JP2015507039A - An azeotrope-like composition comprising cis-1-chloro-3,3,3-trifluoropropene - Google Patents

Abstract

The invention comprises a second substantially selected from the group of cis-1-chloro-3,3,3-trifluoropropene and water, hexane, HFC-365mfc and perfluoro (2-methyl-3-pentanone). Partly related to azeotropes and azeotrope-like mixtures consisting of [Selection] Figure 1

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to US Provisional Patent Application No. 61 / 578,974, filed Dec. 22, 2011. The contents of the provisional patent application are incorporated herein by reference in their entirety.

  This application claims the benefit of priority of US Provisional Patent Application No. 61/109007, filed October 28, 2008, and is a continuation-in-part of US Application No. 12/259694, filed October 28, 2008. This is a continuation-in-part of US Application No. 13 / 298,452 filed on November 17, 2011, which is a continuation application of US Application No. 12/605609 filed on October 26, 2009. The contents of each of these are incorporated herein by reference in their entirety.

  The present invention relates generally to compositions comprising 1-chloro-3,3,3-trifluoropropene. More specifically, the present invention provides azeotrope-like compositions comprising cis-1-chloro-3,3,3-trifluoropropene and uses thereof.

  Fluorocarbon-based fluids such as chlorofluorocarbon ("CFC") or hydrochlorofluorocarbon ("HCFC") have desirable properties for industrial refrigerants, blowing agents, heat transfer media, solvents, gaseous dielectrics, and other applications . In these applications, it is particularly desirable to use single component fluids or azeotrope-like mixtures, i.e. those that are not substantially fractionated by boiling and evaporation.

  Unfortunately, suspicious environmental issues such as global warming and ozone depletion are believed to be attributed to some uses of these fluids, which currently limit their use. Hydrofluoroolefins (“HFO”) have been proposed as a possible alternative to such CFCs, HCFCs, and HFCs. However, the identification of new, environmentally friendly and unfractionated mixtures containing HFO is complicated by the fact that the formation of azeotropes is not easily predictable.

  Therefore, the industry is continually looking for new HFO-based mixtures that are acceptable and environmentally friendly substitutes for CFC, HCFC and HFC. The present invention fulfills these needs among others.

  Applicants have found that azeotropes and / or azeotrope-like compositions are cis-1-chloro-3,3,3-trifluoropropene (“cis-HFO-1233zd”), water, hexane, HFC. Formed by mixing with a second component selected from the group consisting of -365mfc (or 1,1,1,3,3-pentafluorobutane) and perfluoro (2-methyl-3-pentanone). discovered.

FIG. 1 provides a graph of cis-1233zd and water showing azeotropic behavior. In the figure, the weight percentage of water is provided on the X axis. FIG. 2 provides a graphical representation of cis-1233zd and n-hexane showing azeotropic behavior. In the figure, the weight percentage of n-hexane is provided on the X-axis. FIG. 3 provides a graph of cis-1233zd and HFC-365mfc showing azeotropic behavior. In the figure, a weight percent of HFC-365mfc is provided on the X axis. FIG. 4 provides a graph of cis-1233zd and perfluoro (2-methyl-3-pentanone) showing azeotropic behavior. In the figure, the weight percent of perfluoro (2-methyl-3-pentanone) is provided on the X axis.

  Preferred azeotropes or azeotrope-like mixtures of the present invention are used in some applications, such as as refrigerants, as blowing agents in the manufacture of insulating foams, and as solvents in some washings, and aerosols and other It exhibits properties that make it particularly desirable for other applications, such as in sprayable compositions. In particular, Applicants tend to have these compositions exhibit a relatively low global warming potential ("GWP"), preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150. I confirmed that there was.

  Accordingly, one aspect of the present invention is a group consisting essentially of cis-1-chloro-3,3,3-trifluoropropene and water, hexane, HFC-365mfc and perfluoro (2-methyl-3-pentanone). A composition comprising a binary azeotrope or azeotrope-like mixture consisting of a second component more selected. In certain preferred embodiments, the composition further comprises one or more of the following: co-blowing agents, co-solvents, active components, and / or lubricants, stabilizers, metal passivators, corrosion inhibitors, and combustion. Additives such as sex inhibitors. In certain preferred embodiments, nitromethane is included in the mixture as a stabilizer. In certain embodiments, nitromethane also contributes to the azeotrope or azeotrope-like properties of the composition.

  Another aspect of the present invention is to provide at least about 15% by weight of the azeotrope or azeotrope-like mixture described herein, optionally with an foaming agent, filler, vapor pressure modifier, combustion inhibitor. And / or a foaming agent comprising a stabilizer.

  Another aspect of the present invention provides solvents for use in steam degreasing, low temperature cleaning, wiping and similar solvent applications, including the azeotropes or azeotrope-like mixtures described herein.

  Other aspects of the invention are nebulizable, including the azeotropes or azeotrope-like mixtures described herein, active components, and optionally inert components and / or solvents and aerosol propellants. A composition is provided.

  Yet another aspect of the present invention is a closed cell foam comprising a cell wall based on polyurethane, polyisocyanurate or phenolic resin, and a cell gas placed inside at least a portion of the cell wall structure, The closed cell foam is provided wherein the cell gas comprises an azeotrope or azeotrope-like mixture as described herein.

In accordance with another aspect, there is provided a polyol premix comprising an azeotrope or azeotrope-like mixture as described herein.
In accordance with another aspect, an effervescent composition comprising an azeotrope or azeotrope-like mixture as described herein is provided.

  According to another aspect, (a) adding a blowing agent comprising an azeotrope or azeotrope-like composition provided herein to a foamable mixture comprising a thermosetting resin; (b) said foamable mixture To produce a thermoset foam; and (c) volatilize the azeotrope or azeotrope-like composition during the reaction.

  According to another embodiment, (a) adding a blowing agent comprising an azeotrope or azeotrope-like composition provided herein to a foamable mixture comprising a thermoplastic resin; (b) adding said foamable mixture Reacting to produce a thermoplastic foam; and (c) volatilizing the azeotrope or azeotrope-like composition during the reaction.

In accordance with another aspect, a thermoplastic foam is provided having a cellular wall comprising a thermoplastic polymer and a cellular gas comprising an azeotrope or azeotrope-like mixture as described herein. Preferably, the thermoplastic foam comprises a cellular gas having an azeotrope or azeotrope-like mixture as described herein, and is selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate or combinations thereof Having a cellular wall composed of a thermoplastic polymer.

  In accordance with another aspect, a thermosetting foam is provided having a cellular wall comprising a thermosetting polymer and a cellular gas comprising an azeotrope or azeotrope-like mixture as described herein. Preferably, the thermosetting foam is selected from a cellular gas having an azeotrope or azeotrope-like mixture as described herein and polyurethane, polyisocyanurate, phenolic resin, epoxy resin, or combinations thereof And a cell wall containing a thermosetting polymer.

In accordance with another aspect of the present invention, there is provided a refrigerant comprising an azeotrope or azeotrope-like mixture as described herein.
According to certain embodiments, the present invention relates to cis-HFO-1233zd and water, hexane, HFC-365mfc (or 1,1,1,3,3-pentafluorobutane) and perfluoro (2-methyl-3-pentanone). An azeotrope or azeotrope-like composition is provided, preferably consisting essentially of at least one compound component selected from the group consisting of:

  As used herein, the term “azeotrope-like” refers to a composition that is strictly azeotropic or generally behaves like an azeotropic mixture. An azeotropic mixture is a system of two or more components in which the composition of the liquid and the composition of the vapor are equal at a specified pressure and temperature. In practice, this means that the components of the azeotropic mixture have a constant boiling point or a substantially constant boiling point and generally cannot be separated thermodynamically during the phase change. The vapor composition formed by boiling or evaporation of the azeotropic mixture is the same or substantially the same as the original liquid composition. Thus, the concentration of components in the liquid and vapor phases of an azeotrope-like composition changes minimally, if at all, when the composition boils or otherwise evaporates. In contrast, when a non-azeotropic mixture is boiled or evaporated, the concentration of components in the liquid phase changes to a significant degree.

  As used herein with respect to components of an azeotrope or azeotrope-like composition, the term “consisting essentially of” means that the composition contains the indicated components in an azeotropic or azeotrope-like ratio. , Meaning that additional components may be included provided that they do not form a new azeotrope or azeotrope-like system. For example, an azeotrope or azeotrope-like mixture consisting essentially of two compounds, 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. It forms a binary azeotrope that may include one or more additional components.

As used herein, the term “effective amount” refers to the amount of each component that, in combination with other components, results in the formation of an azeotrope or azeotrope-like composition of the invention.
The term cis-HFO-1233zd as used herein with respect to components of an azeotrope or azeotrope-like mixture is the term cis-HFO for all isomers of HFO-1233zd in an azeotrope or azeotrope-like composition. It means that the amount of −1233zd 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 cis-HFO-1233zd component in the azeotrope or azeotrope-like composition of the present invention is substantially pure cis-HFO-1233zd.

  As used herein with respect to boiling point data, the term “ambient pressure” refers to the atmospheric pressure surrounding the associated medium. Generally, ambient pressure is 14.7 psia, but can vary +/− 0.5 psi.

  An azeotrope or azeotrope-like composition of the invention can be produced by combining an effective amount of cis-HFO-1233zd with one or more other ingredients, 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 method. For example, cis-HFO-1233zd and any second component provided herein as part of a batch or continuous reaction and / or process, or a combination of two or more such steps. And can be mixed, blended or otherwise combined manually and / or mechanically. In view of the disclosure herein, one of ordinary skill in the art will be able to readily prepare an azeotrope or azeotrope-like composition according to the present invention without undue experimentation.

Fluoropropenes such as CF ₃ CCl═CH ₂ are known methods such as the vapor phase fluorination of various saturated and unsaturated halogen-containing C3 compounds by catalysis, for example, US, each incorporated herein by reference. It can be produced by the methods described in Patent Publication Nos. 2889379; 4798818 and 4465786.

European Patent No. 974571, also incorporated herein by reference, contacts 1,1,1,3,3-pentafluoropropane (HFC-245fa) with a chromium-based catalyst at high temperature in the vapor phase. Or the preparation of 1,1,1,3-chlorotrifluoropropene by contacting with an alcohol solution of KOH, NaOH, Ca (OH) 2 or Mg (OH) 2 in the liquid phase. The final product is about 90% by weight trans isomer and 10% by weight cis. It is preferred to substantially separate the cis isomer from the trans form so that the resulting preferred form of 1-chloro-3,3,3-trifluoropropene is more abundant in the cis isomer. Since the cis isomer has a boiling point of about 40 ° C. as opposed to the trans isomer having a boiling point of about 20 ° C., these two are easily separated by a number of distillation methods known in the art. be able to. However, another method is batch distillation. According to this method, a mixture of cis and trans 1-chloro-3,3,3-trifluoropropene is placed in a reboiler. When the trans isomer is removed at the top of the column, the cis isomer remains in the reboiler. Distillation can also be carried out by continuous distillation, in which case the trans isomer is removed at the top and the cis isomer is removed at the bottom. This distillation process yielded about 99.9 +% of trans-1-chloro-3,3,3-trifluoropropene and 99.9 +% cis-1-chloro-3,3,3-trifluoropropene. Can be obtained.
cis-HFO-1233zd / water azeotrope-like composition In one embodiment, the azeotrope or azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and water. More preferably, these binary azeotrope-like compositions are substantially about 50 to about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 50% by weight water, more preferably About 70 to about 99.99 wt% cis-HFO-1233zd and about 0.01 to about 30 wt% water, even more preferably about 74 to about 99.99 wt% cis-HFO-1233zd and about 0 0.01 to about 26% by weight water.

Preferably, the cis-HFO-1233zd / water composition of the present invention has a normal boiling point of about 37 ° C. ± 1 ° C. at ambient pressure.
cis-HFO-1233zd / hexane azeotrope-like composition In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and n-hexane. More preferably, these binary azeotrope-like compositions comprise substantially about 70 to about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 30% by weight n-hexane, More preferably from about 90 to about 99.99% by weight cis-HFO-1233zd and from about 0.01 to about 10% by weight n-hexane, even more preferably from about 94 to about 99.99% by weight cis-HFO. -1233zd and about 0.01 to about 6 wt% n-hexane.

  In certain preferred embodiments, the composition comprises an effective amount of a binary azeotrope of cis-1-chloro-3,3,3-trifluoropropene and n-hexane. More preferably, such effective amounts include cis-1-chloro-3,3,3-trifluoropropene provided in an amount of about 94 to about 99.99 weight percent, and n-hexane is about 0.0. Provided in an amount of 01 to about 6 weight percent n-hexane; in other embodiments, the amount of cis-1-chloro-3,3,3-trifluoropropene is about 97 to about 99.99 weight percent. Wherein n-hexane is provided in an amount of about 0.01 to about 3 weight percent n-hexane; or cis-1-chloro-3,3,3-trifluoropropene is about 98- Provided in an amount of about 99.99 weight percent, and n-hexane is provided in an amount of about 0.01 to about 2 weight percent n-hexane.

Preferably, the cis-HFO-1233zd / n-hexane azeotrope or azeotrope-like composition of the present invention has a normal boiling point of about 37.8 ° C. ± 1 ° C. at ambient pressure.
cis-HFO-1233zd / HFC-365mfc azeotrope-like composition In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and HFC-365mfc. More preferably, these binary azeotrope-like compositions are substantially about 60 to about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 40% by weight HFC-365mfc, More preferably from about 62 to about 99.99% by weight cis-HFO-1233zd and from about 0.01 to about 38% by weight HFC-365mfc, even more preferably from about 63 to about 99% by weight cis-HFO-1233zd. And about 1 to about 37% by weight of HFC-365mfc.

  In certain preferred embodiments, the composition comprises a binary azeotrope of an effective amount of cis-1-chloro-3,3,3-trifluoropropene and HFC-365mfc. In certain aspects, such effective amounts include cis-1-chloro-3,3,3-trifluoropropene from about 63 to about 73 weight percent cis-1-chloro-3,3,3- An embodiment provided in an amount of trifluoropropene and about 27 to about 37 weight percent HFC-365mfc; or cis-1-chloro-3,3,3-trifluoropropene is about 67 to about 69 weight percent embodiments provided in an amount of cis-1-chloro-3,3,3-trifluoropropene and from about 31 to about 33 weight percent HFC-365mfc.

Preferably, the cis-HFO-1233zd / HFC-365mfc composition of the present invention has a normal boiling point of about 36.7 ° C. ± 1 ° C. at ambient pressure.
cis-HFO-1233zd / perfluoro (2-methyl-3-pentanone) azeotrope-like composition In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and perfluoro (2-methyl-3). -Pentanone). More preferably, these binary azeotrope-like compositions are substantially about 50 to about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 50% by weight perfluoro (2-methyl). -3-pentanone), more preferably from about 55 to about 99.99% by weight cis-HFO-1233zd and from about 0.01 to about 45% by weight perfluoro (2-methyl-3-pentanone), even more preferably About 60 to about 88 wt% cis-HFO-1233zd and about 12 to about 40 wt% perfluoro (2-methyl-3-pentanone).

Preferably, the cis-HFO-1233zd / perfluoro (2-methyl-3-pentanone) composition of the present invention has a normal boiling point of about 33.5 ° C. ± 2 ° C. at ambient pressure.
The azeotrope or azeotrope-like composition of the present invention may further include various optional additives such as, but not limited to, lubricants, stabilizers, metal passivators, corrosion inhibitors, combustion Sex inhibitors and the like can be included. Examples of suitable stabilizers include diene-based compounds and / or phenolic compounds and / or epoxides selected from the group consisting of aromatic epoxides, alkyl epoxides, alkenyl epoxides and combinations of two or more thereof. It is done. These optional additives preferably do not affect the basic azeotrope or azeotrope-like properties of the composition.
In another aspect of the present invention, there is provided a blowing agent comprising at least one azeotrope or azeotrope-like mixture as described herein. Polymer foams are generally of two general classes: thermoplastic foams and thermoset foams.

  Thermoplastic foams can generally be obtained by any method known in the art, such as Throne, Thermoplastic Foams, 1996, Sherwood Publishers, Hinkley, Ohio, or Klempner and Sendijartic, Polyfoam 2nd Edition. Hander Gardner Publications. Produced by the method described in Inc, Cincinnati, Ohio. For example, extruded thermoplastic foam can be obtained by passing a solution of blowing agent in a molten polymer formed in an extruder under pressure through an orifice at ambient temperature or pressure, or optionally under reduced pressure to assist in expansion of the foam. It can be prepared by an extrusion process that is extruded onto a moving belt. The blowing agent vaporizes and causes the polymer to expand. The polymer is simultaneously expanded and cooled under conditions that provide sufficient strength to maintain dimensional stability at a time corresponding to maximum expansion. Polymers used to produce extruded thermoplastic foams include, but are not limited to, polystyrene, polyethylene (HDPE, LDPE and LLDPE), polypropylene, polyethylene terephthalate, ethylene vinyl acetate, and mixtures thereof. In order to optimize the processing and properties of the foam, several additives such as, but not limited to, nucleating agents (eg talc), flame retardants, colorants, processing aids (eg wax), Crosslinkers, permeability modifiers and the like may be added to the molten polymer solution. Manufacturing additional processing steps such as irradiation to increase cross-linking, lamination of surface films to improve foam skin quality, trimming and design to achieve foam dimensional requirements, and other processes It can also be included in the process.

  Generally, the blowing agent can include a wide range of amounts of the azeotrope or azeotrope-like composition of the present invention. In general, however, it is preferred that the blowing agent composition comprises at least about 15% by weight of one or more of the present azeotrope or azeotrope-like composition. In certain preferred embodiments, the blowing agent composition comprises at least about 50% by weight of one or more of the azeotrope or azeotrope-like composition, and in certain embodiments, the blowing agent composition is substantially It consists of one or more of a boiling or azeotrope-like composition. In certain preferred embodiments, the blowing agent is in addition to the azeotrope or azeotrope-like mixture, one or more azeotropes, fillers, vapor pressure modifiers, combustion inhibitors, stabilizers, and the like Includes adjuvants.

  In certain preferred embodiments, the blowing agent is characterized as a physical (ie, volatile) blowing agent comprising the azeotrope or azeotrope-like mixture of the present invention. In general, the amount of blowing agent present in the blended mixture depends on the desired foam density of the final foam product and process pressure and solubility limits. For example, the proportion of blowing agent in parts by weight can be in the range of about 1 to about 45 parts, more preferably about 4 to about 30 parts blowing agent per 100 parts by weight polymer. The blowing agent is an additional component mixed with the azeotrope or azeotrope-like composition, for example, chlorofluorocarbons such as trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1- Hydrochlorofluorocarbons such as dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1,1,2-tetra Fluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-penta Hydrofluorocarbons such as fluorobutane (HFC-365mfc), propane, Emissions may include isobutane, hydrocarbons such as 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 decompose and release gases, typically carbon dioxide, carbon monoxide, nitrogen, hydrogen, ammonia, nitrous oxide, or mixtures thereof when exposed to temperature and pressure conditions in the extruder. Material. The amount of chemical blowing agent present depends on the desired final foam density. The proportion by weight of the total chemical blowing agent blend can range from less than 1 to about 15 parts, preferably from about 1 to about 10 parts blowing agent per 100 parts by weight polymer.

  In certain preferred embodiments, dispersants, foam stabilizers, surfactants and other additives can also be incorporated into the blowing agent compositions of the present invention. A surfactant is desired, but is preferably added to act as a foam stabilizer. Some representative materials are sold under the names DC-193, B-8404, and L-5340, which are generally U.S. Pat. Nos. 2,834,748, 2,917,480, each incorporated herein by reference. And polysiloxane polyoxyalkylene block copolymers such as those disclosed in US Pat. No. 2,846,458. Other optional additives for the blowing agent mixture include flame retardants or flame retardants such as tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri (2,3-dibromopropyl) -Phosphate, tri (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride and the like. For thermosetting foams, generally any thermosetting polymer can be used, including but not limited to polyurethane, polyisocyanurate, phenolic resin, epoxy resin, and combinations thereof. In general, these foams include one or more blowing agents including the azeotropes or azeotrope-like compositions of the present invention, and optionally other additives such as, but not limited to, cell stabilizers. Produced by combining chemically reactive components in the presence of solubility improvers, catalysts, flame retardants, auxiliary blowing agents, inert fillers, dyes, and the like.

  For the preparation of polyurethane or polyisocyanurate foams using the azeotrope or azeotrope-like composition described in the present 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, NY. In general, polyurethane or polyisocyanurate foams are isocyanates, polyols or mixtures of polyols, blowing agents or mixtures of blowing agents, and other materials such as catalysts, surfactants and optionally flame retardants, colorants or other additives. It is prepared by combining agents.

  For many applications, it is advantageous to provide the components for the polyurethane or polyisocyanurate foam in the form of a pre-blended formulation. Most typically, the foam formulation is preblended into two components. Isocyanates and optionally certain surfactants and blowing agents constitute the first component, commonly referred to as the “A” component. The polyol or polyol mixture, surfactant, catalyst, blowing agent, flame retardant and other isocyanate-reactive components constitute the second component, commonly referred to as the “B” component. Thus, polyurethane or polyisocyanurate foams are hand mixed when preparing small amounts of A and B subcomponents, and preferably blocks, slabs, laminates, in-situ foam panels and other products, spray application It is easily prepared by bringing together by any of the mechanical mixing techniques to form foams, froth, etc. If desired, other components such as flame retardants, colorants, auxiliary blowing agents, water and even other polyols can be added as a third stream to the mixing head or reaction site. However, it is most convenient to incorporate them all in one B component.

  Any organic polyisocyanate can be employed in the synthesis of polyurethane or polyisocyanurate foams, including aliphatic and aromatic polyisocyanates. Preferred as a class is an aromatic polyisocyanate. Typical aliphatic polyisocyanates are alkylene diisocyanates such as tri, tetra and hexamethylene diisocyanate, isophorene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate); typical aromatic polyisocyanates include m -And p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanate) Natophenyl) methene, bis (2-methyl-4-isocyanatophenyl) methane and the like.

  A preferred polyisocyanate is a polymethylene polyphenyl isocyanate, especially a mixture containing from about 30 to about 85 weight percent methylene bis (phenyl isocyanate), with the remainder of the mixture being a polymethylene polyphenyl polyisocyanate having a functionality greater than 2. Is included.

  Typical polyols used in the production of polyurethane foams include, but are not limited to, polyether polyols based on aromatic amino acids such as 2,4- and 2, condensed with ethylene oxide and / or propylene oxide. Those based on a mixture of 6-toluenediamine. These polyols have found utility in in situ foamed foams. Another example is based on polyether polyols based on aromatic alkylamino, for example on ethoxylated and / or propoxylated aminoethylated nonylphenol derivatives. These polyols generally have found utility in spray applied polyurethane foams. Another example is based on polyols based on sucrose, for example sucrose derivatives condensed with ethylene oxide and / or propylene oxide and / or mixtures of sucrose and glycerin derivatives.

  Examples of polyols used in polyurethane-modified polyisocyanurate foams include, but are not limited to, aromatic polyester polyols such as phthalate or terephthalate esters formed from polyols such as ethylene glycol, diethylene glycol or propylene glycol Based on a complex mixture of These polyols are used in rigid laminated boardstocks and can be blended with other types of polyols such as sucrose based polyols and used in other polyurethane foam applications as described above.

  Catalysts used in the production of polyurethane foams are typically tertiary amines such as, but not limited to, N-alkylmorpholines, N-alkyls in which the alkyl group is methyl, ethyl, propyl, butyl, etc. Alkanolamines, N, N-dialkylcyclohexylamines and alkylamines, and their isomeric forms; and heterocyclic amines. Typical but non-limiting examples are triethylenediamine, tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine N, N-dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, N, N-dimethylethanolamine, tetramethylpropanediamine, methyltriethylenediamine, and the like, and mixtures thereof.

  If desired, non-amine polyurethane catalysts are used. Typical of such catalysts are organometallic compounds such as bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium It is. Illustrative examples include bismuth nitrate, lead 2-ethylhexoate, lead benzoate, ferric chloride, antimony trichloride, and antimony glycolate. Preferred organotin classes include stannous salts of carboxylic acids such as stannous octoate, stannous 2-ethylhexoate, stannous laurate, and dibutyltin diacetate, dibutyltin dilaurate, diacetic acid Examples thereof include dialkyltin salts of carboxylic acids such as dioctyltin.

  In the preparation of polyisocyanurate foam, a trimerization catalyst is used for the purpose of converting the blend into polyisocyanurate-polyurethane foam in combination with excess A component. The trimerization catalyst employed may be any catalyst known to those skilled in the art, such as, but not limited to, glycine and tertiary amine trimerization catalysts and alkali metal carboxylates and various It can be a mixture of types of catalysts. Preferred species within this class are potassium acetate, potassium octoate, and N- (2-hydroxy-5-nonylphenol) methyl-N-methylglycinate.

  Dispersants, foam stabilizers, and surfactants can be incorporated into the blend. The surfactant is generally a polysiloxane polyoxyalkylene block copolymer such as those disclosed in US Pat. Nos. 2,834,748, 2,917,480 and 2,846,458, which are incorporated herein by reference.

  Other optional additives for blends include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) Mention may be made of flame retardants such as phosphates, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride and the like. Other optional components can include 0 to about 3 percent water, which chemically reacts with the isocyanate to yield carbon dioxide. This carbon dioxide acts as an auxiliary blowing agent.

  Mixtures also include blowing agents or blowing agent blends disclosed in the present invention. Generally speaking, the amount of blowing agent present in the blended mixture depends on the desired foam density of the final polyurethane or polyisocyanurate foam product. The proportion by weight of the total blowing agent blend can range from 1 to about 45 parts, preferably from about 4 to about 30 parts blowing agent per 100 parts polyol.

The density of the polyurethane foam produced is about 0.5 pounds per cubic foot to about 40 pounds per cubic foot, preferably about 1.0 to 20.0 pounds per cubic foot, most preferably per cubic foot. It can be about 1.5 to 6.0 pounds. The resulting density is a function of the amount of blowing agent or blowing agent mixture disclosed in the present invention present in the A and / or B component or added during the preparation of the foam.
Foams and foamable compositions A particular embodiment of the present invention is a foam comprising a foam wall based on polyurethane, polyisocyanurate or phenolic resin and a foam gas placed inside at least a portion of the foam, Includes the foam, wherein the bubble gas comprises an azeotrope-like mixture as described herein. In certain embodiments, the foam is an extruded thermoplastic foam. Preferred foams are 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 about 1 pound per cubic foot. It has a density of 6.0 pounds. Foam density is the amount of blowing agent or blowing agent mixture present in the molten polymer (ie azeotrope-like mixture and any auxiliary blowing agent such as carbon dioxide, chemical blowing agent or other co-blowing agent). It is a function. These foams are generally rigid, but can be made with various grades of softness to meet end use requirements. The foam can have a closed cell structure, an open cell structure, or a mixture of open and closed cells, with a closed cell structure being preferred. These foams are used in a variety of well-known applications such as, but not limited to, thermal insulation, flotation, packaging, void filling, craft and decoration, and shock absorption.

  In another aspect, the present invention provides a foamable composition. The foamable composition of the present invention generally comprises at least one azeotrope described herein with one or more components capable of forming foams, such as compositions based on polyurethanes, polyisocyanurates and phenolic resins. And a foaming agent containing the mixture. In certain embodiments, the foamable composition comprises a thermoplastic material, especially a thermoplastic polymer and / or resin. Examples of thermoplastic foam components include polyolefins such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET), and foams formed from them, preferably low density foams. In certain embodiments, the thermoplastic foamable composition is an extrudable composition.

In certain embodiments, a method for producing such foam is provided. One skilled in the art will recognize that the order and method of forming the foaming agent and / or adding to the foamable composition generally will not affect the feasibility of the present invention, especially in light of the disclosure contained herein. You will understand. For example, in the case of an extrudable foam, the various components of the blowing agent can be premixed. In certain embodiments, the components of the foamable composition are not mixed prior to introduction into the extrusion apparatus or added to the same location on the extrusion apparatus. Thus, in certain aspects, it may be desirable to introduce one or more components of the blowing agent to a first location in the extruder that is upstream of the addition site of the other one or more components of the blowing agent; In this way, the components are expected to come together and / or act more effectively in the extruder. In certain other embodiments, two or more components of the blowing agent are pre-combined and introduced directly into the foamable composition, or introduced together as part of the premix, and then the other of the foamable composition. Add more to the part.
Sprayable Composition In a preferred embodiment, the azeotrope-like composition of the present invention can be used as a solvent in the sprayable composition, alone or in combination with other known propellants. The solvent composition comprises an azeotrope-like composition of the invention, more preferably consists essentially of the azeotrope-like composition of the invention, and even more preferably from the azeotrope-like composition of the invention. Become. In certain embodiments, the sprayable composition is an aerosol.

In certain preferred embodiments, sprayable compositions are provided comprising a solvent as described above, an active component, and optionally other components such as an inert component, a solvent, and the like.
Suitable active materials to spray include, without limitation, pharmaceutical materials such as deodorants, perfumes, cosmetic materials such as hair sprays, cleaning solvents, lubricants, insecticides, and anti-asthma drugs. As used herein, the term pharmaceutical material is intended to encompass any and all materials that are effective or at least considered effective in connection with therapeutic, diagnostic, analgesic and similar treatments. , In its broadest sense. Thus, for example, drugs and biologically active substances are included.
Solvents and cleaning compositions In other embodiments of the present invention, various soils such as mineral oil, rosin-based flux, silicone oil, lubricants, etc. are wiped, vapor degreased, flushed or otherwise from various substrates. The azeotrope or azeotrope-like composition described herein can be used as a solvent for cleaning by means. In certain preferred embodiments, the cleaning composition is an aerosol.

  The invention is further illustrated in the following examples. The examples are intended to be illustrative and are not intended to be limiting in any way. In a related example, a general-type boiling point measuring device described by Swietolslowski in his book “Ebulliometric Measurements” (Reinhold, 1945) was used.

Example 1-cis-HFO-1233zd / water azeotrope-like composition A boiling point measuring device comprising a vacuum jacketed tube equipped with a condenser on top and equipped with a quartz thermometer or a thermistor was used. About 10 cc of cis-HFO-1233zd was placed in the boiling point measuring device and then water was added in small measured increments. As shown in Table 1 below, compositions comprising about 73 to about 84 weight percent cis-HFO-1233zd had boiling point changes of 0.4 ° C. or less. Therefore, the composition exhibited azeotrope and / or azeotrope-like properties over at least this range.

Example 2-cis-HFO-1233zd / hexane azeotrope-like composition A boiling point measurement apparatus consisting of a vacuum jacketed tube equipped with a condenser on top and equipped with a quartz thermometer or a thermistor was used. After about 10 cc of cis-HFO-1233zd was placed in the boiling point measurement apparatus, n-hexane was added in small measured increments. As shown in Table 2 below, the composition comprising about 99.99 to about 94.33 weight percent cis-HFO-1233zd had a boiling point change of about 0.1 ° C. or less. Therefore, the composition exhibited azeotrope and / or azeotrope-like properties over at least this range.

Example 3-cis-HFO-1233zd / HFC-365mfc azeotrope-like composition A boiling point measuring device consisting of a vacuum jacketed tube with a condenser on top and equipped with a quartz thermometer or thermistor was used. After about 10 cc of cis-HFO-1233zd was placed in the boiling point measurement apparatus, HFC-365mfc was added in small measured increments. As shown in Table 3 below, compositions comprising about 63 to about 84 weight percent cis-HFO-1233zd had boiling point changes of 0.5 ° C. or less. Therefore, the composition exhibited azeotrope and / or azeotrope-like properties over at least this range.

Example 4-cis-HFO-1233zd / perfluoro (2-methyl-3-pentanone) azeotrope-like composition Boiling point consisting of a vacuum jacketed tube with a condenser on top and equipped with a quartz thermometer or thermistor A measuring device was used. After about 10 cc of cis-HFO-1233zd was placed in the boiling point measurement apparatus, perfluoro (2-methyl-3-pentanone) was added in small measured increments. As shown in Table 4 below, compositions comprising about 59 to about 65 weight percent cis-HFO-1233zd had boiling point changes of 0.2 ° C. or less. Therefore, the composition exhibited azeotrope and / or azeotrope-like properties over at least this range.

Examples 5-8
For each of the following compositions, an azeotrope or azeotrope-like mixture is filled into an aerosol can. The aerosol valve is crimped in place and HFC-134a is added through the valve to achieve an in-can pressure of about 20 PSIG. The mixture is then sprayed onto the surface to indicate whether the azeotropic mixture is useful as an aerosol. Optionally, the aerosol has a different co-aerosol or no co-aerosol and is optionally selected from the group consisting of deodorants, fragrances, hair sprays, cleaning solvents, lubricants, insecticides, and pharmaceutical materials. Having at least one active component.

Examples 9-12
For each of the following compositions, an azeotrope or azeotrope-like mixture is filled into an aerosol can. The aerosol valve is crimped in place and HFC-134a is added through the valve to achieve an in-can pressure of about 20 PSIG. The mixture is then sprayed onto a metal coupon soiled with solder flux. Remove the flux and evaluate the coupon to see if the coupon is visually clean and whether the azeotropic mixture is useful as a solvent. If desired, the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping rather than spraying. If desired, the azeotropic mixture detergent is applied neat by itself. If desired, the material to be cleaned is changed from solder flux to mineral oil, silicon oil, or other lubricants.

Examples 13-16
For each of the following compositions, an azeotrope or azeotrope-like mixture was prepared, silicone oil was mixed with the blend, and the solvent was evaporated. If a thin coating of silicone oil remains on the coupon, this indicates that the solvent blend can be used for silicone oil deposition on various substrates.

Examples 17-20
For each of the following compositions, an azeotrope or azeotrope-like mixture is prepared and the mineral oil is mixed with the blend. If the mineral oil is evenly distributed throughout the blend, this indicates that the azeotrope or azeotrope-like composition can be used as a solvent.

Examples 21-24
For each of the following compositions, an azeotrope or azeotrope-like mixture is prepared and used as a blowing agent to prepare closed cell polyurethane foam and closed cell polyisocyanate foam. The foam gas of the resulting foam is analyzed to determine whether it contains at least a portion of the azeotropic mixture.

Examples 25-28
For each of the following compositions, an azeotrope or azeotrope-like mixture is prepared and several stainless steel coupons are soiled with mineral oil. These coupons are then immersed in these solvent blends and the coupons are observed to ascertain whether the azeotropic mixture has removed oil in a short time.

Examples 29-32
Prepare a solvent blend for the azeotrope or azeotrope-like mixture of each of the following compositions. Kester 1544 rosin solder flux is placed on a stainless steel coupon and heated to about 300-400 ° F. This simulates contact with wave solder that is commonly used to solder electronic components in the manufacture of printed circuit boards. The coupon is then immersed in the solvent mixture and removed without rinsing after 15 seconds. Thereafter, the coupons were visually inspected to determine if they were clean.

Examples 33-36
A measured amount of commercial solder paste is applied to the printed circuit board with a brush and then reflowed as is done in a commercial soldering operation. The circuit board is immersed in a beaker using 100% of the following azeotropic solvent blend to clean the board: As shown, after operation, each substrate appears visually clean.

Examples 37-40
After soiling the fabric pieces with standard mineral oil, the fabric is washed with a 100% solution of the following azeotropic solvent blend to simulate a dry cleaning operation. After operation, the fabric is visually clean. This indicates that these solvent blends can be used for dry cleaning applications.

Examples 41-44
Prepare a solvent blend for the azeotrope or azeotrope-like mixture of each of the following compositions. Mineral oil or other contaminants, such as refrigerant oil, silicone oil, particulates or other residue, are distributed within lines, heat exchangers, valves or other partially sealed parts. The azeotrope or azeotrope-like mixture is then combined with a propellant or pressurized in several ways, such as with nitrogen in the container. The azeotrope or azeotrope-like mixture is then flowed through the contaminated part to remove the contaminants. Gravimetric analysis shows that after flushing with an azeotrope or azeotrope-like mixture, all contaminants are almost completely removed.

  Having thus described several specific aspects of the present invention, various changes, modifications and improvements will readily occur to those skilled in the art. Such changes, modifications, and improvements apparently provided by the present disclosure are intended to be part of this description, even if not expressly presented herein, and are within the spirit and scope of the present invention. Intended to be. Accordingly, the foregoing description is by way of example only and is not limiting. The invention is limited only as defined in the following claims and the equivalents thereto.

Having thus described several specific aspects of the present invention, various changes, modifications and improvements will readily occur to those skilled in the art. Such changes, modifications, and improvements apparently provided by the present disclosure are intended to be part of this description, even if not expressly presented herein, and are within the spirit and scope of the present invention. Intended to be. Accordingly, the foregoing description is by way of example only and is not limiting. The invention is limited only as defined in the following claims and the equivalents thereto.
The present invention includes the following aspects.
[1] Two consisting essentially of cis-1-chloro-3,3,3-trifluoropropene and a second component selected from the group consisting of water and perfluoro (2-methyl-3-pentanone) A composition comprising a component azeotrope or azeotrope-like mixture.
[2] The azeotrope or azeotrope-like mixture is substantially about 50 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about The composition according to [1], comprising 50 weight percent water.
[3] The azeotrope or azeotrope-like mixture is substantially about 70 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about The composition according to [1], comprising 30 weight percent water.
[4] The azeotrope or azeotrope-like mixture is substantially about 74 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about The composition according to [1], comprising 26 weight percent water.
[5] The azeotrope or azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and water at about 36.7 ° C. ± 1 ° C. at ambient pressure. The composition according to [1], which has a boiling point.
[6] The azeotrope or azeotrope-like mixture is substantially about 50 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about The composition according to [1], comprising 50 weight percent perfluoro (2-methyl-3-pentanone).
[7] The azeotrope or azeotrope-like mixture is substantially about 55 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about The composition according to [1], comprising 45 weight percent perfluoro (2-methyl-3-pentanone).
[8] The azeotrope or azeotrope-like mixture is substantially about 60 to about 88 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 12 to about 40 weight percent. The composition according to [1], comprising perfluoro (2-methyl-3-pentanone).
[9] The azeotrope or azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and perfluoro (2-methyl-3-pentanone) at ambient pressure. The composition according to [1], which has a boiling point of about 33.5 ° C. ± 2 ° C.
[10] The composition according to [1], further comprising at least one adjuvant.
[11] The composition according to [10], wherein the auxiliary agent is selected from the group consisting of a co-foaming agent, a filler, a vapor pressure modifier, a combustion inhibitor, a stabilizer, a lubricant, and combinations thereof. A heat transfer composition containing an object.
[12] A heat transfer composition comprising at least about 50% by weight of the composition according to [1].
[13] A foaming agent comprising the composition according to [1].
[14] A foaming agent comprising at least about 5% by weight of the composition according to [1].
[15] A foamable composition comprising one or more components capable of forming a foam and the composition according to [1].
[16] A foam formed from the foamable composition according to [15].
[17] A closed cell foam comprising the foam according to [16].
[18] A sprayable composition comprising a material to be sprayed and a propellant comprising the composition according to [1].
[19] The sprayable composition according to [18], which is in the form of an aerosol.
[20] The sprayable composition according to [18], wherein the material to be sprayed is selected from the group consisting of cosmetics, cleaning solvents, lubricants, and pharmaceutical materials.
[21] A solvent composition comprising the composition according to [1].
[22] A binary azeotrope consisting essentially of cis-1-chloro-3,3,3-trifluoropropene and a second component selected from the group consisting of n-hexane and HFC-365mfc A composition comprising.
[23] The composition according to [22], wherein the azeotropic mixture substantially consists of cis-1-chloro-3,3,3-trifluoropropene and n-hexane.
[24] cis-1-Chloro-3,3,3-trifluoropropene is provided in an amount of about 97 to about 99.99 weight percent, and n-hexane is about 0.01 to about 3 weight percent of n- The composition of [23], provided in an amount of hexane.
[25] cis-1-Chloro-3,3,3-trifluoropropene is provided in an amount of about 98 to about 99.99 weight percent, and n-hexane is about 0.01 to about 2 weight percent of n- The composition of [23], provided in an amount of hexane.
[26] The composition of [23], wherein the azeotrope has a boiling point of about 37.8 ° C. ± 1 ° C. at ambient pressure.
[27] The composition according to [22], wherein the azeotropic mixture substantially consists of cis-1-chloro-3,3,3-trifluoropropene and HFC-365mfc.
[28] cis-1-chloro-3,3,3-trifluoropropene is about 63 to about 73 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 27 to about 37 weight percent. The composition of [27], provided in an amount of percent HFC-365mfc.
[29] cis-1-chloro-3,3,3-trifluoropropene is about 67 to about 69 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 31 to about 33 weight The composition of [27], provided in an amount of percent HFC-365mfc.
[30] The azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and HFC-365mfc and has a boiling point of about 36.7 ° C. ± 1 ° C. at ambient pressure. The composition according to [27].
[31] The composition according to [22], further comprising at least one adjuvant.
[32] The composition according to [31], wherein the auxiliary agent is selected from the group consisting of a co-foaming agent, a filler, a vapor pressure modifier, a combustion inhibitor, a stabilizer, a lubricant, and combinations thereof. A heat transfer composition containing an object.
[33] A heat transfer composition comprising at least about 50% by weight of the composition according to [22].
[34] A foaming agent comprising the composition according to [22].
[35] A foaming agent comprising at least about 5% by weight of the composition according to [22].
[36] A foamable composition comprising one or more components capable of forming a foam and the composition according to [22].
[37] A foam formed from the foamable composition according to [36].
[38] A closed-cell foam comprising the foam according to [37].
[39] A sprayable composition comprising a material to be sprayed and a propellant comprising the composition according to [22].
[40] The sprayable composition according to [39], which is in the form of an aerosol.
[41] The sprayable composition according to [39], wherein the material to be sprayed is selected from the group consisting of cosmetics, cleaning solvents, lubricants, and pharmaceutical materials.
[42] A solvent composition comprising the composition according to [22].

Claims (42)

A binary azeotrope consisting essentially of cis-1-chloro-3,3,3-trifluoropropene and a second component selected from the group consisting of water and perfluoro (2-methyl-3-pentanone) A composition comprising a mixture or an azeotrope-like mixture. The azeotrope or azeotrope-like mixture is substantially about 50 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about 50 weight percent. The composition according to claim 1, comprising: The azeotrope or azeotrope-like mixture is substantially about 70 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about 30 weight percent. The composition according to claim 1, comprising: The azeotrope or azeotrope-like mixture is substantially about 74 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about 26 weight percent. The composition according to claim 1, comprising: The azeotrope or azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and water and has a boiling point of about 36.7 ° C. ± 1 ° C. at ambient pressure. The composition of claim 1. The azeotrope or azeotrope-like mixture is substantially about 50 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about 50 weight percent. The composition according to claim 1, comprising perfluoro (2-methyl-3-pentanone). The azeotrope or azeotrope-like mixture is substantially about 55 to about 99.99 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 0.01 to about 45 weight percent. The composition according to claim 1, comprising perfluoro (2-methyl-3-pentanone). The azeotrope or azeotrope-like mixture is substantially about 60 to about 88 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 12 to about 40 weight percent perfluoro (2 The composition according to claim 1, comprising -methyl-3-pentanone). The azeotrope or azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and perfluoro (2-methyl-3-pentanone) at about 33. The composition of claim 1 having a boiling point of 5 ° C ± 2 ° C. The composition of claim 1 further comprising at least one adjuvant. 11. The composition of claim 10, wherein the adjuvant is selected from the group consisting of co-foaming agents, fillers, vapor pressure modifiers, combustion inhibitors, stabilizers, lubricants, and combinations thereof. Heat transfer composition. A heat transfer composition comprising at least about 50% by weight of the composition of claim 1. A foaming agent comprising the composition according to claim 1. A blowing agent comprising at least about 5% by weight of the composition of claim 1. A foamable composition comprising one or more components capable of forming a foam and the composition of claim 1. A foam formed from the foamable composition of claim 15. A closed cell foam comprising the foam of claim 16. A sprayable composition comprising a material to be sprayed and a propellant comprising the composition of claim 1. 19. A sprayable composition according to claim 18 in the form of an aerosol. 19. A sprayable composition according to claim 18, wherein the material to be sprayed is selected from the group consisting of cosmetics, cleaning solvents, lubricants, and pharmaceutical materials. A solvent composition comprising the composition according to claim 1. A composition comprising a binary azeotrope consisting essentially of cis-1-chloro-3,3,3-trifluoropropene and a second component selected from the group consisting of n-hexane and HFC-365mfc. object. 23. The composition of claim 22, wherein the azeotrope consists essentially of cis-1-chloro-3,3,3-trifluoropropene and n-hexane. cis-1-Chloro-3,3,3-trifluoropropene is provided in an amount of about 97 to about 99.99 weight percent, and n-hexane is in an amount of about 0.01 to about 3 weight percent n-hexane. 24. The composition of claim 23 provided in. cis-1-Chloro-3,3,3-trifluoropropene is provided in an amount of about 98 to about 99.99 weight percent, and n-hexane is in an amount of about 0.01 to about 2 weight percent n-hexane. 24. The composition of claim 23 provided in. 24. The composition of claim 23, wherein the azeotrope has a boiling point of about 37.8 ° C. ± 1 ° C. at ambient pressure. 23. The composition of claim 22, wherein the azeotrope consists essentially of cis-1-chloro-3,3,3-trifluoropropene and HFC-365mfc. The cis-1-chloro-3,3,3-trifluoropropene is about 63 to about 73 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 27 to about 37 weight percent HFC. 28. The composition of claim 27, provided in an amount of -365mfc. The cis-1-chloro-3,3,3-trifluoropropene is about 67 to about 69 weight percent cis-1-chloro-3,3,3-trifluoropropene and about 31 to about 33 weight percent HFC. 28. The composition of claim 27, provided in an amount of -365mfc. The azeotrope-like mixture consists essentially of cis-1-chloro-3,3,3-trifluoropropene and HFC-365mfc and has a boiling point of about 36.7 ° C. ± 1 ° C. at ambient pressure. Item 28. The composition according to item 27. 23. The composition of claim 22, further comprising at least one adjuvant. 32. The composition of claim 31, wherein the adjuvant is selected from the group consisting of co-foaming agents, fillers, vapor pressure modifiers, combustion inhibitors, stabilizers, lubricants, and combinations thereof. Heat transfer composition. 23. A heat transfer composition comprising at least about 50% by weight of the composition of claim 22. A foaming agent comprising the composition of claim 22. 23. A blowing agent comprising at least about 5% by weight of the composition of claim 22. 23. A foamable composition comprising one or more components capable of forming a foam and the composition of claim 22. A foam formed from the foamable composition of claim 36. 38. A closed cell foam comprising the foam of claim 37. 23. A sprayable composition comprising a material to be sprayed and a propellant comprising the composition of claim 22. 40. A sprayable composition according to claim 39 in the form of an aerosol. 40. The sprayable composition of claim 39, wherein the material to be sprayed is selected from the group consisting of cosmetics, cleaning solvents, lubricants, and pharmaceutical materials. A solvent composition comprising the composition of claim 22.

Images