TW201313660A - Azeotrope-like composition of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and 1-chloro-3,3,3-trifluoropropene - Google Patents

Abstract

Provided are azeotrope-like compositions comprising 1, 1, 1, 2, 2, 3, 3-heptafluoro-3-methoxypropane and E-1-chloro-3, 3, 3-trifluoropropene (E-1233zd) and uses thereof, including use in refrigerant compositions, refrigeration systems, blowing agent compositions, solvent, and aerosol propellants.

Description

Composition of azeotrope-like mixture of 1,1,1,2,2,3,3,-heptafluoro-3-methoxypropane and 1-chloro-3,3,3-trifluoropropene

The present invention relates to a class of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd). A composition of a boiling mixture and its use.

Halothane-based fluids have been found to be widely used in a variety of applications in the industry, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics. Due to suspected environmental issues associated with the use of some of these fluids, including the associated higher global warming potential, it is desirable to use fluids with low or even zero ozone depletion potential. Furthermore, it is desirable to use a single component fluid or azeotrope which is not fractionated upon boiling and evaporation. However, the identification of new, environmentally safe, non-fractionated mixtures is complicated by the fact that the formation of azeotropes is not readily predictable.

The industry is constantly seeking new halothane-based mixtures that offer alternatives and are considered as environmentally safer alternatives to CFCs and HCFCs.

The Montreal Protocol for the Protection of the Ozone Layer, signed in October 1987, ordered the phase-out of the use of chlorofluorocarbons (CFCs). Materials that are more "friendly" to the ozone layer, such as hydrofluorocarbons (HFCs), such as HFC-134a, replace chlorofluorocarbons. The latter compounds have been confirmed to be greenhouse gases, leading to global warming and are subject to the Kyoto Protocol signed in 1998 to address climate change. Alternative materials (hydrofluoropropene) appearing to be environmentally acceptable That has zero ozone depletion potential (ODP) and an acceptable low GWP.

Currently proposed for hydrofluorocarbons "Natural" refrigerants, such as HFC-134a based alternative refrigerant comprises HFC-152a, pure hydrocarbons such as butane or propane, or such as CO _2. Many of the suggested alternatives are flammable and/or have low energy efficiency. Therefore, new alternative refrigerants are being sought. Fluoroolefin materials such as hydrofluoropropenes and/or hydrochlorofluoropropenes have attracted interest as alternatives to HFCs.

The object of the present invention is to provide novel compositions which can function as refrigerants, heat transfer fluids, blowing agents, solvents, degreasers, degreasers, aerosols, etc., which provide unique Features to meet low or zero ozone depletion potential and lower global warming potential compared to current HFC.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The inventors have developed compositions that help meet the continuing need for alternatives to CFCs and HCFCs. According to certain embodiments, the present invention provides 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E A composition of an azeotrope-like mixture of -1233zd).

The preferred compositions of the present invention tend to be both non-flammable and tend to exhibit a lower global warming potential ("GWP"). Accordingly, applicants have recognized that such compositions can be used in a variety of applications with great advantages, including as targets for CFCs, HCFCs, and HFCs (such as HCFC123, HFC134a, HFC). Alternatives to 245fa, HFC 365mfc, etc. are used in refrigerants, aerosols, and other applications.

In addition, applicants have surprisingly realized that 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoro can be formed. Azeotrope-like composition of propylene (E-1233zd). Accordingly, in other embodiments, the present invention provides a method of producing a composition of an azeotrope-like mixture comprising mixing 1,1,1,2,2,3,3-heptafluoro- in an effective amount. 3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd) to produce azeotrope-like compositions.

Moreover, Applicants have recognized that the azeotrope-like compositions of the present invention exhibit a variety of properties that make them advantageous for use in or in refrigerant compositions as well as in blowing agents. Accordingly, in still other embodiments, the present invention provides refrigerant compositions and/or fluid foaming agents, and solvents, which comprise 1, 1, 1, 2, 2, 3, 3 A composition of an azeotrope-like mixture of heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd).

Azeotrope-like composition

As used herein, the term "azeotrope-like" is intended to include, in a broad sense, both a strictly azeotropic composition class and a composition class that behaves like an azeotrope. From a fundamental point of view, the thermodynamic state of a fluid is defined by pressure, temperature, liquid composition, and vapor composition. An azeotropic mixture is a system of two or more components wherein the liquid composition and vapor composition are the same at a specified pressure and temperature. In practice, this means that the various components of an azeotrope are azeotrope and cannot be separated during phase change. from.

The compositions of such azeotrope-like compositions of the present invention may include additional components that do not form a new azeotrope-like mixture system, or additional components that are not among the initial distillation fractions. The primary distillate fraction is the first fraction taken after the distillation column exhibits a steady state operation under the entire reflux conditions. One way of determining whether a component is added to form a new azeotrope-like mixture system (and thus outside of the present invention) is that the distillation is expected to separate a non-azeotropic mixture into its individual components. A sample of the composition of the components. If the mixture comprising the additional component is a non-azeotropic composition, the additional component will be fractionated from the components of the azeotrope-like mixture. If the mixture is azeotrope-like, a finite amount of the initial distillation fraction will be obtained which contains all of the components which are azeotrope or which behave as a single substance.

It is thus inferred that another feature of the azeotrope-like composition is the presence of a series of compositions comprising a plurality of identical components in varying proportions, the compositions being azeotrope-like or azeotrope-like. It is intended to cover all such compositions by the terms "azeotrope-like" and "azeotropic". As an example, it is well known that at a given pressure, the composition of a given azeotrope will vary at least slightly, such as the boiling point of the composition. Thus, an azeotrope of A and B represents a unique type of relationship, but one of the variable compositions depends on temperature and/or pressure. For compositions of azeotrope-like compositions, it is followed that there is a series of compositions comprising a plurality of identical components in varying proportions, the compositions being azeotrope-like. Designed to cover all of this with the term azeotrope-like mixture as used herein. Such a composition.

It is generally accepted in the art that it is not possible to predict the formation of an azeotrope. Applicants have unexpectedly disclosed 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene ( E-1233zd) forms an azeotrope-like composition.

According to certain preferred embodiments, the compositions of the azeotrope-like compositions of the present invention comprise, and preferably are, a major composition of effective azeotrope-like mixtures of 1,1,1,2,2 3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd). As used herein, the term "effective azeotrope-like amount" refers to the amount of each component that, when combined with another component, results in the formation of a composition of the azeotrope-like mixture of the present invention. Preferably, the compositions of the azeotrope-like compositions of the present invention comprise, and preferably comprise, a major composition of from about 99 weight percent to about 1 weight percent of 1,1,1,2,2,3 , 3-heptafluoro-3-methoxypropane and from about 1 weight percent to about 99 weight percent of E-1-chloro-3,3,3-trifluoropropene (E-1233zd). More preferably, the compositions of such azeotrope-like compositions comprise, and preferably are, predominantly from about 85 weight percent to about 10 weight percent of 1,1,1,2,2,3,3- Heptafluoro-3-methoxypropane and from about 15 weight percent to about 90 weight percent of E-1-chloro-3,3,3-trifluoropropene (E-1233zd). Even more preferably, the compositions of such azeotrope-like compositions comprise, and preferably comprise, from about 75 weight percent to about 20 weight percent of 1,1,1,2,2,3,3- Heptafluoro-3-methoxypropane and from about 25 weight percent to about 80 weight percent of E-1-chloro-3,3,3-trifluoropropene (E-1233zd). Unless otherwise indicated, the weights disclosed herein The percentages are based on 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E) in one composition. -1233zd) total weight.

The azeotrope-like composition described herein preferably has a boiling point of from about 10 ° C to about 34 ° C at a pressure of about 1.013 bar. In certain preferred embodiments, the compositions of the azeotrope-like compositions of the present invention have a boiling point of from about 12 ° C to about 28 ° C at a pressure of about 1.013 bar, and more preferably about 1.013 bar. The boiling point from about 14 ° C to about 26 ° C under pressure.

The compositions of the azeotrope-like compositions of the present invention are capable of reacting with an effective azeotrope-like mixture of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E. 1-Chloro-3,3,3-trifluoropropene (E-1233zd) was prepared in combination. Any of the methods known in the art for combining two or more components to form a composition can be adapted to the present invention for producing azeotrope-like compositions. In the method. For example, 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene (E-1233zd) can be artificially and / or mechanically mixing, blending, or other means of contact, as part of a batch or continuous reaction and / or method, or by combining two or more such steps. In view of the disclosure herein, those skilled in the art will be able to readily fabricate azeotrope-like compositions in accordance with the present invention without undue experimentation.

Composition additive

The compositions of the azeotrope-like compositions of the present invention may further comprise any of a wide variety of optional additives, including stabilizers, metal passivators, corrosion inhibitors, and the like.

In certain preferred embodiments, the compositions of the present invention further comprise a lubricant. Any of a variety of conventional lubricants can be used in the compositions of the present invention. An important requirement for this lubricant is that when used in a refrigerant system, sufficient lubricant must be returned to the compressor of the system so that the compressor is lubricated. Thus, the suitability of the lubricant for any given system is determined in part by the characteristics of the refrigerant/lubricant and in part by the characteristics of the system in which it is intended. Examples of suitable lubricants include mineral oils, alkyl benzenes, polyol esters, including polyalkylene glycols, PAG oils, and the like. Mineral oils (including paraffinic or naphthenic oils) are commercially available. Commercially available mineral oils include Witco LP 250 (registered trademark) from Witco, Zerool 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Vitco, and from Calumet's Calumet R015. Commercially available alkylbenzene lubricants include Zerol 150 (registered trademark). Commercially available esters include neopentyl glycol dicaprate, which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark). Other useful esters include phosphates, dibasic esters, and fluoroesters. Preferred lubricants include polyalkylene glycols and esters. Some of the more preferred lubricants include polyalkylene glycols.

Composition use

The compositions of the present invention have utility for a wide range of applications. For example, one embodiment of the invention relates to a refrigerant composition comprising a composition of the azeotrope-like mixture of the invention.

The refrigerant compositions of the present invention can be used in any of a variety of refrigeration systems In either case, the systems include air conditioning, refrigeration, heat pumps, chillers, heat engines, high temperature heat pumps, HVAC systems, and the like. Vapor compression refrigeration, air conditioning, or heat pump systems typically include an evaporator, a compressor, a condenser, and an expansion device. A vapor compression cycle reuses the refrigerant in multiple steps, resulting in a cooling effect in one step and a heating effect in a different step. A typical cycle can be briefly described as follows: a liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant is boiled in the evaporator at a low temperature to form a gas and cause cooling. The low pressure gas enters a compressor where it is compressed to increase its pressure and temperature. The higher pressure (compressed) gaseous refrigerant then enters the condenser where it condenses and releases its heat to the environment. The refrigerant is returned to the expansion device, by which the liquid expands from a higher pressure level in the condenser to a lower pressure level in the evaporator, the cycle being repeated as such. A heat pump system is typically used to move heat from one source (a "source") to another source (a "heat sink"); a reversible heat pump can be used for heating or cooling, depending on the operation. In HVACR operation, a heat pump is typically a vapor compression refrigeration unit that includes a reversible valve to change the direction of heat flow. Thermal engines, such as Rankine cycles or organic Rankine cycles, are typically used to convert thermal energy into mechanical work, particularly for power generation.

In certain preferred embodiments, the compositions of the present invention are used in refrigeration systems that are initially designed to use an HCFC refrigerant, such as, for example, HCFC 123. Preferred compositions of the invention tend to exhibit HCFC 123 as well A number of desirable properties of some other HFC coolants include as low or lower GWP as conventional HFC refrigerants, and as high or higher than such refrigerants. Moreover, the relatively constant boiling nature of the compositions of the present invention makes them even more desirable as refrigerants in many applications compared to certain conventional HFCs.

In certain other preferred embodiments, the compositions of the present invention are used in refrigeration systems that are initially designed to use CFC refrigerant. The preferred refrigeration compositions of the present invention can be used to include a lubricant (such as mineral oils, eucalyptus oils, polyalkylene glycol oils, and the like) conventionally used with CFC-refrigerants. In refrigeration systems, it can be used with other lubricants that are traditionally used with HFC refrigerants. As used herein, the term "refrigeration system" generally refers to any system or device that utilizes a refrigerant to provide cooling, or any component or portion of such a system or device. Such refrigeration systems include, for example, air conditioners, refrigerators, chillers, transport refrigeration systems, commercial refrigeration systems, and the like.

Any of a wide variety of methods for introducing the coolant composition of the present invention into a refrigeration system can be used in the present invention. For example, a method includes attaching a refrigerant container to a low pressure side of a refrigeration system and opening a compressor of the refrigeration system to draw the refrigerant into the system. In such embodiments, the refrigerant container can be placed on a ruler such that the amount of refrigerant composition entering the system can be monitored. The feed is stopped when the desired amount of refrigerant composition has been introduced into the system. Alternatively, a wide range of feed tools known to those skilled in the art are commercially available. Therefore, in view of the above disclosure, those skilled in the art will The refrigerant compositions of the present invention can be readily introduced into a refrigeration system in accordance with the present invention without undue experimentation.

According to certain other embodiments, the present invention provides a refrigeration system comprising a refrigerant of the present invention and a method of heating or cooling by condensing and/or evaporating a composition of the present invention. In certain preferred embodiments, a method for cooling an article according to the present invention comprises: condensing a refrigerant composition comprising the azeotrope-like composition of the present invention, and thereafter in the vicinity of an article to be cooled The refrigerant composition is allowed to evaporate. Some preferred methods for heating an article include condensing a refrigerant composition comprising the azeotrope-like composition of the present invention in the vicinity of the article to be heated, and thereafter evaporating the refrigerant composition. In view of the disclosure herein, those skilled in the art will be able to readily heat and cool articles in accordance with the present invention without undue experimentation.

In another embodiment, the compositions of the azeotrope-like compositions of the present invention can be used as propellants in sprayable compositions, either alone or in combination with known propellants. The propellant composition comprises, more preferably, a major composition, and even more preferably a composition thereof: an azeotrope-like composition of the invention. The active ingredient to be sprayed with inert ingredients, solvents, and other materials may also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol. Suitable active materials to be sprayed include, but are not limited to, cosmetic materials such as deodorants, perfumes, hair sprays, detergents, and polishes, as well as medical materials such as anti-asthma and anti-bad breath. drug.

Yet another embodiment of the present invention is directed to a blowing agent comprising the presenting agent A composition of one or more azeotrope-like mixtures of the invention. In other embodiments, the present invention provides foamable compositions, and is preferably a polyurethane and polyisocyanurate foam composition, and a method of making a foam. In such foam embodiments, one or more azeotrope-like compositions of the present invention are included as a blowing agent in a foamable composition, as is well known in the art, such compositions are It is preferred to include one or more additional components which are capable of reacting under suitable conditions and foaming to form a foam or a honeycomb structure. Any of the methods well known in the art can be used or adapted for use with the foam embodiment in accordance with the present invention.

Another embodiment of the present invention is directed to a method for preparing a foamed thermoplastic product, which is prepared by blending a plurality of components comprising a foamable polymer composition in any order. A foamable polymer composition. Typically, a foamable polymer composition is prepared by plasticizing a polymeric resin and then blending it into the components of a blowing agent composition under initial pressure. A common method of plasticizing a polymeric resin is thermal plasticizing, which involves heating a polymeric resin sufficiently to soften it for blending into a blowing agent composition. In general, thermal plasticization involves heating or heating a thermoplastic polymer resin to near its glass transition temperature (Tg), or melting temperature (Tm) for crystalline polymers.

Other uses of the azeotrope-like compositions of the present invention include use as solvents, detergents, and the like. Examples include vapor degreasing, precision cleaning, electronics cleaning, dry cleaning, solvent etching, and application The carrier solvent for the deposition of the slip agent as well as the release agent, as well as other solvents or surface treatments. Those skilled in the art will be able to readily adapt the compositions of the present invention for use in such applications without undue experimentation.

Instance

The invention is further illustrated in the following examples, which are intended to be illustrative and not limiting in any way.

Example 1

Gas-liquid equilibrium measurement for binary systems of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene It was carried out in a vacuum unit equipped with a sapphire tube, which was heated at 100 ° C with an oil bath. Once the temperature equilibration was reached, the unit was filled with a known amount of E-1-chloro-3,3,3-trifluoropropene, which had the lowest boiling point and the pressure at equilibrium was recorded. A known amount of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane is introduced into the unit, and the contents of the unit are mixed to accelerate the equilibrium. At equilibrium, a very small amount of sample is taken from the gaseous phase, along with the liquid phase for analysis by gas chromatography using a thermal detector. Figure 1 is the pressure (bar) and molar ratio of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane (for 1,1,1,2,2,3,3 A plot of the ratio of the ratio of -heptafluoro-3-methoxypropane and E-1-chloro-3,3,3-trifluoropropene) showing the azeotropy of the combinations of the invention The characteristics of the mixture.

The present invention has been shown and described herein with reference to the particular embodiments thereof, and is not intended to limit the scope of the appended claims. On the contrary, it is expected that those skilled in the art will be able to make various changes in the details, and such changes will still be in the spirit and scope of the claimed subject matter. It is intended that the scope of the patent application be interpreted accordingly.

Figure 1 is a graph of the ratio of pressure (bar) to molar ratio of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane.

Claims (15)

An azeotrope-like composition comprising an effective amount of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane and E-1-chloro-3,3,3- Trifluoropropene (E-1233zd). The azeotrope-like composition of claim 1, wherein the amount of 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane is as described above. The composition ranges from about 99 weight percent to about 1 weight percent, and the amount of E-1-chloro-3,3,3-trifluoropropene (E-1233zd) is from about 1 weight percent of the composition. Up to about 99 weight percent. A composition of an azeotrope such as described in claim 1 having a boiling point of from about 10 ° C to about 34 ° C at a pressure of about 1.013 bar. The composition of claim 1, further comprising a lubricant. The composition of claim 4, wherein the lubricant is selected from the group consisting of mineral oil, alkylbenzenes, polyol esters, polyalkylenes. A glycol, a polyvinyl ether, a poly-α-olefin, and a combination of two or more thereof. A heat transfer composition comprising a composition of an azeotrope as described in claim 1 of the patent application. A refrigeration, air conditioning, cooling, heat engine or heat pump system comprising the heat transfer composition of claim 6. A method for cooling an article, the method comprising condensing a heat transfer composition as described in claim 6 of the patent application, and thereafter making the system The refrigerant composition evaporates near the item to be cooled. A method for heating an article, the method comprising condensing a heat transfer composition as described in claim 6 of the invention in the vicinity of the article to be heated, and thereafter evaporating the refrigerant composition. A sprayable composition comprising a material to be sprayed and a propellant comprising a composition of an azeotrope as described in claim 1 of the patent application. The sprayable composition of claim 10, wherein the sprayable composition is an aerosol. A foaming agent comprising a composition of an azeotrope as described in claim 1 of the patent application. A foamable premix formulation comprising a blowing agent as described in claim 12 and a polyol. The foamable premix formulation of claim 13, further comprising at least one additive selected from the group consisting of surfactants, catalysts, and compatibilizers. Classes, flame retardants, UV stabilizers, and mixtures thereof. A solvent comprising a composition of an azeotrope as described in claim 1 of the patent application.