,3,3,6,6,7,7,8,9,9.9-penta ecafluoro-8-
(trifluoromethyl)non-4-ene
F35tE CFCF-CH=CH-C(CF)2C2Fs sks ,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct
4-ene
F3i5E (CF)CFCH=CH (CF)CF ,1,1,2,5,5,6,6,7,7,8,8,9,9.9-penta ecafluoro-2-
(trifluoromethyl)non-3-ene
F3i5iE (CF)CFCH=CH-CFCF-CF (CF), 1,1, ,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct
3-ene
F3i5tE (CF)CFCH=CH-C(CF)2C2Fs s ,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene
F44E CF (CF)CH=CH-(CF)CF ,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10, 0-octadecafluorodec-5-ene
F44iE CF (CF)-CH=CH-CFCF (CF), ,1,1,2,3,3,6,6,7,7,8,8,9,9.9-penta ecafluoro-2-
(trifluoromethyl)non-4-ene
F44sE CF (CF)CH=CH-CF (CF)C2Fs ,1,1,2,2,3,6,6,7,7,8,8,9,9.9-penta ecafluoro-3-
(trifluoromethyl)non-4-ene
F44tE CF (CF)CH=CH-C(CF). sks 5,5,6,6,7,7,8,8,8-dodecafluoro-2,2-bis(trifluoromethyl)oct
3-ene
F414iE (CF)CFCF-CH=CH-CFCF (CF), 1,1, ,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct
4-ene
F414sE (CF). CFCF-CH=CH-CF (CF)CFs 1,1, ,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct
5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-ene
,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct
4-ene
F4s4tE CFCF (CF)CH=CH-C(CF). sks ,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-ene
F4t4tE (CF). CCH=CH-C(CF). sks ,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a In some embodiments, temperatures for contacting of said
perfluoroalkyl iodide of the formula R'I with a perfluoroalky perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin
ltrihydroolefin of the formula RCH=CH to form a trihy 40 are preferably within the range of about 150° C. to 300° C.,
droiodoperfluoroalkane of the formula R'CHCHIR. This preferably from about 170° C. to about 250° C., and most
trihydroiodoperfluoroalkane can then be dehydroiodinated to preferably from about 180° C. to about 230° C. Suitable
form RCH=CHR. Alternatively, the olefin R'CH=CHR contact times for the reaction of the perfluoroalkyl iodide with
may be prepared by dehydroiodination of a trihydroiodoper the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18
fluoroalkane of the formula RCHICHR formed in turn by 45 hours, preferably from about 4 to about 12 hours.
reacting a perfluoroalkyl iodide of the formula RI with a The trihydroiodoperfluoroalkane prepared by reaction of
perfluoroalkyltrihydroolefin of the formula RCH=CH. the perfluoroalkyl iodide with the perfluoroalkyltrihydroole
This contacting of a perfluoroalkyl iodide with a perfluoro fin may be used directly in the dehydroiodination step or in
alkyltrihydroolefin may take place in batch mode by combin some embodiments be recovered and purified by distillation
ing the reactants in a Suitable reaction vessel capable of oper 50 prior to the dehydroiodination step.
ating under the autogenous pressure of the reactants and In some embodiments, the dehydroiodination step is car
products at reaction temperature. Suitable reaction vessels ried out by contacting the trihydroiodoperfluoroalkane with a
include fabricated from stainless steels, in particular of the basic substance. Suitable basic substances include alkali
austenitic type, and the well-known high nickel alloys such as metal hydroxides (e.g., sodium hydroxide or potassium
nickel-copper alloys, sold under the trademark Monel(R), 55 hydroxide), alkali metal oxide (for example, sodium oxide),
nickel based alloys, Hastelloy(R), and nickel-chromium alkaline earth metal hydroxides (e.g., calcium hydroxide),
alloys, sold under the trademark Inconel(R). alkaline earth metal oxides (e.g., calcium oxide), alkali metal
Alternatively, the reaction may take be conducted in semi alkoxides (e.g. sodium methoxide or sodium ethoxide), aque
batch mode in which the perfluoroalkyltrihydroolefin reac ous ammonia, Sodium amide, or mixtures of basic Substances
tant is added to the perfluoroalkyl iodide reactant by means of 60 Such as Soda lime. Preferred basic Substances are sodium
a suitable addition apparatus Such as a pump at the reaction hydroxide and potassium hydroxide. Said contacting of the
temperature. The ratio of perfluoroalkyl iodide to perfluoro trihydroiodoperfluoroalkane with a basic Substance may take
alkyltrihydroolefin should be between about 1:1 to about 4:1, place in the liquid phase preferably in the presence of a
preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 Solvent capable of dissolving at least a portion of both reac
tend to result in large amounts of the 2:1 adduct as reported by 65 tants. Solvents suitable for the dehydroiodination step include
Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, one or more polar organic solvents such as alcohols (e.g.,
pages 261-270 (1974). methanol, ethanol, n-propanol, isopropanol, n-butanol,
 US 8,070,355 B2
11 12
isobutanol, and tertiary butanol), nitrites (e.g., acetonitrile, dimethoxyethane, diglyme, or tetraglyme) in the presence of
propionitrile, butyronitrile, benzonitrile, or adiponitrile), a phase transfer catalyst. Suitable phase transfer catalysts
dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethy include quaternary ammonium halides (e.g., tetrabutylam
lacetamide, or Sulfolane. The choice of Solvent may depend monium bromide, tetrabutylammonium hydrosulfate, trieth
on the boiling point product and the ease of separation of 5 ylbenzylammonium chloride, dodecyltrimethylammonium
traces of the solvent from the product during purification. chloride, and tricaprylylmethylammonium chloride), quater
nary phosphonium halides (e.g., triphenylmethylphospho
Typically, ethanol or isopropanol are good solvents for the nium bromide and tetraphenylphosphonium chloride), or
reaction. cyclic polyether compounds known in the art as crown ethers
In some embodiments, the dehydroiodination reaction may 10 (e.g., 18-crown-6 and 15-crown-5).
be carried out by addition of one of the reactants (either the Accoording to alternative embodiments, the dehydroiodi
basic substance or the trihydroiodoperfluoroalkane) to the nation reaction may be conducted in the absence of solvent by
other reactant in a Suitable reaction vessel. Said reaction may adding the trihydroiodoperfluoroalkane to a solid or liquid
be fabricated from glass, ceramic, or metal and is preferably basic Substance.
agitated with an impeller or stirring mechanism. 15 In some embodiments, suitable reaction times for the dehy
In certain embodiments, the temperatures suitable for the droiodination reactions are from about 15 minutes to about
dehydroiodination reaction are from about 10° C. to about six hours or more depending on the solubility of the reactants.
100° C., preferably from about 20°C. to about 70° C. In other In Some embodiments, the dehydroiodination reaction is
embodiments, the dehydroiodination reaction may be carried rapid and requires about 30 minutes to about three hours for
out at ambient pressure or at reduced or elevated pressure. In completion.
certain embodiments, dehydroiodination reactions is one in The compound of Formula I may be recovered from the
which the compounds of Formula I is distilled out of the dehydroiodination reaction mixture by phase separation after
reaction vessel as it is formed. addition of water, by distillation, or by a combination thereof.
In alternative embodiments, the dehydroiodination reac The compositions in some embodiments may comprise a
tion may be conducted by contacting an aqueous solution of as single compound of Formula I, for example, one of the com
said basic substance with a solution of the trihydroiodoper pounds in Table 1, or may comprise a combination of com
fluoroalkane in one or more organic solvents of lowerpolarity pounds of Formula I.
Such as an alkane (e.g., hexane, heptane, or octane), aromatic In another embodiment, fluoroolefins may be compounds
hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., as presented in Table 2 (including mixtures thereof. The com
methylene chloride, chloroform, carbon tetrachloride, or per 30 positions in some embodiment may comprise a single com
chloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl pound in Table 2, or may comprise a combination of com
ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, pounds of Table 2, that is, a mixture thereof.
TABLE 2
Structure Chemical name

225ye CFCF-CHF 2,3,3,3-pentafluoro-1-propene

225zc CFCH=CF, ,1,3,3,3-pentafluoro-1-propene
225yc CHF.CF–CF, ,1,2,3,3-pentafluoro-1-propene
234ye CHF.CF–CHF ,2,3,3-tetrafluoro-1-propene
234yf CFCF-CH 2,3,3,3-tetrafluoro-1-propene
234ze CFCH=CHF ,3,3,3-tetrafluoro-1-propene
234yc CHFCF-CF, ,1,2,3-tetrafluoro-1-propene
234zc CHF.CH=CF, ,1,3,3-tetrafluoro-1-propene
234ye CHF.CF=CHF ,2,3,3-tetrafluoro-1-propene
243yf CHF.CF=CH, 2,3,3-trifluoro-1-propene
243Zf CFCH=CH, 3,3,3-trifluoro-1-propene
243yc CHCF=CF, ,1,2-trifluoro-1-propene
243zc CHFCH=CF, 1,3-trifluoro-1-propene
243ye CHF.CF=CHF 2,3-trifluoro-1-propene
243Ze CHF.CH=CHF ,3,3-trifluoro-1-propene
FC-1318my CFCF-CFCF ,1,1,2,3,444-octafluoro-2-butene
FC-1318cy CFCFCF-CF, ,1,2,3,3,444-octafluoro-1-butene
327my CFCF-CHCF, ,1,1,2,444-heptafluoro-2-butene
327ye CHF-CFCFCF, 2,3,3,444-heptafluoro-1-butene
327py CHF.CF–CFCF ,1,1,2,3,4,4-heptafluoro-2-butene
327et (CF)2C=CHF ,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-
propene
CF=CHCFCF ,1,3,3,444-heptafluoro-1-butene
CF–CFCHFCF ,1,2,3,444-heptafluoro-1-butene
CF–CFCFCHF, ,1,2,3,3,4,4-heptafluoro-1-butene
CFCFCF-CH, 2,3,3,444-hexafluoro-1-butene
CFCH=CHCF, 1,144.4-hexafluoro-2-butene
CHF-CHCFCF 3.3.4.4.4-hexafluoro-1-butene
CHF-CFCHFCF, 2.3.4.4.4-hexafluoro-1-butene
CHF-CFCFCHF, 2,3,3,4,4-hexafluoro-1-butene
CHF.CF–CFCHF, ,1,2,3,4,4-hexafluoro-2-butene
CHFCF–CFCF, ,1,1,2,3,4-hexafluoro-2-butene
CHF.CH=CFCF ,1,1,2,4,4-hexafluoro-2-butene
CFCH=CFCHF, ,1,1,3,4,4-hexafluoro-2-butene
CF=CFCFCHF ,1,2,3,3,4-hexafluoro-1-butene
CF–CFCHFCHF, ,1,2,3,4,4-hexafluoro-1-butene
CH2=C(CF). 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene
 US 8,070,355 B2
17 18
1,1,1,3,4-pentafluoro-2-butene may be prepared by dehy (CFCH=CHCF) with tetrafluoroethylene (CF–CF) and
drofluorination of 1,1,1,3,3,4-hexafluorobutane antimony pentafluoride (SbF).
(CFCHCFCHF) using solid KOH. 2,3,3,4,4-pentafluoro-1-butene may be prepared by dehy
1,1,1,3-tetrafluoro-2-butene may be prepared by reacting drofluorination of 1,1,2,2,3,3-hexafluorobutane over fluo
1,1,1,3,3-pentafluorobutane (CFCHCFCH) with aqueous 5 rided alumina at elevated temperature.
KOH at 120° C. 2.3.3.4.4.5.5.5-ocatafluoro-1-pentene may be prepared by
1.1.1.4.4.5.5.5-octafluoro-2-pentene may be prepared dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane
from (CFCHICHCFCF) by reaction with KOH using a over Solid KOH.
phase transfer catalyst at about 60° C. The synthesis of 1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared by
4-iodo-1,1,1,2,2,5,5,5-octafluoropentane may be carried out 10 dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane
by reaction of perfluoroethyliodide (CFCFI) and 3,3,3-tri- over fluorided alumina at elevated temperature.
fluoropropeneatabout 200° C. under autogenous pressure for Many of the compounds of Formula I, Table 1 and Table 2
about 8 hours. exist as different configurational isomers or Stereoisomers.
1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared When the specific isomer is not designated, the present inven
from 1.1.1.2.2.5.5.6,6,6-decafluoro-3-iodohexane 15 tion is intended to include all single configurational isomers,
(CFCFCHICHCFCF) by reaction with KOH using a single stereoisomers, or any combination thereof. For
phase transfer catalyst at about 60° C. The synthesis of 1,1, instance, F11E is meant to represent the E-isomer, Z-isomer,
1.2.2.5.5,6,6,6-decafluoro-3-iodohexane may be carried out or any combination or mixture of both isomers in any ratio. As
by reaction of perfluoroethyliodide (CFCFI) and 3.3.4.4.4- another example, HFC-1225ye is meant to represent the
pentafluoro-1-butene (CFCF-CH=CH-) at about 200° C. 20 E-isomer, Z-isomer, or any combination or mixture of both
under autogenous pressure for about 8 hours. isomers in any ratio.
1,1,1,4,5,5.5-heptafluoro-4-(trifluoromethyl)-2-pentene The heat transfer fluid compositions of the present inven
may be prepared by the dehydrofluorination of 1,1,1,2,5,5.5- tion may be generally useful when the fluoroolefin is present
heptafluoro-4-iodo-2-(trifluoromethyl)-pentane at about 1 weight percent to about 99 weight percent, prefer
(CFCHICHCF(CF)) with KOH in isopropanol. 25 ably about 20 weight percent to about 99 weight percent,
CFCHICHCF (CF) is made from reaction of (CF)CFI more preferably about 40 weight percent to about 99 weight
with CFCH=CH at high temperature, such as about 200° percent and still more preferably 50 weight percent to about
C. 99 weight percent.
1.1.1.4.4.5.5.6,6,6-decafluoro-2-hexene may be prepared The present invention further provides compositions as
by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene listed in Table 3.
TABLE 3
Concentration ranges (wt %
Most
Components Preferred More preferred preferred
HFC-1225ye/HFC-32 -9999-1 30-99,70-1 90-99/10-1;
95.5/97.3
HFC-1225ye/HFC-134a -9999-1 40-9960-1 90.10
HFC-1225ye/CO, O.1-99.9999-0.1 70-99.7.30-0.3 99.
HFC-1225yef ammonia 0.1-99.90.1-99.9 40-99.90.1-60 90/10, 85/15, 80/
20, 95/5
HFC-1225ye/HFC-1234yf -9999-1 51-99.49-1 and 60/40, 51/49
60-90,40-10
HFC-1225ye/HFC- -981-981-98 50-981-40.1-40 85/10.5
52a HFC-32 81,154
82.15.3
HFC-1225ye/HFC- -981-98.0.1-98 50-981-400.3-30 84,151
52a/CO, 84f15.S.O.S
HFC-1225ye/HFC- -981-981-98 50-981-401-20 85.13.2
52a propane
HFC-1225ye/HFC-152a?i- -981-981-98 50-981-401-20 85.13.2
butane
HFC-1225ye/HFC- -981-981-98 50-981-401-20 85.13.2
52a DME
HFC-1225ye/HFC- -981-981-98 20-901-501-60
52a/CFI
HFC-1225ye/HFC- -981-981-98 40-981-50. 1-40 76.9/15
34a HFC-152a.
HFC-1225ye/HFC- -981-981-98 1-801-801-80 88.9.3
34a, HFC-32
HFC-1225ye/HFC- -981-981-98 40-981-501-20 86.104
34a HFC-16
HFC-1225ye/HFC- -981-98.0.1-98 40-981-500.3-30 88.5.110.5
34a/CO2
HFC-1225ye/HFC- -981-981-98 40-981-501-20 87.10.3
34a.propane
HFC-1225ye/HFC-134a/i- -981-981-98 40-981-501-20 87.10.3
butane
HFC-1225ye/HFC- -981-981-98 40-981-501-20 87.10.3
34a DME
HFC-1225ye/HFC- -981-981-98 40-981-50. 1-40 88.9.3
34, HFC-32
 US 8,070,355 B2
25 26
TABLE 3-continued
Concentration ranges (wt %
Most
Components Preferred More preferred preferred
HFC-1225ye/HFC-32/HFC- -971-97.1-97, 5-705-705-70
125/propane -SO 1-3O
HFC-1225ye/HFC-32/HFC- -971-97.1-97, 5-705-705-70
12S,DME -SO 1-3O
HFC-1225ye/HFC- -971-97.1-97, 5-705-705-70
32/CFI/DME -SO 1-3O
HFC-1225ye/HFC-32/HFC- -97.1-97.1-97, 10-80, S-70, S-70,
125/CFI -97 1-80
HFC-1234yf HFC-32/CFI -981-981-98 10-801-701-80
HFC-1234yf HFC-32/HFC- -97.1-97.1-97, S-70 S-8O,1-70,
134a/CFI -97 5-70
HFC-1234yf HFC-32/HFC- -981-981-98 10-805-8010-80
125
HFC-1234yf HFC-32/HFC- -97.1-97.1-97, 10-80, S-70,10-80,
125. CF3I. -97 S-80

The most preferred compositions of the present invention TABLE 4

listed in Table 3 are generally expected to maintain the desired
properties and functionality when the components are present Component A Component B
W9%
A. Psia kPa
in the concentrations as listed +/-2 weight percent. The com
positions containing CO would be expected to maintain the 25 HFC HFC-32 7.4 92.6 49.2 339 -25
desired properties and functionality when the CO, was HFC
HFC
HFC-12S
HFC-134a
10.9
704
89.1
29.6
40.7
8.4
281
127
-25
-25
present at the listed concentration +/-0.2 weight percent. HFC HFC-152a. 91.0 9.O 7.9 123 -25
The compositions of the present invention may be azeotro HFC HFC-143a 17.3 82.7 39.5 272 -25
pic or near-azeotropic compositions. By azeotropic compo HFC HFC-227 ea 846 15.4 8.0 124 -25
sition is meant a constant-boiling mixture of two or more 30 HFC propane 51.5 48.5 33.5 231 -25
HFC n-butane 98.1 1.9 7.9 123 -25
Substances that behave as a single Substance. One way to HFC isobutane 88.1 11.9 9.O 131 -25
characterize an azeotropic composition is that the vapor pro HFC DME 53.5 46.5 3.1 90 -25
duced by partial evaporation or distillation of the liquid has HFC trans-HFC- 63.0 37.0 1.7 81 -25
the same composition as the liquid from which it is evapo 225ye
234ze
HFC-1243Zf 40.O
rated or distilled, i.e., the mixture distills/refluxes without 35 HFC 6O.O 3.6 94 -25
HFC 225ye HFC-134 52.2 47.8 2.8 88 -25
compositional change. Constant-boiling compositions are HFC 225ye HFC-152a. 7.3 92.7 4.5 100 -25
characterized as azeotropic because they exhibit either a HFC 225ye propane 29.7 70.3 30.3 209 -25
maximum or minimum boiling point, as compared with that HFC 225ye Il-butane 89.5 1O.S 2.3 85 -25
of the non-azeotropic mixture of the same compounds. An HFC 225ye isobutane 79.3 20.7 3.9 96 -25
40 HFC 225ye DME 82.1 17.9 O.8 74 -25
azeotropic composition will not fractionate within a refrig HFC 225ye CFSCF 37.0 63.0 2.4 85 -25
eration or air conditioning system during operation, which 8S HFC 234ze HFC-1243Zf 17.0 83.0 3.0 90 -25
may reduce efficiency of the system. Additionally, an azeo 8S HFC
HFC
234ze
234ze
HFC-134
HFC-134a
45.7
9.5
S4.3
9 O.S
2.5
5.5
86
107
-25
-25
tropic composition will not fractionate upon leakage from a HFC 234ze HFC-152a. 21.6 78.4 4.6 101 -25
refrigeration or air conditioning system. In the situation HFC 234ze HFC-227 ea 59.2 40.8 1.7 81 -25
where one component of a mixture is flammable, fraction 45 HFC 234ze propane 28.5 71.5 30.3 209 -25
ation during leakage could lead to a flammable composition HFC
HFC
234ze
234ze
Il-butane
isobutane
886
77.9
11.4
22.1
1.9
2.9
82
89
-25
-25
either within the system or outside of the system. HFC 234ze DME 84.1 15.9 O.8 74 -25
A near-azeotropic composition (also commonly referred to HFC 234ze CFSCF 34.3 65.7 2.7 88 -25
as an “azeotrope-like composition') is a Substantially con 243Z HFC-134 63.0 37.0 3.5 93 -25
stant boiling liquid admixture of two or more Substances that 50 243Z HFC-134A 25.1 74.9 5.9 110 -25
243Z HFC-152A 40.7 59.3 5.2 104 -25
behaves essentially as a single Substance. One way to char 243Z HFC-227 ea 78.5 21.5 3.1 90 -25
acterize a near-azeotropic composition is that the vapor pro 243Z propane 32.8 67.2 31.0 213 -25
duced by partial evaporation or distillation of the liquid has 243Z Il-butane 90.3 9.7 3.5 93 -25
Substantially the same composition as the liquid from which 243Z isobutane 80.7 19.3 4.3 98 -25
it was evaporated or distilled, that is, the admixture distills/ 55 HFC DME 72.7 27.3 2.O 83 -25
cis-HFC-1234ze HFC-236ea 20.9 79.1 30.3 209 25
refluxes without Substantial composition change. Another cis-HFC-1234ze HFC-245fa 76.2 23.8 26.1 18O 25
way to characterize a near-azeotropic composition is that the cis-HFC-1234ze Il-butane 514 48.6 6.08 42 -25
bubble point vapor pressure and the dew point vapor pressure cis-HFC-1234ze isobutane 26.2 73.8 8.74 60 -25
of the composition at a particular temperature are Substan cis-HFC-1234ze 2-methylbutane 86.6 13.4 27.2 188 25
tially the same. Herein, a composition is near-azeotropic if 60 cis-HFC-1234ze
HFC-1234ye
Il-bentane
HFC-236ea
92.9
24.0
7.1
76.O
26.2
3.35
181
23.1
25
-25
after 50 weight percent of the composition is removed, such HFC-1234ye HFC-245fa 42.5 57.5 22.8 157 25
as by evaporation or boiling off, the difference in vapor pres HFC-1234ye Il-butane 41.2 58.8 38.0 262 25
Sure between the original composition and the composition HFC-1234ye isobutane 16.4 83.6 SO.9 351 25
remaining after 50 weight percent of the original composition HFC-1234ye 2-methylbutane 80.3 19.7 23.1 159 25
has been removed is less than about 10 percent. 65 HFC-1234ye Il-bentane 87.7 12.3 21.8 150 25
AZeotropic compositions of the present invention at a
specified temperature are shown in Table 4.
 US 8,070,355 B2
29 30
TABLE 5-continued
Pres Pres Temp
Component A Component B Component C Wt 9%. A Wt 9% B Wt 9% C (psi) (kPa) ( C.)
HFC-134 HFC 63.6 26.8 9.6 2.38 85.4 -25
152a.
HFC-134 HFC 1.3 52.3 46.4 2.32 84.9 -25
227ea
HFC-134 n-butane 18.1 67.1 14.9 4.54 -25

HFC-134 isobutane 0.7 74.O 25.3 6.68 115 -25

HFC-134 DME 29.8 52.5 17.8 9.78 67.4 -25

HFC DME 63.1 31.0 5.8 75.4 -25

227ea
n-butane DME 66.O 13.0 21.1 1.34 78.2 -25

n-butane CFSCF 71.3 S.6 23.0 2.25 84.5 -25

isobutane DME 49.9 29.7 20.4 2.83 88.5 -25

isobutane CFI 27.7 2.2 70.1 3.19 90.9 -25

7.1 73.7 19.2 3.11 90.4 -25

n-butane 9.5 81.2 9.3 3.48 92.9 -25

isobutane 3.3 77.6 19.1 4.26 98.3 -25

DME 2.6 70.O 27.4 2.03 82.9 -25

HFC-134 HFC S2.0 42.9 S.1 2.37 85.3 -25

152a.

43.2 26.8 2.61 86.9 -25

DME 27.7 54.7 17.7 9.76 67.3 -25

HFC-134a HFC 14.4 34.7 51.0 4.42 99.4 -25

152a.

HFC-152a. n-butane 5.4 14.1 5.41 106 -25

HFC-152a. DME 59.1 16.4 24.5 O.80 74.5 -25

n-butane 40.1 48.5 11.3 2.61 86.9 -25

DME 68.1 13.0 18.9 1.29 77.8 -25

Il-butane CFI 81.2 9.7 9.1 1.87 81.8 -25

isobutane DME 55.5 28.7 15.8 2.38 85.4 -25

isobutane CFI 34.9 6.1 59.0 2.57 86.7 -25

isobutane CFSCF 37.7 1.1 61.7 2.66 87.3 -25

HFC-134 HFC 58.6 34.1 7.3 3.54 93.4 -25

227ea
HFC-134 n-butane 27.5 58.7 13.9 4.72 101 -25

HFC-134 DME 18.7 63.5 17.8 O.11 69.7 -25

HFC-134 CFI 11.4 23.9 64.7 4.45 99.6 -25

 US 8,070,355 B2
33 34
TABLE 7 TABLE 7-continued
Near-azeotrope range Temp Near-azeotrope range Temp
Components (weight percent) (° C.) Components (weight percent) (° C.)
HFC-1225ye/HFC-134a/HFC-152a 1-981-981-98 25 5 trans-HFC-1234zef HFC-134, HFC- -981-981-98 -25
HFC-1225ye/HFC-134a/HFC-161 1-981-981-98 25 52a.
HFC-1225ye/HFC-134a, isobutane 1-981-981-40 25 trans-HFC-1234zef HFC-134, HFC- -981-981-98 -25
HFC-1225ye/HFC-134a/DME 1-981-981-20 25 227 ea
HFC-1225ye/HFC-152a isobutane 1-981-981-50 25 trans-HFC-1234zef HFC-134, DME -981-981-40 -25
HFC-1225ye/HFC-152a/DME 1-981-981-98 25 trans-HFC-1234zef HFC-134a HFC- -981-981-98 -25
HFC-1225ye/HFC-1234yf HFC-134a 1-981-981-98 25 10 52a.
HFC-1225ye/HFC-1234yf HFC-152a. 1-981-981-98 25 trans-HFC-1234zef HFC-152an- -981-981-50 -25
HFC-1225ye/HFC-1234yf HFC-125 1-981-981-20 25 butane
HFC-1225ye/HFC-1234yfCFI 1-981-981-98 25 trans-HFC-1234zef HFC-152a DME -981-981-98 -25
HFC-1225ye/HFC-134a/HFC- 1-97.1-97.1-97.1-10 25 trans-HFC-1234zef HFC-227 ean- -981-981-40 -25
52a HFC-32 butane
HFC-125/HFC-1225ye/isobutane 80-981-19.1-10 25 15 trans-HFC-1234zen-butane/DME -981-401-98 -25
HFC-125/trans-HFC- 80-981-19.1-10 25 trans-HFC-1234zefn-butane/CFI -981-301-98 -25
234zef isobutane trans-HFC-1234zef isobutane/DME -981-601-98 -25
HFC-125/HFC-1234yfisobutane 80-981-19.1-10 25 trans-HFC-1234zef isobutane/CFI -981-401-98 -25
HFC-32/HFC-125/HFC-1225ye -981-98. 1-4 25 trans-HFC-1234zef isobutane? -981-401-98 -25
HFC-32 HFC-125/trans-HFC-1234ze -981-981-50 25 CFSCF
HFC-32/HFC-125/HFC-1234yf -98.1-98,1-5S 25 HFC-1243Zf HFC-134, HFC-227ea -981-981-98 -25
HFC-125/trans-HFC-1234Zein-butane 80-981-19.1-10 25 HFC-1243Zf HFC-134n-butane -981-981-40 -25
HFC-125/HFC-1234yfin-butane 80-981-19.1-10 25 HFC-1243Zf HFC-134, DME -981-981-98 -25
HFC-1234yf HFC-32/HFC-143a -501-981-98 -25 HFC-1243zf HFC-134/CFI -981-981-98 -25
HFC-1234yf HFC-32, isobutane -4059-98.1-30 -25 HFC-1243Zf HFC-134a, HFC-152a. -981-981-98 -25
HFC-1234yf HFC-125/HFC-143a -601-981-98 -25 HFC-1243Zf HFC-134ain-butane -981-981-40 -25
HFC-1234yf HFC-125/isobutane -4059-981-20 -25 HFC-1243zf HFC-152a propane -701-70,29-98 -25
HFC-1234yf HFC-134 propane -801-70.19-90 -25 25 HFC-1243Zf HFC-152an-butane -981-98.1-30 -25
HFC-1234yf HFC-134/DME -701-98.29-98 -25 HFC-1243Zf HFC-152a isobutane -981-981-40 -25
HFC-1234yf HFC-134a/propane -801-80; 19-98 -25 HFC-1243Zf HFC-152a DME -981-981-98 -25
HFC-1234yf HFC-134a/n-butane -981-98.1-30 -25 HFC-1243Zf HFC-227 ean-butane -981-981-40 -25
HFC-1234yf HFC-134a/isobutane -981-98.1-30 -25 HFC-1243Zf HFC-227 ea isobutane -981-901-50 -25
HFC-1234yf HFC-134a/DME -981-981-40 -25 HFC-1243Zf HFC-227eaf)ME -981-801-90 -25
HFC-1234yf HFC-143a, propane -801-981-98 -25 30 HFC-1243Zf n-butane, DME -981-401-98 -25
HFC-1234yf HFC-143a/DME -4059-981-20 -25 HFC-1243Zlf isobutane, DME -981-601-98 -25
HFC-1234yf. HFC-152ain-butane -981-98.1-30 -25 HFC-1243zfisobutane/CFI -981-401-98 -25
HFC-1234yf HFC-152a isobutane -981-90.1-40 -25 HFC-1243zf DME/CFSCF, -981-401-90 -25
HFC-1234yf HFC-152a/DME -701-981-98 -25
HFC-1234yf HFC-227ea?propane -801-70,29-98 -25
HFC-1234yf HFC-227ean-butane 40-981-591-20 -25 35 Additional compositions comprising fluoroolefins as dis
HFC-1234yf HFC-227 ea?isobutane 30-981-691-30 -25
closed in U.S. patent application Ser. No. 1 1/369,227 filed
HFC-1234yf HFC-227ea/DME -981-801-98 -25
HFC-1234yfin-butane/DME -981-401-98 -25 Mar. 2, 2006: U.S. patent application Ser. No. 1 1/393,109
HFC-1234yfisobutane/DME -981-501-98 -25 filed Mar. 30, 2006; and U.S. patent application Ser. No.
HFC-1234yf DME/CFI -981-981-98 -25
1 1/486,791 filed Jul. 13, 2006; are intended to be included
HFC-1234yf DME/CFSCF, -981-401-80 -25
HFC-1225ye/trans-HFC- -981-981-98 -25 40 within the scope of the present invention.
234zef HFC-134 Certain of the compositions of the present invention are
HFC-1225ye/trans-HFC- -981-981-98 -25 non-azeotropic compositions. Those compositions of the
234zef HFC-227ea
HFC-1225ye/trans-HFC- -601-601-98 -25
present invention falling within the preferred ranges of Table
234zeipropane 3, but outside of the near-azeotropic ranges of Table 6 and
HFC-1225ye/trans-HFC-1234ze/n- -981-98.1-30 -25 45 Table 7 may be considered to be non-azeotropic.
butane
HFC-1225ye/trans-HFC-1234ze/DME -981-981-98 -25
A non-azeotropic composition may have certain advan
HFC-1225ye/trans-HFC-1234zef -981-981-98 -25
tages over azeotropic or near azeotropic mixtures. A non
CFSCF azeotropic composition is a mixture of two or more Sub
HFC-1225ye/HFC-1243zf HFC-134 -981-981-98 -25 stances that behaves as a mixture rather than a single
HFC-1225ye/HFC-1243zfn-butane
HFC-1225ye/HFC-1243zfisobutane
-981-98.1-30
-981-981-40
-25
-25
50 Substance. One way to characterize a non-azeotropic compo
HFC-1225ye/HFC-1243zf DME -981-981-98 -25
sition is that the vapor produced by partial evaporation or
HFC-1225ye/HFC-1243zfCFI -981-981-98 -25 distillation of the liquid has a substantially different compo
HFC-1225ye/HFC-134/HFC-152a. -981-981-98 -25 sition as the liquid from which it was evaporated or distilled,
HFC-1225ye/HFC-134/HFC-227ea -981-981-98 -25 that is, the admixture distills/refluxes with substantial com
HFC-1225ye/HFC-134/n-butane -981-90.1-40 -25
HFC-1225ye/HFC-134 isobutane -981-90.1-40 -25
55 position change. Another way to characterize a non-azeotro
HFC-1225ye/HFC-134/DME -981-981-40 -25 pic composition is that the bubble point vapor pressure and
HFC-1225ye/HFC-227ea/DME 40-981-591-30 -25 the dew point vapor pressure of the compositionata particular
HFC-1225ye/n-butane/DME
HFC-1225ye/n-butane/CFSCF
-981-301-98
-981-201-98
-25
-25
temperature are Substantially different. Herein, a composition
HFC-1225ye/isobutane/DME -981-601-98 -25
is non-azeotropic if, after 50 weight percent of the composi
HFC-1225ye/isobutane/CFI -981-401-98 -25 60 tion is removed. Such as by evaporation or boiling off the
trans-HFC-1234zef HFC-1243Zf HFC- -981-981-98 -25 difference in vapor pressure between the original composi
227 ea
trans-HFC-1234zef HFC-1243Zfin- -981-98.1-30 -25
tion and the composition remaining after 50 weight percent of
butane
the original composition has been removed is greater than
trans-HFC-1234zef HFC- -981-981-40 -25 about 10 percent.
243zfisobutane 65 The compositions of the present invention may be prepared
trans-HFC-1234zef HFC-1243Zf DME -981-981-98 -25 by any convenient method to combine the desired amounts of
the individual components. A preferred method is to weigh
 US 8,070,355 B2
35 36
the desired component amounts and thereafter combine the R12 (CFC-12, dichlorodifluoromethane), R245fa (or HFC
components in an appropriate vessel. Agitation may be used, 245fa, 1,1,1,3,3-pentafluoropropane). R114 (or CFC-114,
if desired. 1,2-dichloro-1,1,2,2-tetrafluoroethane), R236fa (or HFC
An alternative means for making compositions of the 236fa, 1,1,1,1,3,3,3-hexafluoropropane), R124 (or HCFC
present invention may be a method for making a refrigerant 124, 2-chloro-1,1,1,2-tetrafluoroethane), R407C (ASHRAE
blend composition, wherein said refrigerant blend composi designation for a blend of 52 weight percent R134a, 25
tion comprises a composition as disclosed herein, said weight percent R125 (pentafluoroethane), and 23 weight per
method comprising (i) reclaiming a Volume of one or more cent R32 (difluoromethane), R410A (ASHRAE designation
components of a refrigerant composition from at least one for a blend of 50 weight percent R125 and 50 weight percent
refrigerant container, (ii) removing impurities Sufficiently to 10 R32), R417A, (ASHRAE designation for a blend of 46.6
enable reuse of said one or more of the reclaimed compo weight percent R125, 50.0 weight percent R134a, and 3.4
nents, (iii) and optionally, combining all or part of said weight percent n-butane), R422A, R422B, R422C and
reclaimed Volume of components with at least one additional R422D, (ASHRAE designation for a blend of 85.1 weight
refrigerant composition or component. percent R125, 11.5 weight percent R134a, and 3.4 weight
A refrigerant container may be any container in which is 15 percent isobutane), R404A, (ASHRAE designation for a
stored a refrigerant blend composition that has been used in a blend of 44 weight percent R125, 52 weight percent R143a
refrigeration apparatus air-conditioning apparatus or heat (1,1,1-trifluoroethane), and 4.0 weight percent R134a) and
pump apparatus. Said refrigerant container may be the refrig R507A (ASHRAE designation for a blend of 50 weight per
eration apparatus, air-conditioning apparatus or heat pump cent R125 and 50 weight percent R143a). Additionally, the
apparatus in which the refrigerant blend was used. Addition compositions of the present invention may be useful as
ally, the refrigerant container may be a storage container for replacements for R12 (CFC-12, dichlorodifluoromethane) or
collecting reclaimed refrigerant blend components, including R502 (ASHRAE designation for a blend of 51.2 weight per
but not limited to pressurized gas cylinders. cent CFC-115 (chloropentafluoroethane) and 48.8 weight
Residual refrigerant means any amount of refrigerant percent HCFC-22).
blend or refrigerant blend component that may be moved out 25 Often replacement refrigerants are most useful if capable
of the refrigerant container by any method known for trans of being used in the original refrigeration equipment designed
ferring refrigerant blends or refrigerant blend components. for a different refrigerant. The compositions of the present
Impurities may be any component that is in the refrigerant invention may be useful as replacements for the above-men
blend or refrigerant blend component due to its use in a tioned refrigerants in original equipment. Additionally, the
refrigeration apparatus, air-conditioning apparatus or heat 30 compositions of the present invention may be useful as
pump apparatus. Such impurities include but are not limited replacements for the above mentioned refrigerants in equip
to refrigeration lubricants, being those described earlier ment designed to use the above-mentioned refrigerants.
herein, particulates including but not limited to metal, metal The compositions of the present invention may further
salt or elastomer particles, that may have come out of the comprise a lubricant. Lubricants of the present invention
refrigeration apparatus, air-conditioning apparatus or heat 35 comprise refrigeration lubricants, i.e. those lubricants Suit
pump apparatus, and any other contaminants that may able for use with refrigeration, air-conditioning, or heat pump
adversely effect the performance of the refrigerant blend apparatus. Among these lubricants are those conventionally
composition. used in compression refrigeration apparatus utilizing chlorof
Suchimpurities may be removed sufficiently to allow reuse luorocarbon refrigerants. Such lubricants and their properties
of the refrigerant blend or refrigerant blend component with 40 are discussed in the 1990 ASHRAE Handbook, Refrigeration
out adversely effecting the performance or equipment within Systems and Applications, chapter 8, titled “Lubricants in
which the refrigerant blend or refrigerant blend component Refrigeration Systems, pages 8.1 through 8.21. Lubricants
will be used. of the present invention may comprise those commonly
It may be necessary to provide additional refrigerant blend known as “mineral oils” in the field of compression refrigera
or refrigerant blend component to the residual refrigerant 45 tion lubrication. Mineral oils comprise paraffins (i.e. straight
blend or refrigerant blend component in order to produce a chain and branched-carbon-chain, Saturated hydrocarbons),
composition that meets the specifications required for a given naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsatur
product. For instance, ifa refrigerant blend has 3 components ated, cyclic hydrocarbons containing one or more rings char
inaparticular weight percentage range, it may be necessary to acterized by alternating double bonds). Lubricants of the
add one or more of the components in a given amount in order 50 present invention further comprise those commonly known as
to restore the composition to within the specification limits. “synthetic oils” in the field of compression refrigeration
The heat transfer fluid compositions of the present inven lubrication. Synthetic oils comprise alkylaryls (i.e. linear and
tion will have global warming potential (GWP) that are less branched alkyl alkylbenzenes), synthetic paraffins and
than many hydrofluorocarbon refrigerants currently in use. napthenes, and poly(alphaolefins). Representative conven
Preferably, such compositions will also have Zero or low 55 tional lubricants of the present invention are the commer
oZone depletion potential. One aspect of the present invention cially available BVM 100 N (paraffinic mineral oil sold by
is to provide a refrigerant with a global warming potential of BVA Oils), Suniso(R) 3GS and Suniso(R) 5GS (naphthenic
less than 1000, less than 500, less than 150, less than 100, or mineral oil sold by Crompton Co.), Sontex.R. 372LT (naph
less than 50. Another aspect of the present invention is to thenic mineral oil sold by Pennzoil), Calumet(R) RO-30 (naph
reduce the net GWP of refrigerant mixtures by adding fluo 60 thenic mineral oil sold by Calumet Lubricants), ZerolR 75,
roolefins to said mixtures. ZerolR 150 and ZerolR 500 (linear alkylbenzenes sold by
The compositions of the present invention may be useful as Shrieve Chemicals) and HAB 22 (branched alkylbenzene
low global warming potential (GWP) replacements for cur sold by Nippon Oil).
rently used refrigerants, including but not limited to R134a Lubricants of the present invention further comprise those
(or HFC-134a 1,1,1,2-tetrafluoroethane), R22 (or HCFC-22, 65 that have been designed for use with hydrofluorocarbon
chlorodifluoromethane), R123 (or HFC-123, 2,2-dichloro-1, refrigerants and are miscible with refrigerants of the present
1,1-trifluoroethane). R11 (CFC-11, fluorotrichloromethane), invention under compression refrigeration, air-conditioning,
 US 8,070,355 B2
37 38
or heat pump apparatus operating conditions. Such lubri tracer type compound Such as a dye is needed to detect the
cants and their properties are discussed in “Synthetic Lubri leakage, even at a low concentration level Such as would be
cants and High-Performance Fluids’. R. L. Shubkin, editor, produced by a small leak site.
Marcel Dekker, 1993. Such lubricants include, but are not In another embodiment, the present invention provides a
limited to, polyol esters (POEs) such as Castrol(R) 100 (Cas method for detecting a leak in a refrigeration or air-condition
trol, United Kingdom), polyalkylene glycols (PAGs) Such as ing system wherein the fluid is a refrigerant composition
RL488A from Dow (Dow Chemical, Midland, Mich.), and comprising carbon dioxide, said method comprising adding a
polyvinyl ethers (PVEs). These lubricants are readily avail Small amount of fluoroolefin to said refrigerant composition.
able from various commercial sources.
Lubricants of the present invention are selected by consid 10
This inventive method makes it possible to detect a leak or
ering a given compressor's requirements and the environment carbon dioxide from the system even in the presence of ambi
to which the lubricant will be exposed. Lubricants of the ent carbon dioxide in the air. The sensors of the present
present invention preferably have a kinematic viscosity of at invention will respond to the fluoroolefin thus signaling that a
least about 5 cs (centistokes) at 40°C. leak is present. For the addition of fluoroolefin to be effective
Commonly used refrigeration system additives may 15 in the present method for detecting a leak of carbon dioxide,
optionally be added, as desired, to compositions of the the fluoroolefin may be present at less than about 1 weight
present invention in order to enhance lubricity and system percent. In another embodiment, the fluoroolefin may be
stability. These additives are generally known within the field present in the range of about 0.1 weight percent (or 1000 ppm
of refrigeration compressor lubrication, and include antiwear by weight) to about 0.01 weight percent (or 100 ppm by
agents, extreme pressure lubricants, corrosion and oxidation weight).
inhibitors, metal Surface deactivators, free radical scavengers,
foaming and antifoam control agents, leak detectants and the EXAMPLE
like. In general, these additives are present only in Small
amounts relative to the overall lubricant composition. They Near-infrared Spectrum for Fluoroolefin
are typically used at concentrations of from less than about 25
0.1% to as much as about 3% of each additive. These additives This example demonstrates that a NIR spectrum can be
are selected on the basis of the individual system require obtained for a fluoroolefin as described herein. A sample of
ments. Some typical examples of such additives may include, 1,2,3,3,3-pentafluoropropene (HFC-1225ye) was analyzed
but are not limited Soto, lubrication enhancing additives, such with a Varian Cary 500 UV/Vis/NIR spectrophotometer at
as alkyl or aryl esters of phosphoric acid and of thiophos 30 ambient temperature. A 10 millimeter sample cell was
phates. Additionally, the metal dialkyl dithiophosphates (e.g. charged with HFC-1225ye to a pressure of 748 torr on a
Zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and vacuum line, having previously been evacuated. A back
other members of this family of chemicals may be used in ground spectrum of the same evacuated (<1 mTorr) cell was
compositions of the present invention. Other antiwear addi acquired and Subtracted from the sample spectrum. For both
tives include natural product oils and assymetrical polyhy 35 sample and background, points were acquired at 1 nanometer
droxyl lubrication additives such as Synergol TMS (interna (nm) resolution and averaging 0.2 seconds per point, with a
tional Lubricants). Similarly, stabilizers such as antioxidants, spectral bandwidth of 4 nm, the detector and grating
free radical scavengers, and water Scavengers may be changeover occurred at 800 nm and the UV source was acti
employed. Compounds in this category can include, but are vated at 350 nmi; and the spectrum was scanned from 2600 to
not limited to, butylated hydroxy toluene (BHT) and 40 190 nm. FIG. 2 shows the raw NIR spectral data for the
epoxides. HFC-1225ye sample. FIG. 3 shows the background NIR
The compositions of the present invention may further spectrum acquired for the evacuated sample cell. And FIG. 4
comprise about 0.01 weight percent to about 5 weight percent shows the background subtracted NIR spectrum for HFC
of an additive such as, for example, a stabilizer, free radical 1225ye. These data verify that NIR spectra for fluoroolefins
Scavenger and/or antioxidant. Such additives include but are 45 may be obtained that provide a unique fingerprint for detec
not limited to, nitromethane, hindered phenols, hydroxy tion of this class of compound.
lamines, thiols, phosphites, or lactones. Single additives or
combinations may be used. What is claimed is:
The compositions of the present invention may further 1. A method for detecting a leak of a composition compris
comprise about 0.01 weight percent to about 5 weight percent 50 ing a fluoroolefin from a fluid system containing said com
of a water Scavenger (drying compound). Such water scaven position, comprising sensing the leaked fluoroolefin with a
gers may comprise ortho esters such as trimethyl-, triethyl-, or sensing means proximate the components of the fluid system,
tripropylortho formate. wherein said sensing means uses a NIR sensor that uses a
In one embodiment, the present composition comprising a light-emitting diode as the Source of near infrared radiation
fluoroolefin may further comprise at least one compound 55 for detecting the double bond structure of the leaked fluo
selected from the group consisting of: HFC-1225ye, HFC roolefin.
1234ze, HFC-1234yf. HFC-1234ye, HFC-1243zf, HFC-32, 2. The method of claim 1, wherein the sensing means
HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, comprises a hand-held device.
HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC 3. The method of claim 1, wherein the fluid system is a
245fa, HFC-365mfc, propane, n-butane, isobutane, 2-meth 60 cooling system of an automotive vehicle.
ylbutane, n-pentane, cyclopentane, dimethylether, CF3SCF3, 4. The method of claim 1, wherein the fluoroolefin com
CO2, ammonia, and CF3I. These additional components are prises a compound having the formula E- or
available commercially. Z R'CH=CHR (Formula I), wherein R' and Rare, inde
The fluoroolefin compositions of the present invention are pendently, C to Ce perfluoroalkyl groups.
more easily detected at low levels as compared to the more 65 5. The method of claim 4, wherein the RandR groups are
conventional saturated fluorocarbon working fluids by virtue CF, CFs, CFCFCF, CF(CF), CFCFCFCF,
of the double bond. Therefore, with the present invention, no CF(CF)CFCF CFCF (CF), C(CF).
 US 8,070,355 B2
39 40
CFCFCFCFCF, CFCFCF (CF), C(CF)CFs, CFCF-CHCH(CF)(CH),
CFCFCFCFCFCF, CF(CF) CFCFCF, and CFCF–CFCFCFCF,
C(CF). CFCFs. CFCH=CFCFCFCF CFCF-CHCFCFCF
6. The method of claim 1, wherein the fluoroolefin com CFCF-CH=CFCFCF CFCFCF-CHCFCF
prises a compound selected from the group consisting of 5 cyclo-CFCFCF–CF cyclo-CFCF-CH=CH-, cyclo
CFCF-CHF, CFCH=CF, CHF.CF–CF, CFCFCF-CH=CH-, cyclo-CFCF–CFCFCF, , and
CHF.CF–CHF, CFCF-CH, CFCH-CHF, cyclo-CFCF–CFCFCFCF.
CHFCF–CF, CHF.CH=CF, CHF.CF–CHF, prising 7. The method of claims 1, wherein the composition com
CHF.CF=CH, CFCH=CH CHCF=CF, 10 pound selecteda fluoroolefin further comprises at least one com
CHFCH=CF, CHFCF–CHF, CHF CH-CHF, from the group consisting of: HFC-1225ye,
CFCF–CFCF, CFCFCF-CF, CFCF-CHCF, HFC-1234ze, HFC-1234yf. HFC-1234ye, HFC-1243zf,
CHF-CFCFCF, CHF.CF–CFCF (CF),C–CHF, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC
152a, HFC-161, HFC-227ea, HFC-236ea,
CF=CHCFCF, CF, CFCHFCF, CF=CFCFCHF, 245fa, HFC-365mfc, propane, n-butane, isobutane, 2-meth HFC-236fa, HFC
CFCFCF-CH, CFCH=CHCF, CHF=CHCFCF, 15 ylbutane, n-pentane, cyclopentane, dimethylether, CFSCF,
CHF-CFCHFCF, CHF-CFCFCHF,
CHF.CF–CFCHF, CHFCF–CFCF, CO8. Aammonia, method
and CFI.
for detecting a leak of a refrigerant fluid
CHF CH-CFCF, CFCH-CFCHF, CF, CFCFCHF, comprising carbon dioxide from a refrigeration or air-condi
CF=CFCHFCHF, CH=C(CF), CHFCH=CFCF, tioning system containing said refrigerant fluid, comprising
CFCH=CFCHF, CFCF-CH=CH, CHFCH=CHCF, (a) adding a fluoroolefin to said refrigerant fluid; and (b)
CFCF-CFCH, CH=CFCFCHF, sensing the leaked fluoroolefin with a sensing means proxi
CHF.CF–CHCHF, CHCFCF-CF, mate the components of the system, wherein said sensing
CHFCF–CFCHF, CHFCFCF-CF, CF=C(CF) means uses a sensor for detecting the double bond structure of
(CH), CH=C(CHF) (CF), CH=CHCFCHF, CF–C the fluoroolefin.
(CHF)(CH), CHF-C(CF)(CH), CH=C(CHF), 25 9. A fluid system, comprising (a) a refrigeration or air
CFCF-CHCH, CH=CFCHFCF, CHF-CFCH.CF, conditioning system containing a refrigerant fluid comprising
CHF-CHCHFCF, CHF-CHCFCHF, a fluoroolefin and (b) a sensing means proximate the compo
CHF-CFCHFCHF CHCF–CHCF, CFCF-CFCF, nents of the refrigeration of air conditioning system for
CF–CFCFCFCF (CF)C=CHCF, detecting a leak from said refrigeration or air conditioning
CFCF-CHCFCF, CFCH=CFCFCF, 30 system, wherein said sensing means uses a NIR sensor that
CHF-CFCFCFCF, CF=CHCFCFCF, uses a light-emitting diode as the source of near infrared
CF=CFCFCFCHF, CHF.CF–CFCFCF, radiation for detecting the double bond structure of the leaked
CFCF–CFCFCHF, CFCF–CFCHFCF, CHF-CFCF fluoroolefin.
(CFs). CF–CFCH(CF), CFCH=C(CF), 10. The fluid system of claim 9, wherein the sensing means
CF–CHCF(CF). CH=CFCFCFCF, 35 comprises a wand tip.
CHF-CFCFCFCHF, CH=C(CF)CFCF, 11. The method of claim 8 wherein the fluoroolefin is
CF–CHCH(CF), CHF=CHCF(CF), CF=C(CF) added at less than about 1 weight percent.
CHCF, CFCH=CHCFCF (CF). CFCH=CH, 12. The fluid system of claim 9 wherein (a) is the cooling
CFCFCF-CH=CH, CH=CFCFCFCHF, system of an automotive vehicle.
CF=CHCFCHCF, CFCF–C(CF)(CH), 40 13. The method of claim 1 wherein the sensor detects the
CH=CFCH(CF), CHF=CHCH(CF), CHFCH=C double bond structure by measuring the near-infrared spec
(CFs). CHCF=C(CF), (CF),C—CHCH trum of the leaked fluoroolefin.
CFCF-CHCH CFC(CH)—CHCF, 14. The method of claim 13 wherein the sensor is a NIR
CH=CHCFCHFCF, CH=C(CF)CHCFCF (CF). sensor that uses a light-emitting diode as the Source of near
CF=CF, CFCFCF–CFCFCF (CF),C=C(CF), 45 infrared radiation for detecting the double bond structure of
(CF)CFCF–CFCF (CF),C=CHCFs (CF). the leaked fluoroolefin.
CFCF-CHCF, CFCH=CHCF(CF), 15. The method of claim 8, wherein the sensing means
CFCH=CHCFCFCFCFCF-CH=CHCFCF, comprises a sensor selected from the group consisting of
CFCFCFCF-CH=CH-CH=CHC(CF), (CF),C—C infrared sensors, UV sensors, NIR sensors, ion mobility or
(CH)(CF), H=CFCF-CH(CF), CFCF–C(CH) 50 plasma chromatographs, gas chromatography, refractometry,
CFCFCF-CH=CHCH(CF), CFCFCF-CHCH mass spectroscopy, high temperature thick film sensors, thin
CH=CHCFCFCFCHF (CF),C=CHCFCH, film field effect sensors, pellistor sensors, Taguchi sensors
CH=C(CF)CHCFs, CFCFCFC(CH)—CH, and quartz microbalance sensors.
CFCFCF-CH=CHCH, CH=CHCHCFCF,
CFCFCF-CFCH CH=CHCHCF(CF), k k k k k