WO2014164587A1 - Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene - Google Patents

Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene Download PDF

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Publication number
WO2014164587A1
WO2014164587A1 PCT/US2014/022937 US2014022937W WO2014164587A1 WO 2014164587 A1 WO2014164587 A1 WO 2014164587A1 US 2014022937 W US2014022937 W US 2014022937W WO 2014164587 A1 WO2014164587 A1 WO 2014164587A1
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Prior art keywords
hfo
azeotrope
compositions
yes
trans
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PCT/US2014/022937
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French (fr)
Inventor
Kane D. Cook
Rajat S. Basu
Ryan Hulse
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Honeywell International Inc.
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Priority to JP2016501105A priority Critical patent/JP2016521194A/en
Publication of WO2014164587A1 publication Critical patent/WO2014164587A1/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/26—Cleaning or polishing of the conductive pattern
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02809—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02809—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine
    • C23G5/02825—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing chlorine and fluorine containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3489—Composition of fluxes; Methods of application thereof; Other methods of activating the contact surfaces

Definitions

  • 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.
  • Fluorocarbon based fluids including chlorofluorocarbons (“CFCs”) or
  • hydrochlorofluorocarbons have properties that are desirable in industrial refrigerants, blowing agents, heat transfer media, solvents, gaseous dielectrics, and other applications.
  • HCFCs hydrochlorofluorocarbons
  • 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
  • HFOs Hydrofluoroolefins
  • 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
  • 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-trifluoropropene (particularly its cis isomer) and petroleum ether.
  • Applicants have also discovered the formation of certain binary azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene (particularly its cis isomer) and either methanol or isopropanoU (IP A), and the advantageous us of such azeotrope- like compositions in removing rosin solder flux, particularly and preferably form printed circuit boards and other electronic components, preferably by using a vapor degreasing-type process/system.
  • IP A isopropanoU
  • azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene (particularly its cis isomer), cyclopentane and a C1-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.
  • 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.
  • GWPs global warming potentials
  • one aspect of the present invention involves a composition
  • 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.
  • co-blowing agent such as lubricants, stabilizers, metal passivators, corrosion inhibitors, and flammability suppressants.
  • nitromethane is included in the mixture as a stabilizer.
  • 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
  • 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.
  • a polyol premix comprising the azeotrope-like mixture described herein.
  • a foamable composition comprising the azeotrope-like mixture described herein.
  • 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.
  • 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.
  • thermoplastic foam having a cell wall comprising a thermoplastic polymer and a cell gas comprising an azeotrope-like mixture as described herein.
  • 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,
  • thermoset foam having a cell wall comprising a thermosetting polymer and a cell gas comprising an azeotrope-like mixture as described herein.
  • 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.
  • a refrigerant comprising an azeotrope-like mixture as described herein.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • boiling or evaporating non-azeotropic mixtures changes the component concentrations in the liquid phase to a significant degree.
  • azeotrope-like 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.
  • 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.
  • HFO-1233zd means the cz ' s-isomer, the transisomer, or some mixture thereof.
  • 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 %.
  • the cz ' s-HFO-1233zd component in azeotrope-like compositions of the present invention is essentially pure cz ' s-HFO-1233zd.
  • 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 %.
  • compositions of the present invention is essentially pure trans- FO- ⁇ 233zd.
  • 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.
  • EP 974,571 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.
  • 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.
  • 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.
  • the azeotrope-like composition comprises effective amounts of HFO-1233zd and a Ci - C 3 alcohol.
  • the Ci - C 3 alcohol is selected from the group consisting of methanol, ethanol, and isopropanol.
  • the HFO-1233zd is trans-HFO- ⁇ 233zd.
  • the HFO-1233zd is cw-HFO-1233zd.
  • 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.
  • compositions of the present invention comprise from about 0.1 to about 5 weight percent methanol, and even more preferably from about one to about five weight percent methanol, and from about 95 weight percent to about 99.9 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent cz ' s-HFO-1233zd.
  • the czs-HFO-1233zd/methanol compositions of the present invention have a boiling point of about 35.2 ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of cz ' s-HFO-1233zd and isopropanol (IPA). More preferably, these binary azeotrope- like compositions consist essentially of about 85 to about 99.9 wt. % cz ' s-HFO-1233zd and from about 0.1 to about 15 wt. % IPA, and even more preferably from about 90 to about 99.9 wt. % cz ' s-HFO-1233zd and about 0.1 to about 10 wt. % IPA.
  • compositions of the present invention comprise from about 0.1 to about 5 weight percent IP A, and even more preferably from about 1 to about 5 weight percent IP A, and from about 95 weight percent to about 99.9 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent cz ' s-HFO-1233zd.
  • the cz ' s-HFO-1233zd/IPA compositions of the present invention have a boiling point of about 38.4 ⁇ 1 °C, and even more preferably 38.4 ⁇ 0.1 at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of trans-HFO- ⁇ 233zd and methanol. 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. % methanol, more preferably from about 90 to about 99.95 wt. % trans-HFO- ⁇ 233zd and about 0.05 to about 10 wt. % methanol, and even more preferably from about 95 to about 99.95 wt. % tr ⁇ ms-HFO-1233zd and from about 0.05 to about 5 wt. % methanol.
  • the tr «s-HFO-1233zd/metfianol 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.
  • 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.
  • the czs-HFO-1233zd/ethanol compositions of the present invention have a normal boiling point of about 37.4 °C ⁇ 1 °C at ambient pressure.
  • 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.
  • the tr 3 ⁇ 4s-HFO-1233zd/ethanol compositions of the present invention have a normal boiling point of about 18.1 °C ⁇ 1 °C at ambient pressure.
  • 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.
  • 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.
  • 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. % tr ⁇ my-HFO-1233zd and from about 0.1 to about 5 wt. % isopropanol.
  • the tra3 ⁇ 4s-HFO-1233zd/isopropanol compositions of the present invention have a normal boiling point of about 17.9 °C ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of HFO-1233zd and a C 5 - C 6 hydrocarbon.
  • the C 5 - C 6 hydrocarbon is selected from the group consisting of n-pentane, isopentane, neopentane, cyclopentane, cyclopentene, n-hexane, and isohexane.
  • the HFO-1233zd is trans-HFO- ⁇ 233zd. In certain other embodiments, the HFO-1233zd is cz ' s-HFO-1233zd.
  • 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. % trans- FO- ⁇ 233zd 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.
  • the tr 3 ⁇ 4s-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.
  • 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.
  • 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.
  • the azeotrope-like composition comprises effective amounts of tr ⁇ ms-HFO-1233zd and isopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 60 to about 99.95 wt. % tr ⁇ ms-HFO-1233zd and from about 0.05 to about 40 wt. % isopentane, more preferably from about 70 to about 95 wt. % tr ⁇ ms-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.
  • the tr ⁇ ms-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.
  • 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. % tr ⁇ ms-HFO-1233zd 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 ⁇ ms-HFO-1233zd and from about 50 to about 80 wt. % neopentane.
  • 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.
  • 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.
  • the cz ' s-HFO-1233zd/neopentane compositions of the present invention have a normal boiling point of about 8 °C ⁇ 1 °C.
  • 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. % trans- FO- ⁇ 233zd and from about 0.1 to about 5 wt. % cyclopentane, more preferably from about 97 to about 99.9 wt. % trans-HFO- ⁇ 233zd 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.
  • the tr «s-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 :
  • 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.
  • 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.
  • 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. % trans- FO- ⁇ 233zd and from about 0.1 to about 5 wt. % cyclopentene, more preferably from about 97 to about 99.9 wt. % tr ⁇ my-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.
  • the tra3 ⁇ 4s-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:
  • 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 ⁇ my-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.
  • 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.
  • 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.
  • 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.
  • the azeotrope-like composition comprises effective amounts of tr ⁇ ms-HFO-1233zd 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. % tr ⁇ ms-HFO-1233zd and about 0.01 to about 4 wt. % isohexane, and even more preferably from about 97 to about 99.99 wt. % tr ⁇ ms-HFO-1233zd and from about 0.01 to about 3 wt. % isohexane.
  • 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.
  • 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.
  • the czs-HFO-1233zd/isohexane compositions of the present invention have a normal boiling point of about 37°C ⁇ 1 °C.
  • the azeotrope-like composition comprises effective amounts of HFO-1233zd and a hydrohalocarbon.
  • 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).
  • the HFO-1233zd is tr ⁇ ms-HFO-1233zd.
  • the HFO-1233zd is cw-HFO-1233zd. rraws-HFO-1233zd/l-Chloropropane Azeotrope-Like Compositions:
  • the azeotrope-like composition comprises effective amounts of tr ⁇ ms-HFO-1233zd and l-chloropropane. More preferably, these binary azeotrope- like compositions consist essentially of about 96 to about 99.9 wt. % tr ⁇ ms-HFO-1233zd 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. % l-chloropropane.
  • the tra «s-HFO-1233zd/l-chloropropane compositions of the present invention have a normal boiling point of about 18°C ⁇ 1 °C at ambient pressure.
  • 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.
  • 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.
  • 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.
  • 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.
  • the tr ⁇ ms-HFO-1233zd/ trans- ⁇ ,2-DCE 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.
  • 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- 1,2-DCE, more preferably from about 55 to about 99.5 wt. % cz ' s-HFO-1233zd and about 0.5 to about 45 wt. % trans -1,2-DCE, 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.
  • the cz ' s-HFO-1233zd/ trans-1 ,2-DCE compositions of the present invention have a boiling point of about 37.0°C ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of tr «s-HFO-1233zd 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% trcms-EFO- ⁇ 233zd and from about 0.1 to about 1.5 wt. % methylal.
  • the tr ⁇ ms-HFO-1233zd I methylal compositions of the present invention have a normal boiling point of about 17.3°C ⁇ 1 °C at ambient pressure.
  • the azeotrope-like composition comprises effective amounts of tr ⁇ ms-HFO-1233zd 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. % tr ⁇ ms-HFO-1233zd 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.
  • 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.
  • 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. % tr ⁇ ms-HFO-1233zd 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.
  • 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:
  • the azeotrope-like composition comprises effective amounts of trans-HFO- ⁇ 233zd 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.
  • 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.
  • 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.
  • 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:
  • the azeotrope-like composition comprises effective amounts of tr ⁇ ms-HFO-1233zd, 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-l, 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 -1, 2-DCE and most preferably from about 95 to about 99.9 wt. % tr ⁇ ms-HFO-1233zd, from about 0.05 to about 5 wt. % methanol, and from about 0.05 to about 3 wt. % trans- 1,2-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:
  • the azeotrope-like composition comprises effective amounts of trans-HFO- ⁇ 233zd, 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.
  • the tra «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
  • 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. % trcms- ⁇ ,2-DCE; and most preferably from about 90 to about 96 wt. % tr ⁇ ms-HFO-1233zd, 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 mmHg.
  • 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-
  • the czs-HFO-1233zd/methanol/tr 3 ⁇ 4s-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 mmHg.
  • s-HFO-1233zd/petroleum ether Azeotrope-Like Compositions :
  • 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.
  • 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
  • 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.
  • 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 mmHg.
  • 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.
  • 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 mmHg.
  • 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.
  • 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.
  • 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.
  • these optional additives do not affect the basic azeotrope-like characteristic of the composition.
  • 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.
  • 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.
  • polystyrene polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE low density polyethylene
  • 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.
  • 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.
  • the blowing agent is characterized as a physical (i.e., volatile) blowing agent comprising the azeotrope-like mixture of the present invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • dispersing agents 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.
  • 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.
  • 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.
  • thermoset foams in general any thermoset polymer can be used, including but not limited to polyurethane, polyisocyanurate
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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-isocyanatophen
  • 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.
  • 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.
  • 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.
  • 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, ⁇ , ⁇ -dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, ⁇ , ⁇ -dimethylethanolamine, tetramethylpropanediamine,
  • methyltriethylenediamine and the like, and mixtures thereof.
  • non-amine polyurethane catalysts are used.
  • bismuth nitrate, lead 2- ethylhexoate, lead benzoate, ferric chloride, antimony trichloride and antimony glycolate are included as illustrative.
  • 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.
  • 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.
  • 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.
  • blowing agents or blowing agent blends as disclosed in this invention.
  • 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.
  • 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.
  • 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
  • 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.
  • the invention provides foamable compositions.
  • the foamable compositions of the present invention generally include one or more components
  • the foamable composition comprises thermoplastic materials, particularly thermoplastic polymers and/or resins. Examples of thermoplastic foam
  • thermoplastic foamable composition is an extrudable composition.
  • 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.
  • 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.
  • 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.
  • 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.
  • the sprayable composition is an aerosol.
  • 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.
  • cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides as well as medicinal materials, such as anti-asthma medications.
  • 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.
  • 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.
  • the cleaning composition is an aerosol.
  • 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.
  • 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.
  • 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 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 Example 27:
  • 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-pentane is added in small, measured increments.
  • 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.
  • 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.
  • 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.
  • 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 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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 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.
  • Example 31 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.
  • 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.
  • 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 :
  • Example 58 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.
  • the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping instead of spraying.
  • the azeotropic mixture cleaning agent is applied neat.
  • 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.
  • a Kester 1544 rosin Flux is deposited onto a stainless steel coupon.
  • the coupon is heated to about 400°F and then allowed to cool.
  • the coupon is then immersed in azeotrope- like mixtures comprising from about 0.6wt% to about 15wt% IPA and from about 99.4 wt% to about 85 wt% cis-1233zd according to each of the compositions identified in Table 19 for about 1.5 min.
  • the coupon is removed from the solvent, and the extent of removal of the rosin flux is determined gravimetrically from about 95% to about 100% for each of the mixtures.
  • Example 75A Example 75A:
  • a Kester 1544 rosin Flux was deposited onto a stainless steel coupon.
  • the coupon was heated to about 400°F and then allowed to cool.
  • the coupon was then immersed in an azeotropic mixture of 98 wt% cis-1233zd/2wt% methanol for about 1.5 min.
  • the coupon was removed from the solvent, and the extent of removal of the rosin flux was determined gravimetrically to be 100%.
  • Example 75BA A Kester 1544 rosin Flux is deposited onto a stainless steel coupon.
  • the coupon is heated to about 400°F and then allowed to cool.
  • the coupon is then immersed in azeotrope- like mixtures comprising from about 0.6 wt% to about 30 wt% methanol and from about 99.4 wt% to about 70 wt% cis-1233zd according to each of the compositions identified in Table 17 for about 1.5 min.
  • the coupon is removed from the solvent, and the extent of removal of the rosin flux is determined gravimetrically to be from about 95% to about 100% for each of the mixtures.
  • 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.
  • Example 85 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.
  • Example 112 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.
  • 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.
  • Example 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.
  • Example 154 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.
  • a solvent blend was prepared containing 98% by wt of tr 3 ⁇ 4y-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.
  • Example 181 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.
  • 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)
  • An ebulliometer consisteing 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.
  • 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.
  • 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.
  • 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 Compositions with cis-1233zd/methanol/t-l,2-DCE
  • 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 Compositions with cis-1233zd/methanol/isohexane
  • 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 at a pressure of about 756.5 mm Hg indicating the formation of an azeotrope-like ternary mixture.
  • 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 Compositions with cis-1233zd/methanol/cyclopentane
  • 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.
  • 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.
  • Example 31 The steps of Example 31 are generally repeated for Examples 217 - 228, except that the azeotrope-like mixture identified in the Table below is used instead of trans-HFO- ⁇ 233zd and methanol.
  • 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 58 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.
  • the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping instead of spraying.
  • the azeotropic mixture cleaning agent is applied neat.
  • 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 85 The steps of Example 85 are generally repeated for Examples 241 - 252, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO- ⁇ 233zd and methanol.
  • Example 112 The steps of Example 112 are generally repeated for Examples 253 - 264, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO- ⁇ 233zd and methanol.
  • Example 139 The steps of Example 139 are generally repeated for Examples 265 - 289, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO- ⁇ 233zd and trans- 1,2-DCE.

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  • Cleaning By Liquid Or Steam (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The present invention relates, in part, to binary azeotropic compositions and mixtures including chlorotrifluoropropene and petroleum ether and to ternary azeotropic compositions and mixtures including chlorotrifluoropropene, methanol, and a third component selected from isohexane, trans- 1,2-dichloroethylene, and petroleum ether. The present invention further relates to ternary azeotropic compositions and mixtures including chlorotrifluoropropene, cyclopentane, and a alcohol selected from methanol, ethanol, and isopropanol.

Description

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 Serial No. 61/779,950, filed March 13, 2013, the contents of which are incorporated herein by reference in its entirety. The present application is also a continuation-in-part (CIP) of US Application No. 13/593,323, filed August 23, 2012, which claims the priority benefit of US Provisional Application No. 61/642,907, filed May 4, 2012, 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
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 - C3 alcohol, a C5 - C6 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-trifluoropropene (particularly its cis isomer) and petroleum ether. Applicants have also discovered the formation of certain binary azeotrope-like compositions that are formed upon mixing l-chloro-3,3,3-trifluoropropene (particularly its cis isomer) and either methanol or isopropanoU (IP A), and the advantageous us of such azeotrope- like compositions in removing rosin solder flux, particularly and preferably form printed circuit boards and other electronic components, preferably by using a vapor degreasing-type process/system. 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 C1-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.
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 - C3 alcohol, a C5 - C6 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 transisomer, 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 CF3CC1=CH2, 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 - C3 alcohol. Preferably, the Ci - C3 alcohol is selected from the group consisting of methanol, ethanol, and isopropanol. In certain preferred embodiments, the HFO-1233zd is trans-HFO-\233zd. In certain other embodiments, the HFO-1233zd is cw-HFO-1233zd. Cw-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. In certain embodiments, and in particular embodiments involving solvent compositions and methods of removing soils, particularly rosin solder flux from printed circuit boards, the compositions of the present invention comprise from about 0.1 to about 5 weight percent methanol, and even more preferably from about one to about five weight percent methanol, and from about 95 weight percent to about 99.9 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent cz's-HFO-1233zd.
Preferably, the czs-HFO-1233zd/methanol compositions of the present invention have a boiling point of about 35.2 ± 1 °C at ambient pressure.
C¾-HFO-1233zd/IPA Azeotrope-Like Compositions:
In a preferred embodiment, the azeotrope-like composition comprises effective amounts of cz's-HFO-1233zd and isopropanol (IPA). More preferably, these binary azeotrope- like compositions consist essentially of about 85 to about 99.9 wt. % cz's-HFO-1233zd and from about 0.1 to about 15 wt. % IPA, and even more preferably from about 90 to about 99.9 wt. % cz's-HFO-1233zd and about 0.1 to about 10 wt. % IPA. In certain embodiments, and in particular to embodiments involving solvent compositions and methods of removing soils, particularly rosin solder flux from printed circuit boards, the compositions of the present invention comprise from about 0.1 to about 5 weight percent IP A, and even more preferably from about 1 to about 5 weight percent IP A, and from about 95 weight percent to about 99.9 weight percent, and even more preferably from about 95 weight percent to about 99 weight percent cz's-HFO-1233zd.
Preferably, the cz's-HFO-1233zd/IPA compositions of the present invention have a boiling point of about 38.4 ± 1 °C, and even more preferably 38.4 ± 0.1 at ambient pressure.
rraws-HFO-1233zd/Methanol Azeotrope-Like Compositions:
In a preferred embodiment, the azeotrope-like composition comprises effective amounts of trans-HFO-\233zd and methanol. 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. % methanol, more preferably from about 90 to about 99.95 wt. % trans-HFO-\233zd and about 0.05 to about 10 wt. % methanol, and even more preferably from about 95 to about 99.95 wt. % tr<ms-HFO-1233zd and from about 0.05 to about 5 wt. % methanol.
Preferably, the tr «s-HFO-1233zd/metfianol 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 czs-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. %
Figure imgf000014_0001
and from about 0.1 to about 4 wt. % ethanol.
Preferably, the tr ¾s-HFO-1233zd/ethanol compositions of the present invention have a normal boiling point of about 18.1 °C ± 1 °C at ambient pressure.
Cw-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. % tr<my-HFO-1233zd 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 C5 - C6 hydrocarbon. Preferably, the C5 - C6 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 is trans-HFO-\233zd. 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. % trans- FO-\233zd 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. s-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.
7>«ws-HFC)-1233zd/Isopentane Azeotrope-Like Compositions: In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and isopentane. More preferably, these binary azeotrope-like compositions consist essentially of about 60 to about 99.95 wt. % tr<ms-HFO-1233zd and from about 0.05 to about 40 wt. % isopentane, more preferably from about 70 to about 95 wt. % tr<ms-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 tr<ms-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. rraws-HFO-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. % tr<ms-HFO-1233zd 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<ms-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. % trans- FO-\233zd and from about 0.1 to about 5 wt. % cyclopentane, more preferably from about 97 to about 99.9 wt. % trans-HFO-\233zd 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 tr «s-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. % trans- FO-\233zd and from about 0.1 to about 5 wt. % cyclopentene, more preferably from about 97 to about 99.9 wt. % tr<my-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 tra¾s-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<my-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. Trans-Άΐ O-1233zd/Isohexane Azeotrope-Like Compositions:
In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd 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. % tr<ms-HFO-1233zd and about 0.01 to about 4 wt. % isohexane, and even more preferably from about 97 to about 99.99 wt. % tr<ms-HFO-1233zd 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 tr<ms-HFO-1233zd. In certain other embodiments, the HFO-1233zd is cw-HFO-1233zd. rraws-HFO-1233zd/l-Chloropropane Azeotrope-Like Compositions:
In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd and l-chloropropane. More preferably, these binary azeotrope- like compositions consist essentially of about 96 to about 99.9 wt. % tr<ms-HFO-1233zd 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. % l-chloropropane.
Preferably, the tra«s-HFO-1233zd/l-chloropropane compositions of the present invention have a normal boiling point of about 18°C ± 1 °C at ambient pressure.
7>flws-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-DCE 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- 1,2-DCE, more preferably from about 55 to about 99.5 wt. % cz's-HFO-1233zd and about 0.5 to about 45 wt. % trans -1,2-DCE, 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-1 ,2-DCE 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 tr «s-HFO-1233zd 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% trcms-EFO-\233zd and from about 0.1 to about 1.5 wt. % methylal.
Preferably, the tr<ms-HFO-1233zd I methylal compositions of the present invention have a normal boiling point of about 17.3°C ± 1 °C at ambient pressure.
Traws-HFC)-1233zd/methyl acetate Azeotrope-Like Compositions:
In a preferred embodiment, the azeotrope-like composition comprises effective amounts of tr<ms-HFO-1233zd 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. % tr<ms-HFO-1233zd 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. % tr<ms-HFO-1233zd 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 trans-HFO-\233zd 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 tr<ms-HFO-1233zd, 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-l, 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 -1, 2-DCE, and most preferably from about 95 to about 99.9 wt. % tr<ms-HFO-1233zd, from about 0.05 to about 5 wt. % methanol, and from about 0.05 to about 3 wt. % trans- 1,2-DCE.
Preferably, the
Figure imgf000027_0001
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 trans-HFO-\233zd, 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 tra«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. % trcms-\,2-DCE; and most preferably from about 90 to about 96 wt. % tr<ms-HFO-1233zd, 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 mmHg.
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 ¾s-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 mmHg. 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 mmHg.
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 mmHg.
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, 2nd 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 Polyurethanes 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 2nd 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-HFO- 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-HFO- 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 ro« -HFO-1233zd/n-Pentane compositions at ambient pressure
Wt. %trans- Wt %
Temp (°C) HFO-1233zd n-penta
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-HFO- 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 ft¾ms-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 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 neopentane is charged to the ebulliometer and then tr<ms-HFO-1233zd was added in small, measured increments. Temperature depression was observed when tr<ms-HFO-1233zd 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
/m«s-HFO-1233zd/ trans-l,2-DCE compositions at ambient pressure
Wt.% trans- Wt.%
T(°C) HFO-1233zd tr-l,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:
Figure imgf000048_0001
Azeotrope-like mixture Relative Concentration Boiling Data
1233zd : Other Point (°C) Table Component(s) (wt. %)
@ ambient pressure
tr<ms-HFO-1233zd + isopropanol 90-99.9/0.1-10 17.9 ± 1 8 tr<ms-HFO-1233zd + l-chloropropane 96-99.9/0.1-4 18± 1 9 tr<ms-HFO-1233zd + 2-chloropropane 94-99.99/0.01-6 17.8 ± 1 10 tr<my-HFO-1233zd + cyclopentene 95-99.9/0.1-5 18.1 ± 1 11 tr<ms-HFO-1233zd + cyclopentane 95-99.9/0.1-5 17.5 ± 1 12 tr<ms-HFO-1233zd + methylal 95-99.9/0.1-5 17.3 ± 1 13 tr<ms-HFO-1233zd + methyl acetate 90-99.9/0.1-5 17.5 ± 1 14 tra¾s-HFO-1233zd + HFC-365mfc 89-99.9/0.1-11 17.5 ± 1 15 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
Figure imgf000050_0001
isohexane (wt. %) trans-l233zd (wt. %) Boiling Point (°C)
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
Figure imgf000051_0001
EtOH (wt. %) trans-l233zd (wt. %) Boiling Point (°C)
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
Figure imgf000052_0001
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
Figure imgf000053_0001
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
Figure imgf000054_0001
-chloropropane (wt. %) trans-l233zd (wt. %) Boiling Point (°C)
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-W O-1233zd / cyclopentene compositions at ambient pressure
Figure imgf000055_0001
3.1 96.9 18.3
3.3 96.7 18.3
3.5 96.5 18.3
3.7 96.3 18.4
3.9 96.1 18.4
4.1 95.9 18.4
4.2 95.8 18.4
4.4 95.6 18.5
4.6 95.4 18.5
4.8 95.2 18.5
TABLE 12 ft¾ms-HFO-1233zd / cyclopentane compositions at ambient pressure
Figure imgf000056_0001
5.7 94.3 18.4
TABLE 13
#¾ms-HFO-1233zd / methylal compositions at ambient pressure
Figure imgf000058_0001
TABLE 14
#¾ms-HFO-1233zd / methyl acetate compositions at ambient pressure
Figure imgf000059_0001
TABLE 15
#¾ms-HFO-1233zd / HFC-365mfc compositions at ambient pressure
Figure imgf000059_0002
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
Figure imgf000060_0001
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
Figure imgf000061_0001
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
Figure imgf000062_0001
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
Figure imgf000064_0001
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
Figure imgf000066_0001
trans-12-DCE (wt. %) cw-1233zd (wt. %) Boiling Point (°C)
48.7 51.3 37.4
49.2 50.8 37.4
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
Figure imgf000067_0001
n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)
1.7 96.3 2.0 17.1
1.9 96.1 2.0 17.0
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 n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)
6.2 91.9 1.9 17.1
6.3 91.8 1.9 17.1
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 n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)
9.9 88.3 1.8 17.2
10.1 88.1 1.8 17.2
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
11.1 87.1 1.8 17.2
11.3 86.9 1.8 17.2
11.5 86.7 1.8 17.2
11.7 86.6 1.8 17.2
11.9 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 n-pentane (wt. %) trans-l233zd (wt. %) methanol (wt. %) Boiling Point (°C)
15.6 82.7 1.7 17.5
TABLE 23
ft¾ms-HFO-1233zd / methanol / #¾ms-l,2-DCE compositions at ambient pressure
Figure imgf000071_0001
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.
Figure imgf000072_0001
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 tra«s-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. Temp (°C) Wt.% trans-l233zd Wt.% Water
17.9 100 0
17.7 99.7 1.4
17.5 98.6 2.6
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 is 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.
Figure imgf000076_0001
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.
Figure imgf000078_0001
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 66A:
A Kester 1544 rosin Flux is deposited onto a stainless steel coupon. The coupon is heated to about 400°F and then allowed to cool. The coupon is then immersed in azeotrope- like mixtures comprising from about 0.6wt% to about 15wt% IPA and from about 99.4 wt% to about 85 wt% cis-1233zd according to each of the compositions identified in Table 19 for about 1.5 min. The coupon is removed from the solvent, and the extent of removal of the rosin flux is determined gravimetrically from about 95% to about 100% for each of the mixtures. Example 75A:
A Kester 1544 rosin Flux was deposited onto a stainless steel coupon. The coupon was heated to about 400°F and then allowed to cool. The coupon was then immersed in an azeotropic mixture of 98 wt% cis-1233zd/2wt% methanol for about 1.5 min. The coupon was removed from the solvent, and the extent of removal of the rosin flux was determined gravimetrically to be 100%.
Example 75BA: A Kester 1544 rosin Flux is deposited onto a stainless steel coupon. The coupon is heated to about 400°F and then allowed to cool. The coupon is then immersed in azeotrope- like mixtures comprising from about 0.6 wt% to about 30 wt% methanol and from about 99.4 wt% to about 70 wt% cis-1233zd according to each of the compositions identified in Table 17 for about 1.5 min. The coupon is removed from the solvent, and the extent of removal of the rosin flux is determined gravimetrically to be from about 95% to about 100% for each of the mixtures.
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.
Figure imgf000080_0001
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.
Figure imgf000082_0001
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
Figure imgf000083_0001
and trans- 1,2-DCE.
Figure imgf000083_0002
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.
Figure imgf000084_0001
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.
Figure imgf000086_0001
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
Figure imgf000087_0001
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.
Figure imgf000088_0001
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.
Figure imgf000089_0001
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.
Figure imgf000090_0001
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.
Figure imgf000092_0001
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 at a pressure of about 756.5 mm Hg indicating the formation of an azeotrope-like ternary mixture.
Figure imgf000093_0001
Compositions with cis-1233zd/pet ether wt% cis-1233zd wt % pet. ether B.P. (°C)
98.17 1.83 36.03
97.58 2.42 35.64
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 Compositions with cis-1233zd/pet ether wt% cis-1233zd wt % pet. ether B.P. (°C)
77.80 22.20 32.35
77.43 22.57 32.34
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 Compositions with cis-1233zd/pet ether
wt% cis-1233zd wt % pet. ether B.P. (°C)
64.44 35.56 32.27
64.18 35.82 32.28
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.
Figure imgf000097_0001
Compositions with cis-1233zd/methanol/cyclopentane
wt% cis-1233zd wt% methanol wt % cyclopentane B.P. (°C)
61.661 14.359 23.979 31.92
61.460 14.639 23.901 31.94
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.
Figure imgf000098_0001
Compositions with cis-1233zd/ethanol/cyclopentane
wt% cis-1233zd wt% ethanol wt % cyclopentane B.P. (°C)
71.326 8.557 20.118 34.45
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.
Figure imgf000099_0001
Examples 217 - 228:
The steps of Example 31 are generally repeated for Examples 217 - 228, 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.
Figure imgf000100_0001
Examples 229 - 240
For Examples 229-240, 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.
Figure imgf000101_0001
Examples 241 - 252
The steps of Example 85 are generally repeated for Examples 241 - 252, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.
Figure imgf000101_0002
244 cz's-1233zd + methanol + isohexane Yes
245 cz's-1233zd + methanol + trans-l,2-DCE Yes
246 cz's-1233zd + petroleum ether Yes
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 253 - 264, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.
Figure imgf000102_0001
Example Azeotrope-like Composition Good Solvency No.
264 trcms-\233zd + water Yes
Examples 265 - 289:
The steps of Example 139 are generally repeated for Examples 265 - 289, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and trans- 1,2-DCE.
Figure imgf000103_0001
275 cz's-1233zd + isopropanol + Yes Yes Yes cyclopentane
276 tr<ms-1233zd + methanol Yes Yes Yes
277 cz's-1233zd + methanol Yes Yes Yes
278 tr<ms-1233zd + ethanol Yes Yes Yes
279 cz's-1233zd + ethanol Yes Yes Yes
280 tr<ms-1233zd + isopropanol Yes Yes Yes
281 cz's-1233zd + isopropanol Yes Yes Yes
282 cz's-1233zd + n-pentane Yes Yes Yes
283 tr<ms-1233zd + n-hexane Yes Yes Yes
284 cz's-1233zd + n-hexane Yes Yes Yes
285 tr<ms-1233zd + isohexane Yes Yes Yes
286 cz's-1233zd + 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 290 - 301, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.
Figure imgf000104_0001
Example Azeotrope-like Composition Visually Clean No.
296 cz's-1233zd + methanol + cyclopentane Yes
297 cz's-1233zd + ethanol + cyclopentane Yes
298 cz's-1233zd + isopropanol + cyclopentane Yes
299 tr<ms-1233zd + isopentane Yes
300 trcms-\233zd + HFC-365mfc Yes
301 tr<ms-1233zd + water Yes
Examples 302 - 313:
The steps of Example 181 are generally repeated for Examples 302 - 313, except that the azeotrope-like mixture identified in the Table below is used instead of trans- FO-\233zd and methanol.
Figure imgf000105_0001
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.
Figure imgf000106_0001
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 tr<ms-1233zd + 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 trcms-\233zd + 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.
Figure imgf000107_0001
358 trans-\233zd + methanol/n-pentane Yes
359 tr<ms-1233zd + methanol/trans-l,2-DCE Yes
360 tr<ms-1233zd + ethanol Yes
361 tr<ms-1233zd + isopropanol Yes
362 tr<ms-1233zd + 1-chloropropane Yes
363 tr<ms-1233zd + 2-chloropropane Yes
364 tr<ms-1233zd + cyclopentane Yes
365 tr<ms-1233zd + cyclopentene Yes
366 tr<ms-1233zd + methylal Yes
367 tr<ms-1233zd + 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-1233zd + 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 trcms-\233zd + isopentane Yes
390 trcms-\233zd + HFC-365mfc Yes
391 trcms-\233zd + water Yes
Example 392 Solvent Degreasing of Solder Flux by Cis-1233zd/Methanol
The cleaning of parts to remove rosin solder flux in a vaopr degreasing-type operation is demonstrated for several of the compositions of the prepsent invention. In these tests, a small 2" by 1" stainless steel coupon is made to contain on its surface a Kester 1544 rosin flux in an amount and condition to simulate the presence of such material on a printed circuit board to be removed during the manufacturing thereof. The coupons are immersed in boiling solvent according each of the mixtures identified in the Table below at about ambient pressure for 2 minutes and then dried in the solvent vapors. This test is performed in small beakers with condenser coils near its lips which emulate conditions to represent a vapor degreaser. The coupons are visually observed for cleanliness and weight changes of the coupons are also noted. Cleaning results are given in the table below and it shows that it the flux is removed quite well.
Figure imgf000109_0001
SOLVENT
methanol (wt. %) cw-1233zd iwt. %) % Flux Removed
6.9 93.1 >95%
8.0 92.0 >95%
9.1 90.9 >95%
10.1 89.9 >95%
11.1 88.9 >95%
12.0 88.0 >95%
13.0 87.0 >95%
13.9 86.1 >95%
14.8 85.2 >95%
15.7 84.3 >95%
16.6 83.4 >95%
17.5 82.5 >95%
18.3 81.7 >95%
19.1 80.9 >95%
19.9 80.1 >95%
20.7 79.3 >95%
21.5 78.5 >95%
22.2 77.8 >95%
23.0 77.0 >95%
23.7 76.3 >95%
24.4 75.6 >95%
25.1 74.9 >95%
25.8 74.2 >95%
26.5 73.5 >95%
27.2 72.8 >95%
27.8 72.2 >95%
Example 393 Solvent Degreasing of Solder Flux by Cis-1233zd/IPA
The cleaning of parts to remove rosin solder flux in a vaopr degreasing-type operation is demonstrated for several of the compositions of the prepsent invention. In these tests, a small 2" by 1" stainless steel coupon is made to contain on its surface a Kester 1544 rosin flux in an amount and condition to simulate the presence of such material on a printed circuit board to be removed during the manufacturing thereof. The coupons are immersed in boiling solvent according each of the mixtures identified in the Table below at about ambient pressure for 2 minutes and then dried in the solvent vapors. This test is performed in small beakers with condenser coils near its lips which emulate conditions to represent a vapor degreaser. The coupons are visually observed for cleanliness and weight changes of the coupons are also noted. Cleaning results are given in the table below and it shows that it the flux is removed quite well. c/s-HFO-1233zd / isopropanol
Figure imgf000111_0001
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.

Claims

CLAIMS What is claimed is:
1. A method of removing rosin solder flux from a substrate comprising contacting said
substrate with a solvent composition comprising a binary azeotrope-like mixture consisting essentially of czs-l-chloro-3,3,3-trifluoropropene and methanol.
2. The method of claim 1 wherein said substrate is a printed circuit board having rosin solder flux on at least one surface, and wherein at least a substantial portion of said rosin solder flux is removed from said printed circuit board.
3. The method of claim 2 wherein said contacting step comprises contacting said printed circuit board with said solvent composition in the liquid phase, in the vapor phase, or combinations thereof.
4. The method of claim 3 wherein said liquid phase comprises a boiling liquid phase in
substantial equilibrium with said vapor phase.
5. The method of claim 3 wherein said azeotrope-like composition comprises from about 78 wt.% to about 99.9 wt. % c/s-HFO-1233zd and from about 0.1 wt.% to about 22 wt. % methanol.
6. A method of removing rosin solder flux from a substrate comprising contacting said
substrate with a solvent composition comprising a binary azeotrope-like mixture consisting essentially of czs-l-chloro-3,3,3-trifluoropropene and isopropanol.
7. The method of claim 6 wherein said substrate is a printed circuit board having rosin solder flux on at least one surface, and wherein at least a substantial portion of said rosin solder flux is removed from said printed circuit board.
I l l
8. The method of claim 7 wherein said contacting step comprises contacting said printed circuit board with said solvent composition in the liquid phase, in the vapor phase, or combinations thereof.
9. The method of claim 8 wherein said liquid phase comprises a boiling liquid phase in substantial equilibrium with said vapor phase.
10. The method of claim 8 wherein said azeotrope-like composition comprises from about 78 wt.% to about 99.9 wt. % cw-HFO-1233zd and from about 0.1 wt.% to about 22 wt. % methanol.
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KR20190083347A (en) * 2016-12-02 2019-07-11 허니웰 인터내셔날 인코포레이티드 How to dry HCFO-1233ZD
KR102652080B1 (en) * 2016-12-02 2024-03-28 허니웰 인터내셔날 인코포레이티드 How to Dry HCFO-1233ZD

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