AZEOTROPE-LIKE COMPOSITIONS

COMPRISING l-CHLORO-3,3,3-TRIFLUOROPROPENE

CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority to U.S. Provisional application Ser. No.

61/642,907, filed on May 4, 2012, the contents of which is incorporated herein by reference in its entirety.

This application is also a continuation-in-part (CIP) of US Application No. 13/298,483, filed November 17, 2011, which is a continuation-in-part of US Application No. 12/605,609, filed October 26, 2009, (now US Patent No. 8,163,196) which claims the priority benefit of US Provisional Application No. 61/109,007, filed October 28, 2008, and which is also a continuation-in-part (CIP) of US Application No. 12/259,694, filed October 28, 2008, (now US Patent No. 7,935,268) the contents each of which are incorporated herein by reference in its entirety.

BACKGROUND

Field of Invention:

The present invention relates generally to compositions comprising l-chloro-3,3,3 trifluoropropene. More specifically, the present invention provides azeotrope-like

compositions comprising l-chloro-3,3,3-trifluoropropene and uses thereof.

Description of Related Art:

Fluorocarbon based fluids, including chlorofluorocarbons ("CFCs") or

hydrochlorofluorocarbons ("HCFCs"), have properties that are desirable in industrial refrigerants, blowing agents, heat transfer media, solvents, gaseous dielectrics, and other applications. For these applications, the use of single component fluids or azeotrope-like mixtures, i.e., those which do not substantially fractionate on boiling and evaporation, are particularly desirable.

Unfortunately, suspected environmental problems, such as global warming and ozone depletion, have been attributed to the use of some of these fluids, thereby limiting their contemporary use. Hydrofluoroolefins ("HFOs") have been proposed as possible replacements for such CFCs, HCFCs, and HFCs. However, the identification of new, environmentally-safe, non- fractionating mixtures comprising HFOs are complicated due to the fact that azeotrope formation is not readily predictable. Therefore, industry is continually seeking new HFO- based mixtures that are acceptable and environmentally safer substitutes for CFCs, HCFCs, and HFCs. This invention satisfies these needs among others.

SUMMARY OF INVENTION

Applicants have discovered the formation of certain azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene ("HFO-1233zd") with a second and, optionally, third component selected from a Ci - C ₃ alcohol, a C ₅ - C ₆ hydrocarbon, cyclopentene, a halogenated hydrocarbon (e.g. 1-chloropropane, 2-chloropropane, and

1,1,1,3,3-pentafluorobutane), water, petroleum ether and nitromethane. In further aspects, Applicants have discovered the formation of certain ternary azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene (particularly its cis isomer), methanol, and a third component including one of isohexane and trans- 1,2-dichloroethylene. Applicants have also discovered the formation of certain binary azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifiuoropropene (particularly its cis isomer) and petroleum ether. Applicants have further discovered the formation of certain ternary azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene (particularly its cis isomer), cyclopentane and a C 1-C3 alcohol, such as methanol, ethanol, or isopropanol.

Preferred azeotrope-like mixtures of the invention exhibit characteristics which make them particularly desirable for number of applications, including as refrigerants, as blowing agents in the manufacture of insulating foams, and as solvents in a number of cleaning and other applications, including in aerosols and other sprayable compositions. In particular, applicants have recognized that these compositions tend to exhibit relatively low global warming potentials ("GWPs"), preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150.

Accordingly, one aspect of the present invention involves a composition comprising a binary or ternary azeotrope-like mixture provided herein and, optionally, one or more of the following: co-blowing agent, co-solvent, active ingredient, and additive such as lubricants, stabilizers, metal passivators, corrosion inhibitors, and flammability suppressants. In certain preferred embodiments, nitromethane is included in the mixture as a stabilizer. In certain embodiments, nitromethane also contributes to the azeotrope-like properties of the composition.

Another aspect of the invention provides a blowing agent comprising at least about 15 wt. % of an azeotrope-like mixture as described herein, and, optionally, co-blowing agents, fillers, vapor pressure modifiers, flame suppressants, and stabilizers.

Another aspect of the invention provides a solvent for use in vapor degreasing, cold cleaning, wiping, solder flux cleaning, dry cleaning, and similar solvent applications

comprising an azeotrope-like mixture as described herein. Another aspect of the invention provides a sprayable composition comprising an azeotrope-like mixture as described herein, an active ingredient, and, optionally, inert ingredients and/or solvents and aerosol propellants.

Yet another aspect of the invention provides closed cell foam comprising a

polyurethane-, polyisocyanurate-, or phenolic-based cell wall and a cell gas disposed within at least a portion of the cell wall structure, wherein the cell gas comprises the azeotrope-like mixture as described herein.

According to another embodiment, provided is a polyol premix comprising the azeotrope-like mixture described herein.

According to another embodiment, provided is a foamable composition comprising the azeotrope-like mixture described herein.

According to another embodiment, provided is a method for producing thermoset foam comprising (a) adding a blowing agent comprising an azeotrope-like composition provided herein to a foamable mixture comprising a thermosetting resin; (b) reacting said foamable mixture to produce a thermoset foam; and (c) volatilizing said azeotrope-like composition during said reacting.

According to another embodiment, provided is a method for producing thermoplastic foam comprising (a) adding a blowing agent comprising an azeotrope-like composition provided herein to a foamable mixture comprising a thermoplastic resin; (b) reacting said foamable mixture to produce a thermoplastic foam; and (c) volatilizing said azeotrope-like composition during said reacting.

According to another embodiment, provided is a thermoplastic foam having a cell wall comprising a thermoplastic polymer and a cell gas comprising an azeotrope-like mixture as described herein. Preferably, the thermoplastic foam comprises a cell gas having an azeotrope- like mixture as described herein and having a cell wall constructed of a thermoplastic polymer selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride,

polytheyeneterephthalate or combinations thereof.

According to another embodiment, provided is a thermoset foam having a cell wall comprising a thermosetting polymer and a cell gas comprising an azeotrope-like mixture as described herein. Preferably, the thermoset foam comprises a cell gas having an azeotrope-like mixture as described herein and a cell wall comprising a thermoset polymer selected from polyurethane, polyisocyanurate, phenolic, epoxy, or combinations thereof.

According to another embodiment of the invention, provided is a refrigerant comprising an azeotrope-like mixture as described herein. Such refrigerants may be used in any refrigerant system known in the art, particularly, though not exclusively, systems that employ a refrigerant to provide heating or cooling. Such refrigeration systems include, but are not limited to, air conditioners, electric refrigerators, chillers (including chillers using centrifugal compressors), transport refrigeration systems, heat pump systems, commercial refrigeration systems and the like.

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 illustrates the change in boiling point of a composition of cis-1233zd and methanol as trans- 1,2-DCE is gradually added.

FIG. 2 illustrates the change in boiling point of a composition of cis-1233zd and methanol as isohexane is gradually added. FIG. 3 illustrates the change in boiling point of a composition of cis-1233zd as petroleum ether is gradually added.

FIG. 4 illustrates the change in boiling point of a composition of cis-1233zd and cyclopentane as ethanol is gradually added.

FIG. 5 illustrates the change in boiling point of a composition of cis-1233zd and cyclopentane as isopropanol (IP A) is gradually added.

FIG. 6 illustrates the change in boiling point of a composition of cis-1233zd and cyclopentane as methanol is gradually added.

FIG. 7 illustrates the change in boiling point of a composition of cis-1233zd and methanol as isohexane is gradually added.

DESCRIPTION OF PREFERRED EMBODIMENTS

According to certain embodiments, the present invention provides binary and ternary azeotrope-like compositions comprising, and preferably consisting essentially of, HFO-1233zd and one or two of a Ci - C ₃ alcohol, a C ₅ - C ₆ hydrocarbon, cyclopentene, a halogenated hydrocarbon selected from l-chloropropane, 2-chloropropane, trans- 1 ,2-dichloroethylene, and 1 , 1 ,1 ,3,3-pentafluorobutane, petroleum ether, nitromethane, or water. Thus, the present invention overcomes the aforementioned shortcomings by providing azeotrope-like compositions that are, in preferred embodiments, substantially free of CFCs, HCFCs, and HFCs and have very low global warming potentials have low ozone depletion potential, and which exhibit relatively constant boiling point characteristics.

As used herein, the term "azeotrope-like" relates to compositions that are strictly azeotropic or that generally behave like azeotropic mixtures. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant-boiling or essentially constant-boiling and generally cannot be thermodynamically separated during a phase change. The vapor composition formed by boiling or evaporation of an azeotropic mixture is identical, or substantially identical, to the original liquid composition. Thus, the concentration of components in the liquid and vapor phases of azeotrope-like compositions change only minimally, if at all, as the composition boils or otherwise evaporates. In contrast, boiling or evaporating non-azeotropic mixtures changes the component concentrations in the liquid phase to a significant degree.

As used herein, the term "consisting essentially of," with respect to the components of an azeotrope-like composition, means the composition contains the indicated components in an azeotrope-like ratio, and may contain additional components provided that the additional components do not form new azeotrope-like systems. For example, azeotrope-like mixtures consisting essentially of two compounds are those that form binary azeotropes, which optionally may include one or more additional components, provided that the additional components do not render the mixture non-azeotropic and do not form an azeotrope with either or both of the compounds.

The term "effective amounts" as used herein refers to the amount of each component which, upon combination with the other component, results in the formation of an azeotrope- like composition of the present invention.

Unless otherwise specified, the term HFO-1233zd means the cz ^' s-isomer, the trans- isomer, or some mixture thereof. As used herein, the term cz ^' s-HFO-1233zd with respect to a component of an azeotrope- like mixture, means the amount cz ^' s-HFO-1233zd relative to all isomers of HFO-1233zd in azeotrope-like compositions is at least about 95 %, more preferably at least about 98 %, even more preferably at least about 99 %, even more preferably at least about 99.9 %. In certain preferred embodiments, the cz ^' s-HFO-1233zd component in azeotrope-like compositions of the present invention is essentially pure cz ^' s-HFO-1233zd.

As used herein, the term tr<ms-HFO-1233zd with respect to a component of an azeotrope-like mixture, means the amount trans-HFO-\233zd relative to all isomers of HFO- 1233zd in azeotrope-like compositions is at least about 95 %, more preferably at least about 98%, even more preferably at least about 99 %, even more preferably at least about 99.9 %. In certain preferred embodiments, the trans-HFO-\233zd component in azeotrope-like

compositions of the present invention is essentially pure trans- FO-\233zd.

As used herein, the term "ambient pressure" with respect to boiling point data means the atmospheric pressure surrounding the relevant medium. In general, ambient pressure is 14.7 psia, but could vary +/- 0.5 psi.

The azeotrope-like compositions of the present invention can be produced by combining effective amounts of HFO-1233zd with one or more other components, preferably in fluid form. Any of a wide variety of methods known in the art for combining two or more components to form a composition can be adapted for use in the present methods. For example, HFO-1233zd and methanol can be mixed, blended, or otherwise combined by hand and/or by machine, as part of a batch or continuous reaction and/or process, or via combinations of two or more such steps. In light of the disclosure herein, those of skill in the art will be readily able to prepare azeotrope-like compositions according to the present invention without undue experimentation.

Fluoropropenes, such as CF ₃ CC1=CH ₂ , can be produced by known methods such as catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C3 compounds, including the method described in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each of which is incorporated herein by reference.

EP 974,571 , also incorporated herein by reference, discloses the preparation of 1 , 1 ,1 ,3- chlorotrifluoropropene by contacting 1 , 1 ,1 ,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with a chromium based catalyst at elevated temperature, or in the liquid phase with an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2. The end product is approximately 90% by weight of the trans isomer and 10% by weight cis. Preferably, the cis isomers are substantially separated from the trans forms so that the resultant preferred form of 1-chloro- 3,3,3-trifluoropropene is more enriched in the cis isomer. Because the cis isomer has a boiling point of about 40°C in contrast with the trans isomer boiling point of about 20 °C, the two can easily be separated by any number of distillation methods known in the art. However, a preferred method is batch distillation. According to this method, a mixture of cis and trans 1- chloro-3,3,3-trifluoropropene is charged to the reboiler. The trans isomer is removed in the overhead leaving the cis isomer in the reboiler. The distillation can also be run in a continuous distillation where the trans isomer is removed in the overhead and the cis isomer is removed in the bottom. This distillation process can yield about 99.9+ % pure trans-\-chloro- 3,3,3-trifluoropropene and 99.9+ % czs-l-chloro-3,3,3-trifluoropropene.

In a preferred embodiments, the azeotrope-like composition comprises effective amounts of HFO-1233zd and a Ci - C ₃ alcohol. Preferably, the Ci - C ₃ alcohol is selected from the group consisting of methanol, ethanol, and isopropanol. In certain preferred embodiments, the HFO-1233zd is tr<ms-HFO-1233zd. In certain other embodiments, the HFO-1233zd is cw-HFO-1233zd. s-HFO-1233zd/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and methanol. More preferably, these binary azeotrope-like compositions consist essentially of about 78 to about 99.9 wt. % cz ^' s-HFO-1233zd and from about 0.1 to about 22 wt. % methanol, more preferably from about 85 to about 99.9 wt. % cis- HFO-1233zd and about 0.1 to about 15 wt. % methanol, and even more preferably from about 88 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 12 wt. % methanol.

Preferably, the czs-HFO-1233zd/methanol compositions of the present invention have a boiling point of about 35.2 ± 1 °C at ambient pressure. 7>flws-HFO-1233zd/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts and methanol. More preferably, these binary azeotrope-like compositions consist essentially of about 70 to about 99.95 wt. % and from about 0.05 to about 30 wt. % methanol, more preferably from about 90 to about 99.95 wt. % and about 0.05 to about 10 wt. % methanol, and even more preferably from about 95 to about 99.95 wt. % tr<my-HFO-1233zd and from about 0.05 to about 5 wt. % methanol. Preferably, the tra«s-HFO-1233zd/methanol compositions of the present invention have a boiling point of from about 17 °C to about 19 °C, more preferably about 17 °C to about 18 °C, even more preferably about 17 °C to about 17.5 °C, and most preferably about 17.15 °C ± 1 °C, all measured at ambient pressure.

C¾-HFO-1233zd/Ethanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and ethanol. More preferably, these binary azeotrope-like compositions consist essentially of about 65 to about 99.9 wt. % cz ^' s-HFO-1233zd and from about 0.1 to about 35 wt. % ethanol, more preferably from about 79 to about 99.9 wt. % cis- HFO-1233zd and about 0.1 to about 21 wt. % ethanol, and even more preferably from about 88 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 12 wt. % ethanol.

Preferably, the cz ^' s-HFO-1233zd/ethanol compositions of the present invention have a normal boiling point of about 37.4 °C ± 1 °C at ambient pressure.

Trans-ΆΈ O-1233zd/Ethanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and ethanol. More preferably, these binary azeotrope-like compositions consist essentially of about 85 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 15 wt. % ethanol, more preferably from about 92 to about 99.9 wt. % trans- HFO-1233zd and about 0.1 to about 8 wt. % ethanol, and even more preferably from about 96 to about 99.9 wt. % and from about 0.1 to about 4 wt. % ethanol. Preferably, the tr<ms-HFO-1233zd/ethanol compositions of the present invention have a normal boiling point of about 18.1 °C ± 1 °C at ambient pressure. s-HFO-1233zd/Isopropanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and isopropanol. More preferably, these binary azeotrope-like compositions consist essentially of about 85 to about 99.99 wt. % cz ^' s-HFO-1233zd and from about 0.01 to about 15 wt. % isopropanol, more preferably from about 88 to about 99.99 wt. % cz ^' s-HFO-1233zd and about 0.01 to about 12 wt. % isopropanol, and even more preferably from about 92 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 8 wt. % isopropanol.

Preferably, the cz ^' s-HFO-1233zd/isopropanol compositions of the present invention have a normal boiling point of about 38.1 °C ± 1 °C at ambient pressure.

Trans-HFO-1233zd/Isopropanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and isopropanol. More preferably, these binary azeotrope-like compositions consist essentially of about 90 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 10 wt. % isopropanol, more preferably from about 94 to about 99.9 wt. % trans-HFO-\233zd and about 0.1 to about 6 wt. % isopropanol, and even more preferably from about 95 to about 99.9 wt. % trans-HFO-\233zd and from about 0.1 to about 5 wt. % isopropanol.

Preferably, the tra¾s-HFO-1233zd/isopropanol compositions of the present invention have a normal boiling point of about 17.9 °C ± 1 °C at ambient pressure. In a preferred embodiments, the azeotrope-like composition comprises effective amounts of HFO-1233zd and a C ₅ - C ₆ hydrocarbon. Preferably, the C ₅ - C ₆ hydrocarbon is selected from the group consisting of n-pentane, isopentane, neopentane, cyclopentane, cyclopentene, n-hexane, and isohexane. In certain preferred embodiments, the HFO-1233zd tr<ms-HFO-1233zd. In certain other embodiments, the HFO-1233zd is cz ^' s-HFO-1233zd.

7>flws-HFO-1233zd/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and n-pentane. More preferably, these binary azeotrope-like compositions consist essentially of about 65 to about 99.95 wt. % tr<ms-HFO-1233zd and from about 0.05 to about 35 wt. % n-pentane, more preferably from about 84 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 16 wt. % n-pentane, and even more preferably from about 92 to about 99.5 wt. % tr<ms-HFO-1233zd and from about 0.5 to about 8 wt. % n-pentane.

Preferably, the tr ¾s-HFO-1233zd/n-pentane compositions of the present invention have a boiling point of from about 17 °C to about 19 °C, more preferably about 17 °C to about 18 °C, even more preferably about 17.3 °C to about 17.6 °C, and most preferably about 17.4 °C ± 1° C, all measured at ambient pressure.

C¾-HFO-1233zd/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and n-pentane. More preferably, these binary azeotrope-like compositions consist essentially of about 20 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 80 wt. % n-pentane, more preferably from about 50 to about 99.5 wt. % cis- HFO-1233zd and about 0.5 to about 50 wt. % n-pentane, and even more preferably from about 60 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 40 wt. % n-pentane.

Preferably, the cz ^' s-HFO-1233zd/n-pentane compositions of the present invention have a normal boiling point of about 35 °C ± 1° C at ambient pressure. rraws-HFO-1233zd/Isopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and isopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 60 to about 99.95 wt. % trans- FO-\233zd and from about 0.05 to about 40 wt. % isopentane, more preferably from about 70 to about 95 wt. % tr<my-HFO-1233zd and about 5 to about 30 wt. % isopentane, and even more preferably from about 80 to about 90 wt. % trans- FO-\233zd and from about 10 to about 20 wt. % isopentane.

Preferably, the tra¾s-HFO-1233zd/isopentane compositions of the present invention have a boiling of from about 15 °C to about 18 °C, more preferably about 16 °C to about 17 °C, even more preferably about 16.7 °C to about 16.9 °C, and most preferably about 16.8 °C ± 1 °C, all measured at ambient pressure.

7>«ws-HFC)-1233zd/Neopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and neopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 5 to about 70 wt. % trans-HFO-\233zd and from about 30 to about 95 wt. % neopentane, more preferably from about 15 to about 55 wt. % trans-HFO-\233zd and about 45 to about 85 wt. % neopentane, and even more preferably from about 20 to about 50 wt. % tr<my-HFO-1233zd and from about 50 to about 80 wt. % neopentane.

Preferably, the tr<ms-HFO-1233zd/neopentane compositions of the present invention have a boiling of from about 7.7 °C to about 8.4 °C, more preferably about 7.7 °C to about 8.0 °C, and most preferably about 7.7 °C ± 1 °C, all measured at ambient pressure.

C¾-HFO-1233zd/Neopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and neopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 5 to about 50 wt. % cz ^' s-HFO-1233zd and from about 50 to about 95 wt. % neopentane, more preferably from about 20 to about 45 wt. % cis-HFO- 1233zd and about 55 to about 80 wt. % neopentane, and even more preferably from about 30 to about 40 wt. % cz ^' s-HFO-1233zd and from about 60 to about 70 wt. % neopentane.

Preferably, the cz ^' s-HFO-1233zd/neopentane compositions of the present invention have a normal boiling point of about 8 °C ± 1 °C.

7>flws-HFO-1233zd/Cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and cyclopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 95 to about 99.9 wt. % tr<my-HFO-1233zd and from about 0.1 to about 5 wt. % cyclopentane, more preferably from about 97 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 3 wt. % cyclopentane, and even more preferably from about 98 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 2 to about 98 wt. % cyclopentane.

Preferably, the tra¾s-HFO-1233zd/cyclopentane compositions of the present invention have a normal boiling point of about 17.5°C ± 1 °C at ambient pressure.

s-HFO-1233zd/Cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and cyclopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 42 to about 99 wt. % cz ^' s-HFO-1233zd and from about 1 to about 58 wt. % cyclopentane, more preferably from about 50 to about 95 wt. % cis- HFO-1233zd and about 5 to about 50 wt. % cyclopentane, and even more preferably from about 60 to about 93 wt. % cz ^' s-HFO-1233zd and from about 7 to about 40 wt. % cyclopentane.

Preferably, the czs-HFO-1233zd/cyclopentane compositions of the present invention have a normal boiling point of about 34.7°C ± 1 °C at ambient pressure.

7>«ws-HFC)-1233zd/Cyclopentene Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and cyclopentene. More preferably, these binary azeotrope-like compositions consist essentially of about 95 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 5 wt. % cyclopentene, more preferably from about 97 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 3 wt. % cyclopentene, and even more preferably from about 98 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 2 to about 98 wt. % cyclopentene.

Preferably, the tr<ms-HFO-1233zd/cyclopentene compositions of the present invention have a normal boiling point of about 18.1°C ± 1 °C at ambient pressure.

rraws-HFO-1233zd/n-Hexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and n-hexane. More preferably, these binary azeotrope-like compositions consist essentially of about 95 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 5 wt. % n-hexane, more preferably from about 97 to about 99.99 wt. % tr<ms-HFO-1233zd and about 0.01 to about 3 wt. % n-hexane, and even more preferably from about 97.2 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 2.8 wt. % n- hexane.

Preferably, the tr<ms-HFO-1233zd/ n-hexane compositions of the present invention have a normal boiling point of about 17.4°C ± 1 °C at ambient pressure.

Cw-HFO-1233zd/n-Hexane Azeotrope-Like Compositions: In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and n-hexane. More preferably, these binary azeotrope-like compositions consist essentially of about 80 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 20 wt. % n-hexane, more preferably from about 90 to about 99.5 wt. % cis- HFO-1233zd and about 0.5 to about 10 wt. % n-hexane, and even more preferably from about 95 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 5 wt. % n-hexane.

Preferably, the cz ^' s-HFO-1233zd/ n-hexane compositions of the present invention have a normal boiling point of about 39 °C ± 1 °C at ambient pressure.

rraws-HFO-1233zd/Isohexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of and isohexane. More preferably, these binary azeotrope-like compositions consist essentially of about 94.4 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 5.6 wt. % isohexane, more preferably from 96 wt. % to about 99.99 wt. % and about 0.01 to about 4 wt. % isohexane, and even more preferably from about 97 to about 99.99 wt. % and from about 0.01 to about 3 wt. % isohexane.

Preferably, the tr<ms-HFO-1233zd/isohexane compositions of the present invention have a boiling point of from about 17 °C to about 19 °C, more preferably about 17 °C to about 18 °C, even more preferably about 17.3 °C to about 17.6 °C, and most preferably about 17.4 °C ± 1 °C, all measured at ambient pressure. C¾-HFO-1233zd/Isohexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and isohexane. More preferably, these binary azeotrope-like compositions consist essentially of about 70 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 30 wt. % isohexane, more preferably from 85 wt. % to about 99.5 wt. % cz ^' s-HFO-1233zd and about 0.5 to about 15 wt. % isohexane, and even more preferably from about 93 to about 99.5 wt. % cz ^' s-HFO-1233zd and from about 0.5 to about 7 wt. % isohexane.

Preferably, the czs-HFO-1233zd/isohexane compositions of the present invention have a normal boiling point of about 37°C ± 1 °C.

In a preferred embodiments, the azeotrope-like composition comprises effective amounts of HFO-1233zd and a hydrohalocarbon. Preferably, the hydrohalocarbon is selected from the group consisting of l-chloropropane, 2-chloropropane, 1,1,1,3,3-pentafluorobutane (HFC-365mfc), and trans- 1 ,2-dichloroethylene {trans- 1,2-DCE). In certain preferred embodiments, the HFO-1233zd is In certain other embodiments, the HFO-1233zd is cw-HFO-1233zd.

7>flws-HFO-1233zd/l-Chloropropane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts and l-chloropropane. More preferably, these binary azeotrope- like compositions consist essentially of about 96 to about 99.9 wt. % and from about 0.1 to about 4 wt. % l-chloropropane, more preferably from about 98 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 2 wt. % l-chloropropane, and even more preferably from about 99 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 1 wt. % 1-chloropropane.

Preferably, the tr «s-HFO-1233zd/l-chloropropane compositions of the present invention have a normal boiling point of about 18°C ± 1 °C at ambient pressure. rraws-HFO-1233zd/2-Chloropropane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and 2-chloropropane. More preferably, these binary azeotrope- like compositions consist essentially of about 94 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 6 wt. % 2-chloropropane, more preferably from about 97 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 3 wt. % 2-chloropropane, and even more preferably from about 99 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 1 wt. % 2-chloropropane.

Preferably, the tr «s-HFO-1233zd/2-chloropropane compositions of the present invention have a normal boiling point of about 17.8°C ± 1 °C at ambient pressure.

TraMS-HFO-1233zd/HFC-365mfc Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and HFC-365mfc. More preferably, these binary azeotrope- like compositions consist essentially of about 89 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 11 wt. % HFC-365mfc, more preferably from about 92.5 to about 99.9 wt. % tr<ms-HFO-1233zd and about 0.1 to about 7.5 wt. % HFC-365mfc, and even more preferably from about 95 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 5 wt. % HFC-365mfc.

Trans-ΆΈ O-1233zd/ trans-l,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and trans- 1,2-DCE. More preferably, these binary azeotrope- like compositions consist essentially of about 60 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 40 wt. % trans- 1,2-DCE, more preferably from about 75 to about 99.99 wt. % tr<ms-HFO-1233zd and about 0.01 to about 25 wt. % trans-l, 2-OCE, and even more preferably from about 95 weight percent to about 99.99 wt% tr<ms-HFO-1233zd and from about 0.01 to about 5 wt. % trans- 1,2-DCE.

Preferably, the tr<ms-HFO-1233zd/ trans-\,2-OCE compositions of the present invention have a boiling of from about 17 °C to about 19° C, more preferably about 17.5 °C to about 18.5 °C, even more preferably about 17.5 °C to about 18 °C, and most preferably about 17.8 °C ± 1 °C, all measured at ambient pressure.

C¾-HFO-1233zd/ trans-l, 2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and trans- 1,2-DCE. More preferably, these binary azeotrope-like compositions consist essentially of about 42 to about 99.9 wt. % cz ^' s-HFO-1233zd and from about 0.1 to about 58 wt. % trans-l, 2-OCE, more preferably from about 55 to about 99.5 wt. % cz ^' s-HFO-1233zd and about 0.5 to about 45 wt. % trans-l, 2-OCE, and even more preferably from about 65 weight percent to about 99 wt% cz ^' s-HFO-1233zd and from about 1 to about 35 wt. % trans- 1,2-DCE.

Preferably, the cz ^' s-HFO-1233zd/ trans-l,2-OCE compositions of the present invention have a boiling point of about 37.0°C ± 1 °C at ambient pressure.

Traws-HFC)-1233zd/methylal Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and methylal. More preferably, these binary azeotrope-like compositions consist essentially of about 95 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 5 wt. % methylal, more preferably from about 97 to about 99.9 wt. % trans- HFO-1233zd and about 0.1 to about 3 wt. % methylal, and even more preferably from about 98.5 weight percent to about 99.9 wt% tr «5-HFO-1233zd and from about 0.1 to about 1.5 wt. % methylal.

Preferably, the tr<ms-HFO-1233zd / methylal compositions of the present invention have a normal boiling point of about 17.3°C ± 1 °C at ambient pressure. rraws-HFO-1233zd/methyl acetate Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-W 0-\233zd and methyl acetate. More preferably, these binary azeotrope- like compositions consist essentially of about 90 to about 99.9 wt. % tr<ms-HFO-1233zd and from about 0.1 to about 10 wt. % methyl acetate, more preferably from about 95 to about 99.9 wt. % trans-W 0-\233zd and about 0.1 to about 5 wt. % methyl acetate, and even more preferably from about 98.5 weight percent to about 99.9 wt% tr<ms-HFO-1233zd and from about 0.1 to about 1.5 wt. % methyl acetate.

Preferably, the tr<ms-HFO-1233zd / methyl acetate compositions of the present invention have a normal boiling point of about 17.5°C ± 1 °C at ambient pressure.

7>flws-HFO-1233zd/water Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and water. More preferably, these binary azeotrope-like compositions consist essentially of about 70 to about 99.95 wt. % trans- FO-\233zd and from about 0.05 to about 30 wt. % water, more preferably from about 86 to about 99.95 wt. % tr<ms-HFO-1233zd and about 0.05 to about 14 wt. % water, and most preferably about 90 to about 99.95 wt. % tr<ms-HFO-1233zd and about 0.05 to about 10 wt. % water.

Preferably, the tr<ms-HFO-1233zd / water compositions of the present invention have a boiling point of about 17.4°C ± 1 °C at ambient pressure. rraws-HFO-1233zd/Nitromethane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and nitromethane. More preferably, these binary azeotrope-like compositions consist essentially of about 98 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 2 wt. % nitromethane, more preferably from about 99 to about 99.99 wt. % tr<ms-HFO-1233zd and about 0.01 to about 1 wt. % nitromethane, and even more preferably from about 99.9 to about 99.99 wt. % tr<ms-HFO-1233zd and from about 0.01 to about 0.1 wt. % nitromethane. Preferably, the tra«s-HFO-1233zd/nitromethane compositions of the present invention have a normal boiling point of about 17.4 °C ± 1 °C at ambient pressure.

Cw-HFO-1233zd/Nitromethane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and nitromethane. More preferably, these binary azeotrope-like compositions consist essentially of about 95 to about 99.9 wt. % cz ^' s-HFO-1233zd and from about 0.1 to about 5 wt. % nitromethane, more preferably from about 97 to about 99.9 wt. % cz ^' s-HFO-1233zd and about 0.1 to about 3 wt. % nitromethane, and even more preferably from about 99 to about 99.9 wt. % cw-HFO-1233zd and from about 0.1 to about 1 wt. %

nitromethane.

Preferably, the czs-HFO-1233zd/nitromethane compositions of the present invention have a normal boiling point of about 39 °C ± 1 °C at ambient pressure. rraws-HFO-1233zd//raws-l,2-DCE/Methanol Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd, methanol, and trans- 1,2-DCE. More preferably, these ternary azeotrope-like compositions consist essentially of about 80 to about 99.9 wt. % trans- FO- 1233zd, from about 0.05 to about 15 wt. % methanol, and from about 0.05 to about 10 wt. % trans- 1,2-DCE, even more preferably from about 90 to about 99.9 wt. % trans-EFO-\233zd, from about 0.05 to about 9 wt. % methanol, and about 0.05 to about 5 wt. % trans -\, 2-OCE, and most preferably from about 95 to about 99.9 wt. % trans-HFO-\233zd, from about 0.05 to about 5 wt. % methanol, and from about 0.05 to about 3 wt. % trans- 1,2-DCE. Preferably, the tr «s-HFO-1233zd/methanol/tr<ms-l,2-DCE compositions of the present invention have a boiling point of from about 16.6 °C ± 1 °C at ambient pressure rraws-HFO-1233zd/Methanol/n-Pentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd, methanol, and n-pentane. More preferably, these ternary azeotrope-like compositions consist essentially of about 55 to about 99.90 wt. % trans- FO- 1233zd, from about 0.05 to about 10 wt. % methanol, and from about 0.05 to about 35 wt. % n-pentane, even more preferably from about 79 to about 98 wt. % tr<ms-HFO-1233zd, from about 0.1 to about 5 wt. % methanol, and about 1.9 to about 16 wt. % n-pentane, and most preferably from about 88 to about 96 wt. % tr<ms-HFO-1233zd, from about 0.5 to about 4 wt. % methanol, and from about 3.5 to about 8 wt. % n-pentane.

Preferably, the tr «s-HFO-1233zd/methanol/n-pentane compositions of the present invention have a boiling point of from about 17 °C to about 19 °C, more

preferably about 17 °C to about 18 °C, even more preferably about 17.1 °C to about 17.6 °C, and most preferably about 17.4 °C ± 1 °C, all measured at a pressure of about 14 psia.

7 ^, ra«s-HFO-1233zd/n-Pentane//m«s-l,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd, n-pentane, and trans-\,2 DCE. More preferably, these ternary azeotrope-like compositions consist essentially of about 85 to about 99.0 wt. % trans- FO- 1233zd, from about 2.0 to about 4.5 wt. % n-pentane, and from about 0.01 to about 13 wt. % trans-\,2-DCE; and even more preferably from about 88 to about 99 wt. % tr<ms-HFO-1233zd, about 3.0 to about 4.5 wt. % n-pentane, and from about 0.01 to about 9.0 wt. % trans- 1,2-DCE; and most preferably from about 90 to about 96 wt. % from about 3.7 to about 4.0 wt. % n-pentane; and from about 0.01 to about 6.3 wt. % trans- 1,2-DCE.

Preferably, the tr «s-HFO-1233zd/n-pentane/tr<ms-l,2-DCE compositions of the present invention have a boiling point of about 19 °C ± 1 °C at ambient pressure.

Cw-HFO-1233zd/isohexane//raws-l,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, isohexane, and trans-\,2 DCE. More preferably, these ternary azeotrope-like compositions consist essentially of about 60 to about 80 wt. % cz ^' s-HFO-1233zd, from greater than 0 to about 20 wt. % isohexane, and from about 20 to about 35 wt. % trans- 1,2-DCE; and even more preferably from about 62 to about 72 wt. % cz ^' s-HFO-1233zd, about 0.01 to about 13 wt. % isohexane, and from about 25 to about 35 wt. % trans- 1,2-DCE; and most preferably from about 64.1 to about 70 wt. % cz ^' s-HFO-1233zd, from about 0.01 to about 8.5 wt. % isohexane; and from about 27.5 to about 30 wt. % trans- 1,2-DCE.

Preferably, the czs-HFO-1233zd/isohexane/tr<ms-l,2-DCE compositions of the present invention have a boiling point of about 36.3 °C ± 1 °C at a pressure of about 767 mmHg.

Cw-HFO-1233zd/ethanol//raws-l,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, ethanol, and trans-\,2 DCE. More preferably, these ternary azeotrope-like compositions consist essentially of about 60 to about 80 wt. % cz ^' s-HFO-1233zd, from greater than 0 to about 20 wt. % ethanol, and from about 20 to about 35 wt. % trans-\,2- DCE; and even more preferably from about 62 to about 72 wt. % cz ^' s-HFO-1233zd, about 0.01 to about 13 wt. % ethanol, and from about 25 to about 35 wt. % trans- 1,2-DCE; and most preferably from about 65 to about 70 wt. % cz ^' s-HFO-1233zd, from about 0.01 to about 7.1 wt. % ethanol; and from about 27.9 to about 30 wt. % trans- 1,2-DCE.

Preferably, the czs-HFO-1233zd/ethanol/tr<ms-l,2-DCE compositions of the present invention have a boiling point of about 35.8 °C ± 1 °C at a pressure of about 767 mmHg.

Cw-HFO-1233zd/methanol/isohexane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, methanol, and isohexane. More preferably, these ternary azeotrope-like compositions consist essentially of about 40.0 to about 99.9 wt. % cis-HFO- 1233zd, from about 0.10 to about 10.0 wt. % methanol, and from greater than 0.0 to about 50.0 wt. % isohexane; and even more preferably from about 70.0 to about 88.0 wt. % cis- HFO-1233zd, about 2.0 to about 5.0 wt. % methanol, and from about 10.0 to about 25.0 wt. % isohexane; and most preferably from about 78.0 to about 88.0 wt. % cz ^' s-HFO-1233zd, from about 2.0 to about 3.0 wt. % methanol; and from about 10.0 to about 19.0 wt. % isohexane.

Preferably, the czs-HFO-1233zd/methanol/isohexane compositions of the present invention have a boiling point of about 34.0 °C ± 0.8 °C at a pressure of about 754.0 mm Hg.

Cw-HFO-1233zd/methanol//raws-l,2-DCE Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, methanol, and trans-\,2 DCE. More preferably, these ternary azeotrope-like compositions consist essentially of about 50.0 to about 99.9 wt. % cis-HFO- 1233zd, from 0.1 to about 10.0 wt. % methanol, and from greater than 0.0 to about 40.0 wt. % trans- 1,2-DCE; and even more preferably from about 60.0 to about 88.0 wt. % cis-EFO- 1233zd, about 2.0 to about 10.0 wt. % methanol, and from about 10.0 to about 30.0 wt. % trans- 1,2-DCE; and most preferably from about 70.0 to about 85.0 wt. % cz ^' s-HFO-1233zd, from about 2.0 to about 3.0 wt. % methanol; and from about 13.0 to about 27.0 wt. % trans- 1,2-DCE.

Preferably, the czs-HFO-1233zd/methanol/tr<ms-l,2-DCE compositions of the present invention have a boiling point of about 33.87 °C ± 0.9 °C at a pressure of about 750.50 mm Hg. s-HFO-1233zd/petroleum ether Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd and petroleum ether. More preferably, this binary azeotrope-like composition consists essentially of about 50.0 to about 99.9 wt. % cz ^' s-HFO-1233zd, and from greater than 0.1 to about 50.0 wt. % petroleum ether; and even more preferably from about

60.0 to about 85.0 wt. % cz ^' s-HFO-1233zd, and from about 15.0 to about 40.0 wt. % petroleum ether; and most preferably from about 67.5 to about 80.0 wt. % cz ^' s-HFO-1233zd, and from about 20.0 to about 32.5 wt. % petroleum ether.

Preferably, the cz ^' s-HFO-1233zd/petroleum ether compositions of the present invention have a boiling point of about 32.24 °C ± 0.8 °C at a pressure of about 756.5 mmHg.

Cw-HFO-1233zd/methanol/cyclopentane Azeotrope-Like Compositions: In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, methanol, and cyclopentane. More preferably, these ternary azeotrope-like compositions consist essentially of about 45.0 to about 99.9 wt. % cis-HFO- 1233zd, from 0.1 to about 20.0 wt. % methanol, and from greater than 0.0 to about 35.0 wt. % cyclopentane; and even more preferably from about 50.0 to about 85.0 wt. % cz ^' s-HFO-1233zd, about 0.5 to about 17.0 wt. % methanol, and from about 14.5 to about 33.0 wt. % cyclopentane; and most preferably from about 56.0 to about 76.5 wt. % cz ^' s-HFO-1233zd, from about 0.5 to about 16.0 wt. % methanol; and from about 23.0 to about 28.0 wt. % cyclopentane.

Preferably, the czs-HFO-1233zd/methanol/cyclopentane compositions of the present invention have a boiling point of about 31.54 °C ± 0.8 °C at a pressure of about 752.0 mm Hg.

Cw-HFO-1233zd/ethanol/cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, ethanol, and cyclopentane. More preferably, these ternary azeotrope-like compositions consist essentially of about 45.0 to about 99.9 wt. % cis-HFO- 1233zd, from 0.1 to about 20.0 wt. % ethanol, and from greater than 0.0 to about 35.0 wt. % cyclopentane; and even more preferably from about 50.0 to about 85.0 wt. % cz ^' s-HFO-1233zd, about 0.5 to about 15.0 wt. % ethanol, and from about 14.5 to about 35.0 wt. % cyclopentane; and most preferably from about 65.0 to about 80.0 wt. % cz ^' s-HFO-1233zd, from about 0.5 to about 10.0 wt. % ethanol; and from about 19.5 to about 25.0 wt. % cyclopentane.

Preferably, the czs-HFO-1233zd/ethanol/cyclopentane compositions of the present invention have a boiling point of about 34.12 °C ± 0.5 °C at a pressure of about 763.5 mm Hg. Cw-HFO-1233zd/isopropanol/cyclopentane Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz ^' s-HFO-1233zd, isopropanol, and cyclopentane. More preferably, these ternary azeotrope-like compositions consist essentially of about 50.0 to about 99.9 wt. % cis-HFO- 1233zd, from 0.1 to about 10.0 wt. % isopropanol, and from greater than 0.0 to about 40.0 wt. % cyclopentane; and even more preferably from about 50.0 to about 85.0 wt. % cis-HFO- 1233zd, about 0.5 to about 10.0 wt. % isopropanol, and from about 14.5 to about 40.0 wt. % cyclopentane; and most preferably from about 65.0 to about 80.0 wt. % cz ^' s-HFO-1233zd, from about 0.5 to about 7.0 wt. % isopropanol; and from about 19.5 to about 28.0 wt. %

cyclopentane.

Preferably, the czs-HFO-1233zd/isopropanol/cyclopentane compositions of the present invention have a boiling point of about 34.30 °C ± 0.5 °C at a pressure of about 748.2 mm Hg.

The azeotrope-like compositions of the present invention may further include a variety of optional additives including, but not limited to, lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants, and the like. Examples of suitable stabilizers include diene-based compounds, and/or phenol compounds, and/or epoxides selected from the group consisting of aromatic epoxides, alkyl epoxides, alkenyl epoxides, and combinations of two or more thereof. Preferably, these optional additives do not affect the basic azeotrope-like characteristic of the composition.

Blowing Agents: In another embodiment of the invention, provided are blowing agents comprising at least one azeotrope-like mixture described herein. Polymer foams are generally of two general classes: thermoplastic foams and thermoset foams.

Thermoplastic foams are produced generally via any method known in the art, including those described in Throne, Thermoplastic Foams, 1996, Sherwood Publishers, Hinkley, Ohio, or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2 ^nd Edition 2004, Hander Gardner Publications. Inc, Cincinnati, OH. For example, extruded thermoplastic foams can be prepared by an extrusion process whereby a solution of blowing agent in molten polymer, formed in an extruder under pressure, is forced through an orifice onto a moving belt at ambient temperature or pressure or optionally at reduced pressure to aid in foam expansion. The blowing agent vaporizes and causes the polymer to expand. The polymer simultaneously expands and cools under conditions that give it enough strength to maintain dimensional stability at the time corresponding to maximum expansion. Polymers used for the production of extruded thermoplastic foams include, but are not limited to, polystyrene, polyethylene (HDPE, LDPE, and LLDPE), polypropylene, polyethylene terephthalate, ethylene vinyl acetate, and mixtures thereof. A number of additives are optionally added to the molten polymer solution to optimize foam processing and properties including, but not limited to, nucleating agents (e.g., talc), flame retardants, colorants, processing aids (e.g., waxes), cross linking agents, permeability modifiers, and the like.

Additional processing steps such as irradiation to increase cross linking, lamination of a surface film to improve foam skin quality, trimming and planning to achieve foam dimension requirements, and other processes may also be included in the manufacturing process. In general, the blowing agent may include the azeotrope-like compositions of the present invention in widely ranging amounts. It is generally preferred, however, that the blowing agents comprise at least about 15 % by weight of the blowing agent. In certain preferred embodiments, the blowing agent comprises at least about 50 % by weight of the present compositions, and in certain embodiments the blowing agent consists essentially of the present azeotrope-like composition. In certain preferred embodiments, the blowing agent includes, in addition to the present azeotrope-like mixtures, one or more co-blowing agents, fillers, vapor pressure modifiers, flame suppressants, stabilizers, and like adjuvants.

In certain preferred embodiments, the blowing agent is characterized as a physical (i.e., volatile) blowing agent comprising the azeotrope-like mixture of the present invention. In general, the amount of blowing agent present in the blended mixture is dictated by the desired foam densities of the final foams products and by the pressure and solubility limits of the process. For example, the proportions of blowing agent in parts by weight can fall within the range of about 1 to about 45 parts, more preferably from about 4 to about 30 parts, of blowing agent per 100 parts by weight of polymer. The blowing agent may comprise additional components mixed with the azeotrope-like composition, including chlorofluorocarbons such as trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12),

hydrochlorofluorocarbons such as 1,1-dichloro-l-fluoroethane (HCFC-141b), l-chloro-1,1- difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), hydro fluorocarbons such as 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difiuoroethane (HFC-152a), 1,1,1,3,3- pentafluoropropane (HFC-245fa), and 1,1,1,3,3-pentafluorobutane (HFC-365mfc),

hydrocarbons such as propane, butane, isobutane, cyclopentane, carbon dioxide, chlorinated hydrocarbons alcohols, ethers, ketones and mixtures thereof. In certain embodiments, the blowing agent is characterized as a chemical blowing agent. Chemical blowing agents are materials that, when exposed to temperature and pressure conditions in the extruder, decompose to liberate a gas, generally carbon dioxide, carbon monoxide, nitrogen, hydrogen, ammonia, nitrous oxide, of mixtures thereof. The amount of chemical blowing agent present is dependent on the desired final foam density. The

proportions in parts by weight of the total chemical blowing agent blend can fall within the range of from less than 1 to about 15 parts, preferably from about 1 to about 10 parts, of blowing agent per 100 parts by weight of polymer.

In certain preferred embodiments, dispersing agents, cell stabilizers, surfactants and other additives may also be incorporated into the blowing agent compositions of the present invention. Surfactants are optional, but preferably are added to serve as cell stabilizers. Some representative materials are sold under the names of DC-193, B-8404, and L-5340 which are, generally, polysiloxane polyoxyalkylene block co-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458, each of which are incorporated herein by reference. Other optional additives for the blowing agent mixture include flame retardants or suppressants such as tri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate, tri(2,3-dibromopropyl)- phosphate, tri(l,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. With respect to thermoset foams, in general any thermoset polymer can be used, including but not limited to polyurethane, polyisocyanurate, phenolic, epoxy, and combinations thereof. In general these foams are produced by bringing together chemically reactive components in the presence of one or more blowing agents, including the azeotrope-like composition of this invention and optionally other additives, including but not limited to cell stabilizers, solubility enhancers, catalysts, flame retardants, auxiliary blowing agents, inert fillers, dyes, and the like. With respect to the preparation of polyurethane or polyisocyanurate foams using the azeotrope like compositions described in the invention, any of the methods well known in the art can be employed, see Saunders and Frisch, Volumes I and II Polyur ethanes Chemistry and

Technology (1962) John Wiley and Sons, New York, N.Y. In general, polyurethane or polyisocyanurate foams are prepared by combining an isocyanate, a polyol or mixture of polyols, a blowing agent or mixture of blowing agents, and other materials such as catalysts, surfactants, and optionally, flame retardants, colorants, or other additives.

It is convenient in many applications to provide the components for polyurethane or polyisocyanurate foams in preblended formulations. Most typically, the foam formulation is preblended into two components. The isocyanate and optionally certain surfactants and blowing agents comprise the first component, commonly referred to as the "A" component. The polyol or polyol mixture, surfactant, catalysts, blowing agents, flame retardant, and other isocyanate reactive components comprise the second component, commonly referred to as the "B" component. Accordingly, polyurethane or polyisocyanurate foams are readily prepared by bringing together the A and B side components either by hand mix for small preparations and, preferably, machine mix techniques to form blocks, slabs, laminates, pour-in-place panels and other items, spray applied foams, froths, and the like. Optionally, other ingredients such as fire retardants, colorants, auxiliary blowing agents, water, and even other polyols can be added as a third stream to the mix head or reaction site. Most conveniently, however, they are all incorporated into one B Component as described above. Any organic polyisocyanate can be employed in polyurethane or polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanates. Preferred as a class are the aromatic polyisocyanates. Typical aliphatic polyisocyanates are alkylene diisocyanates such as tri, tetra, and hexamethylene diisocyanate, isophorene diisocyanate, 4, 4'- methylenebis(cyclohexyl isocyanate), and the like; typical aromatic polyisocyanates include m-, and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6- toluenediisocyanate, dianisidine diisocyanate, bitoylene isocyanate, naphthylene 1 ,4- diisocyanate, bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane, and the like.

Preferred polyisocyanates are the polymethylene polyphenyl isocyanates, particularly the mixtures containing from about 30 to about 85 percent by weight of methylenebis(phenyl isocyanate) with the remainder of the mixture comprising the polymethylene polyphenyl polyisocyanates of functionality higher than 2.

Typical polyols used in the manufacture of polyurethane foams include, but are not limited to, aromatic amino-based polyether polyols such as those based on mixtures of 2,4- and 2,6- toluenediamine condensed with ethylene oxide and/or propylene oxide. These polyols find utility in pour-in-place molded foams. Another example is aromatic alkylamino-based polyether polyols such as those based on ethoxylated and/or propoxylated aminoethylated nonylphenol derivatives. These polyols generally find utility in spray applied polyurethane foams. Another example is sucrose-based polyols such as those based on sucrose derivatives and/or mixtures of sucrose and glycerine derivatives condensed with ethylene oxide and/or propylene oxide. Examples of polyols used in polyurethane modified polyisocyanurate foams include, but are not limited to, aromatic polyester polyols such as those based on complex mixtures of phthalate-type or terephthalate-type esters formed from polyols such as ethylene glycol, diethylene glycol, or propylene glycol. These polyols are used in rigid laminated boardstock, can be blended with other types of polyols such as sucrose based polyols, and used in other polyurethane foam applications such as described above.

Catalysts used in the manufacture of polyurethane foams are typically tertiary amines including, but not limited to, N-alkylmorpholines, N-alkylalkanolamines, N,N- dialkylcyclohexylamines, and alkylamines where the alkyl groups are methyl, ethyl, propyl, butyl, and the like and isomeric forms thereof; and hetrocyclic amines. Typical, but not limiting examples are triethylenediamine, tetramethylethylenediamine, bis(2- dimethylaminoethyl)ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, Ν,Ν-dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, Ν,Ν-dimethylethanolamine, tetramethylpropanediamine,

methyltriethylenediamine, and the like, and mixtures thereof.

Optionally, non-amine polyurethane catalysts are used. Typical of such catalysts are organometallic compounds of bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, and the like. Included as illustrative are bismuth nitrate, lead 2- ethylhexoate, lead benzoate, ferric chloride, antimony trichloride and antimony glycolate. A preferred organo-tin class includes the stannous salts of carboxylic acids such as stannous octoate, stannous 2-ethylhexoate, stannous laurate, and the like, as well as dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin diacetate, and the like.

In the preparation of polyisocyanurate foams, trimerization catalysts are used for the purpose of converting the blends in conjunction with excess A component to polyisocyanurate- polyurethane foams. The trimerization catalysts employed can be any catalyst known to one skilled in the art, including, but not limited to, glycine salts and tertiary amine trimerization catalysts and alkali metal carboxylic acid salts and mixtures of the various types of catalysts. Preferred species within the classes are potassium acetate, potassium octoate, and N-(2- hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Dispersing agents, cell stabilizers, and surfactants can be incorporated into the present blends. Surfactants, which are, generally, polysiloxane polyoxyalkylene block co-polymers, such as those disclosed in U.S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458, which are incorporated herein by reference.

Other optional additives for the blends can include flame retardants such as tris(2- chloroethyl)phosphate, tris(2-chloropropyl)phosphate, tris(2,3-dibromopropyl)phosphate, tris(l,3-dichloropropyl)phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like. Other optional ingredients can include from 0 to about 3 percent water, which chemically reacts with the isocyanate to produce carbon dioxide. This carbon dioxide acts as an auxiliary blowing agent.

Also included in the mixture are blowing agents or blowing agent blends as disclosed in this invention. Generally speaking, the amount of blowing agent present in the blended mixture is dictated by the desired foam densities of the final polyurethane or polyisocyanurate foams product. The proportions in parts by weight of the total blowing agent blend can fall within the range of from 1 to about 45 parts of blowing agent per 100 parts of polyol , preferably from about 4 to about 30 parts.

The polyurethane foams produced can vary in density from about 0.5 pound per cubic foot to about 40 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. The density obtained is a function of how much of the blowing agent or blowing agent mixture disclosed in this invention is present in the A and/or B components, or alternatively added at the time the foam is prepared.

Foams and Foamable Compositions:

Certain embodiments of the present invention involve a foam comprising a

polyurethane-, polyisocyanurate-, or phenolic-based cell wall and a cell gas disposed within at least a portion of the cells, wherein the cell gas comprises the azeotrope-like mixture described herein. In certain embodiments, the foams are extruded thermoplastic foams. Preferred foams have a density ranging from about 0.5 pounds per cubic foot to about 60 pounds per cubic foot, preferably from about 1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to 6.0 pounds per cubic foot. The foam density is a function of how much of the blowing agent or blowing agent mixture (i.e., the azeotrope-like mixture and any auxiliary blowing agent, such as carbon dioxide, chemical blowing agent or other co-blowing agent) is present in the molten polymer. These foams are generally rigid but can be made in various grades of softness to suit the end use requirements. The foams can have a closed cell structure, an open cell structure or a mixture of open and closed cells, with closed cell structures being preferred. These foams are used in a variety of well known applications, including but not limited to thermal insulation, flotation, packaging, void filling, crafts and decorative, and shock absorption.

In other embodiments, the invention provides foamable compositions. The foamable compositions of the present invention generally include one or more components

capable of forming foam, such as polyurethane, polyisocyanurate, and phenolic-based compositions, and a blowing agent comprising at least one azeotrope-like mixture described herein. In certain embodiments, the foamable composition comprises thermoplastic materials, particularly thermoplastic polymers and/or resins. Examples of thermoplastic foam

components include polyolefms, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethyleneterepthalate (PET), and foams formed therefrom, preferably low-density foams. In certain embodiments, the thermoplastic foamable composition is an extrudable composition.

In certain embodiments, provided is a method for producing such foams. It will be appreciated by those skilled in the art, especially in view of the disclosure contained herein, that the order and manner in which the blowing agent is formed and/or added to the foamable composition does not generally affect the operability of the present invention. For example, in the case of extrudable foams, it is possible to mix in advance the various components of the blowing agent. In certain embodiments, the components of the foamable composition are not mixed in advance of introduction to the extrusion equipment or are not added to the same location in the extrusion equipment. Thus, in certain embodiments it may be desired to introduce one or more components of the blowing agent at first location in the extruder, which is upstream of the place of addition of one or more other components of the blowing agent, with the expectation that the components will come together in the extruder and/or operate more effectively in this manner. In certain other embodiments, two or more components of the blowing agent are combined in advance and introduced together into the foamable composition, either directly or as part of premix which is then further added to other parts of the foamable composition.

Sprayable Compositions:

In a preferred embodiment, the azeotrope-like compositions of this invention may be used as solvents in sprayable compositions, either alone or in combination with other known propellants. The solvent composition comprises, more preferably consists essentially of, and, even more preferably, consists of the azeotrope-like compositions of the invention. In certain embodiments, the sprayable composition is an aerosol.

In certain preferred embodiments, provided is a sprayable composition comprising a solvent as described above, an active ingredient, and optionally, other components such as inert ingredients, solvents, and the like.

Suitable active materials to be sprayed include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides as well as medicinal materials, such as anti-asthma medications. The term medicinal materials is used herein in its broadest sense to include any and all materials which are, or at least are believe to be, effective in connection with therapeutic, diagnostic, pain relief, and similar treatments, and as such would include for example drugs and biologically active substances.

Solvents and Cleaning Compositions: In another embodiment of the invention, the azeotrope-like compositions described herein can be used as a solvent in cleaning various soils such as mineral oil, rosin based fluxes, solder fluxes, silicon oils, lubricants, etc., from various substrates by wiping, vapor degreasing, dry cleaning or other means. In certain preferred embodiments, the cleaning composition is an aerosol.

EXAMPLES

The invention is further illustrated in the following example which is intended to be illustrative, but not limiting in any manner. For the relevant examples, an ebulliometer of the general type described by Swietolslowski in his book "Ebulliometric Measurements"

(Reinhold, 1945) was used.

Example 1:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer or a thermistor was used. About 10 cc of trans- HFO-1233zd was charged to the ebulliometer and then methanol was added in small, measured increments. Temperature depression was observed when methanol was added, indicating a binary minimum boiling azeotrope had been formed. From greater than 0 to about 51 weight percent methanol, the boiling point of the composition changes less than about 1.3 °C. The boiling points of the binary mixtures shown in Table 1 changed by less than about 0.02 °C.

Thus the compositions exhibited azeotrope and/or azeotrope-like properties over these ranges. To conform result two such ebuUiometers were set up side by side of which one contained pure solvent and the other one was set up with trans-HFO- 1233zd and 2 ⁿ component was added as mentioned before. The difference of temperatures in the two was also measured.

TABLE 1 frfl«s-HFO-1233zd/Methanol compositions at ambient pressure

Wt. % trans- wt%

Temp (°C ) HFO-1233zd Methanol

17.15 (°C) 98.78 wt. % 1.22 wt. %

17.14 (°C) 98.58 wt. % 1.42 wt. %

17.14 (°C) 98.38 wt. % 1.62 wt. %

17.14 (°C) 98.18 wt. % 1.82 wt. %

17.14 (°C) 97.98 wt. % 2.02 wt. %

17.14 (°C) 97.78 wt. % 2.22 wt. %

17.15 (°C) 97.59 wt. % 2.41 wt. %

Example 2:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer or a thermistor was used. About 35 g trans- FO- 1233zd is charged to the ebulliometer and then n-pentane was added in small, measured increments. Temperature depression was observed when n-pentane was added to trans- FO- 1233zd, indicating a binary minimum boiling azeotrope had been formed. From greater than 0 to about 30 weight percent n-pentane, the boiling point of the composition changes less than about 0.8 °C. The boiling points of the binary mixtures shown in Table 2 changed by less than about 0.02 °C. Thus the compositions exhibited azeotrope and/or azeotrope-like properties over these ranges.

TABLE 2 frfl«s-HFO-1233zd/n-Pentane compositions at ambient pressure Wt. Votrans- Wt %

Temp (°C) HFO-1233zd n-pentane 17.43 (°C) 97.76 wt. % 2.24 wt. %

17.42 (°C) 97.60 wt. % 2.40 wt. %

17.42 (°C) 97.45 wt. % 2.55 wt. %

17.42 (°C) 97.29 wt. % 2.71 wt. %

17.42 (°C) 97.14 wt. % 2.86 wt. %

17.42 (°C) 96.98 wt. % 3.02 wt. %

17.42 (°C) 96.83 wt. % 3.17 wt. %

17.42 (°C) 96.67 wt. % 3.33 wt. %

17.42 (°C) 96.52 wt. % 3.48 wt. %

17.42 (°C) 96.37 wt. % 3.63 wt. %

17.42 (°C) 96.22 wt. % 3.78 wt. %

17.42 (°C) 96.07 wt. % 3.93 wt. %

17.43 (°C) 95.92 wt. % 4.08 wt. %

Example 3:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer or a thermistor was used. About 17 g trans- FO- 1233zd is charged to the ebulliometer and then isopentane was added in small, measured increments. Temperature depression was observed when isopentane was added to trans-WO- 1233zd, indicating a binary minimum boiling azeotrope had been formed. From greater than about 0 to about 30 weight percent isopentane, the boiling point of the composition changed by about 0.8° C or less. The boiling points of the binary mixtures shown in Table 3 changed by less than about 0.2 °C. Thus the compositions exhibited azeotrope and/or azeotrope-like properties over these ranges.

TABLE 3 frfl«s-HFO-1233/isopentane compositions at ambient pressure

Wt % trans- Wt%

Temp(°C ) HFO-1233zd isopentane

16.86 (°C) 92.39 wt. % 7.61 wt. %

16.78 (°C) 90.52 wt. % 9.48 wt. %

16.73 (°C) 88.73 wt. % 11.27 wt. % 16.70 (°C) 87.01 wt. % 12.99 wt. %

16.70 (°C) 85.35 wt. % 14.65 wt. %

16.69 (°C) 83.75 wt. % 16.25 wt. %

16.70 (°C) 82.21 wt. % 17.79 wt. %

16.72 (°C) 80.73 wt. % 19.27 wt. %

16.76 (°C) 79.13 wt. % 20.87 wt. %

16.85 (°C) 77.58 wt. % 22.42 wt. %

Example 4:

An ebuUiometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer or a thermistor was used. About 17 g neopentane is charged to the ebuUiometer and then trans-HFO-\233zd was added in small, measured increments. Temperature depression was observed when trcms-EFO-\233zd was added to neopentane indicating a binary minimum boiling azeotrope had been formed. As shown in Table 4, compositions comprising from about 19 to about 49 weight percent trans-HFO- 1233zd had a change in boiling point of 0.1 °C or less. Thus the compositions exhibited azeotrope and/or azeotrope-like properties over at least this range.

TABLE 4

#¾ms-HFO-1233zd/neopentane compositions at ambient pressure

Wt % trans- Wt%

Temp(°C ) HFO-1233zd neopentane 8.54 (°C) 0.00 wt. % 100.00 wt. % 8.47 (°C) 1.36 wt. % 98.64 wt. % 8.42 (°C) 2.69 wt. % 97.31 wt. % 8.30 (°C) 5.23 wt. % 94.77 wt. % 8.21 (°C) 7.65 wt. % 92.35 wt. % 8.12 (°C) 9.94 wt. % 90.06 wt. % 7.95 (°C) 14.21 wt. % 85.79 wt. %

7.87 (°C) 19.00 wt. % 81.00 wt. % 7.78 (°C) 23.29 wt. % 76.71 wt. % 7.72 (°C) 29.28 wt. % 70.72 wt. % 7.72 (°C) 34.40 wt. % 65.60 wt. % 7.75 (°C) 38.83 wt. % 61.17 wt. % 7.81 (°C) 42.70 wt. % 57.30 wt. % 7.85 (°C) 46.11 wt. % 53.89 wt. %

7.88 (°C) 49.14 wt. % 50.86 wt. %

Example 5:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer or a thermistor was used. About 18 g trans- FO- 1233 is charged to the ebulliometer and then trans- 1,2-DCE was added in small, measured increments. Temperature depression was observed when traps'- 1,2-DCE was added to trans- HFO-1233, indicating a binary minimum boiling azeotrope was formed. From greater than about 0.01 to about 53 weight percent trans- 1,2-DCE, the boiling point of the composition changed by about 0.7 °C or less. The boiling points of the binary mixtures shown in Table 4 changed by less than about 0.3 °C. Thus the compositions exhibited azeotrope and/or azeotrope-like properties over these ranges.

TABLE 5 ft¾ms-HFO-1233zd/ ft¾ms-l.,2-DCE compositions at ambient pressure

Wt.% trans- Wt.%

T(°C) HFO-1233zd tr- 1,2-DCE

17.74 (°C) 100.00 wt. % 0.00 wt. %

17.74 (°C) 99.68 wt. % 0.32 wt. %

17.73 (°C) 99.35 wt. % 0.65 wt. %

17.76 (°C) 99.03 wt. % 0.97 wt. %

17.79 (°C) 98.72 wt. % 1.28 wt. % 17.82 (°C) 98.40 wt. % 1.60 wt. %

17.85 (°C) 98.08 wt. % 1.92 wt. %

17.88 (°C) 97.77 wt. % 2.23 wt. %

17.92 (°C) 97.46 wt. % 2.54 wt. %

17.96 (°C) 97.15 wt. % 2.85 wt. %

Examples 6 - 23:

The general procedure described in examples 1 - 5 above was repeated for examples 6 - 23. Azeotrope-like behavior was observed over a given range of component concentrations where the boiling point changed by < 1 °C. The results are summarized below:

Azeotrope-like mixture Relative Concentration Boiling Data

1233zd : Other Point (°C) Table Component(s) (wt. %)

@ ambient pressure

tr<ms-HFO-1233zd + n-hexane 95-99.99/0.01-5 17.4 ± 1 16 cz ^' s-HFO-1233zd + methanol 78-99.9/0.1-22 35.2 ± 1 17 cz ^' s-HFO-1233zd + ethanol 65-99.9/0.1-35 37.4 ± 1 18 cz ^' s-HFO-1233zd + isopropanol 85-99.99/0.01-15 38.1 ± 1 19 cz ^' s-HFO-1233zd + cyclopentane 42-99/ 1-58 34.7 ± 1 20 cw-HFO-1233zd + trcms-\,2-OCE 42-99.9/0.1-58 37 ± 1 21 tr<ms-HFO-1233zd + methanol + n- 55-99.9/0.05-10/0.05-35 17.4 ± 1 22 pentane

tr<ms-HFO-1233zd + trans-l ,2-OCE + 80-09/0.05-15 /0.05-10 16.6 ± 1 23 methanol

TABLE 6 ft¾ms-HFO-1233zd / isohexane compositions at ambient pressure

isohexane (wt. %) frans-1233zd (wt. %) Boiling Point (°C)

1.0 99.0 17.7

1.2 98.8 17.7

1.3 98.7 17.7

1.5 98.5 17.8

1.7 98.3 17.8

1.8 98.2 17.8

2.0 98.0 17.8

2.2 97.8 17.9

2.3 97.7 17.9

2.5 97.5 17.9

2.6 97.4 18.0

2.8 97.2 18.0

3.0 97.0 18.0

3.1 96.9 18.1

3.3 96.7 18.1

3.4 96.6 18.1

3.6 96.4 18.2

3.8 96.2 18.2

3.9 96.1 18.2

4.1 95.9 18.2

4.2 95.8 18.3

4.4 95.6 18.3

4.5 95.5 18.3

4.7 95.3 18.4

4.9 95.1 18.4

5.0 95.0 18.4

5.2 94.8 18.4

TABLE 7

#¾ms-HFO-1233zd / ethanol compositions at ambient pressure

EtOH (wt. %) trans-l233zd (wt. %) Boiling Point (°C) EtOH iwt. %) trans-l233zd (wt. %) Boiling Point (°C)

0.0 100.0 18.1

0.2 99.8 18.1

0.4 99.6 18.1

0.6 99.4 18.1

0.8 99.2 18.1

1.0 99.0 18.1

1.2 98.8 18.1

1.4 98.6 18.1

1.6 98.4 18.1

1.8 98.2 18.2

2.0 98.0 18.2

2.2 97.8 18.2

2.4 97.6 18.1

2.6 97.4 18.1

2.8 97.2 18.2

3.0 97.0 18.2

3.2 96.8 18.2

3.4 96.6 18.2

3.6 96.4 18.2

3.8 96.2 18.2

4.0 96.0 18.2

4.1 95.9 18.2

4.3 95.7 18.2

4.5 95.5 18.2

4.7 95.3 18.2

4.9 95.1 18.2

5.1 94.9 18.2

TABLE 8 trans-W O-1233zd / isopropanol compositions at ambient pressure IPA (wt. %) trans-l233zd (wt. %) Boiling Point (°C)

0.0 100.0 17.9

0.4 99.6 17.9

0.8 99.2 17.9

1.2 98.8 17.9

1.6 98.4 17.9

2.0 98.0 17.9

2.4 97.6 17.9

2.8 97.2 18.0

3.2 96.8 18.0

3.5 96.5 18.1

3.9 96.1 18.1

4.3 95.7 18.1

4.7 95.3 18.2

5.0 95.0 18.2

5.4 94.6 18.2

5.8 94.2 18.3

6.1 93.9 18.3

6.5 93.5 18.3

6.9 93.1 18.3

7.2 92.8 18.4

7.6 92.4 18.4

7.9 92.1 18.4

8.3 91.7 18.4

8.6 91.4 18.4

8.9 91.1 18.5

9.3 90.7 18.5

9.6 90.4 18.5

TABLE 9

ft¾ms-HFO-1233zd / 1-chloropropane compositions at ambient pressure -chloropropane (wt. %) trans-l233zd (wt. %) Boiling Point (°C) 0.0 100.0 18.0

0.2 99.8 18.0

0.5 99.5 18.0

0.7 99.3 18.0

0.9 99.1 18.0

1.1 98.9 18.1

1.4 98.6 18.1

1.6 98.4 18.2

1.8 98.2 18.2

2.0 98.0 18.3

2.3 97.7 18.3

2.5 97.5 18.4

2.7 97.3 18.5

2.9 97.1 18.5

3.1 96.9 18.6

3.4 96.6 18.6

3.6 96.4 18.6

3.8 96.2 18.7

4.0 96.0 18.8

4.2 95.8 18.8

4.4 95.6 18.8

4.6 95.4 18.9

4.9 95.1 18.9

5.1 94.9 19.0

5.3 94.7 19.0

5.5 94.5 19.1

5.7 94.3 19.1

TABLE 10

ft¾ms-HFO-1233zd / 2-chloropropane compositions at ambient pressure -chloropropane (wt. %) trans-l233zd (wt. %) Boiling Point (°C)

0.2 99.8 17.8

0.4 99.6 17.8

0.7 99.3 17.8

0.9 99.1 17.8

1.1 98.9 17.9

1.3 98.7 17.9

1.5 98.5 17.9

1.8 98.2 17.9

2.0 98.0 18.0

2.2 97.8 18.0

2.4 97.6 18.0

2.6 97.4 18.0

2.8 97.2 18.0

3.0 97.0 18.0

3.3 96.7 18.0

3.5 96.5 18.1

3.7 96.3 18.1

3.9 96.1 18.1

4.1 95.9 18.1

4.3 95.7 18.1

4.5 95.5 18.1

4.7 95.3 18.2

4.9 95.1 18.2

5.1 94.9 18.2

5.3 94.7 18.2

5.5 94.5 18.2

5.7 94.3 18.2

5.9 94.1 18.2

6.1 93.9 18.2

6.3 93.7 18.3

TABLE 11 trans-Άΐ O-1233zd / cyclopentene compositions at ambient pressure

TABLE 12 ft¾ms-HFO-1233zd / cyclopentane compositions at ambient pressure cyclopentane (wt. %) trans-l233zd (wt. %) Boiling Point (°C)

0.0 100.0 17.6

0.2 99.8 17.6

0.4 99.6 17.7

0.6 99.4 17.7

1.0 99.0 17.8

1.3 98.7 17.8

1.7 98.3 17.8

2.1 97.9 17.8

2.5 97.5 17.9

2.8 97.2 17.9

3.2 96.8 18.0

3.6 96.4 18.1

3.9 96.1 18.1

4.3 95.7 18.2

4.6 95.4 18.2

5.0 95.0 18.3

5.3 94.7 18.3

5.7 94.3 18.4

TABLE 13

#¾ms-HFO-1233zd / methylal compositions at ambient pressure TABLE 14

#¾ms-HFO-1233zd / methyl acetate compositions at ambient pressure

TABLE 15

#¾ms-HFO-1233zd / HFC-365mfc compositions at ambient pressure HFC-365mfc (wt. %) trans-l233zd (wt. %) Boiling Point (°C)

1.6 98.4 17.7

1.9 98.1 17.7

2.2 97.8 17.7

2.5 97.5 17.8

2.9 97.1 17.8

3.2 96.8 17.8

3.5 96.5 17.8

3.8 96.2 17.9

4.1 95.9 17.9

4.4 95.6 17.9

4.7 95.3 17.9

5.0 95.0 18.0

5.3 94.7 18.0

5.5 94.5 18.0

5.8 94.2 18.0

6.1 93.9 18.1

6.4 93.6 18.1

6.7 93.3 18.1

7.0 93.0 18.1

7.3 92.7 18.1

7.5 92.5 18.2

7.8 92.2 18.2

8.1 91.9 18.2

8.4 91.6 18.2

TABLE 16 ft¾ms-HFO-1233zd / n-hexane compositions at ambient pressure

0.3 99.7 17.4

0.5 99.5 17.4

0.7 99.3 17.4

0.9 99.1 17.5

1.0 99.0 17.5

1.2 98.8 17.5

1.4 98.6 17.6

1.5 98.5 17.6

1.7 98.3 17.6

1.9 98.1 17.7

2.0 98.0 17.7

TABLE 17 c/s-HFO-1233zd / methanol compositions at ambient pressure

methanol (wt. %) cw-1233zd (wt. %) Boiling Point (°C)

12.0 88.0 35.6

13.0 87.0 35.6

13.9 86.1 35.7

14.8 85.2 35.7

15.7 84.3 35.8

16.6 83.4 35.8

17.5 82.5 35.9

18.3 81.7 35.9

19.1 80.9 36.0

19.9 80.1 36.0

20.7 79.3 36.1

21.5 78.5 36.1

22.2 77.8 36.2

23.0 77.0 36.2

23.7 76.3 36.3

24.4 75.6 36.3

25.1 74.9 36.3

25.8 74.2 36.4

26.5 73.5 36.4

27.2 72.8 36.5

27.8 72.2 36.5

TABLE 18 c/s-HFO-1233zd / ethanol compositions at ambient pressure

ethanol (wt. %) cw-1233zd (wt. %) Boiling Point (°C)

3.0 97.0 37.6

3.6 96.4 37.5

4.2 95.8 37.4

4.7 95.3 37.4

5.9 94.1 37.5

6.9 93.1 37.5

8.0 92.0 37.4

9.1 90.9 37.5

10.1 89.9 37.5

1 1.1 88.9 37.6

12.0 88.0 37.5

13.0 87.0 37.6

13.9 86.1 37.5

14.8 85.2 37.6

15.7 84.3 37.7

16.6 83.4 37.7

17.5 82.5 37.7

18.3 81.7 37.7

19.1 80.9 37.7

19.9 80.1 37.6

20.7 79.3 37.6

21.5 78.5 37.7

22.2 77.8 37.7

23.0 77.0 37.8

23.7 76.3 37.8

24.4 75.6 37.8

25.1 74.9 37.8

25.8 74.2 37.8

26.5 73.5 37.8

27.2 72.8 37.8

27.8 72.2 37.9

28.5 71.5 37.9 ethanol (wt. %) cw-1233zd iwt. %) Boiling Point (°C)

29.1 70.9 37.9

TABLE 19 cw-HFO-1233zd / isopropanol compositions at ambient pressure

IPA iwt. %) cw-1233zd iwt. %) Boiling Point (°C)

0.0 100.0 38.1

0.6 99.4 38.1

1.2 98.8 38.1

1.8 98.2 38.2

3.0 97.0 38.2

4.1 95.9 38.3

5.3 94.7 38.4

6.4 93.6 38.5

7.4 92.6 38.6

8.5 91.5 38.6

9.5 90.5 38.7

10.5 89.5 38.7

1 1.5 88.5 38.8

12.4 87.6 38.8

13.4 86.6 38.8

TABLE 20 c/s-HFO-1233zd / cyclopentane compositions at ambient pressure

cyclopentane (wt. %) cw-1233zd iwt. %) Boiling Point (°C)

6.6 93.4 35.6

7.6 92.4 35.5

8.6 91.4 35.3

9.6 90.4 35.3

10.6 89.4 35.2

1 1.5 88.5 35.1

12.4 87.6 35.0

13.3 86.7 35.0

14.2 85.8 35.0

15.1 84.9 35.0

15.9 84.1 34.9

16.7 83.3 34.9

17.6 82.4 34.9

18.3 81.7 34.9

19.1 80.9 34.9

19.9 80.1 34.9

20.6 79.4 34.9

21.4 78.6 34.9

22.1 77.9 34.8

22.8 77.2 34.8

23.5 76.5 34.7

24.2 75.8 34.7

24.9 75.1 34.7

25.5 74.5 34.7

26.2 73.8 34.7

26.8 73.2 34.8

27.5 72.5 34.8

28.1 71.9 34.8

28.7 71.3 34.8

29.3 70.7 34.8

29.9 70.1 34.8 TABLE 21

c/s-HFO-1233zd / trans-l,2-DCE compositions at ambient pressure trans-12-DCE (wt. %) cw-1233zd (wt. %) Boiling Point (°C)

49.7 50.3 37.4

50.2 49.8 37.4

50.7 49.3 37.5

51.2 48.8 37.5

51.7 48.3 37.5

52.1 47.9 37.5

52.6 47.4 37.6

53.0 47.0 37.6

53.4 46.6 37.6

53.9 46.1 37.6

54.3 45.7 37.6

54.7 45.3 37.6

55.1 44.9 37.6

TABLE 22 #¾ms-HFO-1233zd / methanol / n-pentane compositions at ambient pressure

n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)

2.0 96.0 2.0 17.0

2.2 95.9 2.0 17.0

2.3 95.7 2.0 17.0

2.5 95.6 2.0 17.0

2.6 95.4 1.9 17.0

2.8 95.3 1.9 17.0

2.9 95.1 1.9 17.0

3.1 95.0 1.9 17.0

3.2 94.8 1.9 17.0

3.4 94.7 1.9 17.0

3.5 94.6 1.9 17.0

3.6 94.4 1.9 17.0

3.8 94.3 1.9 17.0

3.9 94.2 1.9 17.0

4.1 94.0 1.9 17.0

4.2 93.9 1.9 17.0

4.3 93.7 1.9 17.0

4.5 93.6 1.9 17.0

4.6 93.5 1.9 17.0

4.7 93.4 1.9 17.0

4.9 93.2 1.9 17.0

5.0 93.1 1.9 17.0

5.1 93.0 1.9 17.0

5.3 92.8 1.9 17.0

5.4 92.7 1.9 17.0

5.5 92.6 1.9 17.0

5.7 92.4 1.9 17.0

5.8 92.3 1.9 17.0

5.9 92.2 1.9 17.0

6.0 92.1 1.9 17.0

6.2 91.9 1.9 17.1

6.3 91.8 1.9 17.1 n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)

6.4 91.7 1.9 17.1

6.5 91.6 1.9 17.1

6.7 91.5 1.9 17.1

6.8 91.3 1.9 17.1

6.9 91.2 1.9 17.1

7.0 91.1 1.9 17.1

7.2 91.0 1.9 17.1

7.3 90.9 1.9 17.1

7.4 90.8 1.9 17.1

7.5 90.6 1.8 17.1

7.6 90.5 1.8 17.1

7.8 90.4 1.8 17.1

7.9 90.3 1.8 17.1

8.0 90.2 1.8 17.1

8.1 90.1 1.8 17.1

8.2 90.0 1.8 17.1

8.3 89.8 1.8 17.1

8.4 89.7 1.8 17.1

8.6 89.6 1.8 17.1

8.7 89.5 1.8 17.1

8.8 89.4 1.8 17.1

8.9 89.3 1.8 17.1

9.0 89.2 1.8 17.1

9.1 89.1 1.8 17.1

9.2 89.0 1.8 17.1

9.3 88.9 1.8 17.1

9.4 88.8 1.8 17.1

9.5 88.6 1.8 17.1

9.6 88.5 1.8 17.1

9.8 88.4 1.8 17.2

9.9 88.3 1.8 17.2

10.1 88.1 1.8 17.2 n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)

10.3 87.9 1.8 17.2

10.5 87.7 1.8 17.2

10.7 87.5 1.8 17.2

10.9 87.3 1.8 17.2

1 1.1 87.1 1.8 17.2

1 1.3 86.9 1.8 17.2

1 1.5 86.7 1.8 17.2

1 1.7 86.6 1.8 17.2

1 1.9 86.4 1.8 17.2

12.1 86.2 1.8 17.3

12.2 86.0 1.8 17.3

12.4 85.8 1.8 17.3

12.6 85.6 1.7 17.3

12.8 85.5 1.7 17.3

13.0 85.3 1.7 17.3

13.2 85.1 1.7 17.3

13.3 84.9 1.7 17.3

13.5 84.8 1.7 17.4

13.7 84.6 1.7 17.4

13.9 84.4 1.7 17.4

14.0 84.3 1.7 17.4

14.2 84.1 1.7 17.4

14.4 83.9 1.7 17.4

14.5 83.8 1.7 17.4

14.7 83.6 1.7 17.4

14.9 83.4 1.7 17.5

15.0 83.3 1.7 17.5

15.2 83.1 1.7 17.5

15.3 83.0 1.7 17.5

15.5 82.8 1.7 17.5

15.6 82.7 1.7 17.5 TABLE 23

ft¾ms-HFO-1233zd / methanol / trans-l,2-DCE compositions at ambient pressure Example 24:

An ebuUiometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer was used. About 10 cc of trcms-EFO-\233zd was charged to the ebuUiometer and then nitromethane was added in small, measured increments. Temperature depression was observed when nitromethane was added, indicating a binary azeotrope-like composition had been formed.

Example 25:

An ebuUiometer consisting of vacuum jacketed tube with a condenser on top which was further equipped with a Quartz Thermometer was used. About 10 cc of tr «5-HFO-1233zd was charged to the ebuUiometer and then water was added in small, measured increments. Temperature depression was observed when water was added, indicating a binary minimum boiling azeotrope had been formed. From greater than 0 to about 30 weight percent water, the boiling point of the composition changes less than about 0.5 °C at ambient pressure.

17.5 95.8 5.3

17.4 93.2 7.9

17.4 90.7 10.3

17.4 87.5 13.6

17.4 84.4 16.5

17.4 81.6 19.3

17.4 79.0 21.9

17.4 76.5 24.4

17.4 74.2 26.7

17.4 72.0 28.8

17.4 69.9 30.9

Example 26:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which is further equipped with a Quartz Thermometer is used. An amount of cz ^' s-HFO-1233zd is charged to the ebulliometer and then nitromethane is added in small, measured increments. Temperature depression is observed when nitromethane is added to cz ^' s-HFO-1233, indicating a binary minimum boiling azeotrope is formed. The compositions exhibit azeotrope and/or azeotrope-like properties over a range of about 95 to 99.9 weight percent cz ^' s-1233zd and about 0.1 to about 5 weight percent nitromethane. More pronounced azeotrope and/or azeotrope-like properties occur over a range of about 97 to 99.9 weight percent cis-1233zd and about 0.1 to about 3 weight percent nitromethane; and even more pronounced over a range of about 99 to 99.9 weight percent cz ^' s-1233zd and about 0.1 to about 1 weight percent nitromethane.

Example 27:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which further equipped with a Quartz Thermometer is used. An amount of cz ^' s-HFO-1233zd is charged to the ebulliometer and then n-pentane is added in small, measured increments. Temperature depression is observed when n-pentane is added to cz ^' s-HFO-1233, indicating a binary minimum boiling azeotrope is formed. The compositions exhibit azeotrope and/or azeotrope-like properties over a range of about 20 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 80 weight percent n-pentane. More pronounced azeotrope and/or azeotrope-like properties occur over a range of about 50 to 99.5 weight percent cis-1233zd and about 0.5 to about 50 weight percent n-pentane; and even more pronounced over a range of about 60 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 40 weight percent n-pentane.

Example 28:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which is further equipped with a Quartz Thermometer is used. An amount of cz ^' s-HFO-1233zd is charged to the ebulliometer and then neopentane is added in small, measured increments. Temperature depression is observed when neopentane is added to cz ^' s-HFO-1233, indicating a binary minimum boiling azeotrope is formed. The compositions exhibit azeotrope and/or azeotrope-like properties over a range of about 5 to 50 weight percent cz ^' s-1233zd and about 50 to about 95 weight percent neopentane. More pronounced azeotrope and/or azeotrope-like properties occur over a range of about 20 to 45 weight percent cis-1233zd and about 55 to about 80 weight percent neopentane; and even more pronounced over a range of about 30 to 40 weight percent cz ^' s-1233zd and about 60 to about 70 weight percent neopentane.

Example 29:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which is further equipped with a Quartz Thermometer is used. An amount of cz ^' s-HFO-1233zd is charged to the ebulliometer and then n-hexane is added in small, measured increments.

Temperature depression is observed when n-hexane is added to cz ^' s-HFO-1233, indicating a binary minimum boiling azeotrope is formed. The compositions exhibit azeotrope and/or azeotrope-like properties over a range of about 80 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 20 weight percent n-hexane. More pronounced azeotrope and/or azeotrope-like properties occur over a range of about 90 to 99.5 weight percent cis-1233zd and about 0.5 to about 10 weight percent n-hexane; and even more pronounced over a range of about 95 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 5 weight percent n-hexane.

Example 30:

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which is further equipped with a Quartz Thermometer is used. An amount of cz ^' s-HFO-1233zd is charged to the ebulliometer and then isohexane is added in small, measured increments.

Temperature depression is observed when isohexane is added to cz ^' s-HFO-1233, indicating a binary minimum boiling azeotrope is formed. The compositions exhibit azeotrope and/or azeotrope-like properties over a range of about 70 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 30 weight percent isohexane. More pronounced azeotrope and/or azeotrope-like properties occur over a range of about 85 to 99.5 weight percent cis-1233zd and about 0.5 to about 15 weight percent isohexane; and even more pronounced over a range of about 93 to 99.5 weight percent cz ^' s-1233zd and about 0.5 to about 7 weight percent isohexane. Example 31:

An azeotrope-like mixture containing 98% by weight tr<ms-HFO-1233zd with about 2% by weight methanol is loaded into an aerosol can. An aerosol valve is crimped into place and HFC- 134a is added through the valve to achieve a pressure in the can of about 20 PSIG. The mixture is then sprayed onto surface demonstrating that the azeotropic mixture is useful as an aerosol.

Examples 32 - 57:

The steps of Example 31 are generally repeated for Examples 32 - 57, except that the azeotrope-like mixture identified in the Table below is used instead of tr<ms-HFO-1233zd and methanol. Optionally, the aerosols have a different co-aerosol agent or no co-aerosol agent, and optionally have at least one active ingredient selected from the group consisting of deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides, and medicinal materials. Similar results are demonstrated.

Example Azeotrope-like Composition Forms Aerosol No.

41 trcms-\233zd + 2-chloropropane Yes

42 tr<ms-1233zd + cyclopentane Yes

43 tr<ms-1233zd + cyclopentene Yes

44 tr<ms-1233zd + methylal Yes

45 tr<ms-1233zd + methyl acetate Yes

46 tr<ms-1233zd + n-hexane Yes

47 tr<ms-1233zd + nitromethane Yes

48 cz ^' s- 1233 zd + methanol Yes

49 cz ^' s-1233zd + ethanol Yes

50 cz ^' s-1233zd + isopropanol Yes

51 cz ^' s-1233zd + n-hexane Yes

52 cz ^' s-1233zd + isohexane Yes

53 cz ^' s-1233zd + cyclopentane Yes

54 cz ^' s-1233zd + n-pentane Yes

55 cz ^' s-1233zd + nitromethane Yes

56 cz ^' s-1233zd + trans-l,2-DCE Yes

57 cz ^' s-1233zd + neopentane Yes

Example 58:

A mixture containing 98% by weight trans-HFO-\233zd with about 2% by weight methanol is loaded into an aerosol can. An aerosol valve is crimped into place and HFC- 134a is added through the valve to achieve a pressure in the can of about 20 PSIG. The mixture is then sprayed onto a metal coupon soiled with solder flux. The flux is removed and the coupon is visually clean. Examples 59 - 84:

For Examples 59 - 84, the steps of Example 58 are generally repeated, except that the azeotrope-like mixture identified in the Table below is used instead of tr<ms-HFO-1233zd and methanol, and instead of HFC-134a, a different co-aerosol or no co-aerosol is used. Optionally, the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping instead of spraying. Optionally, the azeotropic mixture cleaning agent is applied neat. Optionally, the material to be cleaned was changed from solder flux to a mineral oil, silicon oil, or other lubricant. Similar results are demonstrated in each case.

Example Azeotrope-like Composition Visually Clean No.

76 cz ^' s-1233zd + ethanol Yes

77 cz ^' s-1233zd + isopropanol Yes

78 cz ^' s-1233zd + n-hexane Yes

79 cz ^' s-1233zd + isohexane Yes

80 cz ^' s-1233zd + cyclopentane Yes

81 cz ^' s-1233zd + n-pentane Yes

82 cz ^' s-1233zd + nitromethane Yes

83 cz ^' s-1233zd + trans-l,2-DCE Yes

84 cz ^' s-1233zd + neopentane Yes

Example 85:

A mixture containing 98% by wt trans-HFO-\233zd and 2% by wt of methanol is prepared, silicone oil is mixed with the blend and the solvent was left to evaporate, a thin coating of silicone oil is left behind in the coupon. This indicated that the solvent blends can be used for silicone oil deposition in various substrates.

Examples 86 - 111: The steps of Example 85 are generally repeated for Examples 85 - 111, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

89 tr<ms-1233zd + neopentane Yes

90 tr<ms-1233zd + methanol/n-pentane Yes

91 tr<ms-1233zd + methanol/trans-l,2-DCE Yes

92 tr<ms-1233zd + ethanol Yes

93 tr<ms-1233zd + isopropanol Yes

94 tr<ms-1233zd + 1-chloropropane Yes

95 tr<ms-1233zd + 2-chloropropane Yes

96 tr<ms-1233zd + cyclopentane Yes

97 tr<ms-1233zd + cyclopentene Yes

98 tr<ms-1233zd + methylal Yes

99 tr<ms-1233zd + methyl acetate Yes

100 tr<ms-1233zd + n-hexane Yes

101 tr<ms-1233zd + nitromethane Yes

102 cz ^' s- 1233 zd + methanol Yes

103 cz ^' s-1233zd + ethanol Yes

104 cz ^' s-1233zd + isopropanol Yes

105 cz ^' s-1233zd + n-hexane Yes

106 cz ^' s-1233zd + isohexane Yes

107 cz ^' s-1233zd + cyclopentane Yes

108 cz ^' s-1233zd + n-pentane Yes

109 cz ^' s-1233zd + nitromethane Yes

110 cz ^' s-1233zd + trans-l,2-DCE Yes

111 cz ^' s-1233zd + neopentane Yes

Example 112:

A mixture containing 98% by wt tr<my-HFO-1233zd and 2% by wt of methanol is prepared, mineral oil is mixed with the blend. The mineral oil is evenly disbursed throughout the blend. This indicated that the azeotrope-like composition can be used as a solvent. Examples 113 - 138:

The steps of Example 112 are generally repeated for Examples 113 - 138, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Example Azeotrope-like Composition Good Solvency No.

136 cz ^' s-1233zd + nitromethane Yes

137 cz ^' s-1233zd + trans-l,2-DCE Yes

138 cz ^' s-1233zd + neopentane Yes

Example 139:

An azeotrope-like mixture of about 97 weight percent trans-\233zd and about 3 weight percent trans- 1,2-DCE is prepared. This mixture is used as a blowing agent to prepare a closed-cell polyurethane foam and a closed-cell polyisocyanate foam. The cell-gas of the resulting foam is analyzed and is determined to contain at least a portion of the azeotrope-like mixture.

Examples 140 - 153: The steps of Example 139 are generally repeated for Examples 140 - 153, except that the azeotrope-like mixture identified in the Table below is used instead and trans- 1,2-DCE.

146 trcms-\233zd + cyclopentene Yes Yes Yes

147 trans-\233zd + methylal Yes Yes Yes

148 trans-\233zd + methyl acetate Yes Yes Yes

149 trcms-\233zd + water Yes Yes Yes

150 trans-\233zd + nitromethane Yes Yes Yes

151 cis-\233zd + cyclopentane Yes Yes Yes

152 cis-\233zd + n-pentane Yes Yes Yes

153 cis-\233zd + neopentane Yes Yes Yes

Example 154:

Mixtures were prepared containing 98% by weight trcms-EFO-\233zd with about 2 weight percent methanol. Several stainless steel coupons were soiled with mineral oil. Then these coupons were immersed in these solvent blends. The blends removed the oils in a short period of time. The coupons were observed visually and looked clean.

Examples 155 - 180:

The steps of Example 154 are generally repeated for Examples 155 - 180, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Example Azeotrope-like Composition Visually Clean No.

161 trans-\233zA + ethanol Yes

162 tr<ms-1233zd + isopropanol Yes

163 tr<ms-1233zd + 1-chloropropane Yes

164 tr<ms-1233zd + 2-chloropropane Yes

165 tr<ms-1233zd + cyclopentane Yes

166 tr<ms-1233zd + cyclopentene Yes

167 tr<ms-1233zd + methylal Yes

168 tr<ms-1233zd + methyl acetate Yes

169 tr<ms-1233zd + n-hexane Yes

170 tr<ms-1233zd + nitromethane Yes

171 cz ^' s- 1233 zd + methanol Yes

172 cz ^' s-1233zd + ethanol Yes

173 cz ^' s-1233zd + isopropanol Yes

174 cz ^' s-1233zd + n-hexane Yes

175 cz ^' s-1233zd + isohexane Yes

176 cz ^' s-1233zd + cyclopentane Yes

177 cz ^' s-1233zd + n-pentane Yes

178 cz ^' s-1233zd + nitromethane Yes

179 cz ^' s-1233zd + trans-l,2-DCE Yes

180 cz ^' s-1233zd + neopentane Yes

Example 181:

A solvent blend was prepared containing 98% by wt of tr ¾y-HFO-1233zd and 2% by wt of methanol. Kester 1544 Rosin Soldering Flux was placed on stainless steel coupons and heated to approximately 300-400 °F, which simulates contact with a wave soldier normally used to solder electronic components in the manufacture of printed circuit boards. The coupons were then dipped in the solvent mixture and removed after 15 seconds without rinsing. Results show that the coupons appeared clean by visual inspection.

Examples 182 - 207:

The steps of Example 181 are generally repeated for Examples 185 - 207, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Example Azeotrope-like Composition Visually Clean No.

203 cz ^' s-1233zd + cyclopentane Yes

204 cz ^' s-1233zd + n-pentane Yes

205 cz ^' s-1233zd + nitromethane Yes

206 cz ^' s-1233zd + trans-l,2-DCE Yes

207 cz ^' s-1233zd + neopentane Yes

Example 208:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About 10 cc of a mixture of 96 wt% of tr-1233zd and 4 wt% of n-pentane was charged to the flask and tr-l,2-dichloroethylene was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 19 ° C at ambient pressure indicating the formation of an azeotrope-like ternary mixture. wt% tr-1233zd n-pentane wt% tr-l,2 Boiling Point (C)

DCE

84.7 3.5 11.7 20.2

84.2 3.5 12.3 20.3

83.6 3.5 12.9 20.4

83.1 3.5 13.5 20.5

82.6 3.4 14.0 20.6

82.1 3.4 14.5 20.6

81.6 3.4 15.0 20.7

81.0 3.4 15.6 20.8

80.4 3.4 16.2 20.9

79.9 3.3 16.8 21.0

Example 209:

An ebulliometer was used consisting of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About 10 cc of a mixture of 70 wt% of cis-1233zd and 30 wt% of tr-1,2- dichloroethylene was charged to the flask and isohexane was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 36.3° C at a pressure of about 767 mmHg indicating the formation of an azeotrope-like ternary mixture.

65.6 28.1 6.2 36.4

65.4 28.0 6.6 36.5

65.0 27.9 7.1 36.5

64.7 27.7 7.6 36.5

64.4 27.6 8.0 36.5

64.1 27.5 8.5 36.5

Example 210:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About 10 cc of a mixture of 70 wt% of cis-1233zd and 30 wt% of tr-1,2- dichloroethylene was charged to the flask and ethanol was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 35.8° C at a pressure of about 767 mmHg indicating the formation of an azeotrope-like ternary mixture.

Example 211:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of a mixture of 97 wt% of cis-1233zd and 3.0 wt% of methanol was charged to the flask and trans- 1,2 dichloroethylene was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 33.87 ° C at a pressure of about 750.50 mmHg indicating the formation of an azeotrope-like ternary mixture.

Compositions with cis-1233zd/methanol/t-l,2-DCE

wt% cis-1233zd wt% methanol wt% t-l,2-DCE B.P. (°C)

0.785 0.024 0.191 33.87

0.781 0.024 0.194 33.87

0.778 0.024 0.198 33.88

0.774 0.024 0.202 33.89

0.771 0.024 0.205 33.89

0.768 0.024 0.209 33.88

0.764 0.024 0.212 33.88

0.761 0.024 0.215 33.88

0.758 0.023 0.218 33.89

0.755 0.023 0.221 33.88

0.752 0.023 0.224 33.89

0.749 0.023 0.227 33.90

0.747 0.023 0.230 33.90

0.744 0.023 0.233 33.88

0.741 0.023 0.236 33.86

0.738 0.023 0.239 33.88

0.736 0.023 0.241 33.89

0.733 0.023 0.244 33.90

0.731 0.023 0.247 33.90

0.728 0.023 0.250 33.91

0.725 0.022 0.253 33.91

0.722 0.022 0.256 33.93

0.719 0.022 0.259 33.94

0.716 0.022 0.262 33.95

0.713 0.022 0.264 33.95

0.711 0.022 0.267 33.95

0.708 0.022 0.270 33.96

0.706 0.022 0.272 33.97

0.703 0.022 0.275 33.97

0.701 0.022 0.277 33.99

0.698 0.022 0.280 34.00

0.696 0.022 0.282 34.00

0.694 0.021 0.285 34.00

0.692 0.021 0.287 34.01

0.690 0.021 0.289 34.05

Example 212:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of a mixture of 97 wt% of cis-1233zd and 3.0 wt% of methanol was charged to the flask and isohexane was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 34.00° C at a pressure of about 754 mmHg indicating the formation of an azeotrope-like ternary mixture.

Compositions with cis-1233zd/methanol/isohexane

wt% cis-1233zd wt% methanol wt% isohexane B.P. (°C)

83.141 2.571 14.287 34.03

82.825 2.562 14.613 34.02

82.514 2.552 14.934 34.00

82.209 2.543 15.248 34.01

81.910 2.533 15.557 34.01

81.615 2.524 15.861 34.02

81.326 2.515 16.159 34.02

81.042 2.506 16.452 34.03

80.762 2.498 16.740 34.03

80.488 2.489 17.023 34.03

80.218 2.481 17.301 34.01

79.952 2.473 17.575 34.03

79.691 2.465 17.844 34.03

79.435 2.457 18.109 34.06

79.182 2.449 18.369 34.04

78.934 2.441 18.625 34.05

78.689 2.434 18.877 34.05

Example 213:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of cis-1233zd was charged to the flask and petroleum ether was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 32.24° C at a pressure of about 756.5 mm Hg indicating the formation of an azeotrope-like ternary mixture.

Compositions with cis-1233zd/pet ether wt% cis-1233zd wt % pet. ether B.P. (°C)

96.99 3.01 35.33

96.41 3.59 35.00

95.84 4.16 34.73

95.27 4.73 34.52

94.71 5.29 34.35

94.16 5.84 34.16

93.61 6.39 33.98

93.07 6.93 33.81

92.54 7.46 33.67

92.01 7.99 33.54

91.49 8.51 33.41

90.97 9.03 33.30

90.46 9.54 33.23

89.96 10.04 33.18

89.46 10.54 33.10

88.97 11.03 33.03

88.48 11.52 32.99

87.99 12.01 32.94

87.52 12.48 32.89

87.04 12.96 32.84

86.58 13.42 32.81

86.11 13.89 32.77

85.66 14.34 32.74

85.20 14.80 32.71

84.76 15.24 32.68

84.31 15.69 32.65

83.88 16.12 32.63

83.44 16.56 32.59

83.01 16.99 32.56

82.59 17.41 32.55

82.17 17.83 32.52

81.75 18.25 32.50

81.34 18.66 32.48

80.93 19.07 32.46

80.52 19.48 32.46

80.12 19.88 32.43

79.73 20.27 32.42

79.34 20.66 32.40

78.95 21.05 32.39

78.56 21.44 32.37

78.18 21.82 32.36

77.80 22.20 32.35

77.43 22.57 32.34 Compositions with cis-1233zd/pet ether wt% cis-1233zd wt % pet. ether B.P. (°C)

77.06 22.94 32.32

76.69 23.31 32.32

76.33 23.67 32.32

75.97 24.03 32.30

75.62 24.38 32.30

75.26 24.74 32.29

74.91 25.09 32.28

74.57 25.43 32.29

74.22 25.78 32.28

73.88 26.12 32.28

73.55 26.45 32.27

73.21 26.79 32.27

72.88 27.12 32.27

72.55 27.45 32.26

72.23 27.77 32.26

71.91 28.09 32.25

71.59 28.41 32.24

71.27 28.73 32.26

70.96 29.04 32.27

70.65 29.35 32.26

70.34 29.66 32.26

70.03 29.97 32.24

69.73 30.27 32.24

69.43 30.57 32.24

69.13 30.87 32.25

68.84 31.16 32.26

68.54 31.46 32.25

68.25 31.75 32.25

67.97 32.03 32.24

67.68 32.32 32.25

67.40 32.60 32.24

67.12 32.88 32.25

66.84 33.16 32.26

66.56 33.44 32.25

66.29 33.71 32.25

66.02 33.98 32.26

65.75 34.25 32.26

65.48 34.52 32.26

65.22 34.78 32.26

64.95 35.05 32.25

64.69 35.31 32.26

64.44 35.56 32.27

64.18 35.82 32.28 Compositions with cis-1233zd/pet ether

wt% cis-1233zd wt % pet. ether B.P. (°C)

63.92 36.08 32.32

63.67 36.33 32.32

63.42 36.58 32.32

63.17 36.83 32.27

62.93 37.07 32.29

62.68 37.32 32.29

62.44 37.56 32.29

62.20 37.80 32.29

61.96 38.04 32.31

61.72 38.28 32.31

61.49 38.51 32.30

61.25 38.75 32.29

61.02 38.98 32.30

60.79 39.21 32.30

60.56 39.44 32.31

60.34 39.66 32.30

60.11 39.89 32.31

59.89 40.11 32.31

59.67 40.33 32.31

59.45 40.55 32.32

59.23 40.77 32.33

59.01 40.99 32.33

58.80 41.20 32.33

58.58 41.42 32.34

58.37 41.63 32.34

58.16 41.84 32.34

57.95 42.05 32.35

57.74 42.26 32.35

57.54 42.46 32.36

57.33 42.67 32.37

57.13 42.87 32.37

Example 214:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of a mixture of 72 wt% of cis-1233zd and 28 wt% of cyclopentane was charged to the flask and methanol was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 31.54° C at a pressure of about 752 mmHg indicating the formation of an azeotrope-like ternary mixture.

Compositions with cis-1233zd/methanol/cyclopentane

wt% cis-1233zd wt% methanol wt % cyclopentane B.P. (°C)

61.262 14.914 23.824 31.95

61.067 15.185 23.748 31.96

Example 215:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of a mixture of 78 wt% of cis-1233zd and 22 wt% of cyclopentane was charged to the flask and ethanol was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 34.12° C at a pressure of about 763.5 mmHg indicating the formation of an azeotrope-like ternary mixture.

Example 216:

An ebulliometer was used that consisted of a small flask equipped with an automated dispenser and a condenser attached to the flask. The dispenser and the condenser were cooled by a circulating bath. About lOcc of a mixture of 72 wt% of cis-1233zd and 28 wt% of cyclopentane was charged to the flask and isopropanol was added slowly to the flask using the automated dispenser. As shown in the Table below, it was seen that the boiling point of the mixture changed very slowly. Boiling point remained essentially constant around 34.30° C at a pressure of about 748.2 mmHg indicating the formation of an azeotrope-like ternary mixture.

Examples 217 - 228:

The steps of Example 31 are generally repeated for Examples 218 - 229, except that the azeotrope-like mixture identified in the Table below is used instead of trans-HFO-\233zd and methanol. Optionally, the aerosols have a different co-aerosol agent or no co-aerosol agent, and optionally have at least one active ingredient selected from the group consisting of deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides, and medicinal materials. Similar results are demonstrated. Example Azeotrope-like Composition Forms Aerosol No.

217 trans-\233zd + n-pentane + trans- 1,2- Yes

DCE

218 cz ^' s-1233zd + isohexane + trans-l,2-DCE Yes

219 cz ^' s-1233zd + ethanol + trans-l,2-DCE Yes

220 cz ^' s-1233zd + methanol + isohexane Yes

221 cz ^' s-1233zd + methanol + trans-l,2-DCE Yes

222 cz ^' s-1233zd + petroleum ether Yes

223 cz ^' s-1233zd + methanol + cyclopentane Yes

224 cz ^' s-1233zd + ethanol + cyclopentane Yes

225 cz ^' s-1233zd + isopropanol + cyclopentane Yes

226 tr<ms-1233zd + isopentane Yes

227 trcms-\233zd + HFC-365mfc Yes

228 tr<ms-1233zd + water Yes

Examples 229 - 240 For Examples 230-241, the steps of Example 58 are generally repeated, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol, and instead of HFC-134a, a different co-aerosol or no co-aerosol is used. Optionally, the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping instead of spraying. Optionally, the azeotropic mixture cleaning agent is applied neat. Optionally, the material to be cleaned is changed from solder flux to a mineral oil, silicon oil, or other lubricant. Similar results are demonstrated in each case. Example Azeotrope-like Composition Visually Clean No.

229 trans-\233zd + n-pentane + trans- 1,2- Yes

DCE

230 cz ^' s-1233zd + isohexane + trans-l,2-DCE Yes

231 cz ^' s-1233zd + ethanol + trans-l,2-DCE Yes

232 cz ^' s-1233zd + methanol + isohexane Yes

233 cz ^' s-1233zd + methanol + trans-l,2-DCE Yes

234 cz ^' s-1233zd + petroleum ether Yes

235 cz ^' s-1233zd + methanol + cyclopentane Yes

236 cz ^' s-1233zd + ethanol + cyclopentane Yes

237 cz ^' s-1233zd + isopropanol + cyclopentane Yes

238 tr<ms-1233zd + isopentane Yes

239 trcms-\233zd + HFC-365mfc Yes

240 tr<ms-1233zd + water Yes

Examples 241 - 252

The steps of Example 85 are generally repeated for Examples 242 - 253, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

247 cz ^' s-1233zd + methanol + cyclopentane Yes

248 cz ^' s-1233zd + ethanol + cyclopentane Yes

249 cz ^' s-1233zd + isopropanol + cyclopentane Yes

250 tr<ms-1233zd + isopentane Yes

251 trcms-\233zd + HFC-365mfc Yes

252 tr<ms-1233zd + water Yes

Examples 253 - 264:

The steps of Example 112 are generally repeated for Examples 254 - 265, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Examples 265 - 289:

The steps of Example 139 are generally repeated for Examples 266 - 290, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and trans- 1,2-DCE.

280 trcms-\233zd + isopropanol Yes Yes Yes

281 cis-\233zd + isopropanol Yes Yes Yes

282 cis-\233zd + n-pentane Yes Yes Yes

283 trans-\233zd + n-hexane Yes Yes Yes

284 cis-\233zd + n-hexane Yes Yes Yes

285 trans-\233zd + isohexane Yes Yes Yes

286 cis-\233zd + isohexane Yes Yes Yes

287 trcms-\233zd + HFC-365mfc Yes Yes Yes

288 cw-1233zd + 1,2-DCE Yes Yes Yes

289 cz ^' s-1233zd + nitromethane Yes Yes Yes

Examples 290 - 301:

The steps of Example 154 are generally repeated for Examples 291 - 302, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Examples 302 - 313:

The steps of Example 181 are generally repeated for Examples 303 - 314, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.

Example 314-352

Measured amount of commercial solder pastes are applied by a brush in printed circuit boards which are then reflowed as done in a commercial soldering operation. The circuit boards are dipped in a beaker using 100% the following azeotropic solvent blends to clean the boards. As indicated, each board looks visually clean after the operation. 315 trans-\233zd + trans-l,2-DCE Yes

316 tr<ms-1233zd + n-pentane Yes

317 tr<ms-1233zd + isohexane Yes

318 tr<ms-1233zd + neopentane Yes

319 Trans-\233zd + methanol/n-pentane Yes

320 tr<ms-1233zd + methanol/trans-l,2-DCE Yes

321 tr<ms-1233zd + ethanol Yes

322 tr<ms-1233zd + isopropanol Yes

323 tr<ms-1233zd + 1-chloropropane Yes

324 tr<ms-1233zd + 2-chloropropane Yes

325 trcms-\233zd + cyclopentane Yes

326 tr<ms-1233zd + cyclopentene Yes

327 tr<ms-1233zd + methylal Yes

328 trans-\233zd + methyl acetate Yes

329 tr<ms-1233zd + n-hexane Yes

330 tr<ms-1233zd + nitromethane Yes

331 cz ^' s- 1233 zd + methanol Yes

332 cz ^' s-1233zd + ethanol Yes

333 cz ^' s-1233zd + isopropanol Yes

334 cz ^' s-1233zd + n-hexane Yes

335 cz ^' s-1233zd + isohexane Yes

336 cz ^' s-1233zd + cyclopentane Yes

337 cz ^' s-1233zd + n-pentane Yes

338 cz ^' s-1233zd + nitromethane Yes

339 cz ^' s-1233zd + trans-l,2-DCE Yes

340 cz ^' s-1233zd + neopentane Yes

341 trans-\233zd + n-pentane + trans- 1,2- Yes

DCE

342 cz ^' s-1233zd + isohexane + trans-l,2-DCE Yes

343 cz ^' s-1233zd + ethanol + trans-l,2-DCE Yes

344 cz ^' s-1233zd + methanol + isohexane Yes

345 cz ^' s-1233zd + methanol + trans-l,2-DCE Yes 346 cz ^' s-1233zd + petroleum ether Yes

347 cz ^' s-1233zd + methanol + cyclopentane Yes

348 cz ^' s-1233zd + ethanol + cyclopentane Yes

349 cz ^' s-1233zd + isopropanol + cyclopentane Yes

350 tr<ms-1233zd + isopentane Yes

351 trcms-\233zd + HFC-365mfc Yes

352 tr<ms-1233zd + water Yes

Example 353-391

Pieces of fabrics are soiled by standard mineral oils, then 100% solutions of the azeotropic solvent blends below are used to clean the fabrics simulating a dry cleaning operation. Fabrics are visually clean after the operation. This indicates that these solvent blends can be used in dry cleaning application.

Example Azeotrope-like Composition Visually Clean No.

367 trans-\233zd + methyl acetate Yes

368 tr<ms-1233zd + n-hexane Yes

369 tr<ms-1233zd + nitromethane Yes

370 cz ^' s- 1233 zd + methanol Yes

371 cz ^' s-1233zd + ethanol Yes

372 cz ^' s-1233zd + isopropanol Yes

373 cz ^' s-1233zd + n-hexane Yes

374 cz ^' s-1233zd + isohexane Yes

375 cz ^' s-1233zd + cyclopentane Yes

376 cz ^' s-1233zd + n-pentane Yes

377 cz ^' s- 1233 zd + nitromethane Yes

378 cz ^' s-1233zd + trans-l,2-DCE Yes

379 cz ^' s-1233zd + neopentane Yes

380 tr<ms-1233zd + n-pentane + trans- 1,2- Yes

DCE

381 cz ^' s-1233zd + isohexane + trans-l,2-DCE Yes

382 cz ^' s-1233zd + ethanol + trans-l,2-DCE Yes

383 cz ^' s-1233zd + methanol + isohexane Yes

384 cz ^' s-1233zd + methanol + trans-l,2-DCE Yes

385 cz ^' s-1233zd + petroleum ether Yes

386 cz ^' s-1233zd + methanol + cyclopentane Yes

387 cz ^' s-1233zd + ethanol + cyclopentane Yes

388 cz ^' s-1233zd + isopropanol + cyclopentane Yes

389 tr<ms-1233zd + isopentane Yes

390 trcms-\233zd + HFC-365mfc Yes

391 trcms-\233zd + water Yes

Example 392-430

This example illustrates that the 1233zd azeotropes of the present invention are useful as organic Rankin cycle working fluids.

The effectiveness of various working fluids in an organic Rankine cycle is compared by following the procedure outlined in Smith, J.M., et al., Introduction to Chemical Engineering Thermodynamics; McGraw-Hill (1996). The organic Rankine cycle calculations are made using the following conditions: pump effience of 75%, expander efficiency of 80%, boiler temperature of 130 °C, condenser temperature of 45 °C and 1000 W of heat supplied to the boiler. The thermal efficiency of each azeotrope is provided below:

Example Azeotrope-like Composition Thermal No. Efficiency

limits

407 trans-\233zd + n-hexane within acceptable limits

408 tr<ms-1233zd + nitromethane within acceptable limits

409 cz ^' s-1233zd + methanol within acceptable limits

410 cz ^' s-1233zd + ethanol within acceptable limits

411 cz ^' s-1233zd + isopropanol within acceptable limits

412 cz ^' s-1233zd + n-hexane within acceptable limits

413 cz ^' s-1233zd + isohexane within acceptable limits

414 cz ^' s-1233zd + cyclopentane within acceptable limits

415 cz ^' s-1233zd + n-pentane within acceptable limits

416 cz ^' s- 1233 zd + nitromethane within acceptable limits

417 cz ^' s-1233zd + trans-l,2-DCE within acceptable limits

418 cz ^' s-1233zd + neopentane within acceptable limits

419 tr<ms-1233zd + n-pentane + trans- 1,2- within acceptable

DCE limits

420 cz ^' s-1233zd + isohexane + trans-l,2-DCE within acceptable limits

421 cz ^' s-1233zd + ethanol + trans-l,2-DCE within acceptable limits

422 cz ^' s-1233zd + methanol + isohexane within acceptable limits

423 cz ^' s-1233zd + methanol + trans-l,2-DCE within acceptable limits

424 cz ^' s-1233zd + petroleum ether within acceptable limits

425 cz ^' s-1233zd + methanol + cyclopentane within acceptable limits

426 cz ^' s-1233zd + ethanol + cyclopentane within acceptable limits

427 cz ^' s-1233zd + isopropanol + cyclopentane within acceptable limits Example Azeotrope-like Composition Thermal No. Efficiency

428 trcms-\233zd + isopentane within acceptable

limits

429 trcms-\233zd + HFC-365mfc within acceptable

limits

430 trcms-\233zd + water within acceptable

limits

Example 431-469

The coefficient of performance (COP) is a universally accepted measure of refrigerant performance, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant, n refrigeration engineering, this term expresses the ratio of useful refrigeration to the energy applied by the compressor in compressing the vapor. The capacity of a refrigerant represents the amount of cooling or heating it provides and provides some measure of the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant. In other words, given a specific compressor, a refrigerant with a higher capacity will deliver more cooling or heating power. One means for estimating COP of a refrigerant at specific operating conditions is from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques (see for example, R. C. Downing, FLUOPvOCAPvBON REFRIGERANTS HANDBOOK, Chapter 3, Prentice-Hall, 1988).

A refrigeration/air conditioning cycle system is provided where the condenser temperature is about 150° F and the evaporator temperature is about -35° F under nominally isentropic compression with a compressor inlet temperature of about 50° F. COP and capacity is evaluated for the azeotropic compositions of the present invention and is reported in the table below: Example Azeotrope-like Composition COP Capacity No.

431 trans-\233zd + methanol within within acceptable acceptable limits limits

432 tr<ms-1233zd + trans-l,2-DCE within within acceptable acceptable limits limits

433 tr<ms-1233zd + n-pentane within within acceptable acceptable limits limits

434 tr<ms-1233zd + isohexane within within acceptable acceptable limits limits

435 tr<ms-1233zd + neopentane within within acceptable acceptable limits limits

436 tr<ms-1233zd + methanol/n- within within pentane acceptable acceptable limits limits

437 tr<ms-1233zd + methanol/trans- within within

1,2-DCE acceptable acceptable limits limits

438 trans-\233zd + ethanol within within acceptable acceptable limits limits

439 tr<ms-1233zd + isopropanol within within acceptable acceptable limits limits

440 tr<ms-1233zd + l-chloropropane within within acceptable acceptable limits limits

441 tr<ms-1233zd + 2-chloropropane within within acceptable acceptable limits limits

442 trcms-\233zd + cyclopentane within within acceptable acceptable limits limits

443 trcms-\233zd + cyclopentene within within acceptable acceptable limits limits

444 tr<ms-1233zd + methylal within within acceptable acceptable Example Azeotrope-like Composition COP Capacity No.

limits limits

445 trans-\233zd + methyl acetate within within acceptable acceptable limits limits

446 trans-\233zd + n-hexane within within acceptable acceptable limits limits

447 trans-\233zd + nitromethane within within acceptable acceptable limits limits

448 cz ^' s-1233zd + methanol within within acceptable acceptable limits limits

449 cz ^' s-1233zd + ethanol within within acceptable acceptable limits limits

450 cz ^' s-1233zd + isopropanol within within acceptable acceptable limits limits

451 cz ^' s-1233zd + n-hexane within within acceptable acceptable limits limits

452 cz ^' s-1233zd + isohexane within within acceptable acceptable limits limits

453 cz ^' s-1233zd + cyclopentane within within acceptable acceptable limits limits

454 cz ^' s-1233zd + n-pentane within within acceptable acceptable limits limits

455 cz ^' s-1233zd + nitromethane within within acceptable acceptable limits limits

456 cz ^' s-1233zd + trans-l,2-DCE within within acceptable acceptable limits limits

457 cz ^' s-1233zd + neopentane within within acceptable acceptable limits limits

458 tr<ms-1233zd + n-pentane + within within trans- 1,2-DCE acceptable acceptable limits limits Example Azeotrope-like Composition COP Capacity No.

459 cz ^' s-1233zd + isohexane + trans- within within

1,2-DCE acceptable acceptable

limits limits

460 cz ^' s- 1233 zd + ethanol + trans- within within

1,2-DCE acceptable acceptable

limits limits

461 cz ^' s-1233zd + methanol + within within

isohexane acceptable acceptable

limits limits

462 cz ^' s-1233zd + methanol + trans- within within

1,2-DCE acceptable acceptable

limits limits

463 cz ^' s-1233zd + petroleum ether within within

acceptable acceptable limits limits

464 cz ^' s-1233zd + methanol + within within

cyclopentane acceptable acceptable

limits limits

465 cz ^' s-1233zd + ethanol + within within

cyclopentane acceptable acceptable

limits limits

466 cz ^' s-1233zd + isopropanol + within within

cyclopentane acceptable acceptable

limits limits

467 tr<ms-1233zd + isopentane within within

acceptable acceptable limits limits

468 trcms-\233zd + HFC-365mfc within within

acceptable acceptable limits limits

469 trcms-\233zd + water within within

acceptable acceptable limits limits

Example 470-508

For thermoset spray foam application, a polyol (B Component) formulation is produced using 100 parts by weight of a polyol blend comprising a mannich base polyol, a polyether polyol, and an aromatic polyester polyol, 1.25 parts by weight of a silicone surfactant, 1.5 parts by weight water, 2.0 parts by weight of a tertiary amine catalyst, 0.05 parts by weight of an organometallic catalyst and 0.15 moles of a blowing agent. The azeotropes listed below are each evaluated as a blowing agent in such compositions.

The total B component composition is combined with 120.0 parts by weight of Lupranate M20S polymeric isocyanate using conventional high pressure spray foam processing equipment using typical processing pressures and temperatures. The results of each azeotrope are provided below. The resultant foam is each a good quality foam with a fine and regular cell structure. Foam reactivity is typical for a spray type foam.

Example Azeotrope-like Foam Cell Foam No. Composition Quality Structure Reactivity

cyclopentene

483 trans-\233zd + methylal Good Good Good

484 tr<ms-1233zd + methyl Good Good Good acetate

485 tr<ms-1233zd + n-hexane Good Good Good

486 tr<ms-1233zd + Good Good Good nitromethane

487 cz ^' s-1233zd + methanol Good Good Good

488 cz ^' s-1233zd + ethanol Good Good Good

489 cz ^' s-1233zd + isopropanol Good Good Good

490 cz ^' s-1233zd + n-hexane Good Good Good

491 cz ^' s-1233zd + isohexane Good Good Good

492 cz ^' s-1233zd + cyclopentane Good Good Good

493 cz ^' s-1233zd + n-pentane Good Good Good

494 cz ^' s-1233zd + nitromethane Good Good Good

495 cz ^' s-1233zd + trans- 1,2- Good Good Good

DCE

496 cz ^' s-1233zd + neopentane Good Good Good

497 trans-\233zd + n-pentane Good Good Good

+ trans- 1,2-DCE

498 cz ^' s-1233zd + isohexane + Good Good Good trans- 1,2-DCE

499 cz ^' s-1233zd + ethanol + Good Good Good trans- 1,2-DCE

500 cz ^' s-1233zd + methanol + Good Good Good isohexane

501 cz ^' s-1233zd + methanol + Good Good Good trans- 1,2-DCE

502 cz ^' s-1233zd + petroleum Good Good Good ether

503 cz ^' s-1233zd + methanol + Good Good Good cyclopentane

504 cz ^' s-1233zd + ethanol + Good Good Good Example Azeotrope-like Foam Cell Foam No. Composition Quality Structure Reactivity

cyclopentane

505 cz ^' s-1233zd + isopropanol Good Good Good

+ cyclopentane

506 trcms-\233zd + isopentane Good Good Good

507 tra¾s-1233zd + HFC- Good Good Good

365mfc

508 tr<ms-1233zd + water Good Good Good

Example 509-547

For a panel foam, a polyol (B Component) formulation is produced using 100 parts by weight of a polyol blend comprising a polyether polyol and an aromatic polyester polyol, 1.5 parts by weight of a silicone surfactant, 2.0 parts by weight water, 2.0 parts by weight of a tertiary amine catalyst, 22 parts by weight of a flame retardant and 0.18 moles of blowing agent. The azeotropes listed below are each evaluated as a blowing agent in such compositions.

The total B component composition is combined with 143.0 parts by weight of Lupranate M20S polymeric isocyanate using conventional high pressure foam processing equipment. The results of each azeotrope are provided below. The resultant foams each are a good quality foam with a fine and regular cell structure. Foam reactivity was typical for discontinuous panel type foam.

Example Azeotrope-like Foam Cell Foam No. Composition Quality Structure Reactivity

511 trans-\233zA + n-pentane Good Good Good

512 tr<ms-1233zd + isohexane Good Good Good

513 tr<ms-1233zd + neopentane Good Good Good

514 tr<ms-1233zd + Good Good Good methanol/n-pentane

515 tr<ms-1233zd + Good Good Good methanol/trans- 1 ,2-DCE

516 tr<ms-1233zd + ethanol Good Good Good

517 tr<ms-1233zd + Good Good Good isopropanol

518 tr<ms-1233zd + 1- Good Good Good chloropropane

519 tr<ms-1233zd + 2- Good Good Good chloropropane

520 tr<ms-1233zd + Good Good Good cyclopentane

521 tr<ms-1233zd + Good Good Good cyclopentene

522 trans-\233zd + methylal Good Good Good

523 tr<ms-1233zd + methyl Good Good Good acetate

524 tr<ms-1233zd + n-hexane Good Good Good

525 + Good Good Good nitromethane

526 cz ^' s-1233zd + methanol Good Good Good

527 cz ^' s-1233zd + ethanol Good Good Good

528 cz ^' s-1233zd + isopropanol Good Good Good

529 cz ^' s-1233zd + n-hexane Good Good Good

530 c 5-1233zd + isohexane Good Good Good

531 cz ^' s-1233zd + cyclopentane Good Good Good

532 c 5-1233zd + n-pentane Good Good Good

533 cz ^' s-1233zd + nitromethane Good Good Good

534 cz ^' s-1233zd + trans-1,2- Good Good Good Example Azeotrope-like Foam Cell Foam No. Composition Quality Structure Reactivity

DCE

535 cz ^' s-1233zd + neopentane Good Good Good

536 tr<ms-1233zd + n-pentane Good Good Good

+ trans- 1,2-DCE

537 cz ^' s-1233zd + isohexane + Good Good Good

trans- 1,2-DCE

538 cz ^' s-1233zd + ethanol + Good Good Good

trans- 1,2-DCE

539 cz ^' s-1233zd + methanol + Good Good Good

isohexane

540 cz ^' s-1233zd + methanol + Good Good Good

trans- 1,2-DCE

541 cz ^' s-1233zd + petroleum Good Good Good

ether

542 cz ^' s-1233zd + methanol + Good Good Good

cyclopentane

543 cz ^' s-1233zd + ethanol + Good Good Good

cyclopentane

544 cz ^' s-1233zd + isopropanol Good Good Good

+ cyclopentane

545 tr<ms-1233zd + isopentane Good Good Good

546 tra¾s-1233zd + HFC- Good Good Good

365mfc

547 tr<ms-1233zd + water Good Good Good

Having thus described a few particular embodiments of the invention, various alterations, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements, as are made obvious by this disclosure, are intended to be part of this description though not expressly stated herein, and are intended to be within the spirit and scope of the invention. Accordingly, the foregoing description is by way of example only, and not limiting. The invention is limited only as defined in the following claims and equivalents thereto.