WO2008065011A1

WO2008065011A1 - Compositions comprising unsaturated hydrofluorocarbon compounds, and methods for heating and cooling using the compositions

Info

Publication number: WO2008065011A1
Application number: PCT/EP2007/062432
Authority: WO
Inventors: Marcello Riva; Reiner Fischer
Original assignee: Solvay Fluor Gmbh
Priority date: 2006-11-29
Filing date: 2007-11-15
Publication date: 2008-06-05

Abstract

The essentially pure isomers of 1,2,3,3,3-pentafluoropropene and specific mixtures thereof together with certain other compounds are suitable for application in refrigerants and other methods of use, e.g. as solvents, blowing agents, fire extinguishants, ORC liquids, heat transformer liquids, heat pipe liquids or aerosol-producing gases.

Description

Compositions comprising unsaturated hydrofluorocarbon compounds, and methods for heating and cooling using the compositions

The present application claims benefit of US provisional patent application no. 60/884741 the entire content of which is incorporated by reference into the present application.

The present invention relates to compositions of matter comprising unsaturated hydrofluorocarbons compounds and methods for heating and cooling using the compositions, for example in refrigeration, air conditioning and heat pump systems.

Apparatus for heating and cooling today are often operated with saturated hydrofluorocarbons compounds, for example with 1,1,1,2-tetrafluoroethane (HFC- 134a) or compositions comprising appreciable amounts of HFC- 134a. Though such saturated hydrofluorocarbons have a low or 0 ozone depletion potential, further environmental regulations may cause a phase-out of certain hydrofluorocarbons compounds. For example, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air conditioning (MAC).

WO 2005/021675 discloses mixtures of HFC- 152a, CF₃I or HFC-161 and CO₂ as substitute for HFC- 134a, especially in mobile air conditioning systems.

There is a need for methods of heating and cooling using novel refrigerants with advantageous properties. There is also still need for composition of matter, especially suitable for use in refrigeration, with a low GWP and, preferably, low toxicity and, preferably, low flammability or non-flammability, respectively.

Object of the present invention is to provide novel compositions of matter suitable especially for refrigeration, but also for other purposes, such as solvent applications, heat transfer, heat pipes, ORC (organic Rankine cycle) applications, fire extinction, foam blowing, or aerosol generation. It is another object of the present invention to provide a novel method for heating and cooling. A preferred object of the present invention is to provide a composition of matter with low flammability or no flammability at all. Another object of the present invention is to provide a composition of matter with a GWP (global warming potential) lower than 150, preferably lower than 140, especially preferably lower than 120. These and other objects are met by the present invention. One aspect of the present invention concerns a composition of matter which is especially suitable for heating and cooling, but also for other purposes,e.g. in solvent applications, heat transfer, heat pipes, ORC (organic Rankine cycle) applications, fire extinction, foam blowing, or aerosol generation. The composition according to the present invention comprises a compound

A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5, and at least one compound B selected from the group consisting of : perfluoro-methylvinylether, perfluoro-ethylvinylether, perfluoro- propylvinylether, perfluoro-methyl-methylvinylether, HFC-1234ze

( 1 ,3 ,3 ,3-tetrafluoropropene), HFC- 1234yf (2,3 ,3 ,3-tetrafluoropropene), HFC-1234ye (l,2,3,3-tetrafluoropropene), HFC-1243zf (3,3,3-trifluoropropene), HFC- 32 (difluoromethane), HFC- 125 (pentafluoroethane), HFC- 134 (1,1,2,2-tetrafiuoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-152a (1,1-difluoroethane), HFC-161 (fluoroethane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-236ea (1,1,1 ,2,3,3-hexafluoroporpane), HFC-236fa (1,1,1 ,3,3,3-hexafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), propane, n-butane, isobutane, 2-methylbutane, n- pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I. The content of the (E) isomer, the (Z) isomer or the mixture of (E) and (Z) isomer in the proportions as indicated above is preferably in the range of 60 to 95 % by weight. The other component or components, together with said isomer or isomers of HFC-1225ye, add up to 100 % by weight. For the compositions of the present invention (and for the methods applying them, as later described), the following proviso applies : If the composition comprises (E)-HFC- 1225ye, then no or at most insignificant amounts of (Z)-HFC- 1225ye are present. If the composition comprises (Z)-HFC- 1225ye, then no or at most insignificant amounts of (E)-HFC- 1225ye are present. The term"insignificant'in this context means that the molar ratio between the excluded isomer and the desired isomer of HFC-1225ye is not greater than 10:100, especially not greater than 5:100. If a mixture of the (Z) and (E) isomers is present, that means that no isomer of HFC-1225ye is additionally comprised which would shift the ratio beyond the given limit of 2,5:1,0 to 1,0:2,5. The chemical compound denoted as"HFC-1225yd'has the chemical formula C₃HF₅, it is a'pentafluoropropend', more exactly it is

'1,2,3,3, 3-pentafluoropropend'. This compound exists in the form of two stereo isomers. In these isomers, the CF₃ group may be in trans position to the hydrogen atom; this isomer is called"(E)-l ,2,3,3, 3-pentafluoropropend'or

'(E)-HFC- 1225yd' in the context of the present invention. Or, the CF₃ group may be in a cis position to the hydrogen group; this isomer is called'1(Z)-l,2,3,3,3- pentafluoropropend'or"(Z)-HFC- 1225yd' in the context of the present invention. The (Z) isomer is the preferred one. (E)-1225ye can be prepared as described by D.J. Burton, T.D. Spawn,

P.L. Heinze, A.R. Bailey and S. Shin- Ya in J. Fluorine Chemistry 44 (1989), pages 167 to 174. The reaction starts with hexafluoropropene (HFC- 1216), a well-known chemical which is commercially available and in used in great quantities for the preparation of, i.a., 1,1,1,2,3,3,3-heptafluoropropane. Hexafluoropropene is reacted with tri-n-butylphosphine under cooling to form an intermediate which then is hydro lyzed to give the (E)-1225ye compound which may be isolated by condensing it under reduced pressure into a cooled tank.

D.J. Burton et al. also describe that the (E)-isomer can be transformed into the (Z)-isomer by contacting it with SbF₅. The isolation can be effected by condensing it under reduced pressure into a cooled storage tank.

Mixtures of the (E)-isomer and the (Z)-isomer in the molar ratio mentioned above can be prepared, for example, by mixing appropriate amounts of the isomers or by adding the (E)-isomer or the (Z)-isomer, respectively, to 'HFC- 1225yd' as obtained by processes described in the prior art, e.g. in US-A 6,369,284 where 1,1,1,2,3,3,-hexafluoropropane is dehydrofluorinated in the presence of a catalyst which comprises the oxides, fluorides or oxyfluorides of magnesium or zinc or both, and optionally aluminium, or which comprises lanthanum fluoride or fluorided lanthanum oxide, or a three-dimensional matrix carbonaceous material. The content of the E isomer in the reaction product of such high-temperature catalytic processes, as well as the content of the E isomer in other processes, can be reduced by converting it to the Z isomer, as described above. The preparation of the perfluoroalkylvinylether compounds mentioned above is known. The perfluoromethylvinylether can for example prepared by the addition of perfluoroxyfluorides to l,2-dichloro-l,2-difluoroethylene or l,2-dibromo-l,2-difluoroethylene and subsequent reduction with Zinc. The first - A -

step is described in US 4900872, the complete sequence is described by W.S. Durell et al. J. Polymer Sci. Part A, 3 (1965), pages 4065ff.

Mixtures of the E and Z isomer can also be purchased, e.g. from ABCR GmbH & Co. KG, Karlsruhe/Germany (ratio of E isomer to Z isomer 70:30).

In a preferred embodiment, the composition according to the invention comprises or consists of a compound A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5 , and one or more compounds B wherein at least one compound B is selected from the group consisting of

HFC-32, HFC- 134, HFC- 134a, HFC- 152a, HFC-227ea, HFC-1234yf, propane, n-butane, i-butane, 2-methylbutane, n-pentane, perfluoro-methylvinylether, perfluoro-ethylvinylether, CO₂ and CF3I, and optionally, additionally one or more compounds B selected from the group consisting of HFC-1234ze, HFC-1234ye, HFC-1243zf, HFC-125, HFC-143a, HFC-161, HFC-227ea,

HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, 2-methylbutane, n-pentane, cyclopentane, dimethylether, andCF₃SCF₃.

In a very preferred embodiment, the composition comprises or consists of a compound A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5 , and one or two compounds B selected from the group consisting of HFC-32; HFC-125, HFC-134; HFC-134a; HFC-152a, HFC-1234yf; propane; n-butane; i-butane; perfluoro-methylvinylether : perfluoro-ethylvinylether; CO₂; CF₃I; and optionally one or more compound B selected from the group consisting of HFC-1234ze, HFC-1234ye, HFC-1243zf, HFC-125, HFC-143a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, 2-methylbutane, n-pentane, cyclopentane, dimethylether, and CF₃SCF₃.

A highly preferred embodiment provides a composition consisting of a compound A selected from the group consisting of (E)-HFC- 1225ye,

(Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5 and one compound B or a combination of two compounds B selected from the group consisting of perfluoro-methylvinylether; HFC-32; HFC-125; HFC-134; HFC-134 and HFC-32; HFC-134a; HFC-152a; HFC-152a and HFC-32; CO₂; CF₃I; HFC-1234yf; HFC-1234yf and HFC-134a; HFC- 1234yf and HFC-32; HFC- 134a and CO₂; HFC- 134a and HFC- 152a; HFC- 134a, HFC- 152a and CO₂; HFC- 134a and HFC-32; HFC- 134a and

HFC-1234ze; HFC- 134a and HFC-1234yf; HFC- 134a and HFC-1234ye;

HFC-134a and HFC-1243zf; HFC-134a and propane; HFC-134a and n-butane;HFC-134a and i-butane; HFC- 134a and dimethylether; HFC- 152a and CO₂; HFC-152a and HFC-32; HFC-152a and propane; HFC-125a and

HFC-1234ze; HFC-152a and HFC-1234yf; HFC-125a and HFC-1234ye;

HFC-125a and HFC-1243zf.

A most preferred embodiment provides a composition consisting of a compound A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5 and at least one compound of the group consisting of perfluoro-methylvinylether, HFC-32, HFC- 134, HFC- 134a, HFC- 152a, and

HFC-1234yf, optionally together with at least one other compound B selected from the group consisting of CO₂, propane, n-butane and i-butane. In such mixtures, the content of HFC-1225ye is often in the range of 60 to 90 % by weight, but sometimes also may be lower. For example, in a mixture of

HFC-1225ye with HFC- 1234yf and HFC-32, the content of HRC-1225ye may be as low as 20 to 30 % by weight.

It is often preferred to select compound A from the (E)-isomer, the (Z)-isomer or the mixture of (E) isomer and (Z) isomer in a molar ratio between

2,5 : 1 to 2,5 : 1. Very preferably, compound A is the (Z) isomer with at most insignificant amounts of the other isomer.

Compositions of matter which are inflammable are preferred embodiments of the present invention. The term"inflammabld'in the context of the present invention is defined by ASTM standard E-681. This standard describes how to evaluate the lower and upper flammability ranges, performed in a open glass bowl with electric ignition.

In a preferred embodiment, constituents and their amounts are chosen such that the composition has a GWP lower than 150. The GWP can be determined according to the method devised by Scientific Assessment of Stratospheric

Ozone : 1989' sponsored by the U.N. Environment Programme. The general definition is

GWP = Calculated IR forcing due to agent/Emission rate (steady state) of agent divided by the same parameters for CFCI₃. In a preferred embodiment, the GWP of the composition is lower than 140. In an especially preferred embodiment, the GWP of the composition is lower than 120.

In the following tables 1 to 6, highly suitable mixtures according to the present invention are compiled. Data are given in % by weight. The amounts add up to 100 % by weight. Table 1 shows preferable ranges of suitable mixtures comprising (E)-1225ye :

PMVE = perfluoro-methylvinylether ** more preferred range

Table 2 shows preferable ranges of suitable mixtures comprising (Z)-1225ye

^: more preferred range

Table 3 shows preferable ranges of suitable mixtures comprising (E)-1225ye and (Z)-1225ye, molar ratio 2,5:1 to 1 :2,5

* more preferred range Table 4 shows optimum ranges of suitable mixtures comprising (E)-1225ye

Table 5 shows optimum ranges of suitable mixtures comprising (Z)-1225ye

Table 6 shows optimum ranges of suitable mixtures comprising (E)-1225ye and (Z)-1225ye, molar ratio 2,5:1 to 1 :2,5

Binary mixtures and ternary mixtures are preferred, especially those consisting of the E isomer, the Z isomer or the mixture of E and Z isomer of HFC-1225ye and perfluoro-methylvinyl ether, HFC-32 or HFC- 152a.

It has been found that mixtures of the E isomer, the Z isomer or the mixtures of E and Z isomer of HFC-1225ye as described above, and perfluoro- methylvinyl ether form an azeotrope-like mixture. Azeotrope-like mixtures which have an ODP of 0 and a GWP lower than 10, are a preferred embodiment of the present invention and are described in the following.

An azeotrope-like mixture in the frame of the present invention is a mixture of two or more fluids having a vapor composition substantially equal to that of the liquid and which undergoes phase changes without substantially modifying its composition and temperature. According to the present invention, a mixture is azeotrope-like when, after evaporation at a constant temperature of 50 % of the initial liquid mass, the per cent variation of the vapor pressure between that of the initial mixture and that of the final mixture results lower than about 10 %. See on the matter the paper of D.A. Didion and D. B. Bivens in Int. J. of Refrigeration 13 (1990), pages 163 to 175.

Binary mixtures of perfluoro-methylvinyl ether and the E isomer, the Z isomer or the mixture of E and Z isomers of HFC-1225ye as defined above form a azeotrope-like mixture in a broad range. Mixtures of perfluoromethylvinyl ether and the E isomer, the Z isomer or mixtures of the E and Z isomer of HFC-1225ye with a content of equal to or more than 8 % by weight, preferably equal to or more than 10 % by weight of perfluoro-methylvinyl ether are very advantageous. The content in PVME can even be higher, for example, it can be equal to or more than 15 % by weight Advantageously, the content of perfluoro-methylvinyl ether is equal to or lower than 30 % by weight.

A very preferred azeotrope-like mixture comprises 20 - 25 % by weight of perfluoro-methylvinyl ether and 75 to 80 % by weight of the E isomer, the Z isomer or the mixtures of the E and Z isomers of HFC-1225ye. In another embodiment, preferred mixture consists of 88 to 92 % by weight of the (E) isomer, the (Z) isomer or the (E)/(Z) mixtures of the isomer as described above of HFC-1225ye and 8 to 12 % by weight of PVME. An outstandingly good mixture consists of 90 % by weight of the (E) isomer, the (Z) isomer or the (E)/(Z) mixtures as described above of HFC-1225ye and 10 % by weight of PVME.

The (Z) isomer is especially preferred. A mixture comprising equal to or more than 8 % by weight, and equal to or less than 20 % by weight of perfluoro-methylvinyl ether, the remainder to 100 % by weight being the E isomer, the Z isomer or a mixture of the E and the Z isomer of HFC-1225ye is non-flammable. It has a temperature glide of about 1 to 2 K at p_s 2 bar. The term"P_g' denotes the saturation pressure. The temperature glide can be utilized to enhance performance. It was found that a mixture consisting of 10 % by weight of PVME and 90 % by weight of the (E) isomer, the (Z) isomer or mixtures of both isomers in the ranges given above has very adavantageous properties : it is non-flammable, has a very low temperature glide and an acceptable coefficient of performance. Tests have shown that they have a good miscibility and compatibility with oils (lubricants), have a good material compatibility with metals and plastics, a low permeability through plastics,a good stability, and a good thermodynamic behaviour.

Another embodiment of the present invention are ternary compositions comprising the azeotrope-like mixture of perfluoro-methylvinyl ether and the E isomer, Z isomer of HFC-1225ye or the mixtures thereof, and, as the third component, a compound suitable as refrigerant selected from the group consisting of perfluoro-ethylvinylether, perfluoro-propylvinylether, perfluoro-methyl-methylvinylether, HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I. Preferred azeotrope-like mixtures of FHC-1225ye and perfluoro-methylvinyl ether which are comprised in these ternary compositions are described above.

If the ternary compositions of perfluoro-methylvinyl ether, HFC-1225ye and the third component are intended to be a substitute for HFC- 134a, the third component preferably has a boiling point which is lower than that of the azeotrope-like mixture. For example, compounds with a boiling point in the range of -25 to -100⁰C are advantageously used as a third component.

In ternary compositions, the content of the azeotrope-like mixture as described above can be higher or equal to 1 % by weight, preferably equal to or higher than 10 % by weight, still more preferably equal to or higher than 20 % by weight, especially equal to or higher than 30 % by weight. Very preferably, the content of the azeotrope-like mixture is equal to or higher than 50 % by weight. The content of the azeotrope-like mixture in ternary compositions can be equal to or lower than 99 % by weight, preferably equal to or lower than 97 % by weight. The azeotropic mixture and of the third component add up to 100 % by weight. It is assumed that the composition has a low toxicity.

If the ternary mixture is intended to be a substitute for HFC- 134a, the amount of the azeotrope-like mixture of perfluoro-methylvinyl ether and

HFC-1225ye are selected such that the vapor pressure curve is similar to that of HFC- 134a.

The composition of matter is especially suitable as refrigerant for refrigeration. The term' tefrigeranf includes the compositions described above which optionally may comprise additives which will be described later. The compositions are also suitable for other purposes, e.g. in solvent applications, heat transfer, heat pipes, ORC (organic Rankine cycle) applications, fire extinction, foam blowing, or aerosol generation. For each of these purposes, additives known to be advantageous for the respective purpose may be comprised. For example, when applied as fire extinguishing agent, propellants, for example nitrogen, can be comprised. When applied as blowing agent, chemical blowing agents, for example, water, or other additives used in foam blowing may be comprised.

The composition of matter is especially suitable for heating and cooling, and in the following, additives which may be advantageously comprised for this purpose are explained in detail now.

Such additives, which are named'tompounds C'in the present application, improve the performance of the application process. Preferred compounds C in the present invention are lubricants, stabilizers, other additives, for example corrosion inhibitors or metal-passivating agents, e.g. combinations of aminoacid derivatives and amines, or imidazoles, benzimidazoles, pyrazoles or triazoles, or antioxidants, for example secondary arylamines, phenyl naphtylamines, diphenylamines, or hindered phenolics, for example 2-t-butylphenol, 2,6-di-t- butylphenol or 4-methyl.2,6-di-t-butylphenol, solubility compatibilizers, UV fluorescent dyes, or tracer compounds.

Stabilizers can for example be comprised if the mixture comprises CF₃I. Suitable stabilizers are disclosed in WO 2005/233923. Any of a variety of compounds suitable for stabilizing the compositions of the present invention may be used, for example phenol compounds and epoxide compounds. Examples of certain preferred stabilizers include stabilizer compositions comprising at least one phenol composition and/or at least one epoxide selected from the group consisting of aromatic epoxides, alkyl epoxides, alkenyl epoxides, and combinations of two or more thereof.

Certain preferred phenols include alkylated monophenols such as tocopherol, BHT, hydroquinones, and the like. Certain particularly preferred phenols include tocopherol, and the like. Most phenols are commercially available. A single phenol compound and/or mixtures of two or more phenols may be used in the present compositions.

Examples of aromatic epoxides include butylphenylglycidyl ether; pentylphenylglycidyl ether; hexylphenylglycidyl ether; heptylphenylglycidyl ether; octylphenylglycidyl ether; nonylphenylglycidyl ether; decylphenylglycidyl ether; glycidyl methyl phenyl ether; 1 ,4-diglycidyl phenyl diether; 4-methoxyphenyl glycidyl ether; and derivatives thereof. Certain other preferred aromatic epoxides include naphthyl glycidyl ether; 1 ,4-diglycidyl naphthyl diether; and derivatives thereof. Examples of other suitable aromatic epoxides include bisoxiranes, such as, 2,2'[[[5-heptadecafluorooctyl] 1 ,3phenylene]- bis [ [2 ,2 ,2trifluoromethy 1] ethy lidene] -oxymethy lene]bisoxirane .

Examples of preferred alkyl epoxides include n-butyl glycidyl ether, isobutyl glycidyl ether, hexanediol diglycidyl ether, and the like, as well as, fluorinated and perfluorinated alkyl epoxides. Certain more preferred alkyl epoxides comprise hexanediol diglycidyl ether, and the like. Examples of other preferred alkenyl epoxides include allyl glycidyl ether, fluorinated and perfluorinated alkenyl epoxides, and the like. Examples of polypropylene glycol diglycidyl ethers suitable for use in the present invention includes the ether available commercially from SACHEM, Europe. In certain preferred embodiments, an "effective stabilizing amount" of stabilizer comprises an amount which, when added to a composition, especially if it contains trifluoroiodomethane, results in a stabilized composition which 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 J 1662 (issued June 1993) and/or ASHRAE 97- 1983R; especially, this holds true for trifluoroiodomethane if it is comprised therein. 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- 12) in mineral oil, under at least one of the standard tests SAE J 1662 (issued June 1993) and/or ASHRAE 97-1983R. Certain preferred effective amounts of stabilizer for use in the present invention comprise from about 0.001 to about 10, more preferably from about 0.01 to about 5, even more preferably from about 0.3 to about 4 weight percent, and even more preferably from about 0.3 to about 1 weight percent based on the total weight of the composition, or, if trifluoroiodomethane is contained, based on the total weight of trifluoroiodomethane in the composition of the present invention.

Certain unsaturated compounds are another especially suitable type of stabilizers. As unsaturated hydrocarbons, especially terpenes, for example, monoterpenes, diterpenes and sesquiterpenes are to be mentioned. Preferred terpenes which can be applied as a stabilizer are citral, citronellal, citronellol, limonene, dipentene, menthol, terpinene, terpinolene, sylvestrene, sabinene, menthadiene, zingiberene,ocimene, myrcene, α-pinene, β-pinene, turpentine, camphor, phytol, squalene, and lycopene. Of course, if desired, mixtures of 2 or more terpenes can be used as stabilizer. Preferably, the terpene is comprised in an amount of equal to or more than 0.1 %, especially preferably equal to or more than 0.2 % by weight of the total weight of the composition. Preferably, the terpene is comprised in an amount equal to or less than 3 %, preferably 2 % by weight of the total weight of the composition. Any of a variety of conventional lubricants may be used in the compositions of the present invention, optionally in the presence of solubility compatibilizers. 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 include mineral oil, alkyl benzenes, polyol esters, polyalkylene glycols, PAG oils, phosphate esters, dibasic acid esters, fluoroesters, synthetic paraffins, synthetic naphthenes, or poly(alpha)olefms. Mineral oil, which comprises paraffin oil or naphthenic oil, is commercially available. Commercially available mineral oils include Witco LP 250 (registered trademark) from Witco, Zerol 300 (registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco, and Calumet RO 15 from Calumet. Commercially available alkyl benzene lubricants include Zerol 150 (registered trademark) and Fuchs Reniso S46F (registered trademark), the latter is very suitable. Commercially available esters include neopentyl glycol dipelargonate which is available as Emery 2917 (registered trademark) and Hatcol 2370 (registered trademark). Other useful esters include phosphate esters, dibasic acid esters, and fluoroesters. Preferred lubricants include polyalkylene glycols and esters and especially alkyl benzene lubricants. A very suitable PAG oil is ND8 of Denso.

The amount of lubricant is selected so that the apparatus works reliably. The amount of lubricant may be comprised in the refrigerant composition in the range of 1 to 35 % by weight of the total refrigerant composition (including compounds A, compounds B, and compounds C like stabilizers, lubricants, other additives). A preferred range is 5 to 30 % by weight.

The composition may further comprise other additives as compound C. Metal passivators and corrosion inhibitors such as those described above can be comprised in the range of 0.01 to 5 %, preferably 0.05 to 2 % by weight of the total composition. Other additives like antioxidants can each be present in the range of 0.01 to 5 %, preferably 0.05 to 2 % by weight of the total composition. Of course, if desired, the refrigerant may comprise two or more different kinds of compounds C, e.g. stabilizers together with lubricants and/or corrosion inhibitors. Also, solubility compatibilizers may be present to optimize solubility of the refrigerant in the selected oil. Suitable compatibilizers may be selected for example from the group of polyoxyalkylene glycol ethers, amides, ketones, nitriles, 1,1,1-trifluoroalkanes, chlorocarbons, fluoroethers, lactones or esters.

Suitable examples of polyoxyalkylene glycol ether compatibilizers are propyleneglycol methyl ether, dipropyleneglycol methyl ether, tripropyleneglycol methyl ether, the respective ethyl ethers, n-propyl ethers, t-butyl ethers or n-butyl ethers, the respective dimethyl ethers, diethyl ethers, di-n-propyl ethers, di-n-butyl ethers or di-t-butyl ethers, or trimethylolpropane- di-n-butyl or tri-n-butyl ethers.

Suitable examples for amide compatibilizers are for example l-octyl-pyrrolidin-2one, 1-butylcaprolactame, N,N-dibutylformamide and N,N-diisopropylacetamide.

Suitable examples for ketone compatibilizers are 2-butanone, acetophenone, 3-octanone, and dihexylketone.

Suitable examples for nitrile compatibilizers are compounds of formula RCN wherein R is pentyl, neopentyl, isopentyl, cyclopentyl, or octyl. Suitable examples for chlorocarbon compatibilizers are alkylchlorides and dichlorides, wherein alkyl is for example methyl, ethyl, propyl, up to undecyl and dodecyl.

Suitable examples for ester compatibilizers are ethyl hexanoate, n- butylpropionate, ethyl benzoate, dipropylcarbonate, dibutylphthalate and t-butyl acetate.

Suitable examples for lactone compatibilizers are (E,Z)-3-ethylidene-5- methyl-dihydro-furan-2-one, the respective propylidene and butylidene homologues up to the decylidene homologues or γ-octalactone. UV dyes are useful for detecting leaks in refrigeration, air-conditioning or heat-pump apparatus. They may be selected, for example, from naphthalimides, perylenes, cumarins, anthracenes, fluoresceins or derivatives thereof. Optionally, they are applied together with a solubilizer. Examples are hydrocarbons, hydrocarbon ethers or the compounds useful as compatibilizers mentioned above.

A preferred aspect of the present invention is a method for refrigeration whereby use is made of the compositions which optionally comprise additives as refrigerants. The term'tefrigeratiori'as used in the present invention includes methods which comprise condensing the refrigerant composition of the invention and thereafter evaporating it in the vicinity of a body to be cooled. Similarly, the term' tefrigeratiorP includes methods of condensing the composition in the presence of a body to be heated and thereafter evaporating the composition. The heating or cooling can be performed directly or indirectly or by immersion. The term'tefrigeratiori'also includes air-conditioning and a method of operating a heat-pump apparatus.

The method of refrigeration is performed by applying a composition of matter as described above.

The method for refrigeration according to the present invention comprises preferably using a refrigerant comprising a compound A selected from the group consisting of (E)- HFC-1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1,0 to 1,0:2,5 , and at least one compound B selected from the group consisting of : HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC-125, HFC-134, HFC-134a, HFC- 143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, perfluoro-methylvinyl ether, propane, n-butane, isobutane, 2- methylbutane, n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I. For the refrigeration method of the present invention, the following proviso applies : If the composition comprises (E)-HFC- 1225ye, then no or at most insignificant amounts of (Z)-HFC- 1225ye are present. If the composition comprises (Z)-HFC- 1225ye, then no or at most insignificant amounts of (E)-HFC- 1225ye are present. The term"insignificant'in this context means that the molar ratio between the excluded isomer and the desired isomer of HFC-1225ye is not greater than 5:100. If a mixture of the (Z) and (E) isomers is present, that means that no isomer of HFC-1225ye is additionally comprised which would shift the ratio beyond the given limit of 2,5:1,0 to 1.0:2,5. Preferred embodiments of the inventive method are performed with the preferred compositions of matter as outlined above. Binary mixtures and ternary mixtures are preferred.

Of course, additives like stabilizers, for example, terpenes, lubricants etc as mentioned above may be optionally comprised. One embodiment of the invention concerns a method for refrigeration in situations where flammability is of no concern. This may be the case in stationary refrigeration apparatus such as freezers where leakage of the refrigerant caused e.g. by mechanical impact is not to be expected, in situations where any leakage does not lead to danger of fire. The term'flammability'in the context of the present invention is defined by ASTM standard E-681. This standard describes how to evaluate the lower and upper flammability ranges, performed in a open glass bowl with electric ignition.

In this variant of the embodiment where flammability is of no concern, the refrigerants which are applied may comprise flammable components B such as alkanes, for example propane, cyclopropane, n-butane, i-butane, or the pentanes, flammable fluoroalkanes for example HFC-161 or HFC-32, HFC- 152a, perfluoro-methylvinyl ether, tri- or tetrafluoropropenes or dimethylether in amounts which render the compositions flammable.

In a preferred embodiment, the method for refrigeration is performed with an nonflammable refrigerant mixture. Though flammable components B, for example. HFC-32, HFC- 152a or perfluoro-methylvinyl ether, may be comprised, they are comprised only in amounts below those which would render the composition flammable. The limits can easily be checked by tests, e.g. according to the ASTM Standard. The refrigeration method according to the present invention is preferably performed with refrigerants with a GWP lower than 150, especially preferably lower than 140 still more preferably lower than 120. The compositions given in tables 1 to 6, optionally applied together with additives, are highly suitable. They are inflammable and have the desired low GWP.

Accordingly, the compositions according to the invention can be used as substitutes for refrigerants with undesirably high GWP, and the method according to the invention can be applied to substitute respective methods for refrigeration. For example, refrigerants that can be substituted are HFCs 134a, 245fa, 236fa, and other HFCs, HCFCs, for example, HFC-114, HCFC-124, or mixtures, for example, R 410A, R 407C, R 417A, R 422A, R 507A and R 404A. The method for heating or cooling using the non-flammable compositions described above is especially suitable for mobile air conditioning in cars, lorries, buses, trains, airplanes, ships, space ships. It also can be applied for cooling of goods to be transported or to cool refrigerated transport boxes or refrigerated containers. Of course, it can also be applied in stationary machinery, like household appliances (freezers in private locations such as households) or industrial locations such as working rooms, production sites, hospitals, devices or rooms for storing or treating food or drugs, in heat pumps, and other apparatus wherein heat or cold is transported.

For many applications like mobile air conditioning, the apparatus often is designed to cool down to approximately 5°C. Here, the pressure at condensation often is about 12 to 18 bars (abs), preferably about 15 bars (abs.). The pressure at evaporation often is about 3 to 4 bars (abs.), preferably about 3.5 bars (abs.). The upper limit of the temperature of the room or item to be cooled is often about 55°C, while the temperature achievable by cooing is, as mentioned, about 5°C.

For freezers, the values can be somewhat different. Typical upper temperature limit of the room to be cooled is 55°C, the pressure of the refrigerant at condensation is around 15 bars (abs.). The temperature to be achieved by cooling is often- 10⁰C, the pressure of the refrigerant at evaporation at that temperature is often around 1.5 bars (abs.).

For certain compositions of those mentioned above which comprise optionally lubricants, stabilizers and/or other additives, it is possible to use them preferably as drop-in or retrofit for machines which are designed to operate with HFC- 134a or similar refrigerants. "Drop-iri' means the lubrication oil can be reused, while'tetrofit'means that suitable fresh oil must be used. For machines which are designed to operate with refrigerants with higher or lower boiling point than HFC- 134a, it is possible to tailor compositions with a boiling point comparable to the boiling point of the refrigerant to be substituted by selecting suitable compounds A and/or B. For example, to the compositions mentioned above; one can add a compound B with a higher or lower boiling point, respectively, than the boiling point of the isomers of HFC-1225ye or the specified mixtures thereof. Such tailored compositions can be used as a drop-in or retrofit for refrigeration machines designed to operate with refrigerants of higher or lower boiling point than HFC- 134a.

It is advantageous that the refrigerant compositions of the present invention are suitable for heat exchangers manufactured at least partially from aluminium parts which are brazed using non-corrosive fluxes, especially alkali fluoroaluminates such as potassium fluoroaluminate or cesium-containing potassium fluoroaluminate, or potassium hexafluorosilicate.

For some of these purposes, e.g. for heat pipe applications, ORC processes, heat transfer applications and solvent applications, compositions with a boiling point in the range of 20 to 70⁰C are especially suitable.

Another object of the present invention is to provide systems comprising the compositions according to the present invention. Simple'systems"of the present invention are containers, mostly made of metal, which comprise the composition, e.g. pressure bottles. Preferred"systems" denote apparatus which allow the application of the composition of matter. For example, the system of the present invention may be a portable fire extinguisher or a total flooding system comprising the composition of matter.

A preferred system of the present invention is a machine for cooling or heating comprising the composition of matter according to the present invention. Usually, such a machine comprises a condenser, an evaporator, lines to transport the composition between the different parts of the apparatus, heat exchangers, valves, pumps and other parts used in such apparatus and can be used in a mobile or stationary way. Stationary systems are freezers, air conditioning systems in houses, factories, hospitals, working rooms, rooms for storing food or drugs, refrigerated boxes or containers for storage or transport, and the like. A very preferred system of the present invention is a mobile air conditioning system, especially for cars, lorries, trucks, buses, airplanes, trains, spaceships and the like. If desired, compounds A can be purified before applying them as refrigerant or other purposes. The compounds have a very low GWP and no ozone destruction potential. Using essentially pure (E) or (Z) isomers or defined mixtures thereof guarantees defined properties of the mixtures.

The following examples shall describe the invention in further detail without being intended to limit the scope of it. Examples

General remark : Alkyl benzene compounds are especially suitable lubricants. Fuchs Reniso S46F can for example be used. It is an alkyl benzene lubricants with a kinematic viscosity at 40⁰C in the range of 46 mm²/s. Instead of this oil, ND8 PAG of Denso can be applied.

Example 1 : Preparation of a composition of matter suitable for refrigeration Ia) Preparation of (E)-HFC- 1225ye :

As described by D.J. Burton et al. in J. Fluorine Chem., 44 (1989), page 167 and 168, hexafluoropropene is added through a cooled condensor into a flask equipped with a magnetic stirrer, dry ice condenser, rubber septum and glass stopper containing dry ether. Tri-n-butylphosphine is added dropwise to the solution which is cooled to -78°C. The mixture is then slowly allowed to warm up to room temperature. Then, the ether is removed applying a flash distillation apparatus. Triglyme and water are added, and after fmalization of the reaction, the product is removed under vacuum and condensed in a cooled trap.

Boiling point of the (E) isomer : -18.5°C (see also D. Sianesi and R. Fontanelli, Ann.Chim.(Rome); 55; 1965; pages 850-861, especially 853 to 854 and 857 to 859. Ib) Preparation of (Z)-HFC- 1225ye : as described by D.J. Burton, I.e., page 169, SbF₅ is placed in a tube, and (E)-isomer produced according to example Ib) is condensed into the tube. The tube is then allowed to come to room temperature and transferred to another tube with sodium fluoride. Then, the product is condensed under vacuum into a cooled tube for storage.

Boiling point of the (Z) isomer : -18°C (see D. Sianesi, R. Fontanelli, I.e.). IcI) Preparing defined mixtures of the (E)- and (Z)-isomer

Mixtures in the molar range of 2,5:1 to 1 :2,5 are prepared by mixing appropriate amounts of the (E) and (Z) isomer the preparation of which is described in examples Ia). and Ib). Ic2) A mixture of Z and E isomer in the ratio 30:70 can be purchased from

ABCR GmbH und Co KG, Karlsruhe/Germany. Example 2 : Preparation of refrigerants General procedure :

The components are condensed together in the amounts given in the following table into a storage tank under vacuum and mixed by shaking it.

The E and Z isomers are prepared as described above. The mixture of E and Z isomer with molar ratio 70:30 can be purchased from ABCR, the 1 : 1 and 1 :2 mixtures can be produced by mixing respective ratios of the E and Z isomers.

Refrigerant mixtures comprising (E)-1225ye

* PVME = perfluoro-methylvinylether Refrigerant mixtures comprising (Z)-1225ye

^: PVME = perfluoro-methylvinylether Refrigerant mixtures comprising (E)-1225ve and (Z)-isomer, molar ratio (E) : (Z) 70:30

* PVME = perfluoro-methylvinylether Refrigerant mixtures comprising (E)-1225ve and (Z)-isomer, molar ratio (E) : (Z) 1 :1

PVME = perfluoro-methylvinylether Refrigerant mixtures comprising (E)-1225ve and (Z)-isomer, molar ratio (E) : (Z) 1 :2

PVME = perfluoro-methylvinylether Example 3 : A mobile air conditioning system comprising a refrigerant according to the invention :

In a mobile air conditioning system, the used refrigerant (which may be, for example, HFC-134a) is removed and 85Og of the refrigerant mixture comprising 75 % by weight of the E isomer, the Z isomer or their mixtures and 25 % by weight of HFC- 152a is filled into the system under pressure. The oil, especially if it is an alkyl benzene oil, remains in the system. If another oil type is comprised, it may be substituted by an alkyl benzene oil, e.g. by Fuchs Reniso S46F. Example 4 : A mobile air conditioning system comprising other refrigerants according to the invention :

4.1. In a mobile air conditioning (MAC) system, the used refrigerant (which may be, for example, HFC- 134a) is removed and 85Og of the refrigerant mixture comprising 50 % by weight of the E isomer, the Z isomer or their mixtures and 50 % by weight of perfluoro-methylvinyl ether is filled into the system under pressure. The oil, especially if it is an alkyl benzene oil, remains in the system. If another oil type is comprised, it may be substituted by an alkyl benzene oil, e.g. by Fuchs Reniso S46F.

4.2. As in example 4.1., the other mixtures given in the tables of example 4 are filled into the refrigerant system after removal of the refrigerant originally comprised therein. Fuchs Reniso S46F can be applied as suitable lubricant.

4.3. 850 g of the mixtures given in the tables of example 2 are filled together with alkyl benzene lubricant into an unused MAC system. Example 5 : A mobile air conditioning system comprising an azeotrope-like composition of HFC-1225ye and perfluoro-methylvinyl ether (PVME)

HFC-1225ye was used in the form of a mixture of the E and Z isomer in a molar ratio of 70:30, as purchased from ABCR GmbH und Co KG, Karlsruhe, Germany. The mixture was condensed into a storage tank, as well as perfluoro-methylvinyl ether. The mass ratio of HFC-1225ye to PVME was 75:25.

The mixture was identified to be non-flammable. The temperature glide at p_s 2 bar was estimated to be around 1 to 2 K. The ODP of the mixture is 0, the GWP is lower than 10. Its boiling point under normal conditions (1 bar pressure) was determined to be -22.5°C. This boiling point is lower than that of PVME which is -21.3°C, and of HFC-1225ye which is -18.0⁰C. The binary composition can then be filled into a mobile air conditioning system; suitable oil, for example a polyalkylbenzene oil, can be added. Example 6 : A mobile air conditioning system comprising an azeotrope-like composition of HFC-1225ye and perfluoro-methylvinyl ether (PVME) Example 5 is repeated, the molar ratio of the HFC-1225ye isomer mixture and PVME is now 80:20.

Example 7 : 10/90 mixture of perfluoromethyl-vinyl ether(PVME) and (E)/(Z)-pentafluoropropene

By condensing perfluoro-methylvinyl ether and HFC-1225ye mixtures with an E:Z ratio of 70:30, obtained from ABCR GmbH & Co. KG,

Karlsruhe/Germany, a refrigerant mixture with a weight ratio of PVME and pentafluoropropene of 10:90 was prepared.

The composition was identified to be non-flammable. Example 8 : 10/90 mixture of perfluoromethyl-vinyl ether(PVME) and (Z)-pentafluoropropene

By condensing perfluoro-methylvinyl ether and (Z)-HFC- 1225ye, a refrigerant composition with a weight ratio of PVME and (Z)- pentafluoropropene of 10:90 is, prepared.

The mixture is identified to be non-flammable. Example 9 : 10/10/80 mixture of perfluoromethyl-vinyl ether (PVME), HFC- 134a and pentafluoropropene

By condensing perfluoro-methylvinyl ether, HFC- 134a and HFC-1225ye, a refrigerant composition with a weight ratio of PVME, HFC- 134a and pentafluoropropene of 10:10:80 is prepared. The mixture is identified to be non-flammable.

Example 10 : Mixture of (Z)-HFC- 1225ye and pentafluoroethane (HFC- 125)

By condensing the (Z) isomer of HFC-1225ye and HFC- 125 in a weight ratio of 96.5:3.5, a refrigerant mixture is prepared.

Example 11 : Thermodynamic data of some compositions according to the invention compared to the data of pure HFC-134a.

The thermodynamic data of the components perfluoromethyl-vinyl ether (PVME) and the (E)/(Z) mixture of pentafluoropropene were measured, and with these data and the known data for HFC- 134a and HFC- 125, the C_op (coefficient of performance) and Q_voi. (volumetric efficiency) of the compositions of examples were calculated using "Refbrop 7.0' for a single cycle with T₀ = 0⁰C, TsubH. = 10 K, T_subC = 2 K, T_c = 40⁰C, η_ls. = f(p_c/po). The resulting figures were compared to those of HFC- 134a.

* Boiling point of the saturated liquid at 1.013 bar : -26.7°C ** Boiling point of the saturated liquid at 1.013 bar : -18.4°C *** Boiling point of the saturated liquid at 1.013 bar : -20.5⁰C **** Boiling point of the saturated liquid at 1.013 bar : -19.5°C υT Glide 0⁰C - T"(p'(0°C)), K

The results show that the composition of example 7 performs very good and better than the compositions of examples 9 and 10 because the higher the c_op, the better the performance of the respective refrigerant. The low temperature glide of 0.6⁰C of the composition of example 7, lowest value of all compositions, is especially advantageous. The low temperature glide at evaporation at 0⁰C has high advantages when the refrigerant is applied because evaporation must be performed in a very narrow temperature band, and a low temperature glide gives high flexibility. It is expected that compositions comprising the (Z) isomer give comparable results, too. Example 12 : Mixtures stabilized with Terpenes

To the mixture of example 7, beta-pinene was added so that the content in alpha-pinene was 0.5 % by weight of the composition. Other suitable stabilizers are for example other terpene compounds, for example, limonene, alpha-pinene, dipentene or citronellol.

Determination of certain properties of the composition of example 7 A) Permeability of standard sealing materials :

General procedure : The tested polymers were applied as slabs with a thickness of 2 mm. They were put into a high pressure permeation cell. The refrigerant was filled into a space on one side of the slab. Permeated refrigerant was analyzed by gas chromatograph. The permeation cells were stored for 100 h at 90⁰C.

Slabs made of several EPDM (ethylene propylene diene monomer rubber) plastic, and HNBR (hydrogenated acrylnitrile butadiene rubber) plastic were tested. The lowest permeation was observed for EPDM plastic slab made from material available from Freudenberg.

B) Permeation of hoses

General procedure : the refrigerant was filled into the respective hose. Then the hose was kept for 500 h at 90⁰C. The permeation was analyzed by gas chromatography of the gas space around the hose.

Several high temperature hoses and normal temperature hoses made from polyamide, chloroprene, butyl and rubber were tested. The permeation through hoses made from polyamide and chloroprene was very low. The permeation tests also revealed that the rate of permeation of PVME through the different items is by far lower than the speed of permeation of the (E) and (Z) isomers of HFC-1225ye.

C) Compatibility of a refrigerant/oil composition with sealing, o-ring and slab material Several o-rings made of EPDM and HNBR material, several high temperature hoses made of polyamide and chloroprene and normal temperature hoses made of polyamide, butyl or comprising an inner butyl layer were tested.

Mechanical properties (tensile properties, IRHD (international rubber hardness degree), geometrical dimensions and hardness) were determined. General procedure :

The tests were performed in autoclaves suitable for the o-rings and dumb bells, respectively. The hose material was applied to dumb bells. 60 ml of ND8 PAG oil and the material to be tested was put into the autoclave which then was evacuated were evacuated, and 60 ml refrigerant (for oil rings) or 30 ml (for dumb bells) were condensed in the autoclave. The autoclave was then transferred to a thermo chamber and, in case of the o-rings, kept there for 500 h at 100⁰C and, in another experiment, for 168 h at 150⁰C. The high temperature hose material was tested for 500 h at 100⁰C and for 168 h at 140⁰C. The normal temperature hose material was treated for 500 h at 100⁰C and 168 h at 125°C. The refrigerant was then removed, the samples were pruned to remove adhering oil, afterwards, the samples were kept for 30 minutes at 60⁰C in a thermo chamber.

Tensile properties were then tested according to ISO 37 (2005), IRDH hardness according to ISO 48 (2003). Dimensions and volumes were determined by measuring the dimensions and calculation of the volumes and their changes. Results :

Changes of volume : target limit ± 15 %. All tested samples fulfilled this requirement.

Claims

C L A I M S

1. A composition comprising

a compound A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1 to 1 :2,5 ,

and at least one compound B selected from the group consisting of : HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC- 125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, perfluoro-methylvinyl ether, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂ and CF₃I.

2. A composition according to claim 1 comprising one or more compounds B wherein at least one compound B is selected from the group consisting of HFC- 134a, HFC- 152a, HFC-227ea, perfluoro-methylvinyl ether, propane, n-butane, i-butane, 2-methylbutane, n-pentane, CO₂ and CF3I.

3. A composition according to claim 1 or 2 where compound A is comprised in an amount of 1 to 99 % by weight of the sum of compounds A and compounds B, and compound B or, if there are more than one compounds B, the sum of compounds B is comprised in an amount of 99 to 1 % by weight in the sum of compounds A and B.

4. A composition according to any of claims 1 to 3 consisting of

a compound A selected from the group consisting of (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5:1 to 1 :2,5 and

one or two compounds B selected from the group consisting of HFC-32; HFC-134a; HFC-152a; propane; n-butane; i-butane; CO₂; CF₃I; and

optionally a second compound B selected from the group consisting of HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC- 32, HFC- 125, HFC-134, HFC-143a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, perfluoro-methylvinyl ether, 2-methylbutane, n-pentane, cyclopentane, dimethylether, and CF₃SCF₃.

5. A composition according to claim 4 consisting of

one compound B or a combination of two compounds B selected from the group consisting of HFC-32; HFC- 134a; HFC- 152a; perfluoro-methylvinyl ether; CO₂;

CF₃I; HFC- 134a and CO₂; HFC- 134a and HFC- 152a; HFC- 134a, HFC- 152a and CO₂; HFC- 134a and HFC-32; HFC- 134a and HFC-1234ze; HFC- 134a and

HFC-1234yf; HFC- 134a and HFC-1234ye; HFC- 134a and HFC-1243zf;

HFC- 134a and propane; HFC- 134a and n-butane;HFC-134a and i-butane;

HFC- 134a and dimethylether; HFC- 152a and CO₂; HFC- 152a and HFC-32;

HFC-152a and propane; HFC-125a and HFC-1234ze; HFC-152a and HFC-1234yf; HFC-125a and HFC-1234ye; HFC-125a and HFC-1243zf;

6. A composition according to claim 1 which has a GWP of less than 150, preferably less than 140, especially preferably of less than 120.

7. A composition according to claim 1 which is non-flammable.

8. A composition according to claim 1 wherein compound B is selected from HFC-32, HFC- 152a and perfluoro-methylvinyl ether.

9. An azeotrope-like composition comprising (E)-HFC- 1225ye, (Z)-HFC- 1225ye or a mixture of the (E) isomer and the (Z) isomer in a molar ratio of 2,5 : 1 to 1 :2,5 and perfluoro-methylvinyl ether in a mass ratio of 85 : 15 to 70:30.

10. A refrigerant comprising a composition according to any of claims 1 to 9 and refrigerant additives.

11. A refrigerant according to claim 10 which comprises one or more additives selected from the group consisting of lubricants, stabilizers, UV fluorescent dyes, tracer compounds, and solubility compatibilizers, metal passivators and corrosion inhibitors.

12. A method for heating or cooling wherein a composition according to claims 1 to 10 or a refrigerant according to claims 10 or 11 is applied.

13. A method according to claim 12 for mobile air cooling.

14. A method according to claims 12 or 13, wherein the composition or refrigerant is a drop-in or retrofit substitute for HFC- 134a.

15. A method according to any of claims 12 to 14 wherein the refrigerant has a GWP of less than 150, preferably less than 140, especially preferably less than 120, and is non-flammable.