Patent Description:
Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol propellants, blowing agents, heat transfer media, and gaseous dielectrics. Because of the suspected environmental problems associated with the use of some of these fluids, including the relatively high global warming potentials associated therewith, it is desirable to use fluids having low or even zero ozone depletion potential, such as hydrofluorocarbons ("HFCs"). Thus, the use of fluids that do not contain chlorofluorocarbons ("CFCs") or hydrochlorofluorocarbons ("HCFCs") is desirable. Additionally, the use of single component fluids or azeotropic mixtures, which do not fractionate on boiling and evaporation, is desirable. Furthermore, some MFC fluids may have relatively high global warming potentials associated therewith, and it is desirable to use hydrofluorocarbon or other fluorinated fluids having as low global warming potentials as possible while maintaining the desired performance in use properties. Additionally, the use of single component fluids or azeotrope-like mixtures, which do not substantially fractionate on boiling and evaporation, is desirable. However, the identification of new, environmentally-safe, non-fractionating mixtures is complicated due to the fact that azeotrope formation is not readily predictable.

Documents <CIT>, <CIT>, <CIT> and <CIT> disclose hydrofluorocarbons suitable for use as heat transfer compositions.

The industry is continually seeking new fluorocarbon based mixtures that offer alternatives, and are considered environmentally safer substitutes for CFCs and HCFCs. Of particular interest are mixtures containing both hydrofluorocarbons and other fluorinated compounds, both of low ozone depletion potentials. Such mixtures and their uses are the subject of this invention.

The present inventors have developed several compositions that help to satisfy the continuing need for alternatives to CFCs and HCFCs. According to certain embodiments, the present invention provides the use of an azeotrope-like composition comprising <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoropropene ("HFO-1234yf') and (Z)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentafluoropropene ("HFO- 1225yeZ") as a heat transfer composition, for use in an air conditioning system, a refrigeration system or a heat pump, in accordance with claim <NUM>.

The preferred compositions of the invention lend both to be nonflammable preferably less than about <NUM>, more preferably less than about <NUM>, and even more preferably less than about <NUM>. Accordingly, applicants have recognized that such compositions can be used to great advantage in a number of applications, including as replacements for CFCs, such as dichlorodifluormethane (CFC-<NUM>), HCFCs, such as chlorodifluoromethane (HCFC-<NUM>), HFCs, such as
tetrafluoroethane (HFC-134a), and combinations of HFCs and CFCs, such as the combination of CFC-<NUM> and <NUM>,<NUM>-difluorethane (HFC-152a) (the combination CFC-<NUM>:HFC-152a in a <NUM>:<NUM> mass ratio being known as R-<NUM>) in refrigerant, aerosol, and other applications.

Additionally, applicants have recognized surprisingly that azeotrope-like compositions of HFO-1234yf and HFO-1225yeZ can be formed. Accordingly, described herein are methods of producing an azeotrope-like composition comprising combining HFO-1234ze and HFO- 1225yeZ in amounts effective to produce an azeotrope-like composition.

In addition, applicants have recognized that the azeotrope-like compositions of the present invention exhibit properties that make that make them advantageous for use as, or in, refrigerant compositions. Accordingly, in yet other embodiments, the present invention provides refrigerant compositions comprising an azeotrope-like composition of HFO-1234yf and HFO-1225yeZ. The term "HFO-<NUM>" is used herein to refer to all tetrafluoropropenes. Among
the tetrafluoropropenes are included HFO-1234yf and both cis- and trans-<NUM>, <NUM>,<NUM>, <NUM>-pentafluoropropene (HFO-1234ze). Likewise, the term "HFO-<NUM>" is used herein to refer to all pentafluoropropenes. Among the pentafluoropropenes are included (Z)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentafluoropropenee (HFO-1225yeZ).

Although the properties of the isomers of each of HFO-<NUM> and HFO- <NUM> differ in at least some respects, and while the present azeotrope-like compositions are based mainly on HFO-1234yf and HFO-1225yeZ, it is contemplated that the various other isomers may be may be present in certain embodiments in amounts which do not negate the essential nature of the azeotrope-like composition.

HFO-<NUM> compounds are known materials and are listed in Chemical Abstracts databases. The production of fluoropropenes such as CF<NUM>CH=CH<NUM> by catalytic vapor phase fluorination of various saturated and unsaturated halogen containing C<NUM> compounds is described in <CIT>; <CIT> and <CIT>. <CIT>, discloses the preparation of <NUM>,<NUM>,<NUM>,<NUM>- tetrafluoropropene by contacting <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-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)<NUM> or Mg(OH)<NUM> In addition, methods for producing compounds in accordance with the present invention are described generally in <CIT>.

In addition, applicants have recognized that the azeotrope-like compositions of the present invention exhibit properties that make that make them advantageous for use as, or in, numerous applications, including as heat transfer compositions (including as refrigerants in automotive air conditioning and heat pump systems, and in stationary air conditioning and refrigeration systems), blowing agents, propellants and sterilizing agents. Accordingly, in yet other embodiments, the present invention provides compositions and methods associated with these and other uses.

As used herein, the term "azeotrope-like" is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. From fundamental principles, 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 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 and cannot be separated during a phase change.

The azeotrope-like compositions of the invention may include additional components that do not form new azeotrope-like systems, or additional components that are not in the first distillation cut. The first distillation cut is the first cut taken after the distillation column displays steady state operation under total reflux conditions. One way to determine whether the addition of a component forms a new azeotrope-like system so as to be outside of this invention is to distill a sample of the composition with the component under conditions that would be expected to separate a non-azeotropic mixture into its separate components. If the mixture containing the additional component is nonazeotrope-like, the additional component will fractionate from the azeotrope-like components. If the mixture is azeotrope-like, some finite amount of a first distillation cut will be obtained that contains all of the mixture components that is constant boiling or behaves as a single substance.

It follows from this that another characteristic of azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions that are azeotrope-like or constant boiling. All such compositions are intended to be covered by the terms "azeotrope-like" and "constant boiling". As an example, it is well known that al differing pressures, the composition of a given azeotrope will vary at least slightly, as does the boiling point of the composition. Thus, an azeotrope of A and B represents a unique type of relationship, but with a variable composition depending on temperature and/or pressure. It follows that, for azeotrope-like compositions, there is a range of compositions containing the same components in varying proportions that are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein.

It is well-recognized in the art that it is not possible to predict the formation of azeotropes. , for example, <CIT> (column <NUM>, lines <NUM>-<NUM>) and <CIT> (column <NUM>, lines <NUM>-<NUM>). Applicants have discovered unexpectedly that HFO-1234ze and CF3I form azeotrope-like compositions.

According to certain preferred embodiments, the azeotrope-like compositions of the present invention comprise, and preferably consist essentially of, effective azeotrope-like amounts of HFO-1234yf and HFO-1225yeZ. The term "effective azeotrope-like 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. Preferably, the present azeotrope-like compositions comprise, and preferably consist essentially of, from about <NUM> to less than <NUM> weight percent HFO-1234yf and from greater than zero to about <NUM> weight percent of HFO-1225yeZ. Unless otherwise indicated, the weight percents disclosed herein are based on the total weight of HFO-1225yeZ and HFO-1234yf in a composition.

The azeotrope-like compositions described herein preferably have a boiling point of from about -<NUM> to about -<NUM> at a pressure of about <NUM> kPaa (<NUM> psia). In certain more preferred embodiments, the present azeotrope-like compositions
have a boiling point of from about -<NUM> to about -<NUM> at a pressure of about <NUM> kPaa (<NUM> psia), and in even more preferred embodiments, from about -<NUM> to about - <NUM> at a pressure of about <NUM> kPaa (<NUM> psia).

The azeotrope-like compositions of the present invention can be produced by combining effective azeotrope-like amounts of HFO-1234yf and HFO- 1225yeZ. 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 to produce an azeotrope-like composition. For example, HFO-1234yf and HFO-1225yeZ can be mixed, blended, or otherwise contacted 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.

The azeotrope-like compositions of the present invention may further include any of a variety of optional additives including lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability suppressants.

According to certain embodiments, the azeotrope-like compositions described herein further comprise a stabilizer. Any of a variety of compounds suitable for stabilizing an azeotrope-like composition of the present invention may be used. Examples of certain preferred stabilizers include stabilizer compositions comprising stabilizing 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.

As the term is used herein, "diene-based compound" refers to C3 - C5 dienes and to compounds formed by reaction of any two or more C3 - C5 dienes. In the case of diene-based compounds which are formed by a combination of C3- C5 dienes, the molecules which are combined can be the same or different. Certain of the preferred compositions comprise at least one diene-based compound in an amount effective under conditions of use to stabilize the iodocarbon against degradation. The type and nature of the diene-based compound(s) to be used may depend, to at least some degree, upon the particular iodocarbon compound(s) being used in the composition, the expected conditions of use of the compositions, and related factors.

It is generally contemplated that the amount of the diene-based stabilizer used in the compositions of the present invention can vary widely, depending upon factors such as the type and amount of compounds in the composition which may undergo degradation of conversion under the expected conditions of storage and/or use, such as may be the case, for example, in composition which include iodocarbon compounds, such as CF<NUM>l. In general, it is preferred to use diene based stabilizer in an effective amount relative to the amount of such compounds being used or intended for use in the composition. As used herein, the term "effective amount" refers to an amount of diene-based compound(s) which, when added to a composition comprising the relevant compound, such as trifluoroiodomethane, results in a stabilized composition wherein the compound degrades more slowly and/or to lesser degree relative to the same composition, under the same, or similar, conditions, but in the absence of the diene-based compounds. In the particular example of trifluoroiodomethane, one of the important potential breakdown products under certain severe conditions is trifluoromethane, which is formed by the substitution of hydrogen for iodine in the CF<NUM>I molecule. Similarly, hydrogen can be substituted for iodine in other iodocarbons, thereby forming compounds that can have GWP values greater than <NUM>. These breakdown products have the effect of raising the GWP of the refrigerant blends that use iodocarbons. The goal of having a low global warming potential is therefore defeated. An effective amount of stabilizer will reduce the amount of decomposition of the compound, particularly, iodocarbon such that the GWP of the refrigerant composition is below <NUM>. Even without the consideration of GWP values, breakdown of a component of a refrigerant composition is undesirable. Thus it is preferred that the level of the breakdown product described above be less than <NUM> wt. % of the total refrigerant composition. In certain preferred embodiments, the amount of the diene-based compound(s) is sufficient to result in a stabilized composition wherein at least one of the degradable compounds, such as iodocarbon compound(s), therein degrades more slowly and/or to a lesser degree relative to the same composition but in the absence of the diene-base compound, when tested according to SAE J1662 (issued June <NUM>)
and/or ASHRAE <NUM>-1983R standard tests. For example, in certain preferred embodiments, the amount of breakdown product, for example product formed by the substitution of hydrogen for iodine in the iodocarbon, is less than about <NUM> wt. % after the composition is maintained at about <NUM> (<NUM> °F) for about two weeks.

In certain preferred embodiments, the diene-based compounds are present <NUM> in the composition in amounts of from about <NUM> % to about <NUM> % by weight, more preferably from about <NUM> wt. % to about <NUM> wt. %, and even more preferably from about <NUM> wt. % to about <NUM> wt. %, based on the total weight of composition.

In preferred embodiments the diene-based compounds are selected from <NUM> the group consisting of allyl ethers, propadiene, butadiene, isoprene, terpenes such as myrcene, terpene derivatives and combinations of any two or more of these. As used herein, each of the compounds identified in the immediately preceding list is intended to include both substituted and unsubstituted forms of the identified compounds. In certain preferred embodiments, the diene-based
compounds comprise in major proportion, and even more preferably consist essentially of, propadiene.

In certain other preferred embodiments, the diene-based compounds comprise in major proportion, and even more preferably consist essentially of, terpenes, terpene derivatives or combinations of these. As used herein, the term <NUM> "terpene" means a compound, which is comprised of at least ten carbon atoms and contains at least one, and preferably at least two isoprene moieties. In many preferred embodiments, the terpene compound of the present in vention is formed from the reaction of at least two isoprene C5 units (CH2=C(CH3)-CH=CH2) (each unit being substituted or unsubstituted), and thus many of the terpene compounds of the present invention preferably have as at least <NUM> carbon atoms and include at least one isoprene moiety. As used herein, the term "isoprene
moiety" refers to any portion of a molecule, which includes a radical, which can be formed from substituted or unsubstituted isoprene. In certain preferred embodiments, unsubstituted terpenes are preferred.

In many preferred embodiments, the terpene compound described herein comprises at least one head-to-tail condensation product of modified or unmodified isoprene molecules. It is contemplated that any one or more terpene compounds are adaptable for use in accordance with the present invention and that those skilled in the art will be able, in view of the teachings contained herein, to select the number and type of terpene compound(s) for any particular application without undue experimentation. The preferred terpenes of the present invention are hydrocarbons having molecular formula (C<NUM>H<NUM>)n in a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted structure, with n preferably being from <NUM> to about <NUM>, and even more preferably <NUM> to <NUM>. Terpenes according to the present invention having the formula C<NUM>H<NUM> (including substituted forms) are sometimes referred to herein as monoterpenes, while terpenes having the formula C<NUM>H<NUM> (including substituted forms) are sometimes referred to herein as sesquiterpenes. Terpenes according to the present invention having the formula C<NUM>H<NUM> (including substituted forms) are sometimes referred to herein as diterpenes, while terpenes having the formula C<NUM>H<NUM> (including substituted forms) are sometimes referred to as triterpenes, and so on. Terpenes containing <NUM> or more carbons are usually formed by the fusion of two terpene precursors in a regular pattern. While it is contemplated that all such terpenes are adaptable for use in accordance with the present invention, the use of monoterpenes is generally preferred.

In certain preferred embodiments, the terpene compound(s) described herein comprise, preferably in major proportion, and even more preferably consist essentially of, one or more acyclic terpene compounds. Among the acyclic terpenes, it is contemplated that such compounds may be within the class of compounds identified as head-to-tail linked isoprenoids or within the class of compounds that are not joined in that manner. Acyclic terpenes which are preferred as described herein include myrcene (<NUM>-methyl-<NUM>-methyleneocta-<NUM>,<NUM>-diene), allo-cimene, beta-ocimene.

In certain embodiments, the terpene compounds described herein may comprise cyclic terpene compounds. Among the cyclic terpenes, mono-, bi-, tri-, or tetracyclic compounds having varying degrees of unsaturation are contemplated for use in accordance with the present invention.

Examples of terpene compounds adaptable for use as described include terebene, myrcene, limonene, retinal, pinene, menthol, geraniol, farnesol, phytol. Vitamin A<NUM>, terpinene, delta-<NUM> carene, terpinolene, phellandrene, fenchene, as well as blends thereof, including all their isomers.

Examples of terpene derivatives include oxygen-containing derivatives of terpenes such as alcohols, aldehydes or ketones containing hydroxyl groups or carbonyl groups, as well as hydrogenated derivates. Oxygen-containing derivatives of terpenes are sometimes referred to herein as terpenoids. In certain embodiments, the diene-based compounds described herein comprise the terpenoid Carnosic acid. Carnosic acid is a phenolic diterpene that corresponds to the empirical formula C<NUM>H<NUM>O<NUM>. It occurs naturally in plants of the Libiatae family. For instance, carnosic acid is a constituent of the species Salvia officinalis (sage) and Rosmarinus officinalis (rosemary) where it is mainly found in the leaves. Carnosic acid is also found in thyme and marjoram. It was discovered by <NPL>)] and by <NPL>)]. It was then positively identified in various other species of sage, such as for example Salvia canariensis [<NPL>)] or Salvia willeana [<NPL>)]. It is also present in Salvia triloba and Salvia sclarea.

Any suitable relative amount of the at least one diene-based compound and supplemental optional stabilizer compound(s) may be used. For example, in certain preferred embodiments the weight ratio of the diene-based compound(s) to other stabilizer compound(s) is in the range of from about <NUM>:<NUM> to about <NUM>:<NUM>. In more preferred embodiments, the weight ratio of diene-based compound(s) to the optional stabilizers is from about <NUM>:<NUM> to about <NUM>:<NUM>, more preferably from about <NUM>:<NUM> to about <NUM>:<NUM>, and even more preferably about <NUM>:<NUM>.

Preferred terpene stabilizers are disclosed in <CIT> (<CIT>).

Any of a variety of phenol compounds and/or epoxides is also suitable for use as stabilizers in the compositions described herein. While applicants do not wish to be bound by or to any theory of operation, it is believed that the present phenols act as radical scavengers in the CF<NUM>I compositions and thereby tend to increase the stability of such compositions. As used herein the term "phenol compound" refers generally to any substituted or unsubstituted phenol. Examples of suitable phenol compounds include phenols comprising one or more substituted or unsubstituted cyclic, straight-chain, or branched aliphatic substituent group, such as, alkylated monophenols including: <NUM>,<NUM>-di-tert-butyl-<NUM>-methylphenol; <NUM>,<NUM>-di- tert-butyl-<NUM>-ethylphenol; <NUM>,<NUM>-dimethyl-<NUM>-tertbutylphenol; tocopherol; hydroquinone and alkylated hydroquinones including: t-butyl hydroquinone; other derivatives of hydroquinone; hydroxylated thiodiphenyl ethers including: <NUM>,<NUM>'-thiobis (<NUM>-methyl-<NUM>-tert-butylphenol); <NUM>,<NUM>'-thiobis (<NUM> -methyl-<NUM>- tertbutylphenol); <NUM>,<NUM>'-thiobis (<NUM>-methyl-<NUM>-tert-butylphenol); alkylidene-bisphenols including: <NUM>,<NUM>'-methylenebis(<NUM>,<NUM>-di-tert-butylphenol); <NUM>,<NUM>'- bis(<NUM>,<NUM>-di-tert-butylphenol; derivatives of <NUM>,<NUM>- or <NUM>,<NUM>-biphenyldiols; <NUM>,<NUM>'- methylenebis(<NUM>-ethyl-<NUM>-tertbutylphenol); <NUM>,<NUM>'-methylenebis(<NUM>-methyl-<NUM>-tert- butylphenol); <NUM>,<NUM>,-butylidenebis(<NUM>-methyl-<NUM>-tertbutylphenol); <NUM>,<NUM>,- isopropylidenebis(<NUM>,<NUM>-di-tert-butylphenol); <NUM>,<NUM>'-methylenebis(<NUM>-methyl-<NUM>- nonylphenol); <NUM>,<NUM>'-isobutylidenebis(<NUM>,<NUM>-dimethylphenol); <NUM>,<NUM>'-melhylenebis(<NUM>- methyl-<NUM>-cyciohexylphenol), <NUM>,<NUM>- or <NUM>,<NUM>- biphenyldiols including <NUM>,<NUM>'-methylenebis(<NUM>-ethyl-<NUM>-tertbutylphenol), butylated hydroxy toluene (BHT), bisphenols comprising heteroatoms including: <NUM>,<NUM>-di-tert-. -dimethylamino- p-cresol; <NUM>,<NUM>-thiobis(<NUM>-tert-butyl-m-cresol); acylaminophenols; <NUM>,<NUM>- di-tert-butyl-<NUM>(N,N'-dimethylaminomethylphenol); sulfides including: bis(<NUM> - methyl-<NUM>-hydioxy-<NUM>-tert-butylbenzyl) sulfide; bis(<NUM>,<NUM>-di-tert-butyl-<NUM>-hydroxybenzyl)sulfide; as well as, phenolic UV absorb and light stabilizers. Certain preferred phenols include alkylated monophenols such as tocopherol, BHT, hydroquinones. Certain particularly preferred phenols include tocopherol Most phenols are commercially available. A single phenol compound and/or mixtures of two or more phenols may be used in the present compositions. Any of a variety of epoxides are suitable for use in the compositions described herein. While applicants do not wish to be bound by or to any theory of operation, it is believed that the epoxides described herein act as acid scavengers, particularly in compositions containing iodocarbon compounds such as CF<NUM>I and thereby tend to increase the stability of such compositions. A single aromatic epoxide and/or mixtures of two or more aromatic epoxides may be used in the present compositions.

Examples of suitable aromatic epoxides include those defined by the formula I below:
<CHM>
wherein: R is hydrogen, hydroxyl, alkyl, fluoroalkyl, aryl, fluoroaryl, or
<CHM>
and Ar is a substituted or unsubstituted phenylene or napthylene moiety. Certain preferred aromatic epoxides of Formula I include those wherein Ar is phenylene or phenylene substituted with one or more substituents including alkyls, alkenyls, alkynyls, aryls, alkylaryls, halogens, halogenated alkyls, halogenated alkenyls, halogenated alkynyls, halogenated aryls, halogenated arylalkyls, hydroxyls, heteroatom moieties. Examples of suitable compounds of Formula I wherein Ar is an unsubstituted or substituted phenylene include butylphenylglycidyl ether; pentylphenylglycidyl ether; hexylphenyl glycidyl ether; heptylphenylglycidyl ether; octyiphenylglycidyl ether; nonylphenylglycidyl ether; decylphenylglycidyl ether; glycidyl methyl phenyl ether; <NUM>,<NUM>-diglycidyl phenyl diether; <NUM>-methoxyphenyl glycidyl ether; derivatives thereof.

Certain other preferred aromatic epoxides of Formula I include those Certain other preferred aromatic epoxides of Formula I include those wherein Ar is napthylene or napthylene substituted with one or more substituents including alkyls, alkenyls, alkynyls, aryls, alkylaryls, halogens, halogenated alkyls, halogenated alkenyls, halogenated alkynyls, halogenated aryls, halogenated arylalkyls, hydroxyls, heteroatom moieties. Examples of suitable compounds of Formula I wherein Ar is an unsubstituted napthylene include naphthyl glycidyl ether; <NUM>,<NUM>-diglycidyl naphthyl diether; derivatives thereof.

Examples of other suitable aromatic epoxides include bisoxiranes, such as, <NUM>,<NUM>'[n5-heptadecafluorooctyl]<NUM>,3phenylene]bis[[<NUM>,<NUM>,2trifluoromethyl]ethylidene]oxymeth ylene] bisoxirane.

In certain preferred embodiments, the aromatic epoxides for use as described herein comprise an epoxide of Formula I wherein Ar is phenylene, substituted phenylene, napthylene, or substituted napthylene. More preferably,
the aromatic epoxides comprise an epoxide of Formula I wherein Ar is phenylene or substituted phenylene. Examples of certain more preferred aromatic epoxides include butylphenyl glycidyl ether.

Any of a variety of alkyl and/or alkenyl epoxides are suitable for use in the present compositions. Examples of suitable alkyl and alkenyl epoxides include those of those of Formula II:
<CHM>
wherein Ralk is a substituted or unsubstituted alkyl or alkenyl group. Certain preferred epoxides of Formula <NUM> comprise alkyl epoxide compounds wherein Ralk is an alkyl group having from about <NUM> to about <NUM> carbon atoms, more preferably from about <NUM> to about <NUM> carbon atoms, and wherein the alkyl may be unsubstituted or further substituted with one or more substituents including alkyls, alkenyls, alkynyls, aryls, alkylaryls, halogens, halogenated alkyls, halogenated alkenyls, halogenated alkynyls, halogenated aryls, halogenated arylalkyls, hydroxyls, heteroatom moieties. Examples of such preferred alkyl epoxides of Formula II include n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether, as well as, fluorinated and perfluorinated alkyl epoxides. Certain more preferred alkyl epoxides comprise hexanediol diglycidyl ether.

Certain other preferred epoxides of Formula II comprise alkenyl epoxide compounds wherein Raik is an alkenyl group having from about <NUM> to about <NUM> carbon atoms, more preferably from about <NUM> to about <NUM> carbon atoms, and wherein the alkenyl may be unsubstituted or further substituted with one or more substituents including alkyls, alkenyls, alkynyls, aryls, alkylaryls, halogens, halogenated alkyls, halogenated alkenyls, halogenated alkynyls, halogenated aryls, halogenated arylalkyls, hydroxyls, heteroatom moieties. Examples of such preferred alkenyl epoxides of Formula II include allyl glycidyl ether, fluorinated and perfluorinated alkenyl epoxidesMore preferred alkenyl epoxides include allyl glycidyl ether. A single alkyl epoxide or alkenyl epoxide and/or combinations of two or more thereof may be used in the present compositions.

In certain other preferred embodiments, the alkyl epoxide for use as an acid scavenger in the described composition comprises polypropylene glycol diglycidyl ether. Examples of polypropylene glycol diglycidyl ether suitable for use in as described includes the ether available commercially from SACHEM, Europe.

In addition, in certain embodiments, the epoxide for use as described comprises combinations of two or more aromatic, alkyl, and/or alkenyl substituents. Such epoxides are referred to generally as "multisubstituted epoxides.

According to certain preferred embodiments, the stabilizer for use as described comprises one or more diene-based compounds, preferably a terpene and/or a terpene-based compound. In certain embodiments the stabilizer comprises such diene-based compound(s) in combination with at least one phosphite compound, and/or at least one phenol compound and/or at least one aromatic, alkyl, or alkenyl epoxide. Examples of suitable combinations of phenols and epoxides include stabilizers comprising: tocopherol and allyl glycidyl ether, BHT and glycidyl butyl etherCertain particularly preferred combinations include stabilizers comprising: tocopherol and allyl glycidyl ether. In certain embodiments the preferred stabilizers comprise at least one diene-based compound in combination with at. least one phosphite compound.

Any suitable relative amount of the at least one phenol compound and the at least one aromatic, alkyl, or alkenyl epoxide may be used in the preferred stabilizers. For example, the weight ratio of phenol compound(s) to aromatic or fluorinated alkyl epoxide(s) can be varied from about <NUM>:<NUM> to about <NUM>:<NUM>. In certain preferred embodiments, the weight ratios of phenol compound(s) to aromatic, alkyl, alkenyl, multisubstituted, or fluorinated alky) epoxide(s) is from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, and even more preferably about <NUM>:<NUM>.

Any suitable effective amount of stabilizer may be used in the described compositions. As used herein, the term "effective stabilizing amount" refers to an amount of stabilizer described which, when added to a composition comprising trifluoroiodomethane, results in a stabilized composition wherein the trifluoroiodomethane therein degrades more slowly and/or to a lesser degree relative to the original composition, under the same, or similar, conditions. In certain preferred embodiments, an "effective stabilizing amount" of stabilizer comprises an amount which, when added to a composition comprising the degradable compound, such as the iodocarbon trifluoroiodomethane, results in a stabilized composition wherein the degradably compound degrades more slowly and/or to a lesser degree relative to the original composition under the conditions of at least one, or both, of the standards tests SAE J1662 (issued June <NUM>) and/or ASHRAE <NUM>-1983R. In certain more preferred embodiments, an "effective stabilizing amount" of stabilizer comprises an amount which, when added to a composition comprising trifluoroiodomethane, results in a composition having a stability that is at least as good as, if not better, than the stability of a comparable composition comprising dichlorodifluoromethane (R-<NUM>) in mineral oil, under at least one of the standard tests SAE J1662 (issued June <NUM>) and/or ASHRAE <NUM>-1983R. Certain preferred effective amounts of stabilizer for use as described comprise from about <NUM> to about <NUM>, more preferably from about <NUM> to about <NUM>, even more preferably from about <NUM> to about <NUM> weight percent, and even more preferably from about <NUM> to about <NUM> weight percent based on the total weight of trifluoroiodomethane in the described composition.

In certain preferred embodiments, the described compositions further comprise a lubricant. Any of a variety of conventional and unconventional lubricants may be used in the described compositions. An important requirement for the lubricant is that, when in use in a refrigerant system, there must be sufficient lubricant returning to the compressor of the system such that the compressor is lubricated. Thus, suitability of a lubricant for any given system is determined partly by the refrigerant/lubricant characteristics and partly by the characteristics of the system in which it is intended to be used. Examples of suitable lubricants, which are generally those commonly used in refrigeration machinery using or designed to use hydrofluorocarbon (HFC) refrigerants, chloroflurocarbon refrigerants and hydrochlorofluorocarbons refrigerants, include mineral oil, silicone oil, polyalkyl benzenes (sometimes referred to as PABs), polyol esters (sometimes referred to as POEs), polyalkylene glycols (sometimes referred to as PAGs), polyalkylene glycol esters (sometimes referred to as PAG esters), polyvinyl ethers (sometimes referred to as PVEs), poly(alpha-olefin) (sometimes referred to as PAOs), and halocarbon oils, particularly poly(chlorotrifluorethylene). Mineral oil, which comprises paraffin oil or naphthenic oil, is commercially available. Commercially available mineral oils include Witco LP <NUM> (registered trademark) from Witco, Zerol <NUM> (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet R015 from Calumet. Commercially available polyalkyl benzene lubricants include Zerol <NUM> (registered trademark). Commercially available esters include neopentyl glycol dipelargonate which is available as Emery <NUM> (registered trademark) and Hatcol <NUM> (registered trademark). Commercially available PAGs include Motorcraft PAG Refrigerant Compressor Oil, available from Ford, with similar products being available from Dow. Commercially available PAOs include CP-<NUM> from CPI Engineering. Commercially available PVEs are available from Idemitsu Kosan. Commercially available PAG esters are available from Chrysler. Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters.

For refrigeration systems using or designed to use HFCs, it is generally preferred to use as lubricants PAGs, PAG esters, PVEs, and POEs, particularly for systems comprising compression refrigeration, air-conditioning (especially for automotive air conditioning) and heat pumps. For refrigeration systems using or designed to use CFCs or HCFCs, it is generally preferred to use as lubricants mineral oil or PAB. In certain preferred embodiments, the lubricants of this invention are organic compounds which are comprised of carbon, hydrogen and oxygen with a ratio of oxygen to carbon and are included to provide, in combination with the amounts used, effective solubility and/or miscibility with the refrigerant to ensure sufficient return of the lubricant to the compressor. This solubility or miscibility preferably exists at least one temperature from about - <NUM> and <NUM>.

PAGs and PAG esters are highly preferred in certain embodiments because they are currently in use in particular applications such as original equipment mobile air-conditioning systems. Polyol esters are highly preferred in other certain embodiments because they are currently in use in particular nonmobile applications such as residential, commercial, and industrial air conditioning and refrigeration. Of course, different mixtures of different types of lubricants may be used.

The present compositions have utility in a wide range of applications. For example, included in the present invention are methods and compositions relating to heat transfer applications, foam and blowing agent applications, propellant applications, sprayable composition applications, sterilization application, and others, comprising the present azeotrope-like compositions.

The heat transfer compositions of the present invention are generally adaptable for use in heat transfer applications, that is, as a heating and/or cooling medium. Although it is contemplated that the compositions of the present invention may include the present azeotrope-like composition in combination with one or more other compounds or combinations of compounds in widely ranging amounts, it is generally preferred that heat transfer compositions of the present invention, including refrigerant compositions, consist essentially of, and in some embodiments consist of the present azeotrope-like compositions.

The heat transfer compositions of the present invention may be used in any of a wide variety of refrigeration systems such as including air-conditioning (including both stationary and mobile air conditioning systems), refrigeration, heat-pump systemsIn certain preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed for use with an HFC refrigerant, such as, for example, HFC-134a, or an HCFC refrigerant, such as, for example, HCFC-<NUM>. The preferred compositions of the present invention tend to exhibit many of the desirable characteristics of HFC-134a and other HFC refrigerants, including a GWP that is as low, or lower than that of conventional HFC refrigerants and a capacity that is as high or higher than such refrigerants and a capacity that is substantially similar to or substantially matches, and preferably is as high as or higher than such refrigerants. In particular, applicants have recognized that the present compositions tend to exhibit relatively low global warming potentials ("GWPs"), preferably less than about <NUM>, more preferably less than about <NUM>, and even more preferably less than about <NUM>. In addition, the relatively constant boiling nature of the compositions of the present invention makes them even more desirable than certain conventional HFCs, such as R-404A or combinations of HFC-<NUM>, HFC- <NUM> and HFC-134a (the combination HFC-<NUM>:HFC-<NUM>:HFC134a in approximate <NUM>:<NUM>:<NUM> weight ratio is referred to as R-407C), for use as refrigerants in many applications. Heat transfer compositions of the present invention are particularly preferred as replacements for HFC-<NUM>, HFC-152a, HFC-<NUM>, R-<NUM> and R-<NUM>.

In certain other preferred embodiments, the present compositions are used in refrigeration systems originally designed for use with a CFC-refrigerant. Preferred refrigeration compositions of the present invention may be used in refrigeration systems containing a lubricant used conventionally with CFC- refrigerants, such as mineral oils, polyalkylbenzene, polyalkylene glycol oils, or may be used with other lubricants traditionally used with HFC refrigerants. As used herein the term "refrigeration system" refers generally to any system or apparatus, or any part or portion of such a system or apparatus, which employs a refrigerant to provide cooling. Such refrigeration systems include, for example, air conditioners, electric refrigerators, chillers (including chillers using centrifugal compressors), transport refrigeration systems, commercial refrigeration systems.

Many existing refrigeration systems are currently adapted for use in connection with existing refrigerants, and the compositions of the present invention are believed to be adaptable for use in many of such systems, either with or without system modification. In many applications the compositions of the present invention may provide an advantage as a replacement in smaller systems currently based on certain refrigerants, for example those requiring a small refrigerating capacity and thereby dictating a need for relatively small compressor displacements. Furthermore, in embodiments where it is desired to use a lower capacity refrigerant composition of the present invention, for reasons of efficiency for example, to replace a refrigerant of higher capacity, such embodiments of the present compositions provide a potential advantage. Thus, it is preferred in certain embodiments to use compositions of the present invention, particularly compositions comprising a substantial proportion of, and in some embodiments consisting essentially of the present azeotrope-like compositions, as a replacement for existing refrigerants, such as: HFC-134a; CFC-<NUM>; HCFC-<NUM>; HFC-152a; combinations of pentfluoroethane (HFC-<NUM>), trifluorethane (HFC- 143a) and tetrafluoroethane (HFC-134a) (the combination HFC-<NUM>:HFC- 143a:HFC134a in approximate <NUM>:<NUM>:<NUM> weight ratio is referred to as R-404A);
combinations of HFC-<NUM>, HFC-<NUM> and HFC-134a (the combination HFC- <NUM>:HFC-<NUM>:HFC134a in approximate <NUM>:<NUM>:<NUM> weight ratio is referred to as R- 407C); combinations of methylene fluoride (HFC-<NUM>) and pentfluoroethane (HFC-<NUM>) (the combination HFC-<NUM>:HFC-<NUM> in approximate <NUM>:<NUM> weight ratio is referred to as R-410A); the combination of CFC-<NUM> and <NUM>,<NUM>-difluorethane (HFC-152a) (the combination CFC-<NUM>:HFC-152a in a <NUM>:<NUM> weight ratio is referred to R-<NUM>); and combinations of HFC-<NUM> and HFC-143a (the combination HFC-<NUM>:HFC143a in approximate <NUM>:<NUM> weight ratio is referred to as R-507A). In certain embodiments it may also be beneficial to use the present compositions in connection with the replacement of refrigerants formed from the combination HFC-<NUM>:HFC-<NUM>:HFC134a in approximate <NUM>:<NUM>:<NUM> weight ratio, which is referred to as R-407A, or in approximate <NUM>:<NUM>:<NUM> weight ratio, which is referred to as R-407D. The present compositions are also believed to be suitable as replacements for the above noted compositions in other applications, such as aerosols, blowing agents.

In certain applications, the refrigerants of the present invention potentially permit the beneficial use of larger displacement compressors, thereby resulting in better energy efficiency than other refrigerants, such as HFC-134a. Therefore the refrigerant compositions of the present invention provide the possibility of achieving a competitive advantage on an energy basis for refrigerant replacement
applications.

It is contemplated that the compositions of the present also have advantage (either in original systems or when used as a replacement for refrigerants such as CFC-<NUM>, HCFC-<NUM>, HFC-134a, HFC-152a, R-<NUM> and R-507A), in chillers typically used in connection with commercial air conditioning and refrigeration systems. In certain of such embodiments it is preferred to include in the described compositions from about <NUM> to about <NUM>% of a supplemental flammability suppressant, and in certain cases more preferably <NUM>% to about <NUM>% by weight and even more preferably from about <NUM> to about <NUM>% on a weight basis. In this regard it is noted that the certain of HFO-<NUM> and/or HFO-<NUM> components of the present compositions may in certain embodiments act as flammability suppressants with respect to other components in the composition. Thus, components other than HFO <NUM> and HFO-<NUM> which have flammability suppressant functionality in the composition will sometimes be referred to herein as a supplemental flammability suppressant.

In certain embodiments, co-refrigerants, including for example HFCs, HCFCs and CFCs may be included in the heat transfer described compositions, including one or more of the following, including any and all isomers thereof,:.

The relative amount of any of the above noted components, as well as any additional components which may be included in described compositions, may be incorporated into the described composition in amounts depending on the particular application for the composition, and all such relative amounts are considered to be within the scope hereof, provided preferably that such components do not negate the azeotrope-like nature of the HFO-<NUM> and HFO-<NUM> described herein.

The described methods, systems and compositions are thus adaptable for use in connection with automotive air conditioning systems and devices, commercial refrigeration systems and devices, chillers (including systems which utilize centrifugal compressors), residential refrigerator and freezers, general air conditioning systems, heat pumps.

Any of a wide range of methods described herein for introducing the described refrigerant compositions to a refrigeration system can be used. For example, one method comprises attaching a refrigerant container to the low- pressure side of a refrigeration system and turning on the refrigeration system compressor to pull the refrigerant into the system. In such embodiments, the refrigerant container may be placed on a scale such that the amount of refrigerant composition entering the system can be monitored. When a desired amount of refrigerant composition has been introduced into the system, charging is stopped. Alternatively, a wide range of charging tools, known to those of skill in the art, is commercially available. Accordingly, in light of the above disclosure, those of skill in the art will be readily able to introduce the refrigerant compositions of the present invention into refrigeration systems according to the present invention without undue experimentation.

Aslo described herein are refrigeration systems comprising a refrigerant as described herein and methods of producing heating or cooling by condensing and/or evaporating a described composition. In certain preferred embodiments, the methods for cooling, including cooling of other fluid either directly or indirectly or a body directly or indirectly, comprise condensing a refrigerant composition comprising an azeotrope-like composition of the present invention and thereafter evaporating said refrigerant composition in the vicinity of the article to be cooled. As used herein, the term "body" is intended to refer not only to inanimate objects but also to living tissue, including animal tissue in general and human tissue in particular. Also described herein is application of the described composition to human tissue for one or more therapeutic purposes, such as a pain killing technique, as a preparatory anaesthetic, or as part of a therapy involving reducing the temperature of the body being treated. In certain embodiments, the application to the body comprises providing the described compositions in liquid form under pressure, preferably in a pressurized container having a one-way discharge valve and/or nozzle, and releasing the liquid from the pressurized container by spraying or otherwise applying the composition to the body. As the liquid evaporates from the surface being sprayed, the surface cools.

Certain preferred methods for heating a fluid or body comprise condensing a refrigerant composition comprising an azeotrope-like composition of the present invention in the vicinity of the fluid or body to be heated and thereafter evaporating said refrigerant composition. In light of the disclosure herein, those of skill in the art will be readily able to heat and cool articles according to the present inventions without undue experimentation.

Applicants have found that in the systems described herein many of the important refrigeration system performance parameters are relatively close to the parameters for R-134a. Since many existing refrigeration systems have been designed for R-134a, or for other refrigerants with properties similar to R-134a, those skilled in the art will appreciate the substantial advantage of a low GWP and/or a low ozone depleting refrigerant that can be used as replacement for R- 134a or like refrigerants with relatively minimal modifications to the system. Also described herein are retrofitting methods which comprise replacing the refrigerant in an existing system with a described composition, without substantial modification of the system. In certain preferred embodiments the replacement step is a drop-in replacement in the sense that no substantial redesign of the system is required and no major item of equipment needs to be replaced in order to accommodate the described refrigerant. In certain preferred embodiments, the methods comprise a drop-in replacement in which the capacity of the system is at least about <NUM>%, preferably at least about <NUM>%, and even more preferably at least about <NUM>% of the system capacity prior to replacement. In certain preferred embodiments, the methods comprise a drop-in replacement in which the suction pressure and/or the discharge pressure of the system, and even more preferably both, is/are at least about <NUM>%, more preferably at least about <NUM>% and even
more preferably at least about <NUM>% of the system capacity prior to replacement. In certain preferred embodiments, the methods comprise a drop-in replacement in which the mass flow of the system is at least about <NUM>%, and even more preferably at least <NUM>% of the system capacity prior to replacement.

In another embodiment, the azeotrope-like compositions of this invention may be used as propellants in sprayable compositions, either alone or in combination with known propellants. The propellant composition comprises, more preferably consists essentially of, and, even more preferably, consists of the azeotrope-like compositions of the invention. The active ingredient to be sprayed together 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, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, and lubricants, 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.

Yet another embodiment of the present invention relates to a blowing agent comprising one or more azeotrope-like compositions of the invention. 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 the present azeotrope-like compositions in amounts at least about <NUM> % by weight, and even more preferably at least about <NUM> % by weight, of the blowing agent. In certain preferred embodiments, the blowing agent comprises at least about <NUM>% by weight of the present azeotrope-like 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 compositions, one or more of co-blowing agents, fillers, vapor pressure modifiers, flame suppressants, stabilizers and like adjuvants.

Also described herein are foamable compositions. The described foamable compositions generally include one or more components capable of forming foam having a generally cellular structure and a blowing agent in accordance with the present invention. In certain embodiments, the one or more components comprise a thermosetting composition capable of forming foam and/or foamable compositions. Examples of thermosetting compositions include polyurethane and polyisocyanurate foam compositions, and also phenolic foam compositions. In such thermosetting foam embodiments, one or more of the present compositions are included as or part of a blowing agent in a foamable composition, or as a part of a two or more part foamable composition, which preferably includes one or more of the components capable of reacting and/or foaming under the proper conditions to form a foam or cellular structure. In certain other embodiments, the one or more components comprise thermoplastic materials, particularly thermoplastic polymers and/or resins. Examples of thermoplastic foam components include polyolefins, such as polystyrene (PS), polyethylene (PE), polypropylene (PP) and polyethyleneterepthalate (PET), and foams formed there from, preferably low- density foams. In certain embodiments, the thermoplastic foamable composition is an extrudable composition.

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 of the present invention 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 that the various components of the blowing agent, and even the components of the present composition, be not be mixed in advance of introduction to the extrusion equipment, or even that the components 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. Nevertheless, in certain 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.

Also described herein is foam, and preferably closed cell foam, prepared from a polymer foam formulation containing a composition of the invention, preferably as part of blowing agent.

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 optionally but preferably added to serve as cell stabilizers. Some representative materials are sold under the names of DC-<NUM>, B-<NUM>, and L-<NUM> which are, generally, polysiloxane polyoxyalkylene block co-polymers such as those disclosed in <CIT><CIT> and <CIT>. Other optional additives for the blowing agent mixture may include flame retardants or suppressants such as tri(<NUM>-chloroethyl)phosphate, tri(<NUM>-chloropropyl)phosphate, tri(<NUM>,<NUM>-dibromopropyl)-phosphate, tri(<NUM>,<NUM>-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride.

Any of the methods well known in the art, such as those described in "<NPL>, , may be used or adapted for use in accordance with the foam embodiments of the present invention.

Other uses of the present azeotrope-like compositions include use as solvents, cleaning agents. Those of skill in the art will be readily
able to adapt the present compositions for use in such applications without undue experimentation.

The invention is further illustrated in the following example which is intended to be illustrative, but not limiting in any manner.

An ebulliometer consisting of vacuum jacketed tube with a condenser on top which is further equipped with a Quartz Thermometer K96S4771 is used. About <NUM> HFO-1234yf is charged to the ebulliometer and then HFO-1225yeZ is added in small, measured increments. Temperature depression is observed when HFO-1225yeZ is added to HFO-1234yf, indicating a binary minimum boiling azeotrope is formed. From greater than about <NUM> to about <NUM> weight percent HFO- 1225yeZ, the boiling point of the composition changed by about <NUM> or less. The binary mixtures shown in Table <NUM> were studied and the boiling point of the compositions changed by about <NUM> or less. The compositions exhibit azeotrope and/or azeotrope-like properties over this range.

Claim 1:
The use of an azeotrope-like composition comprising effective amounts of HFO-1234yf and HFO-1225yeZ as a heat transfer composition, for use in an air conditioning system, a refrigeration system or a heat pump,
wherein the azeotrope-like composition consists essentially of from <NUM> to less than <NUM> weight percent HFO-1234yf and from greater than zero to <NUM> weight percent of HFO-1225yeZ.