CN110003859A

CN110003859A - Composition comprising fluoroolefin

Info

Publication number: CN110003859A
Application number: CN201910001471.7A
Authority: CN
Inventors: B.H.米诺尔; V.N.M.劳; D.B.比文斯; D.珀蒂
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2005-03-04
Filing date: 2006-03-03
Publication date: 2019-07-12
Also published as: CN110003858A; CN113549426A; CN109897604A; CN113845884B; CN109971431A; CN109971428B; CN110564372A; CN109897605A; CN109897605B; CN113845884A; CN101297016A; CN113549426B; CN109971428A

Abstract

Composition comprising fluoroolefin.The present invention relates to for freezing, the composition of air-conditioning and heat pump system, wherein the composition include fluoroolefin and at least one other component.Composition of the invention can be used for freezing or heating method, is used as heat transfer liquids, foaming agent, atomization propellant and suppression fire and extinguishing chemical.

Description

Composition comprising fluoroolefin

The information of related application

The application is the divisional application of Chinese patent application 201510623155.5, aforementioned Chinese patent application 201510623155.5 be again international application no be PCT/US2006/008164, international filing date be on March 3rd, 2006, invention The divisional application original application of the application for a patent for invention of entitled " including the composition of fluoroolefin " enters National Phase in China and obtains The national application number obtained is 2006800154380.

This application claims the U.S. Provisional Application submitted on March 4th, 2005 on August 23rd, 60/658,543,2005 to mention The priority for the U.S. Provisional Application 60/732,769 that the U.S. Provisional Application 60/710,439 and 2005 year of friendship was submitted at November 1 Equity.

Technical field

The present invention relates to for freezing, the composition of air-conditioning and heat pump system, wherein the composition include fluoroolefin With at least one other component.Composition of the invention can be used for freezing or heating method, is used as heat-transfer fluid, foaming agent, gas Aerosol propellant and flame-out and extinguishing chemical.

Background technique

Refrigeration industry had made great efforts the chlorofluorocarbons (CFC) and hydrochlorofluorocarbons of finding consumption ozone in decades in the past (HCFC) substitute refrigerants of (they require phased out use due to Montreal Agreement).Most of refrigerant producers Solution be by hydrofluorocarbon (hydrofluorocarbon) (HFC) refrigerant industrialize.(HFC-134a is mesh to new HFC refrigerant It is preceding most widely used) there is zero ozone depletion potential and therefore not mandatory by current regulation as defined in Montreal Agreement It is required that the influence tapered off.

The whole world that other legislationss of environmental protection can eventually lead to certain HFC refrigerant tapers off use.Currently, automobile Industry faces the limitation of the regulation related with global warming potential for the refrigerant used in mobile air conditioner.Therefore, It is highly desirable to the new refrigerant for determining and reducing global warming potential at present for mobile air conditioner market.If the regulation it is following more It is widely applicable in, even more there is an urgent need to can be in refrigerant used in all spectra of refrigeration and air-conditioning industry.

The refrigerant of the substitution HFC-134a suggested at present includes HFC-152a, pure hydrocarbon such as butane or propane, or " natural " Refrigerant such as CO₂.Many in these substitutes suggested be it is toxic, it is inflammable, and/or with low energy efficiency.Cause This, is seeking new substitute refrigerants.

The object of the present invention is to provide novel refrigerant compositions and heat-transfer fluid composition, they provide unique Characteristic is to meet low or zero ozone depletion potential requirement and provide the lower global warming potential compared with current refrigerant.

General introduction of the invention

The present invention relates to the compositions comprising HFC-1225ye and at least one compound selected from following substance:

HFC-1234ze、HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、 HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、 HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂With CF₃I。

The invention further relates to the compositions comprising HFC-1234ze and at least one compound selected from following substance: HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、 HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, positive fourth Alkane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

The invention further relates to the compositions comprising HFC-1234yf and at least one compound selected from following substance: HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC- 161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- Methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

The invention further relates to the compositions comprising HFC-1234ye and at least one compound selected from following substance: HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC- 227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, Pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

The invention further relates to the compositions comprising HFC-1243zf and at least one compound selected from following substance: HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC- 236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, ring Pentane, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

The invention further relates to the compositions comprising following substance:

(a) at least one to be selected from polyol ester, polyalkylene glycol, polyvingl ether, mineral oil, alkylbenzene, compound stone Wax, the lubricant for synthesizing cycloalkane and poly- (α) alkene；With

(b) it is selected from the composition of group constituted by the following substances:

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf；

The trans- HFC-1234ze of about 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134a；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea；With

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF₃I。

A) refrigerant or heat-transfer fluid composition, the composition are selected from:

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf；

The trans- HFC-1234ze of about 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF₃I；With

Expanding material selected from following substance:

I) by general formula R¹[(OR²)xOR³] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3；Y is 1-4 Integer；R¹Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions；R²Selected from the rouge containing 2-4 carbon atom Race's alkylene；R³Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom；R¹And R³In at least one be selected from the hydrocarbon Base；And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-；

Ii) by general formula R¹C(O)NR²R³With ring-[R⁴CON(R⁵The amide that) -] indicates, wherein R¹、R², R3 and R⁵Independently select The aliphatic series and alicyclic alkyl of self-contained 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom；R⁴Selected from containing The aliphatic hydrocarbylene of 3-12 carbon atom；And wherein the amide has point of about 300 atomic mass unit of about 100- Son amount；

Iii) by general formula R¹C(O)R²The ketone of expression, wherein R¹And R²Independently selected from the aliphatic series containing 1-12 carbon atom, rouge Ring race and Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-；

Iv) by general formula R¹The nitrile that CN is indicated, wherein R¹Selected from aliphatic, the alicyclic or Arylalkvl containing 5-12 carbon atom, And wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-；

V) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2；R is selected from aliphatic series and alicyclic ring containing 1-12 carbon atom Race's alkyl；And wherein the chlorohydrocarbon has the molecular weight of about 200 atomic mass unit of about 100-；

Vi) by general formula R¹OR²The aryl ether of expression, in which: R¹Selected from the Arylalkvl containing 6-12 carbon atom；R²It is selected from Aliphatic hydrocarbyl containing 1-4 carbon atom；And wherein the aryl ether has point of about 150 atomic mass unit of about 100- Son amount；

Vii) by general formula CF₃R¹1,1, the 1- trifluoroalkanes indicated, wherein R¹Selected from about 15 carbon atoms Han about 5- Aliphatic series and alicyclic alkyl；

Viii) by general formula R¹OCF₂CF₂The fluoro-ether that H is indicated, wherein R¹Rouge selected from about 15 carbon atoms Han about 5- Race, alicyclic and aromatic hydrocarbyl；Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin With CF₂=CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_r, wherein R_fIt is CF₃、C₂F₅Or C₃F₇；And institute Stating polyalcohol is linear or branching, wherein the polyalcohols have HOCH₂(CHOH)x(CRR′)yCH₂OH pattern, wherein R and R ' is hydrogen, CH₃Or C₂H₅, x is the integer of 0-4, and y is the integer of 0-3, and z is that 0 or 1 and the Branched polyol have C (OH)t(R)u(CH₂OH)v[(CH₂)mCH₂OH] w pattern, wherein R can be hydrogen, CH₃Or C₂H₅, m is the integer of 0-3, and t and u are 0 or 1, v and w are the integers of 0-4, furthermore wherein t+u+v+w=4；With

Ix) the lactone indicated by structure [B], [C] and [D]:

Wherein, R₁-R₈Independently selected from hydrogen, linearly, branching is cyclic annular, two rings, saturation and undersaturated alkyl；And molecule Amount is about 100 to about 300 atomic mass units；With

X) by general formula R¹CO₂R²The ester of expression, wherein R¹And R²Independently selected from linear and cyclic annular, saturation and unsaturated, Alkyl and aryl；And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.

(a) at least one UV fluorescent dye, is selected from naphthalimide, cumarin, anthracene is luxuriant and rich with fragrance, xanthene, thiophene Ton, naphthoxanthene, fluorescein, the derivative and their combination of the dyestuff；With

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF₃I。

The invention further relates to selected from mineral oil, alkylbenzene, synthesis paraffin, synthesis cycloalkane and poly- (α) alkene By the method for refrigerant or heat-transfer fluid composition solubilising in refrigeration lubricant, wherein the method includes in a effective amount of increasing Contact the lubricant with the refrigerant or heat-transfer fluid composition in the presence of appearance agent, wherein the refrigerant or heat pass Baffle includes composition selected from the following:

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1234yf；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I；

And wherein the expanding material is selected from:

A) by general formula R¹[(OR²)xOR³] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3；Y is 1-4 Integer；R¹Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions；R²Selected from the rouge containing 2-4 carbon atom Race's alkylene；R3 is selected from hydrogen and aliphatic series and alicyclic alkyl containing 1-6 carbon atom；R¹And R³In at least one be selected from the hydrocarbon Base；And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-；

B) by general formula R¹C(O)NR²R³With ring-[R⁴CON(R⁵The amide that) -] indicates, wherein R¹、R²、R³And R⁵Independently select The aliphatic series and alicyclic alkyl of self-contained 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom；R⁴Selected from containing The aliphatic hydrocarbylene of 3-12 carbon atom；And wherein the amide has point of about 300 atomic mass unit of about 100- Son amount；

C) by general formula R¹C(O)R²The ketone of expression, wherein R¹And R²Independently selected from the aliphatic series containing 1-12 carbon atom, alicyclic ring Race and Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-；

D) by general formula R¹The nitrile that CN is indicated, wherein R¹Selected from aliphatic, the alicyclic or Arylalkvl containing 5-12 carbon atom, And wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-；

E) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2；R is selected from aliphatic series and alicyclic ring containing 1-12 carbon atom Race's alkyl；And wherein the chlorohydrocarbon has the molecular weight of about 200 atomic mass unit of about 100-；

F) by general formula R¹OR²The aryl ether of expression, in which: R¹Selected from the Arylalkvl containing 6-12 carbon atom；R²Selected from containing The aliphatic hydrocarbyl of 1-4 carbon atom；And wherein the aryl ether has the molecule of about 150 atomic mass unit of about 100- Amount；

G) by general formula CF₃R¹1,1, the 1- trifluoroalkanes indicated, wherein R¹Rouge selected from about 15 carbon atoms Han about 5- Race and alicyclic alkyl；

H) by general formula R¹OCF₂CF₂The fluoro-ether that H is indicated, wherein R¹Aliphatic series selected from about 15 carbon atoms Han about 5- And alicyclic alkyl；Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin has CF₂= CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_f, wherein R_fIt is CF₃、C₂F₅Or C₃F₇；With the linear multiple Alcohol has HOCH₂CRR′(CH₂)z(CHOH)xCH₂(CH₂OH) y pattern, wherein R and R ' is hydrogen, CH₃Or C₂H₅, x is the whole of 0-4 Number, y is the integer of 0-3, and z is 0 or 1；With

I) lactone indicated by structure [B], [C] and [D]:

.j) by general formula R¹CO₂R²The ester of expression, wherein R¹And R²Independently selected from linear and cyclic annular, saturation and unsaturated, Alkyl and aryl；And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.

The invention further relates to the methods of high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the height GWP refrigerant be selected from R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502 and R404A, the method includes by composition selected from the following

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-152a；

About 1wt%- about 99wt%HFC1225ye and about 99wt%- about 1wt%HFC-1234yf；

About 1wt%- about 99wt%HFC-1225ye and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF3I；

It is supplied to use, is used to or is designed to set using the refrigeration, air-conditioning or the heat pump of the high GWP refrigerant It is standby.

The invention further relates to the method for coolant leaks in early detection refrigeration, air-conditioning or heat-pump apparatus, the sides Method includes in the apparatus using the reduction of non-azeotropic compositions and monitoring cooling performance.

Detailed description of the invention

The present invention relates to the compositions comprising at least one fluoroolefin.Composition of the invention further includes at least one Kind additional component, the component can be the second fluoroolefin, hydrofluorocarbon (HFC), hydrocarbon, dimethyl ether, bis- (trifluoromethyl) thioethers, CF₃I or CO₂.The fluoroolefin compounds of the present composition and other components are listed in Table 1 below.

Table 1

The each component being listed in Table 1 below can be prepared by method as known in the art.

Fluoroolefin compounds used in the present composition (HFC-1225ye, HFC-1234ze and HFC-1234ye) The isomers or stereoisomer that can be used as various configuration exist.The present invention is intended to include all single configuration isomers, list One stereoisomer or any combination of them or mixture.For example, 1,3,3,3- tetrafluoropropene (HFC-1234ze) means Indicate any combination or mixture that any ratio is pressed along isomers, trans isomer or both isomers.Another example is HFC-1225ye, it is taken over any combination or mixture table of what ratio by suitable isomers, trans isomer or both isomers Show.

Composition of the invention include the following: HFC-1225ye and at least one compound selected from following substance: HFC- 1234ze、HFC-1234yf、HFC-1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC- 143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, third Alkane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I；

HFC-1234ze and at least one compound selected from following substance: HFC-1225ye, HFC-1234yf, HFC- 1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、 HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methyl Butane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I；

HFC-1234yf and at least one compound selected from following substance: HFC-1234ye, HFC-1243zf, HFC- 32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、 HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, two Methyl ether, CF₃SCF₃、CO₂And CF₃I；With

HFC-1243zf and at least one compound selected from following substance: HFC-1234ye, HFC-32, HFC-125, HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC- 245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、 CO₂And CF₃I；With

HFC-1234ye and at least one compound selected from following substance: HFC-32, HFC-125, HFC-134, HFC- 134a、HFC-143a、HFC-152a、HFC-161、HFC-227ea、HFC-236ea、HFC-236fa、HFC-245fa、HFC- 365mfc, propane, normal butane, iso-butane, 2- methybutane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

When the fluoroolefin is with about 1wt%- about 99wt%, preferably approximately 20wt%- about 99wt%, more preferably In the presence of the concentration of about 40wt%- about 99wt%, still more preferably 50wt%- about 99wt%, composition of the invention is logical It often may be useful.

The present invention further provides the compositions being listed in Table 2 below.

Table 2

In the presence of each component is with the concentration of such as listed +/- 2wt%, of the invention being listed in Table 2 below is most preferred Composition is generally expected to performance and function needed for maintaining.Work as CO₂In the presence of the listed +/- 0.2wt% of concentration, contain CO₂'s Composition maintains required performance and function for expected.

Composition of the invention can be azeotropic or the composition close to azeotropic.So-called Azeotrope compositions, which refer to, to be shown as The constant boiling point mixture of two or more substances of single substance.A kind of method for characterizing Azeotrope compositions is by liquid The steam that part is evaporated or distillation generates evaporates or distills liquid composition having the same certainly with it, i.e. the mixture is not having Distillation/reflux in the case where composition variation.Constant boiling point composition is characterized as Azeotrope compositions, because of them and the same compound The boiling point of zeotrope is compared to display maximum or the smallest boiling point.Azeotrope compositions will not in operation refrigeration or Fractionation in air-conditioning system, this may be decreased the efficiency of the system.In addition, Azeotrope compositions will not be in leakage from refrigeration or air-conditioning System fractionation.In the case that a kind of component is combustible components in the mixture, fractionation may be in the system in leakage process Flammable compositions are generated outside the interior or system.

Composition (also usually referred to as " Azeotrope-like compositions ") close to azeotropic is substantially behaved as single substance The liquid mixture of the generally constant boiling point of two or more substances.A kind of method of characterization close to the composition of azeotropic is logical The steam that the part evaporation or distillation for crossing liquid generate, which evaporates or distill liquid certainly with it, has substantially the same composition, i.e., Mixture distillation/reflux in the case where no significantly composition variation.Characterize another method close to the composition of azeotropic Be the composition at a certain temperature bubble point vapor pressure and dew point vapor pressure it is substantially the same.Here, if being combined removing After the 50wt% of object (such as by evaporating or boiling removing), original composition and 50wt% original composition is being removed The vapour pressure difference between remaining composition is less than about 10% later, then the composition is proximate to azeotropic.

Azeotrope compositions of the invention are shown in table 3 at the specified temperature.

Table 3

Further, it is found that the ternary azeotropic compositions as listed by table 4.

Table 4

The composition of the invention close to azeotropic is listed in Table 5 below at the specified temperature.

Table 5

Ternary and higher order as listed by table 6 comprising fluoroolefin have also been determined close to Azeotrope compositions.

Table 6

Certain compositions of the invention are non-azeotropic compositions.Belong to the preferred scope of table 2, but connecing in table 5 and table 6 Those compositions of the invention except nearly azeotropic range may be considered non-azeotrope.

Non-azeotropic compositions can have it is certain better than azeotropic or close to azeotropic mixture the advantages of.Non-azeotropic compositions is Show as mixture rather than the mixture of two or more substances of single substance.Characterize a kind of side of non-azeotropic compositions Method is that have to evaporate or distill the dramatically different group of liquid certainly with it by the steam of part evaporation or the distillation generation of liquid At i.e. mixture distillation/reflux under the variation of sizable composition.Another method for characterizing non-azeotropic compositions is in spy The bubble point vapor pressure and dew point vapor pressure for determining the composition at temperature are dramatically different.Here, if removing composition After 50wt% (such as by evaporating or boiling removing), original composition and after having removed 50wt% original composition Vapour pressure difference between remaining composition is greater than about 10%, then the composition is non-azeotrope.

Composition of the invention can be mixed the desired amount of each component to prepare by any suitable method.Preferred side Method is the amount of component needed for weighing, and later mixes these components in suitable container.If necessary, it can be used and stir It mixes.

The replacement means for preparing the present composition can be the method for preparing refrigerant blend composition, wherein described Refrigerant blend composition includes compositions disclosed herein, which comprises (i) is returned from least one cryogen vessel A large amount of one or more components of refrigerant compositions are received, (ii) removes impurity to being enough to make one or more recycling Component can reuse, (iii) and optionally, by the component of all or part of yields and at least one additional refrigeration Agent composition or component mixing.

Cryogen vessel can be any container, wherein storing once for refrigeration equipment, air-conditioning equipment or heat-pump apparatus Refrigerant blend composition.The cryogen vessel can be wherein using the refrigerant blend refrigeration equipment, Air-conditioning equipment or heat-pump apparatus.In addition, cryogen vessel can be the storage for collecting recycled refrigerant blend component Storage, including but not limited to pressurized cylinder.

Residual refrigerant refers to any amount of refrigerant blend or refrigerant blend component, can be by any Become known for transmitting refrigerant blend or the method for refrigerant blend component is discharged from cryogen vessel.

Impurity can be any use due to it in refrigeration equipment, air-conditioning equipment or heat-pump apparatus and be total in refrigerant Component in mixed object or refrigerant blend component.These impurity include but is not limited to refrigeration lubricant, they are previous herein Those of description, the including but not limited to particle of metal, metal salt or elastomer particles, they may be from refrigeration equipment, sky Adjust the impurity of equipment or heat-pump apparatus and any other performance that may negatively affect refrigerant blend composition.

Can by these impurity except go to be enough to allow to reuse refrigerant blend or refrigerant blend component without The refrigerant blend or refrigerant blend component can be negatively affected will be in the performance of the device wherein used.

In order to generate the composition in accordance with specification needed for given product, additional refrigerant blend or refrigerant are blended Object component is supplied to residual refrigerant blend or refrigerant blend component and may be necessary.For example, if refrigerant is total Mixed object has 3 kinds of components in specified weight percent ranges, then adds one or more components so that the group by specified rate It closes object and is restored in specification limitation and may be necessary.

Composition of the invention has zero or low ozone depleting potential and low global warming potential (GWP).In addition, this The composition of invention by have than at present the low global warming potential of many hydrofluorocarbon refrigerant.A side of the invention Face is to provide refrigerant of the global warming potential less than 1000, less than 500, less than 150, less than 100 or less than 50.Of the invention It is to reduce the net GWP of refrigerant mixture by adding fluoroolefin to the mixture on the other hand.

The present composition may be used as low global warming potential (GWP) sub of refrigerant used at present, described Refrigerant used at present includes but is not limited to: R134a (or HFC-134a, HFA 134a), R22 (or HCFC- 22, F-22), R123 (or HFC-123,2,2- bis- chloro- 1,1,1- trifluoroethane), R11 (CFC-11, a fluorine trichlorine Methane), R12 (CFC-12, dicholorodifluoromethane), R245fa (or HFC-245fa, 1,1,1,3,3- pentafluoropropane), R114 (or CFC-114,1,2- bis- chloro- 1,1,2,2- tetrafluoroethane), R236fa (or HFC-236fa, 1,1,1,3,3,3- hexafluoropropane), R124 (or the chloro- HFA 134a of HCFC-124,2-), R407C (52wt%R134a, 25wt%R125 (pentafluoroethane) Named with the ASHRAE of the blend of 23wt%R32 (difluoromethane)), the R410A (blending of 50wt%R125 and 50wt%R32 The ASHRAE of object is named), R417A (blend of 46.6wt%R125,50.0wt%R134a and 3.4wt% normal butane ASHRAE name), (ASHRAE of the blend of 85.1wt%R125,11.5wt%R134a and 3.4wt% iso-butane is ordered R422A Name), R404A (blend of 44wt%R125,52wt%R143a (1,1,1- trifluoroethane) and 4.0wt%R134a ASHRAE name) and R507A (ASHRAE of the blend of 50wt%R125 and 50wt%R143a is named).In addition, of the invention Composition may be used as R12 (CFC-12, dicholorodifluoromethane) or R502 (51.2wt%CFC-115 (chloropentafluoroethane) and The ASHRAE of the blend of 48.8wt%HCFC-22 is named) sub.

In general, sub refrigerant is most if can be used in the original chiller designed for different refrigerant Useful.Composition of the invention may be used as the sub of the above-mentioned refrigerant in primitive apparatus.In addition, combination of the invention Object may be used as design and use the sub of the above-mentioned refrigerant in the device of above-mentioned refrigerant.

The present composition can further include lubricant.

Lubricant of the invention includes refrigeration lubricant, i.e., suitable for those of refrigeration, air-conditioning or heat-pump apparatus lubrication Agent.These lubricants include those of common in the compression refrigeration equipment using fluorochlorohydrocarbon refrigerant.These lubricants and it Performance in 1990 ASHRAEH Handbook, Refrigeration Systems and Applications, the 8th chapter, topic For " Lubricants in Refrigeration Systems ", it is discussed in page 8.1 to 8.21.Lubrication of the invention It is commonly referred to as those of " mineral oil " that agent, which may include in compression refrigeration lubrication field,.Mineral oil includes paraffin (i.e. straight chain and branch Change carbochain, saturated hydrocarbons), naphthalene (i.e. cyclic paraffins) and aromatic compounds (be to replace the ring of double bond containing one or more features Unsaturated cyclic hydrocarbon).Lubricant of the invention further comprise compress refrigeration lubrication field in commonly referred to as " synthetic oil " that A bit.Synthetic oil includes alkyl aryl compound (i.e. linear and branched-alkyl alkylbenzene), synthesizes paraffin and cycloalkane and poly- (α alkene Hydrocarbon).Representative conventional lubricantss of the invention are commercially available BVM 100N (paraffinic mineral oils sold by BVA Oils),3GS and5GS (naphthenic mineral oil sold by Crompton Co.),372LT (by The naphthenic mineral oil of Pennzoil sale),RO-30 (the naphthenic mineral sold by Calumet Lubricants Oil),75、150 Hes500 (linear alkyl benzenes sold by Shrieve Chemicals) and HAB22 (the branched-alkyl benzene sold by Nippon Oil).

Lubricant of the invention further comprises having designed to be used together with hydrofluorocarbon refrigerant and in compression refrigeration, sky Adjust or the operating condition of heat-pump apparatus under can be those of with refrigerant mixing of the present invention.These lubricants and their performance exist " Synthetic Lubricants and High-Performance Fluids ", R.L.Shubkin, editor, Marcel Dekker is discussed in 1993.These lubricants include but is not limited to that polyol ester (POE) is for example100 (Castrol, United Kingdom), polyalkylene glycol (PAG) for example derived from Dow (Dow Chemical, Midland, Michigan RL-488A and polyvingl ether (PVE)).These lubricants can be obtained easily from various commercial sources.

Lubricant of the invention pass through by the requirement of given compressor and lubricant into contact with environment take in To select.Lubricant of the invention is preferably at 40 DEG C with the dynamic viscosity of at least about 5cs (centistoke).

As needed, common refrigerating system additive can be optionally added in composition of the invention, to improve Lubricity and system stability.These additives are known in refrigeration compressor lubricating area, and including wear-resistant Agent, limit lubricant, corrosion and oxidation retarder, metal surface deactivators, free radical scavenger, blistering and defoaming control Agent, leak detectants etc..In general, these additives only exist in a small amount relative to total lubricant compositions.Typically, with from low Them are used to the concentration for being up to about 3% each additive in about 0.1%.These additives are according to respective system requirements Target selection.Some representative instances of these additives may include, but be not limited to, lubrication enhancing additive, such as phosphoric acid and thio The alkyl or aryl ester of phosphate.In addition, dialkyl dithiophosphoric acid metal salt (such as zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other members of this kind of chemicals can be used in composition of the invention.It is other wear-resistant to add Adding agent includes natural products oil and asymmetric polyhydroxy lubricating additive, such as Synergol TMS (International Lubricants).Similarly, stabilizer such as antioxidant, free radical scavenger and water scavenger can use.In this one kind Compound in class may include, but be not limited to, butylated hydroxytoluene (BHT) and epoxides.

Composition of the invention can further include about 0.01wt% to about 5wt% additive, for example, stablizing Agent, free radical scavenger and/or antioxidant.These additives include but is not limited to nitromethane, hindered phenol, azanol, mercaptan, Phosphite ester or lactone.Single additive or combination can be used.

The water scavenger that composition of the invention can further include about 0.01wt% to about 5wt% is (dry to use Compound).These water scavengers may include ortho esters such as trimethyl-, triethyl group-or tripropyl orthoformate.

Composition of the invention can further include tracer, be selected from hydrofluorocarbon (HFC), deuteroparaffin, hydrogen deuteride fluorine Carbon, perfluoroparaffin, fluoro-ether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N₂) and their combination O. Tracer compounds are added in composition by predetermined quantities with allow any dilution of detection combination object, pollution or its It changes, as described in 2 months 2005 U.S. Patent Application Serial Numbers 11/062044 submitted for 18th.

Typical tracer compounds for the present composition are shown in Table 7.

Table 7

The compound being shown in Table 7 is commercially available (chemically commercially available from product supplier) or can be by as known in the art Method preparation.

Single tracer compounds and refrigerating/heating combination of fluids can be used in the present compositions or can be with Multitracer compound is mixed to serve as tracer blend in any proportion.Tracer blend may include from phase The multitracer compound of generic compound or multitracer compound from different classes of compound.For example, showing Track agent blend may include two or more deuterate hydrofluorocarbon or a kind of deuterate hydrofluorocarbon and one kind in combination or more Kind perfluoroparaffin.

In addition, some compounds in table 7 exist as multiple isomers (constitutional isomer or optical isomer).It is identical The individual isomer of compound or multiple isomers can be used in any proportion to prepare tracer compounds.In addition, given The single or multiple isomers of compound can serve as tracer blend in conjunction with many other compounds in any proportion.

Tracer compounds or tracer blend can be by about 50 parts by weight/mono- million parts by weight (ppm)-about The total concentration of 1000ppm is present in composition.Preferably, tracer compounds or tracer blend are big with about 50ppm- The total concentration of about 500ppm exists, most preferably, tracer compounds or tracer blend with about 100ppm- about The total concentration of 300ppm exists.

Composition of the invention can be further included selected from polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorohydrocarbon, Ester, lactone, aryl ether, fluoro-ether and 1, the expanding material of 1,1- trifluoroalkanes.The expanding material is used to improve hydrofluorocarbon refrigerant Dissolubility in conventional refrigerant lubricant.Refrigeration lubricant is needed to lubricate refrigeration, air-conditioning or the compressor of heat-pump apparatus.Profit Lubrication prescription must be mobile with refrigerant in whole equipment, and particularly, it must be from uncompressed machine area back to compressor to continue Super fatting agent acts on and avoids compressor failure.

Hydrofluorocarbon refrigerant usually not with conventional refrigerant lubricant for example mineral oil, alkylbenzene, synthesis paraffin, synthesis cycloalkane It is compatible with poly- (α) alkene.Many sub lubricants have been proposed, it is suggested, however, that be used together with hydrofluorocarbon refrigerant Polyalkylene glycol, polyol ester and polyvingl ether are expensive and are easy water suction.In refrigeration, air-conditioning system or heat pump Water can cause corrosion and particle formation, the particle may block other apertures in capillary and system, thus most Lead to thrashing eventually.In addition, needing time-consuming and expensive cleaning procedure to be made according to new lubricant in existing equipment and changing Become.Therefore, it is desirable for continuing to use original lubricant if possible.

Expanding material of the invention improve dissolubility of the hydrofluorocarbon refrigerant in conventional refrigerant lubricant and therefore improve to The oil return of compressor.

Polyoxyalkylene glycol ether expanding material of the invention is by general formula R¹[(OR²)xOR³] y expression, in which: x is the whole of 1-3 Number；Y is the integer of 1-4；R¹Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions；R²Selected from containing 2-4 carbon The aliphatic hydrocarbylene of atom；R³Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom；R¹And R³In at least one choosing From the alkyl；And wherein the polyoxyalkylene glycol ether has the molecule of about 300 atomic mass unit of about 100- Amount.Bonded position used herein refers to the position that can be used to that covalent bond is formed with other groups.Alkylene refers to divalent Alkyl.In the present invention, it is preferred to polyoxyalkylene glycol ether expanding material by general formula R¹[(OR²)xOR³] y expression, x is preferably 1- 2；Y is preferably 1；R¹And R³Preferably independently it is selected from hydrogen and the aliphatic hydrocarbyl containing 1-4 carbon atom；R²It is preferably selected from containing 2 or 3 Carbon atom, the aliphatic hydrocarbylene of most preferably 3 carbon atoms；The polyoxyalkylene glycol ether molecular weight preferably about 100- is big About 250 atomic mass units, about 250 atomic mass unit of most preferably about 125-.R containing 1-6 carbon atom¹And R³Hydrocarbon Base can be linear, branching or cricoid.Representative R1 and R3 alkyl includes methyl, ethyl, propyl, isopropyl, and butyl is different Butyl, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta and cyclohexyl.When in the polyoxyalkylene Free hydroxyl group on glycol ethers expanding material may with certain compression refrigeration equipment structural materials (such as) it is incompatible when, R¹And R³Preferably contain 1 to 4 carbon atoms, the aliphatic hydrocarbyl of most preferably 1 carbon atom.R containing 2-4 carbon atom²Aliphatic is sub- Alkyl forms duplicate oxyalkylene group-(OR²) x-, the latter includes oxygen ethylene group, oxygen propylidene group and oxygen Butylene.That in a polyoxyalkylene glycol ether increase-volume agent molecule includes R²Oxyalkylene group can be phase A same or molecule may include different R²Alkylidene oxide.Polyoxyalkylene glycol ether expanding material of the invention is preferred Include at least one oxygen propylidene group.Work as R¹It is aliphatic or alicyclic hydrocarbon group containing 1-6 carbon atom and y bonded positions When, which can be linearly branching or cricoid.Representative R containing two bonded positions¹Aliphatic hydrocarbyl includes, for example, sub- Ethyl, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene and sub- cyclohexyl.Representativeness containing 3 or 4 bonded positions R¹Aliphatic hydrocarbyl includes from polyalcohol, such as trimethylolpropane, glycerol, pentaerythrite, 1,2,3- trihydroxy hexamethylene and 13, 5- trihydroxy hexamethylene, by removing residue derived from their hydroxyl.

Representative polyoxyalkylene glycol ether expanding material includes but is not limited to: CH₃OCH₂CH(CH₃) O (H or CH₃) (third Glycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropylene glycol methyl (or dimethyl) ether), CH₃O [CH₂CH(CH₃)O]₃(H or CH₃) (tripropylene glycol methyl (or dimethyl) ether), C₂H₅OCH₂CH(CH₃) O (H or C₂H₅) (the third two Alcohol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₂(H or C₂H₅) (dipropylene glycol ethyl (or diethyl) ether), C₂H₅O [CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (or diethyl) ether), C₃H₇OCH₂CH(CH₃) O (H or C₃H₇) (the third two Alcohol n-propyl (or diη-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropylene glycol n-propyl (or diη-propyl) Ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇) (tripropylene glycol n-propyl (or diη-propyl) ether), C₄H₉OCH₂CH(CH₃)OH (propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉) (dipropylene glycol normal-butyl (or di-n-butyl) ether), C₄H₉O [CH₂CH(CH₃)O]₃(H or C₄H₉) (tripropylene glycol normal-butyl (or di-n-butyl) ether), (CH₃)₃COCH₂CH(CH₃) OH (the third two Alcohol tertbutyl ether), (CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (dipropylene glycol tert-butyl (or di-t-butyl) ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropylene glycol tert-butyl (or di-t-butyl) ether), C₅H₁₁OCH₂CH(CH₃) OH (propylene glycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅) OH (butanediol n-butyl ether), C₄H₉O[CH₂CH(C₂H₅)O]₂H (two fourths two Alcohol n-butyl ether), trimethylolpropane tris n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) and trimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH)。

Amide expanding material of the invention includes by general formula R¹C(O)NR²R³With ring-[R⁴C(O)N(R⁵Those of)] indicate, In: R¹、R²、R³And R⁵Independently selected from aliphatic series and alicyclic alkyl containing 1-12 carbon atom；R⁴Selected from containing 3-12 carbon atom Aliphatic hydrocarbylene；And wherein the amide has the molecular weight of about 300 atomic mass unit of about 100-.The amide About 250 atomic mass unit of molecular weight preferably about 160-.R¹, R², R³And R⁵Substituted hydrocarbon can be optionally included Base, that is, contain the group selected from halogen (such as fluorine, chlorine) and the substituents of alkoxy (such as methoxyl group).R¹, R², R³With R⁵The substituted alkyl of hetero atom-can be optionally included, that is, contain Nitrogen Atom in the group chain being in addition made of carbon atom (azepine -), the group of oxygen (oxa- -) or sulphur (thia -).Typically in R^1-3In every 10 carbon atoms will be present and be no more than Three substituents and hetero atom, and preferably more than one, and must be taken into consideration and appoint when being applicable in the limitation of above-mentioned molecular weight What these substituents and heteroatomic presence.Preferred amide expanding material is made of carbon, hydrogen, nitrogen and oxygen.Representative R¹, R², R³And R⁵Aliphatic series and alicyclic alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, Amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl With their configurational isomer.One preferred embodiment of Amide solubilizing agents is wherein in above-mentioned general formula ring-[R⁴C(O)N (R⁵R in) -]⁴It can be by alkylene (CR⁶R⁷Those of) n expression, in other words, general formula: ring-[(CR⁶R⁷)nC(O)N(R⁵) -], Wherein: equally applicable for the described value before molecular weight；N is the integer of 3-5；R⁵It is the saturation containing 1-12 carbon atom Hydrocarbyl group；R⁶And R⁷By being previously used for defining R^1-3Rule be selected independently (for each n).By general formula: ring-[(CR⁶R⁷) nC(O)N(R⁵In the lactams that) -] indicates, whole R⁶And R⁷Preferably hydrogen, or containing single among n methylene units Saturated hydrocarbons group, R⁵It is the saturated hydrocarbons group containing 3-12 carbon atom.For example, 1- (saturated hydrocarbyl) -5- methylpyrrolidin- 2- Ketone.

Representative Amide solubilizing agents include but is not limited to: 1- octyl pyrrolidin-2-one, 1- decyl pyrrolidine -2- ketone, 1- Octyl -5- methylpyrrolidin- 2- ketone, 1- butyl caprolactam, 1- cyclohexyl pyrrolidin-2-one, 1- butyl -5- methyl piperidine - 2- ketone, 1- amyl-5- methyl piperidine-2- ketone, 1- hexyl caprolactam, 1- hexyl-5- methylpyrrolidin- 2- ketone, 5- methyl-1- Amyl piperidine -2- ketone, 1,3- lupetidine -2- ketone, 1- methyl caprolactam, 1- Butyl-pyrrol alkane -2- ketone, 1,5- diformazan Phenylpiperidines -2- ketone, 1- decyl -5- methylpyrrolidin- 2- ketone, 1- dodecyl pyrrolidine -2- ketone, N, N- dibutyl formamide and Bis-, isopropyl yl acetamide of N, N-.

Ketone expanding material of the invention includes by general formula R¹C(O)R²The ketone of expression, wherein R¹And R²Independently selected from containing 1-12 Aliphatic, the alicyclic and Arylalkvl of a carbon atom, and wherein the ketone has about 300 atomic mass unit of about 70- Molecular weight.R in the ketone¹And R²Preferably independently it is selected from aliphatic series and alicyclic alkyl containing 1-9 carbon atom.The ketone Molecular weight preferably about 100-200 atomic mass unit.R¹And R²It can be formed together alkylene, which connects simultaneously Form five, six or heptatomic ring cyclic ketones, such as cyclopentanone, cyclohexanone and cycloheptanone.R¹, R², R³And R⁵It can optionally include and take The alkyl in generation, that is, contain the group selected from halogen (such as fluorine, chlorine) and the substituents of alkoxy (such as methoxyl group).R¹ And R²The alkyl of hetero atom substitution can be optionally included, that is, contain Nitrogen Atom in the group chain being in addition made of carbon atom (azepine -), the group of oxygen (ketone-, oxa- -) or sulphur (thia -).Typically in R¹And R²In every 10 carbon atoms will be present No more than three substituents and hetero atom, and preferably more than one, and it is necessary when being applicable in the limitation of above-mentioned molecular weight Consider any of these substituents and heteroatomic presence.In general formula R¹COR²In representative R¹And R²Aliphatic, alicyclic ring Race and Arylalkvl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isoamyl Base, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and they Configurational isomer and phenyl, benzyl, cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl and phenethyl.

Representative ketone solubilizer includes but is not limited to: 2- butanone, 2 pentanone, acetophenone, butyrophenone, amyl phenyl ketone, hexamethylene Ketone, cycloheptanone, 2-HEPTANONE, 3- heptanone, 5 methy 12 hexanone, methyl hexyl ketone (methyln-hexyl ketone), 3- octanone, diisobutyl ketone, 4- ethyl cyclohexanone, methyl n-heptyl ketone, butyl ketone, 2- decanone, 4- decanone, 2- decalone, methyl n-undecyl ketone, dihexyl ketone and two hexamethylenes Base ketone.

Nitrile expanding material of the invention includes by general formula R¹The nitrile that CN is indicated, wherein R¹Selected from containing 5-12 carbon atom aliphatic series, Alicyclic or Arylalkvl, and wherein the nitrile has the molecular weight of about 200 atomic mass unit of about 90-.Described R in nitrile expanding material¹It is preferably selected from aliphatic series and alicyclic alkyl containing 8-10 carbon atom.The molecular weight of the nitrile expanding material is excellent It is selected as about 140 atomic mass unit of about 120-.R¹Substituted alkyl can be optionally included, that is, containing selected from halogen (example Such as fluorine, chlorine) and alkoxy (such as methoxyl group) substituents group.R¹The hydrocarbon of hetero atom substitution can be optionally included Base, that is, contain Nitrogen Atom (azepine -), oxygen (ketone-, oxa- -) or sulphur (thia -) in the group chain being in addition made of carbon atom Group.Typically in R¹In every 10 carbon atoms will be present no more than three substituents and hetero atom, and preferably No more than one, and any of these substituents must be taken into consideration when being applicable in the limitation of above-mentioned molecular weight and heteroatomic deposit ?.In general formula R¹Representative R in CN¹Aliphatic series, alicyclic and Arylalkvl group includes amyl, and isopentyl, neopentyl, uncle penta Base, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, the configurational isomer of dodecyl and they, and Phenyl, benzyl, cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl and phenethyl.

Representative nitrile expanding material includes but is not limited to: 1- cyanopentane, 2,2- dimethyl -4- cyanopentanes, 1- cyano Hexane, 1- cyanoheptane, 1- cyanooctane, 2- cyanooctane, 1- cyanononane, 1- cyanodecane, 2- cyanodecane, 1- cyano Hendecane and 1- cyanododecane.

Chloro hydrocarbon compatibilizer of the invention includes the chlorohydrocarbon indicated by general formula R Clx, in which: x is selected from an integer of 1 or 2；R Selected from aliphatic series and alicyclic alkyl containing 1-12 carbon atom；And wherein the chlorohydrocarbon has about 100- about 200 former The molecular weight of protonatomic mass unit.The molecular weight of the chloro hydrocarbon compatibilizer preferably about 120-150 atomic mass unit.Logical Representative R aliphatic series and alicyclic alkyl in formula RClx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Zhong Ding Base, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, hendecane Base, the configurational isomer of dodecyl and they.

Representative chloro hydrocarbon compatibilizer includes but is not limited to: 3- (chloromethyl) pentane, the chloro- 3- methylpentane of 3-, 1- chlorine Hexane, 1,6- dichloro hexane, 1- chloroheptane, 1- chloro-octane, 1- chlorononane, 1- chlorodecane and 1,1,1- trichlorodecane.

Ester expanding material of the invention includes by general formula R¹CO₂R²The ester of expression, wherein R¹And R²Independently selected from linear and ring Shape, saturation and unsaturated alkyl and aryl.Preferred ester is mainly made of Elements C, H and O, has about 550 atom of about 80- The molecular weight of mass unit.

Representative ester includes but is not limited to: (CH₃)₂CHCH₂OOC(CH₂)_2-4OCOCH₂CH(CH₃)₂(two isobutyl of binary acid Base ester), ethyl hexanoate, cognac oil, n-butyl propionate, propionic acid n-propyl ester, ethyl benzoate, phthalic acid diη-propyl Ester, benzoic acid ethoxymethyl ethyl ester, dipropyl carbonate, " Exxate 700 " (commodity acetic acid C₇Arrcostab), " Exxate 800 " (commodity acetic acid C₈Arrcostab), dibutyl phthalate and tert-butyl acetate.

Lactone expanding material of the invention includes the lactone indicated by structure [A], [B] and [C]:

These lactones contain the ring (A) in six atoms, or the functional group-CO in the ring (B) of preferably five atoms₂, In for structure [A] and [B], R¹To R⁸Independently selected from hydrogen or linear, branching, ring-type, two rings, saturation and undersaturated alkyl. R¹To R⁸Each of can be with R¹To R⁸In another be connected to form ring.The lactone can have outside the ring in structure [C] Alkylidene radical, wherein R¹To R⁶Independently selected from hydrogen or linear, branching, ring-type, two rings, saturation and undersaturated alkyl.R¹To R⁶In Each can be with R¹To R⁶In another be connected to form ring.The lactone expanding material has about 300 atom matter of about 80- Measure unit, the molecular weight of about 200 atomic mass unit of preferably approximately 80-.

Representative lactone expanding material includes but is not limited to the compound listed in table 8.

Table 8

Lactone expanding material has the dynamic viscosity lower than about 7 centistokes generally at 40 DEG C.For example, at 40 DEG C, γ-ten One alkanoic acid lactone has the dynamic viscosity of 5.4 centistokes, has the viscous of 4.5 centistokes along (3- hexyl -5- methyl) dihydrofuran -2- ketone Degree.Lactone expanding material can be as described in the commercially available or U.S. Patent application 10/910,495 by submitting for 3rd such as August in 2004 Method preparation, the document is hereby incorporated by reference.

Aryl ether expanding material of the invention further comprises by general formula R¹OR²The aryl ether of expression, in which: R¹Selected from containing 6- The aryl hydrocarbon of 12 carbon atoms；R²Selected from the aliphatic hydrocarbyl containing 1-4 carbon atom；And wherein the aryl ether has about The molecular weight of about 150 atomic mass unit of 100-.In general formula R¹OR²In representative R¹Aryl includes phenyl, xenyl, Cumenyl, 2,4,6- trimethylphenyls, tolyl, 3,5-dimethylphenyl, naphthalene and pyridyl group.In general formula R¹OR²In representative R² Aliphatic hydrocarbyl includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl and tert-butyl.Representative aromatic oxide increases Solvent includes but is not limited to: methyl phenyl ether (anisole), 1,3- dimethoxy benzene, ethylphenyl ether and butyl phenylate.

Fluoro-ether expanding material of the invention includes by general formula R¹OCF₂CF₂H those of indicates, wherein R¹Selected from containing about 5- Aliphatic, the alicyclic and aromatic hydrocarbyl of about 15 carbon atoms, preferably primary, linear, saturated alkyl.Representative fluoro-ether increase-volume Agent includes but is not limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H.It should be noted that if the refrigerant is fluoro-ether, The expanding material can not be identical fluoro-ether.

Fluoro-ether expanding material may further include the ether derived from fluoroolefin and polyalcohol.The fluoroolefin can be with With CF₂=CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_f, wherein R_fIt is CF₃、C₂F₅Or C₃F₇.It represents The fluoroolefin of property is tetrafluoroethene, chloro trifluoro ethylene, hexafluoropropene and perfluoro methyl vinyl ether.The polyalcohol can be with It is linear or branching.Polyalcohols can have HOCH₂(CHOH)x(CRR′)yCH₂OH pattern, wherein R and R ' be hydrogen, CH₃Or C₂H₅And wherein x is the integer of 0-4, and y is the integer of 0-4.Branched polyol has C (OH) t (R) u (CH₂OH)v [(CH₂)mCH₂OH] w pattern, wherein R can be hydrogen, CH₃Or C₂H₅, m is the integer of 0-3, and t and u can be 0 or 1, and v and w are 0- 4 integer, furthermore wherein t+u+v+w=4.Representative polyalcohol is trimethylolpropane, pentaerythrite, butanediol and second two Alcohol.

Of the invention 1,1,1- trifluoroalkanes expanding material include by general formula CF₃R¹1,1, the 1- trifluoroalkanes indicated, wherein R¹ Aliphatic series and alicyclic alkyl selected from about 15 carbon atoms Han about 5-, preferably primary, linear, saturated alkyl.Representative 1, 1,1- trifluoroalkanes expanding material includes but is not limited to: 1,1,1- trifluorohexane and 1,1,1- trifluorododecane.

The effective quantity of expanding material refer to cause lubricant in the composition effective solubilization and therefore provide enough oil returns with Optimization refrigeration, air-conditioning or heat-pump apparatus operation expanding material amount.

Composition of the invention, which will generally comprise, accounts for the present composition about 0.1- about 40wt%, preferably approximately 0.2- The expanding material of about 20wt%, most preferably from about 0.3- about 10wt%.

The invention further relates to refrigerant or the solubilization method of heat-transfer fluid composition, the composition is included in and is selected from Mineral oil alkylbenzene, synthesizes paraffin, synthesizes the present composition in the refrigeration lubricant of cycloalkane and poly- (α) alkene, wherein The method includes contacting the lubricant with the composition in the presence of effective quantity expanding material, wherein the expanding material selects From polyoxyalkylene glycol ethers, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoro-ether and 1,1,1- trifluoroalkanes.

It is described the invention further relates to the method improved in compression refrigeration, air-conditioning or heat-pump apparatus to compressor oil return Method includes using the composition comprising expanding material in the apparatus.

Composition of the invention can further include ultraviolet light (UV) dyestuff and optional solubilizer.The UV dyestuff is Allow people in the leakage point of refrigeration, air-conditioning or heat-pump apparatus or observes in composition dye fluorescence near the equipment to examine Survey the useful constituent of the leakage of the composition.People can observe the fluorescence of dyestuff under ultraviolet light.Solubilizer is desirable , due to the dissolubility of difference of such UV dyestuff in some compositions.

" ultraviolet light " dyestuff refers to the UV that the light in the ultraviolet light of electromagnetic spectrum or " close " ultraviolet range can be absorbed Fluorescent composition.By photograph of the UV fluorescent dye in UV light for launching the radiation with any wavelength from 10 nanometers -750 nanometers The fluorescence for penetrating lower generation may detect that.Therefore, if the composition containing such UV fluorescent dye is in refrigeration, air-conditioning or warm It is leaked on the set point of pumping unit, then the fluorescence can be detected in the leakage point.Such UV fluorescent dye includes but is not limited to Naphthalimide, cumarin, anthracene is luxuriant and rich with fragrance, xanthene, thioxanthene, naphthoxanthene, fluorescein and their derivative or group It closes.

Solubilizer of the invention may include at least one selected from hydrocarbon, hydrocarbyl ether, polyoxyalkylene glycol ether, amide, nitrile, Ketone, chlorocarbon, ester, lactone, aryl hydrocarbon, fluoro-ether and 1, the compound of 1,1- trifluoroalkanes.The polyoxyalkylene glycol ether, acyl Amine, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoro-ether and 1,1,1- Trifluoroalkane solubilizing agents be defined herein before this for In the expanding material of conventional refrigerant lubricant.

Hydrocarbon solubilizer of the invention includes hydrocarbon comprising containing 5 or less carbon atoms and only has hydrogen but not other Straight chain, branch or the cyclic-paraffins or alkene of functional group.Representative hydrocarbon solubilizer includes propane, propylene, cyclopropane, positive fourth Alkane, iso-butane, 2- methybutane and pentane.It should be noted that the solubilizer can be with if the composition includes hydrocarbon It is not identical hydrocarbon.

Hydrocarbon ether solubilizing agents of the invention include the ether only containing carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Solubilizer of the invention can be used as single compound presence, or can be used as the mixture of more than one solubilizer In the presence of.The mixture of solubilizer can be containing belonging to two kinds of solubilizer in same category compound, such as two kinds of lactones, or The two kinds of solubilizer to belong to a different category in compound, such as lactone and polyoxyalkylene glycol ether.

In the present invention combination comprising refrigerant and UV Fluorescence Fluorescence dyestuff or comprising heat-transfer fluid and UV fluorescent dye In object, the about 0.001wt%- about 1.0wt% of the composition be UV dyestuff, preferably approximately 0.005wt%- about 0.5wt%, most preferably 0.01wt%- about 0.25wt%.

Solubilizer such as ketone has unfavorable smell, it can be covered by the addition of odor masking agent or fragrance.Smell The representative instance of screening agent or fragrance may include evergreen (Evergreen), Fresh Lemon, cherry, cortex cinnamomi, peppermint, Hua Huo Orange peel, their all commercially available and carvenes and firpene.Such odor masking agent can be by based on odor masking agent and solubilizer The concentration that the about 0.001wt%- of total weight is up to about 15wt% uses.

These dissolubilities of UV fluorescent dye in the compositions of the present invention may be difference.Therefore, these dyestuffs are introduced Be to the method in refrigeration, air-conditioning or heat-pump apparatus it is clumsy, it is expensive and time-consuming.U.S. Patent number RE36,951 is described A kind of method, it uses dye powder, solid grain or the dyestuff being inserted into the component of refrigeration, air-conditioning or heat-pump apparatus Slurry.When refrigerant and lubricant recycle in the device, which dissolves or disperses and spread whole equipment.In the literature Describe many other methods dyestuff being introduced into refrigeration or air-conditioning equipment.

It is desirable that the UV fluorescent dye may be dissolved in refrigerant itself, therefore it is not required to be introduced into refrigeration, air-conditioning Any ad hoc approach in equipment or heat pump.The present invention relates to the compositions including UV fluorescent dye, it can be used as in refrigeration Solution in agent is introduced in system.Composition of the invention can be while keeping the dyestuff under dissolved state even Allow to contain the composition storage and conveying of dyestuff at low temperatures.

Comprising refrigerant, UV fluorescent dye and solubilizer or comprising heat-transfer fluid and UV fluorescent dye and solubilizer In the present composition, about 1- about 50wt%, preferably approximately the 2- about 25wt%, most preferably from about 5- of total composition are big About 15wt% is solubilizer.In the present compositions, the UV fluorescent dye with about 0.001wt%- about The concentration of 1.0wt%, preferably 0.005wt%- about 0.5wt%, most preferably 0.01wt%- about 0.25wt% exist.

The invention further relates in refrigeration, air-conditioning or heat-pump apparatus using further including UV fluorescent dye, With the method for the composition of optional solubilizer.This method includes introducing the composition in refrigeration, air-conditioning or heat-pump apparatus. This can by the presence of solubilizer by UV fluorescent dye be dissolved in the composition and by the combination be introduced into the equipment come It realizes.Alternatively, this can be by being introduced into solubilizer and UV fluorescent dye in conjunction with and by the combination containing refrigerant and/or heat It conducts in the refrigeration or air-conditioning equipment of fluid and realizes.Resulting composition can be used for refrigeration, air-conditioning or heat-pump apparatus.

The invention further relates to the methods for using the combination analyte detection leakage comprising UV fluorescent dye.The dyestuff exists Presence permission in composition detects the refrigerant leaked in refrigeration, air-conditioning or heat-pump apparatus.Leak detection facilitates Tackle, solve or prevent the operating of the inefficiency of the equipment or system or failure of apparatus.Leak detection also helps it to contain in device Operating used in chemicals.

This method includes providing into refrigeration, air-conditioning or heat-pump apparatus comprising refrigerant, ultraviolet fluorescent described here The composition of dyestuff and non-essential solubilizer described here, and using for refrigerant of the detection containing UV fluorescent dye Appropriate device.The suitable equipment of detection dyestuff includes, but are not limited to ultraviolet radiator, usually referred to as " black light " or " blue light ".These Ultraviolet radiator can be commercially available from many sources of supply specially designed for this purpose.Once the composition containing UV fluorescent dye It has been incorporated into the refrigeration, air-conditioning or heat-pump apparatus and it is allowed to cycle through the system, by irradiating the ultraviolet radiator The fluorescence of the dyestuff is observed on the device and near any breakthrough it can be found that leakage.

The invention further relates to the methods of high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the height GWP refrigerant is selected from R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A And R404A, the method includes composition of the invention is supplied to use, is used to or is designed to cause using the high GWP The refrigeration, air-conditioning or the heat-pump apparatus of cryogen.Vapor compression refrigeration, air-conditioning or heat pump system include evaporator, and compressor is cold Condenser and expansion device.Vapor-compression cycle reuses refrigerant in multiple steps, to generate cooling in one step Effect generates heating effect in different steps.The circulation can easily describe as follows.Liquid refrigerant passes through expansion dress It sets and enters evaporator, then boiling forms gas and generates cooling effect the liquid refrigerant at low temperature in evaporator.It should Low-pressure gas enters in compressor, its pressure and temperature is increased after wherein gas is compressed.Elevated pressures (compression) gas State refrigerant condenses in wherein refrigerant subsequently into condenser and its heat is discharged in environment.The refrigerant returns to In the expansion device, it is expanded into evaporator by the liquid after the device from higher-pressure level within the condenser Low voltage level, therefore repeat the circulation.

Movement refrigeration equipment used herein or movement air-conditioning equipment, which refer to, is integrated to road, track, ocean or sky Delivery unit in any refrigeration or air-conditioning equipment.In addition, being used to as the system independent of any mobile vehicle (referred to as " through transport (intermodal) " system) offer is freezed or the equipment of air-conditioning is also included in the present invention.Such intermodal system includes " container " (in conjunction with ocean/land transport) and " permutoid " (in conjunction with road and railway transportation).Present invention is particularly useful for roads Road transport refrigeration or air-conditioning equipment, such as air conditioning equipment of car or the road transporting tool of refrigeration.

The invention further relates to refrigerating method, including evaporating composition of the invention near body to be cooled, and The composition is condensed later.

The invention further relates to the methods for generating heat, including in the condensed around combination of the invention of body to be heated Object, and later evaporate the composition.

The invention further relates to the refrigeration comprising the present composition, air-conditioning or heat-pump apparatus, wherein the composition Include at least one fluoroolefin.

The invention further relates to the movement air-conditioning equipments comprising the present composition, wherein the composition includes at least A kind of fluoroolefin.

The invention further relates to the method for coolant leaks in early detection refrigeration, air-conditioning or heat-pump apparatus, the sides Method includes in the apparatus using the reduction of non-azeotropic compositions and monitoring cooling performance.The non-azeotropic compositions will let out When leakage from refrigeration, air-conditioning or heat-pump apparatus be fractionated and will be first from the equipment leakage compared with the component of low boiling point (higher vapor pressure) Out.When it happens, if the more low-boiling component in the composition provides most of refrigerating capacity, there is refrigeration energy Power significantly reduces simultaneously the therefore significant decrease of equipment performance.Passenger in automotive air-conditioning system, such as in automobile will test To the reduction of system cooling capacity.This reduction of cooling capacity can be construed to refer to that refrigerant is leaking and the system It needs to repair.

The invention further relates to use composition of the invention as the method for heat-transfer fluid composition, the method Including the composition is transported to radiator from heat source.

Heat-transfer fluid is utilized to through radiation, conduction or convection current, by heat from a space, position, object or machine Different spaces, position, object or body are shifted, migrate or separated in body.Heat-transfer fluid can be by providing from remote Refrigeration (or heating) system carry out the transfer equipment of cooling (or heating) and be used as secondary coolant.In some systems, institute Steady state (that is, do not evaporate or condense) can be maintained in the whole process by stating heat-transfer fluid.Alternatively, evaporation cooling procedure Heat-transfer fluid can similarly be utilized.

Heat source can be defined as any space for wishing therefrom to shift, migrate or separate heat, position, object or body. The example of heat source can be the space (open or closed) for needing refrigeration or cooling, such as the refrigerator or refrigerator at the supermarket Cabinet, needs the space of air-conditioning, or needs the seating compartment of the automobile of air-conditioning.Radiator can be defined as that heat can be absorbed Any space, position, object or body.Vapor compression refrigeration system is an example of such radiator.

In another embodiment, the present invention relates to the foaming agent for being used to prepare foam, it includes retouch herein The composition containing fluoroolefin stated.In other embodiments, the present invention provides foamable composite, preferably polyurethane and more Isocyanate foams composition, and the method for preparing foam.In these foam embodiments, including one or more present invention The composition containing fluoroolefin as the foaming agent in foamable composite, which preferably includes a kind of or more Kind can be reacted under proper condition and be foamed to form the annexing ingredient of foam or honeycomb structure.Foam according to the present invention Embodiment, any method well known in the art, such as " Polyurethanes Chemistry and Technology ", the I and II volumes, described in Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y. that (document is hereby incorporated by reference) can be used or use through reorganization a bit.

The invention further relates to the forming methods of foam, comprising: (a) adds the composition of the invention containing fluoroolefin It is added in foamable composite；(b) foamable composite is reacted.

Another embodiment of the invention is related to the composition described herein containing fluoroolefin in Sprayable composition In be used as the purposes of propellant.In addition, the present invention relates to sprayable group comprising the composition described herein containing fluoroolefin Close object.Active constituent and inert component to be sprayed, solvent and other materials can also exist in Sprayable composition.It is excellent Selection of land, the Sprayable composition are aerosols.Suitable active material to be sprayed includes but is not limited to cosmetic material, such as Deodorant, aromatic, hair spray, detergent and polishing agent and for example anti-asthma of medicinal materials and anti-halitosis medications.

The invention further relates to the preparation methods of aerosol product, comprising steps of containing fluoroolefin for described herein Composition be added in the active constituent in aerosol container, wherein the composition plays propellant.

The method for inhibiting flame is provided on the other hand, the method includes making flame and comprising the disclosure of invention The fluid of composition containing fluoroolefin contacts.Any suitable side for contacting the flame with the present composition can be used Method.For example, can by the composition containing fluoroolefin of the disclosure of invention by being sprayed, toppling over, etc. in modes to flame, Or at least part of flame can be immersed in the flame suppressant composition.In view of teaching herein, the skill of this field Art personnel will easily vary various conventional equipments and the method for suppression for the disclosure of invention.

Another embodiment, which is provided, puts out or inhibits the method for fire by total flooding (total-flood) applying mode, It include: that the reagent of the composition containing fluoroolefin comprising the disclosure of invention is provided；The reagent is arranged in pressurization row In place system；It is discharged into a region with by the reagent to put out or inhibit the fire in that region.Another is implemented Scheme provides the method for making islands inert to prevent fire or explosion, comprising: provides fluorine-containing comprising the disclosure of invention For the reagent of the composition of alkene；The reagent is arranged in pressurized discharge system；The region is discharged by the reagent In with prevent fire or explosion occur.

Term " putting out ", which is conventionally used to indicate, completely eliminates fire；And " inhibition " is conventionally used to indicate reduction, and not necessarily Completely eliminate fire or explosion.Term as used herein " putting out " and " inhibition " will be interchangeably used.It is general there are four kinds The halocarbon fire and explosion proof applications of type.(1) in total flooding fire suppression and/or inhibition application, the reagent is discharged into To obtain the concentration for being enough to put out or inhibit existing fire in space.Total flooding purposes includes protecting sky that is closed, may occupying Between, such as computer room and dedicated, usually idle space such as cabin in aero-engine gondola and carrier.(2) it is spraying It penetrates in (streaming) application, the reagent is applied directly in the region on fire or to fire.This is usually using artificial The wheel or mancarried device of operation are realized.The second method for including as spray application uses " localization (localized) " system discharges reagent towards fire by one or more fixed nozzles.Localizing system can manually or from Start dynamicly.(3) in explosion suppression, the composition containing fluoroolefin of the disclosure of invention is discharged to inhibit to be drawn The explosion of hair.Term " inhibition " is generally used in this application, because explosion is usually self limiting.However, this art The use of language is not necessarily mean that the reagent does not put out explosion.In this application, detector derives from quick-fried commonly used to detection Fried expansion fireball, and discharge the reagent promptly to inhibit to explode.Explosion suppression is main but is not only used for defence application. (4) in deactivation, the composition containing fluoroolefin of the disclosure of invention is discharged into space to prevent explosion or fire Calamity is initiated.In general, using the system similar or identical used with total flooding fire suppression or inhibition.In general, detection is dangerous The presence of condition (for example, flammable or explosive gas dangerous concentrations), then discharge the disclosure of invention containing fluoroolefin Composition is to prevent explosion or fire from occurring until that can remedy the condition.

It can carry out putting out method by the enclosed area for introducing the composition around fire.What be can be used is any Known introducing method, as long as being spaced suitable by the proper amount of metered enclosed area of composition.For example, can To introduce composition as follows: injection is for example using Conventional portable (or fixed) fire-extinguishing apparatus；Atomization；Or flood (flooding), the closing of corral a fire such as by composition release (using suitable pipeline, valve and controller) is arrived Qu Zhong.The composition can optionally with inert propellant, such as nitrogen, argon gas, Glycidyl azide polymer Decomposition product or carbon dioxide combine, to improve the rate that the composition is discharged from the injection used or flood device.

Preferably, putting out method includes to be enough to stamp out a fire or the amount of flame is by the alkene containing fluoro of the disclosure of invention The composition of hydrocarbon is introduced into fire or flame.Those skilled in the art will recognize that the fire inhibitor for putting out that specific fire needs Amount will depend on the property and degree of harm.When that will introduce fire inhibitor by flood, cup burner test data can For determining the amount or concentration of putting out fire inhibitor required for the fire of specific type and scale.

When combination is put out or inhibits fire in a manner of total flooding application or fire deactivation, can be used for determining alkene containing fluoro The laboratory test of the Valid concentration of the composition of hydrocarbon is for example described in U.S. Patent number 5,759,430, should Document is incorporated herein for reference.

Embodiment

Embodiment 1

The influence of vapour leakage

If at -25 DEG C or having a regulation, 25 DEG C at a temperature of initial composition is fitted into container, and measure the composition Initial vapour pressure.Allow the composition from container leakage, while keeping temperature-resistant, until the 50wt% of initial composition is removed It goes, measures the vapour pressure of remaining composition in container at this time.As a result it is shown in table 9.

Table 9

For composition of the invention, original composition and after removing 50wt% between remaining composition Vapour pressure difference is then less than about 10%.This shows that composition of the invention may be azeotropic or close to azeotropic.

Embodiment 2

Refrigeration performance data

Table 10 shows the performance of various refrigerant compositions of the invention compared with HFC-134a.In table 10, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compressor outlet temperature, and COP is energy Efficiency, CAP are capacity (capacity).Data are based on following condition.

It is noted that considering overheat in cooling capacity calculating.

Table 10

Several compositions have even energy efficiency (COP) more higher than HFC-134a, while lower discharge being maintained to press Power and temperature.The capacity of the present composition is also similar to R134a, this shows that they may especially be transported in refrigeration and air-conditioning Be used as R134a in dynamic air conditioning applications replaces refrigerant.Those of hydrocarbonaceous composition can also improve and conventional mineral oil and alkane The oily dissolubility of base benzene lubricant.

Embodiment 3

Refrigeration performance data

Table 11 shows the performance of various refrigerant compositions of the invention compared with R404A and R422A.

In table 11, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is pressure Contracting device outlet temperature, EER are energy efficiencies, and CAP is capacity.Data are based on following condition.

It is noted that considering overheat in cooling capacity calculating.

Table 11

Several compositions have the energy efficiency (COP) similar with R404A and R422A.Exhaust temperature also below R404A and R507A.The capacity of the present composition is also similar to R404A, R507A and R422A, this shows that they may be in refrigeration and air-conditioning In be used as instead of refrigerant.Those of hydrocarbonaceous composition can also be improved to be dissolved with the oil of conventional mineral oil and alkyl benzene lubricants Property.

Embodiment 4

Refrigeration performance data

Table 12 shows various refrigerant compositions of the invention compared with HCFC-22, R410A, R407C and R417A Performance.In table 12, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compression Device outlet temperature, EER are energy efficiencies, and CAP is capacity.Data are based on following condition.

It is noted that considering overheat in cooling capacity calculating.

Table 12

Composition has the energy efficiency (EER) similar with R22, R407C, R417A and R410A, while maintaining low row Put temperature.The capacity of the present composition is also similar to R22, R407C and R417A, this shows that they may be in refrigeration and air-conditioning In be used as instead of refrigerant.Those of hydrocarbonaceous composition can also be improved to be dissolved with the oil of conventional mineral oil and alkyl benzene lubricants Property.

Embodiment 5

Refrigeration performance data

Table 13 shows the performance of various refrigerant compositions of the invention compared with HCFC-22 and R410A.In table 13 In, Evap Pres is evaporator pressure, and Cond Pres is condenser pressure, and Comp Disch T is compressor outlet temperature, EER is energy efficiency, and CAP is capacity.Data are based on following condition.

It is noted that considering overheat in cooling capacity calculating.

Table 13

Composition has the energy efficiency (EER) similar with R22 and R410A, while maintaining reasonable exhaust temperature.This hair The capacity of bright composition is also similar to R22, this shows that they may be used as in refrigeration and air-conditioning instead of refrigerant.

Embodiment 6

Flammability

Combustible cpd can be by ASTM (American Society of Testing and Materials) Under E681-01, test determination is carried out using electronic ignition source.In 101kPa (14.7psia), 100 DEG C (212 °F) and 50% phase To under humidity, with aerial various concentration to the mixture of HFC-1234yf, HFC-1225ye and the disclosure of invention Such burning test is carried out to determine flammability lower limit (LFL) and the flammability upper limit (UFL).As a result it is provided in table 14.

Table 14

The result shows that the addition of HFC-1225ye reduces flammability when HFC-1234yf is flammable.Therefore, comprising big The composition of about 1wt%- about 49wt%HFC-1234yf and about 99wt%- about 51wt%HFC-1225ye are preferred 's.

Claims

1. including the composition of HFC-1234ze and at least one compound selected from following substance: HFC-1234yf, HFC- 1234ye、HFC-1243zf、HFC-32、HFC-125、HFC-134、HFC-134a、HFC-143a、HFC-152a、HFC-161、 HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, normal butane, iso-butane, 2- methyl Butane, pentane, pentamethylene, dimethyl ether, CF₃SCF₃、CO₂And CF₃I。

2. the composition of claim 1, is selected from:

Cis- HFC-1234ze and HFC-1234ye；

Cis- HFC-1234ze and HFC-236ea；

Cis- HFC-1234ze and HFC-236fa；

Cis- HFC-1234ze and HFC-245fa；

Cis- HFC-1234ze and normal butane；

Cis- HFC-1234ze and iso-butane；

Cis- HFC-1234ze and 2- methybutane；

Cis- HFC-1234ze and pentane；

Trans- HFC-1234ze and HFC-1234yf；

Trans- HFC-1234ze and HFC-134a；

Trans- HFC-1234ze and HFC-152a；

Trans- HFC-1234ze and HFC-32；

Trans- HFC-1234ze, HFC-125 and normal butane；

Trans- HFC-1234ze, HFC-32 and HFC-125；

Trans- HFC-1234ze, HFC-125 and iso-butane；

Trans- HFC-1234ze, HFC-1243zf and HFC-227ea；

Trans- HFC-1234ze, HFC-1243zf and normal butane；

Trans- HFC-1234ze, HFC-1243zf and iso-butane；

Trans- HFC-1234ze, HFC-1243zf and dimethyl ether；

Trans- HFC-1234ze, HFC-134 and HFC-152a；

Trans- HFC-1234ze, HFC-134 and HFC-227ea；

Trans- HFC-1234ze, HFC-134 and dimethyl ether；

Trans- HFC-1234ze, HFC-134a and HFC-152a；

Trans- HFC-1234ze, HFC-152a and normal butane；

Trans- HFC-1234ze, HFC-152a and dimethyl ether；

Trans- HFC-1234ze, HFC-227ea and normal butane；

Trans- HFC-1234ze, normal butane and dimethyl ether；

Trans- HFC-1234ze, normal butane and CF₃I；

Trans- HFC-1234ze, iso-butane and dimethyl ether；

Trans- HFC-1234ze, iso-butane and CF₃I；With

Trans- HFC-1234ze, iso-butane and CF₃SCF₃。

3. the composition of claim 1, is selected from:

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-1234ye；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-236ea；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-236fa；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-245fa；

About 1wt%- about 80wt% cis- HFC-1234ze and about 99wt%- about 20wt% normal butane；

About 1wt%- about 69wt% cis- HFC-1234ze and about 99wt%- about 31wt% iso-butane；

About 60wt%- about 99wt% cis- HFC-1234ze and about 40wt%- about 1wt%2- methybutane；

About 63wt%- about 99wt% cis- HFC-1234ze and about 37wt%- about 1wt% pentane；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-32；

About 0.1wt%- about 98wt%HFC-32, about 0.1wt%- about 98wt%HFC-125 and about 0.1wt%- The trans- HFC-1234ze of about 98wt%；

About 0.1wt%- about 98wt%HFC-125, the trans- HFC-1234ze of about 0.1wt%- about 98wt% and about 0.1wt%- about 98wt% normal butane；

About 0.1wt%- about 98wt%HFC-125, the trans- HFC-1234ze of about 0.1wt%- about 98wt% and about 0.1wt%- about 98wt% iso-butane；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-1243zf and about 1wt%- about 98wt%HFC-227ea；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-1243zf and about 1wt%- about 30wt% normal butane；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-1243zf and about 1wt%- about 40wt% iso-butane；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-1243zf and about 1wt%- about 98wt% dimethyl ether；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-134 and about 1wt%- About 98wt%HFC-152a；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-134 and about 1wt%- About 98wt%HFC-227ea；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-134 and about 1wt%- About 40wt% dimethyl ether；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-134a and about 1wt%- about 98wt%HFC-152a；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-152a and about 1wt%- about 50wt% normal butane；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-152a and about 1wt%- about 98wt% dimethyl ether；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 98wt%HFC-227ea and about 1wt%- about 40wt% normal butane；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 40wt% normal butane and about 1wt%- About 98wt% dimethyl ether；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 30wt% normal butane and about 1wt%- About 98wt%CF₃I；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 60wt% iso-butane and about 1wt%- About 98wt% dimethyl ether；

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 40wt% iso-butane and about 1wt%- About 98wt%CF₃I；With

The trans- HFC-1234ze of about 1wt%- about 98wt%, about 1wt%- about 40wt% iso-butane and about 1wt%- About 98wt%CF₃SCF₃。

4. the composition of claim 1, is selected from:

About 30wt%- about 99wt% trans- HFC-1234ze and about 70wt%- about 1wt%HFC-134a；

About 40wt%- about 99wt% trans- HFC-1234ze and about 60wt%- about 1wt%HFC-32；

About 40wt%- about 99wt% trans- HFC-1234ze and about 60wt%- about 1wt%HFC-152a；

About 5wt%- about 70wt%HFC-32, about 5wt%- about 70wt%HFC-125 and about 5wt%- are about The trans- HFC-1234ze of 70wt%；

About 5wt%- about 70wt%HFC-125, about 5wt%- about 70wt% trans- HFC-1234ze and about 1wt%- About 20wt% normal butane；With

About 5wt%- about 70wt%HFC-125, about 5wt%- about 70wt% trans- HFC-1234ze and about 1wt%- About 20wt% iso-butane；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-1243zf and about 10wt%- about 80wt%HFC-227ea；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-1243zf and about 1wt%- about 20wt% normal butane；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-1243zf and about 1wt%- about 30wt% iso-butane；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-1243zf and about 1wt%- about 40wt% dimethyl ether；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-134 and about 1wt%- about 50wt%HFC-152a；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-134 and about 10wt%- about 80wt%HFC-227ea；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-134 and about 1wt%- about 30wt% dimethyl ether；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-134a and about 1wt%- about 50wt%HFC-152a；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-152a and about 1wt%- about 30wt% normal butane；

The trans- HFC-1234ze of about 20wt%- about 90wt%, about 1wt%- about 50wt%HFC-152a and about 1wt%- about 30wt% dimethyl ether；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 10wt%- about 80wt%HFC-227ea and about 1wt%- about 30wt% normal butane；

The trans- HFC-1234ze of about 10wt%- about 90wt%, about 1wt%- about 30wt% normal butane and about 1wt%- About 30wt% dimethyl ether；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 1wt%- about 20wt% normal butane and about 10wt%- about 80wt%CF₃I；

The trans- HFC-1234ze of about 10wt%- about 90wt%, about 1wt%- about 30wt% iso-butane and about 1wt%- About 30wt% dimethyl ether；

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 1wt%- about 20wt% iso-butane and about 10wt%- about 80wt%CF₃I；With

The trans- HFC-1234ze of about 10wt%- about 80wt%, about 1wt%- about 20wt% iso-butane and about 10wt%- about 80wt%CF₃SCF₃。

5. the composition of claim 1, is selected from:

About 90wt% trans- HFC-1234ze and about 10wt%HFC-134a；

About 95wt% trans- HFC-1234ze and about 5wt%HFC-32；

About 80wt% trans- HFC-1234ze and about 20wt%HFC-152a；

The trans- HFC-1234ze of about 30wt%HFC-32, about 50wt%HFC-125 and about 20wt%；

The trans- HFC-1234ze of about 23wt%HFC-32, about 25wt%HFC-125 and about 52wt%；

About 66wt%HFC-125, about 32wt% trans- HFC-1234ze and about 2wt% normal butane；With

About 86.1wt%HFC-125, about 11.5wt% trans- HFC-1234ze and about 2.4wt% iso-butane.

6. the composition of claim 1, including azeotropic selected from the following or close to Azeotrope compositions:

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-1234yf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-1243zf；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-134；

About 1wt%- about 52wt% trans- HFC-1234ze and about 99wt%- about 48wt%HFC-161 and about 87wt%- about 99wt% trans- HFC-1234ze and about 13wt%- about 1wt%HFC-161；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%HFC-227ea；

About 54wt%- about 99wt% trans- HFC-1234ze and about 46wt%- about 1wt%HFC-236ea；

About 44wt%- about 99wt% trans- HFC-1234ze and about 56wt%- about 1wt%HFC-236fa；

About 67wt%- about 99wt% trans- HFC-1234ze and about 33wt%- about 1wt%HFC-245fa；

About 1wt%- about 71wt% trans- HFC-1234ze and about 99wt%- about 29wt% propane；

About 62wt%- about 99wt% trans- HFC-1234ze and about 38wt%- about 1wt% normal butane；

About 39wt%- about 99wt% trans- HFC-1234ze and about 61wt%- about 1wt% iso-butane；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt% dimethyl ether；

Bis- (trifluoromethyl) thioethers of about 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%；

About 1wt%- about 99wt% trans- HFC-1234ze and about 99wt%- about 1wt%CF₃I；

About 80wt%- about 98wt%HFC-125, the trans- HFC-1234ze of about 1wt%- about 19wt% and about 1wt%- about 10wt% iso-butane；

About 1wt%- about 98wt%HFC-32, about 1wt%- about 98wt%HFC-125 and about 1wt%- are about The trans- HFC-1234ze of 5wt%；

About 80wt%- about 98wt%HFC-125, the trans- HFC-1234ze of about 1wt%- about 19wt% and about 1wt%- about 10wt% normal butane；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-236ea；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-236fa；

About 1wt%- about 99wt% cis- HFC-1234ze and about 99wt%- about 1wt%HFC-245fa；

About 63wt%- about 99wt% cis- HFC-1234ze and about 37wt%- about 1wt% pentane；

7. the composition of claim 1, including Azeotrope compositions selected from the following:

In the trans- HFC-1234ze of 17.0wt% that about -25 DEG C of at a temperature of vapour pressure is about 13.0psia (90kPa) and 83.0wt%HFC-1243zf；

In the trans- HFC-1234ze of 45.7wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.5psia (86kPa) and 54.3wt%HFC-134；

In the trans- HFC-1234ze of 9.5wt% that about -25 DEG C of at a temperature of vapour pressure is about 15.5psia (107kPa) and 90.5wt%HFC-134a；

In the trans- HFC-1234ze of 21.6wt% that about -25 DEG C of at a temperature of vapour pressure is about 14.6psia (101kPa) and 78.4wt%HFC-152a；

In the trans- HFC-1234ze of 59.2wt% that about -25 DEG C of at a temperature of vapour pressure is about 11.7psia (81kPa) and 40.8wt%HFC-227ea；

In the trans- HFC-1234ze of 28.5wt% that about -25 DEG C of at a temperature of vapour pressure is about 30.3psia (209kPa) and 71.5wt% propane；

In the trans- HFC-1234ze of 88.6wt% that about -25 DEG C of at a temperature of vapour pressure is about 11.9psia (82kPa) and 11.4wt% normal butane；

In the trans- HFC-1234ze of 77.9wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.9psia (89kPa) and 22.1wt% iso-butane；

In the trans- HFC-1234ze of 84.1wt% that about -25 DEG C of at a temperature of vapour pressure is about 10.8psia (74kPa) and 15.9wt% dimethyl ether；

In the trans- HFC-1234ze of 34.3wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.7psia (88kPa) and 65.7wt%CF₃SCF₃；

The trans- HFC-1234ze of 7.1wt% that about -25 DEG C of at a temperature of vapour pressure is about 13.1psia (90.4kPa), 73.7wt%HFC-1243zf and 19.2wt%HFC-227ea；

The trans- HFC-1234ze of 9.5wt% that about -25 DEG C of at a temperature of vapour pressure is about 13.5psia (92.9kPa), 81.2wt%HFC-1243zf and 9.3wt% normal butane；

The trans- HFC-1234ze of 3.3wt% that about -25 DEG C of at a temperature of vapour pressure is about 14.3psia (98.3kPa), 77.6wt%HFC-1243zf and 19.1wt% iso-butane；

The trans- HFC-1234ze of 2.6wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.0psia (82.9kPa), 70.0wt%HFC-1243zf and 27.4wt% dimethyl ether；

The trans- HFC-1234ze of 52.0wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.4psia (85.3kPa), 42.9wt%HFC-134 and 5.1wt%HFC-152a；

The trans- HFC-1234ze of 30.0wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.6psia (86.9kPa), 43.2wt%HFC-134 and 26.8wt%HFC-227ea；

The trans- HFC-1234ze of 27.7wt% that about -25 DEG C of at a temperature of vapour pressure is about 9.8psia (67.3kPa), 54.7wt%HFC-134 and 17.7wt% dimethyl ether；

The trans- HFC-1234ze of 14.4wt% that about -25 DEG C of at a temperature of vapour pressure is about 14.4psia (99.4kPa), 34.7wt%HFC-134a and 51.0wt%HFC-152a；

The trans- HFC-1234ze of 5.4wt% that about -25 DEG C of at a temperature of vapour pressure is about 15.4psia (106kPa), 80.5wt%HFC-152a and 14.1wt% normal butane；

The trans- HFC-1234ze of 59.1wt% that about -25 DEG C of at a temperature of vapour pressure is about 10.8psia (74.5kPa), 16.4wt%HFC-152a and 24.5wt% dimethyl ether；

The trans- HFC-1234ze of 40.1wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.6psia (86.9kPa), 48.5wt%HFC-227ea and 11.3wt% normal butane；

The trans- HFC-1234ze of 68.1wt% that about -25 DEG C of at a temperature of vapour pressure is about 11.3psia (77.8kPa), 13.0wt% normal butane and 18.9wt% dimethyl ether；

The trans- HFC-1234ze of 81.2wt% that about -25 DEG C of at a temperature of vapour pressure is about 11.9psia (81.8kPa), 9.7wt% normal butane and 9.1wt%CF₃I；

The trans- HFC-1234ze of 55.5wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.4psia (85.4kPa), 28.7wt% iso-butane and 15.8wt% dimethyl ether；

The trans- HFC-1234ze of 34.9wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.6psia (86.7kPa), 6.1wt% iso-butane and 59.0wt%CF₃I；

The trans- HFC-1234ze of 37.7wt% that about -25 DEG C of at a temperature of vapour pressure is about 12.7psia (87.3kPa), 1.1wt% iso-butane and 61.7wt%CF₃SCF₃；

In the cis- HFC-1234ze of 20.9wt% that about -25 DEG C of at a temperature of vapour pressure is about 30.3psia (209kPa) and 79.1wt%HFC-236ea；

In the cis- HFC-1234ze of 76.2wt% that about -25 DEG C of at a temperature of vapour pressure is about 26.1psia (180kPa) and 23.8wt%HFC-245fa；

In the cis- HFC-1234ze of 51.4wt% that about -25 DEG C of at a temperature of vapour pressure is about 6.1psia (41.9kPa) and 48.6wt% normal butane；

In the cis- HFC-1234ze of 26.2wt% that about -25 DEG C of at a temperature of vapour pressure is about 8.7psia (60.3kPa) and 73.8wt% iso-butane；

In the cis- HFC-1234ze of 86.6wt% that about 25 DEG C of at a temperature of vapour pressure is about 27.2psia (188kPa) and 13.4wt%2- methybutane；

In the cis- HFC-1234ze of 92.9wt% that about 25 DEG C of at a temperature of vapour pressure is about 26.2psia (181kPa) and 7.1wt% pentane.

8. the composition of any one of claim 1-7, also comprising selected from polyol ester, polyalkylene glycol, polyvingl ether, Mineral oil, alkylbenzene, synthesis paraffin, the lubricant for synthesizing cycloalkane and poly- (α) alkene.

9. the composition of any one of claim 1-7 also includes tracer, is selected from hydrofluorocarbon, deuteroparaffin, hydrogen deuteride fluorine Carbon, perfluoroparaffin, fluoro-ether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N₂) and their combination O.

10. the composition of claim 9, also comprising the tracer selected from following substance:

CD₃CD₃, CD₃CD₂CD₃, CD₂F₂, CF₃CD₂CF₃, CD₂FCF₃, CD₃CF₃, CDF₂CF₃, CF₃CDFCF₃, CF₃CF₂CDF₂, CDF₂CDF₂, CF₃CF₂CD₃, CF₃CD₂CH₃, CF₂CH₂CD₃, CF₃CF₃, ring-CF₂CF₂CF₂, CF₃CF₂CF₃, ring- CF₂CF₂CF₂CF₂, CF₃CF₂CF₂CF₃, CF₃CF(CF₃)₂, ring-CF (CF₃)CF₂CF(CF₃)CF₂, trans- ring-CF₂CF(CF₃) CF(CF₃)CF₂, cis- ring-CF₂CF(CF₃)CF(CF₃)CF₂, CF₃OCHF₂, CF₃OCH₂F, CF₃OCH₃, CF₃OCHFCF₃, CF₃OCH₂CF₃, CF₃OCH₂CHF₂, CF₃CH₂OCHF₂CH₃OCF₂CF₃, CH₃CF₂OCF₃CF₃CF₂CF₂OCHFCF₃, CF₃CF₂CF₂OCF (CF₃)CF₂OCHFCF₃, CHF₃, CH₂FCH₃, CHF₂CH₃, CHF₂CHF₂, CF₃CHFCF₃, CF₃CF₂CHF₂, CF₃CF₂CH₂F, CHF₂CHFCF₃, CF₃CH₂CF₃, CF₃CF₂CH₃, CF₃CH₂CHF₂, CHF₂CF₂CH₃, CF₃CHFCH₃, CF₃CH₂CH₃, CH₃CF₂CH₃, CH₃CHFCH₃, CH₂FCH₂CH₃, CHF₂CF₂CF₂CF₃, (CF₃)₂CHCF₃, CF₃CH₂CF₂CF₃, CHF₂CF₂CF₂CHF₂, CH₃CF₂CF₂CF₃, CF₃CHFCHFCF₂CF₃,

Trifluoromethyl-cyclopentane, perfluoromethylcyclohexane (PFMCH), perfluorodimethylcyclohexane (o-, m- or p-), perfluoro-ethyl hexamethylene, Perfluoroindan, perfluor trimethyl-cyclohexane and their isomers, perfluoroisopropyl hexamethylene, suitable perfluorodecalin, anti-perfluor naphthalene Alkane, suitable or anti-perfluoromethyidecalin and their isomers, CH₃Br、CH₂FBr、CHF₂Br、CHFBr₂、CHBr₃、CH₂BrCH₃、 CHBr=CH₂、CH₂BrCH₂Br, CFBr=CHF, CF₃I、CHF₂I、CH₂FI、CF₂ICH₂F、CF₂ICHF₂、CF₂ICF₂I、C₆F₅I、 Ethyl alcohol, normal propyl alcohol, isopropanol, acetone, positive propionic aldehyde, n-butanal, methyl ethyl ketone, nitrous oxide and their combination.

11. the composition of any one of claim 1-7, also comprising the expanding material selected from following substance:

A) by general formula R¹[(OR²)xOR³] y indicate polyoxyalkylene glycol ether, in which: x is the integer of 1-3；Y is the whole of 1-4 Number；R¹Aliphatic hydrocarbyl selected from hydrogen and containing 1-6 carbon atom and y bonded positions；R²It is sub- selected from the aliphatic series containing 2-4 carbon atom Alkyl；R³Aliphatic series and alicyclic alkyl selected from hydrogen and containing 1-6 carbon atom；R¹And R³In at least one be selected from the alkyl；And And wherein the polyoxyalkylene glycol ether has the molecular weight of about 300 atomic mass unit of about 100-；

B) by general formula R¹C(O)NR²R³With ring-[R⁴CON(R⁵The amide that) -] indicates, wherein R¹、R²、R³And R⁵Independently selected from containing The aliphatic series and alicyclic alkyl of 1-12 carbon atom, and an at most aromatic group containing 6-12 carbon atom；R⁴Selected from containing 3-12 The aliphatic hydrocarbylene of a carbon atom；And wherein the amide has the molecular weight of about 300 atomic mass unit of about 100-；

C) by general formula R¹C(O)R²The ketone of expression, wherein R¹And R²Independently selected from aliphatic, alicyclic containing 1-12 carbon atom and Arylalkvl, and wherein the ketone has the molecular weight of about 300 atomic mass unit of about 70-；

E) chlorohydrocarbon indicated by general formula R Clx, in which: x is 1 or 2；R is selected from aliphatic series and clicyclic hydrocarbon containing 1-12 carbon atom Base；And wherein the chlorocarbon has the molecular weight of about 200 atomic mass unit of about 100-；

F) by general formula R¹OR²The aryl ether of expression, in which: R¹Selected from the Arylalkvl containing 6-12 carbon atom；R²Selected from containing 1-4 The aliphatic hydrocarbyl of carbon atom；And wherein the aryl ether has the molecular weight of about 150 atomic mass unit of about 100-；

G) by general formula CF₃R¹1,1, the 1- trifluoroalkanes indicated, wherein R¹Selected from about 15 carbon atoms Han about 5- aliphatic series and Alicyclic alkyl；

H) by general formula R¹OCF₂CF₂The fluoro-ether that H is indicated, wherein R¹Aliphatic series selected from about 15 carbon atoms Han about 5-, alicyclic ring Race and aromatic hydrocarbyl；Or in which the fluoro-ether is derived from fluoroolefin and polyalcohol, wherein the fluoroolefin has CF₂ =CXY pattern, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_f, wherein R_fIt is CF₃、C₂F₅Or C₃F₇；With the polyalcohol It is linear or branching, wherein the polyalcohols have HOCH₂(CHOH)x(CRR')yCH₂OH pattern, wherein R and R' are Hydrogen, CH₃Or C₂H₅, x is the integer of 0-4, and y is the integer of 0-3, and z is that 0 or 1 and the Branched polyol have C (OH) t (R) u (CH₂OH)v[(CH₂)mCH₂OH] w pattern, wherein R can be hydrogen, CH₃Or C₂H₅, m is the integer of 0-3, and t and u are 0 or 1, v and w It is the integer of 0-4, furthermore wherein t+u+v+w=4；With

I) lactone indicated by structure [B], [C] and [D]:

Wherein, R¹- R⁸Independently selected from hydrogen, linearly, branching is cyclic annular, two rings, saturation and undersaturated alkyl；And molecular weight It is about 100 to about 300 atomic mass units；With

J) by general formula R¹CO₂R²The ester of expression, wherein R¹And R²Independently selected from linear and cyclic annular, saturation and unsaturated, alkyl And aryl；And wherein the ester has the molecular weight of from about 80 to about 550 atomic mass units.

12. the composition of any one of claim 1-7 is also selected from naphthalimide comprising at least one, cumarin, Anthracene, it is luxuriant and rich with fragrance,Ton, thioxanthene, naphthoxanthene, fluorescein, the derivative of the dyestuff and the ultraviolet fluorescent of their combination Dyestuff.

13. the composition of claim 12 is also selected from hydrocarbon, dimethyl ether, polyoxyalkylene glycol ether, acyl comprising at least one Amine, ketone, nitrile, chlorohydrocarbon, ester, lactone, aryl ether, hydrogen fluoro-ether and 1,1,1- trifluoroalkanes solubilizer.

14. the composition of any one of claim 1-7 also includes stabilizer, water scavenger or odor masking agent.

15. the composition of claim 14, wherein the stabilizer is selected from nitromethane, hindered phenol, azanol, mercaptan, phosphorous acid Ester and lactone.

16. refrigerating method, which comprises by the composition of any one of claim 1-7 near body to be cooled Evaporation, later condenses the composition.

17. the method for generating heat, which comprises by the group of any one of claim 1-7 near body to be heated Object condensation is closed, later evaporates the composition.

18. the method for high GWP refrigerant in substitution refrigeration, air-conditioning or heat-pump apparatus, wherein the high GWP refrigerant is selected from R134a、R22、R123、R11、R245fa、R114、R236fa、R124、R12、R410A、R407C、R417A、R422A、R507A、 R502 and R404A, which comprises the composition of any one of claim 1-7 is supplied to use, is used to or designs use Carry out the refrigeration, air-conditioning or the heat-pump apparatus using the high GWP refrigerant.

19. use the composition of any one of claim 1-7 as the method for heat-transfer fluid composition, the method includes The composition is transported to radiator from heat source.

20. a kind of refrigeration, air-conditioning or the heat-pump apparatus of the composition containing any one of claim 1-7.

21. a kind of refrigeration, air-conditioning or heat-pump apparatus including moving the claim 20 of air-conditioning equipment.

22. a kind of foaming agent of the composition comprising any one of claim 1-7.

23. a kind of method for forming foam, comprising:

(a) composition of any one of claim 1-7 is added in foamable composite；With

(b) foamable composite is reacted.

24. the Sprayable composition of the composition comprising any one of claim 1-7.

25. a kind of preparation method of aerosol product, comprising steps of addition right is wanted in active constituent into aerosol container The composition of any one of 1-7 is sought, wherein the composition plays propellant.