CN102876294A

CN102876294A - Compositions comprising fluoroolefins and uses thereof

Info

Publication number: CN102876294A
Application number: CN2012103401419A
Authority: CN
Inventors: A.C.斯伊韦特; M.J.纳帕; B.H.米诺尔; T.J.雷克; V.N.M.劳; E.N.斯维林根; C.施米茨; N.莫利; D.佩蒂
Original assignee: EI Du Pont de Nemours and Co
Current assignee: Chemours Co FC LLC
Priority date: 2005-11-01
Filing date: 2006-10-31
Publication date: 2013-01-16
Anticipated expiration: 2026-10-31
Also published as: JP5550667B2; CN104745148A; JP2016145350A; MY154466A; BR122017013121B1; JP2013117034A; HK1128487A1; CN102911640A; MY154559A; JP2017215140A; JP6442011B2; CA2922197A1; JP6250483B2; ES2646463T3; CN105349106A; CN102911640B; CN104745148B; CA3044769C; CN102876294B; BR122017013146B1

Abstract

The present invention relates to fluoroolefin compositions. The fluoroolefin compositions of the present invention are used as refrigerants or heat transfer fluids and in processes for producing cooling or heat. Additionally, the fluoroolefin compositions of the present invention can be used to replace current refrigerant or heat transfer fluid compositions that have higher global warming potential.

Description

The composition and use thereof that comprises fluoroolefins

The application is that international filing date is that on October 31st, 2006, national applications number are dividing an application of 2006800488601.0 (international application no is PCT/US2006/042686), the denomination of invention application that is " composition and use thereof that comprises fluoroolefins ".

The cross reference of related application

The application requires the right of priority of the U.S. Provisional Application 60/732,581 of submitting on November 1st, 2005 and the U.S. Patent application 11/486,791 of submitting on July 13rd, 2006.

Technical field

The present invention relates to the composition for refrigeration, air-conditioning or heat pump, wherein said composition comprises at least one fluoroolefins.Composition of the present invention can be used as the method for heat-transfer fluid for freezing or heating, and also can be used for many other purposes.

Background technology

Refrigeration industry is attempting to find the alternative refrigerant of Chlorofluorocarbons (CFCs) (CFC) and the Hydrochlorofluorocarbons (HCFC) of depletion ozone in the past few decades always, and CFC and HCFC are just eliminated gradually because of the signing of Montreal Protocol (Montreal Protocol).Most of refrigeration agent manufacturers' terms of settlement is business promotion hydrogen fluorohydrocarbon (HFC) refrigeration agent.The ozone depletion potential of new HFC refrigeration agent (that the most widely use at present is HFC-134a) is zero, therefore is not subject to the impact of the existing superseded control under Montreal Protocol.

Further environmental legislation may finally cause some HFC refrigeration agent to be eliminated in the whole world.At present, automobile industry is being faced with the rules of the global warming potential that relates to the used for automobile air conditioning refrigeration agent.Therefore, the current utmost point is required to be automative air conditioning market and determines the novel refrigerant that global warming potential reduces.If these rules scope of application in the future enlarges more, more needing can be for the refrigeration agent of all areas of refrigeration and air conditioner industry.

The alternative refrigerant of the HFC-134a proposed at present comprises that HFC-152a, pure hydrocarbon are as butane or propane, or " natural " refrigeration agent is as CO ₂.The substitute of many these proposals be all poisonous, flammable and/or energy efficiency low.Therefore, seeking new binary mixtures.

The purpose of this invention is to provide novel refrigerant composition and heat transfer fluid composition, these compositions can provide unique characteristic, take that to meet ozone depletion potential low or be zero; And compare lower these requirements of global warming potential with existing refrigeration agent.

Summary of the invention

The present invention relates to comprise at least one refrigeration agent that is selected from following compound or heat transfer fluid composition:

(i) formula E-or Z-R ¹cH=CHR ²fluoroolefins, R wherein ¹and R ²independent is C ₁-C ₆perfluoro alkyl group, and wherein the carbon in this compound adds up at least 5;

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

(iii) be selected from following fluoroolefins:

The fluoro-1-propylene of 2,3,3-tri-(CHF ₂CF=CH ₂); The fluoro-1-propylene of 1,1,2-tri-(CH ₃CF=CF ₂); The fluoro-1-propylene of 1,2,3-tri-(CH ₂FCF=CF ₂); The fluoro-1-propylene of 1,1,3-tri-(CH ₂FCH=CF ₂); The fluoro-1-propylene of 1,3,3-tri-(CHF ₂CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF ₃CF=CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (CF ₃CF=CHCF ₃); The fluoro-1-butylene of 1,2,3,3,4,4,4-seven (CHF=CFCF ₂CF ₃); The fluoro-2-butylene of 1,1,1,2,3,4,4-seven (CHF ₂CF=CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF ₃) ₂C=CHF); The fluoro-1-butylene of 1,1,3,3,4,4,4-seven (CF ₂=CHCF ₂CF ₃); The fluoro-1-butylene of 1,1,2,3,4,4,4-seven (CF ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,1,2,3,3,4,4-seven (CF ₂=CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF ₃CF ₂CF=CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF ₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF ₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF ₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF ₂CF=CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH ₂FCF=CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF ₂CH=CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF ₃CH=CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF ₂=CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF ₂=CFCHFCHF ₂); The fluoro-2-of 3,3,3-tri-(trifluoromethyl)-1-propylene (CH ₂=C (CF ₃) ₂); The fluoro-2-butylene of 1,1,1,2,4-five (CH ₂FCH=CFCF ₃); The fluoro-2-butylene of 1,1,1,3,4-five (CF ₃CH=CFCH ₂F); The fluoro-1-butylene of 3,3,4,4,4-five (CF ₃CF ₂CH=CH ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five (CHF ₂CH=CHCF ₃); The fluoro-2-butylene of 1,1,1,2,3-five (CH ₃CF=CFCF ₃); The fluoro-1-butylene of 2,3,3,4,4-five (CH ₂=CFCF ₂CHF ₂); The fluoro-2-butylene of 1,1,2,4,4-five (CHF ₂CF=CHCHF ₂); The fluoro-1-butylene of 1,1,2,3,3-five (CH ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,2,3,4-five (CH ₂FCF=CFCHF ₂); The fluoro-2-methyl-1-propylene of 1,1,3,3,3-five (CF ₂=C (CF ₃) (CH ₃)); 2-(difluoromethyl)-3,3, the fluoro-1-propylene of 3-tri-(CH ₂=C (CHF ₂) (CF ₃)); The fluoro-1-butylene of 2,3,4,4,4-five (CH ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,2,4,4,4-five (CHF=CFCH ₂CF ₃); The fluoro-1-butylene of 1,3,4,4,4-five (CHF=CHCHFCF ₃); The fluoro-1-butylene of 1,3,3,4,4-five (CHF=CHCF ₂CHF ₂); The fluoro-1-butylene of 1,2,3,4,4-five (CHF=CFCHFCHF ₂); 3,3,4,4-tetrafluoro-1-butylene (CH ₂=CHCF ₂CHF ₂); The fluoro-2-of 1,1-bis-(difluoromethyl)-1-propylene (CF ₂=C (CHF ₂) (CH ₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propylene (CHF=C (CF ₃) (CH ₃)); The fluoro-2-of 3,3-bis-(difluoromethyl)-1-propylene (CH ₂=C (CHF ₂) ₂); 1,1,1,2-tetrafluoro-2-butylene (CF ₃CF=CHCH ₃); 1,1,1,3-tetrafluoro-2-butylene (CH ₃CF=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (CF ₃CF=CFCF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5,5-ten (CF ₂=CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (CF ₃CF=CHCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (CF ₃CH=CFCF ₂CF ₃); The fluoro-1-amylene of 1,2,3,3,4,4,5,5,5-nine (CHF=CFCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,3,3,4,4,5,5,5-nine (CF ₂=CHCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5-nine (CF ₂=CFCF ₂CF ₂CHF ₂); The fluoro-2-amylene of 1,1,2,3,4,4,5,5,5-nine (CHF ₂CF=CFCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5-nine (CF ₃CF=CFCF ₂CHF ₂); The fluoro-2-amylene of 1,1,1,2,3,4,5,5,5-nine (CF ₃CF=CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF ₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CFCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF ₃CH=C (CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CHCF (CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH ₂=CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF ₂CF ₂CHF ₂); The fluoro-2-of 3,3,4,4,4-five (trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CF ₂CF ₃); 1, Isosorbide-5-Nitrae, the fluoro-3-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=CHCH (CF ₃) ₂); The fluoro-3-of 1,3,4,4,4-five (trifluoromethyl)-1-butylene (CHF=CHCF (CF ₃) ₂); 1, Isosorbide-5-Nitrae, the fluoro-2-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=C (CF ₃) CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF ₃) ₂CFCH=CH ₂); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂CH=CH ₂); The fluoro-1-amylene of 2,3,3,4,4,5,5-seven (CH ₂=CFCF ₂CF ₂CHF ₂); The fluoro-1-butylene of 1,1,3,3,5,5,5-seven (CF ₂=CHCF ₂CH ₂CF ₃); The fluoro-3-methyl-2-butene of 1,1,1,2,4,4,4-seven (CF ₃CF=C (CF ₃) (CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH ₂=CFCH (CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₂FCH=C (CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₃CF=C (CF ₃) ₂); The fluoro-2-of 1,1,1-tri-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCH ₃); 3,4,4,5,5,5-hexafluoro-2-amylene (CF ₃CF ₂CF=CHCH ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-methyl-2-butene (CF ₃C (CH ₃)=CHCF ₃); 3,3,4,5,5,5-hexafluoro-1-amylene (CH ₂=CHCF ₂CHFCF ₃); The fluoro-3-of 4,4,4-tri-(trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CH ₂CF ₃); The fluoro-1-hexene of 1,1,2,3,3,4,4,5,5,6,6,6-12 (CF ₃(CF ₂) ₃CF=CF ₂); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (CF ₃CF ₂CF=CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3- ₃) ₂C=C (CF ₃) ₂); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CHCF ₃); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (CF ₃CF ₂CF ₂CF ₂CH=CH ₂); 4,4,4-tri-is fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3- ₂=CHC (CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF ₃) ₂C=C (CH ₃) (CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CFCF ₂CH (CF ₃) ₂); The fluoro-3-methyl of 1,1,1,2,4,4,5,5,5-nine-2-amylene (CF ₃CF=C (CH ₃) CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF ₃CH=CHCH (CF ₃) ₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF ₃CF ₂CF ₂CF=CHCH ₃); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH ₂=CHCF ₂CF ₂CF ₂CHF ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-of 4-five (trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHCF ₂CH ₃); The fluoro-2-of 4,4,5,5,5-five (trifluoromethyl)-1-amylene (CH ₂=C (CF ₃) CH ₂C ₂F ₅); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂C (CH ₃)=CH ₂); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (CF ₃CF ₂CF ₂CH=CHCH ₃); The fluoro-1-hexene of 4,4,5,5,6,6,6-seven (CH ₂=CHCH ₂CF ₂C ₂F ₅); The fluoro-3-hexene of 1,1,1,2,2,3,4-seven (CF ₃CF ₂CF=CFC ₂H ₅); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CHCH ₂CF (CF ₃) ₂); The fluoro-4-methyl of 1,1,1,2,5,5,5-seven-2-amylene (CF ₃CF=CHCH (CF ₃) (CH ₃)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CFC ₂H ₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF ₃CF=CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF ₃CF ₂CF=CFCF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 (CF ₃CH=CFCF ₂CF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 (CF ₃CF=CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CH=CFCF ₂C ₂F ₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CF=CHCF ₂C ₂F ₅); CF ₂=CFOCF ₂CF ₃And CF (PEVE) ₂=CFOCF ₃(PMVE).

The invention further relates to and comprise (i) at least one fluoroolefin compounds and (ii) composition of at least one flammable refrigeration agent, wherein said fluoroolefins is selected from following:

(a) formula E-or Z-R ¹cH=CHR ²fluoroolefins, R wherein ¹and R ²independent is C ₁-C ₆perfluoro alkyl group;

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

(c) be selected from following fluoroolefins:

The fluoro-1-propylene of 1,2,3,3,3-five (CF ₃CF=CHF); The fluoro-1-propylene of 1,1,3,3,3-five (CF ₃CH=CF ₂); The fluoro-1-propylene of 1,1,2,3,3-five (CHF ₂CF=CF ₂); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF ₃CF=CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (CF ₃CF=CHCF ₃); The fluoro-1-butylene of 1,2,3,3,4,4,4-seven (CHF=CFCF ₂CF ₃); The fluoro-2-butylene of 1,1,1,2,3,4,4-seven (CHF ₂CF=CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF ₃) ₂C=CHF); The fluoro-1-butylene of 1,1,3,3,4,4,4-seven (CF ₂=CHCF ₂CF ₃); The fluoro-1-butylene of 1,1,2,3,4,4,4-seven (CF ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,1,2,3,3,4,4-seven (CF ₂=CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF ₃CF ₂CF=CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF ₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF ₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF ₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF ₂CF=CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH ₂FCF=CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF ₂CH=CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF ₃CH=CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF ₂=CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF ₂=CFCHFCHF ₂); The fluoro-2-of 3,3,3-tri-(trifluoromethyl)-1-propylene (CH ₂=C (CF ₃) ₂); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (CF ₃CF=CFCF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5,5-ten (CF ₂=CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (CF ₃CF=CHCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (CF ₃CH=CFCF ₂CF ₃); The fluoro-1-amylene of 1,2,3,3,4,4,5,5,5-nine (CHF=CFCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,3,3,4,4,5,5,5-nine (CF ₂=CHCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5-nine (CF ₂=CFCF ₂CF ₂CHF ₂); The fluoro-2-amylene of 1,1,2,3,4,4,5,5,5-nine (CHF ₂CF=CFCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5-nine (CF ₃CF=CFCF ₂CHF ₂); The fluoro-2-amylene of 1,1,1,2,3,4,5,5,5-nine (CF ₃CF=CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF ₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CFCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF ₃CH=C (CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CHCF (CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH ₂=CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF ₂CF ₂CHF ₂); The fluoro-2-of 3,3,4,4,4-five (trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CF ₂CF ₃); 1, Isosorbide-5-Nitrae, the fluoro-3-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=CHCH (CF ₃) ₂); The fluoro-3-of 1,3,4,4,4-five (trifluoromethyl)-1-butylene (CHF=CHCF (CF ₃) ₂); 1, Isosorbide-5-Nitrae, the fluoro-2-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=C (CF ₃) CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF ₃) ₂CFCH=CH ₂); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂CH=CH ₂); The fluoro-1-amylene of 2,3,3,4,4,5,5-seven (CH ₂=CFCF ₂CF ₂CHF ₂); The fluoro-1-butylene of 1,1,3,3,5,5,5-seven (CF ₂=CHCF ₂CH ₂CF ₃); The fluoro-3-methyl-2-butene of 1,1,1,2,4,4,4-seven (CF ₃CF=C (CF ₃) (CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH ₂=CFCH (CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₂FCH=C (CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₃CF=C (CF ₃) ₂); The fluoro-1-hexene of 1,1,2,3,3,4,4,5,5,6,6,6-12 (CF ₃(CF ₂) ₃CF=CF ₂); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (CF ₃CF ₂CF=CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3- ₃) ₂C=C (CF ₃) ₂); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CHCF ₃); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (CF ₃CF ₂CF ₂CF ₂CH=CH ₂); 4,4,4-tri-is fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3- ₂=CHC (CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF ₃) ₂C=C (CH ₃) (CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CFCF ₂CH (CF ₃) ₂); The fluoro-3-methyl of 1,1,1,2,4,4,5,5,5-nine-2-amylene (CF ₃CF=C (CH ₃) CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF ₃CH=CHCH (CF ₃) ₂); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF ₃CF=CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF ₃CF ₂CF=CFCF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 (CF ₃CH=CFCF ₂CF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 (CF ₃CF=CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CH=CFCF ₂C ₂F ₅) and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CF=CHCF ₂C ₂F ₅).

The invention further relates in refrigeration, air-conditioning or thermal-pump unit the method for using refrigeration agent or heat transfer fluid composition, described method comprises described composition is incorporated into and has (a) centrifugal compressor; (b) multistage centrifugal compressor or (c) in the described device of veneer (single slab)/one way (single pass) interchanger, wherein said refrigeration agent or heat transfer compositions are used for causing heating or cooling in described device; And wherein said refrigeration agent or heat transfer compositions comprise at least one and are selected from following fluoroolefins:

(i) formula E-or Z-R ¹cH=CHR ²fluoroolefins, R wherein ¹and R ²independent is C ₁-C ₆perfluoro alkyl group;

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

(iii) be selected from following fluoroolefins:

The fluoro-1-propylene of 1,2,3,3,3-five (CF ₃CF=CHF); The fluoro-1-propylene of 1,1,3,3,3-five (CF ₃CH=CF ₂); The fluoro-1-propylene of 1,1,2,3,3-five (CHF ₂CF=CF ₂); 1,2,3,3-tetrafluoro-1-propene (CHF ₂CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃CF=CH ₂); 1,3,3,3-tetrafluoro-1-propene (CF ₃CH=CHF); 1,1,2,3-tetrafluoro-1-propene (CH ₂FCF=CF ₂); 1,1,3,3-tetrafluoro-1-propene (CHF ₂CH=CF ₂); The fluoro-1-propylene of 2,3,3-tri-(CHF ₂CF=CH ₂); The fluoro-1-propylene of 3,3,3-tri-(CF ₃CH=CH ₂); The fluoro-1-propylene of 1,1,2-tri-(CH ₃CF=CF ₂); The fluoro-1-propylene of 1,1,3-tri-(CH ₂FCH=CF ₂); The fluoro-1-propylene of 1,2,3-tri-(CH ₂FCF=CHF); The fluoro-1-propylene of 1,3,3-tri-(CHF ₂CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF ₃CF=CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (CF ₃CF=CHCF ₃); The fluoro-1-butylene of 1,2,3,3,4,4,4-seven (CHF=CFCF ₂CF ₃); The fluoro-2-butylene of 1,1,1,2,3,4,4-seven (CHF ₂CF=CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF ₃) ₂C=CHF); The fluoro-1-butylene of 1,1,3,3,4,4,4-seven (CF ₂=CHCF ₂CF ₃); The fluoro-1-butylene of 1,1,2,3,4,4,4-seven (CF ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,1,2,3,3,4,4-seven (CF ₂=CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF ₃CF ₂CF=CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF ₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF ₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF ₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF ₂CF=CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH ₂FCF=CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF ₂CH=CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF ₃CH=CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF ₂=CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF ₂=CFCHFCHF ₂); The fluoro-2-of 3,3,3-tri-(trifluoromethyl)-1-propylene (CH ₂=C (CF ₃) ₂); The fluoro-2-butylene of 1,1,1,2,4-five (CH ₂FCH=CFCF ₃); The fluoro-2-butylene of 1,1,1,3,4-five (CF ₃CH=CFCH ₂F); The fluoro-1-butylene of 3,3,4,4,4-five (CF ₃CF ₂CH=CH ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five (CHF ₂CH=CHCF ₃); The fluoro-2-butylene of 1,1,1,2,3-five (CH ₃CF=CFCF ₃); The fluoro-1-butylene of 2,3,3,4,4-five (CH ₂=CFCF ₂CHF ₂); The fluoro-2-butylene of 1,1,2,4,4-five (CHF ₂CF=CHCHF ₂); The fluoro-1-butylene of 1,1,2,3,3-five (CH ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,2,3,4-five (CH ₂FCF=CFCHF ₂); The fluoro-2-methyl-1-propylene of 1,1,3,3,3-five (CF ₂=C (CF ₃) (CH ₃)); 2-(difluoromethyl)-3,3, the fluoro-1-propylene of 3-tri-(CH ₂=C (CHF ₂) (CF ₃)); The fluoro-1-butylene of 2,3,4,4,4-five (CH ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,2,4,4,4-five (CHF=CFCH ₂CF ₃); The fluoro-1-butylene of 1,3,4,4,4-five (CHF=CHCHFCF ₃); The fluoro-1-butylene of 1,3,3,4,4-five (CHF=CHCF ₂CHF ₂); The fluoro-1-butylene of 1,2,3,4,4-five (CHF=CFCHFCHF ₂); 3,3,4,4-tetrafluoro-1-butylene (CH ₂=CHCF ₂CHF ₂); The fluoro-2-of 1,1-bis-(difluoromethyl)-1-propylene (CF ₂=C (CHF ₂) (CH ₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propylene (CHF=C (CF ₃) (CH ₃)); 2-difluoromethyl-3, the fluoro-1-propylene of 3-bis-(CH ₂=C (CHF ₂) ₂); 1,1,1,2-tetrafluoro-2-butylene (CF ₃CF=CHCH ₃); 1,1,1,3-tetrafluoro-2-butylene (CH ₃CF=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (CF ₃CF=CFCF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5,5-ten (CF ₂=CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (CF ₃CF=CHCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (CF ₃CH=CFCF ₂CF ₃); The fluoro-1-amylene of 1,2,3,3,4,4,5,5,5-nine (CHF=CFCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,3,3,4,4,5,5,5-nine (CF ₂=CHCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5-nine (CF ₂=CFCF ₂CF ₂CHF ₂); The fluoro-2-amylene of 1,1,2,3,4,4,5,5,5-nine (CHF ₂CF=CFCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5-nine (CF ₃CF=CFCF ₂CHF ₂); The fluoro-2-amylene of 1,1,1,2,3,4,5,5,5-nine (CF ₃CF=CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF ₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CFCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF ₃CH=C (CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CHCF (CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH ₂=CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF ₂CF ₂CHF ₂); The fluoro-2-of 3,3,4,4,4-five (trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CF ₂CF ₃); 1, Isosorbide-5-Nitrae, the fluoro-3-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=CHCH (CF ₃) ₂); The fluoro-3-of 1,3,4,4,4-five (trifluoromethyl)-1-butylene (CHF=CHCF (CF ₃) ₂); 1, Isosorbide-5-Nitrae, the fluoro-2-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=C (CF ₃) CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF ₃) ₂CFCH=CH ₂); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂CH=CH ₂); The fluoro-1-amylene of 2,3,3,4,4,5,5-seven (CH ₂=CFCF ₂CF ₂CHF ₂); The fluoro-1-butylene of 1,1,3,3,5,5,5-seven (CF ₂=CHCF ₂CH ₂CF ₃); The fluoro-3-methyl-2-butene of 1,1,1,2,4,4,4-seven (CF ₃CF=C (CF ₃) (CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH ₂=CFCH (CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₂FCH=C (CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₃CF=C (CF ₃) ₂); The fluoro-2-of 1,1,1-tri-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCH ₃); 3,4,4,5,5,5-hexafluoro-2-amylene (CF ₃CF ₂CF=CHCH ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-methyl-2-butene (CF ₃C (CH ₃)=CHCF ₃); 3,3,4,5,5,5-hexafluoro-1-amylene (CH ₂=CHCF ₂CHFCF ₃); 3-(trifluoromethyl)-4,4, the fluoro-1-butylene of 4-tri-(CH ₂=C (CF ₃) CH ₂CF ₃); The fluoro-1-hexene of 1,1,2,3,3,4,4,5,5,6,6,6-12 (CF ₃(CF ₂) ₃CF=CF ₂); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (CF ₃CF ₂CF=CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3- ₃) ₂C=C (CF ₃) ₂); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CHCF ₃); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (CF ₃CF ₂CF ₂CF ₂CH=CH ₂); 4,4,4-tri-is fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3- ₂=CHC (CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=C (CH ₃) (CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CFCF ₂CH (CF ₃) ₂); The fluoro-3-methyl of 1,1,1,2,4,4,5,5,5-nine-2-amylene (CF ₃CF=C (CH ₃) CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF ₃CH=CHCH (CF ₃) ₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF ₃CF ₂CF ₂CF=CHCH ₃); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH ₂=CHCF ₂CF ₂CF ₂CHF ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-of 4-five (trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHCF ₂CH ₃); The fluoro-2-of 4,4,5,5,5-five (trifluoromethyl)-1-amylene (CH ₂=C (CF ₃) CH ₂C ₂F ₅); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂C (CH ₃)=CH ₂); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (CF ₃CF ₂CF ₂CH=CHCH ₃); The fluoro-1-hexene of 4,4,5,5,6,6,6-seven (CH ₂=CHCH ₂CF ₂C ₂F ₅); The fluoro-3-hexene of 1,1,1,2,2,3,4-seven (CF ₃CF ₂CF=CFC ₂H ₅); 4,5,5,5-tetrafluoro-4-Trifluoromethyl-1-amylene (CH ₂=CHCH ₂CF (CF ₃) ₂); The fluoro-4-methyl of 1,1,1,2,5,5,5-seven-2-amylene (CF ₃CF=CHCH (CF ₃) (CH ₃)); 1,1,1,3-tetrafluoro-2-trifluoromethyl-2-amylene ((CF ₃) ₂C=CFC ₂H ₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF ₃CF=CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF ₃CF ₂CF=CFCF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 (CF ₃CH=CFCF ₂CF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 (CF ₃CF=CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CH=CFCF ₂C ₂F ₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CF=CHCF ₂C ₂F ₅); CF ₂=CFOCF ₂CF ₃(PEVE); CF ₂=CFOCF ₃And their combination (PMVE).

detailed Description Of The Invention

The present invention relates to the composition that comprises at least one fluoroolefins.So-called fluoroolefins refers to that any carbon, fluorine and optional hydrogen or oxygen of containing also also contains the compound of at least one two key.These fluoroolefins can be straight chain, side chain or ring-type.

These compositions serve many purposes in working fluid, comprise such as being used as whipping agent (foaming agent), pore forming material (blowing agent), fire-fighting medium, heat-transfer medium (as heat-transfer fluid and the refrigeration agent for refrigeration system, refrigerator, air-conditioning system, heat pump, water cooler etc.).

Heat-transfer fluid (also claiming in this article heat transfer compositions or heat transfer fluid composition) is in order to heat is sent to the working fluid of heat sink from thermal source.

Refrigeration agent is to serve as the compound of heat-transfer fluid or the mixture of compound in the circulation that fluid experience liquid-gas and gas and liquid phase become therein.

The invention provides and there is formula E-or Z-R ¹cH=CHR ²the fluoroolefins of (formula I), wherein R ¹and R ²independent is C ₁-C ₆perfluoro alkyl group.R ¹and R ²the example of group includes but not limited to CF ₃, C ₂f ₅, CF ₂cF ₂cF ₃, CF (CF ₃) ₂, CF ₂cF ₂cF ₂cF ₃, CF (CF ₃) CF ₂cF ₃, CF ₂cF (CF ₃) ₂, C (CF ₃) ₃, CF ₂cF ₂cF ₂cF ₂cF ₃, CF ₂cF ₂cF (CF ₃) ₂, C (CF ₃) ₂c ₂f ₅, CF ₂cF ₂cF ₂cF ₂cF ₂cF ₃, CF (CF ₃) CF ₂cF ₂c ₂f ₅and C (CF ₃) ₂cF ₂c ₂f ₅.In one embodiment, in the molecule of formula I fluoroolefins, have at least about 3 carbon atoms.In another embodiment, in the molecule of formula I fluoroolefins, have at least about 4 carbon atoms.In another embodiment, in the molecule of formula I fluoroolefins, have at least about 5 carbon atoms.Table 1 provides exemplary non-limiting formula I compound.

table 1

Can prepare by formula I compound: make formula R like this ¹the perfluoroalkyl iodides of I and formula R ²cH=CH ₂perfluoroalkyl three hydrogen alkene contact and form formula R ¹cH ₂cHIR ²three hydrogen iodo perfluoro alkane.Then this three hydrogen iodo perfluoro alkane can form R through dehydrogenation iodine (dehydroiodinated) ¹cH=CHR ².Perhaps, alkene R ¹cH=CHR ²can prepare like this: make formula R ²the perfluoroalkyl iodides of I and formula R ¹cH=CH ₂perfluoroalkyl three hydrogen olefine reactions form formula R ¹cHICH ₂r ²three hydrogen iodo perfluoro alkane, then the latter is carried out to the dehydrogenation Iod R.

Contacting of described perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene can be with batch mode, by being mixed to occur in the suitable reaction vessels that each reactant is operated under the autogenous pressure that can produce under temperature of reaction at each reactant and product.Suitable reaction vessel comprise by stainless steel (particularly austenitic stainless steel) and known Langaloy as

nickel-copper alloy,

nickel-base alloy and

the reaction vessel that nickel-chromium alloy is manufactured.

Perhaps, reaction can be carried out in the semi-batch mode, in such a way, by suitable adding apparatus, as pump, perfluoroalkyl three hydrogen olefin reactants is joined to the perfluoroalkyl iodides reactant under temperature of reaction.

The ratio of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene should approximately 1: 1 to approximately between 4: 1, preferably approximately 1.5: 1-2.5: 1.As Journal of Fluorine Chemistry such as Jeanneaux, Vol.4, pages 261-270 (1974) reports, the ratio that is less than 1.5: 1 easily causes producing a large amount of 2: 1 adductss (adduct).

The preferred temperature contacted of described perfluoroalkyl iodides and described perfluoroalkyl three hydrogen alkene, preferably approximately 150 ℃-300 ℃, preferably approximately 170 ℃ to approximately 250 ℃, 180 ℃ of extremely about scopes of 230 ℃ most preferably from about.

Perfluoroalkyl iodides be the suitable duration of contact of reacting of perfluoroalkyl three hydrogen alkene approximately 0.5 hour-18 hours, preferably approximately 4 to approximately 12 hours.

The three hydrogen iodo perfluoro alkane that prepare with reacting of perfluoroalkyl three hydrogen alkene by perfluoroalkyl iodides can be directly used in dehydrogenation Iod R step, or preferably before for dehydrogenation Iod R step, are first reclaimed and distillation purifying.

Dehydrogenation Iod R step is by making three hydrogen iodo perfluoro alkane be contacted to carry out with alkaline matter.Suitable alkaline matter comprises that the mixture of alkali metal hydroxide (for example sodium hydroxide or potassium hydroxide), alkalimetal oxide (for example sodium oxide), alkaline earth metal hydroxides (for example calcium hydroxide), alkaline earth metal oxide (for example calcium oxide), alkali metal alcoholates (for example sodium methylate or sodium ethylate), ammoniacal liquor, sodium amide or alkaline matter is as soda-lime.Preferred alkaline matter is sodium hydroxide and potassium hydroxide.

Described three hydrogen iodo perfluoro alkane contact with alkaline matter, can, in liquid phase, preferably under the solvent of at least a portion that can dissolve two kinds of reactants exists, occur.The solvent that is adapted to dehydrogenation Iod R step comprises that one or more polar organic solvents for example, for example, as alcohol (methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol), nitrile (acetonitrile, propionitrile, butyronitrile, benzonitrile or adiponitrile), methyl-sulphoxide, N, dinethylformamide, N,N-dimethylacetamide or tetramethylene sulfone.The selection of solvent can according in the boiling point of product and purge process from the easy degree of product separation trace solvent and determine.Usually, ethanol or Virahol are the good solvents of reaction.

Usually, the dehydrogenation Iod R can be undertaken by the another kind of reactant that a kind of reactant (alkaline matter or three hydrogen iodo perfluoro alkane) is added in suitable reaction vessels.Described reaction vessel can be by glass, pottery or metal manufacture, and preferably with impeller or stirring mechanism, is stirred.

The optimal temperature of dehydrogenation Iod R is approximately 10 ℃ to approximately 100 ℃, preferably approximately 20 ℃ to approximately 70 ℃.The dehydrogenation Iod R can carry out under environmental stress, or carries out in decompression or under boosting.It is worth mentioning that such dehydrogenation Iod R, the formation along with formula I compound in this reaction distills it from reaction vessel.

Perhaps, the dehydrogenation Iod R can contact to carry out with under the existence of solution at phase-transfer catalyst of three hydrogen iodo perfluoro alkane in one or more low polar organic solvents by the aqueous solution that makes described alkaline matter, described organic solvent for example, as alkane (hexane, heptane or octane), aromatic hydrocarbons (for example toluene), halohydrocarbon (methylene dichloride for example, chloroform, tetracol phenixin or tetrachloroethylene) or ether (diethyl ether for example, methyl tertiary butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, diglyme or tetraethylene glycol dimethyl ether).Suitable phase-transfer catalyst comprises quaternary ammonium halides salt (for example Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride and three capryloyl ammonio methacrylates), halogenation season salt (trityl group bromination for example and tetraphenylphosphonichloride chloride

) or this area be called the cyclic polyether compound (for example 18-hat-6 and 15-hat-5) of crown ether.

Perhaps, the dehydrogenation Iod R can be undertaken by three hydrogen iodo perfluoro alkane are added to solid-state or liquid alkaline matter in the presence of not at solvent.

The suitable reactions time of dehydrogenation Iod R be approximately 15 minutes to approximately 6 hours or the longer time, this depends on the solubleness of reactant.Usually, the dehydrogenation Iod R is fast, needs approximately within 30 minutes, extremely approximately within 3 hours, just to complete.

Formula I compound can be separated after adding water, by distilling or reclaiming from dehydrogenation Iod R mixture by the combination of aforementioned two kinds of methods.

In another embodiment of the invention, fluoroolefins comprises ring-type fluoroolefins (ring-[CX=CY (CZW) _n-] (formula II), wherein X, Y, Z and W independently are selected from H and F, the integer that n is 2-5).Table 2 is listed representational formula II ring-type fluoroolefins.

Table 2

In another embodiment, fluoroolefins can comprise those compounds that table 3 is listed.

table 3

The listed compound of table 2 and table 3 is commercially available, or can be prepared by method well known in the art or described herein.

1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five can pass through 1,1,1,2,4,4-hexafluoro butane (CHF ₂cH ₂cHFCF ₃) at room temperature with gas phase state, with solid KOH, carry out dehydrogenation fluorine reaction (dehydrofluorination) and prepare.The synthetic US6 that is described in of 1,1,1,2,4,4-hexafluoro butane, 066,768, this patent is incorporated herein by reference.

1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene can be by with phase-transfer catalyst, making 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-sec.-butyl iodide (CF ₃cHICH ₂cF ₃) with KOH, approximately reacted to prepare under 60 ℃.1,1, Isosorbide-5-Nitrae, the synthetic of 4,4-hexafluoro-sec.-butyl iodide can be by making perfluoro-methyl iodine (CF ₃i) and 3,3,3-trifluoro propene (CF ₃cH=CH ₂) approximately reacting and approximately within 8 hours, carrying out under autogenous pressure under 200 ℃.

3,4,4,5,5,5-hexafluoro-2-amylene can be by carrying out 1,1,1,2,2,3,3-, seven amyl fluoride (CF under 200-300 ℃ with solid KOH or with C catalyst ₃cF ₂cF ₂cH ₂cH ₃) the dehydrogenation fluorine react to prepare.1,1,1,2,2,3,3-, seven amyl fluorides can pass through the fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃cF ₂cF ₂cH=CH ₂) hydrogenation prepare.

1,1,1,2,3,4-hexafluoro-2-butylene can be by carrying out 1,1,1,2,3,3,4-, seven fluorine butane (CH with solid KOH ₂fCF ₂cHFCF ₃) the dehydrogenation fluorine react to prepare.

1,1,1,2,4,4-hexafluoro-2-butylene can be by carrying out 1,1,1,2,2,4,4-, seven fluorine butane (CHF with solid KOH ₂cH ₂cF ₂cF ₃) the dehydrogenation fluorine react to prepare.

1,1,1,3,4,4-hexafluoro 2-butylene can be by carrying out 1,1,1,3,3,4,4-, seven fluorine butane (CF with solid KOH ₃cH ₂cF ₂cHF ₂) the dehydrogenation fluorine react to prepare.

The fluoro-2-butylene of 1,1,1,2,4-five can be by carrying out 1,1,1,2,2,3-hexafluoro butane (CH with solid KOH ₂fCH ₂cF ₂cF ₃) the dehydrogenation fluorine react to prepare.

The fluoro-2-butylene of 1,1,1,3,4-five can be by carrying out 1,1,1,3,3,4-hexafluoro butane (CF with solid KOH ₃cH ₂cF ₂cH ₂f) dehydrogenation fluorine reacts to prepare.

1,1,1,3-tetrafluoro-2-butylene can be by making 1,1,1,3,3-3-pentafluorobutane (CF ₃cH ₂cF ₂cH ₃) with the KOH aqueous solution, under 120 ℃, react to prepare.

1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene can be by making (CF with phase-transfer catalyst ₃cHICH ₂cF ₂cF ₃) with KOH, approximately reacting to prepare under 60 ℃.4-is iodo-1,1,1,2,2,5,5, and the synthetic of 5-octafluoro pentane can be by making perfluoro ethyl iodide (CF ₃cF ₂i) and 3,3,3-trifluoro propene approximately reacting under 200 ℃ and approximately within 8 hours, carrying out under autogenous pressure.

The fluoro-3-hexene of 1,1,1,2,2,5,5,6,6,6-ten can be by making the fluoro-3-iodohexane of 1,1,1,2,2,5,5,6,6,6-ten (CF with phase-transfer catalyst ₃cF ₂cHICH ₂cF ₂cF ₃) with KOH, approximately reacting to prepare under 60 ℃.The synthetic of the fluoro-3-iodohexane of 1,1,1,2,2,5,5,6,6,6-ten can be by making perfluoro ethyl iodide (CF ₃cF ₂i) and the fluoro-1-butylene (CF of 3,3,4,4,4-five ₃cF ₂cH=CH ₂) approximately reacting and approximately within 8 hours, carrying out under autogenous pressure under 200 ℃.

1,1, Isosorbide-5-Nitrae, the fluoro-4-of 5,5,5-seven (trifluoromethyl)-2-amylene can be by making the iodo-2-of the fluoro-4-of 1,1,1,2,5,5,5-seven (trifluoromethyl)-pentane (CF in Virahol with KOH ₃cHICH ₂cF (CF ₃) ₂) the dehydrogenation fluorine occurs react to prepare.CF ₃cHICH ₂cF (CF ₃) ₂by making (CF ₃) ₂cFI and CF ₃cH=CH ₂react under 200 ℃ and prepare according to appointment at high temperature.

1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten can be by 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (CF ₃cH=CHCF ₃) and tetrafluoroethylene (CF ₂=CF ₂) and antimony pentafluoride (SbF ₅) reaction prepare.

The fluoro-1-butylene of 2,3,3,4,4-five can react to prepare by high temperature make 1,1,2,2,3,3-hexafluoro butane carry out the dehydrogenation fluorine by fluorided alumina.

2,3,3,4,4,5,5,5-octafluoro-1-amylene can react to prepare by make 2,2,3,3,4,4,5,5,5-, nine amyl fluorides carry out the dehydrogenation fluorine with solid KOH.

1,2,3,3,4,4,5,5-octafluoro-1-amylene can react to prepare by high temperature make 2,2,3,3,4,4,5,5,5-, nine amyl fluorides carry out the dehydrogenation fluorine by fluorided alumina.

Composition of the present invention can comprise the single compound of formula I, formula II or table 3, or can comprise the combination of described compound.Perhaps, many formula I, formula II and table 3 compound can exist with the form of different configurational isomers or steric isomer.The invention is intended to comprise all single configurational isomers, single stereoisomers or their any combination.For example, 1,3,3,3-tetrafluoeopropene (HFC-1234ze) means to represent E-isomer, Z-isomer or this two kinds of isomer any combination or mixture with any ratio.Another example is F12E, and it is representing E-isomer, Z-isomer or this two kinds of isomer any combination or mixture with any ratio.

Composition of the present invention has zero or low-ozone depletion potential and low global warming potential (GWP).The mixture of fluoroolefins of the present invention or fluoroolefins of the present invention and other refrigeration agent, its global warming potential can be less than many fluoroether refrigerants of current use.One aspect of the present invention is to provide global warming potential and is less than 1000, is less than 500, is less than 150, is less than 100 or be less than 50 refrigeration agent.Another aspect of the present invention is by add fluoroolefins to reduce the clean GWP of described mixture to refrigerant mixture.

The present composition as combination or mixture can be mixed each composition of aequum to prepare by any method easily.Preferred method is to take the required component that respectively becomes, and then each composition is mixed in suitable container.Can adopt if needed and stir operation.

The method for preparing the present composition of alternative comprises: one or more refrigerant composition compositions that (i) from least one cryogen vessel, reclaim certain volume, (ii) fully remove impurity, the composition of described one or more recovery can be re-used, (iii) optionally, by each composition of the described recovery volume of all or part, refrigerant composition or the composition other with at least one mixed.

Cryogen vessel can be any container that wherein stores the refrigeration agent blend composition (refrigerant blend composition) that has been used to refrigeration plant, air-conditioning plant or thermal-pump unit.Described cryogen vessel can be refrigeration plant, air-conditioning plant or the thermal-pump unit that wherein uses this refrigeration agent adulterant (refrigerant blend).In addition, cryogen vessel can be for collecting the storage vessel of each refrigeration agent fusion composition (refrigerant blend components) reclaimed, including but not limited to pressurized gas cylinder.

The residual refrigeration agent refers to refrigeration agent adulterant or refrigeration agent fusion composition any amount, that can shift out from cryogen vessel by any method that becomes known for diverted refrigerant adulterant or refrigeration agent fusion composition.

Impurity can be that any because of refrigeration agent adulterant or refrigeration agent fusion composition, the use in refrigeration plant, air-conditioning plant or thermal-pump unit is present in the composition in this refrigeration agent adulterant or refrigeration agent fusion composition.This impurity includes but not limited to refrigeration lubricant (those refrigeration lubricants as herein described); Particulate matter, as may be from refrigeration plant, air-conditioning plant or thermal-pump unit metal or elastomerics out; With any other pollutent that may adversely affect the performance of refrigeration agent blend composition.

This impurity fully can be removed, minute be re-used to allow refrigeration agent adulterant or refrigeration agent be blended into, and don't can disadvantageous effect wherein use the performance of the equipment of refrigeration agent adulterant or refrigeration agent fusion composition.

May need provides other refrigeration agent adulterant or refrigeration agent fusion composition to remaining refrigeration agent adulterant or refrigeration agent fusion composition, to produce the composition that meets given product regulation.For example, if the refrigeration agent adulterant has 3 kinds of compositions in the specified weight percentage range, may add one or more compositions with specified rate, so that composition returns in the regulation compass.

The present composition that can be used as refrigeration agent or heat-transfer fluid comprises at least one and is selected from following fluoroolefins:

(iii) be selected from following fluoroolefins:

The fluoro-1-propylene of 1,2,3,3,3-five (CF ₃CF=CHF); The fluoro-1-propylene of 1,1,3,3,3-five (CF ₃CH=CF ₂); The fluoro-1-propylene of 1,1,2,3,3-five (CHF ₂CF=CF ₂); 1,2,3,3-tetrafluoro-1-propene (CHF ₂CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃CF=CH ₂); 1,1,2,3-tetrafluoro-1-propene (CH ₂FCF=CF ₂); 1,1,3,3-tetrafluoro-1-propene (CHF ₂CH=CF ₂); The fluoro-1-propylene of 2,3,3-tri-(CHF ₂CF=CH ₂); The fluoro-1-propylene of 3,3,3-tri-(CF ₃CH=CH ₂); The fluoro-1-propylene of 1,1,2-tri-(CH ₃CF=CF ₂); The fluoro-1-propylene of 1,2,3-tri-(CH ₂FCF=CF ₂); The fluoro-1-propylene of 1,1,3-tri-(CH ₂FCH=CF ₂); The fluoro-1-propylene of 1,3,3-tri-(CHF ₂CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF ₃CF=CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (CF ₃CF=CHCF ₃); The fluoro-1-butylene of 1,2,3,3,4,4,4-seven (CHF=CFCF ₂CF ₃); The fluoro-2-butylene of 1,1,1,2,3,4,4-seven (CHF ₂CF=CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF ₃) ₂C=CHF); The fluoro-1-butylene of 1,1,3,3,4,4,4-seven (CF ₂=CHCF ₂CF ₃); The fluoro-1-butylene of 1,1,2,3,4,4,4-seven (CF ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,1,2,3,3,4,4-seven (CF ₂=CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF ₃CF ₂CF=CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF ₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF ₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF ₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF ₂CF=CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH ₂FCF=CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF ₂CH=CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF ₃CH=CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF ₂=CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF ₂=CFCHFCHF ₂); The fluoro-2-of 3,3,3-tri-(trifluoromethyl)-1-propylene (CH ₂=C (CF ₃) ₂); The fluoro-2-butylene of 1,1,1,2,4-five (CH ₂FCH=CFCF ₃); The fluoro-2-butylene of 1,1,1,3,4-five (CF ₃CH=CFCH ₂F); The fluoro-1-butylene of 3,3,4,4,4-five (CF ₃CF ₂CH=CH ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five (CHF ₂CH=CHCF ₃); The fluoro-2-butylene of 1,1,1,2,3-five (CH ₃CF=CFCF ₃); The fluoro-1-butylene of 2,3,3,4,4-five (CH ₂=CFCF ₂CHF ₂); The fluoro-2-butylene of 1,1,2,4,4-five (CHF ₂CF=CHCHF ₂); The fluoro-1-butylene of 1,1,2,3,3-five (CH ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,2,3,4-five (CH ₂FCF=CFCHF ₂); The fluoro-2-methyl-1-propylene of 1,1,3,3,3-five (CF ₂=C (CF ₃) (CH ₃)); 2-(difluoromethyl)-3,3, the fluoro-1-propylene of 3-tri-(CH ₂=C (CHF ₂) (CF ₃)); The fluoro-1-butylene of 2,3,4,4,4-five (CH ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,2,4,4,4-five (CHF=CFCH ₂CF ₃); The fluoro-1-butylene of 1,3,4,4,4-five (CHF=CHCHFCF ₃); The fluoro-1-butylene of 1,3,3,4,4-five (CHF=CHCF ₂CHF ₂); The fluoro-1-butylene of 1,2,3,4,4-five (CHF=CFCHFCHF ₂); 3,3,4,4-tetrafluoro-1-butylene (CH ₂=CHCF ₂CHF ₂); The fluoro-2-of 1,1-bis-(difluoromethyl)-1-propylene (CF ₂=C (CHF ₂) (CH ₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propylene (CHF=C (CF ₃) (CH ₃)); The fluoro-2-of 3,3-bis-(difluoromethyl)-1-propylene (CH ₂=C (CHF ₂) ₂); 1,1,1,2-tetrafluoro-2-butylene (CF ₃CF=CHCH ₃); 1,1,1,3-tetrafluoro-2-butylene (CH ₃CF=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (CF ₃CF=CFCF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5,5-ten (CF ₂=CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (CF ₃CF=CHCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (CF ₃CH=CFCF ₂CF ₃); The fluoro-1-amylene of 1,2,3,3,4,4,5,5,5-nine (CHF=CFCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,3,3,4,4,5,5,5-nine (CF ₂=CHCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5-nine (CF ₂=CFCF ₂CF ₂CHF ₂); The fluoro-2-amylene of 1,1,2,3,4,4,5,5,5-nine (CHF ₂CF=CFCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5-nine (CF ₃CF=CFCF ₂CHF ₂); The fluoro-2-amylene of 1,1,1,2,3,4,5,5,5-nine (CF ₃CF=CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF ₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CFCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF ₃CH=C (CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CHCF (CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH ₂=CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF ₂CF ₂CHF ₂); The fluoro-2-of 3,3,4,4,4-five (trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CF ₂CF ₃); 1, Isosorbide-5-Nitrae, the fluoro-3-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=CHCH (CF ₃) ₂); The fluoro-3-of 1,3,4,4,4-five (trifluoromethyl)-1-butylene (CHF=CHCF (CF ₃) ₂); 1, Isosorbide-5-Nitrae, the fluoro-2-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=C (CF ₃) CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF ₃) ₂CFCH=CH ₂); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂CH=CH ₂); The fluoro-1-amylene of 2,3,3,4,4,5,5-seven (CH ₂=CFCF ₂CF ₂CHF ₂); The fluoro-1-butylene of 1,1,3,3,5,5,5-seven (CF ₂=CHCF ₂CH ₂CF ₃); The fluoro-3-methyl-2-butene of 1,1,1,2,4,4,4-seven (CF ₃CF=C (CF ₃) (CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH ₂=CFCH (CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₂FCH=C (CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₃CF=C (CF ₃) ₂); The fluoro-2-of 1,1,1-tri-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCH ₃); 3,4,4,5,5,5-hexafluoro-2-amylene (CF ₃CF ₂CF=CHCH ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-methyl-2-butene (CF ₃C (CH ₃)=CHCF ₃); 3,3,4,5,5,5-hexafluoro-1-amylene (CH ₂=CHCF ₂CHFCF ₃); The fluoro-3-of 4,4,4-tri-(trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CH ₂CF ₃); The fluoro-1-hexene of 1,1,2,3,3,4,4,5,5,6,6,6-12 (CF ₃(CF ₂) ₃CF=CF ₂); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (CF ₃CF ₂CF=CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3- ₃) ₂C=C (CF ₃) ₂); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CHCF ₃); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (CF ₃CF ₂CF ₂CF ₂CH=CH ₂); 4,4,4-tri-is fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3- ₂=CHC (CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF ₃) ₂C=C (CH ₃) (CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CFCF ₂CH (CF ₃) ₂); The fluoro-3-methyl of 1,1,1,2,4,4,5,5,5-nine-2-amylene (CF ₃CF=C (CH ₃) CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF ₃CH=CHCH (CF ₃) ₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF ₃CF ₂CF ₂CF=CHCH ₃); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH ₂=CHCF ₂CF ₂CF ₂CHF ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-of 4-five (trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHCF ₂CH ₃); The fluoro-2-of 4,4,5,5,5-five (trifluoromethyl)-1-amylene (CH ₂=C (CF ₃) CH ₂C ₂F ₅); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂C (CH ₃)=CH ₂); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (CF ₃CF ₂CF ₂CH=CHCH ₃); The fluoro-1-hexene of 4,4,5,5,6,6,6-seven (CH ₂=CHCH ₂CF ₂C ₂F ₅); The fluoro-3-hexene of 1,1,1,2,2,3,4-seven (CF ₃CF ₂CF=CFC ₂H ₅); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CHCH ₂CF (CF ₃) ₂); The fluoro-4-methyl of 1,1,1,2,5,5,5-seven-2-amylene (CF ₃CF=CHCH (CF ₃) (CH ₃)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CFC ₂H ₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF ₃CF=CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF ₃CF ₂CF=CFCF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 (CF ₃CH=CFCF ₂CF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 (CF ₃CF=CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CH=CFCF ₂C ₂F ₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CF=CHCF ₂C ₂F ₅); CF ₂=CFOCF ₂CF ₃(PE VE) and CF ₂=CFOCF ₃(PMVE).

The invention still further relates to the composition that comprises at least one fluoroolefins and at least one flammable refrigeration agent or heat-transfer fluid, wherein said fluoroolefins is selected from:

(iii) be selected from following fluoroolefins:

The fluoro-1-propylene of 1,2,3,3,3-five (CF ₃CF=CHF); The fluoro-1-propylene of 1,1,3,3,3-five (CF ₃CH=CF ₂); The fluoro-1-propylene of 1,1,2,3,3-five (CHF ₂CF=CF ₂); 1,2,3,3-tetrafluoro-1-propene (CHF ₂CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF ₃CF=CH ₂); 1,1,2,3-tetrafluoro-1-propene (CH ₂FCF=CF ₂); 1,1,3,3-tetrafluoro-1-propene (CHF ₂CH=CF ₂); The fluoro-1-propylene of 2,3,3-tri-(CHF ₂CF=CH ₂); The fluoro-1-propylene of 3,3,3-tri-(CF ₃CH=CH ₂); The fluoro-1-propylene of 1,1,2-tri-(CH ₃CF=CF ₂); The fluoro-1-propylene of 1,2,3-tri-(CH ₂FCF=CF ₂); The fluoro-1-propylene of 1,1,3-tri-(CH ₂FCH=CF ₂); The fluoro-1-propylene of 1,3,3-tri-(CHF ₂CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF ₃CF=CFCF ₃); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (CF ₃CF=CHCF ₃); The fluoro-1-butylene of 1,2,3,3,4,4,4-seven (CHF=CFCF ₂CF ₃); The fluoro-2-butylene of 1,1,1,2,3,4,4-seven (CHF ₂CF=CFCF ₃); 1,3,3,3-tetrafluoro-2-(trifluoromethyl)-1-propylene ((CF ₃) ₂C=CHF); The fluoro-1-butylene of 1,1,3,3,4,4,4-seven (CF ₂=CHCF ₂CF ₃); The fluoro-1-butylene of 1,1,2,3,4,4,4-seven (CF ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,1,2,3,3,4,4-seven (CF ₂=CFCF ₂CHF ₂); 2,3,3,4,4,4-hexafluoro-1-butylene (CF ₃CF ₂CF=CH ₂); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF ₂CF ₃); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF ₃); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF ₂CHF ₂); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF ₂CF=CFCHF ₂); 1,1,1,2,3,4-hexafluoro-2-butylene (CH ₂FCF=CFCF ₃); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF ₂CH=CFCF ₃); 1,1,1,3,4,4-hexafluoro-2-butylene (CF ₃CH=CFCHF ₂); 1,1,2,3,3,4-hexafluoro-1-butylene (CF ₂=CFCF ₂CH ₂F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF ₂=CFCHFCHF ₂); The fluoro-2-of 3,3,3-tri-(trifluoromethyl)-1-propylene (CH ₂=C (CF ₃) ₂); The fluoro-2-butylene of 1,1,1,2,4-five (CH ₂FCH=CFCF ₃); The fluoro-2-butylene of 1,1,1,3,4-five (CF ₃CH=CFCH ₂F); The fluoro-1-butylene of 3,3,4,4,4-five (CF ₃CF ₂CH=CH ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five (CHF ₂CH=CHCF ₃); The fluoro-2-butylene of 1,1,1,2,3-five (CH ₃CF=CFCF ₃); The fluoro-1-butylene of 2,3,3,4,4-five (CH ₂=CFCF ₂CHF ₂); The fluoro-2-butylene of 1,1,2,4,4-five (CHF ₂CF=CHCHF ₂); The fluoro-1-butylene of 1,1,2,3,3-five (CH ₃CF ₂CF=CF ₂); The fluoro-2-butylene of 1,1,2,3,4-five (CH ₂FCF=CFCHF ₂); The fluoro-2-methyl-1-propylene of 1,1,3,3,3-five (CF ₂=C (CF ₃) (CH ₃)); 2-(difluoromethyl)-3,3, the fluoro-1-propylene of 3-tri-(CH ₂=C (CHF ₂) (CF ₃)); The fluoro-1-butylene of 2,3,4,4,4-five (CH ₂=CFCHFCF ₃); The fluoro-1-butylene of 1,2,4,4,4-five (CHF=CFCH ₂CF ₃); The fluoro-1-butylene of 1,3,4,4,4-five (CHF=CHCHFCF ₃); The fluoro-1-butylene of 1,3,3,4,4-five (CHF=CHCF ₂CHF ₂); The fluoro-1-butylene of 1,2,3,4,4-five (CHF=CFCHFCHF ₂); 3,3,4,4-tetrafluoro-1-butylene (CH ₂=CHCF ₂CHF ₂); The fluoro-2-of 1,1-bis-(difluoromethyl)-1-propylene (CF ₂=C (CHF ₂) (CH ₃)); 1,3,3,3-tetrafluoro-2-methyl-1-propylene (CHF=C (CF ₃) (CH ₃)); The fluoro-2-of 3,3-bis-(difluoromethyl)-1-propylene (CH ₂=C (CHF ₂) ₂); 1,1,1,2-tetrafluoro-2-butylene (CF ₃CF=CHCH ₃); 1,1,1,3-tetrafluoro-2-butylene (CH ₃CF=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (CF ₃CF=CFCF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5,5-ten (CF ₂=CFCF ₂CF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCF ₃); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (CF ₃CF=CHCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (CF ₃CH=CFCF ₂CF ₃); The fluoro-1-amylene of 1,2,3,3,4,4,5,5,5-nine (CHF=CFCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,3,3,4,4,5,5,5-nine (CF ₂=CHCF ₂CF ₂CF ₃); The fluoro-1-amylene of 1,1,2,3,3,4,4,5,5-nine (CF ₂=CFCF ₂CF ₂CHF ₂); The fluoro-2-amylene of 1,1,2,3,4,4,5,5,5-nine (CHF ₂CF=CFCF ₂CF ₃); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5-nine (CF ₃CF=CFCF ₂CHF ₂); The fluoro-2-amylene of 1,1,1,2,3,4,5,5,5-nine (CF ₃CF=CFCHFCF ₃); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF ₃) ₂); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CFCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF ₃CH=C (CF ₃) ₂); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF ₂=CHCF (CF ₃) ₂); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH ₂=CFCF ₂CF ₂CF ₃); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF ₂CF ₂CHF ₂); The fluoro-2-of 3,3,4,4,4-five (trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CF ₂CF ₃); 1, Isosorbide-5-Nitrae, the fluoro-3-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=CHCH (CF ₃) ₂); The fluoro-3-of 1,3,4,4,4-five (trifluoromethyl)-1-butylene (CHF=CHCF (CF ₃) ₂); 1, Isosorbide-5-Nitrae, the fluoro-2-of 4,4-five (trifluoromethyl)-1-butylene (CF ₂=C (CF ₃) CH ₂CF ₃); 3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene ((CF ₃) ₂CFCH=CH ₂); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂CH=CH ₂); The fluoro-1-amylene of 2,3,3,4,4,5,5-seven (CH ₂=CFCF ₂CF ₂CHF ₂); The fluoro-1-butylene of 1,1,3,3,5,5,5-seven (CF ₂=CHCF ₂CH ₂CF ₃); The fluoro-3-methyl-2-butene of 1,1,1,2,4,4,4-seven (CF ₃CF=C (CF ₃) (CH ₃)); 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CH ₂=CFCH (CF ₃) ₂); Isosorbide-5-Nitrae, 4,4-tetrafluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF ₃) ₂); 1,1, Isosorbide-5-Nitrae-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₂FCH=C (CF ₃) ₂); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-butylene (CH ₃CF=C (CF ₃) ₂); The fluoro-2-of 1,1,1-tri-(trifluoromethyl)-2-butylene ((CF ₃) ₂C=CHCH ₃); 3,4,4,5,5,5-hexafluoro-2-amylene (CF ₃CF ₂CF=CHCH ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-methyl-2-butene (CF ₃C (CH ₃)=CHCF ₃); 3,3,4,5,5,5-hexafluoro-1-amylene (CH ₂=CHCF ₂CHFCF ₃); The fluoro-3-of 4,4,4-tri-(trifluoromethyl)-1-butylene (CH ₂=C (CF ₃) CH ₂CF ₃); The fluoro-1-hexene of 1,1,2,3,3,4,4,5,5,6,6,6-12 (CF ₃(CF ₂) ₃CF=CF ₂); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (CF ₃CF ₂CF=CFCF ₂CF ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (trifluoromethyl)-2-butylene ((CF of 3- ₃) ₂C=C (CF ₃) ₂); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CFCF ₃); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHC ₂F ₅); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF ₃) ₂CFCF=CHCF ₃); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (CF ₃CF ₂CF ₂CF ₂CH=CH ₂); 4,4,4-tri-is fluoro-3, two (the trifluoromethyl)-1-butylene (CH of 3- ₂=CHC (CF ₃) ₃); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF ₃) ₂C=C (CH ₃) (CF ₃)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CFCF ₂CH (CF ₃) ₂); The fluoro-3-methyl of 1,1,1,2,4,4,5,5,5-nine-2-amylene (CF ₃CF=C (CH ₃) CF ₂CF ₃); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF ₃CH=CHCH (CF ₃) ₂); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF ₃CF ₂CF ₂CF=CHCH ₃); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH ₂=CHCF ₂CF ₂CF ₂CHF ₂); 1,1, Isosorbide-5-Nitrae, the fluoro-2-of 4-five (trifluoromethyl)-2-amylene ((CF ₃) ₂C=CHCF ₂CH ₃); The fluoro-2-of 4,4,5,5,5-five (trifluoromethyl)-1-amylene (CH ₂=C (CF ₃) CH ₂C ₂F ₅); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (CF ₃CF ₂CF ₂C (CH ₃)=CH ₂); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (CF ₃CF ₂CF ₂CH=CHCH ₃); The fluoro-1-hexene of 4,4,5,5,6,6,6-seven (CH ₂=CHCH ₂CF ₂C ₂F ₅); The fluoro-3-hexene of 1,1,1,2,2,3,4-seven (CF ₃CF ₂CF=CFC ₂H ₅); 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-amylene (CH ₂=CHCH ₂CF (CF ₃) ₂); The fluoro-4-methyl of 1,1,1,2,5,5,5-seven-2-amylene (CF ₃CF=CHCH (CF ₃) (CH ₃)); 1,1,1,3-tetrafluoro-2-(trifluoromethyl)-2-amylene ((CF ₃) ₂C=CFC ₂H ₅); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-, ten tetrafluoros-2-heptene (CF ₃CF=CFCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,3,4,5,5,6,6,7,7,7-, ten tetrafluoros-3-heptene (CF ₃CF ₂CF=CFCF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 (CF ₃CH=CFCF ₂CF ₂C ₂F ₅); The fluoro-2-heptene of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 (CF ₃CF=CHCF ₂CF ₂C ₂F ₅); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CH=CFCF ₂C ₂F ₅); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF ₃CF ₂CF=CHCF ₂C ₂F ₅); CF ₂=CFOCF ₂CF ₃And CF (PEVE) ₂=CFOCF ₃(PMVE).

Being specially adapted to comprise the fluoroolefins of the composition of at least one flammable refrigeration agent and at least one fluoroolefins, is non-flammable fluoroolefins itself.It is relevant with number of fluorine atoms and number of hydrogen atoms in molecule that the combustibility of fluoroolefins seems.Following equation can calculate the flammable factor, is used as the flammable index of prediction.

In formula:

Number of fluorine atoms in the F=molecule;

Number of hydrogen atoms in the H=molecule.

Because the measuring of some compound is flammable, the cutoff value (cut-off) of the flammable factor of non-flammable fluoroolefins is determined.Fluoroolefins can be by using the electronics ignition source in ASHRAE (U.S. heating, refrigeration and air-conditioning man IEEE, American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) under the condition of standard 34-2001 (under ASTM (American Society Testing and Materials, American Society of Testing and Materials) E681-01) defined, testing to determine is that the flammable right and wrong of going back are flammable.This flammability test is to use test compounds under 101kPa (14.7psia) and specified temperature (common 100 ℃ (212 °F)), with concentration in different air, carry out, to determine the aerial lean flammability of this test compound (LFL) and/or upper limit of flammability (UFL).

Table 4 is listed the flammable factor of several fluoroolefins and the measuring result of combustibility or non-combustible.Therefore, in measurable other fluoroolefins disclosed by the invention, which is the non-flammable fluoroolefins of optimum and combustible refrigerant disclosed by the invention combination in fact.

table 4

According to the numerical value of the flammable factor, can determine that the listed fluoroolefins of table 4 is that the flammable right and wrong of going back are flammable.If show that the flammable factor is equal to or greater than 0.70, can expect that these fluoroolefins right and wrong are flammable.If the flammable factor is less than 0.70, can expect that this fluoroolefins is flammable.

In another embodiment of the invention, becoming the fluoroolefins of composition for the refrigeration agent with flammable is to be selected from following fluoroolefins:

(b) formula ring-[CX=CY (CZW) _n-] the ring-type fluoroolefins, wherein X, Y, Z and W are independently H or F, the integer that n is 2-5, and wherein the flammable factor is more than or equal to 0.70;

(c) be selected from following fluoroolefins:

In another embodiment, the fluoroolefins of the present invention that can be specially adapted to be combined with combustible refrigerant can be that at least one is selected from following fluoroolefins:

(a) formula E-or Z-R ¹cH=CHR ²fluoroolefins, R wherein ¹and R ²independent is C ₁-C ₆perfluoro alkyl group, and wherein the flammable factor is more than or equal to 0.70;

Although the flammable factor provides the flammable basis of predicting some fluoroolefin compounds, but may have some variable, position as hydrogen atom on molecule, it is flammable can causing some isomer of given molecular formula, other isomer right and wrong is flammable.Therefore, the flammable factor is only as the instrument of predicting flammable characteristic.

When comprising any provable and air mixed, combustible refrigerant of the present invention can make the compound of propagation of flame under temperature, pressure and the composition condition of regulation.Combustible refrigerant can be by using the electronics ignition source in ASHRAE (U.S. heating, refrigeration and air-conditioning man IEEE, AmericanSociety of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) under the condition of standard 34-2001 (under ASTM (American Society Testing and Materials, American Society of Testing and Materials) E681-01) defined, tested to identify.This flammability test be with this refrigeration agent under 101kPa (14.7psia) and specified temperature (common 100 ℃ (212 °F)) or room temperature (approximately 23 ℃ (73 °F)) with different air in concentration carry out, to determine the aerial lean flammability of this test compound (LFL) and/or upper limit of flammability (UFL).

With regard to practical situation, if certain refrigeration agent can cause catching fire when refrigeration plant or air-conditioning plant leak and touch ignition source, can classify as combustible refrigerant.Composition of the present invention causes that in this leakage process the possibility of catching fire is low.

Combustible refrigerant of the present invention comprises hydrogen fluorohydrocarbon (HFC), fluoroolefins, fluoroether, hydrocarbyl ether, hydrocarbon, ammonia (NH ₃) and their combination.

Flammable HFC refrigeration agent includes but not limited to: methylene fluoride (HFC-32), fluoromethane (HFC-41), 1,1,1-Halothane (HFC-143a), 1,1,2-Halothane (HFC-143), 1,1-C2H4F2 C2H4F2 (HFC-152a), fluoroethane (HFC-161), 1,1,1-trifluoro propane (HFC-263fb), 1,1,1,3,3-pentafluoropropane (HFC-365mfc) and their combination.These are flammable the HFC refrigeration agent is can be available from a plurality of sources the commercially available prod as chemical Synesis Company, or can be prepared by the disclosed synthetic method in this area.

Combustible refrigerant of the present invention also comprises and includes but not limited to following fluoroolefins: 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); The fluoro-1-propylene of 2,3,3-tri-(HFC-1243yf); The fluoro-1-propylene of 3,3,3-tri-(HFC-1243zf); The fluoro-1-propylene of 1,1,2-tri-(HFC-1243yc); The fluoro-1-propylene of 1,1,3-tri-(HFC-1243zc); The fluoro-1-propylene of the fluoro-1-propylene of 1,2,3-tri-(HFC-1243ye) and 1,3,3-tri-(HFC-1243ze).

Combustible refrigerant of the present invention also comprises fluoroether, and this compound and hydrogen fluorohydrocarbon are similar, also contains at least one ether group Sauerstoffatom.Representational fluoroether refrigerant includes but not limited to C ₄f ₉oC ₂h ₅, it is commercially available.

Combustible refrigerant of the present invention also comprises hydrocarbon coolant.Representational hydrocarbon coolant includes but not limited to propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, 2-methylbutane (iso-pentane), tetramethylene, pentamethylene, 2,2-dimethylpropane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2-methyl hexane, 3-methyl hexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, hexanaphthene, normal heptane, methylcyclopentane and normal hexane.Flammable hydrocarbon coolant can easily obtain from a plurality of commercial source.

Combustible refrigerant of the present invention also comprises hydrocarbyl ether, as dme (DME, CH ₃oCH ₃) and methyl tertiary butyl ether (MTBE, (CH ₃) ₃cOCH ₃), both all can obtain from a plurality of commercial source.

Combustible refrigerant of the present invention also comprises ammonia (NH ₃), this is a kind of compound be commercially available.

Combustible refrigerant of the present invention also can comprise the mixture that surpasses a kind of refrigeration agent, for example, mixture as two or more combustible refrigerants (two kinds of HFC or a kind of HFC and a kind of hydrocarbon), the mixture that perhaps comprises combustible refrigerant and non-combustible refrigerant, a rear mixture is identified or still can be thought combustible refrigerant generally with regard to practical situation under ASTM condition as herein described.

The example of the non-combustible refrigerant that can be mixed with other refrigeration agent of the present invention comprises R-134a, R-134, R-23, R125, R-236fa, (the ASHRAE label is R401 or R-401A for R-245fa and HCFC-22/HFC-152a/HCFC-124 mixture, R-401B and R-401C), HFC-125/HFC-143a/HFC-134a mixture (the ASHRAE label is R-404 or R-404A), (the ASHRAE label is R407 or R-407A to the HFC-32/HFC-125/HFC-134a mixture, R-407B and R-407C), HCFC-22/HFC-143a/HFC-125 mixture (the ASHRAE label is R408 or R-408A), HCFC-22/HCFC-124/HCFC-142b mixture (the ASHRAE label is R-409 or R-409A), HFC-32/HFC-125 mixture (the ASHRAE label is R-410A) and HFC-125/HFC-143a mixture (the ASHRAE label is R-507 or R507A) and carbonic acid gas.

The example that surpasses a kind of mixture of combustible refrigerant comprises that propane/Trimethylmethane mixture, HFC-152a/ Trimethylmethane mixture, R32/ propane mixture, R32/ Trimethylmethane mixture and HFC/ carbon dioxide mixture are as HFC-152a/CO ₂.

One aspect of the present invention provides global warming potential to be less than 150, preferably is less than 50 non-combustible refrigerant.Another aspect of the present invention is by add non-flammable fluoroolefins to reduce the combustibility of described mixture to flammable frigorific mixture.

Can prove, although some refrigeration agent is flammable, can produce non-combustible refrigerant composition by add another kind of non-flammable compound to combustible refrigerant.The example of this non-combustible refrigerant adulterant comprises R-410A (HFC-32 is combustible refrigerant, and HFC-125 is non-combustible) and R-407C (HFC-32 is combustible refrigerant, and HFC-125 and HFC-134a are non-combustible).

Can be used as comprising at least one fluoroolefins and the refrigeration agent of at least one combustible refrigerant or the present composition of heat-transfer fluid, the fluoroolefins that can contain significant quantity belongs to non-flammable composition to produce according to the result of ASTM E681-01.

The present composition that comprises at least one combustible refrigerant and at least one fluoroolefins, can containing have an appointment 1 weight percent to the fluoroolefins of about 99 weight percents and approximately 99 weight percents to the about combustible refrigerant of 1 weight percent.

In another embodiment, the present composition can containing have an appointment 10 weight percents to the fluoroolefins of about 80 weight percents and approximately 90 weight percents to the about combustible refrigerant of 20 weight percents.In another embodiment, the present composition can containing have an appointment 20 weight percents to the fluoroolefins of about 70 weight percents and approximately 80 weight percents to the about combustible refrigerant of 30 weight percents.

A what is worth mentioning embodiment of the present invention is that fluoroolefins comprises HFC-1225ye and combustible refrigerant comprises HFC-32 (methylene fluoride).Measure and to know by ASTM 681-01, the composition right and wrong of the HFC-32 that comprises maximum 37 weight percents are flammable, and the composition that comprises 38 weight percents or above HFC-32 is flammable.The invention provides comprise about 1.0 weight percents to the HFC-32 of about 37.0 weight percents and approximately 99.0 weight percents to the about non-flammable composition of the HFC-1225ye of 63 weight percents.

An embodiment of the present invention of being worth mentioning equally is that composition comprises HFC-1225ye, HFC-32 and HFC-125.This composition of the present invention comprise about 20 weight percents to the HFC-1225ye of about 95 weight percents, approximately 1.0 weight percents to the HFC-32 of about 65 weight percents and approximately 1.0 weight percents to the about HFC-125 of 40 weight percents.In another embodiment, composition comprise about 30 weight percents to the HFC-1225ye of about 90 weight percents, approximately 5.0 weight percents to the HFC-32 of about 55 weight percents and approximately 1.0 weight percents to the about HFC-125 of 35 weight percents.In another embodiment, composition comprise about 40 weight percents to the HFC-1225ye of about 85 weight percents, approximately 10 weight percents to the HFC-32 of about 45 weight percents and approximately 1.0 weight percents to the about HFC-125 of 28 weight percents.Contain and be less than the approximately flammable composition of those compositions contemplated right and wrong of the HFC-32 of 40 weight percents.Depend on the HFC-1225ye that exists in composition and the relative proportion of HFC-125, this limit of combustibility can change from the HFC-32 that is less than about 45 weight percents to the HFC-32 that is less than about 37 weight percents.

In another what is worth mentioning embodiment, combustible refrigerant comprises HFC-1243zf, and non-flammable fluoroolefins is intended to reduce the combustibility of Overall Group's compound.Composition can comprise about 1.0 weight percents to the HFC-1243zf of about 99 weight percents and approximately 99 weight percents to the about HFC-1225ye of 1.0 weight percents.Perhaps, composition can comprise about 40 weight percents to the HFC-1243zf of about 70 weight percents and approximately 60 weight percents to the about HFC-1225ye of 30 weight percents.

In another what is worth mentioning embodiment, composition comprises approximately 1.0 weight percents to the about HFC-1243zf of 98 weight percents; Approximately 1.0 weight percents to the HFC-1225ye of about 98 weight percents and approximately 1.0 weight percents to the about HFC-125 of 50 weight percents.Perhaps, composition comprise about 40 weight percents to the HFC-1243zf of about 70 weight percents, approximately 20 weight percents to the HFC-1225ye of about 60 weight percents and approximately 1.0 weight percents to the about HFC-125 of 10 weight percents.

In another what is worth mentioning embodiment, composition comprises approximately 1.0 weight percents to the about HFC-1243zf of 98 weight percents; Approximately 1.0 weight percents are to the about HFC-1225ye of 98 weight percents; With about 1.0 weight percents to the about HFC-32 of 50 weight percents.In another embodiment, composition comprise about 40 weight percents to the HFC-1243zf of about 70 weight percents, approximately 20 weight percents to the HFC-1225ye of about 60 weight percents and approximately 1.0 weight percents to the about HFC-32 of 10 weight percents.

In another what is worth mentioning embodiment, composition comprises approximately 1.0 weight percents to the about HFC-1243zf of 97 weight percents; Approximately 1.0 weight percents are to the about HFC-1225ye of 97 weight percents; Approximately 1.0 weight percents to the HFC-125 of about 50 weight percents and approximately 1.0 weight percents to the about HFC-32 of 50 weight percents.

Perhaps, composition comprises approximately 40 weight percents to the about HFC-1243zf of 70 weight percents; Approximately 20 weight percents are to the about HFC-1225ye of 60 weight percents; Approximately 1.0 weight percents to about 10 weight percent HFC-125 and approximately 1.0 weight percents to the about HFC-32 of 10 weight percents.

The invention still further relates to the flammable method that reduces combustible refrigerant, described method comprises is mixed combustible refrigerant with at least one fluoroolefins.The amount of the fluoroolefins added must be significant quantity, to produce by ASTM 681-01, measures and belongs to non-flammable composition.

Composition of the present invention can be used in combination with siccative in refrigeration, air-conditioning or heat pump, so that dry-off moisture.Siccative can comprise activated alumina, silica gel or zeolite based molecular sieve.Representational molecular sieve comprises that MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL), the refrigeration agent less for molecular size are as HFC-32, preferably the XH-11 siccative.

Composition of the present invention also can comprise at least one lubricant.Lubricant of the present invention comprises those lubricants that are applicable to refrigeration or air-conditioning plant.In the middle of these lubricants, conventional those lubricants for the compression refrigerating apparatus that adopts the Chlorofluorocarbons (CFCs) refrigeration agent are arranged.This lubricant and their characteristic are at 1990ASHRAE Handbook, Refrigeration Systems and Applications (refrigeration system and application), the 8th chapter, title " Lubricants in Refrigeration Systems (lubricant in refrigeration system) ", discussion is arranged in the 8.1-8.21 page, and this piece of document is incorporated herein by reference.Lubricant of the present invention can comprise those lubricants that the lubricated field of compression refrigeration is commonly referred to as " mineral oil ".Mineral oil comprises paraffin (being straight chain and branched-chain saturated hydrocarbon), cycloalkanes (being cyclic paraffins) and aromatic hydrocarbons (containing one or more unsaturated cyclic hydrocarbon that replace the ring that two keys are feature of take).Lubricant of the present invention also comprises those lubricants that the lubricated field of compression refrigeration is commonly referred to as " synthetic oil ".Synthetic oil comprises alkylaryl material (being straight chain and branched-chain alkyl alkylbenzene), synthetic paraffin and cycloalkanes and poly-(alhpa olefin).Representative traditional lubrication agent of the present invention be commercially available BVM 100N (paraffin mineral oil, BVA Oils sells),

3GS and 5GS (naphthenic mineral oil, Crompton Co. sells),

372LT (naphthenic mineral oil, Pennzoil sells), rO-30 (naphthenic mineral oil, Calumet Lubricants sells),

75,

150 Hes

500 (linear alkylbenzenes, Shrieve Chemicals sells) and HAB 22 (branched alkylbenzene, Nippon Oil sells).

Lubricant of the present invention also comprise be designed to fluoroether refrigerant and with refrigeration agent of the present invention mixable those lubricants under the operational condition of compression refrigeration and air-conditioning plant.The character of this lubricant and they is at " Synthetic Lubricants and High-Performance Fluids (synthetic lubricant and high efficiency fluid) ", R.L.Shubkin (editor), and Marcel Dekker, have discussion in 1993.This lubricant include but not limited to polyol ester (POE) as

100 (Castrol, United Kingdom), polyalkylene glycol (PAG) are as RL-488A (Dow Chemical, Midland, Michigan) and polyvingl ether (PVE).

Lubricant of the present invention is that the environment that requirement by considering given compressor and lubricant will be exposed to is selected.

Can optionally add refrigeration system additives commonly used to composition of the present invention as required, to improve oilness and system stability.These additives are that the lubricated field of refrigeration compressor is known, comprise anti-wear agent, extreme pressure lubricant, corrosion and oxidation retarder, metallic surface deactivator, foam and anti-Foam Control, leak detectants etc.In general, these additives are with respect to the only a small amount of existence of overall lubricant compositions.The working concentration of every kind of additive is normally from being less than approximately 0.1% to as high as approximately 3%.These additives are selected on the basis required in different system.Some representative instances of these additives can include but not limited to strengthen lubricated additive, as alkyl ester or the aryl ester of phosphoric acid and thiophosphate.In addition, metal dialkyl dithiophosphates (for example zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and other member of this class chemical also can be used for composition of the present invention.Other anti-wear agent comprises that natural product oil (natural product oil) and asymmetric poly-hydroxy slip additive are as Synergol TMS (International Lubricants).Equally, also can adopt stablizers such as antioxidant, free-radical scavengers and dehydrating agent (the dry compound of using).This additive comprises but is not limited to Nitromethane 99Min., hindered phenol (as Butylated Hydroxytoluene or BHT), azanol, mercaptan, phosphite, epoxide or lactone.Dehydrating agent includes but not limited to that ortho ester is as trimethyl orthoformate, triethyl orthoformate or tripropyl orthoformate.Can use the combination of single additive or additive.

In one embodiment, the invention provides and comprise at least one fluoroolefins and at least one and be selected from the composition of following stablizer: thiophosphatephosphorothioate, butylation triphenyl thiophosphatephosphorothioate, organophosphate, the dialkyl group thiophosphatephosphorothioate, terpene, terpenoid, soccerballene, functionalized PFPE, polyoxyalkylated aromatic substances (polyoxyalkylated aromatics), epoxide, fluorinated epoxide, trimethylene oxide, xitix, mercaptan, lactone, thioether, Nitromethane 99Min., alkyl silane, methanone derivatives, aromatic yl sulfide, terephthalic acid divinyl ester, terephthaldehyde's diphenyl phthalate, alkylamine, hindered amine antioxidant and phenol.Alkylamine can comprise other member of triethylamine, Tributylamine, Diisopropylamine, tri-isopropyl amine, tri-isobutylamine and this class alkyl ammonium compounds.

In another embodiment, stablizer of the present invention can comprise the concrete combination of each stablizer.A what is worth mentioning combination of stabilizers comprises at least one terpene or terpenoid.These terpenes or terpenoid can be mixed with at least one compound that is selected from epoxide, fluorinated epoxide and trimethylene oxide.

Terpene is to contain to surpass the hydrocarbon compound that a structure that repeats isoprene (2-methyl isophthalic acid, 3-divinyl) unit is feature.Terpene can be acyclic or ring-type.Representational terpene includes but not limited to myrcene (2-methyl-6-methylene radical suffering-1,7-diene), alloocimene, β-ocimene, terebene, limonene (or (R)-4-isopropenyl-1-methyl-1-cyclohexene), retinene, firpene (or α-pinene), menthol, Geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, phellandrene, fenchene and their mixture.The terpene stablizer is commercially available, or can prepare by means commonly known in the art or separate from natural origin.

Terpenoid is to contain to surpass natural product and the related compound optional containing aerobic that a structure that repeats isoprene unit is feature.Representational terpenoid comprises that carotenoid is zeaxanthin (CAS reg.no.[144-68-3]) as Lyeopene (CAS reg.no.[502-65-8]), β-carotene (CAS reg.no.[7235-40-7]) and xenthophylls; Retinoids is as vitamin A epoxide (CAS reg.no.[512-39-0]) and isotretinoin (CAS reg.no.[4759-48-2]); Abietane (CAS reg.no.[640-43-7]); Ambrosane (CAS reg.no.[24749-18-6]); Aristolane (CAS reg.no.[29788-49-6]); Ah 's alkane (CAS reg.no.[24379-83-7]); Beyerane (CAS reg.no.[2359-83-3]), bisabolane (CAS reg.no.[29799-19-7]); Camphane (CAS reg.no.[464-15-3]); Caryophyllane (CAS reg.no.[20479-00-9]); Cedrane (CAS reg.no.[13567-54-9]); Dammarane (CAS reg.no.[545-22-2]); Drimane (CAS reg.no.[5951-58-6]); Eremophilane (CAS reg.no.[3242-05-5]); Eudesmane (CAS reg.no.[473-11-0]); Fenchane (CAS reg.no.[6248-88-0]); Gammacerane (CAS reg.no.[559-65-9]); Germacrane (CAS reg.no.[645-10-3]); Gibberellane (CAS reg.no.[6902-95-0]); Grayanotoxane (CAS reg.no.[39907-73-8]); Guainane (CAS reg.no.[489-80-5]); Cedrane (CAS reg.no.[20479-45-2]); Humulane (CAS reg.no.[471-62-5]); Humulane (CAS reg.no.[430-19-3]); Kaurane (CAS reg.no.[1573-40-6]); Ladanum alkane (CAS reg.no.[561-90-0]); Lanostane (CAS reg.no.[474-20-4]); Lupinane (CAS reg.no.[464-99-3]); P-menthane (CAS reg.no.[99-82-1]); Volatile oil (CAS reg.no.[471-67-0]); Ophiobolane (CAS reg.no.[20098-65-1]); Picrasane (CAS reg.no.[35732-97-9]); Pimarane (CASreg.no.[30257-03-5]); Pinane (CAS reg.no.[473-55-2]); Podocarpane (CASreg.no.[471-78-3]); Protostane (CAS reg.no.[70050-78-1]); Rose alkane (CASreg.no.[6812-82-4]); Taxan (CAS reg.no.[1605-68-1]); Thujane (CASreg.no.[471-12-5]); Spore bacterium alkane (CAS reg.no.[24706-08-9]) and aromadendrane (CASreg.no.[464-93-7]).Terpenoid of the present invention is commercially available, or can prepare by means commonly known in the art or can separate from natural origin.

In one embodiment, terpene or terpenoid stablizer can be mixed with at least one epoxide.Representational epoxide comprises 1,2 epoxy prapane (CAS reg.no.[75-56-9]), 1,2-butylene oxide ring (CAS reg.no.[106-88-7]) or their mixture.

In another embodiment, terpene of the present invention or terpenoid stablizer can be mixed with at least one fluorinated epoxide.Fluorinated epoxide of the present invention can be as shown in Equation 3, wherein R ²to R ⁵in each is the alkyl of H, a 1-6 carbon atom or the fluoro-alkyl of 1-6 carbon atom, condition is R ²to R ⁵in at least one is the fluoro-alkyl group.

Formula 3

Representational fluorinated epoxide stablizer comprises but is not limited to trifluoromethyl oxyethane and two (trifluoromethyl) oxyethane of 1,1-.Can prepare by this compound, for example pass through by means commonly known in the art journal of Fluorine Chemistry, 24 volumes, 93-104 page (1984), journal of Organic Chemistry, 56 volumes, 3187-3189 page (1991) and journal of fluorine Chemistry, 125 volumes, the method for describing in 99-105 page (2004) preparation.

In another embodiment, terpene of the present invention or terpenoid stablizer can be mixed with at least one trimethylene oxide.Trimethylene oxide stablizer of the present invention can be the compound with one or more oxetane groups, as shown in Equation 4, and R wherein ₁-R ₆identical or different, can be selected from hydrogen, alkyl or substituted alkyl, aryl or substituted aryl.

Formula 4

Representational trimethylene oxide stablizer comprises but is not limited to 3-ethyl-3-methylol-trimethylene oxide as OXT-101 (Toagosei Co., Ltd), 3-ethyl-3-((phenoxy group) methyl)-trimethylene oxide is as OXT-211 (Toagosei Co., Ltd) and 3-ethyl-3-((2-ethyl-hexyloxy) methyl)-trimethylene oxide as OXT-212 (Toagosei Co., Ltd).

Another what is worth mentioning embodiment is the combination of stabilizers that comprises soccerballene.The compound that fullerene stabilizers and at least one can be selected to epoxide, fluorinated epoxide and trimethylene oxide is mixed.Supply as previously described the epoxide, fluorinated epoxide and the trimethylene oxide that are mixed with terpene or terpenoid for the epoxide, fluorinated epoxide and the trimethylene oxide that are mixed with soccerballene.

Another what is worth mentioning embodiment is the combination of stabilizers that comprises phenol.The compound that phenol stablizer and at least one can be selected to epoxide, fluorinated epoxide and trimethylene oxide is combined.Supply the epoxide, fluorinated epoxide and the trimethylene oxide that are combined with phenol to supply as previously described the epoxide, fluorinated epoxide and the trimethylene oxide that are combined with terpene or terpenoid.

The phenol stabilizer package is containing any substituted or unsubstituted oxybenzene compound, described oxybenzene compound comprises and comprises the substituent phenol of one or more substituted or unsubstituted ring-types, straight or branched aliphatic series, phenol as single as alkylation, comprise 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol, 2,4 dimethyl 6 tert butyl phenol, tocopherol etc., quinhydrones and alkylation quinhydrones, comprise tertiary butylated hydroquinone, other hydroquinone derivatives etc., hydroxylation sulfo-diphenyl ether, comprise 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol) etc., alkylidene bisphenols, comprise 4, 4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4, 4 '-bis-(2, the 6-DI-tert-butylphenol compounds), 2, 2 '-or 4, the derivative of 4-'-biphenyl diphenol, 2, 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, the 4-butylidene-bis(3-methyl-6-t-butyl phenol), 4, 4-isopropylidene two (2, the 6-DI-tert-butylphenol compounds), 2, 2 '-methylene-bis(4-methyl-6-nonyl phenol), 2, 2 '-isobutylene two (4, the 6-xylenol, 2, 2 '-methylene-bis (4-methyl-6-cyclohexylphenol, 2,2-or 4,4-'-biphenyl diphenol, comprise 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), Butylated Hydroxytoluene (BHT), comprise heteroatomic bis-phenol, comprise 2,6-, bis--uncle-alpha-alpha-dimethyl amino-p-cresol, 4,4-thiobis (the 6-tertiary butyl-meta-cresol) etc., acyl aminophenols, 2,6-di-t-butyl-4 (N, N '-dimethylaminomethyl phenol), sulfide, comprise two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide, two (3,5-di-tert-butyl-4-hydroxyl benzyl) sulfide etc.

In one embodiment of the invention, these comprise terpene or terpenoid or soccerballene or phenol and at least one and are selected from epoxide, the combination of stabilizers of the compound of fluorinated epoxide and trimethylene oxide, also can comprise and be selected from following other stabilizer compounds: two (benzylidene hydrazine) (areoxalyl bis (benzylidene) hydrazide) (the CAS reg.no.6629-10-3) of oxalyl, N, N '-bis-(3, 5-di-t-butyl-4-hydroxyl hydrocinnamamide hydrazine) (CAS reg.no.32687-78-8), 2, 2 '-oxamido-is two-ethyl-(3, 5-d-tertiary butyl-4-hydroxy hydrogenated cinnamate) (CAS reg.no.70331-94-1), N, N '-(two salicylidenes)-1, 2-propylene diamine (CAS reg.no.94-91-1) and ethylenediamine tetraacetic acid (EDTA) (CAS reg.no.60-00-4) and salt thereof.

In another embodiment of the invention, these comprise terpene or terpenoid or soccerballene or phenol and at least one and are selected from the combination of stabilizers of the compound of epoxide, fluorinated epoxide and trimethylene oxide, also can comprise at least one and be selected from following alkylamine: triethylamine, Tributylamine, tri-isopropyl amine, diisobutylamine, tri-isopropyl amine, tri-isobutylamine and hindered amine antioxidant.

Composition of the present invention also can comprise compound or the composition as tracer agent, and described compound or composition are selected from hydrogen fluorohydrocarbon (HFC), deuteroparaffin, hydrogen deuteride fluorohydrocarbon, perfluoroparaffin, fluoroether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N ₂o) and their combination.For tracer agent of the present invention, be the composition different from the composition as refrigeration agent or heat-transfer fluid, with predetermined amount, join in refrigeration agent and heat transfer fluid composition, so that any dilution of detection composition, pollution or other changing conditions, this has description in the U.S. Patent Application Serial 11/062,044 of submitting on February 18th, 2005.

Table 5 is listed the typical tracer compounds for the present composition.

table 5

The listed compound of table 5 is commercially available (from the chemical supplier row), or can prepare by means commonly known in the art.

Each is single plant tracer compounds can with the present composition in the refrigerating/heating combination of fluids use, or multiple tracer compounds can be combined with any ratio, as the tracer agent adulterant.The tracer agent adulterant can contain the multiple tracer compounds from similar compound, or from the multiple tracer compounds of inhomogeneity compound.For example, the tracer agent adulterant can contain 2 kinds or multiple hydrogen deuteride fluorohydrocarbon, or the combination of a kind of hydrogen deuteride fluorohydrocarbon and one or more perfluoroparaffins.

In addition, some compounds in table 4 exist with the form of various structures isomer or optically active isomer.The individual isomer of same compound or multiple isomer can be used with any ratio, with the preparation tracer compounds.In addition, the single or multiple isomer of given compound can be combined with any ratio with any amount of other compound, as the tracer agent adulterant.

Tracer compounds or tracer agent adulterant with about 50ppm (1,000,000/, be present in composition to the total concn of about 1000ppm by weight).Preferably, tracer compounds or tracer agent adulterant exist to the total concn of about 500ppm with about 50ppm, and most preferably tracer compounds or tracer agent adulterant exist to the total concn of about 300ppm with about 100ppm.

Composition of the present invention also can comprise ultraviolet (UV) dyestuff and optionally comprise solubilizing agent.The UV dyestuff is the useful component that detects the leakage of refrigerant composition or heat-transfer fluid, and it is by allowing people can observe near refrigeration agent leakage point in refrigeration, air-conditioning, thermal-pump unit or leakage point or the fluorescence of the dyestuff in heat transfer fluid composition detects leakage.People can observe the fluorescence of dyestuff under ultraviolet lamp.Because the solubleness of this UV dyestuff in some refrigeration agents and heat-transfer fluid is low, may need solubilizing agent.

So-called " ultraviolet " dyestuff refers to the ultraviolet of energy electromagnetic wave absorption frequency spectrum or the UV fluorescent composition of the light in " closely " ultraviolet region.The fluorescence produced under the ultra violet lamp that is the radiation between 10nm to 750nm at the energy emission wavelength by the Ultraluminescence dyestuff can detect.Therefore, if the refrigeration agent that contains this Ultraluminescence dyestuff or the heat-transfer fluid set point from refrigeration, air-conditioning or thermal-pump unit leaks out, can near this leakage point or this leakage point, detect fluorescence.This Ultraluminescence dyestuff includes but not limited to the derivative of naphthalimide, perylene, tonka bean camphor, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein and described dyestuff or their combination.Solubilizing agent of the present invention comprises at least one and is selected from following compound: hydrocarbon, hydrocarbyl ether, polyoxyalkylene glycol ether, acid amides, nitrile, ketone, chlorocarbon, ester, lactone, aryl ethers, fluoroether and 1,1,1-trifluoro alkane.

The hydrocarbon that hydrocarbon solubilizing agent of the present invention comprises comprises and contains the carbon atom below 16 or 16 and only have hydrogen and without straight chain, side chain or cyclic alkane or the alkene of other functional group.Representational hydrocarbon solubilizing agent comprises propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, octane, decane and n-Hexadecane.Be to be noted that, if refrigeration agent is certain hydrocarbon, solubilizing agent can not be the same hydrocarbon.

The ether that hydrocarbyl ether solubilizing agent of the present invention comprises a carbon containing, hydrogen and oxygen is as dme (DME).

Polyoxyalkylene glycol ether solubilizing agent of the present invention is by formula R ¹[(OR ²) _xoR ³] _yshown in, wherein: the integer that x is 1-3; The integer that y is 1-4; R ¹be selected from hydrogen and the aliphatic hydrocarbyl with 1-6 carbon atom and y bonding point; R ²be selected from the aliphatic alkylene with 2-4 carbon atom; R ³be selected from hydrogen and aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-6 carbon atom; R ¹and R ³in at least one is described alkyl; And the molecular weight of wherein said polyoxyalkylene glycol ether is approximately 100 to about 300 atomic mass units.Bonding point used herein refers to can be for the group site with other group formation covalent linkage.Alkylene refers to bivalent hydrocarbon radical.In the present invention, preferred polyoxyalkylene glycol ether solubilizing agent is by formula R ¹[(OR ²) _xoR ³] _yshown in: x is preferably 1-2; Y is preferably 1; R ¹and R ³preferably independently be selected from hydrogen and the aliphatic hydrocarbyl with 1-4 carbon atom; R ²be preferably selected from there is 2 or 3 carbon atoms, the aliphatic alkylene of 3 carbon atoms most preferably; Described polyoxyalkylene glycol ether molecular weight is preferably approximately 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units.R with 1-6 carbon atom ¹and R ³alkyl can be straight chain, side chain or ring-type.Representational R ¹and R ³alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl and cyclohexyl.Free hydroxyl group on polyoxyalkylene glycol ether solubilizing agent of the present invention may with some compression refrigerating apparatus constituent material (for example

) in inconsistent situation, R ¹and R ³preferably there is 1-4 carbon atom, the aliphatic hydrocarbyl of 1 carbon atom most preferably.R with 2-4 carbon atom ²the oxyalkylene group that the formation of aliphatic series alkylene repeats-(OR ²) _x-, described alkylidene oxide comprises oxidation ethylidene, oxypropylene and oxybutylene.Comprise R in polyoxyalkylene glycol ether solubilizing agent molecule ²alkylidene oxide can be identical, or a molecule can contain different R ²alkylidene oxide.Polyoxyalkylene glycol ether solubilizing agent of the present invention preferably comprises at least one oxypropylene.At R ¹in situation for aliphatic hydrocarbyl with 1-6 carbon atom and y bonding point or alicyclic hydrocarbon radical, this group can be straight chain, side chain or ring-type.The representational R with two bonding points ¹aliphatic hydrocarbyl comprises for example ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylidene and cyclohexylidene.The representational R with three or four bonding points ¹aliphatic hydrocarbyl comprises hydroxyl by removing polyvalent alcohol and from the residue of this polyol derivative, and described polyvalent alcohol is as TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1,2,3-trihydroxy-hexanaphthene and 1,3,5-trihydroxy-hexanaphthene.

Representational polyoxyalkylene glycol ether solubilizing agent includes but not limited to CH ₃oCH ₂cH (CH ₃) O (H or CH ₃) (propylene glycol methyl (or dimethyl) ether), CH ₃o[CH ₂cH (CH ₃) O] ₂(H or CH ₃) (dipropylene glycol methyl (or dimethyl) ether), CH ₃o[CH ₂cH (CH ₃) O] ₃(H or CH ₃) (tripropylene glycol methyl (or dimethyl) ether), C ₂h ₅oCH ₂cH (CH ₃) O (H or C ₂h ₅) (propylene glycol ethyl (or diethyl) ether), C ₂h ₅o[CH ₂cH (CH ₃) O] ₂(H or C ₂h ₅) (dipropylene glycol ethyl (or diethyl) ether), C ₂h ₅o[CH ₂cH (CH ₃) O] ₃(H or C ₂h ₅) (tripropylene glycol ethyl (or diethyl) ether), C ₃h ₇oCH ₂cH (CH ₃) O (H or C ₃h ₇) (propylene glycol n-propyl (or diη-propyl) ether), C ₃h ₇o[CH ₂cH (CH ₃) O] ₂(H or C ₃h ₇) (dipropylene glycol n-propyl (or diη-propyl) ether), C ₃h ₇o[CH ₂cH (CH ₃) O] ₃(H or C ₃h ₇) (tripropylene glycol n-propyl (or diη-propyl) ether), C ₄h ₉oCH ₂cH (CH ₃) OH (propylene glycol n-butyl ether), C ₄h ₉o[CH ₂cH (CH ₃) O] ₂(H or C ₄h ₉) (dipropylene glycol normal-butyl (or di-n-butyl) ether), C ₄h ₉o[CH ₂cH (CH ₃) O] ₃(H or C ₄h ₉) (tripropylene glycol normal-butyl (or di-n-butyl) ether), (CH ₃) ₃cOCH ₂cH (CH ₃) OH (glycol tertiary butyl ether), (CH ₃) ₃cO[CH ₂cH (CH ₃) O] ₂(H or (CH ₃) ₃) (the dipropylene glycol tertiary butyl (or di-t-butyl) ether), (CH ₃) ₃cO[CH ₂cH (CH ₃) O] ₃(H or (CH ₃) ₃) (the tripropylene glycol tertiary butyl (or di-t-butyl) ether), C ₅h ₁₁oCH ₂cH (CH ₃) OH (propylene glycol n-pentyl ether), C ₄h ₉oCH ₂cH (C ₂h ₅) OH (butyleneglycol n-butyl ether), C ₄h ₉o[CH ₂cH (C ₂h ₅) O] ₂h (dibutylene glycol n-butyl ether), trimethylolpropane tris n-butyl ether (C ₂h ₅c (CH ₂o (CH ₂) ₃cH ₃) ₃) and TriMethylolPropane(TMP) di-n-butyl ether (C ₂h ₅c (CH ₂oC (CH ₂) ₃cH ₃) ₂cH ₂oH).

Acid amides solubilizing agent of the present invention comprises formula R ¹c (O) NR ²r ³and ring-[R ⁴c (O) N (R ⁵)] shown in those acid amides, R wherein ¹, R ², R ³and R ⁵independently be selected from aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-12 carbon atom; R ⁴be selected from the aliphatic alkylene with 3-12 carbon atom; And the molecular weight of wherein said acid amides is approximately 100 to about 300 atomic mass units.The molecular weight of described acid amides is preferably approximately 160 to about 250 atomic mass units.R ¹, R ², R ³and R ⁵can optionally comprise substituted alkyl, contain the substituent group of nonhydrocarbon that is selected from halogen (for example fluorine, chlorine) and alkoxyl group (for example methoxyl group).R ¹, R ², R ³and R ⁵can optionally comprise the alkyl replaced by heteroatoms, the group that in the group chain originally formed by carbon atom, contains nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom.In general, for R ^1-3in every 10 carbon atoms, have and be no more than three, preferably be no more than a non-hydrocarbon substituent and heteroatoms and exist, and must consider any this non-hydrocarbon substituent and heteroatomic existence when using above-mentioned molecular weight limit.Preferred acid amides solubilizing agent is comprised of carbon, hydrogen, nitrogen and oxygen.Representational R ¹, R ², R ³and R ⁵aliphatic hydrocarbyl and alicyclic hydrocarbon radical comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer.The preferred embodiment of acid amides solubilizing agent is above formula ring-[R ⁴c (O) N (R ⁵r in)-] ⁴can be by (CR ⁶r ⁷) _nin other words those acid amides shown in alkylene are formula ring-[(CR ⁶r ⁷) _nc (O) N (R ⁵)-], wherein: the values for molecular weight of stipulating previously is applicable; The integer that n is 3-5; R ⁵for the saturated hydrocarbyl that contains 1-12 carbon atom; R ⁶and R ⁷independently by the definition R provided previously ^1-3rule selected (for each n).At formula ring-[(CR ⁶r ⁷) _nc (O) N (R ⁵in lactan shown in)-], all R ⁶and R ⁷be preferably hydrogen, or contain single saturated hydrocarbyl, R in the middle of this n MU (methylene unit) ⁵for the saturated hydrocarbyl that contains 3-12 carbon atom.For example, 1-(saturated hydrocarbyl)-5-methylpyrrolidin-2-ketone.

Representational acid amides solubilizing agent includes but not limited to 1-octyl group pyrrolidin-2-one, 1-decyl pyrrolidin-2-one, 1-octyl group-5-methylpyrrolidin-2-ketone, 1-butyl hexanolactam, 1-cyclohexyl pyrrolidin-2-one, 1-butyl-5-methyl piperidine-2-ketone, 1-amyl group-5-methyl piperidine-2-ketone, 1-hexyl hexanolactam, 1-hexyl-5-methylpyrrolidin-2-ketone, 5-methyl-1-pentene phenylpiperidines-2-ketone, 1, 3-lupetidine-2-ketone, the 1-methyl caprolactam, 1-butyl-pyrrolidin-2-one, 1, 5-lupetidine-2-ketone, 1-decyl-5-methylpyrrolidin-2-ketone, 1-dodecyl pyrrolidin-2-one, N, N-dibutyl formamide and N, N-di-isopropyl ethanamide.

Ketone solubilizing agent of the present invention comprises formula R ¹c (O) R ²shown ketone, wherein R ¹and R ²independently be selected from aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl with 1-12 carbon atom, and the molecular weight of wherein said ketone is approximately 70 to about 300 atomic mass units.R in described ketone ¹and R ²preferably independently be selected from aliphatic hydrocarbyl and the alicyclic hydrocarbon radical with 1-9 carbon atom.The molecular weight of described ketone is preferably approximately 100 to about 200 atomic mass units.R ¹and R ²alkylene be can be connected to form together, thereby five yuan, hexa-atomic or seven-membered ring cyclic ketone, for example cyclopentanone, pimelinketone and suberone formed.R ¹and R ²can optionally comprise substituted alkyl, contain the substituent group of nonhydrocarbon that is selected from halogen (for example fluorine, chlorine) and alkoxyl group (for example methoxyl group).R ¹and R ²can optionally comprise the alkyl replaced by heteroatoms, the group that in the group chain originally formed by carbon atom, contains nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom.In general, for R ¹and R ²in every 10 carbon atoms, have and be no more than three, preferably be no more than a non-hydrocarbon substituent and heteroatoms and exist, and must consider any this non-hydrocarbon substituent and heteroatomic existence when using above-mentioned molecular weight limit.General formula R ¹c (O) R ²in representative R ¹and R ²aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer, and phenyl, benzyl, cumenyl, Lai Ji, tolyl, xylyl and styroyl.

Representational ketone solubilizing agent includes but not limited to 2-butanone, 2 pentanone, methyl phenyl ketone, phenyl propyl ketone, benzene hexanone, pimelinketone, suberone, 2-heptanone, 3-heptanone, 5 methy 12 hexanone, methyln-hexyl ketone, 3-octanone, diisobutyl ketone, 4-ethyl cyclohexanone, methyl n-heptyl ketone, butyl ketone, 2-decanone, propyl hexyl ketone, 2-decalone, 2-ten triketones, two hexanones and two pimelinketone.

Nitrile solubilizing agent of the present invention comprises formula R ¹nitrile shown in CN, wherein R ¹be selected from aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl with 5-12 carbon atom, and the molecular weight of wherein said nitrile is approximately 90 to about 200 atomic mass units.R in described nitrile solubilizing agent ¹be preferably selected from aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 8-10 carbon atom.The molecular weight of described nitrile solubilizing agent is preferably approximately 120 to about 140 atomic mass units.R ¹can optionally comprise substituted alkyl, contain the substituent group of nonhydrocarbon that is selected from halogen (for example fluorine, chlorine) and alkoxyl group (for example methoxyl group).R ¹can optionally comprise the alkyl replaced by heteroatoms, the group that in the group chain originally formed by carbon atom, contains nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom.In general, for R ¹in every 10 carbon atoms, have and be no more than three, preferably be no more than a non-hydrocarbon substituent and heteroatoms and exist, and must consider any this non-hydrocarbon substituent and heteroatomic existence when using above-mentioned molecular weight limit.General formula R ¹representative R in CN ¹aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl comprise amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer, and phenyl, benzyl, cumenyl, Lai Ji, tolyl, xylyl and styroyl.

Representational nitrile solubilizing agent includes but not limited to: 1-cyano group pentane, 2,2-dimethyl-4-cyano group pentane, 1-cyano group hexane, 1-cyano group heptane, 1-cyano group octane, 2-cyano group octane, 1-cyano group nonane, 1-cyano group decane, 2-cyano group decane, 1-cyano group undecane and 1-cyano group dodecane.

Chlorocarbon solubilizing agent of the present invention comprises formula RCl _xshown chlorocarbon, wherein: x is selected from 1 or 2 integer; R is selected from aliphatic hydrocarbyl and the alicyclic hydrocarbon radical with 1-12 carbon atom; And the molecular weight of wherein said chlorocarbon is approximately 100 to about 200 atomic mass units.The molecular weight of described chlorocarbon solubilizing agent is preferably approximately 120 to about 150 atomic mass units.General formula R Cl _xin representative R aliphatic hydrocarbyl and alicyclic hydrocarbon radical comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer.

Representational chlorocarbon solubilizing agent includes but not limited to: 3-(chloromethyl) pentane, the chloro-3-methylpentane of 3-, 1-chlorohexane, 1,6-dichloro hexane, 1-chloroheptane, 1-chloro-octane, 1-chlorononane, 1-chlorodecane and 1,1,1-, tri-chlorodecanes.

Ester solubilizing agent of the present invention comprises general formula R ¹cO ₂r ²shown ester, wherein R ¹and R ²independently be selected from straight chain and ring-type, saturated and undersaturated alkyl and aryl.Preferred ester is comprised of Elements C, H and O basically, and molecular weight is approximately 80 to about 550 atomic mass units.

Representational ester includes but not limited to (CH ₃) ₂cHCH ₂oOC (CH ₂) _2-4oCOCH ₂cH (CH ₃) ₂(diisobutyl dibasic ester), ethyl hexanoate, oil of cognac, n-butyl propionate, n propyl propionate, ethyl benzoate, n-propyl phthalate, phenylformic acid ethoxy ethyl ester, dipropyl carbonate, " Exxate 700 " (commercially available acetic acid C ₇alkyl ester), " Exxate 800 " (commercially available acetic acid C ₈alkyl ester), dibutyl phthalate and tert.-butyl acetate.

Lactone solubilizing agent of the present invention comprises the lactone shown in following structure [A], [B] and [C]:

[A] [B] [C]

These lactones are in six former subrings (A) or preferably in pentatomic ring (B), contain functional group-CO ₂-, wherein for structure [A] and [B], R ₁to R ₈independently be selected from hydrogen or straight chain, side chain, ring-type, dicyclo, saturated and undersaturated alkyl.R ₁to R ₈each can with R ₁to R ₈another is connected to form ring.As in structure [C], lactone can have ring outer alkylidene group, wherein R ¹to R ⁶independently be selected from hydrogen or straight chain, side chain, ring-type, dicyclo, saturated and undersaturated alkyl.R ¹to R ⁶each can with R ¹to R ⁶another is connected to form ring.The molecular weight ranges of lactone solubilizing agent is approximately 80 to about 300 atomic mass units, preferably approximately 80 to about 200 atomic mass units.

Representational lactone solubilizing agent includes but not limited to the compound that table 6 is listed.

table 6

The kinematic viscosity of lactone solubilizing agent under 40 ℃ is less than approximately 7 centistokes usually.For example, under 40 ℃, the kinematic viscosity of γ-undecalactone is 5.4 centistokes, and the kinematic viscosity of cis-(3-hexyl-5-methyl) dihydrofuran-2-ketone is 4.5 centistokes.Lactone solubilizing agent is commercially available, or can be by the described method preparation of the U.S. Patent application 10/910,495 that on August 3rd, 2004 submits to, and this patent application is incorporated herein by reference.

Aryl ethers solubilizing agent of the present invention also comprises formula R ¹oR ²shown aryl ethers, wherein R ¹be selected from the aryl with 6-12 carbon atom; R ²be selected from the aliphatic hydrocarbyl with 1-4 carbon atom; And the molecular weight of wherein said aryl ethers is approximately 100 to about 150 atomic mass units.General formula R ¹oR ²in representative R ¹aryl comprises phenyl, xenyl, cumenyl, Lai Ji, tolyl, xylyl, naphthyl and pyridyl.General formula R ¹oR ²in representative R ²aliphatic hydrocarbyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl and the tertiary butyl.Representational aryl ethers solubilizing agent includes but not limited to methyl phenyl ether (phenylmethylether), 1,3-dimethoxy benzene, ethylphenyl ether and butyl phenylate.

Fluoroether solubilizing agent of the present invention comprises general formula R ¹oCF ₂cF ₂those fluoroethers shown in H, wherein R ¹be selected from and have approximately 5 to approximately aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl of 15 carbon atoms, preferably one-level, straight chain, saturated alkyl.Representational fluoroether solubilizing agent includes but not limited to C ₈h ₁₇oCF ₂cF ₂h and C ₆h ₁₃oCF ₂cF ₂h.Be to be noted that, if refrigeration agent is certain fluoroether, solubilizing agent can not be the same fluoroether.

Fluoroether solubilizing agent also can comprise the ether spread out from fluoroolefins and polyvalent alcohol.Fluoroolefins can be CF ₂=CXY type, wherein X is hydrogen, chlorine or fluorine, Y is chlorine, fluorine, CF ₃or OR _f, R wherein _ffor CF ₃, C ₂f ₅or C ₃f ₇.Representational fluoroolefins is tetrafluoroethylene, chlorotrifluoroethylene, R 1216 and perfluoro methyl vinyl ether.Polyvalent alcohol can be straight chain or side chain.The straight chain polyvalent alcohol can be HOCH ₂(CHOH) _x(CRR ') _ycH ₂the OH type, wherein R and R ' are hydrogen or CH ₃or C ₂h ₅, and the integer that wherein x is 0-4, the integer that y is 0-4.Branched chain polyol can be C (OH) _t(R) _u(CH ₂oH) _v[(CH ₂) _mcH ₂oH] _wtype, wherein R can be hydrogen, CH ₃or C ₂h ₅, m can be the integer of 0-3, and t and u can be 0 or 1, v and the w integer that is 0-4, and t+u+v+w=4 wherein.Representational polyvalent alcohol is TriMethylolPropane(TMP), tetramethylolmethane, butyleneglycol and ethylene glycol.

Of the present invention 1,1,1-trifluoro alkane solubilizing agent comprises general formula CF ₃r ¹shown by 1,1,1-trifluoro alkane, wherein R ¹be selected from and have approximately 5 to approximately aliphatic hydrocarbyl and the alicyclic hydrocarbon radical of 15 carbon atoms, preferably one-level, straight chain, saturated alkyl.Representational 1,1,1-trifluoro alkane solubilizing agent includes but not limited to 1,1,1-trifluoro hexane and 1,1,1-trifluoro dodecane.

Solubilizing agent of the present invention can be used as single compound and exists, or can be used as the mixture existence that surpasses a kind of solubilizing agent.The mixture of solubilizing agent can contain two kinds of solubilizing agent from similar compound, for example two kinds of lactones, or contain two kinds of solubilizing agent from the different compounds of two classes, as lactone and polyoxyalkylene glycol ether.

Comprise refrigeration agent and Ultraluminescence dyestuff or comprise heat-transfer fluid and the present composition of Ultraluminescence dyestuff in, 0.001 weight percent to about 1.0 weight percents of having an appointment are UV dyestuffs, preferably approximately 0.005 weight percent to about 0.5 weight percent, most preferably 0.01 weight percent to about 0.25 weight percent is the UV dyestuff.

The solubleness of these Ultraluminescence dyestuffs in refrigeration agent and heat transfer compositions may be poor.Therefore, the method that these dyestuffs is incorporated into to refrigeration, air-conditioning or thermal-pump unit is inconvenient, expensive and time-consuming always.United States Patent (USP) RE 36,951 (it is incorporated herein by reference) has described a method, and this method adopts dye powder, solid particulate or the slurries of certain assembly that can put into refrigeration or air-conditioning plant.Along with refrigeration agent and lubricant circulates, by this device, dyestuff occurs to dissolve or disperses and be carried through this device.In document, also described many other in order to dyestuff is incorporated into to refrigeration or the method for air-conditioning plant.

Ideally, the Ultraluminescence dyestuff can be dissolved in refrigeration agent, thereby is incorporated in refrigeration, air-conditioning or thermal-pump unit without any need for special method.The present invention relates to comprise the composition of Ultraluminescence dyestuff, this fluorescence dye can be dissolved in refrigeration agent and be introduced in apparatus system together with solubilizing agent.Also can store and transport at low temperatures containing the refrigeration agent of dyestuff and heat-transfer fluid even the present composition can allow, keep dyestuff in solution state simultaneously.

In the present composition that comprises refrigeration agent, Ultraluminescence dyestuff and solubilizing agent or comprise heat-transfer fluid, Ultraluminescence dyestuff and solubilizing agent, in total composition, have an appointment 1 to about 50 weight percents, preferably approximately 2 to about 25 weight percents, most preferably from about 5 to about 15 weight percents be the solubilizing agent in refrigeration agent or heat-transfer fluid.In composition of the present invention, the Ultraluminescence dyestuff in refrigeration agent or heat-transfer fluid with about 0.001 weight percent to about 1.0 weight percents, preferably 0.005 weight percent is to about 0.5 weight percent, and most preferably 0.01 weight percent to the about concentration of 0.25 weight percent exists.

Solubilizing agent such as ketone may have the smell that makes us unhappy, can be covered by adding mask agent or perfume compound.The representative instance of mask agent or perfume compound can comprise Chinese ilex, new lemon, cherry, Chinese cassia tree, Mentha arvensis L. syn.M.haplocalyxBrig, flower (Floral) or tangerine peel (they all are commercially available), and (R)-4-isopropenyl-1-methyl-1-cyclohexene and firpene.The working concentration of this mask agent be mask agent and solubilizing agent gross weight approximately 0.001% to as high as approximately 15%.

The invention still further relates to the method that detects the leakage in refrigeration plant, air-conditioning plant or thermal-pump unit by the refrigeration agent that comprises the Ultraluminescence dyestuff or heat transfer fluid composition.The existence of dyestuff in composition makes the leakage of refrigerant that can detect in refrigeration, air-conditioning or thermal-pump unit.Leak Detection can help that people are careful, fallback or the equipment failure of solution and/or anti-locking apparatus or system.Leak Detection can also help people to install the chemical for the operation of device.

The method comprises to refrigeration, air-conditioning or thermal-pump unit to be provided and comprises refrigeration agent described herein, Ultraluminescence dyestuff or comprise heat-transfer fluid described herein and the Ultraluminescence dye well optionally comprises the composition of solubilizing agent described herein, and adopts suitable means to detect the refrigeration agent containing the Ultraluminescence dyestuff.The appropriate means that detects dyestuff includes but not limited to ultraviolet lamp, and it often is called " black lamp " or " blue-ray light ".This ultraviolet lamp can be from the commercially available acquisition in source of a plurality of special detection Ultraluminescence dyestuffs.Once will contain the composition of Ultraluminescence dyestuff is incorporated in refrigeration, air-conditioning or thermal-pump unit and allows it cycle through this apparatus system, can by by described ultra violet lamp on this device and observe near the fluorescence of the dyestuff any leakage point, locate leakage point or leakage point near zone.

Mechanical refrigeration is mainly to have applied such thermodynamic process: heat-eliminating medium is as refrigeration agent recyclable being reused after a circulation.That circulation commonly used comprises is steam compressed, absorption, vapour injection (steam-jet) or vapor steam blaster (steam-ejector) and air.

Vapor compression refrigeration system comprises that vaporizer, compressor, condenser and expansion gear, vapor-compression cycle reuse refrigeration agent in a plurality of steps, produces cooling effect in a step, and produce heat effect in other step.This circulation can be summarized as follows.Liquid refrigerant enters vaporizer by expansion gear, and this liquid refrigerant, forms gas and produces cooling at low-temperature boiling at vaporizer.It is compressed and improve pressure and temperature that low-pressure gas enters compressor.Then high pressure (compression) gaseous refrigerant enters condenser generation condensation, to environment, emits heat.Refrigeration agent returns to expansion gear, and by this expansion gear, from it, the high-pressure horizontal condenser expand into the low pressure level in vaporizer to this liquid, thereby repeats this circulation.

There is polytype compressor to can be used for refrigeration application.Compressor generally can be divided into reciprocating, rotary, jet-type, centrifugal, vortex, spiral or axial-flow compressor according to the mechanical system of compressed fluid, or generally can be divided into positive-displacement compressor (for example reciprocating, vortex or screw compressor) or dynamical type compressor (for example centrifugal or jet-type compressor) according to the mode that mechanical organ acts on fluid to be compressed.

The present composition that comprises fluoroolefins can be used for any above-mentioned compressor type.For any given compressor, the selection of refrigeration agent will be depended on many factors, comprises for example boiling point and vapour pressure requirement.

Positive-displacement compressor and dynamical type compressor all can be used for the inventive method.The refrigerant composition that comprises at least one fluoroolefins for some, radial compressor is a kind of preferred device type.

Radial compressor radially accelerates refrigeration agent with spinner member, generally includes the impeller and the diffuser (diffuser) that are contained in casing.Radial compressor locates to suck fluid in the central import (central inlet) of impeller eye (impeller eye) or convolution impeller usually, and fluid is radially outward accelerated.There will be certain static pressure liter in impeller, but most of voltage rise appears in the diffuser part of casing, speed is converted into static pressure there.Every group of impeller-diffuser is the one-level of compressor.Depend on required resulting pressure and refrigerant volume to be dealt with, radial compressor is constructed with 1-12 level or more multistage.

The pressure ratio of compressor or compression ratio are the ratios of absolute top hole pressure and absolute intake pressure.In fact the pressure that radial compressor is sent be constant in relatively wide containment.

Positive-displacement compressor is steam suction cavity, thereby and makes cavity volume reduce compressed vapour.After steam compressed, further reduce to zero or approaching zero by the volume that makes cavity and force steam to leave cavity.Positive-displacement compressor meeting accumulated pressure, this pressure only is subject to volumetric efficiency and each parts to bear the restriction of the intensity of pressure.

The formula different from positive-displacement compressor, radial compressor relies on the centrifugal force of quick runner to make the steam compressed impeller that passes through fully.There do not is positive displacement, but have so-called powered compressor.

The developable pressure of radial compressor depends on the tip speed of impeller.Tip speed is the speed of measuring at the tip of impeller, relevant with diameter and the rotations per minute of impeller.The capacity of radial compressor is determined by the size of the passage by impeller.This makes the size of compressor more depend on required pressure rather than capacity.

Because radial compressor is high-speed cruising, it is high volume, low pressure machine basically.Radial compressor gets into smooth best with low pressure refrigerant as trichlorofluoromethane (CFC-11) or 1,2,2-Refrigerant R 113 (CFC-113).Some low pressure refrigerant fluids of the present invention are applicable simple and easy substitute (the drop-in replacement) that makes CFC-113 in existing centrifugation apparatus.

Large radial compressor is usually with the speed operation of 3000-7000 rpm (rpm).Little turbo-centrifugal compressor (Miniature centrifugal compressor) is designed to carry out approximately 40,000 to the about high speed operation of 70,000 (rpm), and its impeller size is little, usually is less than 0.15 meter (approximately 6 inches).

Can use multi-stage impeller in radial compressor, to improve compressor efficiency, thereby need in use less power.For two-stage system, be in operation, the outlet thing of first step impeller enters the suction import of the second impeller.These two impellers can be operated with single axle.Every grade of compression ratio that can accumulate about 4:1; That is to say, absolute top hole pressure can be four times of absolute suction pressure.US 5,065,990 and US 5,363,674 several examples of two-stage centrifugal compressor system (especially for automobile) have been described, these two patents are incorporated herein by reference.

The invention still further relates in refrigeration, air-conditioning or thermal-pump unit heating or the cooling method of producing, described method comprise refrigeration agent or heat transfer fluid composition are incorporated into there is (a) radial compressor, (b) multistage centrifugal compressor or (c) in the described device of veneer/single-pass exchanger; Wherein said refrigeration agent or heat transfer fluid composition comprise at least one and are selected from following fluoroolefins:

(iii) be selected from following fluoroolefins:

Can be used for fixed air-conditioning, heat pump or movable air conditioner and refrigeration system in order to produce heating or cooling method.Fixed air-conditioning and heat pump application comprise window, pipe free, tubular type, sealed terminal are arranged, and refrigerator (chiller) and commercialization, comprise closed roof.Refrigeration application comprises family expenses or houshold refrigerator and reezer system (freezer), ice-making machine, free-standing water cooler (cooler) and reezer system, large built-in wardrobe type water cooler and reezer system and transport refrigeration system.

Composition of the present invention can be used for adopting in air-conditioning, heating and the refrigeration system of plate-fin and tubular heat exchanger, micro-channel type heat exchanger and horizontal or vertical one way pipe or plate type regenerator in addition.

Conventional micro-channel heat exchanger may be unsatisfactory for low pressure refrigerant composition of the present invention.Low operating pressure and density cause high flow rate and in the high frictionloss of all parts.In these cases, can change evaporator designs.Can use veneer/single-pass exchanger to arrange, rather than several microchannel plate link together (with respect to refrigerant path).Therefore, the preferred heat exchanger for refrigeration agent of the present invention or heat transfer fluid composition is veneer/single-pass exchanger.

The invention still further relates to and produce cooling method, described method is included near the evaporation fluoroolefins composition of the present invention of object to be cooled, the described composition of condensation afterwards.

The invention still further relates to the method that produces heating, described method is included near the condensation fluoroolefins composition of the present invention of object to be heated, afterwards by described composition evaporation.

The invention still further relates to the cooling method that produces, described method is included in compressed package in radial compressor and, containing the composition of at least one fluoroolefins, evaporates described composition, afterwards near the described composition of evaporation object to be cooled.In addition, the radial compressor of the inventive method can be multistage centrifugal compressor, preferably 2 grades of radial compressors.

The invention still further relates to the cooling method of generation in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device comprises at least one veneer/single-pass exchanger, described method comprises condensation composition of the present invention, afterwards near the described composition of evaporation object to be cooled.

Composition of the present invention is particularly useful for little turbo-centrifugal compressor (the Miniature centrifugal compressor can be used for automobile and window air-conditioning), heat pump or refrigeration and other application for transportation.These high-level efficiency Miniature centrifugal compressors can, by motor drive, therefore can not rely on motor speed and be operated.Constant compressor speed can allow system that relatively constant cooling power all is provided under all motor speed.Than conventional R-134a automotive air-conditioning system, this provides the chance of efficiency improvement, particularly under higher engine speed.When considering the circular flow of conventional system under high actuating speed, the advantage of these lp systems becomes more outstanding.

Perhaps, the Miniature centrifugal compressor can not use electric power, but the turbine driven by engine exhaust or ratio type gear wheel driving device (ratioed gear drive assembly with a ratioed belt drive) with proportion expression belt drive provide power.In existing Automobile Design, available electric power is approximately 14 volts, but new Miniature centrifugal compressor needs the approximately electric power of 50 volts.Therefore, the use substitute energy will be favourable.The turbine driven by engine exhaust provides the refrigeration plant of power or air-conditioning plant to have a detailed description in the U.S. Patent Application Serial 11/367,517 of submitting on March 3rd, 2006.By ratio type gear wheel driving device, provide the refrigeration plant of power or air-conditioning plant to have a detailed description in the U.S. Patent Application Serial 11/378,832 of submitting on March 17th, 2006.

The invention still further relates to the cooling method that produces, described method is included in the turbine driven by engine exhaust and provides distilled edition inventive composition in the Miniature centrifugal compressor of power; The described composition of condensation; Near the described composition of evaporation object to be cooled afterwards.

The invention still further relates to and produce cooling method, described method is included in distilled edition inventive composition in the Miniature centrifugal compressor that provides power by the ratio type gear wheel driving device with proportion expression belt drive; The described composition of condensation; Near the described composition of evaporation object to be cooled afterwards.

The present invention relates to produce cooling method in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device comprises at least one veneer/single-pass exchanger, described method is included in distilled edition inventive composition in radial compressor, the described composition of condensation and near the described composition of evaporation object to be cooled afterwards.

The invention still further relates to that to substitute or replace GWP with the composition with low GWP be approximately 150 or higher refrigerant composition or the method for high GWP refrigeration agent.The composition that comprises at least one fluoroolefins of the present invention product as an alternative that provide are provided a kind of method.In another embodiment of the invention, will compare refrigeration agent of the present invention or heat transfer fluid composition with low GWP with composition replaced or that replace and be incorporated in refrigeration, air-conditioning or thermal-pump unit.In some cases, before introducing low GWP composition, need to from device, remove the high GWP refrigeration agent wherein existed.In other situation, can be by fluoroolefins composition of the present invention in high GWP refrigeration agent be incorporated into device simultaneously.

Global warming potential (GWP) is the index of the relative Global warming contribution of estimating that the airborne release of 1 kilogram of certain specific greenhouse gases is compared with the discharge of 1 kilogram of carbonic acid gas.Can calculate the GWP of different time scope, with the impact of the atmospheric lifetime that shows given gas.Usually the numerical value of indication is the GWP of 100 year scopes.

High GWP refrigeration agent be anyly can serve as refrigeration agent or heat-transfer fluid, in 100 year scopes its GWP be approximately 1000 or larger or 500 or larger, 150 or larger, 100 or larger or 50 or larger compound.According to inter-governmental climate change work group (Intergovernmental Panel on Climate Change, IPCC) the GWP calculation result of announcing need to be carried out alternative refrigeration agent and heat-transfer fluid, includes but not limited to HFC-134a (1,1,1,2-Tetrafluoroethane).

The present invention will provide the composition with zero or low-ozone depletion potential and low global warming potential (GWP).Fluoroolefins of the present invention or fluoroolefins of the present invention will be lower than many fluoroether refrigerants of current use with its global warming potential of mixture of other refrigeration agent.Usually, fluoroolefins of the present invention expection has and is less than approximately 25 GWP.One aspect of the present invention is to provide global warming potential and is less than 1000, is less than 500, is less than 150, is less than 100 or be less than 50 refrigeration agent.Another aspect of the present invention is by add fluoroolefins to reduce the clean GWP of described mixture to refrigerant mixture.

The invention still further relates to the method for the GWP that reduces refrigeration agent or heat-transfer fluid, described method comprises described refrigeration agent or heat-transfer fluid and at least one fluoroolefins of the present invention is combined.In another embodiment, comprise described the first composition and comprise at least composition of fluoroolefins in order to the method that reduces global warming potential and combined, be suitable as the second composition of refrigeration agent or heat-transfer fluid with generation, and the global warming potential of wherein said the second composition is lower than described the first composition.Confirmable, the mixture of each compound or the GWP of combination can be calculated by the weighted mean of the GWP of every kind of pure compound.

The invention still further relates to the method that reduces the global warming potential of original refrigeration agent or heat transfer fluid composition with the present composition that comprises at least one fluoroolefins, described method comprises described original refrigeration agent or heat transfer fluid composition and the present composition that comprises at least one fluoroolefins is combined, to produce second refrigerant or heat transfer fluid composition, the global warming potential of wherein said second refrigerant or heat transfer fluid composition is lower than described original refrigeration agent or heat transfer fluid composition.

The invention still further relates to the method for the GWP of the original refrigeration agent that reduces in refrigeration, air-conditioning or thermal-pump unit or heat transfer fluid composition, the GWP of wherein said original refrigeration agent or heat-transfer fluid is approximately 150 or higher; Described method comprises to described refrigeration, air-conditioning or thermal-pump unit introduces refrigeration agent of the present invention or heat transfer fluid composition second, low GWP.

Method in order to the GWP that reduces original refrigeration agent of the present invention is first removed original refrigeration agent or heat transfer fluid composition before also can being included in and introducing refrigeration agent or heat-transfer fluid second, low GWP from described refrigeration, air-conditioning or thermal-pump unit.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition by second refrigerant or heat transfer fluid composition, described method comprises provides composition of the present invention as second refrigerant or heat transfer fluid composition.Original refrigeration agent can be the alternative refrigeration agent of needs used in any refrigeration, air-conditioning or thermal-pump unit.

Any in the adulterant that the original refrigeration agent need substituted or heat-transfer fluid can be fluoroether refrigerant, Chlorofluorocarbons (CFCs) refrigeration agent, Hydrochlorofluorocarbons refrigeration agent, fluoroether refrigerant or refrigeration agent compound.

May need alternative fluoroether refrigerant of the present invention to include but not limited to: CHF ₃(HFC-23), CH ₂f ₂(HFC-32), CH ₃f (HFC-41), CHF ₂cF ₃(HFC-125), CHF ₂cHF ₂(HFC-134), CH ₂fCF ₃(HFC-134a), CHF ₂cH ₂f (HFC 143), CF ₃cH ₃(HFC-143a), CHF ₂cH ₃(HFC-152a), CH ₂fCH ₃(HFC-161), CHF ₂cF ₂cF ₃(HFC-227ca), CF ₃cFHCF ₃(HFC-227ea), CHF ₂cF ₂cHF ₂(HFC-236ca), CH ₂fCF ₂cF ₃(HFC-236cb), CHF ₂cHFCF ₃(HFC-236ea), CF ₃cH ₂cF ₃(HFC-236fa), CH ₂fCF ₂cHF ₂(HFC-245ca), CH ₃cF ₂cF ₃(HFC-245cb), CHF ₂cHFCHF ₂(HFC-245ea), CH ₂fCHFCF ₃(HFC-245eb), CHF ₂cH ₂cF ₃(HFC-245fa), CH ₂fCF ₂cH ₂f (HFC-254ca), CH ₃cF ₂cHF ₂(HFC-254cb), CH ₂fCHFCHF ₂(HFC-254ea), CH ₃cHFCF ₃(HFC-254eb), CHF ₂cH ₂cHF ₂(HFC-254fa), CH ₂fCH ₂cF ₃(HFC-254fb), CF ₃cH ₂cH ₃(HFC-263fb), CH ₃cF ₂cH ₂f (HFC-263ca), CH ₃cF ₂cH ₃(HFC-272ca), CH ₃cHFCH ₂f (HFC-272ea), CH ₂fCH ₂cH ₂f (HFC-272fa), CH ₃cH ₂cF ₂h (HFC-272fb), CH ₃cHFCH ₃(HFC-281ea), CH ₃cH ₂cH ₂f (HFC-281fa), CHF ₂cF ₂cF ₂cF ₂h (HFC-338pcc), CF ₃cH ₂cF ₂cH ₃(HFC-365mfa), CF ₃cHFCHFCF ₂cF ₃(HFC-43-10mee).These fluoroether refrigerants are commercially available, or can prepare by means commonly known in the art.

Fluoroether refrigerant of the present invention also can comprise azeotropic, the composition of azeotropic mixture sample (azeotrope-like) and non-azeotropic, these compositions comprise HFC-125/HFC-143a/HFC-134a (the ASHRAE label is R404 or R404A), (the ASHRAE label is R407 or R407A to HFC-32/HFC-125/HFC-134a, R407B or R407C), HFC-32/HFC-125 (R410 or R410A) and HFC-125/HFC-143a (the ASHRAE label is R507 or R507A), R413A (adulterant of R134a/R218/ Trimethylmethane), R423A (adulterant of R134a/R227ea), R507A (adulterant of R125/R143a) and other.

May need alternative Chlorofluorocarbons (CFCs) refrigeration agent of the present invention to comprise R22 (CHF ₂c1), R123 (CHCl ₂cF ₃), R124 (CHClFCF ₃), R502 (CFC-115 (CClF ₂cF ₃) and the adulterant of R22), R503 (R23/R13 (CClF ₃) adulterant) and other.

May need alternative Hydrochlorofluorocarbons of the present invention to comprise R12 (CF ₂cl ₂), R11 (CCl ₃f), R113 (CCl ₂fCClF ₂), R114 (CF ₂clCF ₂cl), R401A or R401B (adulterant of R22/R152a/R124), R408A (adulterant of R22/R125/R143a) and other.

May need alternative fluoroether refrigerant of the present invention can comprise the compound that is similar to the hydrogen fluorohydrocarbon but also contains at least one ether group Sauerstoffatom.Fluoroether refrigerant includes but not limited to C ₄f ₉oCH ₃and C ₄f ₉oC ₂h ₅(all being commercially available).

May need the original refrigeration agent of alternative the present invention or heat transfer fluid composition can optionally also comprise dme or at least one C that contains maximum 10 weight percents ₃-C ₅the combination of the refrigeration agent of hydrocarbon (for example propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, pentamethylene and neopentane (2,2-dimethylpropane)).Contain this C ₃-C ₅the example of the refrigeration agent of hydrocarbon is following azeotropic mixture sample composition: HCFC-22/HFC-125/ propane composition (the ASHRAE label is R402 or R402A and R402B), HCFC-22/ octafluoropropane/propane composition (the ASHRAE label is R403 or R403A and R403B), octafluoropropane/HFC-134a/ Trimethylmethane composition (the ASHRAE label is R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/ Trimethylmethane composition (the ASHRAE label is R414 or R414A and R414B), HFC-134a/HCFC-124/ normal butane composition (the ASHRAE label is R416 or R416A), HFC-125/HFC-134a/ normal butane composition (the ASHRAE label is R417 or R417A), (the ASHRAE label is R422 for HFC-125/HFC-134a/ dimethyl ether composition (the ASHRAE label is R419 or R419A) and HFC-125/HFC-134a/ Trimethylmethane composition, R422A, R422B, R422C, R422D).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R134a (HFC-134a, HFA 134a, the CF in refrigeration plant, air-conditioning plant or thermal-pump unit ₃cH ₂f), wherein said method comprises with the second refrigerant that comprises at least one compound that is selected from trifluoromethyl trifluoro vinyl ether (PMVE) or the alternative R134a of heat transfer fluid composition.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R152a (HFC-152a, 1,1-C2H4F2 C2H4F2, the CHF in refrigeration plant, air-conditioning plant or thermal-pump unit ₂cH ₃), wherein said method comprises with comprising at least one and is selected from E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze), 1,2,3,3,3-, five fluorine propylene (HFC-1225ye), 2,3,3,3-tetrafluoeopropene (HFC-1234yf), 3,3, the second refrigerant of the compound of 3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE) or heat transfer fluid composition substitute R152a.

The invention still further relates to R227ea (HFC-227ea, HFC-227ea, CF in alternative refrigeration plant, air-conditioning plant or thermal-pump unit ₃cHFCF ₃) method, wherein said method comprises providing and comprises at least one and be selected from E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze), 1,2,3,3,3-, five fluorine propylene (HFC-1225ye), 2,3,3,3-tetrafluoeopropene (HFC-1234yf), 3,3, the composition of the compound of 3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE) is product as an alternative.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is that (CFC-113,1,1,2-tri-is chloro-1,2,2-Halothane, CFCl for R113 in refrigeration plant, air-conditioning plant or thermal-pump unit ₂cF ₂cl), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butylene (HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (HFC-1567fts); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (PFBE); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (HFC-1567szz); 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten (F13E); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and the fluoro-3-hexene of 1,1,1,2,2,5,5,6,6,6-ten (F22E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R43-10mee (HFC-43-10mee), 1,1,1,2,3,4,4,5,5 in refrigeration plant, air-conditioning plant or thermal-pump unit, 5-Decafluoropentane, CF ₃cHFCHFCF ₂cF ₃), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butylene (HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (HFC-1567fts); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (PFBE); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (HFC-1567szz); 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten (F13E); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and the fluoro-3-hexene of 1,1,1,2,2,5,5,6,6,6-ten (F22E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the C in refrigeration plant, air-conditioning plant or thermal-pump unit ₄f ₉oCH ₃(perfluorobutyl methyl ethers), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butylene (HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (HFC-1567fts); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (PFBE); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (HFC-1567szz); 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten (F13E); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and the fluoro-3-hexene of 1,1,1,2,2,5,5,6,6,6-ten (F22E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R365mfc (HFC-365mfc, 1,1,1,3,3-3-pentafluorobutane, the CF in refrigeration plant, air-conditioning plant or thermal-pump unit ₃cH ₂cF ₂cH ₃), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene of 1,1,1,2,2,3,4,5,5,6,6,6-12 (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2-butylene (HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene of 3,3,4,4,5,5,5-seven (HFC-1567fts); The fluoro-1-hexene of 3,3,4,4,5,5,6,6,6-nine (PFBE); The fluoro-2-hexene of 4,4,5,5,6,6,6-seven (HFC-1567szz); 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten (F13E); The fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and the fluoro-3-hexene of 1,1,1,2,2,5,5,6,6,6-ten (F22E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R11 (CFC-11, trichlorofluoromethane, the CFCl in refrigeration plant, air-conditioning plant or thermal-pump unit ₃), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (FC-141-10myy); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (HFC-1429myz); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (HFC-1429mzy); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (HFC-1447fz); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (HFC-1429mzt) and 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene (F12E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is that (HCFC-123,2,2-bis-is chloro-1,1,1-Halothane, CF for R123 in refrigeration plant, air-conditioning plant or thermal-pump unit ₃cHCl ₂), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y); The fluoro-2-amylene of 1,1,1,2,3,4,4,5,5,5-ten (FC-141-10myy); The fluoro-2-amylene of 1,1,1,2,4,4,5,5,5-nine (HFC-1429myz); The fluoro-2-amylene of 1,1,1,3,4,4,5,5,5-nine (HFC-1429mzy); The fluoro-1-amylene of 3,3,4,4,5,5,5-seven (HFC-1447fz); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (HFC-1429mzt) and 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene (F12E).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R245fa (HFC-245fa, 1,1,1,3,3-pentafluoropropane, the CF in refrigeration plant, air-conditioning plant or thermal-pump unit ₃cH ₂cHF ₂), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 2,3,3-trifluoro propene (HFC-1243yf); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,3,3,3-tetrafluoeopropene (HFC-1234ze); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (HFC-1327my); 1,2,3,3-tetrafluoeopropene (HFC-1234ye) and pentafluoroethyl group trifluoro vinyl ether (PEVE).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is that (CFC-114,1,2-bis-is chloro-1,1,2,2-Tetrafluoroethane, CFCl for R114 in refrigeration plant, air-conditioning plant or thermal-pump unit ₂cF ₂cl), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,2,3,4,4,4-octafluoro-2-butylene (FC-1318my); 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butylene (HFC-1336yf) and the fluoro-1-butylene of 3,3,4,4,4-five (HFC-1345fz).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R236fa (HFC-236fa, 1,1,1,3,3,3-HFC-236fa, the CF in refrigeration plant, air-conditioning plant or thermal-pump unit ₃cH ₂cF ₃), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,1,1,2,3,4,4,4-octafluoro-2-butylene (FC-1318my); 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butylene (HFC-1336yf) and the fluoro-1-butylene of 3,3,4,4,4-five (HFC-1345fz).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R401A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401A is HCFC-22 (chlorodifluoromethane, the CHF containing 53 weight percents of having an appointment ₂cl), the about HFC-152a of 13 weight percents (1,1-C2H4F2 C2H4F2, CHF ₂cH ₃) and the about HCFC-124 of 34 weight percents (the chloro-HFA 134a of 2-, CF ₃the ASHRAE label of refrigeration agent adulterant CHClF).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R401B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401B is HCFC-22 (chlorodifluoromethane, the CHF containing 61 weight percents of having an appointment ₂cl), the about HFC-152a of 11 weight percents (1,1-C2H4F2 C2H4F2, CHF ₂cH ₃) and the about HCFC-124 of 28 weight percents (the chloro-HFA 134a of 2-, CF ₃the ASHRAE label of refrigeration agent adulterant CHClF).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R409A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409A is HCFC-22 (chlorodifluoromethane, the CHF containing 60 weight percents of having an appointment ₂cl), the about HCFC-124 of 25 weight percents (the chloro-HFA 134a of 2-, CF ₃cHClF) and approximately the HCFC-142b of 15 weight percents (1-chlorine-1,1-difluoroethane, CF ₂clCH ₃) the ASHRAE label of refrigeration agent adulterant.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R409B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409B is HCFC-22 (chlorodifluoromethane, the CHF containing 65 weight percents of having an appointment ₂cl), the about HCFC-124 of 25 weight percents (the chloro-HFA 134a of 2-, CF ₃cHClF) and approximately the HCFC-142b of 10 weight percents (1-chlorine-1,1-difluoroethane, CF ₂clCH ₃) the ASHRAE label of refrigeration agent adulterant.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R414B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R414B is HCFC-22 (chlorodifluoromethane, the CHF containing 50 weight percents of having an appointment ₂cl), the about HCFC-124 of 39 weight percents (the chloro-HFA 134a of 2-, CF ₃cHClF), the about Trimethylmethane of 1.5 weight percents (R600a, CH ₃cH (CH ₃) CH ₃) and the about HCFC-142b of 9.5 weight percents (1-chlorine-1,1-difluoroethane, CF ₂clCH ₃) the ASHRAE label of refrigeration agent adulterant.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R416A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R416A is HFC-134a (HFA 134a, the CF containing 59 weight percents of having an appointment ₃cH ₂f)), the about HCFC-124 of 39.5 weight percents (the chloro-HFA 134a of 2-, CF ₃cHClF) and approximately normal butane (the CH of 1.5 weight percents ₃cH ₂cH ₂cH ₃) the ASHRAE label of refrigeration agent adulterant.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is R12 (CFC-12, Refrigerant 12, the CF in refrigeration plant, air-conditioning plant or thermal-pump unit ₂cl ₂), wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf); With trifluoromethyl trifluoro vinyl ether (PMVE).

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, described original composition is the R500 in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises that use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,3-, five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf); With trifluoromethyl trifluoro vinyl ether (PMVE).R500 is R12 ((CFC-12, Refrigerant 12, the CF containing 73.8 weight percents of having an appointment ₂cl ₂) and the about R152a of 26.2 weight percents (HFC-152a, 1,1-C2H4F2 C2H4F2, CHF ₂cH ₃) the ASHRAE label of azeotrope refrigerant adulterant.

The present invention relates to substitute the method for original refrigeration agent or heat transfer fluid composition, wherein said original refrigeration agent or heat transfer fluid composition are R134a or R12, and wherein said R134a or R12 with comprise about 1.0 weight percents to the HFC-32 of about 37 weight percents and approximately 99 weight percents to approximately second refrigerant or the heat transfer fluid composition of the HFC-1225ye of 63 weight percents are substituted.In another embodiment, second refrigerant or heat transfer fluid composition can comprise about 1.0 weight percents to the HFC-32 of about 10 weight percents and approximately 99 weight percents to the about HFC-1225ye of 90 weight percents.

The present invention relates to substitute the method for original refrigeration agent or heat transfer fluid composition, wherein said original refrigeration agent or heat transfer fluid composition are R22, R404A or R410A, and wherein said R22, R404A or R410A with comprise about 1.0 weight percents to the HFC-32 of about 37 weight percents and approximately 99 weight percents to approximately second refrigerant or the heat transfer fluid composition of the HFC-1225ye of 63 weight percents are substituted.In another embodiment, second refrigerant or heat transfer fluid composition can comprise about 20 weight percents to the HFC-32 of about 37 weight percents and approximately 80 weight percents to the about HFC-1225ye of 63 weight percents.

The invention still further relates to the method that substitutes original refrigeration agent or heat transfer fluid composition, wherein said original refrigeration agent or heat transfer fluid composition are R22, R404A or R410A, and wherein said R22, R404A or R410A with comprise about 20 weight percents to the HFC-1225ye of about 95 weight percents, approximately 1.0 weight percents to the HFC-32 of about 65 weight percents and approximately 1.0 weight percents to approximately second refrigerant or the heat transfer fluid composition of the HFC-125 of 40 weight percents are substituted.In another embodiment, second refrigerant or heat transfer fluid composition comprise about 30 weight percents to the HFC-1225ye of about 90 weight percents, approximately 5.0 weight percents to the HFC-32 of about 55 weight percents and approximately 1.0 weight percents to the about HFC-125 of 35 weight percents.In another embodiment, second refrigerant or heat transfer fluid composition comprise about 40 weight percents to the HFC-1225ye of about 85 weight percents, approximately 10 weight percents to the HFC-32 of about 45 weight percents and approximately 1.0 weight percents to the about HFC-125 of 28 weight percents.

The present invention relates to substitute the method for original refrigeration agent or heat transfer fluid composition, wherein said original refrigeration agent or heat transfer fluid composition are R134a or R12, and wherein said R134a or R12 are with comprising following second refrigerant or heat transfer fluid composition is substituted:

HFC-1243zf and HFC-1225ye;

HFC-1243zf, HFC-1225ye and HFC-125;

HFC-1243zf, HFC-1225ye and HFC-32; Or

HFC-1243zf, HFC-1225ye, HFC-125 and HFC-32.

In the method for all aforesaid alternative refrigerants, all can substitute the refrigeration agent in existing installation with fluoroolefins.In addition, can come alternate design to use this refrigeration agent in the existing installation of certain refrigeration agent with fluoroolefins.In addition, can substitute the refrigeration agent in existing installation and need not change or alternative lubricant with fluoroolefins.

The present invention relates to reduce the method for the fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit, described method comprises composition of the present invention is incorporated in described refrigeration plant or air-conditioning plant.

When considering combustibility, the refrigeration agent that may leak from refrigeration plant, air-conditioning plant or thermal-pump unit is a large problem.Once leak in refrigeration plant or air-conditioning plant, refrigeration agent and possible a small amount of lubricant may discharge from apparatus system.If this leak materials touches ignition source, may cause fire.So-called fire hazard refer in the middle of refrigeration plant, air-conditioning plant or thermal-pump unit or near may presence of fire possibility.Reduce the fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit, can be measured and discriminating is considered to non-flammable refrigeration agent or heat-transfer fluid is realized by using through described method and standard above.In addition, non-flammable fluoroolefins of the present invention can be joined in device or not yet add combustible refrigerant or the heat-transfer fluid in auto levelizer.Non-flammable fluoroolefins of the present invention can reduce just in case the possibility of presence of fire and/or the temperature of the flame by reducing any generation or the degree that size reduces fire hazard while occur leaking.

The invention still further relates to and reduce in refrigeration plant, air-conditioning plant or thermal-pump unit or near the method for fire hazard, described method comprises at least one non-flammable fluoroolefins and combustible refrigerant is combined, and said composition is incorporated in refrigeration plant, air-conditioning plant or thermal-pump unit.

The invention still further relates to and reduce in refrigeration plant, air-conditioning plant or thermal-pump unit or near the method for fire hazard, described method comprises at least one non-flammable fluoroolefins and lubricant is combined, and said composition is incorporated in refrigeration plant, air-conditioning plant or the thermal-pump unit that combustible refrigerant is housed.

The invention still further relates to and reduce in refrigeration plant, air-conditioning plant or thermal-pump unit or near the method for fire hazard, described method comprises at least one fluoroolefins is incorporated in described device.

The invention still further relates in refrigeration plant, air-conditioning plant or thermal-pump unit the method for using combustible refrigerant, described method comprises described combustible refrigerant and at least one fluoroolefins is combined.

The invention still further relates to the flammable method that reduces combustible refrigerant or heat-transfer fluid, described method comprises combustible refrigerant and at least one fluoroolefins is combined.

The invention still further relates to and heat is transferred to the method for heat sink from thermal source, wherein composition of the present invention serves as heat-transfer fluid.Described transfer of heat method comprises composition of the present invention is sent to heat sink from thermal source.

Heat-transfer fluid is used to by radiation, conduction or convection current heat from a space, position, object or object shift, mobile or move to another space, position, object or object.Heat-transfer fluid can serve as secondary coolant by providing by the means of long-range refrigeration (or heating) system transfer cooling (or heating).In some systems, heat-transfer fluid can remain on steady state (not evaporating or condensation) in whole transfer process.Perhaps, transpiration cooling process also can adopt heat-transfer fluid.

Thermal source may be defined as any space, position, object or object that needs to shift, move or move out heat.The example of thermal source can be need refrigeration or cooling space (open or enclosed space) as the refrigerator in supermarket or refrigerator, need the space of air-conditioning or need the car passenger compartment of air-conditioning.Heat sink can be defined as any space, position, object or object that can absorb heat.Vapor compression refrigeration system is an example of this heat sink.

Embodiment

embodiment

embodiment 1

performance data

Table 7 demonstration the compounds of this invention and CFC-113, HFC-43-10mee, C ₄f ₉oCH ₃the refrigeration performance of comparing with HFC-365mfc, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of supercooling temperatures (subcool temperature) (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

table 7

embodiment 2

performance data

Table 8 shows the refrigeration performance that the compounds of this invention is compared with HCFC-123 with CFC-11, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of supercooling temperatures (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

table 8

embodiment 3

performance data

Table 9 shows the refrigeration performance that the compounds of this invention is compared with HFC-245fa, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of supercooling temperatures (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

table 9

embodiment 4

performance data

Table 10 shows the refrigeration performance that the compounds of this invention is compared with HFC-236fa with CFC-114, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of supercooling temperatures (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

table 10

embodiment 5

performance data

Table 11 shows the refrigeration performance that the compounds of this invention is compared with HFC-227ea with HFC-134a, HFC-152a, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of supercooling temperatures (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

table 11

embodiment 6

flammable

Combustible cpd can be by being tested to identify by ASTM (American Society Testing and Materials) E681-01 with the electronics ignition source.This flammability test be to composition of the present invention at the temperature of 101kPa (14.7psia), 50% relative humidity and appointment with different air in concentration carry out, whether flammable to determine it, and flammable words are found out lean flammability (LFL).Result provides in table 12.

table 12

Result shows that HFC-1234yf and E-HFC-1234ze are flammable, and HFC-1225ye, HFC-1429myz/mzy and F12E right and wrong are flammable.For the mixture of HFC-1225ye and HFC-32 (known be flammable under pure state), through determining that the HFC-32 that finds 37 weight percents is the maximum amount for keeping non-flammable characteristic to exist.Those compositions that comprise non-flammable fluoroolefins are more receivable refrigeration agent or heat transfer fluid composition candidate.

embodiment 7

Produce the tip speed of pressure

Tip speed can be by being estimated to the refrigeration equipment of radial compressor, setting up some fundamental relations.The torque that impeller gives gas ideally is defined as:

T=m* (v ₂* r ₂-v ₁* r ₁) equation 1

In formula

The T=torque, Newton meter (n.m.)

The m=mass flow rate, kg/sec

V ₂=refrigeration agent leaves the tangential velocity (tip speed) of impeller, meter per second

R ₂the radius of=outlet impeller, rice

V ₁=refrigeration agent enters the tangential velocity of impeller, meter per second

R ₁the radius of=impeller inlet, rice

Suppose that refrigeration agent enters impeller with the direction of substantial axial, the tangential component v of speed ₁=0:

T=m*v ₂* r ₂equation 2

The power that the axle place needs is the product of torque and speed of rotation.

P=T* ω equation formula 3

In formula

P=power, W

ω=circular frequency, radian/s

?

P=T*w=m*v ₂* r ₂* the ω equation formula 4

Under low refrigeration agent flow velocity, the tip speed of impeller and the tangential velocity of refrigeration agent are almost equal; ?

R ₂* ω=v ₂equation 5

With

P=m*v ₂* v ₂equation 6

Another expression formula of ideal power is the product of mass flow rate and isentropic compression work,

P=m*H _i* (1000J/kJ) equation 7

In formula

H _i=refrigeration agent by the saturated vapo(u)r under evaporation conditions to the enthalpy difference under saturated condensing condition, kJ/kg.

Merge equation 6 and 7 two expression formulas,,

V ₂* v ₂=1000*H _iequation 8

Although equation 8 is based on some basic hypothesis, it can be estimated well the tip speed of impeller and the relatively important way of the tip speed of each refrigeration agent is provided.

Following table 13 has shown the theoretical tip speed that 1,2,2-Refrigerant R 113 (CFC-113) and the present composition are calculated.This assumed conditions relatively is:

40.0 °F of evaporator temperatures (4.4 ℃)

110.0 °F of condenser temperatures (43.3 ℃)

10.0 °F of liquid supercooling temperatures (5.5 ℃)

75.0 °F of reflux gas temperature (23.8 ℃)

Compressor efficiency is 70%

These are representative conditions of small sized turbine radial compressor operation.

table 13

The present embodiment shows, the tip speed of the compounds of this invention and CFC-113 differ approximately in 15%, will be effective substitutes of CFC-113, and required compressor design changes seldom.Its tip speed of most preferred composition and CFC-113 differ approximately in 10%.

embodiment 8

the refrigeration performance data

Table 14 shows the performance that various refrigerant compositions of the present invention are compared with HFC-134a.In table 14, Evap Pres refers to that evaporator pressure, Cond Pres refer to condenser pressure, and Comp Disch T refers to that compressor exit temperature, COP refer to energy efficiency, and CAP refers to capacity.These data are based on following condition.

40.0 °F of evaporator temperatures (4.4 ℃)

130.0 °F of condenser temperatures (54.4 ℃)

Cross 10.0 °F of colds (5.5 ℃)

60.0 °F of reflux gas temperature (15.6 ℃)

Compressor efficiency is 100%

Note overheated being included in cooling capacity.

table 14

There are several compositions to there is the energy-efficient (COP) more than HFC-134a, also keep lower or suitable top hole pressure and temperature simultaneously.The capacity of the composition that table 14 is listed is also similar to R134a, show these compositions can be in refrigeration and air-conditioning particularly in automative air conditioning is applied as the alternative refrigerant of R134a.Result also shows that the cooling capacity of HFC-1225ye can improve as HFC-32 by adding other compound.

embodiment 9

the refrigeration performance data

Table 15 shows the performance that various refrigerant compositions of the present invention are compared with R422A with R404A.In table 15, Evap Pres refers to that evaporator pressure, Cond Pres refer to condenser pressure, and Comp Disch T refers to that compressor exit temperature, EER refer to energy efficiency, and CAP refers to capacity.These data are based on following condition.

Evaporator temperature-17.8 ℃

46.1 ℃ of condenser temperatures

Cross 5.5 ℃ of colds

15.6 ℃ of reflux gas temperature

Compressor efficiency is 70%

Note overheated being included in cooling capacity.

table 15

There is its energy efficiency of several compositions (EER) suitable with R422A with R404A.Temperature out is also low than R404A and R507A.The capacity of the composition that table 15 is listed is also similar with R422A to R404A, R507A, shows that these compositions can be as the alternative refrigerant of R404A, R507A and R422A in refrigeration and air-conditioning.

embodiment 10

the refrigeration performance data

Table 16 shows the performance that various refrigerant compositions of the present invention are compared with R410A with HCFC-22.In table 16, Evap Pres refers to that evaporator pressure, Cond Pres refer to condenser pressure, and Comp Disch T refers to that compressor exit temperature, EER refer to energy efficiency, and CAP refers to capacity.These data are based on following condition.

4 ℃ of evaporator temperatures

43 ℃ of condenser temperatures

Cross 6 ℃ of colds

18 ℃ of reflux gas temperature

Compressor efficiency is 70%

Note overheated being included in cooling capacity.

Table 16

These compositions have the energy efficiency (EER) suitable with R410A with R22, keep rational temperature out simultaneously.The capacity of some composition that table 16 is listed is also similar to R22, shows that these compositions can be as the alternative refrigerant of R22 in refrigeration and air-conditioning.In addition, its capacity of composition had in the listed composition of table 16 approaches or is equivalent to R410A, show these compositions can be in refrigeration and air-conditioning as the alternative refrigerant of R410A.

embodiment 11

the refrigeration performance data

Table 17 shows the performance that various refrigerant compositions of the present invention are compared with HCFC-22, R410A, R407C and R417A.In table 17, Evap Pres refers to that evaporator pressure, Cond Pres refer to condenser pressure, and Comp Disch T refers to that compressor exit temperature, EER refer to energy efficiency, and CAP refers to capacity.These data are based on following condition.

4.4 ℃ of evaporator temperatures

54.4 ℃ of condenser temperatures

Cross 5.5 ℃ of colds

15.6 ℃ of reflux gas temperature

Compressor efficiency is 100%

Note overheated being included in cooling capacity.

table 17

These compositions have the energy efficiency (EER) suitable with R22, R407C, R417A and R410A, keep low temperature out simultaneously.The capacity of the composition that table 17 is listed is also similar with R417A to R22, R407C, shows that these compositions can be as the alternative refrigerant of R22, R407C and R417A in refrigeration and air-conditioning.

Claims

1. a refrigeration agent or heat transfer fluid composition, described composition comprises at least one and is selected from following compound:

Formula ring-[CX=CY (CZW) _n-] the ring-type fluoroolefins, wherein X, Y, Z and W are independently H or F, and the n integer that is 2-5.

2. a composition, described composition comprises: (i) at least one fluoroolefin compounds; (ii) at least one combustible refrigerant; Wherein said fluoroolefins is selected from:

3. a method of cooling, described method comprises the composition of condensation claim 1 or 2, afterwards near the described composition of evaporation object to be cooled.

4. heating means, described method comprises the composition of evaporation claim 1 or 2, near the described composition of condensation object to be heated afterwards.

5. one kind produces heating or cooling method in refrigeration, air-conditioning or thermal-pump unit, described method comprise refrigeration agent or heat transfer fluid composition are incorporated into there is (a) radial compressor, (b) multistage centrifugal compressor or (c) in the described device of veneer/single-pass exchanger; Wherein said refrigeration agent or heat transfer fluid composition comprise at least one and are selected from following fluoroolefins: formula ring-[CX=CY (CZW) _n-] the ring-type fluoroolefins, wherein X, Y, Z and W are independently H or F, the integer that n is 2-5.

6. the composition of a right to use requirement 1 or 2 reduces the method for the fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device is equipped with combustible refrigerant, described method comprises described composition is incorporated in described device, and optionally to added described composition, adds lubricant.

7. the flammable method that the refrigeration agent of a right to use requirement 1 or heat transfer fluid composition reduce combustible refrigerant, described method comprises: described combustible refrigerant is mixed with described composition.

8. a method that substitutes the use of high global warming potential refrigeration agent, described method comprises: in refrigeration, air-conditioning or thermal-pump unit, provide the composition of claim 1 or 2 substitute the high global warming potential refrigeration agent in described device or mixed with this refrigeration agent.

9. the composition of right to use requirement 1 reduces the method for the global warming potential of original refrigeration agent or heat transfer fluid composition, described method comprises is mixed described original refrigeration agent or heat transfer fluid composition with the composition of claim 1, to produce second refrigerant or heat transfer fluid composition, the global warming potential of wherein said second refrigerant or heat transfer fluid composition is lower than described original refrigeration agent or heat transfer fluid composition.

10. a method that reduces the GWP of original refrigeration agent in refrigeration, air-conditioning or thermal-pump unit or heat transfer fluid composition, the GWP of wherein said original refrigeration agent or heat-transfer fluid is 150 or higher; Described method comprises to described refrigeration, air-conditioning or thermal-pump unit introduces claim 1 second, that hang down GWP or 2 refrigeration agent or heat transfer fluid composition.

A 11. method that substitutes original refrigeration agent or heat transfer fluid composition by second refrigerant or heat transfer fluid composition, described method comprises: be provided as the composition containing at least one fluoroolefins of second refrigerant or heat transfer fluid composition, wherein said original refrigeration agent or heat transfer fluid composition are selected from following:

(i) 1,1,2-tri-is chloro-1,2,2-Halothane (R113), wherein said R113 use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);

(ii) 1,1,1,2,3,4,4,5,5,5-Decafluoropentane (R43-10mee), wherein said R43-10mee use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);

(iii) C ₄f ₉oCH ₃, wherein said C ₄f ₉oCH ₃with comprising at least one second refrigerant that is selected from following compound or heat transfer fluid composition, substituted: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);

(iv) 1,1,1,3,3-3-pentafluorobutane (R365mfc), wherein said R365mfc use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);

(v) fluoro trichloromethane (R11), wherein said R11 use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y);

(vi) 2,2 ,-bis-is chloro-1,1,1-Halothane (R123), wherein said R123 use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y);

(vii) 1,2-bis-chloro-1,1,2,2-Tetrafluoroethane (R124), wherein said R124 use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc);

(viii) 1,1,1,3,3,3-HFC-236fa (R236fa), wherein said R236fa use comprises at least one second refrigerant that is selected from following compound or heat transfer fluid composition is substituted: 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc).

12. a right to use requires 1 or 2 the composition method as heat transfer fluid composition, described method comprises described composition is sent to heat sink from thermal source.

A 13. method for preparing the composition of claim 1 or 2, described method comprises: one or more refrigerant composition compositions that (i) from least one cryogen vessel, reclaim certain volume, (ii) fully remove impurity, the composition of described one or more recovery can be re-used, (iii) optionally, by the composition of the described recovery volume of all or part, refrigerant composition or the composition other with at least one mixed.

14. a refrigeration, air-conditioning or thermal-pump unit, described device is equipped with the composition of any one in claim 1 or 2.

15. a mobile refrigerating or air-conditioning plant, described device is equipped with the composition of any one in claim 1 or 2.