CN101522850A - Thiol and thioether stabilizers for fluoroolefins - Google Patents

Abstract

The present disclosure relates to compositions comprising at least one fluoroolefin and an effective amount of a stabilizer comprising at least one thiol or thioether, or mixtures thereof. The stabilized compositions may be useful in cooling apparatus, such as refrigeration, air-conditioning, chillers and heat pumps, as well as in applications as foam blowing agents, solvents, aerosol propellants, fire extinguishants, and sterilants.

Description

The mercaptan of fluoroolefins and thioether stabilizers

Background of invention

1. invention field

The composition that the present invention relates to comprise at least a fluoroolefin and contain the stablizer of at least a mercaptan or thioether.This stabilized composition can be used as the work on hand fluidic substitute with higher Global warming potentiality and is used in the cooling system.

2. description of Related Art

New environmental regulations about working fluid has promoted refrigeration and the industrial novel working fluid with low Global warming potentiality (GWP) of seeking of air-conditioning.

Seeking alternative working fluid with low GWP, nontoxicity, non-inflammability, reasonable cost and excellent refrigeration performance.

Fluoroolefin be suggested separately or with form of mixtures as working fluid.But, observe, when fluoroolefin exposes at high temperature or can show degraded when contacting with other compound (for example moisture, oxygen or other compound of condensation reaction can take place with them).When fluoroolefin during as the working fluid in the heat transfer equipment (for example refrigeration or conditioning unit) maybe in being used in some other purposes the time, this degraded may take place.This degraded can take place by many different mechanisms.In one case, this degraded may be caused in the unstable under the extreme temperature by this compound.In other cases, this degraded may be caused by the oxidation in the presence of the air that is not intended to leak in this system.Regardless of the reason of this degraded, because the unstable of fluoroolefin, these fluoroolefin are mixed refrigeration or air-conditioning system may be unrealistic.Therefore, in order to utilize many other attributes of fluoroolefin, need to reduce the mode of degraded.

Summary of the invention

For avoiding fluoroolefin possible unstable of (especially at high temperature) under the extreme condition of system operation, have been found that, add specific compound in fluoroolefin, promptly at least a mercaptan or thioether can improve its stability in refrigeration or air-conditioning system purposes.

Therefore, according to the present invention, provide to comprise containing of at least a fluoroolefin and significant quantity of at least a mercaptan or the composition of the stablizer of thioether or its mixture.

The fluoroolefin that comprises at least a HFC-1225ye of being selected from, HFC-1234yf, HFC-1234ze and HFC-1243zf also is provided; The composition of stablizer with comprising of significant quantity at least a mercaptan or thioether and at least a amine.

The method that makes the composition stability that comprises at least a fluoroolefin also is provided, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

The method that reduces the degraded of the composition that comprises at least a fluoroolefin also is provided, wherein said degraded causes by the existence that is strayed into air in refrigeration, air-conditioning or the heat pump, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

Also provide and reduced the method that the composition that comprises at least a fluoroolefin and oxygen react, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

Detailed Description Of The Invention

The invention provides and comprise containing of at least a fluoroolefin and significant quantity of at least a mercaptan or the composition of the stablizer of thioether or its mixture.

These compositions serve many purposes in working fluid, described working fluid only gives some instances, and comprises whipping agent, solvent, aerosol propellants, fire-fighting medium, disinfectant or heat-transfer medium (as be used in refrigeration system, refrigerator, air-conditioning system, heat pump, the water cooler etc. heat-transfer fluid and refrigeration agent).

Whipping agent is polymeric matrix to be expanded form the volatile compositions of vesicular structure.

Solvent is to remove crude removal or deposit a material in the substrate or the fluid of support materials from substrate.

Aerosol propellants is to apply greater than an atmospheric pressure to plant the volatile compositions of component with one or more that material is released from container.

Fire-fighting medium is the volatile compositions that extinguishes or suppress flame.

Disinfectant is to destroy the volatility biocidal fluid of biological active materials or analogue or contain volatility biocidal fluidic blend.

Heat-transfer medium (being also referred to as heat-transfer fluid, heat transfer compositions or heat transfer fluid composition herein) is to be used for heat from the working fluid of thermal source biography to scatterer.

Refrigeration agent is to stand from liquid to gas and get back to compound or the compound that serves as heat-transfer fluid in cycle of phase transformation of liquid at this fluid.

Term fluoroolefin used herein has been described the compound that comprises carbon atom, fluorine atom and optional hydrogen atom.In one embodiment, used fluoroolefin comprises the compound with 2 to 12 carbon atoms in the composition of the present invention.In another embodiment, fluoroolefin comprises the compound with 3 to 10 carbon atoms, and in an embodiment again, fluoroolefin comprises the compound with 3 to 7 carbon atoms.Representative fluoroolefin includes but not limited to all listed in table 1, table 2 and the table 3 compounds.

One embodiment of the invention provide has formula E-or Z-R ¹CH=CHR ²The fluoroolefin of (formula I), wherein R ¹And R ²Be C independently ₁To C ₆Perfluoroalkyl.R ¹And R ²Examples of groups includes but not limited to, CF ₃, C ₂F ₅, CF ₂CF ₂CF ₃, CF (CF ₃) ₂, CF ₂CF ₂CF ₂CF ₃, CF (CF ₃) CF ₂CF ₃, CF ₂CF (CF ₃) ₂, C (CF ₃) ₃, CF ₂CF ₂CF ₂CF ₂CF ₃, CF ₂CF ₂CF (CF ₃) ₂, C (CF ₃) ₂C ₂F ₅, CF ₂CF ₂CF ₂CF ₂CF ₂CF ₃, CF (CF ₃) CF ₂CF ₂C ₂F ₅And C (CF ₃) ₂CF ₂C ₂F ₅In one embodiment, the fluoroolefin of formula I has about at least 4 carbon atoms in molecule.In another embodiment, the fluoroolefin of formula I has about at least 5 carbon atoms in molecule.Exemplary non-limiting formula I compound is listed in the table 1.

Table 1

Code	Structure	Chemical name
			F11E	CF 3CH＝CHCF 3	1,1,1,4,4,4-hexafluoro but-2-ene
F12E	CF 3CH＝CHC 2F 5	1,1,1,4,4,5,5,5-octafluoro penta-2-alkene
			F13E	CF 3CH＝CHCF 2C 2F 5	1,1,1,4,4,5,5,6,6,6-ten fluorine oneself-2-alkene
F13iE	CF 3CH＝CHCF(CF 3) 2	1,1,1,4,5,5,5-seven fluoro-4-(trifluoromethyl) penta-2-alkene
			F22E	C 2F 5CH＝CHC 2F 5	1,1,1,2,2,5,5,6,6,6-ten fluorine oneself-3-alkene
F14E	CF 3CH＝CH(CF 2) 3CF 3	1,1,1,4,4,5,5,6,6,7,7,7-ten difluoro hept-2-ene"s
			F14iE	CF 3CH＝CHCF 2CF-(CF 3) 2	1,1,1,4,4,5,6,6,6-nine fluoro-5-(trifluoromethyl) oneself-2-alkene
F14sE	CF 3CH＝CHCF(CF 3)-C 2F 5	1,1,1,4,5,5,6,6,6-nine fluoro-4-(trifluoromethyl) oneself-2-alkene
			F14tE	CF 3CH＝CHC(CF 3) 3	1,1,1,5,5,5-hexafluoro-4, two (trifluoromethyl) penta-2-alkene of 4-
F23E	C 2F 5CH＝CHCF 2C 2F 5	1,1,1,2,2,5,5,6,6,7,7,7-ten difluoros heptan-3-alkene
			F23iE	C 2F 5CH＝CHCF(CF 3) 2	1,1,1,2,2,5,6,6,6-nine fluoro-5-(trifluoromethyl) oneself-3-alkene
F15E	CF 3CH＝CH(CF 2) 4CF 3	1,1,1,4,4,5,5,6,6,7,7,8,8,8-ten tetrafluoro oct-2-enes
			F15iE	CF 3CH＝CH-CF 2CF 2CF(CF 3) 2	1,1,1,4,4,5,5,6,7,7,7-11 fluoro-6-(trifluoromethyl) hept-2-ene"s

F15tE	CF 3CH＝CH-C(CF 3) 2C 2F 5	1,1,1,5,5,6,6,6-octafluoro-4,4-two (trifluoromethyls) oneself-2-alkene
			F24E	C 2F 5CH＝CH(CF 2) 3CF 3	1,1,1,2,2,5,5,6,6,7,7,8,8,8-ten tetrafluoros suffering-3-alkene
F24iE	C 2F 5CH＝CHCF 2CF-(CF 3) 2	1,1,1,2,2,5,5,6,7,7,7-11 fluoro-6-(trifluoromethyl) heptan-3-alkene
			F24sE	C 2F 5CH＝CHCF(CF 3)-C 2F 5	1,1,1,2,2,5,6,6,7,7,7-11 fluoro-5-(trifluoromethyl) heptan-3-alkene
F24tE	C 2F 5CH＝CHC(CF 3) 3	1,1,1,2,2,6,6,6-octafluoro-5,5-two (trifluoromethyls) oneself-3-alkene
			F33E	C 2F 5CF 2CH＝CH-CF 2C 2F 5	1,1,1,2,2,3,3,6,6,7,7,8,8,8-ten tetrafluoros suffering-4-alkene
F3i3iE	(CF 3) 2CFCH＝CH-CF(CF 3) 2	1,1,1,2,5,6,6,6-octafluoro-2,5-two (trifluoromethyls) oneself-3-alkene
			F33iE	C 2F 5CF 2CH＝CH-CF(CF 3) 2	1,1,1,2,5,5,6,6,7,7,7-11 fluoro-2-(trifluoromethyl) heptan-3-alkene
F16E	CF 3CH＝CH(CF 2) 5CF 3	1,1,1,4,4,5,5,6,6,7,7,8,8,, 9,9,9-ten hexafluoros ninth of the ten Heavenly Stems-2-alkene
			F16sE	CF 3CH＝CHCF(CF 3)(CF 2) 2C 2F 5	1,1,1,4,5,5,6,6,7,7,8,8,8-13 fluoro-4-(trifluoromethyl) hept-2-ene"s
F16tE	CF 3CH＝CHC(CF 3) 2CF 2C 2F 5	1,1,1,6,6,6-octafluoro-4, two (trifluoromethyl) hept-2-ene"s of 4-
			F25E	C 2F 5CH＝CH(CF 2) 4CF 3	1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-ten hexafluoros ninth of the ten Heavenly Stems-3-alkene
F25iE	C 2F 5CH＝CH-CF 2CF 2CF(CF 3) 2	1,1,1,2,2,5,5,6,6,7,8,8,8-13 fluoro-7-(trifluoromethyl) suffering-3-alkene
			F25tE	C 2F 5CH＝CH-C(CF 3) 2C 2F 5	1,1,1,2,2,6,6,7,7,7-ten fluoro-5,5-two (trifluoromethyl) heptan-3-alkene
F34E	C 2F 5CF 2CH＝CH-(CF 2) 3CF 3	1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-ten hexafluoros ninth of the ten Heavenly Stems-4-alkene
			F34iE	C 2F 5CF 2CH＝CH-CF 2CF(CF 3) 2	1,1,1,2,2,3,3,6,6,7,8,8,8-13 fluoro-7-(trifluoromethyl) suffering-4-alkene
F34sE	C 2F 5CF 2CH＝CH-CF(CF 3)C 2F 5	1,1,1,2,2,3,3,6,7,7,8,8,8-13 fluoro-6-(trifluoromethyl) suffering-4-alkene
			F34tE	C 2F 5CF 2CH＝CH-C(CF 3) 3	1,1,1,5,5,6,6,7,7,7-ten fluoro-2,2-two (trifluoromethyl) heptan-3-alkene
F3i4E	(CF 3) 2CFCH＝CH-(CF 2) 3CF 3	1,1,1,2,5,5,6,6,7,7,8,8,8-13 fluoro-2 (trifluoromethyl) suffering-3-alkene
			F3i4iE	(CF 3) 2CFCH＝CH-CF 2CF(CF 3) 2	1,1,1,2,5,5,6,7,7,7-ten fluoro-2,6-two (trifluoromethyl) heptan-3-alkene
F3i4sE	(CF 3) 2CFCH＝CH-CF(CF 3)C 2F 5	1,1,1,2,5,6,6,7,7,7-ten fluoro-2,5-two (trifluoromethyl) heptan-3-alkene
			F3i4tE	(CF 3) 2CFCH＝CH-C(CF 3) 3	1,1,1,2,6,6,6-seven fluoro-2,5,5-three (trifluoromethyl) oneself-3-alkene
F26E	C 2F 5CH＝CH(CF 2) 5CF 3	1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-ten octafluoros last of the ten Heavenly stems-3-alkene
			F26sE	C 2F 5CH＝CHCF(CF 3)(CF 2) 2C 2F 5	1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-15 fluoro-5-(trifluoromethyl) ninth of the ten Heavenly Stems-3-alkene

F26tE	C 2F 5CH＝CHC(CF 3) 2CF 2C 2F 5	1,1,1,2,2,6,6,7,7,8,8,8-12 fluoro-5, two (trifluoromethyl) sufferings of 5--3-alkene
			F35E	C 2F 5CF 2CH＝CH-(CF 2) 4CF 3	1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-ten octafluoros last of the ten Heavenly stems-4-alkene
F35iE	C 2F 5CF 2CH＝CH-CF 2CF 2CF(CF 3) 2	1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-15 fluoro-8-(trifluoromethyl) ninth of the ten Heavenly Stems-4-alkene
			F35tE	C 2F 5CF 2CH＝CH-C(CF 3) 2C 2F 5	1,1,1,2,2,3,3,7,7,8,8,8-12 fluoro-6, two (trifluoromethyl) sufferings of 6--4-alkene
F3i5E	(CF 3) 2CFCH＝CH-(CF 2) 4CF 3	1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-15 fluoro-2-(trifluoromethyl) ninth of the ten Heavenly Stems-3-alkene
			F3i5iE	(CF 3) 2CFCH＝CH-CF 2CF 2CF(CF 3) 2	1,1,1,2,5,5,6,6,7,8,8,8-12 fluoro-2, two (trifluoromethyl) sufferings of 7--3-alkene
F3i5tE	(CF 3) 2CFCH＝CH-C(CF 3) 2C 2F 5	1,1,1,2,6,6,7,7,7-nine fluoro-2,5,5-three (trifluoromethyl) heptan-3-alkene
			F44E	CF 3(CF 2) 3CH＝CH-(CF 2) 3CF 3	1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-ten octafluoros last of the ten Heavenly stems-5-alkene
F44iE	CF 3(CF 2) 3CH＝CH-CF 2CF(CF 3) 2	1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-15 fluoro-2-(trifluoromethyl) ninth of the ten Heavenly Stems-4-alkene
			F44sE	CF 3(CF 2) 3CH＝CH-CF(CF 3)C 2F 5	1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-15 fluoro-3-(trifluoromethyl) ninth of the ten Heavenly Stems-4-alkene
F44tE	CF 3(CF 2) 3CH＝CH-C(CF 3) 3	1,1,1,5,5,6,6,7,7,8,8,8-12 fluoro-2,2 ,-two (trifluoromethyl) suffering-3-alkene
			F4i4iE	(CF 3) 2CFCF 2CH＝CH-CF 2CF(CF 3) 2	1,1,1,2,3,3,6,6,7,8,8,8-12 fluoro-2, two (trifluoromethyl) sufferings of 7--4-alkene
F4i4sE	(CF 3) 2CFCF 2CH＝CH-CF(CF 3)C 2F 5	1,1,1,2,3,3,6,7,7,8,8,8-12 fluoro-2, two (trifluoromethyl) sufferings of 6--4-alkene
			F4i4tE	(CF 3) 2CFCF 2CH＝CH-C(CF 3) 3	1,1,1,5,5,6,7,7,7-nine fluoro-2,2,6-three (trifluoromethyl) heptan-3-alkene
F4s4sE	C 2F 5CF(CF 3)CH＝CH-CF(CF 3)C 2F 5	1,1,1,2,2,3,6,7,7,8,8,8-12 fluoro-3, two (trifluoromethyl) sufferings of 6--4-alkene
			F4s4tE	C 2F 5CF(CF 3)CH＝CH-C(CF 3) 3	1,1,1,5,6,6,7,7,7-nine fluoro-2,2,5-three (trifluoromethyl) heptan-3-alkene
F4t4tE	(CF 3) 3CCH＝CH-C(CF 3) 3	1,1,1,6,6,6-hexafluoro-2,2,5,5-four (trifluoromethyl) oneself-3-alkene

The compound of formula I can be by making formula R ¹The perfluoroalkyl iodides of I and formula R ²CH=CH ₂Perfluoroalkyl three hydrogen alkene contacts to form formula R ¹CH ₂CHIR ²Three hydrogen iodo perfluoro alkane prepare.This three hydrogen iodo perfluoro alkane subsequently dehydroiodination to form R ¹CH=CHR ²Perhaps, this alkene R ¹CH=CHR ²Can through type R ¹CHICH ₂R ²The dehydroiodination of three hydrogen iodo perfluoro alkane prepare, the latter is again by making formula R ²The perfluoroalkyl iodides of I and formula R ¹CH=CH ₂Perfluoroalkyl three hydrogen olefine reactions form.

Contacting of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene can be by merging reactant and carrying out with batch mode from depressing at reactant and product in the suitable reaction vessels of moving under temperature of reaction.Suitable reaction vessel comprises by stainless steel, particularly Austenitic stainless steel and known Langaloy, as

Nickel-copper alloy,

Nickel-base alloy and

Those that nickel-chromium alloy is made.

Perhaps, this reaction can be carried out with the semi-batch pattern, wherein under temperature of reaction by suitable feeding device, as pump perfluoroalkyl three hydrogen olefin reactants are added in the perfluoroalkyl iodides reactant.

The ratio of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene should be the extremely about 4:1 of about 1:1, preferably approximately 1.5:1 to 2.5:1.Exist as people such as Jeanneaux Journal of Fluorine Chemistry, the 4th volume is reported in the 261-270 page or leaf (1974), often produces a large amount of 2:1 adductss less than the ratio of 1.5:1.

The preferred temperature that described perfluoroalkyl iodides is contacted with described perfluoroalkyl three hydrogen alkene is preferably about 150 ℃ to 300 ℃, 170 ℃ to about 250 ℃ of preferably approximatelies, most preferably about 180 ℃ to about 230 ℃.Be about 0.5 hour to 18 hours the suitable duration of contact of the reaction of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene, and preferably approximately 4 was to about 12 hours.

The three hydrogen iodo perfluoro alkane of making by the reaction of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene can directly be used in the dehydroiodination step or can preferably reclaim by distillation before the dehydroiodination step and purify.

The dehydroiodination step is undertaken by three hydrogen iodo perfluoro alkane are contacted with alkaline matter.Suitable alkaline matter comprises that alkali metal hydroxide (for example, sodium hydroxide or potassium hydroxide), alkalimetal oxide (for example, sodium oxide), alkaline earth metal hydroxides (for example, calcium hydroxide), alkaline earth metal oxide (for example, calcium oxide), alkali metal alcoholates (for example, sodium methylate or sodium ethylate), the mixture of ammoniacal liquor, sodium amide or alkaline matter, as soda-lime.Preferred alkaline matter is sodium hydroxide and potassium hydroxide.Three hydrogen iodo perfluoro alkane can preferably carry out in the presence of the solvent that can dissolve these two kinds of reactants of at least a portion in liquid phase with described contact of alkaline matter.The solvent that is applicable to the dehydroiodination step comprises one or more polar organic solvents, as alcohol (for example, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol), nitrile (for example, acetonitrile, propionitrile, butyronitrile, benzonitrile or adiponitrile), methyl-sulphoxide, N, dinethylformamide, N,N-dimethylacetamide or tetramethylene sulfone.Choice of Solvent depends on product boiling point and the simplification of separating trace solvent in purification process from product.Usually, ethanol or Virahol are the good solvents of this reaction.

Usually, the dehydroiodination reaction can be by adding one of reactant (alkaline matter or three hydrogen iodo perfluoro alkane) in another reactant to and carry out in suitable reaction vessel.Described reactor can be made and preferably be stirred with impeller or whipping appts by glass, pottery or metal.

The temperature that is applicable to the dehydroiodination reaction is about 10 ℃ to about 100 ℃, 20 ℃ to about 70 ℃ of preferably approximatelies.The dehydroiodination reaction can be carried out at environmental stress or under decompression or elevated pressure.It is to be noted the distilled dehydroiodination reaction from reaction vessel when it forms of the compound of its Chinese style I.

Perhaps, this dehydroiodination reaction can have low polar organic solvent at one or more by the aqueous solution and the three hydrogen iodo perfluoro alkane that make described alkaline matter, as alkane (for example, hexane, heptane or octane), aromatic hydrocarbons (for example, toluene), halohydrocarbon (for example, methylene dichloride, chloroform, tetracol phenixin or tetrachloroethylene), or ether (for example, diethyl ether, methyl tert-butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, diglyme or tetraethylene glycol dimethyl ether) in solution in the presence of phase-transfer catalyst, contact and carry out.Suitable phase-transfer catalyst comprises that quaternary ammonium halide (for example; bromination tetrabutylammonium, hydrogen sulfate tetrabutylammonium, 3-ethyl benzyl ammonium chloride, dodecyltrimethyl ammonium chloride and chlorination three capryloyl first ammonium), quaternary phosphine halogenide are (for example; bromination three phenyl methyl Phosphonium and tetraphenylphosphonium chlorides) or be known as the cyclic polyether compound (for example, 18-hat-6 and 15-hat-5) of crown ether in this area.

Perhaps, this dehydroiodination reaction can be undertaken by three hydrogen iodo perfluoro alkane are added in solid or the liquid basified material under the situation that does not have solvent.

According to the solubleness of reactant, the suitable reactions time of dehydroiodination reaction is about 15 minutes to about 6 hours or more of a specified duration.Usually, dehydroiodination is swift in response and needed finish in about 30 minutes to about 3 hours.Can be by being separated, passing through distillation or making up the compound of recovery type I from the dehydroiodination reaction mixture behind the interpolation water by it.

In another embodiment of the present invention, fluoroolefin comprises ring fluoroolefin (ring-[CX=CY (CZW) _n-] (formula II), wherein X, Y, Z and W are independently selected from H and F, and n is 2 to 5 integer).In one embodiment, the fluoroolefin of formula II has about at least 3 carbon atoms in molecule.In another embodiment, the fluoroolefin of formula II has about at least 4 carbon atoms in molecule.In an embodiment again, the fluoroolefin of formula II has about at least 5 carbon atoms in molecule.The representativeness ring fluoroolefin of formula II is listed in the table 2.

Table 2

The ring fluoroolefin	Structure	Chemical name
			FC-C1316cc	Ring-CF 2CF 2CF＝CF-	1,2,3,3,4,4-hexafluoro cyclobutene
HFC-C1334cc	Ring-CF 2CF 2CH＝CH-	3,3,4,4-ptfe ring butylene
			HFC-C1436	Ring-CF 2CF 2CF 2CH＝CH-	3,3,4,4,5,5 ,-hexafluoro cyclopentenes
FC-C1418y	Ring-CF 2CF＝CFCF 2CF 2-	1,2,3,3,4,4,5,5-octafluoro cyclopentenes
			FC-C151-10y	Ring-CF 2CF＝CFCF 2CF 2CF 2-	1,2,3,3,4,4,5,5,6, the 6-decafluorocyclohexene

Composition of the present invention can comprise the compound of single formula I or formula II, and one of compound in table 1 or the table 2 for example maybe can comprise the combination of compounds of formula I or formula II.

In another embodiment, fluoroolefin can comprise those listed in the table 3 compounds.

Table 3

Title	Structure	Chemical name
			HFC-1225ye	CF 3CF＝CHF	1,2,3,3,3-five fluoro-1-propylene
HFC-1225zc	CF 3CH＝CF 2	1,1,3,3,3-five fluoro-1-propylene
			HFC-1225yc	CHF 2CF＝CF 2	1,1,2,3,3-five fluoro-1-propylene
HFC-1234ye	CHF 2CF＝CHF	1,2,3,3-tetrafluoro-1-propylene
			HFC-1234yf	CF 3CF＝CH 2	2,3,3,3-tetrafluoro-1-propylene
HFC-1234ze	CF 3CH＝CHF	1,3,3,3-tetrafluoro-1-propylene
			HFC-1234yc	CH 2FCF＝CF 2	1,1,2,3-tetrafluoro-1-propylene
HFC-1234zc	CHF 2CH＝CF 2	1,1,3,3-tetrafluoro-1-propylene
			HFC-1243yf	CHF 2CF＝CH 2	2,3,3-three fluoro-1-propylene
HFC-1243zf	CF 3CH＝CH 2	3,3,3-three fluoro-1-propylene
			HFC-1243yc	CH 3CF＝CF 2	1,1,2-three fluoro-1-propylene

HFC-1243zc	CH 2FCH＝CF 2	1,1,3-three fluoro-1-propylene
			HFC-1243ye	CH 2FCF＝CHF	1,2,3-three fluoro-1-propylene
HFC-1243ze	CHF 2CH＝CHF	1,3,3-three fluoro-1-propylene
			FC-1318my	CF 3CF＝CFCF 3	1,1,1,2,3,4,4,4-octafluoro-2-butylene
FC-1318cy	CF 3CF 2CF＝CF 2	1,1,2,3,3,4,4,4-octafluoro-1-butylene
			HFC-1327my	CF 3CF＝CHCF 3	1,1,1,2,4,4,4-seven fluoro-2-butylene
HFC-1327ye	CHF＝CFCF 2CF 3	1,2,3,3,4,4,4-seven fluoro-1-butylene
			HFC-1327py	CHF 2CF＝CFCF 3	1,1,1,2,3,4,4-seven fluoro-2-butylene
HFC-1327et	(CF 3) 2C＝CHF	1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene
			HFC-1327cz	CF 2＝CHCF 2CF 3	1,1,3,3,4,4,4-seven fluoro-1-butylene
HFC-1327cye	CF 2＝CFCHFCF 3	1,1,2,3,4,4,4-seven fluoro-1-butylene
			HFC-1327cyc	CF 2＝CFCF 2CHF 2	1,1,2,3,3,4,4-seven fluoro-1-butylene
HFC-1336yf	CF 3CF 2CF＝CH 2	2,3,3,4,4,4-hexafluoro-1-butylene
			HFC-1336ze	CHF＝CHCF 2CF 3	1,3,3,4,4,4-hexafluoro-1-butylene
HFC-1336eye	CHF＝CFCHFCF 3	1,2,3,4,4,4-hexafluoro-1-butylene
			HFC-1336eyc	CHF＝CFCF 2CHF 2	1,2,3,3,4,4-hexafluoro-1-butylene
HFC-1336pyy	CHF 2CF＝CFCHF 2	1,1,2,3,4,4-hexafluoro-2-butylene
			HFC-1336qy	CH 2FCF＝CFCF 3	1,1,1,2,3,4-hexafluoro-2-butylene
HFC-1336pz	CHF 2CH＝CFCF 3	1,1,1,2,4,4-hexafluoro-2-butylene
			HFC-1336mzy	CF 3CH＝CFCHF 2	1,1,1,3,4,4-hexafluoro-2-butylene
HFC-1336qc	CF 2＝CFCF 2CH 2F	1,1,2,3,3,4-hexafluoro-1-butylene
			HFC-1336pe	CF 2＝CFCHFCHF 2	1,1,2,3,4,4-hexafluoro-1-butylene
HFC-1336ft	CH 2＝C(CF 3) 2	3,3,3-three fluoro-2-(trifluoromethyl)-1-propylene
			HFC-1345qz	CH 2FCH＝CFCF 3	1,1,1,2,4-five fluoro-2-butylene
HFC-1345mzy	CF 3CH＝CFCH 2F	1,1,1,3,4-five fluoro-2-butylene
			HFC-1345fz	CF 3CF 2CH＝CH 2	3,3,4,4,4-five fluoro-1-butylene
HFC-1345mzz	CHF 2CH＝CHCF 3	1,1,1,4,4-five fluoro-2-butylene
			HFC-1345sy	CH 3CF＝CFCF 3	1,1,1,2,3-five fluoro-2-butylene
HFC-1345fyc	CH 2＝CFCF 2CHF 2	2,3,3,4,4-five fluoro-1-butylene
			HFC-1345pyz	CHF 2CF＝CHCHF 2	1,1,2,4,4-five fluoro-2-butylene
HFC-1345cyc	CH 3CF 2CF＝CF 2	1,1,2,3,3-five fluoro-1-butylene

HFC-1345pyy	CH 2FCF＝CFCHF 2	1,1,2,3,4-five fluoro-2-butylene
			HFC-1345eyc	CH 2FCF 2CF＝CF 2	1,2,3,3,4-five fluoro-1-butylene
HFC-1345ctm	CF 2＝C(CF 3)(CH 3)	1,1,3,3,3-five fluoro-2-methyl isophthalic acid-propylene
			HFC-1345ftp	CH 2＝C(CHF 2)(CF 3)	2-(difluoromethyl)-3,3,3-three fluoro-1-propylene
HFC1345fye	CH 2＝CFCHFCF 3	2,3,4,4,4-five fluoro-1-butylene
			HFC-1345eyf	CHF＝CFCH 2CF 3	1,2,4,4,4-five fluoro-1-butylene
HFC-1345eze	CHF＝CHCHFCF 3	1,3,4,4,4-five fluoro-1-butylene
			HFC-1345ezc	CHF＝CHCF 2CHF 2	1,3,3,4,4-five fluoro-1-butylene
HFC-1345eye	CHF＝CFCHFCHF 2	1,2,3,4,4-five fluoro-1-butylene
			HFC-1354fzc	CH 2＝CHCF 2CHF 2	3,3,4,4-tetrafluoro-1-butylene
HFC-1354ctp	CF 2＝C(CHF 2)(CH 3)	1,1,3,3-tetrafluoro-2-methyl isophthalic acid-propylene
			HFC-1354etm	CHF＝C(CF 3)(CH 3)	1,3,3,3-tetrafluoro-2-methyl isophthalic acid-propylene
HFC-1354tfp	CH 2＝C(CHF 2) 2	2-(difluoromethyl)-3,3-two fluoro-1-propylene
			HFC-1354my	CF 3CF＝CHCH 3	1,1,1,2-tetrafluoro-2-butylene
HFC-1354mzy	CH 3CF＝CHCF 3	1,1,1,3-tetrafluoro-2-butylene
			FC-141-10myy	CF 3CF＝CFCF 2CF 3	1,1,1,2,3,4,4,5,5,5-ten fluoro-2-amylenes
FC-141-10cy	CF 2＝CFCF 2CF 2CF 3	1,1,2,3,3,4,4,5,5,5-ten fluoro-1-amylenes
			HFC-1429mzt	(CF 3) 2C＝CHCF 3	1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene
HFC-1429myz	CF 3CF＝CHCF 2CF 3	1,1,1,2,4,4,5,5,5-nine fluoro-2-amylenes
			HFC-1429mzy	CF 3CH＝CFCF 2CF 3	1,1,1,3,4,4,5,5,5-nine fluoro-2-amylenes
HFC-1429eyc	CHF＝CFCF 2CF 2CF 3	1,2,3,3,4,4,5,5,5-nine fluoro-1-amylenes
			HFC-1429czc	CF 2＝CHCF 2CF 2CF 3	1,1,3,3,4,4,5,5,5-nine fluoro-1-amylenes
HFC-1429cycc	CF 2＝CFCF 2CF 2CHF 2	1,1,2,3,3,4,4,5,5-nine fluoro-1-amylenes
			HFC-1429pyy	CHF 2CF＝CFCF 2CF 3	1,1,2,3,4,4,5,5,5-nine fluoro-2-amylenes
HFC-1429myyc	CF 3CF＝CFCF 2CHF 2	1,1,1,2,3,4,4,5,5-nine fluoro-2-amylenes
			HFC-1429myye	CF 3CF＝CFCHFCF 3	1,1,1,2,3,4,5,5,5-nine fluoro-2-amylenes
HFC-1429eyym	CHF＝CFCF(CF 3) 2	1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene
			HFC-1429cyzm	CF 2＝CFCH(CF 3) 2	1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene
HFC-1429mzt	CF 3CH＝C(CF 3) 2	1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene
			HFC-1429czym	CF 2＝CHCF(CF 3) 2	1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene
HFC-1438fy	CH 2＝CFCF 2CF 2CF 3	2,3,3,4,4,5,5,5-octafluoro-1-amylene

HFC-1438eycc	CHF＝CFCF 2CF 2CHF 2	1,2,3,3,4,4,5,5-octafluoro-1-amylene
			HFC-1438ftmc	CH 2＝C(CF 3)CF 2CF 3	3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene
HFC-1438czzm	CF 2＝CHCH(CF 3) 2	1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene
			HFC-1438ezym	CHF＝CHCF(CF 3) 2	1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene
HFC-1438ctmf	CF 2＝C(CF 3)CH 2CF 3	1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene
			HFC-1447fzy	(CF 3) 2CFCH＝CH 2	3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene
HFC-1447fz	CF 3CF 2CF 2CH＝CH 2	3,3,4,4,5,5,5-seven fluoro-1-amylenes
			HFC-1447fvcc	CH 2＝CFCF 2CF 2CHF 2	2,3,3,4,4,5,5-seven fluoro-1-amylenes
HFC-1447czcf	CF 2＝CHCF 2CH 2CF 3	1,1,3,3,5,5,5-seven fluoro-1-amylenes
			HFC-1447mytm	CF 3CF＝C(CF 3)(CH 3)	1,1,1,2,4,4,4-seven fluoro-3-methyl-2-butenes
HFC-1447fyz	CH 2＝CFCH(CF 3) 2	2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene
			HFC-1447ezz	CHF＝CHCH(CF 3) 2	1,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene
HFC-1447qzt	CH 2FCH＝C(CF 3) 2	1,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butylene
			HFC-1447syt	CH 3CF＝C(CF 3) 2	2,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butylene
HFC-1456szt	(CF 3) 2C＝CHCH 3	3-(trifluoromethyl)-4,4,4-three fluoro-2-butylene
			HFC-1456szy	CF 3CF 2CF＝CHCH 3	3,4,4,5,5,5-hexafluoro-2-amylene
HFC-1456mstz	CF 3C(CH 3)＝CHCF 3	1,1,1,4,4,4-hexafluoro-2-methyl-2-butene
			HFC-1456fzce	CH 2＝CHCF 2CHFCF 3	3,3,4,5,5,5-hexafluoro-1-amylene
HFC-1456ftmf	CH 2＝C(CF 3)CH 2CF 3	4,4,4-three fluoro-2-(trifluoromethyl)-1-butylene
			FC-151-12c	CF 3(CF 2) 3CF＝CF 2	1,1,2,3,3,4,4,5,5,6,6,6-12 fluoro-1-hexenes (or perfluor-1-hexene)
FC-151-12mcy	CF 3CF 2CF＝CFCF 2CF 3	1,1,1,2,2,3,4,5,5,6,6,6-12 fluoro-3-hexenes (or perfluor-3-hexene)
			FC-151-12mmtt	(CF 3) 2C＝C(CF 3) 2	1,1,1,4,4,4-hexafluoro-2, two (the trifluoromethyl)-2-butylene of 3-
FC-151-12mmzz	(CF 3) 2CFCF＝CFCF 3	1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylenes
			HFC-152-11mmtz	(CF 3) 2C＝CHC 2F 5	1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene
HFC-152-11mmyyz	(CF 3) 2CFCF＝CHCF 3	1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene
			PFBE (or HFC-1549fz)	CF 3CF 2CF 2CF 2CH＝CH 2	3,3,4,4,5,5,6,6,6-nine fluoro-1-hexenes (or perfluorobutyl ethylene)
HFC-1549fztmm	CH 2＝CHC(CF 3) 3	4,4,4-three fluoro-3, two (the trifluoromethyl)-1-butylene of 3-
			HFC-1549mmtts	(CF 3) 2C＝C(CH 3)(CF 3)	1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butylene

HFC-1549fycz	CH 2＝CFCF 2CH(CF 3) 2	2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene
			HFC-1549myts	CF 3CF＝C(CH 3)CF 2CF 3	1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylenes
HFC-1549mzzz	CF 3CH＝CHCH(CF 3) 2	1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene
			HFC-1558szy	CF 3CF 2CF 2CF＝CHCH 3	3,4,4,5,5,6,6,6-octafluoro-2-hexene
HFC-1558fzccc	CH 2＝CHCF 2CF 2CF 2CHF 2	3,3,4,4,5,5,6,6-octafluoro-2-hexene
			HFC-1558mmtzc	(CF 3) 2C＝CHCF 2CH 3	1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylenes
HFC-1558ftmf	CH 2＝C(CF 3)CH 2C 2F 5	4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylenes
			HFC-1567fts	CF 3CF 2CF 2C(CH 3)＝CH 2	3,3,4,4,5,5,5-seven fluoro-2-Methyl-1-pentenes
HFC-1567szz	CF 3CF 2CF 2CH＝CHCH 3	4,4,5,5,6,6,6-seven fluoro-2-hexenes
			HFC-1567fzfc	CH 2＝CHCH 2CF 2C 2F 5	4,4,5,5,6,6,6-seven fluoro-1-hexenes
HFC-1567sfyy	CF 3CF 2CF＝CFC 2H 5	1,1,1,2,2,3,4-seven fluoro-3-hexenes
			HFC-1567fzfy	CH 2＝CHCH 2CF(CF 3) 2	4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-amylene
HFC-1567myzzm	CF 3CF＝CHCH(CF 3)(CH 3)	1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylenes
			HFC-1567mmtyf	(CF 3) 2C＝CFC 2H 5	1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-amylene
FC-161-14myy	CF 3CF＝CFCF 2CF 2C 2F 5	1,1,1,2,3,4,4,5,5,6,6,7,7,7-ten tetrafluoros-2-heptene
			FC-161-14mcyy	CF 3CF 2CF＝CFCF 2C 2F 5	1,1,1,2,2,3,4,5,5,6,6,7,7,7-ten tetrafluoros-2-heptene
HFC-162-13mzy	CF 3CH＝CFCF 2CF 2C 2F 5	1,1,1,3,4,4,5,5,6,6,7,7,7-13 fluoro-2-heptene
			HFC162-13myz	CF 3CF＝CHCF 2CF 2C 2F 5	1,1,1,2,4,4,5,5,6,6,7,7,7-13 fluoro-2-heptene
HFC-162-13mczy	CF 3CF 2CH＝CFCF 2C 2F 5	1,1,1,2,2,4,5,5,6,6,7,7, the 7-tridecafluoro-3-heptene
			HFC-162-13mcyz	CF 3CF 2CF＝CHCF 2C 2F 5	1,1,1,2,2,3,5,5,6,6,7,7, the 7-tridecafluoro-3-heptene
PEVE	CF 2＝CFOCF 2CF 3	Perfluor ethyl trifluoro vinyl ether
			PMVE	CF 2＝CFOCF 3	Trifluoromethyl trifluoro vinyl ether

Listed compound can be buied maybe and can prepare by method known in the art or as described herein in table 2 and the table 3.

1,1,1,4,4-five fluoro-2-butylene can be by 1,1,1,2,4,4-hexafluoro butane (CHF ₂CH ₂CHFCF ₃) by on the solid KOH in gas phase at room temperature dehydrofluorination prepare.At US 6,066, described 1,1,1,2,4 in 768,4-hexafluoro butane synthetic.1,1,1,4,4,4-hexafluoro-2-butylene can be by 1,1,1,4,4,4-hexafluoro-sec.-butyl iodide (CF ₃CHICH ₂CF ₃) by use phase-transfer catalyst about 60 ℃ down and KOH react and prepare.1,1,1,4,4, the synthetic of 4-hexafluoro-sec.-butyl iodide can pass through perfluoro-methyl iodine (CF ₃I) and 3,3,3-trifluoro propene (CF ₃CH=CH ₂) under about 200 ℃, carried out in about 8 hours depressing reaction certainly.

3,4,4,5,5,5-hexafluoro-2-amylene can be by using solid KOH or descend 1,1,1,2,2,3,3-seven amyl fluoride (CF at 200-300 ℃ on C catalyst ₃CF ₂CF ₂CH ₂CH ₃) dehydrofluorination prepare.1,1,1,2,2,3,3-seven amyl fluorides can be by 3,3,4,4,5,5,5-seven fluoro-1-amylene (CF ₃CF ₂CF ₂CH=CH ₂) hydrogenation preparation.

1,1,1,2,3,4-hexafluoro-2-butylene can be by using 1,1,1,2,3,3 of solid KOH, 4-seven fluorine butane (CH ₂FCF ₂CHFCF ₃) dehydrofluorination prepare.

1,1,1,2,4,4-hexafluoro-2-butylene can be by using 1,1,1,2,2,4 of solid KOH, 4-seven fluorine butane (CHF ₂CH ₂CF ₂CF ₃) dehydrofluorination prepare.

1,1,1,3,4,4-hexafluoro 2-butylene can be by using 1,1,1,3,3,4 of solid KOH, 4-seven fluorine butane (CF ₃CH ₂CF ₂CHF ₂) dehydrofluorination prepare.

1,1,1,2,4-five fluoro-2-butylene can be by using 1,1,1,2,2 of solid KOH, 3-hexafluoro butane (CH ₂FCH ₂CF ₂CF ₃) dehydrofluorination prepare.

1,1,1,3,4-five fluoro-2-butylene can be by using 1,1,1,3,3 of solid KOH, 4-hexafluoro butane (CF ₃CH ₂CF ₂CH ₂F) dehydrofluorination prepares.

1,1,1,3-tetrafluoro-2-butylene can be by making 1,1,1,3,3-3-pentafluorobutane (CF ₃CH ₂CF ₂CH ₃) with the KOH aqueous solution 120 ℃ of following prepared in reaction.

1,1,1,4,4,5,5,5-octafluoro-2-amylene can be by (CF ₃CHICH ₂CF ₂CF ₃) by use phase-transfer catalyst about 60 ℃ down and KOH react and prepare.4-iodo-1,1,1,2,2,5,5, the synthetic of 5-octafluoro pentane can pass through perfluoro ethyl iodide (CF ₃CF ₂I) and 3,3, the 3-trifluoro propene carried out depressing reaction certainly under about 200 ℃ in about 8 hours.

1,1,1,2,2,5,5,6,6,6-ten fluoro-3-hexenes can be by 1,1,1,2,2,5,5,6,6,6-ten fluoro-3-iodohexane (CF ₃CF ₂CHICH ₂CF ₂CF ₃) by use phase-transfer catalyst about 60 ℃ down and KOH react and prepare.1,1,1,2,2,5,5,6,6, the synthetic of 6-ten fluoro-3-iodohexanes can pass through perfluoro ethyl iodide (CF ₃CF ₂I) and 3,3,4,4,4-five fluoro-1-butylene (CF ₃CF ₂CH=CH ₂) under about 200 ℃, carried out in about 8 hours depressing reaction certainly.

1,1,1,4,5,5,5-seven fluoro-4-(trifluoromethyl)-2-amylenes can by in Virahol with KOH with 1,1,1,2,5,5,5-seven fluoro-4-iodo-2-(trifluoromethyl)-pentane (CF ₃CHICH ₂CF (CF ₃) ₂) dehydrofluorination prepares.CF ₃CHICH ₂CF (CF ₃) ₂By (CF ₃) ₂CFI and CF ₃CH=CH ₂At high temperature, the reaction manufacturing under for example about 200 ℃.

1,1,1,4,4,5,5,6,6,6-ten fluoro-2-hexenes can be by 1,1,1,4,4,4-hexafluoro-2-butylene (CF ₃CH=CHCF ₃) and tetrafluoroethylene (CF ₂=CF ₂) and antimony pentafluoride (SbF ₅) prepared in reaction.

2,3,3,4,4-five fluoro-1-butylene can be by 1,1,2,2,3, and the 3-hexafluoro butane is in the preparation of the dehydrofluorination under elevated temperature on the fluorided alumina.

2,3,3,4,4,5,5,5-octafluoro-1-amylene can be by 2,2,3,3,4,4,5,5, the dehydrofluorination preparation of 5-nine amyl fluorides on solid KOH.

1,2,3,3,4,4,5,5-octafluoro-1-amylene can be by 2,2,3,3,4,4,5,5, and 5-nine amyl fluorides are in the preparation of the dehydrofluorination under elevated temperature on the fluorided alumina.

The chemical compound lot of formula I, formula II, table 1, table 2 and table 3 exists as different configurational isomers or steric isomer.When not specifying specific isomer, the present invention is intended to comprise all single configurational isomers, single steric isomer or its any combination.For example, F11E is intended to represent any combination or the mixture of any ratio of E-isomer, Z-isomer or these two kinds of isomer.As another example, HFC-1225ye is intended to represent any combination or the mixture of any ratio of E-isomer, Z-isomer or these two kinds of isomer.

In one embodiment, the invention provides the composition that comprises at least a fluoroolefin and the stablizer of at least a mercaptan that contains significant quantity or thioether or its mixture.

In one embodiment, this stablizer can comprise at least a mercaptan.Mercaptan compound is also referred to as mercaptan (mercaptans) or sulfhydrate, comprises the sulfur analogs of the alcohol of hydroxyl.Representational thiol stabilizer includes but not limited to, methyl mercaptan (methyl mercaptan), ethane mercaptan (ethanethio), coenzyme A (CAS reg.no.[85-61-0]), dimercaptosuccinic acid (DMSA, CAS reg.no.[2418-14-6]), natsudaidai mercaptan ((R)-2-(4-methyl cyclohexane-3-thiazolinyl) propane-2-mercaptan, CAS reg.no.[83150-78-1]), halfcystine ((R)-2-amino-3-sulfane base-propionic acid, CAS reg.no.[52-90-4]) and Thioctamide (1,2-dithiolane-3-valeramide, CASreg.no.[940-69-2]) and composition thereof (being meant the mixture of any mercaptan listed in this section).

In another embodiment, this stablizer can comprise at least a thioether.Thioether includes but not limited to, benzyl phenyl sulphur (CAS reg.no.[831-91-4]), diphenyl sulfide (CAS reg.no.[139-66-2]), dibenzyl sulfide, can be with trade mark PS 802 (Ciba) is available from two (octadecyls) 3 of Ciba, 3 '-thiodipropionate and can be with trade mark PS 800 (Ciba) is available from two (dodecyls) 3 of Ciba, 3 '-thiopropionate, and composition thereof (being meant the mixture of any thioether listed in this section).

In another embodiment, the invention provides and comprise at least a fluoroolefin and contain the stablizer of at least a mercaptan or thioether or its mixture and the composition of at least a additional stability agent, this additional stability agent comprises at least a phenols that is selected from, group thiophosphate, butylation triphenyl group thiophosphate (butylated triphenylphosphorothionates), organophosphate/salt (organophosphate) class, phosphorous acid esters, terpenes, the terpenoid class, fullerene, the arylalkyl ethers, functionalized perfluoropolyether, polyoxyalkylated aromatic substance class, the alkylaromatic class, epoxides, the fluorinated epoxide class, the trimethylene oxide class, amine, the alkyl silane class, benzophenone derivates, xitix, Nitromethane 99Min., terephthalic acid divinyl ester, the compound of terephthaldehyde's diphenyl phthalate and composition thereof.

In one embodiment, this additional stability agent comprises at least a thiophosphatephosphorothioate.Thiophosphoric acid ester stabilizer of the present invention is by replace the compound that one or more Sauerstoffatom generates with divalent sulfur by phosphoric acid.These can be single thiophosphate ester, phosphorodithioate or high-grade thiophosphatephosphorothioate more.Representational phosphorodithioate can be with trade mark 63 available from Ciba Specialty Chemicals of Basel, Switzerland (hereinafter being called " Ciba ").In another embodiment, thiophosphatephosphorothioate comprises the dialkyl group thiophosphatephosphorothioate.Representational dialkyl group thiophosphoric acid ester stabilizer can be with trade mark

353 available from Ciba.

In one embodiment, this additional stability agent comprises at least a butylation triphenyl thiophosphatephosphorothioate (phosphorothionate).Butylation triphenyl thiophosphatephosphorothioate of the present invention (phosphorothionate) stablizer is suc as formula shown in the A.

Formula A

Each R is independently selected from an example of the butylation triphenyl thiophosphatephosphorothioate (phosphorothionate) of the H or the tertiary butyl can be with trade mark

232 available from Ciba.

In one embodiment, this additional stability agent comprises at least a organophosphate/salt.Suitable organophosphate/salt stabilizing agent with used as stabilizers includes but not limited to according to the present invention, phosphamide, trialkylphosphate, triaryl phosphate, mixed alkyl-aryl phosphate ester (alkyl diaryl, di alkylaryl or alkylated aryl), alkylated triaryl phosphates and annular phosphate and composition thereof.Representational phosphamide can be with trade mark

349 available from Ciba.Representational trialkylphosphate comprises: trimethyl phosphite 99 ((CH ₃) ₃PO ₄, Cas reg.no.512-56-1); Triethyl phosphate ((CH ₃CH ₂) ₃PO ₄, Cas reg.no.78-40-0); Tributyl phosphate ((C ₄H ₉) ₃PO ₄, CAS reg.no.126-73-8); Trioctyl phosphate ((C ₈H ₁₇) ₃PO ₄, CAS reg.no.1806-54-8); And tri-2-ethylhexyl phosphate ((CH ₃CH (C ₂H ₅) (CH ₂) ₄) ₃PO ₄, CASreg.no.78-42-2).Representational triaryl phosphate comprises: triphenylphosphate ((C ₆H ₅O) ₃PO, CAS reg.no.115-86-6); Tritolyl Phosphate (TCP, (CH ₃C ₆H ₄O) ₃PO, CAS reg.no.1330-78-5); And trixylyl phosphate (((CH ₃) ₂C ₆H ₃O) ₃PO, CAS reg.no.25155-23-1).Representational mixed alkyl-aryl phosphate ester comprises: p isopropylbenzoic acid base phenyl phenyl ester (IPPP, (C ₆H ₅O) ₂((CH ₃) ₂CHO) PO, CAS reg.no.68782-95-6) and phosphoric acid two (tert-butyl-phenyl) phenyl ester (TBPP, (C ₆H ₅O) ₂((CH ₃) ₃C) PO, CAS reg.no.65652-41-7).Described phosphorus compound.Listed all organophosphate/salt stabilizing agents can be available from many chemical supplier in this section, as Aldrich (Milwaukee, Wisconsin); Alfa Aesar (Ward Hill, MA); Or Akzo Nobel (Arnhem, the Netherlands).Alkylated triaryl phosphates comprises butylation triphenyl, tert-butylation triphenyl, isopropylated triphenyl phosphates.Representational commercially available alkylated triaryl phosphates comprises can be with trade mark

8784 butylation triphenyl available from Akzo Nobel (Arnhem, the Netherlands); Can be with trade mark 620 available from Great Lakes ChemicalCorporation (GLCC, West Lafayette, tert-butylation triphenyl IN); With can be with trade mark 220 and 110 also available from the isopropylated triphenyl phosphates of GLCC.

In another embodiment, this additional stability agent can comprise at least a phosphorous acid ester.Phosphite ester stabilizer can comprise the phosphorous acid ester that is obstructed derived from replacing phosphorous acid ester.Especially, the phosphorous acid ester that is obstructed is the derivative of alkyl, aryl or alkaryl bi-ester of phosphite.The phosphorous acid ester that is obstructed comprises tricresyl phosphite-(two-tert-butyl-phenyl) ester, phosphorous acid di-n-octyl and isodecyl diphenyl phosphate.Tricresyl phosphite-(two-tert-butyl-phenyl) ester is with trade mark

168 sell, and the phosphorous acid di-n-octyl is with trade mark

OPH sells, and phosphorous acid isodecyl diphenyl ester is with trade mark

DDPP sells, and sells by Ciba.

In another embodiment, this additional stability agent can comprise at least a phenol.Phenol stabilizers comprises any replacement or unsubstituted phenolic compound, comprises comprising one or more replacement or unsubstituted ring-type, the substituent phenol of straight or branched aliphatic series, as the single phenol of alkylation, comprises 2,6-di-t-butyl-4-sylvan; 2,6-di-t-butyl-4-ethyl phenol; 2,4-dimethyl-6-tert-butyl phenol; Tocopherol; And analogue, quinhydrones and alkylation quinhydrones comprise other derivative of tertiary butylated hydroquinone, quinhydrones; And analogue, hydroxylation sulfo-diphenyl ether comprises 4,4 '-sulphur-two (2-methyl-6-tert butyl phenol); 4,4 '-sulphur two (3-methyl-6-tert butyl phenol); 2,2 '-sulphur two (4 methyl-6-tert butyl phenol); And analogue, alkylidene group-bis-phenol comprises: 4, and 4 '-methylene-bis (2, the 6-di-tert-butylphenol); 4,4 '-two (2, the 6-di-tert-butylphenol); 2,2 '-or 4, the derivative of 4-bis-phenol glycol (biphenoldiol); 2,2 '-methylene-bis (4-ethyl-6-tert-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4,4-butylidene two (3-methyl-6-tert butyl phenol); 4,4-isopropylidene two (2, the 6-di-tert-butylphenol); 2,2 '-methylene-bis (4-methyl-6-nonyl phenol); 2,2 '-isobutylene two (4, the 6-dimethyl phenol; 2,2 '-methylene-bis (4-methyl-6-cyclohexyl phenol), 2,2-or 4, the 4-'-biphenyl diphenol comprises 2,2 '-methylene-bis (4-ethyl-6-tert-butyl phenol); Yoshinox BHT (BHT), comprise heteroatomic bis-phenol, comprise 2,6-two-uncle-alpha, alpha-dimethyl amino-p-cresol, 4,4-sulphur two (the 6-tertiary butyl-meta-cresol); And analogue; Acyl amino phenol; 2,6-di-t-butyl-4 (N, N '-dimethylamino methyl phenol); Sulfide comprises two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide; Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; And composition thereof (being meant the mixture of any phenol stabilizers listed in this section).

In another embodiment, this additional stability agent can comprise at least a terpenes.It is the hydrocarbon polymer of feature that terpenes comprises to contain more than a unitary structure of repetition isoprene (2-methyl isophthalic acid, 3-divinyl).Representational terpenes includes but not limited to, myrcene (2-methyl-6-methylene radical suffering-1,7-diene), alloocimene, β-ocimene, terebene, limonene (particularly d-limonene), retinene, firpene, menthol, Geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, phellandrene, fenchene, kautschin and composition thereof (being meant the mixture of any terpenes stablizer listed in this section).The terpenes stablizer can be buied maybe and can or separate from natural origin by the methods known in the art preparation.

In another embodiment, this additional stability agent can comprise at least a terpenoid.Terpenoid comprises with the natural product that to contain more than a structure that repeats isoprene unit be feature and related compound and contains oxygen usually.Representational terpenoid comprises carotenoid, as Lyeopene (CAS reg.no.[502-65-8]), beta carotene (CAS reg.no.[7235-40-7]) and xenthophylls, i.e. and zeaxanthin (CAS reg.no.[144-68-3]); Retinoid is as vitamin A epoxide (CAS reg.no.[512-39-0]) and isotretinoin (CAS reg.no.[4759-48-2]); Abietane (CAS reg.no.[640-43-7]); Ambrosine (ambrosane) (CAS reg.no.[24749-18-6]); Aristolane (CAS reg.no.[29788-49-6]); Anthorine (atisane) (CAS reg.no.[24379-83-7]); Beyerane (CAS reg.no.[2359-83-3]), bisabolane (CAS reg.no.[29799-19-7]); Camphane (CAS reg.no.[464-15-3]); Caryophyllane (CAS reg.no.[20479-00-9]); Cedrane (CAS reg.no.[13567-54-9]); Dammarane (CAS reg.no.[545-22-2]); Drimane (drimane) (CAS reg.no.[5951-58-6]); Eremophilane (eremophilane) (CAS reg.no.[3242-05-5]); Eudesmane (CAS reg.no.[473-11-0]); Fenchane (CAS reg.no.[6248-88-0]); γ wax alkane (CAS reg.no.[559-65-9]); Germacrane (CAS reg.no.[645-10-3]); Gibberellane (CAS reg.no.[6902-95-0]); Black laurel alkane (grayanotoxane) (CAS reg.no.[39907-73-8]); Guainane (CAS reg.no.[489-80-5]); Cedrane (CAS reg.no.[20479-45-2]); Hopance (CAS reg.no.[471-62-5]); Humulane (CAS reg.no.[430-19-3]); Kaurane (CAS reg.no.[1573-40-6]); Ladanum alkane (CAS reg.no.[561-90-0]); Lanostane (CASreg.no.[474-20-4]); Lupane (CAS reg.no.[464-99-3]); P-

Alkane (CASreg.no.[99-82-1]); Volatile oil (CAS reg.no.[471-67-0]); Ophiobolane (CAS reg.no.[20098-65-1]); Yellow quassia alkane (picrasane) (CAS reg.no.[35732-97-9]); Pimarane (CAS reg.no.[30257-03-5]); Pinane (CAS reg.no.[473-55-2]); Podocarpane (CAS reg.no.[471-78-3]); Protostane (CAS reg.no.[70050-78-1]); Rose alkane (rosane) (CAS reg.no.[6812-82-4]); Taxane (CAS reg.no.[1605-68-1]); Thujane (CAS reg.no.[471-12-5]); The mould alkane of single-ended spore (trichothecane) (CAS reg.no.[24706-08-9]), ursane (CAS reg.no.[464-93-7]) and composition thereof (being meant the mixture of any terpenoid listed in this section).Terpenoid of the present invention can be buied maybe can be by methods known in the art preparation or separable from natural origin.

In another embodiment, this additional stability agent can comprise at least a soccerballene.Soccerballene comprises as the sealing carbon cage of part via pentagon hexagon carbocyclic ring connected to one another (benzene) bonding.Relation between number of vertex (a, carbon atom) and the hexagon carbocyclic ring number (n) (five side rings are always 12) is passed through: a=2 (n+10) provides.Although this formula is applicable to all theoretical constructs, those molecules that only have relatively low stress and distortion are stable.Representational soccerballene includes but not limited to, Buckminsterfullerene (C60 or " bucky-ball ", CAS reg.no.[99685-96-8]) and [5,6] soccerballene-C ₇₀(C70, CAS reg.no.[115383-22-7]), soccerballene-C ₇₆(CASreg.no.[135113-15-4]), soccerballene-C ₇₈(CAS reg.no.[136316-32-0]) and soccerballene-C ₈₄(CAS reg.no.[135113-16-5]) and composition thereof (being meant the mixture of any fullerene stabilizers listed in this section).Soccerballene can be buied.

In another embodiment, this additional stability agent can comprise at least a epoxide.Epoxide comprises and at least aly is selected from 1, the 2-propylene oxide (CAS reg.no.[75-56-9]), 1, the 2-butylene oxide ring (CAS reg.no.[106-88-7]), butylphenyl glycidyl ether, the amyl group phenyl glycidyl ether, the hexyl phenyl glycidyl ether, the heptyl phenyl glycidyl ether, the octyl phenyl glycidyl ether, the nonyl phenyl glycidyl ether, the decyl phenyl glycidyl ether, the glycidyl methyl phenyl ether, 1,4-glycidyl phenyl diether, the 4-methoxyphenyl glycidyl ether, naphthyl glycidyl ether, 1,4-diglycidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl glycidyl ether, the isobutyl-glycidyl ether, the hexylene glycol diglycidyl ether, glycidyl allyl ether, the compound of polypropylene glycol diglycidyl ether and composition thereof (being meant the mixture of any aforementioned epoxide listed in this section).

In another embodiment, this additional stability agent can comprise at least a fluorinated epoxide.This fluorinated epoxide comprises the compound shown in the formula B, wherein R ²To R ⁵Each naturally H, have the alkyl of 1 to 6 carbon atom or have the fluoroalkyl of 1 to 6 carbon atom, condition is R ²To R ⁵In at least one be fluoroalkyl.

Formula B

Representational fluorinated epoxide stablizer comprises but is not limited to, trifluoromethyl oxyethane and 1, two (trifluoromethyl) oxyethane of 1-and composition thereof (being meant the mixture of any aforementioned fluorinated epoxide stablizer).This compounds can pass through methods known in the art, for example passes through Journal Of Fluorine Chemistry, the 24th volume, 93-104 page or leaf (1984), Journal of Organic Chemistry, the 56th the volume, the 3187th to 3189 page (1991) and Journal of Fluorine Chemistry, the 125th volume, the method preparation described in the 99-105 page or leaf (2004).

In another embodiment, this additional stability agent can comprise at least a trimethylene oxide.This trimethylene oxide stablizer comprises the compound that has one or more oxetane groups.These compounds are represented by formula C, wherein R ₁-R ₆Identical or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

Formula C

Representational trimethylene oxide stablizer comprises but is not limited to, 3-ethyl-3-methylol-trimethylene oxide, as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3-((phenoxy group) methyl)-trimethylene oxide, as OXT-211 (Toagosei Co., Ltd); With 3-ethyl-3-((2-ethyl-hexyloxy) methyl)-trimethylene oxide, as OXT-212 (Toagosei Co., Ltd) and composition thereof (being meant the mixture of any trimethylene oxide listed in this section).

In another embodiment, this additional stability agent can comprise at least a amine.In one embodiment, amine comprises at least a compound that is selected from triethylamine, Tributylamine, Diisopropylamine, tri-isopropyl amine, tri-isobutylamine, Ursol D and diphenylamine.In another embodiment, amine stabiliser comprises dialkylamine, comprise (N-(1-methylethyl)-2-propylamine, CAS reg.no.[108-18-9]).In another embodiment, amine stabiliser comprises hindered amine antioxidant.Hindered amine antioxidant comprises the amine derived from substituted pyridine compound, particularly the derivative of piperidyl (piperidyl), piperidyl (piperidinyl), piperazine ketone or the alkoxyl group piperidinyl compounds of alkyl replacement.Representational hindered amine antioxidant comprises 2,2,6,6-tetramethyl--4-piperidone; 2,2,6,6-tetramethyl--4-piperidines alcohol; Two-(1,2,2,6,6-pentamethyl-piperidyl) sebate (CAS reg.no.[41556-26-7]); Two-(2,2,6,6-tetramethyl--4-piperidyl) sebates, as Ciba with trade mark 770 hindered amines of selling; Poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate (CAS reg.no.[65447-77-0]) is as can be with trade mark

622LD is available from Ciba; The alkylation Ursol D, as N-phenyl-N '-(1, the 3-dimethylbutyl)-Ursol D, or N, N '-two-sec-butyl-Ursol D; And azanol, as tallow amine or two (hydrogenated tallow alkyl) amine of N-methyl.Some other hindered amine antioxidant comprise can be with trade mark

765 available from Ciba or with trade mark

1944 Hes

1770 available from Mayzo, the amine antioxidant of Inc..Amine also comprises the mixture of any amine listed in this section.

In another embodiment, this additional stability agent can comprise at least a alkyl silane.Alkyl silane includes but not limited to, two (dimethylamino) methyl-monosilane (DMAMS, CAS reg.no.[22705-33-5]), three (trimethyl silyl) silane (TTMSS, CAS reg.no.[1873-77-4]), vinyltriethoxysilane (VTES, CAS reg.no.[78-08-0]) and vinyltrimethoxy silane (VTMO, CAS reg.no.[2768-02-7]) and composition thereof (being meant the mixture of any alkyl silane listed in this section).

In one embodiment, this stablizer can comprise at least a aryl alkyl ethers.This aryl alkyl ethers stablizer comprises the compound shown in the formula D, and wherein n is 1,2 or 3 and R ¹It is alkyl with 1 to 16 carbon atom.

Formula D

Representational aryl alkyl ethers includes but not limited to, methyl-phenoxide, 1,4-dimethoxy benzene, 1,4-diethoxybenzene and 1,3,5-trimethoxy-benzene and composition thereof (being meant the mixture of any aryl alkyl ethers listed in this section).

In another embodiment, this stablizer can comprise at least a polyoxyalkylated aromatic substance.This polyoxyalkylated aromatic substance comprises the compound shown in the formula D, wherein R ¹Group be comprise at least one-CH ₂CH ₂The polyoxyalkylated group of O-part.

In another embodiment, this stablizer can comprise at least a alkylaromatic.Can include but not limited to that the alkyl benzene lubricants of side chain and straight chain can be with trade mark by the representational alkylaromatic as the additional stability agent according to the present invention

75,

150 Hes

(linear alkylbenzene) 500 available from Shrieve Chemicals and with HAB 22 (branched alkylbenzene) available from Nippon Oil.

In one embodiment, this additional stability agent comprises at least a functionalized PFPE.Especially, functionalized PFPE comprises perfluoro-polyether-or aryl phosphate, phosphonic acids aryl ester and the salt thereof of perfluoroalkyl and phosphorated partial esterification, it is as U.S. Patent No. 6,184,187 and reference wherein described in (i) between phosphorus and fluorocarbon group, contain single-or many-oxirane connect base, or (ii) between phosphorus and fluorocarbon group, do not contain connect basic.

In another embodiment, this functionalized PFPE stablizer can be to contain the compound shown in the formula D of perfluoroalkyl or PFPE side chain,

Formula D

In another embodiment, as the U.S. Patent application No.11/156 that submitted on June 17th, 2005, described in 348, this functionalized PFPE stablizer can be to comprise perfluoropolyether segment to have general formula-CH with one or more ₂(C _qH _2q) the pure segmental PFPE alkyl alcohol of OH, wherein-C _qH _2qRepresent divalence straight or branched alkyl, wherein q is 1 to about 10 integer.

In another embodiment, as the U.S. Patent application No.11/167 that submitted on June 27th, 2006, described in 330, functionalized PFPE stablizer of the present invention can comprise and has structure [R _f ¹-(C _tR _(u+v))] _mE (O) _n(C _tR ¹ _(u+v+1)) _(3-m)Substituted aryl pnicogen composition, wherein, R _f ¹Be perfluoroalkyl polyether chain, comprise repeating unit, and be selected from formula weight of about 400 to about 15,000:

(a)J-O-(CF(CF ₃)CF ₂O) _c(CFXO) _dCFZ-；

(b)J ¹-O-(CF ₂CF ₂O) _e(CF ₂O) _fCFZ ¹-；

(c)J ²-O-(CF(CF ₃)CF ₂O) _jCF(CF ₃)CF ₂-；

(d)J ³-O-(CQ ₂-CF ₂CF ₂-O) _k-CQ ₂-CF ₂-；

(e)J ³-O-(CF(CF ₃)CF ₂O) _g(CF ₂CF ₂O) _h(CFXO) _i-CFZ-；

(f) J ⁴-O-(CF ₂CF ₂O) _rCF ₂-; With

(h) the wherein combination of two or more, wherein:

J is selected from CF ₃, C ₂F ₅, C ₃F ₇, CF ₂Cl, C ₂F ₄Cl, C ₃F ₆The Cl and the fluoroalkyl of the combination of two or more wherein;

The numerical value of c and d makes that the ratio of c:d is about 0.01 to about 0.5;

X is F, CF ₃Or its combination;

Z is F, Cl or CF ₃

J ¹Be to be selected from CF ₃, C ₂F ₅, C ₃F ₇, CF ₂Cl, C ₂F ₄The Cl and the fluoroalkyl of the combination of two or more wherein;

The numerical value of e and f makes that the ratio of e:f is about 0.3 to about 5;

Z ¹Be F or Cl;

J ²Be C ₂F ₅, C ₃F ₇Or its combination;

J is that mean number is so that R _fFormula weight be about 400 to about 15,000;

J ³Be selected from CF ₃, C ₂F ₅, C ₃F ₇The wherein combination of two or more;

K is that mean number is so that R _fFormula weight be about 400 to about 15,000;

Each Q is F, Cl or H independently;

The numerical value of g, h and i makes that (g+h) is about 1 to about 50, and ratio i:(g+h) is about 0.1 to about 0.5;

J ⁴Be CF ₃, C ₂F ₅Or its combination;

R is that mean number is so that R _fFormula weight be about 400 to about 15,000; And

Each R and R ¹Be H, C independently ₁-C ₁₀Alkyl, halogen, OR ³, OH, SO ₃M, NR ² ₂, R ³OH, R ³SO ₃M, R ³NR ² ₂, R ³NO ₂, R ³CN, C (O) OR ³, C (O) OM, C (O) R ³Or C (O) NR ² ₂Or the wherein combination of two or more;

Wherein

R ²Be H, C independently ₁-C ₁₀Alkyl or the wherein combination of two or more;

R ³Be C ₁-C ₁₀Alkyl; And

M is hydrogen or metal, preferably is not aluminium;

T equals (6+u);

U is any combination of 0,2,4,6,8,10,12,14,16;

V is 2 or 4 independently;

N is 0 or 1;

E is P, As or Sb; And

M is greater than about 0.5 to about 3, and condition is when E=P, m=3.0 and t=6, and R can not be H fully or contain F.

In another embodiment, as the U.S. Patent application No.11/218 that on September 1st, 2005 submitted to, described in 259, functionalized PFPE stablizer of the present invention can comprise the aryl PFPE, and it is to have formula R _f-(Y) _a-(C _tR _(u+v))-(O-C _tR ¹ _(u+v)) _bThe simple function aryl PFPE of-R, has formula R _f ¹-[(Y) _a-(C _tR _(u+v))-(O-C _tR ¹ _(u+v)) _b-R] ₂Two sense aryl PFPE or its combination, wherein:

R _fAnd R _f ¹Has about 400 to about 15,000 formula weight separately;

R _fComprise repeating unit, this repeating unit is selected from

(a)J-O-(CF(CF ₃)CF ₂O) _c(CFXO) _dCFZ-，

(b)J ¹-O-(CF ₂CF ₂O) _e(CF ₂O) _fCFZ ¹-，

(c)J ²-O-(CF(CF ₃)CF ₂O) _jCF(CF ₃)-，

(d)J ³-O-(CQ ₂-CF ₂CF ₂-O) _k-CQ ₂-，

(e)J ³-O-(CF(CF ₃)CF ₂O) _g(CF ₂CF ₂O) _h(CFX-O) _i-CFZ-，

(f) J ⁴-O-(CF ₂CF ₂O) _{K '}CF ₂-and

(g) the wherein combination of two or more; And

Wherein

Formula CF ₂CF ₂O and CF ₂The unit of O is along this chain random distribution;

J is CF ₃, C ₂F ₅, C ₃F ₇, CF ₂Cl, C ₂F ₄Cl, C ₃F ₆Cl or the wherein combination of two or more;

The numerical value of c and d makes that the c/d ratio is about 0.01 to about 0.5;

X is-F ,-CF ₃Or its combination;

Z is-F ,-Cl or-CF ₃

Z ¹Be-F or-Cl,

J ¹Be CF ₃, C ₂F ₅, C ₃F ₇, CF ₂Cl, C ₂F ₄Cl or the wherein combination of two or more;

The numerical value of e and f makes that the e/f ratio is about 0.3 to about 5;

J ²Be-C ₂F ₅,-C ₃F ₇Or its combination;

J is that mean number is so that R _fFormula weight be about 400 to about 15,000;

J ³Be CF ₃, C ₂F ₅, C ₃F ₇Or the wherein combination of two or more;

K is that mean number is so that R _fFormula weight be about 400 to about 15,000;

Each Q is independently-F ,-Cl or-H;

The numerical value of g, h and i makes that (g+h) is about 1 to about 50, and i:(g+h) ratio is about 0.1 to about 0.5;

J ⁴Be CF ₃, C ₂F ₅Or its combination;

K ' is that mean number is so that R _fFormula weight be about 400 to about 15,000;

Each R is independently-H, halogen ,-OH ,-SO ₃M, NR ³ ₂,-NO ₂,-R ⁴OH ,-R ⁴SO ₃M ,-R ⁴NR ³ ₂,-R ⁴NO ₂,-R ⁴CN ,-C (O) OR ⁴,-C (O) OM ,-C (O) R ⁴,-C (O) NR ³ ₂Or the wherein combination of two or more; Just when b=0, R can not be four hydrogen atoms with-OH or-Br or-NH ₂Or R can not be H or-NO ₂Or its combination;

Each R ¹Be independently H ,-R ⁴,-OR ⁴, halogen ,-OH ,-SO ₃M ,-NR ³ ₂,-NO ₂,-CN ,-R ⁴OH ,-R ⁴SO ₃M ,-R ⁴NR ³ ₂,-R ⁴NO ₂,-R ⁴CN ,-C (O) OR ⁴,-C (O) OM ,-C (O) R ⁴, C (O) NR ³ ₂Or the wherein combination of two or more, condition is if b=0, R and R ²Combination can not be four or more hydrogen atoms and-OH ,-Br ,-NH ₂Or-NO ₂

Each R ³Be H, C independently ₁-C ₁₀Alkyl or the wherein combination of two or more;

R ⁴Be C ₁-C ₁₀Alkyl;

M is hydrogen or metal ion;

A is 0 or 1;

B is 0-5;

Y is divalent group-CH ₂OCH ₂-,-(CH ₂) _o-O-,-(CF ₂) _n-,-CF ₂O-,-CF ₂OCF ₂-,-C (O)-,-C (S)-or the wherein combination of two or more;

N is about 1 to about 5;

O is about 2 to about 5;

T equals 6+u;

U is any combination of 0,2,4,6,8,10,12,14,16;

V is 2 or 4 independently;

R _f ¹Be-(CF ₂CF ₂O) _e(CF ₂O) _fCF ₂-,-(C ₃F ₆O) _p(CF ₂CF ₂O) _q(CFXO) _rCF ₂-,-(CF ₂CF ₂O) (C ₃F ₆O) _wCF (CF ₃)-,-CF (CF ₃) O (C ₃F ₆O) _w-R _f ²-O (C ₃F ₆O) _wCF (CF ₃)-,-((CQ ₂) CF ₂CF ₂O) _sCF ₂CF ₂-or the wherein combination of two or more;

Wherein

E, f, X and Q as above define;

The numerical value of p, q and r make (p+q) be 1 to 50 and r/ (p+q) be 0.1 to 0.05;

Each w is 2 to 45 independently;

Rf ²Be straight or branched-C _mF _2m-;

M is 1-10; And

S is that mean number is so that R _f ¹Formula weight be 400 to 15,000.

In another embodiment, this additional stability agent can comprise at least a lactone.Lactone comprises and can react the cyclic ester of making by the carboxylate radical in alcohol groups and the same molecular.Representational lactone stabilizer of the present invention includes but not limited to, gamma-butyrolactone (CAS reg.no.[96-48-0]), δ-glucono-lactone (CAS reg.no.[90-80-2]), γ-Shi Yineizhi (CAS reg.no.[104-67-6]), 6,7-dihydro-4 (5H)-benzofuranone (CAS reg.No.[16806-93-2]) and can be with trade mark HP-136 is available from 5 of Ciba, two (1, the 1-the dimethyl ethyl)-3-[2 of 7-, 3 (or 3,4)-3,5-dimethylphenyls]-2 (3H)-benzofuranones (CAS reg.no[201815-03-4]), and composition thereof (being meant the mixture of any lactone listed in this section).

In another embodiment, this additional stability agent comprises at least a benzophenone derivates.Benzophenone derivates comprises and can be comprised the benzophenone of any combination replacement of halogenide (as fluorine, chlorine, bromine or iodine), amino, hydroxyl, alkyl (as methyl, ethyl or propyl group), aryl (as phenyl), nitro or this class group by side group.Representational benzophenone derivates stablizer comprises but is not limited to: 2, and the 5-difluoro benzophenone; 2 ', 5 '-resacetophenone; The 2-aminobenzophenone; The 2-chlorobenzophenone; 2-fluorine benzophenone; The 2-dihydroxy benaophenonel; 2 methyl benzophenone; 2-amino-4 '-chlorobenzophenone; 2-amino-4 '-the fluorine benzophenone; 2-amino-5-bromo-2 '-chlorobenzophenone; 2-amino-5-chlorobenzophenone; 2-amino-5-chloro-2 '-the fluorine benzophenone; 2-amino-5-nitro benzophenone; 2-amino-5-nitro-2 '-chlorobenzophenone; 2-amino-2 ', the 5-dichloro benzophenone; 2-chloro-4 '-the fluorine benzophenone; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-5-chlorobenzophenone; 2-methylamino--5-chlorobenzophenone; 3-methyldiphenyl ketone; The 3-nitro benzophenone; 3-nitro-4 '-chloro-4-fluorine benzophenone; The 4-chlorobenzophenone; 4-fluorine benzophenone; The 4-dihydroxy benaophenonel; The 4-methoxy benzophenone; 4-methyldiphenyl ketone; The 4-nitro benzophenone; The 4-phenyl benzophenone; 4-chloro-3-nitro benzophenone; 4-hydroxyl-4 '-chlorobenzophenone; 2,4 dihydroxyl benzophenone; 2, the 4-dimethyl benzophenone; 2, the 5-dimethyl benzophenone; 3, the 4-diaminobenzophenone; 3, the 4-dichloro benzophenone; 3, the 4-difluoro benzophenone; 3, the 4-dihydroxy benaophenonel; 3, the 4-dimethyl benzophenone; 4,4 '-two (diethylamine) benzophenone; 4,4 '-two (dimethyl amine) benzophenone; 4,4 '-dichloro benzophenone; 4,4 '-difluoro benzophenone; 4,4 '-dihydroxy benaophenonel; With 4,4 '-dimethoxy-benzophenone and composition thereof (being meant the mixture of any benzophenone derivates listed in this section).

In another embodiment, this additional stability agent comprises at least a alkyl silane.Silane is any silicon analogue of alkane.Silane is made of the Siliciumatom chain that is covalently bound on the hydrogen atom.Alkyl silane stablizer of the present invention comprises general formula Si _nR _2n+2Shown substituted silane, wherein each R can be H independently; Other silyl; Alkyl comprises CH ₃, C ₂H ₅, C ₃H ₇(any isomer), C ₄F ₉(any isomer) and analogue; Alkoxyl group comprises methoxyl group, oxyethyl group and analogue; Amine groups; Vinyl; Or phenyl.The R group also can be comprised Cl, F and analogue by halogen, or amine groups replaces.Alkyl silane includes but not limited to, two (dimethylamino) methyl-monosilane (DMAMS, CAS reg.no.[22705-33-5]), three (trimethyl silyl) silane (TTMSS, CAS reg.no.[1873-77-4]), vinyltriethoxysilane (VTES, CAS reg.no.[78-08-0]) and vinyltrimethoxy silane (VTMO, CAS reg.no.[2768-02-7]) and composition thereof (being meant the mixture of any alkyl silane listed in this section).

In another embodiment, additional stability agent of the present invention comprises xitix (CAS reg.no.[50-81-7]).

In another embodiment, this additional stability agent can comprise at least a terephthalate.Terephthalate of the present invention comprises the mixture of terephthalic acid divinyl ester (CAS reg.no.[13486-19-0]) and terephthaldehyde's diphenyl phthalate (CAS reg.no.[1539-04-4]) and aforementioned terephthalate.

In another embodiment, this additional stability agent can comprise Nitromethane 99Min. (CH ₃NO ₂) CAS reg.no.[75-52-5].

Can use single aryl-alkyl oxide, polyoxyalkylated aromatic substance or alkylaromatic in the present invention.Perhaps, multiple aryl-alkyl oxide, polyoxyalkylated aromatic substance and alkylaromatic can be with any ratio combination to serve as the stablizer blend.This stablizer blend can contain from the multiple stabilizer compounds of identical compounds category or from other multiple stabilizer compounds of different compounds.For example, the stablizer blend can contain two or more aryl-alkyl oxides, polyoxyalkylated aromatic substance or alkylaromatic, or one or more plant aryl-alkyl oxide, polyoxyalkylated aromatic substance or alkylaromatic and one or more plant the combination of additional stability immunomodulator compounds (for example, lactone, amine or phenol).

In addition, some stabilizer compounds exist as multiple configurational isomer or steric isomer.The individual isomer of same compound or multiple isomer can use with preparation stablizer blend with any ratio.In addition, the single or multiple isomer of given compound can make up to serve as the stablizer blend with any ratio with other compound of any number.The present invention is intended to comprise all single configurational isomers, single steric isomer or its any combination or mixture.

Particularly point out the stabiliser composition that comprises the compound combination that unexpected stabilization level is provided.Some these combination can be served as the Synergistic stabilizer composition, promptly strengthens the compound composition of rendeing a service each other in preparation, and the gained stabilization is greater than the stabilization by the summation expection of the contribution of each component.This class Synergistic stabilizer composition can comprise at least a mercaptan or thioether or its mixture and be selected from any additional compound of terpenes and terpenoid class, fullerene, epoxides, fluorinated epoxide class, trimethylene oxide class, terephthalic acid divinyl ester and terephthaldehyde's diphenyl phthalate and composition thereof (being meant the mixture of any aforementioned additional compound and mercaptan or thioether).

The limiting factor of stabiliser composition efficient is stablizer loss and the functional loss that takes place with effective storage life.Particularly point out the Synergistic stabilizer composition that comprises stabilizer blend, this stabilizer blend comprises the stablizer regenerated component that can make consumption in effective use, hereinafter is called the reproducibility stablizer.Different with the polyfunctional single big stabilizer compounds that comprises a plurality of stable functional groups, the reproducibility stablizer that comprises little " working in coordination with " stablizer with high mobility more and more high stable speed (being meant higher rate) so as to the reaction that stabilization takes place play a role.The reproducibility stabiliser composition contains and can additional one or more of oneself plant stablizers after use, so that keep the effectiveness of said composition when life-time service.

An example of reproducibility stablizer is at least a mercaptan or thioether or its mixture and at least a amine.The amine that comprises in the reproducibility stabiliser composition can comprise previously described any hindered amine antioxidant.Particularly point out those hindered amines, particularly the derivative of piperidyl, piperidyl, piperazine ketone or alkoxyl group piperidinyl compounds of alkyl replacement and composition thereof derived from substituted pyridine compound.Representational hindered amine antioxidant is 2,2,6,6-tetramethyl--4-piperidone; 2,2,6,6-tetramethyl--4-piperidines alcohol; Two-(1,2,2,6,6-pentamethyl-piperidyl) sebate (CAS reg.no.[41556-26-7]); Two-(2,2,6,6-tetramethyl--4-piperidyl) sebates are as can be with trade mark

770 hindered amines available from Ciba; Poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate (CAS reg.no.[65447-77-0]) is as can be with trade mark 622LD is available from Ciba, with trade mark

765 available from Ciba or with trade mark

1944 Hes

1770 available from Mayzo, Inc., and composition thereof, comprise the mixture of any hindered amine described in this section.

Another example of reproducibility stablizer is the stablizer that comprises the combination of at least a xitix, terephthalate or Nitromethane 99Min. or its mixture and at least a phosphorous acid ester.Particularly pointing out can be derived from the phosphorous acid ester, particularly alkyl that replace phosphorous acid ester, the derivative of aromatic yl phosphite compound.The representative phosphorous acid ester that can be used for the reproducibility stablizer comprises with trade mark

168 (three-(di-tert-butyl-phenyl) phosphorous acid esters) sold, with trade mark (the phosphorous acid di-n-octyl) that OPH sells and with trade mark (phosphorous acid isodecyl diphenyl ester) (all from the Ciba) that DDPP sells.

In composition of the present invention, can use the stablizer of any suitable effective amount.Term as herein described " significant quantity " is meant the amount of stablizer of the present invention, and its composition that produces in adding the composition that comprises at least a fluoroolefin to the time is non-degradable to cause the same big refrigeration performance reduction when using with the composition that does not have stablizer in refrigerating unit.This significant quantity of stablizer can be by measuring under standard test condition ASHRAE 97-2004.In certain embodiments of the invention, it is the following amount of stablizer that significant quantity can be said to be: when merging with the composition that comprises at least a fluoroolefin, can make and adopt the described refrigerating unit that comprises the composition of at least a fluoroolefin comprising 1 with employing, 1,1,2-Tetrafluoroethane (R-134a) or other standard system cryogen (R-12, R-22, R-502, R-507A, R-508, R401A, R401B, R402A, R402B, R408, R-410A, R-404A, R407C, R-413A, R-417A, R-422A, R-422B, R-422C, R-422D, R-423, R-114, R-11, R-113, R-123, R-124, R236fa or R-245fa) operation under the refrigeration performance of the composition of (depend on past in similar system, use which kind of refrigeration agent) par during as working fluid and the cooling capacity.

Some embodiment comprises, the significant quantity of used stablizer constitutes about 0.001 weight % of the composition total weight that comprises at least a fluoroolefin as herein described to about 10 weight % among the present invention, more preferably about 0.01 weight % is to about 5 weight %, more preferably about again 0.3 weight % is to about 4 weight %, and more preferably about again 0.3 weight % is to about 1 weight %.When using stabilizer blend or stablizer blend, the total amount of this mixture or stablizer blend can exist with above-mentioned concentration.

In another embodiment, the composition of the invention described above can further comprise at least a metal passivator, and it is selected from two (benzylidene) hydrazides (CAS reg.no.6629-10-3) of areoxalyl; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine) (CAS reg.no.32687-78-8); 2,2 '-oxamido-is two-ethyl-(3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate) (CAS reg.no.70331-94-1); N, N '-(two salicylidenes)-1,2-propanediamine (CAS reg.no.94-91-1); Ethylenediamine tetraacetic acid (EDTA) (CAS reg.no.60-00-4) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative, N, N-two salicylidenes-1 and composition thereof (being meant the mixture of any aforementioned metal passivator listed in this section).

In another embodiment, stabiliser composition comprises at least a mercaptan or thioether or its mixture, at least a amine and at least a metal passivator.This metal passivator is selected from two (benzylidene) hydrazides of areoxalyl; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propanediamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative, N, N-two salicylidenes-1 and composition thereof (being meant the mixture of any aforementioned metal passivator listed in this section).

In another embodiment, stabiliser composition comprises at least a mercaptan or thioether or its mixture; At least a additional compound that is selected from epoxides, trimethylene oxide class, terephthalic acid divinyl ester and terephthaldehyde's diphenyl phthalate; With at least a two (benzylidene) hydrazides of areoxalyl that are selected from; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propanediamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole species; Benzotriazole category, 2-mercaptobenzothiazole, tolytriazole derivative, N, the metal passivator of N-two salicylidenes-1 and composition thereof (being meant the mixture of any aforementioned metal passivator listed in this section).

In one embodiment, composition of the present invention can further comprise at least a fluoroolefin (as mentioned above), fluoro hydrocarbon, dimethyl ether, the CF of being selected from ₃I, ammonia, carbonic acid gas (CO ₂) and composition thereof the additional compound of (being meant the mixture of any additional compound listed in this section).

In one embodiment, additional compound comprises hydrofluoric ether (HFC) compound.Hydrofluoric ether comprises the saturated compound of carbon containing, hydrogen and fluorine.Useful especially is to have 1-7 carbon atom and have approximately-90 ℃ of hydrofluoric ethers to about 80 ℃ normal boiling point.Hydrofluoric ether is can be available from many sources such as E.I.du Pont de Nemoursand Company, Fluoroproducts, and Wilmington, DE, 19898, the commodity of USA maybe can prepare by methods known in the art.Representational fluorinated hydrocarbon compound includes but not limited to, methyl fuoride (CH ₃F, HFC-41), methylene fluoride (CH ₂F ₂, HFC-32), trifluoromethane (CHF ₃, HFC-23), pentafluoride ethane (CF ₃CHF ₂, HFC-125), 1,1,2,2-Tetrafluoroethane (CHF ₂CHF ₂, HFC-134), 1,1,1,2-Tetrafluoroethane (CF ₃CH ₂F, HFC-134a), 1,1,1-Halothane (CF ₃CH ₃, HFC-143a), 1,1-C2H4F2 C2H4F2 (CHF ₂CH ₃, HFC-152a), fluoroethane (CH ₃CH ₂F, HFC-161), 1,1,1,2,2,3,3-heptafluoro-propane (CF ₃CF ₂CHF ₂, HFC-227ca), 1,1,1,2,3,3,3-heptafluoro-propane (CF ₃CHFCF ₃, HFC-227ea), 1,1,2,2,3,3 ,-HFC-236fa (CHF ₂CF ₂CHF ₂, HFC-236ca), 1,1,1,2,2,3-HFC-236fa (CF ₃CF ₃CH ₂F, HFC-236cb), 1,1,1,2,3,3-HFC-236fa (CF ₃CHFCHF ₂, HFC-236ea), 1,1,1,3,3,3-HFC-236fa (CF ₃CH ₂CF ₃, HFC-236fa), 1,1,2,2,3-pentafluoropropane (CHF ₂CF ₂CH ₂F, HFC-245ca), 1,1,1,2,2-pentafluoropropane (CF ₃CF ₂CH ₃, HFC-245cb), 1,1,2,3,3-pentafluoropropane (CHF ₂CHFCHF ₂, HFC-245ea), 1,1,1,2,3-pentafluoropropane (CF ₃CHFCH ₂F, HFC-245eb), 1,1,1,3,3-pentafluoropropane (CF ₃CH ₂CHF ₂, HFC-245fa), 1,2,2,3-tetrafluoropropane (CH ₂FCF ₂CH ₂F, HFC-254ca), 1,1,2,2-tetrafluoropropane (CHF ₂CF ₂CH ₃, HFC-254cb), 1,1,2,3-tetrafluoropropane (CHF ₂CHFCH ₂F, HFC-254ea), 1,1,1,2-tetrafluoropropane (CF ₃CHFCH ₃, HFC-254eb), 1,1,3,3-tetrafluoropropane (CHF ₂CH ₂CHF ₂, HFC-254fa), 1,1,1,3-tetrafluoropropane (CF ₃CH ₂CH ₂F, HFC-254fb), 1,1,1-trifluoro propane (CF ₃CH ₂CH ₃, HFC-263fb), 2,2-difluoropropane (CH ₃CF ₂CH ₃, HFC-272ca), 1,2-difluoropropane (CH ₂FCHFCH ₃, HFC-272ea), 1,3-difluoropropane (CH ₂FCH ₂CH ₂F, HFC-272fa), 1,1-difluoropropane (CHF ₂CH ₂CH ₃, HFC-272fb), 2-fluoro-propane (CH ₃CHFCH ₃, HFC-281ea), 1-fluoro-propane (CH ₂FCH ₂CH ₃, HFC-281fa), 1,1,2,2,3,3,4,4-Octafluorobutane (CHF ₂CF ₂CF ₂CHF ₂, HFC-338pcc), 1,1,1,2,2,4,4,4-Octafluorobutane (CF ₃CH ₂CF ₂CF ₃, HFC- ₃38mf), 1,1,1,3,3-3-pentafluorobutane (CF ₃CH ₂CHF ₂, HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-Decafluoropentane (CF ₃CHFCHFCF ₂CF ₃, HFC-43-10mee) with 1,1,1,2,2,3,4,5,5,6,6,7,7,7-ten tetrafluoro heptane (CF ₃CF ₂CHFCHFCF ₂CF ₂CF ₃, HFC-63-14mee).

In another embodiment, this additional compound comprises hydrocarbon polymer.Hydrocarbon polymer of the present invention comprises the compound that has only carbon and hydrogen.Useful especially is the compound with 3-7 carbon atom.Hydrocarbon polymer can be buied by many chemical supplier.Representational hydrocarbon polymer includes but not limited to, propane, normal butane, Trimethylmethane, tetramethylene, Skellysolve A, 2-methylbutane, 2,2-dimethylpropane, pentamethylene, normal hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, 3-methylpentane, hexanaphthene, normal heptane and suberane.

In another embodiment, additional compound comprises and contains heteroatomic hydrocarbon polymer, as dimethyl ether (DME, CH ₃OCH ₃).DME can buy.

In another embodiment, additional compound comprises iodo trifluoromethane (CF ₃I), it can maybe can prepare by methods known in the art available from various sources.

In another embodiment, additional compound comprises ammonia (NH ₃), it can maybe can prepare by methods known in the art available from various sources.

In another embodiment, additional compound comprises carbonic acid gas (CO ₂), it can maybe can prepare by methods known in the art available from various sources.

The additional compound that particularly points out comprises following composition, comprising: HFC-1225ye and HFC-32; HFC-1225ye and HFC-134a; HFC-1225ye, HFC-134a and HFC-32; HFC-1225ye and HFC-1234yf; HFC-1225ye, HFC-1234yf and HFC-32; HFC-1225ye, HFC-1234yf, HFC-32 and CF ₃I; With HFC-1225ye, HFC-1234yf and HFC-125.

In another embodiment, additional compound comprises the U.S. Patent application no.11/369 that comprises as submission on March 2nd, 2006,227, the U.S. Patent application no.11/393 that submitted on March 30th, 2006, the U.S. Patent application no.11/486 that on July 13rd, 109 and 2006 submitted to, the composition of disclosed fluoroolefin in 791, they are intended to comprise within the scope of the invention.

In one embodiment, composition of the present invention can further comprise at least a lubricant.Lubricant of the present invention comprises those that are fit to use with refrigeration or air-conditioning plant.These lubricants comprise those in the compression refrigerating apparatus that is used in employing Chlorofluorocarbons (CFCs) refrigeration agent traditionally.At 1990 ASHRAE Handbook, Refrigeration Systems and Applications, the 8th chapter, title ＂ Lubricants in Refrigeration Systems ＂ has discussed this series lubricant agent and their character in the 8.1st to 8.21 page (being incorporated herein by this reference).Lubricant of the present invention can be included in those that often are known as " mineral oil " in the lubricated field of compression refrigeration.It (is straight chain and side chain carbochain that mineral oil comprises paraffinic hydrocarbons, saturated hydrocarbon), cycloalkanes (be ring-type or ring structure saturated hydrocarbon, it may be a paraffinic hydrocarbons) and aromatic hydrocarbons (promptly containing one or more is the unsaturated cyclic hydrocarbon of the ring of feature with alternately two keys).Lubricant of the present invention further is included in those that often are known as " synthetic oil " in the lubricated field of compression refrigeration.Synthetic oil comprises alkylaryl (being straight chain and branched-chain alkyl alkylbenzene), synthetic alkane and cycloalkanes, silicone and poly-alpha-olefin.Representational conventional lubricant of the present invention be commercially available BVM 100 N (BVA Oils sell paraffinic mineral oil), can be with trade mark

3GS and

5GS available from the naphthenic mineral oil of Crompton Co., can be with trade mark

372LT available from the naphthenic mineral oil of Pennzoil, can be with trade mark

RO-30 available from the naphthenic mineral oil of Calumet Lubricants, can be with trade mark

75,

150 Hes

500 branched alkylbenzenes of selling as HAB 22 available from the linear alkylbenzene of Shrieve Chemicals and Nippon Oil.

In another embodiment, lubricant of the present invention further comprise be designed to the hydrofluoric ether refrigeration agent use and under compression refrigeration and air-conditioning plant operational condition with miscible those of refrigeration agent of the present invention.At ＂ Synthetic Lubricants and High-Performance Fluids ＂, R.L.Shubkin, editor Marcel Dekker has discussed this series lubricant agent and character thereof in 1993.This series lubricant agent includes but not limited to that polyol ester (POE) is for example with trade mark

The 100 commercially available POE (Castrol, United Kingdom) that sell, polyalkylene glycol (PAG) is for example from Dow (Dow Chemical, Midland, RL-488A Michigan), and polyvinyl ether (PVE).

The requirement by considering given compressor and the exposed environments of lubricant are selected lubricant of the present invention.

Composition of the present invention can be by merging aequum each component any make things convenient for the method preparation.Preferred method is to weigh up required group component and after this merge component in proper container.If desired, can use stirring.

The invention further relates to the method that makes the composition stability that comprises at least a fluoroolefin, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

The invention further relates to refrigerating method, comprise make comprise containing of at least a fluoroolefin and significant quantity at least a mercaptan or the composition of the stablizer of thioether or its mixture wanting near the condensation refrigerative object.

Wanting the refrigerative object can be any space, position or the article of requirement refrigeration or air-conditioning.In static purposes, this object can be dwelling house or pattern of trade inside, or perishables, as the storage location of food or medicine.For moving the refrigeration purposes, this object can be in highway, railway, ocean or air transportation instrument.Some refrigeration system is independent of any mobile vehicle operation, and these are known as " intermodal transportation " system.This class combined haulage system comprises " freight container (containers) " (associating ocean/land route transportation) and " removable car body (swap bodies) " (associating highway and transportation by railroad).

The invention further relates to heating method, comprise making comprising near containing of at least a fluoroolefin and significant quantity of at least a mercaptan or the composition condensation object that will heat of the stablizer of thioether or its mixture, after this evaporate described composition.

The object that heats can be any space, position or the article that need heat.The refrigerative object is similar with wanting, and these can be the inside of dwelling house or pattern of trade.In addition, as can be similar with those of needs heating to cooling off described running gear.Some transportation means requires heating to solidify in transport container with the material that prevents to transport.

Air is not seldom to leak in refrigeration, air-conditioning system or the heat pump.Airborne oxygen may cause the oxidation of some component (comprising working fluid) of this system.Therefore, in another embodiment, also disclose the method that reduces the degraded of the composition that comprises at least a fluoroolefin, wherein said degraded is caused by the existence that is strayed into air; For example in refrigeration, air-conditioning or heat pump, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

In another embodiment, also disclose and reduced the method that the composition that comprises at least a fluoroolefin and oxygen react, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

Embodiment

The refrigeration system chemical stability

Under the condition described in ASHRAE (American Society of Heating, Refrigerating andAir-Conditioning Engineers) the standard 97-2004, carry out the chemical stability test to measure the chemical stability of comparing stabilized composition of the present invention with the composition that does not contain stablizer.

Provide program at this:

1. the metal coupons with copper, aluminium and steel places the heavy wall Glass tubing.

2. preparation contains and does not contain the working fluid sample that comprises lubricant of stablizer, and chooses adding 2 volume % air in this pipe wantonly.

3. described in this standard, sample is added in this Glass tubing.

4. seal this pipe with the glass blowtorch.

5. will under assigned temperature, heat 14 days among the Guan Zailu of sealing.

6. after 14 days, will take out and check not existing of metal/liquid appearance, liquid proper volume, glass appearance and foreign material such as metallic fine particle among the Guan Conglu of sealing.

7. specify the grade (according to industrial practice) of each sample based on following standard:

Slight variation on 1=test block and the liquid;

Slight extremely medium variation on 2=test block or the liquid;

Medium on 3=test block or the liquid to noticeable change;

Serious variation on 4=test block or the liquid;

Extreme variation on 5=test block or the liquid, i.e. black liquor or coking also contains many settlings.

Table 4 is listed the assessment result that stablizer of the present invention is compared with the composition of stabilization not.

PAG 488 is can be available from the trade mark of the polyalkylene glycol lubricant of The Dow Chemical Company.

The 63rd, can be available from the trade mark of the phosphorodithioate of Ciba.

The 232nd, can be available from the trade mark of the butylation triphenyl thiophosphatephosphorothioate of Ciba.

The 349th, can be available from the trade mark (example of organophosphate/salt) of the phosphamide mixture of Ciba.

350 Hes

The 353rd, can be available from the trade mark of the dialkyl dithiophosphate of Ciba.

157FSL is can be available from the trade mark of the functionalized PFPE of DuPont. The 150th, the trade mark of the alkyl benzene lubricants that Shrieve Chemical sells.OXT-101 is the 3-ethyl-3-methylol trimethylene oxide from Toagosei Company.

622LD is can be available from the trade mark of the hindered amine antioxidant of Ciba.HP-136 is from 5 of Ciba, 7-di-t-butyl-3-(3-4-3,5-dimethylphenyl)-3H-benzofuran-2-ones (example of lactone).Lubricant

The working fluid of listing in PAG 488 and the following table 4 merges to be fabricated to the composition of 50 weight % working fluids and 50 weight % lubricants.

Table 4

Assessment result shows under the situation that has and do not exist air improved chemical stability in the presence of stablizer.

Claims (16)

1. composition comprises:

A. at least a fluoroolefin; With

B. the stablizer that comprises at least a mercaptan or thioether or its mixture of significant quantity.

2. the composition of claim 1, wherein:

A. described mercaptan is selected from methyl mercaptan, ethane mercaptan, coenzyme A, dimercaptosuccinic acid, (R)-2-(4-methyl cyclohexane-3-thiazolinyl) propane-2-mercaptan, halfcystine, Thioctamide and composition thereof; And

B. described thioether is selected from benzyl phenyl sulphur, diphenyl sulfide, dibenzyl sulfide, two (octadecyl) 3,3 '-thiodipropionate, two (dodecyl) 3,3 '-thiopropionate and composition thereof.

3. the composition of claim 1 further comprises at least a fluoroolefin class, fluorinated hydrocarbon, hydrocarbon, dimethyl ether, the CF of being selected from ₃The additional compound of I, carbonic acid gas, ammonia and composition thereof.

4. the composition of claim 1 further comprises the lubricant that is selected from mineral oil, alkylbenzene, poly-alpha-olefin, silicone oil, polyoxyalkylene diols ether, polyol ester, polyvinyl ether and composition thereof.

5. the composition of claim 1, wherein said stablizer further comprises at least a phosphorous acid esters that are selected from, group thiophosphate, butylation triphenyl group thiophosphate, organophosphate/salt, phenols, terpenes, the terpenoid class, fullerene, the arylalkyl ethers, functionalized perfluoropolyether, polyoxyalkylated aromatic substance class, the alkylaromatic class, epoxides, the fluorinated epoxide class, the trimethylene oxide class, thio-alcohol, lactone, the thioether class, amine, the alkyl silane class, the benzophenone derivates class, the additional compound of aryl sulphur class and composition thereof.

6. the composition of claim 5, wherein:

A. described phosphorous acid esters comprise at least a compound that is selected from alkyl, aryl or alkylaryl bi-ester of phosphite;

B. described group thiophosphate comprises at least a single thiophosphate ester, phosphorodithioate, the compound of high-grade thiophosphatephosphorothioate, dialkyl group thiophosphatephosphorothioate and composition thereof more of being selected from;

C. described butylation triphenyl group thiophosphate comprises at least a compound that is selected from the compound shown in the formula A

Formula A

Wherein each R is independently selected from the H or the tertiary butyl;

D. described organophosphate/salt comprises at least a compound that is selected from phosphamide, trialkylphosphate, triaryl phosphate, alkyl diaryl phosphate, di alkylaryl phosphoric acid ester, alkylated aryl phosphoric acid ester, alkylated triaryl phosphates, annular phosphate and composition thereof

E. described phenols is selected from 2,6-di-t-butyl-4-sylvan; 2,6-di-t-butyl-4-ethyl phenol; 2,4-dimethyl-6-tert-butyl phenol; Tocopherol; Quinhydrones; Tertiary butylated hydroquinone; 4,4 '-sulphur-two (2-methyl-6-tert butyl phenol); 4,4 '-sulphur two (3-methyl-6-tert butyl phenol); 2,2 '-sulphur two (4-methyl-6-tert butyl phenol); 4,4 '-methylene-bis (2, the 6-di-tert-butylphenol); 4,4 '-two (2, the 6-di-tert-butylphenol); 2,2 '-methylene-bis (4-ethyl-6-tert-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4,4-butylidene two (3-methyl-6-tert butyl phenol); 4,4-isopropylidene two (2, the 6-di-tert-butylphenol); 2,2 '-methylene-bis (4-methyl-6-nonyl phenol); 2,2 '-isobutylene two (4, the 6-dimethyl phenol; 2,2 '-methylene-bis (4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (4-ethyl-6-tert-butyl phenol); Yoshinox BHT (BHT); 2,6-two-uncle-alpha, alpha-dimethyl amino-p-cresol; 4,4-sulphur two (the 6-tertiary butyl-meta-cresol); Acyl amino phenol; 2,6-di-t-butyl-4 (N, N '-dimethylamino methyl phenol); Two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide; Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide and composition thereof;

F. described terpenes is selected from isoprene, myrcene, alloocimene, β-ocimene, terebene, limonene, retinene, firpene, menthol, Geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, phellandrene, fenchene, kautschin and composition thereof, and

G. described terpenoid class is selected from Lyeopene, beta carotene, zeaxanthin, vitamin A epoxide, and isotretinoin, abietane, ambrosine, aristolane, Anthorine, beyerane, bisabolane, camphane, caryophyllane, cedrane, dammarane, drimane, eremophilane, eudesmane, fenchane, γ wax alkane, germacrane, gibberellane, black laurel alkane, guainane, cedrane, hopance, humulane, kaurane, Ladanum alkane, lanostane, lupane, p-

Alkane, volatile oil, ophiobolane, yellow quassia alkane, pimarane, pinane, podocarpane, protostane, rose alkane, taxane, thujane, the mould alkane of single-ended spore, ursane and composition thereof;

H. described fullerene is selected from Buckminsterfullerene, [5,6] soccerballene-C ₇₀, soccerballene-C ₇₆, soccerballene-C ₇₈, soccerballene-C ₈₄And composition thereof;

I. described epoxide stabilizer is selected from 1, the 2-propylene oxide, 1, the 2-butylene oxide ring, butylphenyl glycidyl ether, the amyl group phenyl glycidyl ether, the hexyl phenyl glycidyl ether, the heptyl phenyl glycidyl ether, the octyl phenyl glycidyl ether, the nonyl phenyl glycidyl ether, the decyl phenyl glycidyl ether, the glycidyl methyl phenyl ether, 1,4-glycidyl phenyl diether, the 4-methoxyphenyl glycidyl ether, naphthyl glycidyl ether, 1,4-diglycidyl naphthyl diether, butylphenyl glycidyl ether, n-butyl glycidyl ether, the isobutyl-glycidyl ether, the hexylene glycol diglycidyl ether, glycidyl allyl ether, polypropylene glycol diglycidyl ether and composition thereof;

J. described fluorinated epoxide class is represented by formula B

Formula B

R wherein ²To R ⁵Each naturally H, have the alkyl of 1-6 carbon atom or have the fluoroalkyl of 1-6 carbon atom, condition is R ²To R ⁵In at least one be fluoroalkyl;

K. described trimethylene oxide class is represented by formula C

Formula C

R wherein ₁-R ₆Be independently selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl;

L. described lactone is selected from gamma-butyrolactone, δ-glucono-lactone, γ-Shi Yineizhi; 6,7-dihydro-4 (5H)-benzofuranone; 5, two (1, the 1-the dimethyl ethyl)-3-[2 of 7-, 3 (or 3,4)-3,5-dimethylphenyls]-2 (3H)-benzofuranones and composition thereof;

M. described alkyl silane class is selected from two (dimethylamino) methyl-monosilanes, three (trimethyl silyl) silane, vinyltriethoxysilane, vinyltrimethoxy silane and composition thereof;

N. described aryl-alkyl ether comprises the compound shown in the formula D, and wherein n is 1,2 or 3 and R ¹It is alkyl with 1 to 16 carbon atom;

Formula D

O. described polyoxyalkylated aromatic substance class comprises the compound shown in the formula D, wherein R ¹Group be comprise at least one-CH ₂CH ₂The polyoxyalkylated group of O-part; And

P. described alkylaromatic class comprises the straight or branched alkyl benzene lubricants

Q. described benzophenone derivates class is selected from 2, the 5-difluoro benzophenone; 2 ', 5 '-resacetophenone; The 2-aminobenzophenone; The 2-chlorobenzophenone; 2-fluorine benzophenone; The 2-dihydroxy benaophenonel; 2 methyl benzophenone; 2-amino-4 '-chlorobenzophenone; 2-amino-4 '-the fluorine benzophenone; 2-amino-5-bromo-2 '-chlorobenzophenone; 2-amino-5-chlorobenzophenone; 2-amino-5-chloro-2 '-the fluorine benzophenone; 2-amino-5-nitro benzophenone; 2-amino-5-nitro-2 '-chlorobenzophenone; 2-amino-2 ', the 5-dichloro benzophenone; 2-chloro-4 '-the fluorine benzophenone; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-5-chlorobenzophenone; 2-methylamino--5-chlorobenzophenone; 3-methyldiphenyl ketone; The 3-nitro benzophenone; 3-nitro-4 '-chloro-4-fluorine benzophenone; The 4-chlorobenzophenone; 4-fluorine benzophenone; The 4-dihydroxy benaophenonel; The 4-methoxy benzophenone; 4-methyldiphenyl ketone; The 4-nitro benzophenone; The 4-phenyl benzophenone; 4-chloro-3-nitro benzophenone; 4-hydroxyl-4 '-chlorobenzophenone; 2,4 dihydroxyl benzophenone; 2, the 4-dimethyl benzophenone; 2, the 5-dimethyl benzophenone; 3, the 4-diaminobenzophenone; 3, the 4-dichloro benzophenone; 3, the 4-difluoro benzophenone; 3, the 4-dihydroxy benaophenonel; 3, the 4-dimethyl benzophenone; 4,4 '-two (diethylamine) benzophenone; 4,4 '-two (dimethyl amine) benzophenone; 4,4 '-dichloro benzophenone; 4,4 '-difluoro benzophenone; 4,4 '-dihydroxy benaophenonel; 4,4 '-dimethoxy-benzophenone and composition thereof; And

R. described amine is selected from triethylamine; Tributylamine; Diisopropylamine; Tri-isopropyl amine; Tri-isobutylamine; Ursol D; Diphenylamine; N-(1-methylethyl)-2-propylamine; 2,2,6,6-tetramethyl--4-piperidone; 2,2,6,6-tetramethyl--4-piperidines alcohol; Two-(1,2,2,6,6-pentamethyl-piperidyl); Two-(2,2,6,6-tetramethyl--4-piperidyl) sebates; Poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate; N-phenyl-N '-(1, the 3-dimethylbutyl)-Ursol D; N, N '-two-sec-butyl-Ursol D; Tallow amine; Two (hydrogenated tallow alkyl) amine of N-methyl; Phenol-Alpha-Naphthyl amine and composition thereof.

7. the composition of claim 1, wherein said fluoroolefin is at least a compound that is selected from following material:

(i) formula E-or Z-R ¹CH=CHR ²Fluoroolefin, R wherein ¹And R ²Be C independently ₁To C ₆Perfluoroalkyl;

(ii) formula ring-[CX=CY (CZW) _n-] the ring fluoroolefin, wherein X, Y, Z and W are H or F independently, and n is 2 to 5 integer; With

(iii) be selected from the fluoroolefin of following material:

1,2,3,3,3-, five fluoro-1-propylene (CHF=CFCF₃), 1,1,3,3,3-five fluoro-1-propylene (CF₂＝CHCF ₃), 1,1,2,3,3-five fluoro-1-propylene (CF₂＝CFCHF ₂), 1,2,3,3-tetrafluoro-1-propylene (CHF=CFCHF₂), 2,3,3,3-tetrafluoro-1-propene (CH₂＝CFCF ₃), 1,3,3,3-tetrafluoro-1-propene CHF=CHCF₃), 1,1,2,3-tetrafluoro-1-propene (CF₂＝CFCH ₂F), 1,1,3,3-tetrafluoro-1-propene (CF₂＝CHCHF ₂), 1,2,3,3-tetrafluoro-1-propene (CHF=CFCHF₂), 3,3,3-three fluoro-1-propylene (CH₂＝CHCF ₃), 2,3,3-three fluoro-1-propylene (CHF₂CF＝CH ₂); 1,1,2-, three fluoro-1-propylene (CH₃CF＝CF ₂); 1,2,3-, three fluoro-1-propylene (CH₂FCF＝CF ₂); 1,1,3-, three fluoro-1-propylene (CH₂FCH＝CF ₂); 1,3,3-, three fluoro-1-propylene (CHF₂CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF₃CF＝CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF₃CF ₂CF＝CF ₂); 1,1,1,2,4,4,4-, seven fluoro-2-butylene (CF₃CF＝CHCF ₃); 1,2,3,3,4,4,4-, seven fluoro-1-butylene (CHF=CFCF₂CF ₃); 1,1,1,2,3,4,4-, seven fluoro-2-butylene (CHF₂CF＝CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF₃) ₂C=CHF); 1,1,3,3,4,4,4-, seven fluoro-1-butylene (CF₂＝CHCF ₂CF ₃); 1,1,2,3,4,4,4-, seven fluoro-1-butylene (CF₂＝CFCHFCF ₃); 1,1,2,3,3,4,4-, seven fluoro-1-butylene (CF₂＝CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF₃CF ₂CF＝CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF₂CF＝CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH₂FCF＝CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF₂CH＝CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF₃CH＝CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF₂＝CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF₂＝CFCHFCHF ₂); 3,3,3-, three fluoro-2-(trifluoromethyl)-1-propylene (CH₂＝C(CF ₃) ₂); 1,1,1,2,4-, five fluoro-2-butylene (CH₂FCH＝CFCF ₃); 1,1,1,3,4-, five fluoro-2-butylene (CF₃CH＝CFCH ₂F); 3,3,4,4,4-, five fluoro-1-butylene (CF₃CF ₂CH＝CH ₂); 1,1, Isosorbide-5-Nitrae, 4-five fluoro-2-butylene (CHF₂CH＝CHCF ₃); 1,1,1,2,3-, five fluoro-2-butylene (CH₃CF＝CFCF ₃); 2,3,3,4,4-, five fluoro-1-butylene (CH₂＝CFCF ₂CHF ₂); 1,1,2,4,4-, five fluoro-2-butylene (CHF₂CF＝CHCHF ₂); 1,1,2,3,3-, five fluoro-1-butylene (CH₃CF ₂CF＝CF ₂); 1,1,2,3,4-, five fluoro-2-butylene (CH₂FCF＝CFCHF ₂); 1,1,3,3,3-, five fluoro-2-methyl-1-propylene (CF₂＝C(CF ₃)(CH ₃)); 2-(difluoromethyl)-3,3,3-three fluoro-1-propylene (CH₂＝C(CHF ₂)(CF ₃)); 2,3,4,4,4-, five fluoro-1-butylene (CH₂＝CFCHFCF ₃); 1,2,4,4,4-, five fluoro-1-butylene (CHF=CFCH₂CF ₃); 1,3,4,4,4-, five fluoro-1-butylene (CHF=CHCHFCF₃); 1,3,3,4,4-, five fluoro-1-butylene (CHF=CHCF₂CHF ₂); 1,2,3,4,4-, five fluoro-1-butylene (CHF=CFCHFCHF₂); 3,3,4,4-tetrafluoro-1-butylene (CH₂＝CHCF ₂CHF ₂); 1,1-, two fluoro-2-(difluoromethyl)-1-propylene (CF₂＝C(CHF ₂)(CH ₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propylene (CHF=C (CF₃)(CH ₃)); 3,3-, two fluoro-2-(difluoromethyl)-1-propylene (CH₂＝C(CHF ₂) ₂); 1,1,1,2-tetrafluoro-2-butylene (CF₃CF＝CHCH ₃); 1,1,1,3-tetrafluoro-2-butylene (CH₃CF＝CHCF ₃); 1,1,1,2,3,4,4,5,5,5-, ten fluoro-2-amylene (CF₃CF＝CFCF ₂CF ₃); 1,1,2,3,3,4,4,5,5,5-, ten fluoro-1-amylene (CF₂＝CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF₃) ₂C＝CHCF ₃); 1,1,1,2,4,4,5,5,5-, nine fluoro-2-amylene (CF₃CF＝CHCF ₂CF ₃); 1,1,1,3,4,4,5,5,5-, nine fluoro-2-amylene (CF₃CH＝CFCF ₂CF ₃); 1,2,3,3,4,4,5,5,5-, nine fluoro-1-amylene (CHF=CFCF₂CF ₂CF ₃); 1,1,3,3,4,4,5,5,5-, nine fluoro-1-amylene (CF₂＝CHCF ₂CF ₂CF ₃); 1,1,2,3,3,4,4,5,5-, nine fluoro-1-amylene (CF₂＝CFCF ₂CF ₂CHF ₂); 1,1,2,3,4,4,5,5,5-, nine fluoro-2-amylene (CHF₂CF＝CFCF ₂CF ₃); 1,1,1,2,3,4,4,5,5-, nine fluoro-2-amylene (CF₃CF＝CFCF ₂CHF ₂); 1,1,1,2,3,4,5,5,5-, nine fluoro-2-amylene (CF₃CF＝CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF₂＝CFCH(CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF₃CH＝C(CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF₂＝CHCF(CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH₂＝CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF₂CF ₂CHF ₂); 3,3,4,4,4-, five fluoro-2-(trifluoromethyl)-1-butylene (CH₂＝C(CF ₃)CF ₂CF ₃); 1, Isosorbide-5-Nitrae, 4,4-, five fluoro-3-(trifluoromethyl)-1-butylene (CF₂＝CHCH(CF ₃) ₂); 1,3,4,4,4-, five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF₃) ₂); 1, Isosorbide-5-Nitrae, 4,4-, five fluoro-2-(trifluoromethyl)-1-butylene (CF₂＝C(CF ₃)CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF₃) ₂CFCH＝CH ₂); 3,3,4,4,5,5,5-, seven fluoro-1-amylene (CF₃CF ₂CF ₂CH＝CH ₂); 2,3,3,4,4,5,5-, seven fluoro-1-amylene (CH₂＝CFCF ₂CF ₂CHF ₂); 1,1,3,3,5,5,5-, seven fluoro-1-butylene (CF₂＝CHCF ₂CH ₂CF ₃); 1,1,1,2,4,4,4-, seven fluoro-3-methyl-2-butene (CF₃CF＝C(CF ₃)(CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH₂＝CFCH(CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH₂FCH＝C(CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH₃CF＝C(CF ₃) ₂); 1,1,1-, three fluoro-2-(trifluoromethyl)-2-butylene ((CF₃) ₂C＝CHCH ₃); 3,4,4,5,5,5-hexafluoro-2-amylene (CF₃CF ₂CF＝CHCH ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-methyl-2-butylene (CF₃C(CH ₃)＝CHCF ₃); 3,3,4,5,5,5-hexafluoro-1-amylene (CH₂＝CHCF ₂CHFCF ₃); 4,4,4-, three fluoro-2-(trifluoromethyl)-1-butylene (CH₂＝C(CF ₃)CH ₂CF ₃); 1,1,2,3,3,4,4,5,5,6,6,6-, 12 fluoro-1-hexene (CF₃(CF ₂) ₃CF＝CF ₂); 1,1,1,2,2,3,4,5,5,6,6,6-, 12 fluoro-3-hexene (CF₃CF ₂CF＝CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3-₃) ₂C＝C(CF ₃) ₂); 1,1,1,2,3,4,5,5,5-, nine fluoro-4-(trifluoromethyl)-2-amylene ((CF₃) ₂CFCF＝CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF₃) ₂C＝CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF₃) ₂CFCF＝CHCF ₃); 3,3,4,4,5,5,6,6,6-, nine fluoro-1-hexene (CF₃CF ₂CF ₂CF ₂CH＝CH ₂); 4,4,4-, three fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3-₂＝CHC(CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butylene ((CF₃) ₂C＝C(CH ₃)(CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH₂＝CFCF ₂CH(CF ₃) ₂); 1,1,1,2,4,4,5,5,5-, nine fluoro-3-methyl-2-amylene (CF₃CF＝C(CH ₃)CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF₃CH＝CHCH(CF ₃) ₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF₃CF ₂CF ₂CF＝CHCH ₃); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH₂＝CHCF ₂CF ₂CF ₂CHF ₂); 1,1, Isosorbide-5-Nitrae, 4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF₃) ₂C＝CHCF ₂CH ₃); 4,4,5,5,5-, five fluoro-2-(trifluoromethyl)-1-amylene (CH₂＝C(CF ₃)CH ₂C ₂F ₅); 3,3,4,4,5,5,5-, seven fluoro-2-Methyl-1-pentene (CF₃CF ₂CF ₂C(CH ₃)＝CH ₂); 4,4,5,5,6,6,6-, seven fluoro-2-hexene (CF₃CF ₂CF ₂CH＝CHCH ₃); 4,4,5,5,6,6,6-, seven fluoro-1-hexene (CH₂＝CHCH ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4-, seven fluoro-3-hexene (CF₃CF ₂CF＝CFC ₂H ₅); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-amylene (CH₂＝CHCH ₂CF(CF ₃) ₂); 1,1,1,2,5,5,5-, seven fluoro-4-methyl-2-amylene (CF₃CF＝CHCH(CF ₃)(CH ₃)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-amylene ((CF₃) ₂C＝CFC ₂H ₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF₃CF＝CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF₃CF ₂CF＝CFCF ₂C ₂F ₅); 1,1,1,3,4,4,5,5,6,6,7,7,7-, 13 fluoro-2-heptene (CF₃CH＝CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,4,4,5,5,6,6,7,7,7-, 13 fluoro-2-heptene (CF₃CF＝CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-, 13 fluoro-3-heptene (CF₃CF ₂CH＝CFCF ₂C ₂F ₅); With 1,1,1,2,2,3,5,5,6,6,7,7,7-, 13 fluoro-3-heptene (CF₃CF ₂CF＝CHCF ₂C ₂F ₅)。

8. the composition of claim 1 further comprises and is selected from two (benzylidene) hydrazides of areoxalyl; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-two-tertiary butyl-4-hydroxy hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propanediamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative, N, the metal passivator of N-two salicylidenes-1 and composition thereof.

9. composition, it comprises the fluoroolefin of at least a HFC-1225ye of being selected from, HFC-1234yf, HFC-1234ze and HFC-1243zf; Stablizer with comprising of significant quantity at least a mercaptan or thioether or its mixture and any annex compound, described annex compound is selected from phenols, terpenes and terpenoid class, fullerene, epoxides, fluorinated epoxide class, trimethylene oxide class, terephthalic acid divinyl ester, terephthaldehyde's diphenyl phthalate and composition thereof, is meant the mixture of any aforementioned additional compound.

10. composition, it comprises the fluoroolefin of at least a HFC-1225ye of being selected from, HFC-1234yf, HFC-1234ze and HFC-1243zf; Stablizer with comprising of significant quantity at least a mercaptan or thioether or its mixture and at least a amine.

11. the composition of claim 10, wherein said amine are selected from the derivative of piperidyl, piperidyl, piperazine ketone or the alkoxyl group piperidinyl compounds of alkyl replacement.

12. make the method for the composition stability that comprises at least a fluoroolefin, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the composition that comprises at least a fluoroolefin.

13. refrigerating method comprises the composition of condensation claim 1 and is after this wanting to evaporate described composition near the refrigerative object.

14. heating method is included near the composition of the condensation claim 1 of object that will heat and after this evaporates described composition.

15. reduce the method for the degraded of the composition that comprises at least a fluoroolefin, wherein said degraded causes by the existence that is strayed into air in refrigeration, air-conditioning or the heat pump, and described method comprises adds at least a mercaptan of significant quantity or thioether or its mixture in the described composition that comprises at least a fluoroolefin to.

16. alleviate the method for the composition that comprises at least a fluoroolefin and oxygen reaction, described method comprise with comprising of significant quantity at least a mercaptan or thioether or its mixture stablizer add in the described composition that comprises at least a fluoroolefin.