CN101605863A - The amine stabiliser of fluoroolefins - Google Patents

Abstract

The present invention relates to comprise the composition of at least a fluoroolefin and effective amount of stabilizer, this stablizer can be the mixture of amine or amine and other stablizer.This stabilized composition can be used on refrigerating unit, in refrigeration, air-conditioning, water cooler and heat pump, and is used in the purposes as whipping agent, solvent, aerosol propellants, fire-fighting medium and disinfectant.

Description

The amine stabiliser of fluoroolefins

Background of invention

1. invention field

The present invention relates to comprise the composition of at least a fluoroolefin and stablizer.The substitute that this stabilized composition can be used as the existing refrigeration agent with higher Global warming potentiality 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 in mixture 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 may 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 means of degraded.

Summary of the invention

The disclosure provides the composition of the stablizer that comprises at least a amine that comprises at least a fluoroolefin and significant quantity.

The method that makes the composition stability that comprises at least a fluoroolefin also is provided, and described method comprises the stablizer that comprises at least a amine that adds significant quantity.

The method that reduces the degraded of the composition that comprises at least a fluoroolefin also is provided, wherein said degraded is caused that by the existence that is strayed into air in refrigeration, air-conditioning or the heat pump described method comprises that the stablizer that comprises at least a amine with significant quantity adds 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 comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.

Detailed Description Of The Invention

The invention provides the composition of the stablizer that comprises at least a amine that comprises at least a fluoroolefin and significant quantity.

These compositions serve many purposes in working fluid, only give some instances, and comprise as whipping agent, pore forming material, fire-fighting medium, 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 on the base material or the fluid of support materials from base material.

Aerosol propellants is to apply greater than the volatile compositions of an atmospheric pressure with one or more components 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 be in fluid experience 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.

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 in molecule at least about 4 carbon atoms.In another embodiment, the fluoroolefin of formula I has in molecule at least about 5 carbon atoms.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 alkanes prepare.This three hydrogen iodo perfluoro alkanes 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 alkanes 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 can mixed reactant carries out with batch mode in the suitable reaction vessels of moving under temperature of reaction from depressing at reactant and product.Suitable reaction vessel comprises by stainless steel, particularly Austenitic stainless steel and known Langaloy, as Nickel-copper alloy,

Nickel-base alloy and

Nickel-chromium alloy is made.

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

The ratio of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene should be about 1: 1 to about 4: 1, preferred about 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 1.5: 1 ratios.

The preferred temperature that described perfluoroalkyl iodides is contacted with described perfluoroalkyl three hydrogen alkene is preferably about 150 ℃ to 300 ℃, and preferred about 170 ℃ to about 250 ℃, most preferably from 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, preferred about 4 to about 12 hours.

The three hydrogen iodo perfluoro alkanes 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 alkanes are contacted with alkaline matter.Suitable alkaline matter comprises the mixture of 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), ammoniacal liquor, sodium amide or alkaline matter, as soda-lime.Preferred alkaline matter is sodium hydroxide and potassium hydroxide.

Three hydrogen iodo perfluoro alkanes 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 can depend 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 alkanes) 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 ℃, preferred about 20 ℃ to about 70 ℃.The dehydroiodination reaction can be carried out at environmental stress or under decompression or high 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, dehydroiodination reaction can be by making described alkaline matter the aqueous solution and three hydrogen iodo perfluoro alkanes have the solution that hangs down in the polar organic solvent at one or more and in the presence of phase-transfer catalyst, contact and carry out, described organic solvent such as alkane (hexane for example, heptane or octane), aromatic hydrocarbons (for example toluene), halohydrocarbon (methylene dichloride for example, chloroform, tetracol phenixin or tetrachloroethylene), or ether (diethyl ether for example, methyl tert-butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, diglyme or tetraethylene glycol dimethyl ether).Suitable phase-transfer catalyst comprises the cyclic polyether compound (for example 18-hat-6 and 15-hat-5) that is known as crown ether in quaternary ammonium halide (for example bromination tetrabutylammonium, hydrogen sulfate tetrabutylammonium, 3-ethyl benzyl ammonium chloride, dodecyltrimethyl ammonium chloride and chlorination three capryloyl first ammoniums), quaternary phosphine halogenide (for example bromination three phenyl methyl Phosphonium and tetraphenylphosphonium chlorides) or this area.

Perhaps, the dehydroiodination reaction can be undertaken by three hydrogen iodo perfluoro alkanes 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 in molecule at least about 3 carbon atoms.In another embodiment, the fluoroolefin of formula II has in molecule at least about 4 carbon atoms.In an embodiment again, the fluoroolefin of formula II has in molecule at least about 5 carbon atoms.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-1447fycc	??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-161-14mvv	??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 intends comprising 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 of the stablizer that comprises at least a amine that comprises at least a fluoroolefin and significant quantity.

In one embodiment, amine stabiliser 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, piperidino-(1-position only) (piperidinyl), piperazine ketone or the alkoxyl group piperidino-(1-position only) compound 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-butyls-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.

The present invention further comprises at least a additional stability agent in another embodiment, it is selected from phenol, thiophosphatephosphorothioate, butylation triphenyl thiophosphatephosphorothioate (triphenylphosphorothionates), organophosphate, phosphorous acid ester, terpenes, terpenoid, soccerballene, functionalized PFPE, the polyoxyalkylated aromatic substance, alkylaromatic, epoxide, fluorinated epoxide, trimethylene oxide, xitix, mercaptan, lactone, thioether, Nitromethane 99Min., alkyl silane, benzophenone derivates, aryl thioethers, terephthalic acid divinyl ester and terephthaldehyde's diphenyl phthalate and composition thereof are meant the mixture of any stablizer listed in the mixture of any stablizer listed in this section and this section or combination of stabilizers and above-mentioned any stablizer or amine stabiliser combination.

In one embodiment, this additional stability agent can comprise at least a phenol.Phenol stabilizers is any replacement or unsubstituted phenolic compound, comprises comprising one or more replacements or unsubstituted ring-type, the substituent phenol of straight or branched aliphatic series, as the single phenol of alkylation, comprises 2,6 di tert butyl 4 methyl phenol; 2,6-di-t-butyl-4-ethylphenol; 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 '-sulfo--two (2-methyl-6-tert butyl phenol); 4,4 '-thiobis (3 methy 6 tert butyl phenol); 2,2 '-thiobis (4 methyl-6-tert butyl phenol); And analogue, alkylidene group-bis-phenol comprises: 4, and 4 '-methylene-bis (2,6 di t butyl phenol); 4,4 '-two (2,6 di t butyl phenols); 2,2 '-or 4, the derivative of 4-biphenyl glycol (biphenoldiols); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4, the 4-butylidene-bis(3-methyl-6-t-butyl phenol); 4,4-isopropylidene two (2,6 di t butyl phenol); 2,2 '-methylene-bis(4-methyl-6-nonyl phenol); 2,2 '-isobutylene two (4, the 6-xylenol); 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2-or 4,4-biphenyl glycol (biphenyldiols) comprises 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); Yoshinox BHT (BHT), comprise heteroatomic bis-phenol, comprise 2,6-two-uncle-alpha, alpha-dimethyl amino-p-cresol, 4,4-thiobis (the 6-tertiary butyl-meta-cresol); And analogue; Amido phenol; 2,6-di-t-butyl-4 (N, N '-dimethylaminomethylphenol); Sulfide comprises two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide; Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; And analogue.

In another embodiment, this additional stability agent can comprise at least a thiophosphatephosphorothioate.Thiophosphoric acid ester stabilizer of the present invention is by replace the compound that one or more Sauerstoffatoms generate with divalent sulfur by phosphoric acid.These can be single thiophosphate ester, phosphorodithioate or high-grade more.Representational phosphorodithioate can be with trade mark

63 available from CibaSpecialty 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 another embodiment, additional stability agent of the present invention comprises at least a suc as formula the butylation triphenyl thiophosphatephosphorothioate shown in the A.

Formula A

Wherein each R be independently selected from the butylation triphenyl thiophosphatephosphorothioate of the H or the tertiary butyl can be with trade mark

232 available from Ciba.

In another embodiment, this additional stability agent can comprise at least a organophosphate.This organophosphate stablizer comprises but is not limited to amine phosphoric acid ester, trialkylphosphate, triaryl phosphate, mixed alkyl-aryl phosphate ester (alkyl diaryl, di alkylaryl or alkylated aryl) and annular phosphate.Representational amine phosphoric acid ester 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).This phosphorus compound.Listed all organic phosphoric acid ester stabilizers 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 Syn-O-

8784 butylation triphenyl available from Akzo Nobel (Arnhem, the Netherlands); Can be with trade mark

620 available from Great Lakes Chemical Corporation (GLCC, WestLafayette, 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 be derived from replacing phosphorous acid ester.Especially, the phosphorous acid ester that is obstructed is the derivative of alkyl, aryl or alkylaryl bi-ester of phosphite.Tricresyl phosphite (di-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, all from Ciba.

In another embodiment, this additional stability agent can comprise at least a terpenes.Terpenes is that to repeat the unitary structure of isoprene (2-methyl isophthalic acid, 3-divinyl) more than one be the hydrocarbon compound of feature to contain.Terpenes can be acyclic or cyclic.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, limonene and composition thereof.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 is to repeat isoprene unit and optional oxygen containing structure is the natural product and the related compound of feature to contain more than one.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]); Artemisiifolia alkane (ambrosane) (CASreg.no.[24749-18-6]); Aristolane (CAS reg.no.[29788-49-6]); The living alkane (atisane) of Ah Ti (CAS reg.no.[24379-83-7]); Beyerane (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]); The full alkane (drimane) of awl (CASreg.no.[5951-58-6]); Refined maliane (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 poison 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 (CAS reg.no.[474-20-4]); Lupane (CAS reg.no.[464-99-3]); Right

Alkane (CAS reg.no.[99-82-1]); Volatile oil (CAS reg.no.[471-67-0]); Snake born of the same parents bacterium alkane (ophiobolane) (CAS reg.no.[20098-65-1]); Bitter taste 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]); Taxan (taxane) (CAS reg.no.[1605-68-1]); Thujane (CAS reg.no.[471-12-5]); Spore bacterium alkane (trichothecane) (CAS reg.no.[24706-08-9]); With the plain alkane of crow (CAS reg.no.[464-93-7]).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 is 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 deformation 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(CAS reg.no.[135113-15-4]), soccerballene-C ₇₈(CAS reg.no.[136316-32-0]) and soccerballene-C ₈₄(CAS reg.no.[135113-16-5]).

In another embodiment, this additional stability agent can comprise at least a aryl alkyl ethers.Aryl alkyl ethers stablizer of the present invention can be described by formula B, and wherein n is 1,2 or 3 and R ¹It is alkyl with 1 to 16 carbon atom.

Formula B

Representational aryl alkyl ethers includes but not limited to methyl-phenoxide, 1,4-dimethoxy benzene, 1,4-diethoxybenzene and 1,3,5-trimethoxy-benzene.

In another embodiment, this additional stability agent can comprise at least a functionalized PFPE.The functionalized PFPE of this class can be 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 following formula B of perfluoroalkyl or PFPE side chain.In addition, 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 and one or morely have general formula-CH ₂(C _qH _2q) the pure segmental PFPE alkyl alcohol of OH, wherein-C _qH _2qRepresent divalence straight or branched alkyl, wherein q is 0 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 [Rf ¹-(C _tR _(u+v))] _mE (O) _n(C _tR ¹ _(u+v+1)) _(3-m)Substituted aryl pnicogen composition, wherein

Rf 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) wherein two or more combination,

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 two or more combination 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 two or more combination 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 ₇Wherein two or more combination;

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 i: ratio (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 wherein two or more combination;

Wherein

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

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) wherein two or more combination; 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 wherein two or more combination;

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

Z ¹Be-F or-Cl,

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

The numerical value of e and f makes that the ratio of e/f 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 wherein two or more combination;

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: ratio (g+h) 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 wherein two or more combination; 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 wherein two or more combination, condition is if b=0, then 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 wherein two or more combination;

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 wherein two or more combination;

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;

Rf 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-Rf ²-O (C ₃F ₆O) _wCF (CF ₃)-,-((CQ ₂) CF ₂CF ₂O) _sCF ₂CF ₂-or wherein two or more combination;

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 polyoxyalkylated aromatic substance.This polyoxyalkylated aromatic substance is the compound shown in the formula B, wherein R ¹Group be comprise at least one-CH ₂CH ₂The polyoxyalkylated group of O-part.In another embodiment, this additional stability agent can comprise at least a alkylaromatic.Can be used as the alkyl benzene lubricants that includes but not limited to side chain and straight chain according to the representative alkylaromatic of additional stability agent of the present invention, can be with trade mark

75,

150 Hes

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

In another embodiment, this additional stability agent can comprise at least a epoxide.Epoxide comprises 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, hexanediol diglycidyl ether, glycidyl allyl ether, polypropylene glycol diglycidyl ether and composition thereof.

In another embodiment, this additional stability agent can comprise at least a fluorinated epoxide.Fluorinated epoxide stablizer of the present invention can be described by formula C, 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 C

Representational fluorinated epoxide stablizer comprises but is not limited to trifluoromethyl oxyethane and 1, two (trifluoromethyl) oxyethane of 1-.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.Trimethylene oxide stablizer of the present invention can be to have the compound of one or more oxetane groups and represented by formula D, and wherein R1-R6 is identical or different and can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

Formula D

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).

In another embodiment, this additional stability agent can comprise xitix (CAS reg.no.[50-81-7]).

In another embodiment, this additional stability agent can comprise at least a mercaptan (thiol), is also referred to as mercaptan (mercaptans) or sulfhydrate.This class mercaptan compound is the sulfur analogs of the alcohol of hydroxyl.Representational thiol stabilizer includes but not limited to thiomethyl alcohol (methyl mercaptan), sulfur alcohol (ethanethio), coenzyme A (CAS reg.no.[85-61-0]), dimercaptosuccinic acid (DMSA, CASreg.no.[2418-14-6]) natsudaidai mercaptan ((R)-2-(4-methyl cyclohexane-3-thiazolinyl) third-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, CAS reg.no.[940-69-2].

In another embodiment, this additional stability agent can comprise at least a lactone.Lactone is to react the cyclic ester of making by the hydroxy-acid group 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 can comprise at least a thioether.Thioether stabilizers of the present invention include but not limited to benzyl phenyl thioether (CAS reg.no.[831-91-4]), diphenyl sulfide (CAS reg.no.[139-66-2]), 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, this additional stability agent can comprise Nitromethane 99Min. (CH ₃NO ₂, CASreg.no.[75-52-5]).

In another embodiment, this additional stability agent can comprise at least a alkyl silane.Silane is and compound like the hydro carbons that wherein Siliciumatom substitutes each carbon.The alkyl silane stablizer comprises but is 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]).

In another embodiment, this additional stability agent can comprise at least a benzophenone derivates.The benzophenone derivates stablizer comprises the benzophenone that can be replaced by side group, and described side group comprises halogenide, as fluorine, chlorine, bromine or iodine, and amino, hydroxyl, alkyl, as methyl, ethyl or propyl group, aryl, as phenyl, any combination of nitro or this class 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.

In another embodiment, this additional stability agent can comprise at least a aryl thioethers.This aryl thioethers stablizer comprises at least a compound that is selected from benzyl phenyl thioether, diphenyl sulfide and dibenzyl sulfide.

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

Unless above indicate separately, stablizer of the present invention can be available from various chemical supplier.

The single stable immunomodulator compounds can be united and is used in this composition that comprises at least a fluoroolefin or multiple stabilizer compounds can be with the combination of any ratio to serve as stabilizer blend.This stabilizer blend can contain from the multiple stabilizer compounds of identical type compound or from the multiple stabilizer compounds of different sorts compound.For example, stabilizer blend can contain two or more amine stabilisers, or one or more amine stabilisers and one or more additional stability agent (for example phenol, terpenes or lactone).

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 the preparation stabilizer blend with any ratio.In addition, the single or multiple isomer of given compound can be with other compound of any number with any mixed to serve as stabilizer blend.The present invention intends comprising all single configurational isomers, single steric isomer or its any combination or mixture.

The stabiliser composition that particularly importantly comprises the compound combination that unexpected stabilization level is provided.Some these combination can be served as the Synergistic stabilizer composition, promptly strengthen the compound compositions of rendeing a service each other in preparation, and the gained stabilization is greater than the desired stabilization of effect summation by each component.This class Synergistic stabilizer composition can comprise at least a P contained compound and be selected from any compound of terpenes and terpenoid, soccerballene, epoxide, fluorinated epoxide, trimethylene oxide, terephthalic acid divinyl ester and terephthaldehyde's diphenyl phthalate and composition thereof (being meant the mixture of any previous materials and P contained compound).

The limiting factor of stabiliser composition efficient is stablizer loss and the functional loss that takes place with effective storage life.The Synergistic stabilizer composition that particularly importantly comprises stabilizer blend, this stablizer comprise the stablizer regenerated component that can make consumption in effective use, hereinafter are 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 contain can be after use one or more stablizers of replenishing of oneself so that with life-time service, keep the effectiveness of said composition.

An example of reproducibility stablizer is amine and at least a phenol.The phenol that comprises in this reproducibility stablizer can be any phenol mentioned above.Particularly importantly derived from the hindered phenol, particularly alkyl of substituted phenol, the derivative of aryl phenol compounds.Representational hindered phenol can be with trade mark

E201 (two-alpha-tocopherol),

1010,

1976,

L 109,

L 134 (all from Ciba) buys.

Another example of reproducibility stablizer is the stablizer that comprises at least a amine and at least a phosphorous acid ester.The phosphorous acid ester that comprises in this reproducibility stabiliser composition can be any phosphorous acid ester mentioned above.In one embodiment, phosphorous acid ester can be the phosphorous acid ester and can be derived from the derivative that replaces phosphorous acid ester, particularly alkyl, aromatic yl phosphite compound of being obstructed.The representational phosphorous acid ester that is obstructed can be with trade mark

168 (tricresyl phosphite (di-tert-butyl-phenyl) esters),

OPH (phosphorous acid di-n-octyl),

DDPP (phosphorous acid isodecyl diphenyl ester) (all from Ciba) buys.

The amine that comprises in the reproducibility stabiliser composition can comprise previously described any amine stabiliser.Particularly importantly derived from those hindered amines of substituted pyridine compound, the derivative of the piperidyl, piperidino-(1-position only), piperazine ketone or the alkoxyl group piperidino-(1-position only) compound that replace of alkyl particularly.Representational hindered amine as light stabilizer 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, as Ciba with trade mark

770 hindered amines of selling; Poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate (CASreg.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, above-mentioned any stabiliser composition can further comprise at least a two (benzylidene) hydrazides (areoxalyl bis (benzylidene) hydrazide) (CAS reg.no.6629-10-3) of oxalyl that are selected from; 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-di-t-butyl-4-hydroxyl hydrogenated cinnamate) (CAS reg.no.70331-94-1); N, N '-(two salicylidenes)-1,2-propylene diamine (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 and N, the metal passivator of N-two salicylidenes-1.

In another embodiment, stabiliser composition comprises at least a amine, at least a phosphorous acid ester and at least a two (benzylidene) hydrazides of oxalyl that are selected from; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propylene diamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative and N, the metal passivator of N-two salicylidenes-1.

In another embodiment, stabiliser composition comprises at least a amine; At least a compound that is selected from epoxide, trimethylene oxide, lactone, terephthalic acid divinyl ester and terephthaldehyde's diphenyl phthalate; With at least a two (benzylidene) hydrazides of oxalyl that are selected from; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propylene diamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative and N, the metal passivator of N-two salicylidenes-1.

In another embodiment, stabiliser composition comprises at least a amine; At least a P contained compound that is selected from aryl phosphite, phosphoric acid and two (2, two (1, the 1-the dimethyl ethyl)-6-methylphenols of 4-) ethyl ether; With at least a two (benzylidene) hydrazides of oxalyl that are selected from; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propylene diamine; Ethylenediamine tetraacetic acid (EDTA) and salt thereof; Triazole; Benzotriazole, 2-mercaptobenzothiazole, tolytriazole derivative and N, the metal passivator of N-two salicylidenes-1.

Composition of the present invention can further comprise at least a fluoroolefin (as mentioned above), hydrofluoric ether, hydrocarbon, dimethyl ether, the CF of being selected from ₃I, carbonic acid gas (CO ₂) and the additional compound of ammonia.

In one embodiment, this additional compound comprises hydrofluoric ether (HFC) compound.Hydrofluoric ether comprises the saturated compound of carbon containing, hydrogen and fluorine.Useful especially is the hydrofluoric ether that has 1-7 carbon atom and have-90 ℃ to 80 ℃ normal boiling point.Hydrofluoric ether is can be available from many sources such as E.I.du Pont de Nemours﹠amp; Co., Fluoroproducts, 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 (CH3CH2F, 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-fluoropropane (CH ₃CHFCH ₃, HFC-281ea), 1-fluoropropane (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.Hydrocarbon comprises the compound that has only carbon and hydrogen.Useful especially is the compound with 3-7 carbon atom.Hydrocarbon can be buied by many chemical supplier.Representational hydrocarbon 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 can also comprise and contain heteroatomic hydrocarbon, as dimethyl ether (DME, CH ₃OCH ₃).DME can buy.

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

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

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

Additional compound particularly importantly 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 CF3I; 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 intend comprising 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 been discussed this series lubricant agent and their character in the 8.1st to 8.21 page (being hereby incorporated by).Lubricant of the present invention can be included in those that often are known as " mineral oil " in the lubricated field of compression refrigeration.Mineral oil comprises paraffinic hydrocarbons (being straight chain and side chain carbochain stable hydrocarbon), naphthenic hydrocarbon (be ring-type or ring structure stable 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 paraffinic hydrocarbons and naphthenic hydrocarbon, siloxanes and poly-alpha-olefin.Representational conventional lubricant of the present invention be commercially available BVM100N (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 polyol ester (POEs), for example

100 (Castrol, United Kingdom), polyalkylene glycol (PAGs) is for example from Dow (DowChemical, Midland, RL-488A Michigan), and polyvinyl ether (PVEs).

The environment that requirement by considering given compressor and lubricant will expose is selected lubricant of the present invention.

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

In comprising the composition of at least a fluoroolefin, 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 be caused and compare the same big refrigeration performance when using with the composition that does not have stablizer reduce 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, when can being said to be in and mixing with the composition that comprises at least a fluoroolefin, significant quantity allows to 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) amount of the stablizer of 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 used in the present invention stablizer of significant quantity, its about 0.001wt% that constitutes the described composition total weight that comprises at least a fluoroolefin is about 10wt% extremely, more preferably from about 0.01wt% is to about 5wt%, again more preferably from about 0.3wt% to about 4wt%, 0.3wt% about 1wt% extremely more preferably from about again.

The invention further relates to the method that makes the composition stability that comprises at least a fluoroolefin, described method comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.

The invention further relates to refrigerating method, comprise that condensation comprises the composition of the stablizer that comprises at least a amine of at least a fluoroolefin and significant quantity, and after this wanting to evaporate described composition near the 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 a structure, i.e. dwelling house or pattern of trade inside, or perishables are 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 " permutoid (swap bodies) " (associating highway and transportation by railroad).

The invention further relates to heating method, be included near the condensation object that will heat comprise at least a fluoroolefin and significant quantity the stablizer that comprises at least a amine composition and 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, can be similar to cooling off described running gear with those of needs heating.Some transportation means requires heating to solidify in transport container with the material that prevents to transport.

Air seldom leaks 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 comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.In another embodiment, also disclose minimizing and comprised the composition of at least a fluoroolefin and the method for oxygen reaction, described method comprises that the stablizer that comprises at least a amine with significant quantity adds 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 the standard sample is added in the described Glass tubing as described.

4. seal described pipe with the glass blowtorch.

5. the pipe that will seal heated 14 days under assigned temperature in baking oven.

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. point out 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) of the amine phosphate 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 mixes to make the composition of 50wt% working fluid and 50wt% lubricant.

Table 4

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

Claims (13)

1. the composition that comprises the stablizer that comprises at least a amine of at least a fluoroolefin and significant quantity.

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

3. 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.

4. the composition of claim 1 further comprises at least a phenol that is selected from, thiophosphatephosphorothioate, butylation triphenyl thiophosphatephosphorothioate, organophosphate, phosphorous acid ester, terpenes, terpenoid, soccerballene, functionalized PFPE, the polyoxyalkylated aromatic substance, alkylaromatic, epoxide, fluorinated epoxide, trimethylene oxide, xitix, mercaptan, lactone, thioether, Nitromethane 99Min., alkyl silane, benzophenone derivates, aryl thioethers, terephthalic acid divinyl ester, the additional stability immunomodulator compounds of terephthaldehyde's diphenyl phthalate and composition thereof.

5. the composition of claim 4, wherein:

A. phenol is selected from 2,6 di tert butyl 4 methyl phenol; 2,6-di-t-butyl-4-ethylphenol; 2,4 dimethyl 6 tert butyl phenol; Tocopherol; Quinhydrones; Tertiary butylated hydroquinone; 4,4 '-sulfo--two (2-methyl-6-tert butyl phenol); 4,4 '-thiobis (3 methy 6 tert butyl phenol); 2,2 '-thiobis (4-methyl-6-tert butyl phenol); 4,4 '-methylene-bis (2,6 di t butyl phenol); 4,4 '-two (2,6 di t butyl phenols); 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 4, the 4-butylidene-bis(3-methyl-6-t-butyl phenol); 4,4-isopropylidene two (2,6 di t butyl phenol); 2,2 '-methylene-bis(4-methyl-6-nonyl phenol); 2,2 '-isobutylene two (4, the 6-xylenol); 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol); Yoshinox BHT (BHT); 2,6-two-uncle-alpha, alpha-dimethyl amino-p-cresol; 4,4-thiobis (the 6-tertiary butyl-meta-cresol); Amido phenol; 2,6-di-t-butyl-4 (N, N '-dimethylaminomethylphenol); Two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide; Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide and composition thereof;

B. thiophosphatephosphorothioate is selected from single thiophosphate ester, phosphorodithioate, phosphorotrithioate, dialkyl group thiophosphatephosphorothioate and composition thereof;

C. butylation triphenyl thiophosphatephosphorothioate is represented by formula A,

Formula A

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

D. organophosphate is selected from amine phosphoric acid ester, trialkylphosphate, triaryl phosphate, mixed alkyl-aryl phosphate ester, annular phosphate and composition thereof;

E. phosphorous acid ester is selected from tricresyl phosphite (di-tert-butyl-phenyl) ester, phosphorous acid di-n-octyl, phosphorous acid isodecyl diphenyl ester and composition thereof;

F. terpenes is selected from isoprene, myrcene, alloocimene, β-ocimene, terebene, d-limonene, retinene, firpene, menthol, Geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, phellandrene, fenchene, limonene, Lyeopene, beta carotene, zeaxanthin, vitamin A epoxide, isotretinoin and composition thereof;

G. terpenoid is selected from abietane, artemisiifolia alkane, aristolane, the living alkane of Ah Ti, beyerane, bisabolane, camphane, caryophyllane, cedrane, dammarane, the full alkane of awl, refined maliane, eudesmane, fenchane, γ wax alkane, germacrane, gibberellane, black laurel poison alkane, guainane, cedrane, hopance, humulane, kaurane, Ladanum alkane, lanostane, lupane, right

Alkane, volatile oil, snake born of the same parents bacterium alkane, bitter taste alkane, pimarane, pinane, podocarpane, protostane, rose alkane, Taxan, thujane, spore bacterium alkane, black plain alkane and composition thereof;

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

I. the polyoxyalkylated aromatic substance is the compound shown in the formula B,

Formula B

R wherein ¹Group be comprise at least one-CH ₂CH ₂The polyoxyalkylated group of O-part;

J. alkylaromatic is the straight or branched alkyl benzene lubricants;

K. 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, hexanediol diglycidyl ether, glycidyl allyl ether, polypropylene glycol diglycidyl ether and composition thereof;

L. fluorinated epoxide is represented by formula C

Formula C

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;

M. trimethylene oxide is represented by formula D

Formula D

Wherein R1-R6 is independently selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl;

N. mercaptan is selected from thiomethyl alcohol, sulfur alcohol, coenzyme A, dimercaptosuccinic acid, (R)-2-(4-methyl cyclohexane-3-thiazolinyl) third-2-mercaptan, halfcystine, Thioctamide and composition thereof;

O. 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;

P. thioether is selected from benzyl phenyl thioether, diphenyl sulfide, two (octadecyl) 3,3 '-thiodipropionate, two (dodecyl) 3,3 '-thiopropionate and composition thereof;

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

R. benzophenone derivates 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

S. aryl thioethers is selected from benzyl phenyl thioether, diphenyl sulfide, dibenzyl sulfide and composition thereof.

6. the composition of claim 1, wherein at least a amine is selected from triethylamine; Tributylamine; Diisopropylamine; Tri-isopropyl amine; Tri-isobutylamine; Ursol D; Diphenylamine; Dialkylamine; (N-(1-methylethyl)-2-propylamine; Piperidyl, piperidino-(1-position only), piperazine ketone and alkoxyl group piperidino-(1-position only) compound that alkyl replaces; 2,2,6,6-tetramethyl--4-piperidone; 2,2,6,6-tetramethyl--4-piperidines alcohol; Two-(1,2,2,6,6-pentamethyl-piperidyl) sebate; Two-(2,2,6,6-tetramethyl--4-piperidyl) sebates; Poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate; 2,2,6,6-tetramethyl--4-piperidone, 2,2,6,6-tetramethyl--4-piperidines alcohol, two-(1,2,2,6,6-pentamethyl-piperidyl) sebate, two-(2,2,6,6-tetramethyl--4-piperidyl) sebate, poly--(N-hydroxyethyl-2,2,6,6-tetramethyl--4-hydroxy-piperdine base succinate and composition thereof.

11. the composition of claim 1, wherein said fluoroolefin are at least a following compounds that is selected from:

(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 following fluoroolefin:

12. the composition of claim 1 further comprises and is selected from two (benzylidene) hydrazides of oxalyl; N, N '-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine); 2,2 '-oxamido-is two-ethyl-(3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); N, N '-(two salicylidenes)-1,2-propylene diamine; 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.

13. make the method for the composition stability that comprises at least a fluoroolefin, described method comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.

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

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

16. reduce the method for the degraded of the composition that comprises at least a fluoroolefin, wherein said degraded is caused that by the existence that is strayed into air in refrigeration, air-conditioning or the heat pump described method comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.

17. minimizing comprises the composition of at least a fluoroolefin and the method for oxygen reaction, described method comprises that the stablizer that comprises at least a amine with significant quantity adds in the composition that comprises at least a fluoroolefin.