CN104745148B

CN104745148B - Composition and application thereof comprising fluoroolefin

Info

Publication number: CN104745148B
Application number: CN201510055033.0A
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: 2018-11-23
Anticipated expiration: 2026-10-31
Also published as: JP2012140629A; JP6250483B2; CN102876294A; KR20130079626A; CN105349106A; CN102876294B; MY154466A; CN102911640B; CN102911640A; JP6069049B2; KR101399203B1; HK1128487A1; JP2017186567A; ES2429567T3; CN104745148A; JP6442011B2; JP5550667B2; JP2014169455A; ES2646463T3; JP2013117034A

Abstract

The present invention relates to the compositions and application thereof comprising fluoroolefin.The present invention relates to fluoroalkene compositions.Fluoroalkene composition of the invention can be used as refrigerant or heat-transfer fluid and for generating in cooling or heating method.In addition, fluoroalkene composition of the invention can be substituted for the refrigerant or heat transfer fluid composition used at present with higher global warming potential.

Description

Composition and application thereof comprising fluoroolefin

The application be number of patent application be 201210339321.5, the applying date is that October 31, denomination of invention in 2006 are same On divisional application divisional application again.

It is 2006800488601.0 (international application no PCT/US2006/ that the divisional application, which is based on national application number, 042686), the applying date is the application for a patent for invention submission of on October 31st, 2006, denomination of invention ibid.

Cross reference to related applications

This application claims the U.S. Provisional Applications 60/732,581 and 2006 year submitted on November 1st, 2005 to mention July 13 The priority of the U.S. Patent application 11/486,791 of friendship.

Technical field

The present invention relates to for freezing, the composition of air-conditioning or heat pump system, wherein the composition includes at least one Fluoroolefin.Composition of the invention can be used as in method of the heat-transfer fluid for freezing or heating, it may also be used for many other Purposes.

Background technique

Refrigeration industry is attempting to look for always the chlorofluorocarbons (CFC) and hydrochlorofluorocarbons of depletion ozone in the past few decades (HCFC) alternative refrigerant, CFC and HCFC because Montreal Protocol (Montreal Protocol) signing just by by Gradually eliminate.The solution of most of refrigerant manufacturers is business promotion hydrofluorocarbon (HFC) refrigerant.New HFC refrigerant The ozone depletion potential of (that most widely used at present is HFC-134a) is zero, therefore not by existing under Montreal Protocol Eliminate the influence of control.

Further environmental legislation may ultimately cause certain HFC refrigerants and be eliminated in the whole world.Currently, automobile industry It is faced with and is related to the regulation of the global warming potential of refrigerant used for automobile air conditioning.Therefore, current pole need to be automobile air-conditioning market Determine the novel refrigerant that global warming potential reduces.If the scope of application in these regulations future more expands, then more need Want the refrigerant that can be used to freeze with all spectra of air conditioner industry.

The alternative refrigerant of the HFC-134a proposed at present includes HFC-152a, pure hydrocarbon such as butane or propane, or " day So " refrigerant such as CO₂.These many substitutes proposed all are that toxic, flammable and/or energy efficiency is low.Therefore, just Seeking new binary mixtures.

The object of the present invention is to provide novel refrigerant composition and heat transfer fluid composition, these compositions can be provided solely Special characteristic is low or be zero to meet ozone depletion potential；And compared with existing refrigerant global warming potential it is lower these It is required that.

Summary of the invention

The present invention relates to refrigerants or heat transfer fluid composition comprising at least one compound selected from the following：

(i) formula E- or Z-R¹CH=CHR²Fluoroolefin, wherein R¹And R²Stand alone as C₁-C₆Perfluoro alkyl group, and its In carbon sum in the compound be at least 5；

(ii) formula ring-[CX=CY (CZW)_n] cyclic annular fluoroolefin, wherein X, Y, Z and W stand alone as H or F, n 2-5 Integer；

(iii) fluoroolefin selected from the following：

2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂)；1,1,2- tri- fluoro- 1- propylene (CH₃CF=CF₂)；1,2,3- tri- Fluoro- 1- propylene (CH₂FCF=CF₂)；1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂)；1,3,3- tri- fluoro- 1- propylene (CHF₂CH =CHF)；1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)；1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF=CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- Butylene (CHF=CFCF₂CF₃)；1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF)；1,1,3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1, 2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃)；1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂= CFCF₂CHF₂)；2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂)；1,3,3,4,4,4- hexafluoro -1- butylene (CHF =CHCF₂CF₃)；1,2,3,4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃)；1,2,3,3,4,4- hexafluoro -1- butylene (CHF =CFCF₂CHF₂)；1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)；1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1,1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH=CFCF₃)；1,1,1,3,4,4- hexafluoro -2- fourth Alkene (CF₃CH=CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- butylene (CF₂=CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- Butylene (CF₂=CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- propylene (CH₂=C (CF₃)₂)；1,1,1,2,4- five Fluoro- 2- butylene (CH₂FCH=CFCF₃)；1,1,1,3,4- five fluoro- 2- butylene (CF₃CH=CFCH₂F)；3,3,4,4,4- five is fluoro- 1- butylene (CF₃CF₂CH=CH₂)；1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene (CHF of 4- five₂CH=CHCF₃)；1,1,1,2,3- five fluoro- 2- Butylene (CH₃CF=CFCF₃)；2,3,3,4,4- five fluoro- 1- butylene (CH₂=CFCF₂CHF₂)；1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂)；1,1,2,3,3- five fluoro- 1- butylene (CH₃CF₂CF=CF₂)；1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂)；1,1,3,3,3- five fluoro- 2- methyl-1-propylene (CF₂=C (CF₃)(CH₃))；2- (difluoromethyl)- 3,3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃))；2,3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃)；1, 2,4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃)；1,3,4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃)；1,3, 3,4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂)；1,2,3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂)；3,3, 4,4- tetra- fluoro- 1- butylene (CH₂=CHCF₂CHF₂)；1,1- bis- fluoro- 2- (difluoromethyl) -1- propylene (CF₂=C (CHF₂) (CH₃))；1,3,3,3- tetra- fluoro- 2- methyl-1-propylene (CHF=C (CF₃)(CH₃))；3,3- bis- fluoro- 2- (difluoromethyl) -1- Propylene (CH₂=C (CHF₂)₂)；1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃)；1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF=CHCF₃)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3,4,4, 5,5,5- ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5, 5,5- nine fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CHF= CFCF₂CF₂CF₃)；1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂=CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5, The fluoro- 1- amylene (CF of 5- nine₂=CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylene (CHF₂CF= CFCF₂CF₃)；1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylene (CF₃CF=CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine Fluoro- 2- amylene (CF₃CF=CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- six Fluoro- 2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3,3,4,4,5,5,5- octafluoro -1- amylene (CH₂=CFCF₂CF₂CF₃)；1,2,3,3,4,4,5, 5- octafluoro -1- amylene (CHF=CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂)；1,3,4,4,4- five Fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂)；3,3,4,4, 5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven fluoro- 1- amylene (CH₂= CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1,2,4,4,4- seven is fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃)(CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1, the fluoro- 2- (three of Isosorbide-5-Nitrae-four Methyl fluoride) -2- butylene (CH₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,1- tri- fluoro- 2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCH₃)；3,4,4,5,5,5- hexafluoro -2- amylenes (CF₃CF₂CF=CHCH₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butene (CF₃C(CH₃)=CHCF₃)；3,3,4,5,5, 5- hexafluoro -1- amylene (CH₂=CHCF₂CHFCF₃)；4,4,4- tri- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=C (CF₃) CH₂CF₃)；1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2,2,3,4, 5,5,6,6,6- ten two fluoro- 3- hexene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, the bis- (fluoroforms of 4,4- hexafluoros -2,3- Base) -2- butylene ((CF₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)；1,1,1, 3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6,6- nine is fluoro- 1- hexene (CF₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂=CHC (CF₃)₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -3- methyl-2-butene ((CF₃)₂C=C (CH₃)(CF₃))；2,3, 3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine is fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH =CHCH (CF₃)₂)；3,4,4,5,5,6,6,6- octafluoro -2- hexene (CF₃CF₂CF₂CF=CHCH₃)；3,3,4,4,5,5,6,6- Octafluoro 1- hexene (CH₂=CHCF₂CF₂CF₂CHF₂)；1,1, Isosorbide-5-Nitrae, five fluoro- 2- (trifluoromethyl) -2- amylene ((CF of 4-₃)₂C= CHCF₂CH₃)；4,4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylene (CH₂=C (CF₃)CH₂C₂F₅)；3,3,4,4,5,5, The fluoro- 2- Methyl-1-pentene (CF of 5- seven₃CF₂CF₂C(CH₃)=CH₂)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (CF₃CF₂CF₂CH=CHCH₃)；4,4,5,5,6,6,6- seven fluoro- 1- hexene (CH₂=CHCH₂CF₂C₂F₅)；1,1,1,2,2,3, The fluoro- 3- hexene (CF of 4- seven₃CF₂CF=CFC₂H₅)；4,5,5,5- tetra- fluoro- 4- (trifluoromethyl) -1- amylene (CH₂=CHCH₂CF (CF₃)₂)；1,1,1,2,5,5,5- seven fluoro- 4- methyl -2- amylene (CF₃CF=CHCH (CF₃)(CH₃))；1,1,1,3- tetra- is fluoro- 2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CFC₂H₅)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptan Alkene (CF₃CF=CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF= CFCF₂C₂F₅)；1,1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1, 2,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7, 7,7- tridecafluoro-3-heptene (CF₃CF₂CH=CFCF₂C₂F₅)；1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF=CHCF₂C₂F₅)；CF₂=CFOCF₂CF₃(PEVE) and CF₂=CFOCF₃ (PMVE)。

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

(a) formula E- or Z-R¹CH=CHR²Fluoroolefin, wherein R¹And R²Stand alone as C₁-C₆Perfluoro alkyl group；

(b) formula ring-[CX=CY (CZW)_n] cyclic annular fluoroolefin, wherein X, Y, Z and W stand alone as H or F, n 2-5 Integer；With

(c) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)； 1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF= CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF=CFCF₂CF₃)；1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF)；1,1,3,3,4,4,4- Seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃)；1,1,2,3,3, 4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂)；1,3,3, 4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2,3,4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃)；1,2, 3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)； 1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1,1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH= CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- butylene (CF₂= CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂=CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- Propylene (CH₂=C (CF₃)₂)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3, 4,4,5,5,5- ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5, 5,5- nine fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CHF= CFCF₂CF₂CF₃)；1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂=CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5,5- Nine fluoro- 1- amylene (CF₂=CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylene (CHF₂CF= CFCF₂CF₃)；1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylene (CF₃CF=CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine Fluoro- 2- amylene (CF₃CF=CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- six Fluoro- 2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3,3,4,4,5,5,5- octafluoro -1- amylene (CH₂=CFCF₂CF₂CF₃)；1,2,3,3,4,4,5, 5- octafluoro -1- amylene (CHF=CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH2=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂)；1,3,4,4,4- five Fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂)；3,3,4,4, 5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven fluoro- 1- amylene (CH₂= CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1,2,4,4,4- seven is fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃)(CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1, the fluoro- 2- (three of Isosorbide-5-Nitrae-four Methyl fluoride) -2- butylene (CH₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2,2,3,4, 5,5,6,6,6- ten two fluoro- 3- hexene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, the bis- (fluoroforms of 4,4- hexafluoros -2,3- Base) -2- butylene ((CF₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)； 1,1,1,3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6, The fluoro- 1- hexene (CF of 6- nine₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂=CHC (CF₃)₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -3- methyl-2-butene ((CF₃)₂C=C (CH₃)(CF₃))；2,3, 3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine is fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH =CHCH (CF₃)₂)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptene (CF₃CF=CFCF₂CF₂C₂F₅)； 1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF=CFCF₂C₂F₅)；1,1,1,3,4,4,5, 5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1,2,4,4,5,5,6,6,7,7,7- ten three Fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CH=CFCF₂C₂F₅) and 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF= CHCF₂C₂F₅)。

The invention further relates to the sides that refrigerant or heat transfer fluid composition are used in refrigeration, air-conditioning or heat pump assembly Method, the method includes introducing the composition into have (a) centrifugal compressor；(b) multistage centrifugal compressor or (c) veneer In the described device of (single slab)/one way (single pass) heat exchanger, wherein the refrigerant or heat transfer compositions It is used to cause to be heated or cooled in said device；And wherein the refrigerant or heat transfer compositions include it is at least one selected from Under fluoroolefin：

(i) formula E- or Z-R¹CH=CHR²Fluoroolefin, wherein R¹And R²Stand alone as C₁-C₆Perfluoro alkyl group；

(ii) formula ring-[CX=CY (CZW)_n] cyclic annular fluoroolefin, wherein X, Y, Z and W stand alone as H or F, n 2-5 Integer；Or

(iii) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,2,3,3- tetra- fluoro- 1- propylene (CHF₂CF=CHF)；2,3,3,3- Tetrafluoro-1-propene (CF₃CF=CH₂)；1,3,3,3- tetrafluoro-1-propene (CF₃CH=CHF)；1,1,2,3- tetrafluoro-1-propene (CH₂FCF=CF₂)；1,1,3,3- tetrafluoro-1-propene (CHF₂CH=CF₂)；2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂)； 3,3,3- tri- fluoro- 1- propylene (CF₃CH=CH₂)；1,1,2- tri- fluoro- 1- propylene (CH₃CF=CF₂)；1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂)；1,2,3- tri- fluoro- 1- propylene (CH₂FCF=CHF)；1,3,3- tri- fluoro- 1- propylene (CHF₂CH=CHF)；1, 1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)；1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF =CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF=CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF =CFCF₂CF₃)；1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (fluoroform Base) -1- propylene ((CF₃)₂C=CHF)；1,1,3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4, The fluoro- 1- butylene (CF of 4- seven₂=CFCHFCF₃)；1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3, 4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂)；1,3,3,4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2, 3,4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃)；1,2,3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1, 1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)；1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)； 1,1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH=CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH= CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- butylene (CF₂=CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂= CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- propylene (CH₂=C (CF₃)₂)；1,1,1,2,4- five fluoro- 2- butylene (CH₂FCH=CFCF₃)；1,1,1,3,4- five fluoro- 2- butylene (CF₃CH=CFCH₂F)；3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂)；1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene (CHF of 4- five₂CH=CHCF₃)；1,1,1,2,3- five fluoro- 2- butylene (CH₃CF=CFCF₃)；2,3,3,4,4- five fluoro- 1- butylene (CH₂=CFCF₂CHF₂)；1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂)；1,1,2,3,3- five fluoro- 1- butylene (CH₃CF₂CF=CF₂)；1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂)；1,1,3,3,3- five fluoro- 2- methyl-1-propylene (CF₂=C (CF₃)(CH₃))；2- (difluoromethyl)- 3,3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃))；2,3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃)；1, 2,4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃)；1,3,4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃)；1,3, 3,4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂)；1,2,3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂)；3,3, 4,4- tetra- fluoro- 1- butylene (CH₂=CHCF₂CHF₂)；1,1- bis- fluoro- 2- (difluoromethyl) -1- propylene (CF₂=C (CHF₂) (CH₃))；1,3,3,3- tetra- fluoro- 2- methyl-1-propylene (CHF=C (CF₃)(CH₃))；The fluoro- 1- third of 2- difluoromethyl -3,3- bis- Alkene (CH₂=C (CHF₂)₂)；1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃)；1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF =CHCF₃)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3,4,4,5,5, The fluoro- 1- amylene (CF of 5- ten₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C =CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5,5,5- nine Fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CHF=CFCF₂CF₂CF₃)；1,1, 3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂=CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylene (CF₂ =CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylene (CHF₂CF=CFCF₂CF₃)；1,1,1,2,3,4,4, 5,5- nine fluoro- 2- amylene (CF₃CF=CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylene (CF₃CF= CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- Hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- fourths Alkene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3, 3,4,4,5,5,5- octafluoro -1- amylene (CH₂=CFCF₂CF₂CF₃)；1,2,3,3,4,4,5,5- octafluoro -1- amylene (CHF= CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- Five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂)；1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4, Tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF of 4-₃)₂CFCH=CH₂)；3,3,4,4,5,5,5- seven fluoro- 1- amylenes (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven fluoro- 1- amylene (CH₂=CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- Seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1,2,4,4,4- seven fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃) (CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoros Methyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1, fluoro- 2- (the trifluoromethyl) -2- butylene of Isosorbide-5-Nitrae-four (CH₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,1- tri- fluoro- 2- (fluoroform Base) -2- butylene ((CF₃)₂C=CHCH₃)；3,4,4,5,5,5- hexafluoro -2- amylene (CF₃CF₂CF=CHCH₃)；1,1, Isosorbide-5-Nitrae, 4, 4- hexafluoro -2- methyl-2-butene (CF₃C(CH₃)=CHCF₃)；3,3,4,5,5,5- hexafluoro -1- amylene (CH₂= CHCF₂CHFCF₃)；3- (trifluoromethyl) -4,4,4- tri- fluoro- 1- butylene (CH₂=C (CF₃)CH₂CF₃)；1,1,2,3,3,4,4, 5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2,2,3,4,5,5,6,6,6- ten two fluoro- 3- oneself Alkene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, bis- (trifluoromethyl) -2- the butylene ((CF of 4,4- hexafluoros -2,3-₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)；1,1,1,3,4,5,5,5- octafluoro -4- (three Methyl fluoride) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6,6- nine fluoro- 1- hexenes (CF₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂=CHC (CF₃)₃)；1,1,1, 4,4,4- hexafluoro -3- methyl -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=C (CH₃)(CF₃))；2,3,3,5,5,5- hexafluoros- 4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH=CHCH (CF₃)₂)； 3,4,4,5,5,6,6,6- octafluoro -2- hexene (CF₃CF₂CF₂CF=CHCH₃)；3,3,4,4,5,5,6,6- octafluoro -1- hexenes (CH₂=CHCF₂CF₂CF₂CHF₂)；1,1, Isosorbide-5-Nitrae, five fluoro- 2- (trifluoromethyl) -2- amylene ((CF of 4-₃)₂C=CHCF₂CH₃)；4, 4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylene (CH₂=C (CF₃)CH₂C₂F₅)；3,3,4,4,5,5,5- seven fluoro- 2- first Base -1- amylene (CF₃CF₂CF₂C(CH₃)=CH₂)；4,4,5,5,6,6,6- seven fluoro- 2- hexene (CF₃CF₂CF₂CH=CHCH₃)； 4,4,5,5,6,6,6- seven fluoro- 1- hexene (CH₂=CHCH₂CF₂C₂F₅)；1,1,1,2,2,3,4- seven fluoro- 3- hexene (CF₃CF₂CF=CFC₂H₅)；4,5,5,5- tetra- fluoro- 4- Trifluoromethyl-1-amylene (CH₂=CHCH₂CF(CF₃)₂)；1,1,1,2, 5,5,5- seven fluoro- 4- methyl -2- amylene (CF₃CF=CHCH (CF₃)(CH₃))；1,1,1,3- tetra- fluoro- 2- trifluoromethyl -2- amylene ((CF₃)₂C=CFC₂H₅)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptene (CF₃CF= CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF=CFCF₂C₂F₅)；1, 1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1,2,4,4,5,5,6, 6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7,7,7- ten three fluoro- 3- Heptene (CF₃CF₂CH=CFCF₂C₂F₅)；1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF= CHCF₂C₂F₅)；CF₂=CFOCF₂CF₃(PEVE)；CF₂=CFOCF₃(PMVE) and their combination.

Detailed description of the invention

The present invention relates to the compositions comprising at least one fluoroolefin.So-called fluoroolefin refers to any containing carbon, fluorine With optional hydrogen or oxygen and also containing the compound of at least one double bond.These fluoroolefins can be it is straight chain, branch or It is cricoid.

These compositions serve many purposes in working fluid, including are used for example as foaming agent (foaming Agent), foaming agent (blowing agent), extinguishing chemical, heat transfer medium are (as being used for refrigeration system, refrigerator, air-conditioning system, heat The heat-transfer fluid and refrigerant of pump, cooler etc.).

Heat-transfer fluid (also referred to as heat transfer compositions or heat transfer fluid composition herein) is to pass heat from heat source It is sent to the working fluid of thermoreceptor.

Refrigerant be served as in the circulation that wherein fluid undergoes liquid-gas and gas and liquid phase to become heat-transfer fluid compound or The mixture of compound.

The present invention, which provides, has formula E- or Z-R¹CH=CHR²The fluoroolefin of (Formulas I), wherein R¹And R²Stand alone as C₁-C₆ Perfluoro alkyl group.R¹And R²The example of group includes but is not limited to CF₃、C₂F₅、CF₂CF₂CF₃、CF(CF₃)₂、CF₂CF₂CF₂CF₃、 CF(CF₃)CF₂CF₃、 CF₂CF(CF₃)₂、C(CF₃)₃、CF₂CF₂CF₂CF₂CF₃、CF₂CF₂CF(CF₃)₂、 C(CF₃)₂C₂F₅、 CF₂CF₂CF₂CF₂CF₂CF₃、CF(CF₃)CF₂CF₂C₂F₅With C (CF₃)₂CF₂C₂F₅.In one embodiment, Formulas I fluoroolefin Molecule in have at least about 3 carbon atoms.In another embodiment, have at least about 4 in the molecule of Formulas I fluoroolefin A carbon atom.In yet another embodiment, there are at least about 5 carbon atoms in the molecule of Formulas I fluoroolefin.Table 1 is shown The non-limiting compound of formula I of example property.

Table 1

Compound of formula I can be prepared：Formula R¹The perfluoroalkyl iodides and formula R of I²CH=CH₂Three hydrogen alkene of perfluoroalkyl It carries out contact and forms formula R¹CH₂CHIR²Three hydrogen iodo perfluoro alkane.The three hydrogen iodo perfluoro alkane then can be through dehydrogenation iodine (dehydroiodinated) R is formed¹CH=CHR².Alternatively, alkene R¹CH=CHR²It can be prepared：Formula R²The perfluor alkane of I Base iodine and formula R¹CH=CH₂Three hydrogen olefine reaction of perfluoroalkyl form formula R¹CHICH₂R²Three hydrogen iodo perfluoro alkane, then Dehydrogenation Iod R is carried out to the latter.

The perfluoroalkyl iodides and the contact of three hydrogen alkene of perfluoroalkyl can in a batch manner, by by each reactant It can carried out in the suitable reaction vessels that each reactants and products operate under generated self-generated pressure under reaction temperature Mixing is to occur.Suitable reaction vessel include by stainless steel (especially austenitic stainless steel) and well known Langaloy such asNickel-copper alloy,Nickel-base alloy andThe reaction vessel of nickel-chromium alloy manufacture.

Alternatively, reaction can be carried out with half point batch mode, in such a way, by suitable adding apparatus as pumped perfluor Three hydrogen olefin reactant of alkyl is added to perfluoroalkyl iodides reactant at the reaction temperatures.

The ratio between three hydrogen alkene of perfluoroalkyl iodides and perfluoroalkyl should between about 1: 1 to about 4: 1, preferably from about 1.5: 1-2.5: 1.Such as Jeanneaux Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974) are reported Road is easy to cause less than 1.5: 1 ratio and generates a large amount of 2: 1 adduct (adduct).

The preferable temperature of the perfluoroalkyl iodides and the contact of the three hydrogen alkene of perfluoroalkyl, preferably about 150 DEG C- 300 DEG C, preferably from about 170 DEG C to about 250 DEG C, most preferably from about 180 DEG C to about 230 DEG C of range.

Perfluoroalkyl iodides are -18 hours about 0.5 hour with the appropriate contact time of three hydrogen alkene of perfluoroalkyl reacted, Preferably from about 4 to about 12 hours.

It can directly be used by perfluoroalkyl iodides with the three hydrogen iodo perfluoro alkane for reacting preparation of three hydrogen alkene of perfluoroalkyl In dehydrogenation Iod R step, or recycling and distillation purifying are preferably first carried out before for dehydrogenation Iod R step.

Dehydrogenation Iod R step is executed by contacting three hydrogen iodo perfluoro alkane with alkaline matter.Suitable alkali Property substance includes alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide), alkali metal oxide (such as sodium oxide molybdena), alkali Earth metal hydroxide (such as calcium hydroxide), alkaline earth oxide (such as calcium oxide), alkali metal alcoholates (such as sodium methoxide Or sodium ethoxide), ammonium hydroxide, Sodamide or alkaline matter mixture such as soda lime.Preferred alkaline matter be sodium hydroxide and Potassium hydroxide.

Contact of the three hydrogen iodo perfluoro alkane with alkaline matter preferably can dissolve two kinds in the liquid phase Occur in the presence of at least part of solvent of reactant.The solvent for being adapted to dehydrogenation Iod R step includes one or more poles Property organic solvent such as alcohol (such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol and tert-butyl alcohol), nitrile (such as second Nitrile, propionitrile, butyronitrile, benzonitrile or adiponitrile), dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide or ring fourth Sulfone.Solvent selection can according in the boiling point of product and purification process from product separation trace solvent easy degree depending on.In general, Ethyl alcohol or isopropanol are the good solvents of reaction.

In general, dehydrogenation Iod R can be by the way that a kind of reactant (alkaline matter or three hydrogen iodo perfluoro alkane) to be added to properly Another reactant in reaction vessel carries out.The reaction vessel can be manufactured by glass, ceramics or metal, and preferably use leaf Wheel or rabbling mechanism are stirred.

The preference temperature of dehydrogenation Iod R is about 10 DEG C to about 100 DEG C, preferably from about 20 DEG C to about 70 DEG C.Dehydrogenation Iod R It can carry out, or be carried out under decompression or boosting under ambient pressure.It is worth mentioning that such dehydrogenation Iod R, anti-at this It is distilled from reaction vessel with the formation of compound of formula I in answering.

Alternatively, dehydrogenation Iod R can by make the alkaline matter aqueous solution and three hydrogen iodo perfluoro alkane in a kind of or A variety of solution compared in low polar organic solvent contact to carry out in the presence of a phase transfer catalyst, the organic solvent such as alkane Hydrocarbon (such as hexane, heptane or octane), aromatic hydrocarbons (such as toluene), halogenated hydrocarbons (such as methylene chloride, chloroform, carbon tetrachloride or complete Vinyl chloride) or ether (such as diethyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, 2- methyltetrahydrofuran, dioxane, two Ethyl Methyl Ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether).Suitable phase transfer catalyst include quaternary ammonium halides salt (such as Tetrabutylammonium bromide, 4-butyl ammonium hydrogen sulfate, triethyl benzyl ammonia chloride, dodecyl trimethyl ammonium chloride and three caprylyl first Ammonium chloride), halogenation seasonSalt (such as triphenylmethylphosphonium bromideAnd tetraphenylphosphonichloride chloride) or this field be known as crown ether Cyclic polyether compound (such as 18- crown- 6 and 15- crown- 5).

Alternatively, dehydrogenation Iod R can be in the absence of solvent by the way that three hydrogen iodo perfluoro alkane are added to solid-state or liquid alkali Property substance carries out.

The suitable reactions time of dehydrogenation Iod R is about 15 minutes to about 6 hours or the longer time, this depends on reaction The solubility of object.In general, dehydrogenation Iod R is quickly, to need just complete within about 30 minutes to about 3 hours.

Compound of formula I can by mutually being separated after adding water, by distill or by the combinations of aforementioned two methods from It is recycled in dehydrogenation Iod R mixture.

In another embodiment of the present invention, fluoroolefin includes cyclic annular fluoroolefin (ring-[CX=CY (CZW)_n] (Formula II), wherein X, Y, Z and W are independently selected from H and F, and n is the integer of 2-5).Table 2 lists representative Formula II ring Shape fluoroolefin.

Table 2

In another embodiment, fluoroolefin may include those of the listed compound of table 3.

Table 3

Compound listed by table 2 and table 3 is commercially available, or can pass through well known in the art or method described herein It is prepared.

1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene of 4- five can be by by 1,1,1,2,4,4- hexafluoro butane (CHF₂CH₂CHFCF₃) in room Dehydrogenation fluorine reaction (dehydrofluorination) is carried out with solid KOH to prepare with gas phase state under temperature.1,1,1,2,4, The synthesis of 4- hexafluoro butane is described in US 6, and 066,768, the patent is incorporated herein by reference.

1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene can be by making 1,1 with phase transfer catalyst, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- iodine fourths Alkane (CF₃CHICH₂CF₃) reacted at about 60 DEG C with KOH to prepare.1,1, Isosorbide-5-Nitrae, the synthesis of 4,4- hexafluoro -2- iodobutanes It can be by making perfluoro-methyl iodine (CF₃I) and 3,3,3- trifluoro propene (CF₃CH=CH₂) anti-at autogenous pressures at about 200 DEG C It about 8 hours should carry out.

3,4,4,5,5,5- hexafluoro -2- amylenes can be by carrying out at 200-300 DEG C with solid KOH or with C catalyst 1,1,1,2,2,3,3- seven amyl fluoride (CF₃CF₂CF₂CH₂CH₃) dehydrogenation fluorine react to prepare.1,1,1,2,2,3,3- seven fluorine penta Alkane can pass through 3,3,4,4,5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂) 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 with solid KOH (CH₂FCF₂CHFCF₃) 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 with solid KOH (CHF₂CH₂CF₂CF₃) 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 with solid KOH (CF₃CH₂CF₂CHF₂) dehydrogenation fluorine react to prepare.

1,1,1,2,4- five fluoro- 2- butylene can be by carrying out 1,1,1,2,2,3- hexafluoro butane with solid KOH (CH₂FCH₂CF₂CF₃) dehydrogenation fluorine react to prepare.

1,1,1,3,4- five fluoro- 2- butylene can be by carrying out 1,1,1,3,3,4- hexafluoro butane with solid KOH (CF₃CH₂CF₂CH₂F dehydrogenation fluorine) reacts to prepare.

1,1,1,3- tetra- fluoro- 2- butylene can be by making 1,1,1,3,3- 3-pentafluorobutane (CF₃CH₂CF₂CH₃) water-soluble with KOH Liquid reacts at 120 DEG C to prepare.

1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- amylenes can be by making (CF with phase transfer catalyst₃CHICH₂CF₂CF₃) with KOH reacts at about 60 DEG C to prepare.The synthesis of iodo- 1,1,1,2,2,5,5,5- octafluoro pentane of 4- can be by making perfluoro-ethyl Iodine (CF₃CF₂I) and 3,3,3- trifluoro propenes react about 8 hours at about 200 DEG C at autogenous pressures to carry out.

1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- hexene can by making 1,1,1,2,2,5,5 with phase transfer catalyst, 6,6,6- ten fluoro- 3- iodohexane (CF₃CF₂CHICH₂CF₂CF₃) reacted at about 60 DEG C with KOH to prepare.1,1,1,2,2,5, The synthesis of 5,6,6,6- ten fluoro- 3- iodohexanes can be by making perfluoro ethyl iodide (CF₃CF₂I) and 3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂) react about 8 hours at autogenous pressures at about 200 DEG C to carry out.

1,1, Isosorbide-5-Nitrae, 5,5,5- seven fluoro- 4- (trifluoromethyl) -2- amylenes can by making 1,1,1,2 in isopropanol with KOH, 5,5, the 5- seven fluoro- iodo- 2- of 4- (trifluoromethyl)-pentane (CF₃CHICH₂CF(CF₃)₂) reaction of dehydrogenation fluorine occurs to prepare. CF₃CHICH₂CF(CF₃)₂By making (CF₃)₂CFI and CF₃CH=CH₂Reaction is at high temperature such as from about 200 DEG C to prepare.

1,1, Isosorbide-5-Nitrae, 4,5,5,6,6,6- ten fluoro- 2- hexenes can be by 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene (CF₃CH= CHCF₃) and tetrafluoroethene (CF₂=CF₂) and antimony pentafluoride (SbF₅) reaction prepare.

2,3,3,4,4- five fluoro- 1- butylene can be by making 1,1,2,2,3,3- hexafluoro fourth with fluorided alumina at high temperature Alkane carries out the reaction of dehydrogenation fluorine to prepare.

2,3,3,4,4,5,5,5- octafluoro -1- amylenes can be by making 2,2,3,3,4,4,5,5,5- nine fluorine penta with solid KOH Alkane carries out the reaction of dehydrogenation fluorine to prepare.

1,2,3,3,4,4,5,5- octafluoro -1- amylene can by making 2,2,3,3,4,4 at high temperature with fluorided alumina, 5,5,5- nine amyl fluorides carry out the reaction of dehydrogenation fluorine to prepare.

Composition of the invention may include the single compound of Formulas I, Formula II or table 3, or may include the compound Combination.Alternatively, many Formulas I, Formula II and 3 compound of table can be deposited in the form of different configurational isomer or stereoisomer ?.The invention is intended to include all single configuration isomers, single stereoisomers or any combination of them.For example, 1, 3,3,3- tetrafluoropropenes (HFC-1234ze) mean to represent E- isomers, second isomers or both isomers with any ratio Any combination or mixture of example.Another example is F12E, represents E- isomers, Z- isomers or both are different Structure body any combination in any proportion or mixture.

Composition of the invention has zero or low-ozone depletion potential and low global warming potential (GWP).Fluorine of the invention For alkene or the mixture of fluoroolefin of the present invention and other refrigerants, global warming potential can be than many hydrogen used at present Fluorohydrocarbon refrigerant wants small.It is an aspect of the invention to provide global warming potentials less than 1000, less than 500, less than 150, it is small In 100 or the refrigerant less than 50.Another aspect of the present invention is subtracted by the way that fluoroolefin is added to refrigerant mixture The net GWP of few mixture.

It can be by any convenient method by the desired amount of each ingredient as the present composition of combination or mixture It is mixed to prepare.Preferred method is to weigh required each component amount, then carries out each ingredient in container appropriate Mixing.Agitation operation can be used if needed.

The alternative method for preparing the present composition includes：(i) certain volume is recycled from least one cryogen vessel One or more refrigerant composition ingredients, (ii) sufficiently remove impurity, enable the ingredient of one or more recycling Reuse, (iii) optionally, by each ingredient of all or part of recovery volumes and at least one other refrigerant group It closes object or ingredient is mixed.

Cryogen vessel can be any system for wherein storing and having been used for refrigerating plant, air-conditioning device or heat pump assembly The container of cryogen blend composition (refrigerant blend composition).The cryogen vessel can be wherein Use refrigerating plant, air-conditioning device or the heat pump assembly of the refrigerant admixture (refrigerant blend).In addition, refrigeration Agent container, which can be, blends ingredient (refrigerant blend components) for collecting each refrigerant recycled Storage container, including but not limited to pressurized gas cylinder.

Residual refrigeration agent refer to any amount, can be blended by any known for diverted refrigerant admixture or refrigerant The refrigerant admixture or refrigerant that the method divided is removed from cryogen vessel blend ingredient.

Impurity can be any because refrigerant admixture or refrigerant blend ingredient in refrigerating plant, air-conditioning device or heat pump Use in device and be present in the refrigerant admixture or refrigerant and blend ingredient in ingredient.This impurity includes but unlimited In refrigeration lubricant (those described herein refrigeration lubricant)；Particulate matter, such as may be from refrigerating plant, air-conditioning device or warm The metal or elastomer that pump installation comes out；With any other performance that may negatively affect refrigerant blend composition Pollutant.

This impurity can sufficiently be removed, be got with allowing refrigerant admixture or refrigerant to be blended into reuse, and Adversely influence the performance that the equipment of ingredient is wherein blended using refrigerant admixture or refrigerant.

May need to blend to remaining refrigerant admixture or refrigerant ingredient provide other refrigerant admixture or Refrigerant blends ingredient, meets composition as defined in given product to produce.For example, if refrigerant admixture has 3 kinds Ingredient in specified weight percentage range may then need that one or more ingredients are added with specified rate, so that composition It is restored in regulation compass.

The present composition that can be used as refrigerant or heat-transfer fluid includes at least one fluoroolefin selected from the following：

(iii) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,2,3,3- tetra- fluoro- 1- propylene (CHF₂CF=CHF)；2,3,3,3- Tetrafluoro-1-propene (CF₃CF=CH2)；1,1,2,3- tetrafluoro-1-propene (CH₂FCF=CF₂)；1,1,3,3- tetrafluoro-1-propene (CHF₂CH=CF₂)；2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂)；3,3,3- tri- fluoro- 1- propylene (CF₃CH=CH₂)；1,1, The fluoro- 1- propylene (CH of 2- tri-₃CF=CF₂)；1,2,3- tri- fluoro- 1- propylene (CH₂FCF=CF₂)；1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂)；1,3,3- tri- fluoro- 1- propylene (CHF₂CH=CHF)；1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)；1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- Butylene (CF₃CF=CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF=CFCF₂CF₃)；1,1,1,2,3,4,4- seven Fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF)；1,1, 3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃)； 1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF= CH₂)；1,3,3,4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2,3,4,4,4- hexafluoro -1- butylene (CHF= CFCHFCF₃)；1,2,3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)；1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1,1,1,2,4,4- hexafluoro -2- fourth Alkene (CHF₂CH=CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- Butylene (CF₂=CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂=CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (three Methyl fluoride) -1- propylene (CH₂=C (CF₃)₂)；1,1,1,2,4- five fluoro- 2- butylene (CH₂FCH=CFCF₃)；1,1,1,3,4- five Fluoro- 2- butylene (CF₃CH=CFCH₂F)；3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂)；1,1, Isosorbide-5-Nitrae, 4- five is fluoro- 2- butylene (CHF₂CH=CHCF₃)；1,1,1,2,3- five fluoro- 2- butylene (CH₃CF=CFCF₃)；2,3,3,4,4- five fluoro- 1- fourths Alkene (CH₂=CFCF₂CHF₂)；1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂)；1,1,2,3,3- five fluoro- 1- fourth Alkene (CH₃CF₂CF=CF₂)；1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂)；1,1,3,3,3- five fluoro- 2- methyl- 1- propylene (CF₂=C (CF₃)(CH₃))；2- (difluoromethyl) -3,3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃))；2, 3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃)；1,2,4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃)；1,3, 4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃)；1,3,3,4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂)；1,2, 3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂)；3,3,4,4- tetra- fluoro- 1- butylene (CH₂=CHCF₂CHF₂)；1,1- bis- Fluoro- 2- (difluoromethyl) -1- propylene (CF₂=C (CHF₂)(CH₃))；1,3,3,3- tetra- fluoro- 2- methyl-1-propylene (CHF=C (CF₃)(CH₃))；3,3- bis- fluoro- 2- (difluoromethyl) -1- propylene (CH₂=C (CHF₂)₂)；1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃)；1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF=CHCF₃)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- Amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3,4,4,5,5,5- ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- penta Alkene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4, 4,5,5,5- nine fluoro- 1- amylene (CHF=CFCF₂CF₂CF₃)；1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂= CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylene (CF₂=CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5, The fluoro- 2- amylene (CHF of 5- nine₂CF=CFCF₂CF₃)；1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylene (CF₃CF= CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂ =CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂)；1,1,3,4,4, 4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3,3,4,4,5,5,5- octafluoro -1- amylene (CH₂= CFCF₂CF₂CF₃)；1,2,3,3,4,4,5,5- octafluoro -1- amylene (CHF=CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂= CHCH(CF₃)₂)；1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five Fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂)；3,3,4,4,5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven Fluoro- 1- amylene (CH₂=CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1, 2,4,4,4- seven fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃)(CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- fourths Alkene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1,1, Tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH of 4-₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,1- tri- fluoro- 2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCH₃)；3,4,4,5,5,5- six Fluoro- 2- amylene (CF₃CF₂CF=CHCH₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butene (CF₃C(CH₃)=CHCF₃)；3, 3,4,5,5,5- hexafluoro -1- amylene (CH₂=CHCF₂CHFCF₃)；4,4,4- tri- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂= C(CF₃)CH₂CF₃)；1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2, 2,3,4,5,5,6,6,6- ten two fluoro- 3- hexene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, the bis- (trifluoros of 4,4- hexafluoros -2,3- Methyl) -2- butylene ((CF₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)； 1,1,1,3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6, The fluoro- 1- hexene (CF of 6- nine₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂= CHC(CF₃)₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -3- methyl-2-butene ((CF₃)₂C=C (CH₃)(CF₃))； 2,3,3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine Fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH=CHCH (CF₃)₂)；3,4,4,5,5,6,6,6- octafluoro -2- hexene (CF₃CF₂CF₂CF=CHCH₃)；3,3,4,4,5, 5,6,6- octafluoro 1- hexene (CH₂=CHCF₂CF₂CF₂CHF₂)；1,1, Isosorbide-5-Nitrae, 4- five fluoro- 2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHCF₂CH₃)；4,4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylene (CH₂=C (CF₃)CH₂C₂F₅)；3,3, 4,4,5,5,5- seven fluoro- 2- Methyl-1-pentene (CF₃CF₂CF₂C(CH₃)=CH₂)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (CF₃CF₂CF₂CH=CHCH₃)；4,4,5,5,6,6,6- seven fluoro- 1- hexene (CH₂=CHCH₂CF₂C₂F₅)；1,1,1,2,2,3, The fluoro- 3- hexene (CF of 4- seven₃CF₂CF=CFC₂H₅)；4,5,5,5- tetra- fluoro- 4- (trifluoromethyl) -1- amylene (CH₂=CHCH₂CF (CF₃)₂)；1,1,1,2,5,5,5- seven fluoro- 4- methyl -2- amylene (CF₃CF=CHCH (CF₃)(CH₃))；1,1,1,3- tetra- is fluoro- 2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CFC₂H₅)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptan Alkene (CF₃CF=CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF= CFCF₂C₂F₅)；1,1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1, 2,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7, 7,7- tridecafluoro-3-heptene (CF₃CF₂CH=CFCF₂C₂F₅)；1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF=CHCF₂C₂F₅)；CF₂=CFOCF₂CF₃(PEVE) and CF₂=CFOCF₃ (PMVE)。

The invention further relates to the groups comprising at least one fluoroolefin and at least one flammable refrigerant or heat-transfer fluid Object is closed, wherein the fluoroolefin is selected from：

(iii) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,2,3,3- tetra- fluoro- 1- propylene (CHF₂CF=CHF)；2,3,3,3- Tetrafluoro-1-propene (CF₃CF=CH₂)；1,1,2,3- tetrafluoro-1-propene (CH₂FCF=CF₂)；1,1,3,3- tetrafluoro-1-propene (CHF₂CH=CF₂)；2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂)；3,3,3- tri- fluoro- 1- propylene (CF₃CH=CH₂)；1,1, The fluoro- 1- propylene (CH of 2- tri-₃CF=CF₂)；1,2,3- tri- fluoro- 1- propylene (CH₂FCF=CF₂)；1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂)；1,3,3- tri- fluoro- 1- propylene (CHF₂CH=CHF)；1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)；1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- Butylene (CF₃CF=CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF=CFCF₂CF₃)；1,1,1,2,3,4,4- seven Fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF)；1,1, 3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃)； 1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF= CH₂)；1,3,3,4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2,3,4,4,4- hexafluoro -1- butylene (CHF= CFCHFCF₃)；1,2,3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)；1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1,1,1,2,4,4- hexafluoro -2- fourth Alkene (CHF₂CH=CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- Butylene (CF₂=CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂=CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoros Methyl) -1- propylene (CH₂=C (CF₃)₂)；1,1,1,2,4- five fluoro- 2- butylene (CH₂FCH=CFCF₃)；1,1,1,3,4- five Fluoro- 2- butylene (CF₃CH=CFCH₂F)；3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂)；1,1, Isosorbide-5-Nitrae, 4- five is fluoro- 2- butylene (CHF₂CH=CHCF₃)；1,1,1,2,3- five fluoro- 2- butylene (CH₃CF=CFCF₃)；2,3,3,4,4- five fluoro- 1- fourths Alkene (CH₂=CFCF₂CHF₂)；1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂)；1,1,2,3,3- five fluoro- 1- fourth Alkene (CH₃CF₂CF=CF₂)；1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂)；1,1,3,3,3- five fluoro- 2- methyl- 1- propylene (CF₂=C (CF₃)(CH₃))；2- (difluoromethyl) -3,3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃))；2, 3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃)；1,2,4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃)；1,3, 4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃)；1,3,3,4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂)；1,2, 3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂)；3,3,4,4- tetra- fluoro- 1- butylene (CH₂=CHCF₂CHF₂)；1,1- bis- Fluoro- 2- (difluoromethyl) -1- propylene (CF₂=C (CHF₂)(CH₃))；1,3,3,3- tetra- fluoro- 2- methyl-1-propylene (CHF=C (CF₃)(CH₃))；3,3- bis- fluoro- 2- (difluoromethyl) -1- propylene (CH₂=C (CHF₂)₂)；1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃)；1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF=CHCF₃)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- Amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3,4,4,5,5,5- ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- penta Alkene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4, 4,5,5,5- nine fluoro- 1- amylene (CHF=CFCF₂CF₂CF₃)；1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂= CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylene (CF₂=CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5, The fluoro- 2- amylene (CHF of 5- nine₂CF=CFCF₂CF₃)；1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylene (CF₃CF= CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂= CFCH(CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- Hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3,3,4,4,5,5,5- octafluoro -1- amylene (CH₂= CFCF₂CF₂CF₃)；1,2,3,3,4,4,5,5- octafluoro -1- amylene (CHF=CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂= CHCH(CF₃)₂)；1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five Fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂)；3,3,4,4,5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven Fluoro- 1- amylene (CH₂=CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1, 2,4,4,4- seven fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃)(CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- fourths Alkene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1,1, Tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH of 4-₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,1- tri- fluoro- 2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCH₃)；3,4,4,5,5,5- six Fluoro- 2- amylene (CF₃CF₂CF=CHCH₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butene (CF₃C(CH₃)=CHCF₃)；3, 3,4,5,5,5- hexafluoro -1- amylene (CH₂=CHCF₂CHFCF₃)；4,4,4- tri- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂= C(CF₃)CH₂CF₃)；1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2, 2,3,4,5,5,6,6,6- ten two fluoro- 3- hexene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoros -2,3- bis- (three Methyl fluoride) -2- butylene ((CF₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)； 1,1,1,3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6, The fluoro- 1- hexene (CF of 6- nine₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂=CHC (CF₃)₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -3- methyl-2-butene ((CF₃)₂C=C (CH₃)(CF₃))；2,3, 3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine is fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH =CHCH (CF₃)₂)；3,4,4,5,5,6,6,6- octafluoro -2- hexene (CF₃CF₂CF₂CF=CHCH₃)；3,3,4,4,5,5,6,6- Octafluoro 1- hexene (CH₂=CHCF₂CF₂CF₂CHF₂)；1,1, Isosorbide-5-Nitrae, five fluoro- 2- (trifluoromethyl) -2- amylene ((CF of 4-₃)₂C= CHCF₂CH₃)；4,4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylene (CH₂=C (CF₃)CH₂C₂F₅)；3,3,4,4,5,5, The fluoro- 2- Methyl-1-pentene (CF of 5- seven₃CF₂CF₂C(CH₃)=CH₂)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (CF₃CF₂CF₂CH=CHCH₃)；4,4,5,5,6,6,6- seven fluoro- 1- hexene (CH₂=CHCH₂CF₂C₂F₅)；1,1,1,2,2,3, The fluoro- 3- hexene (CF of 4- seven₃CF₂CF=CFC₂H₅)；4,5,5,5- tetra- fluoro- 4- (trifluoromethyl) -1- amylene (CH₂=CHCH₂CF (CF₃)₂)；1,1,1,2,5,5,5- seven fluoro- 4- methyl -2- amylene (CF₃CF=CHCH (CF₃)(CH₃))；1,1,1,3- tetra- is fluoro- 2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CFC₂H₅)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptan Alkene (CF₃CF=CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF= CFCF₂C₂F₅)；1,1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1, 2,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7, 7,7- tridecafluoro-3-heptene (CF₃CF₂CH=CFCF₂C₂F₅)；1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF=CHCF₂C₂F₅)；CF₂=CFOCF₂CF₃(PEVE) and CF₂=CFOCF₃ (PMVE)。

Especially suitable for the fluoro alkene comprising at least one flammable refrigerant and the composition of at least one fluoroolefin Hydrocarbon is the fluoroolefin of non-flammable itself.The combustibility of fluoroolefin seem in molecule number of fluorine atoms and number of hydrogen atoms have It closes.Following equation can calculate flammable sex factor, as the flammable index of prediction.

In formula：

Number of fluorine atoms in F=molecule；

Number of hydrogen atoms in H=molecule.

Due to the measuring of certain compounds be it is flammable, to the truncation of the flammable sex factor of non-flammable fluoroolefin Value (cut-off) is determined.Fluoroolefin can by with electronics incendiary source in ASHRAE (U.S. heating, refrigeration and air-conditioning Society of Engineers, American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) standard 34-2001 (ASTM (American Society Testing and Materials, American Society of Testing and Materials) under E681-01) to be tested to determination under conditions of defined be that flammable also right and wrong can Combustion.This flammability test is with test compound in 101kPa (14.7psia) and (usual 100 DEG C (212 ° of predetermined temperature F under)), in different air concentration carry out, with determine the aerial lean flammability of the test compound (LFL) and/ Or upper limit of flammability (UFL).

Table 4 lists the flammable sex factor of several fluoroolefins and the measuring result of combustibility or non-combustible.Therefore, It is actually optimum and combustible refrigerant group disclosed by the invention which, which can be predicted in other fluoroolefins disclosed by the invention, The non-flammable fluoroolefin of conjunction.

Table 4

According to the numerical value of flammable sex factor, it may be determined that fluoroolefin listed by table 4 is flammable or non-flammable.If Show that flammable sex factor is equal to or more than 0.70, then the expectable fluoroolefin is non-flammable.If flammable sex factor is less than 0.70, then the expectable fluoroolefin is flammable.

In another embodiment of the present invention, at the fluoroolefin of composition being to be selected from flammable refrigerant Fluoroolefin below：

(b) formula ring-[CX=CY (CZW)_n] cyclic annular fluoroolefin, wherein X, Y, Z and W stand alone as H or F, n 2-5 Integer, and wherein flammable sex factor be greater than or equal to 0.70；

(c) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)； 1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF=CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF= CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF=CFCF₂CF₃)；1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (trifluoromethyl) -1- propylene ((CF₃)₂C=CHF)；1,1,3,3,4,4,4- Seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4,4- seven fluoro- 1- butylene (CF₂=CFCHFCF₃)；1,1,2,3,3, 4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3,4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂)；1,3,3, 4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2,3,4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃)；1,2, 3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1,1,2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)； 1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1,1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH= CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂)；1,1,2,3,3,4- hexafluoro -1- butylene (CF₂= CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂=CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- Propylene (CH₂=C (CF₃)₂)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3, 4,4,5,5,5- ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5, 5,5- nine fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CHF= CFCF₂CF₂CF₃)；1,1,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂=CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5, The fluoro- 1- amylene (CF of 5- nine₂=CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylene (CHF₂CF= CFCF₂CF₃)；1,1,1,2,3,4,4,5,5- nine fluoro- 2- amylene (CF₃CF=CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine Fluoro- 2- amylene (CF₃CF=CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- six Fluoro- 2- (trifluoromethyl) -2- butylene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3,3,4,4,5,5,5- octafluoro -1- amylene (CH₂=CFCF₂CF₂CF₃)；1,2,3,3,4,4,5, 5- octafluoro -1- amylene (CHF=CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂)；1,3,4,4,4- five Fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF₃)₂CFCH=CH₂)；3,3,4,4, 5,5,5- seven fluoro- 1- amylene (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven fluoro- 1- amylene (CH₂= CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1,2,4,4,4- seven is fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃)(CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1, the fluoro- 2- (three of Isosorbide-5-Nitrae-four Methyl fluoride) -2- butylene (CH₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,2,3,3,4,4,5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2,2,3,4, 5,5,6,6,6- ten two fluoro- 3- hexene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, the bis- (fluoroforms of 4,4- hexafluoros -2,3- Base) -2- butylene ((CF₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)； 1,1,1,3,4,5,5,5- octafluoro -4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6, The fluoro- 1- hexene (CF of 6- nine₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂= CHC(CF₃)₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -3- methyl-2-butene ((CF₃)₂C=C (CH₃)(CF₃))； 2,3,3,5,5,5- hexafluoro -4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine Fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH=CHCH (CF₃)₂)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptene (CF₃CF= CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF=CFCF₂C₂F₅)；1, 1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1,2,4,4,5,5,6, 6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7,7,7- ten three fluoro- 3- Heptene (CF₃CF₂CH=CFCF₂C₂F₅) and 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF= CHCF₂C₂F₅)。

In yet another embodiment, it may be particularly useful for the fluoroolefin of the present invention being combined with combustible refrigerant It can be at least one fluoroolefin selected from the following：

(a) formula E- or Z-R¹CH=CHR²Fluoroolefin, wherein R¹And R²Stand alone as C₁-C₆Perfluoro alkyl group, and its In flammable sex factor be greater than or equal to 0.70；

Although flammable sex factor provides the flammable basis for predicting certain fluoroolefin compounds, might have Certain variables, such as position of the hydrogen atom on molecule, it is flammable, and other different for will cause certain isomers of given molecular formula Structure body is then non-flammable.Therefore, flammable sex factor is only used as the tool of prediction flammability properties.

Combustible refrigerant of the invention include it is any it is provable when mixing with air in defined temperature, pressure and composition item It can make the compound of propagation of flame under part.Combustible refrigerant can by with electronics incendiary source ASHRAE (U.S. heating, refrigeration and Air-conditioning man's teachers learn, American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc.) standard 34-2001 (ASTM (American Society Testing and Materials, American Society of Testing and Materials) under E681-01) be tested to identify under conditions of defined.This flammability test is With the refrigerant in 101kPa (14.7psia) and predetermined temperature (100 DEG C usual (212 °F)) or room temperature (about 23 DEG C (73 °F)) Under carried out with concentration in different air, with determination it is the aerial lean flammability of the test compound (LFL) and/or flammable The property upper limit (UFL).

For actual conditions, if meeting when certain refrigerant leaks from refrigerating plant or air-conditioning device and touches incendiary source Cause to catch fire, then can be classified as combustible refrigerant.Composition of the invention causes a possibility that catching fire in this leakage process It is low.

Combustible refrigerant of the invention includes hydrofluorocarbon (HFC), fluoroolefin, fluoro-ether, hydrocarbyl ether, hydrocarbon, ammonia (NH₃) and it Combination.

Flammable HFC refrigerant includes but is not limited to：Difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1- trifluoro Ethane (HFC-143a), 1,1,2- trifluoroethane (HFC-143), 1,1- Difluoroethane (HFC-152a), fluoroethane (HFC- 161), 1,1,1- trifluoro propane (HFC-263fb), 1,1,1,3,3- 3-pentafluorobutane (HFC-365mfc) and their combination. These are flammable HFC refrigerant is available from multiple sources such as chemicals Synesis Company commercial product, or this field can be passed through It is prepared by disclosed synthetic method.

Combustible refrigerant of the invention also includes but fluoroolefin not limited to the following：1,2,3,3- tetra- fluoro- 1- third Alkene (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)；2,3, The fluoro- 1- propylene (HFC-1243yf) of 3- tri-；3,3,3- tri- fluoro- 1- propylene (HFC-1243zf)；1,1,2- tri- fluoro- 1- propylene (HFC-1243yc)；1,1,3- tri- fluoro- 1- propylene (HFC-1243zc)；1,2,3- tri- fluoro- 1- propylene (HFC-1243ye) and 1, 3,3- tri- fluoro- 1- propylene (HFC-1243ze).

Combustible refrigerant of the invention also includes fluoro-ether, and this compound and hydrogen fluorohydrocarbon class seemingly, also contain at least one Ether group oxygen atom.Representative fluoroether refrigerant includes but is not limited to C₄F₉OC₂H₅, it is commercially available.

Combustible refrigerant of the invention also includes hydrocarbon coolant.Representative hydrocarbon coolant includes but is not limited to propane, third Alkene, cyclopropane, normal butane, iso-butane, pentane, 2- methybutane (isopentane), cyclobutane, pentamethylene, 2,2- dimethyl propylene Alkane, 2,2- dimethylbutane, 2,3- dimethylbutane, 2,3- dimethyl pentane, 2- methyl hexane, 3- methyl hexane, 2- methyl Pentane, 3- ethylpentane, 3- methylpentane, hexamethylene, normal heptane, methyl cyclopentane and n-hexane.Flammable hydrocarbon coolant can hold Easily obtained from multiple commercial sources.

Combustible refrigerant of the invention also includes hydrocarbyl ether, such as dimethyl ether (DME, CH₃OCH₃) and methyl tertiary butyl ether(MTBE) (MTBE, (CH₃)₃COCH₃), it can both be obtained from multiple commercial sources.

Combustible refrigerant of the invention also includes ammonia (NH₃), this is a kind of compound being commercially available.

Combustible refrigerant of the invention also may include the mixture more than a kind of refrigerant, such as two or more flammables The mixture of agent (such as two kinds of HFC perhaps a kind of HFC and a kind of hydrocarbon) or comprising combustible refrigerant and non-flammable refrigerant Mixture, latter mixture carry out identifying or generally can still recognizing for actual conditions under the conditions of ASTM as described herein To be combustible refrigerant.

The example for the non-flammable refrigerant that can be mixed with other refrigerants of the invention include R-134a, R-134, (ASHRAE is marked as R401 for R-23, R125, R-236fa, R-245fa and HCFC-22/HFC-152a/HCFC-124 mixture Or R-401A, R-401B and R-401C), HFC-125/HFC-143a/HFC-134a mixture (ASHRAE marked as R-404 or R-404A), (ASHRAE is marked as R407 or R-407A, R-407B and R- for HFC-32/HFC-125/HFC-134a mixture 407C), HCFC-22/HFC-143a/HFC-125 mixture (ASHRAE is marked as R408 or R-408A), HCFC-22/ HCFC-124/HCFC-142b mixture (ASHRAE is marked as R-409 or R-409A), HFC-32/HFC-125 mixture (ASHRAE is marked as R-410A) and HFC-125/HFC-143a mixture (ASHRAE is marked as R-507 or R507A) and two Carbonoxide.

Example more than a kind of mixture of combustible refrigerant includes propane/iso-butane mixture, HFC-152a/ isobutyl Alkane mixture, R32/ propane mixture, R32/ iso-butane mixture and HFC/ carbon dioxide mixture such as HFC-152a/CO₂。

One aspect of the present invention provides global warming potential less than 150, preferably smaller than 50 non-flammable refrigerant.This hair Bright is to reduce the flammable of the mixture by the way that non-flammable fluoroolefin is added to flammable mixture on the other hand Property.

Although it can be proved that certain refrigerants be it is flammable, can by combustible refrigerant be added another kind can not The compound of combustion generates non-flammable refrigerant composition.The example of this non-flammable refrigerant admixture includes R-410A (HFC-32 is combustible refrigerant, and HFC-125 by (HFC-32 is combustible refrigerant, and HFC-125 is then non-combustible) and R-407C It is then non-combustible with HFC-134a).

It can be used as the sheet of refrigerant or heat-transfer fluid comprising at least one fluoroolefin and at least one combustible refrigerant Inventive composition produces the group of the result category non-flammable according to ASTM E681-01 containing a effective amount of fluoroolefin Close object.

The present composition comprising at least one combustible refrigerant and at least one fluoroolefin can contain about 1 weight Percentage is to the fluoroolefin of about 99 weight percent and the combustible refrigerant of about 99 weight percent to about 1 weight percent.

In another embodiment, the present composition contains about 10 weight percent to about 80 weight percent The combustible refrigerant of fluoroolefin and about 90 weight percent to about 20 weight percent.In yet another embodiment, this hair Fluoroolefin of the bright composition containing about 20 weight percent to about 70 weight percent and about 80 weight percent are to about 30 The combustible refrigerant of weight percent.

One what is worth mentioning embodiment of the present invention is that fluoroolefin includes HFC-1225ye and flammable Agent includes HFC-32 (difluoromethane).It is known by ASTM 681-01 measurement, the HFC-32's comprising most 37 weight percent Composition is non-flammable, and include 38 weight percent or more than the composition of HFC-32 be flammable.The present invention provides HFC-32 and about 99.0 weight percent comprising about 1.0 weight percent to about 37.0 weight percent are to about 63 weight percents The non-flammable composition of the HFC-1225ye of ratio.

One embodiment of the present invention being equally worth mentioning is that composition includes HFC-1225ye, HFC-32 and HFC- 125.This composition of the invention includes HFC-1225ye, about 1.0 weights of about 20 weight percent to about 95 weight percent Percentage is measured to the HFC-32 of about 65 weight percent and the HFC-125 of about 1.0 weight percent to about 40 weight percent. In another embodiment, composition includes the HFC-1225ye, about of about 30 weight percent to about 90 weight percent The HFC-32 and about 1.0 weight percent of 5.0 weight percent to about 55 weight percent to about 35 weight percent HFC- 125.In yet another embodiment, composition include about 40 weight percent to about 85 weight percent HFC-1225ye, The HFC-32 and about 1.0 weight percent of about 10 weight percent to about 45 weight percent are to about 28 weight percent HFC-125.It is non-flammable composition containing those of the HFC-32 for being less than about 40 weight percent compositions contemplated.Depending on group The relative scale of HFC-1225ye and HFC-125 present in object is closed, this limit of combustibility can be from less than about 45 weight percents It is changed between the HFC-32 of ratio to the HFC-32 for being less than about 37 weight percent.

In another what is worth mentioning embodiment, combustible refrigerant includes HFC-1243zf, non-flammable fluoro Alkene is intended to reduce the combustibility of overall composition.Composition can include about 1.0 weight percent to about 99 weight percent The HFC-1225ye of HFC-1243zf and about 99 weight percent to about 1.0 weight percent.Alternatively, composition can include about The HFC-1243zf and about 60 weight percent of 40 weight percent to about 70 weight percent are to about 30 weight percent HFC-1225ye。

In another what is worth mentioning embodiment, composition includes about 1.0 weight percent to about 98 weight The HFC-1243zf of percentage；The HFC-1225ye and about 1.0 weight percents of about 1.0 weight percent to about 98 weight percent Than the HFC-125 to about 50 weight percent.Alternatively, composition includes about 40 weight percent to about 70 weight percent HFC-1243zf, the HFC-1225ye of about 20 weight percent to about 60 weight percent and about 1.0 weight percent are to about 10 The HFC-125 of weight percent.

In another what is worth mentioning embodiment, composition includes about 1.0 weight percent to about 98 weight The HFC-1243zf of percentage；The HFC-1225ye of about 1.0 weight percent to about 98 weight percent；About 1.0 weight hundred Divide than the HFC-32 to about 50 weight percent.In yet another embodiment, composition includes about 40 weight percent to about The HFC-1243zf of 70 weight percent, about 20 weight percent to the HFC-1225ye of about 60 weight percent and about 1.0 Weight percent to about 10 weight percent HFC-32.

In another what is worth mentioning embodiment, composition includes about 1.0 weight percent to about 97 weight The HFC-1243zf of percentage；The HFC-1225ye of about 1.0 weight percent to about 97 weight percent；About 1.0 weight percents Than the HFC-32 of HFC-125 and about 1.0 weight percent to about 50 weight percent to about 50 weight percent.

Alternatively, composition includes the HFC-1243zf of about 40 weight percent to about 70 weight percent；About 20 weight hundred Divide than the HFC-1225ye to about 60 weight percent；About 1.0 weight percent to about 10 weight percent HFC-125 peace treaties 1.0 weight percent is to the HFC-32 of about 10 weight percent.

The invention further relates to the flammable methods for reducing combustible refrigerant, and the method includes by combustible refrigerant and extremely A kind of few fluoroolefin is mixed.The amount for the fluoroolefin being added must be effective quantity, to produce by ASTM 681-01 Measurement belongs to the composition of non-flammable.

Composition of the invention can be applied in combination in refrigeration, air-conditioning or heat pump system with desiccant, dry to remove Gas.Desiccant may include activated alumina, silica gel or zeolite-based molecular sieves.Representative molecular sieve include MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL), refrigerant lesser for molecular size such as HFC-32, it is excellent Select XH-11 desiccant.

Composition of the invention also may include at least one lubricant.Lubricant of the invention includes suitable for refrigeration or sky Adjust those of device lubricant.In these lubricants, have conventionally used for the compression refrigerating apparatus using chlorofluorocarbon refrigerant Those of lubricant.This lubricant and their characteristic are in 1990ASHRAE Handbook, Refrigeration Systems and Applications (refrigeration system and application), the 8th chapter, title " Lubricants in Refrigeration Systems (lubricant in refrigeration system) " has discussion in the 8.1-8.21 pages, and this article passes through Reference is incorporated herein in.Lubricant of the invention may include that compression refrigeration lubrication field is commonly referred to as those of " mineral oil " lubrication Agent.Mineral oil includes that paraffin (i.e. straight chain and branched-chain saturated hydrocarbon), cycloalkanes (i.e. cyclic paraffins) and aromatic hydrocarbons (contain one or more The unsaturated cyclic hydrocarbon of ring characterized by alternately double bond).Lubricant of the invention also includes the common name of compression refrigeration lubrication field For those of " synthetic oil " lubricant.Synthetic oil includes alkylaryl substance (i.e. straight chain and branched alkyl alkylbenzene), compound stone Wax and cycloalkanes and poly- (alhpa olefin).Representative conventional lubricantss of the invention are commercially available BVM 100N (paraffinic mineral oil, BVA Oils is sold),3GS knows5GS (naphthenic mineral oil, Crompton Co. are sold), 372LT (naphthenic mineral oil, Pennzoil are sold),RO-30 (naphthenic mineral oil, Calumet Lubricants Sell),75、150 Hes500 (linear alkylbenzene (LAB), Shrieve Chemicals are sold) and HAB 22 (branched alkylbenzene, Nippon Oil are sold).

Lubricant of the invention also includes to be designed to fluoroether refrigerant and made with refrigerant of the present invention in compression Those of miscible lubricant under cold and air-conditioning device operating condition.This lubricant and their property are in " Synthetic Lubricants and High-Performance Fluids (syntholube and high efficiency fluid) ", R.L.Shubkin (are compiled Volume), Marcel Dekker has discussion in 1993.This lubricant include but is not limited to polyol ester (POE) such as100 (Castrol, United Kingdom), polyalkylene glycol (PAG) such as RL-488A (Dow Chemical, Midland, Michigan) and polyvingl ether (PVE).

The environment that lubricant of the invention is requirement by considering given compressor and lubricant will be exposed to come into Row selection.

Common refrigeration system additives optionally can be added to composition of the invention on demand, to improve lubricity and system Stability.These additives are well known to refrigeration compressor lubricating area, including antiwear additive, extreme pressure lubricant, corrosion With oxidation retarder, metal surface deactivators, foam and anti-foaming controlling agent, leak detectants etc..In general, these add Agent is added only to exist on a small quantity relative to overall lubricant composition.The use concentration of every kind of additive is usually from less than about 0.1% Up to about 3%.These additives are that selection is carried out on the basis of different system requirements.Some typical cases of these additives Example may include but be not limited to the additive of enhancing lubrication, such as the Arrcostab or aryl ester of phosphoric acid and thiophosphate.In addition, golden Belong to dialkyl dithiophosphate (such as zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and this kind chemistry Other members of product can also be used for composition of the invention.Other antiwear additives include natural products oil (natural product ) and asymmetry polyhydroxy lubricating additive such as Synergol TMS (International Lubricants) oil.Equally, The stabilizers such as antioxidant, free radical scavenger and dehydrating agent (dry compound) can be used.This additive includes But it is not limited to nitromethane, hindered phenol (such as Butylated Hydroxytoluene or BHT), azanol, mercaptan, phosphite, epoxides or lactone.It goes Aqua includes but is not limited to ortho esters such as trimethyl orthoformate, triethyl orthoformate or tripropyl orthoformate.It can be used single The combination of additive or additive.

In one embodiment, the present invention provides selected from the following steady comprising at least one fluoroolefin and at least one Determine the composition of agent：Thiophosphate, butylated triphenyl thiophosphate, organophosphorus ester, dialkylthiophosphate esters, Terpene, terpenoid, fullerene, functionalized perfluoropolyether, polyoxyalkylated aromatic substances (polyoxyalkylated aromatics), Epoxides, fluorinated epoxide, oxetanes, ascorbic acid, mercaptan, lactone, thioether, nitromethane, alkyl silane, benzene Ketone derivatives, aromatic yl sulfide, terephthalic acid (TPA) diethyl enester, terephthaldehyde's diphenyl phthalate, alkylamine, hindered amine are anti-oxidant Agent and phenol.Alkylamine may include triethylamine, tri-n-butylamine, diisopropylamine, tri-isopropyl amine, triisobutylamine and this kind of alkyl amine compounds Other members of object.

In another embodiment, stabilizer of the invention may include the specific combination of each stabilizer.One is especially worth Obtaining a combination of stabilizers proposed includes at least one terpene or terpenoid.These terpenes or terpenoid can at least one selected from epoxides, The compound of fluorinated epoxide and oxetanes is mixed.

Terpene is to contain the hydrocarbon for having more than the structure of a repetition isoprene (2- methyl-1,3- butadiene) unit and being characterized Compound.Terpene can be acyclic or cricoid.Representative terpene includes but is not limited to laurene (2- methyl -6- methylene octyl- 1,7- diene), alloocimene, β-ocimenum, terebene, limonene (or (R)-4-isopropenyl-1-methyl-1-cyclohexene), retinene, firpene (or australene), Menthol, geraniol, farnesol, phytol, vitamin A, terpinene, δ -3- carene, terpinolene, phellandrene, fenchene and they Mixture.Terpene stabilizer is commercially available, or can be prepared or be separated by methods known in the art from natural origin.

Terpenoid is containing the natural products and related compounds characterized by having more than the structure of a repetition isoprene unit Object simultaneously optionally contains aerobic.Representative terpenoid includes carotenoid such as lycopene (CAS reg.no. [502-65-8]), β- Carrotene (CAS reg.no. [7235-40-7]) and lutein, that is, luteole (CAS reg.no. [144-68-3])；Class Visual pigment such as hepaxanthin (CAS reg.no. [512-39-0]) and isotretinoin (CAS reg.no. [4759-48-2])；Rosin Alkane (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])；Gamma Wax alkane (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])；Himachalane (CAS reg.no. [20479-45-2])；Humulane (CAS reg.no. [471- 62-5])；Humulane (CAS reg.no. [430-19-3])；Kaurene (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- terpane (CAS reg. no. [99-82-1])；Oleanane (CAS reg.no. [471- 67-0])；ophiobolane(CAS reg. no.[20098-65-1])；picrasane(CAS reg.no.[35732-97- 9])；Pimarane (CAS reg.no. [30257-03-5])；Pinane (CAS reg.no. [473-55-2])；Podocarpane (CAS reg.no.[471-78-3])；Protostane (CAS reg.no. [70050-78-1])；Rose alkane (CAS reg.no. [6812- 82-4])；Taxane (CAS reg.no. [1605-68-1])；Thujane (CAS reg.no. [471-12-5])；Spore bacterium alkane (CAS reg.no. [24706-08-9]) and aromadendrane (CAS reg.no. [464-93-7]).Terpenoid of the invention is commercially available to be obtained , or can prepare or can be separated from natural origin by methods known in the art.

In one embodiment, terpene or terpenoid stabilizer can be mixed at least one epoxides.It is representative Epoxides include 1,2- propylene oxide (CAS reg.no. [75-56-9]), 1,2- epoxy butane (CAS reg.no. [106-88-7]) or their mixture.

In another embodiment, can by terpene of the invention or terpenoid stabilizer and at least one fluorinated epoxide into Row mixing.Fluorinated epoxide of the invention can be as shown in Equation 3, wherein R²To R⁵In each be the alkane of H, 1-6 carbon atoms The fluoro-alkyl of base or 1-6 carbon atom, condition are R²To R⁵In at least one be fluoroalkyl group.

Formula 3

Representative fluorinated epoxide stabilizer includes but is not limited to trifluoromethyl ethylene oxide and 1, the bis- (fluoroforms of 1- Base) ethylene oxide.This compound can be prepared by methods known in the art, such as be passed throughJournal of Fluorine Chemistry, volume 24,93-104 pages (1984),Journal of Organic Chemistry, volume 56,3187-3189 pages (1991) andJournal of Fluorine Chemistry, volume 125, the preparation of method described in 99-105 pages (2004).

In another embodiment, terpene of the invention or terpenoid stabilizer and at least one oxetanes can be carried out Mixing.Oxetanes stabilizer of the invention can be the compound with one or more oxetane groups, such as formula 4 It is shown, wherein R₁-R₆It is identical or different, it can be selected from hydrogen, alkyl or replace alkyl, aryl or substituted aryl.

Formula 4

Representative oxetanes stabilizer includes but is not limited to 3- ethyl -3- methylol-oxetanes such as OXT- 101 (Toagosei Co., Ltd), 3- ethyl -3- ((phenoxy group) methyl)-oxetanes such as OXT-211 (Toagosei Co., Ltd) and 3- ethyl -3- ((2- ethyl-hexyloxy) methyl)-oxetanes such as OXT-212 (Toagosei Co., Ltd)。

Another what is worth mentioning embodiment is the combination of stabilizers comprising fullerene.It can be by fullerene stabilizers It is mixed at least one compound selected from epoxides, fluorinated epoxide and oxetanes.For with fullerene into Row mixed epoxides, fluorinated epoxide and oxetanes supply the ring mixed with terpene or terpenoid as previously described Oxide, fluorinated epoxide and oxetanes.

Another what is worth mentioning embodiment is the combination of stabilizers comprising phenol.Can by phenolic stabilizers with extremely A kind of few compound selected from epoxides, fluorinated epoxide and oxetanes is combined.For being combined with phenol Epoxides, fluorinated epoxide and oxetanes as previously described for the epoxidation that is combined with terpene or terpenoid Object, fluorinated epoxide and oxetanes.

Phenolic stabilizers include any substituted or unsubstituted oxybenzene compound, the oxybenzene compound include comprising One or more substituted or unsubstituted cyclic annular, linear chain or branched chain aliphatic series substituent group phenol, such as alkylation monophenols, including 2,6- di-tert-butyl-4-methy phenols, 2,6- di-t-butyl -4- ethyl -phenol, 2,4- dimethyl -6- tert-butyl phenol, fertility Phenol etc.；Quinhydrones and alkvlated hvdroquinones, including tert-butyl hydroquinone, other hydroquinone derivatives etc.；Hvdroxvlated thiodiphenvl ether, including 4,4 '-thiobis (2- methyl-6-tert-butylphenol), 4,4 '-thiobis (3- methyl -6- tert-butyl phenol), 2,2 '-is thio Bis- (4- methyl-6-tert-butylphenols) etc.；Alkylidene bisphenols, including 4,4 '-di-2-ethylhexylphosphine oxides (2,6- DI-tert-butylphenol compounds), 4, 4 '-bis- (2,6- DI-tert-butylphenol compounds), 2,2 '-or 4, the derivative of 4- '-biphenyl diphenol, 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl -6- Tert-butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 4,4- butylidenebis (3- methyl-6-tert butyl Phenol), 4,4- isopropylidene bis- (2,6- DI-tert-butylphenol compounds), 2,2 '-methylene-bis(4-methyl-6-nonyl phenol)s, 2, 2 '-isobutylenes bis- (4,6- xylenols, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl -6- cyclohexylphenols；2,2- or 4,4- biphenyl Diphenol, including 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, Butylated Hydroxytoluene (BHT)；Include heteroatomic bis-phenol, packet Include 2,6- di-tert-alpha-alpha-dimethyl amino-paracresol, 4,4- thiobis (6- tert-butyl-metacresol) etc.；Acyl aminophenols； 2,6- di-t-butyls -4 (N, N '-dimethyl amino methyl phenol)；Sulfide, including bis- (3- methyl -4- hydroxyl -5- tert-butyls Benzyl) sulfide, bis- (3,5- di-tert-butyl-4-hydroxyl benzyl) sulfide etc..

In one embodiment of the invention, these include terpene or terpenoid or fullerene or phenol and at least one choosing It also may include selected from the following another from the combination of stabilizers of the compound of epoxides, fluorinated epoxide and oxetanes Outer stabilizer compounds：Oxalyl bis- (benzal hydrazines) (areoxalyl bis (benzylidene) hydrazide) (CAS Reg.no.6629-10-3), N, N '-bis- (3,5- di-t-butyl -4- hydroxyhydrocinnamoyl hydrazine) (CAS reg.no. 32687-78-8), 2,2 '-oxamidobis-ethyls-(3,5-d- tertiary butyl-4-hydroxy hydrogenated cinnamate) (CAS Reg.no.70331-94-1), N, N '-(two salicylidenes) -1,2- propane diamine (CAS reg. no.94-91-1) and ethylenediamine Tetraacethyl (CAS reg.no.60-00-4) and its salt.

In another embodiment of the present invention, these include terpene or terpenoid or fullerene or phenol and at least one The combination of stabilizers of compound selected from epoxides, fluorinated epoxide and oxetanes also may include at least one choosing From alkylamine below：Triethylamine, tri-n-butylamine, tri-isopropyl amine, di-iso-butylmanice, tri-isopropyl amine, triisobutylamine and hindered amine antioxygen Agent.

Composition of the invention also may include the compound or composition as tracer, the compound or composition choosing From hydrofluorocarbon (HFC), deuteroparaffin, deuterated hydrofluorocarbons, perfluoroparaffin, fluoro-ether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, Nitrous oxide (N₂) and their combination O.It is and the combination as refrigerant or heat-transfer fluid for tracer of the invention The different composition of object, is added in refrigerant and heat transfer fluid composition with predetermined quantities, so as to detection combination object Any dilution, pollution or other situations of change, this in 2 months 2005 U.S. Patent Application Serials 11/062 submitted for 18th, It is described in 044.

Table 5 lists the typical tracer compounds for the present composition.

Table 5

Compound listed by table 5 is commercially available (chemically product supply firm), or can pass through side well known in the art Method preparation.

Each single tracer compounds can with the refrigerating/heating combination of fluids in the present composition use or it is a variety of Tracer compounds can be combined in any proportion, as tracer admixture.Tracer admixture can be containing from same A variety of tracer compounds of class compound, or a variety of tracer compounds from inhomogeneity compound.For example, tracer Admixture can the combination containing 2 kinds or a variety of deuterated hydrofluorocarbons or a kind of deuterated hydrofluorocarbons and one or more perfluoroparaffins.

In addition, some compounds in table 4 exist in the form of various structures isomers or optical isomer.Identical chemical combination The individual isomer of object or a variety of isomers can be carried out in any proportion using to prepare tracer compounds.In addition, given One or more isomers of compound list can be combined in any proportion with any amount of other compounds, as tracer Admixture.

Tracer compounds or tracer admixture are with about 50ppm (hundred a ten thousandths, by weight) to about 1000ppm's Total concentration is present in composition.Preferably, tracer compounds or tracer admixture are with the total of about 50ppm to about 500ppm Concentration exists, and most preferably tracer compounds or tracer admixture exist with the total concentration of about 100ppm to about 300ppm.

Composition of the invention also may include ultraviolet (UV) dyestuff and optionally include solubilizer.UV dyestuff is detection refrigeration The useful component of the leakage of agent composition or heat-transfer fluid, it be by allow people it is observed that refrigeration, air-conditioning, in heat pump assembly The fluorescence of the dyestuff in refrigerant or heat transfer fluid composition near leakage point or leakage point detects leakage.People can be with The fluorescence of dyestuff is observed in the UV lamp.Since solubility of this UV dyestuff in some refrigerants and heat-transfer fluid is low, It may need solubilizer.

So-called " ultraviolet " dyestuff refers to that the UV of ultraviolet or in " close " ultraviolet region the light of energy electromagnetic wave absorption frequency spectrum is glimmering Light composition.It can produced under ultraviolet light irradiation of the launch wavelength by 10nm to the radiation between 750nm by ultra-violet fluorescent dye Raw fluorescence can detecte.Therefore, if refrigerant or heat-transfer fluid containing this ultra-violet fluorescent dye are from refrigeration, empty Set point in tune or heat pump assembly leaks out, and can detect fluorescence near the leakage point or the leakage point.This purple Outer fluorescent dye include but is not limited to naphthalimide, it is cumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, glimmering The derivative or their combination of light element and the dyestuff.Solubilizer of the invention includes at least one chemical combination selected from the following Object：Hydrocarbon, hydrocarbyl ether, polyoxyalkylene glycol ether, amide, nitrile, ketone, chlorocarbon, ester, lactone, aryl ether, fluoro-ether and 1,1,1- tri- Fluothane hydrocarbon.

The hydrocarbon that hydrocarbon solubilizer of the invention is included includes nothing containing 16 or 16 carbon atoms below and only hydrogen Straight chain, branch or the cyclic alkane or alkene of other functional groups.Representative hydrocarbon solubilizer includes propane, propylene, cyclopropane, just Butane, iso-butane, pentane, octane, decane and hexadecane.It should be pointed out that solubilizer can if refrigerant is certain hydrocarbon Not to be same hydrocarbon.

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

Polyoxyalkylene glycol ether solubilizer of the invention is by formula R¹[(OR²)_xOR³]_yIt is shown, wherein：X is the whole of 1-3 Number；Y is the integer of 1-4；R¹Aliphatic hydrocarbyl selected from hydrogen and with 1-6 carbon atom and y bonding point；R²Selected from 2-4 The aliphatic hydrocarbylene of carbon atom；R³Aliphatic hydrocarbyl and alicyclic hydrocarbon radical selected from hydrogen and with 1-6 carbon atom；R¹And R³In at least One is the alkyl；And wherein the molecular weight of the polyoxyalkylene glycol ether is about 100 to about 300 atomic masses Unit.Bonding point used herein refers to form the group site of covalent bond with other groups.Alkylene refers to bivalent hydrocarbon radical.? In the present invention, preferred polyoxyalkylene glycol ether solubilizer is by formula R¹[(OR²)_xOR³]_yIt is shown：X is preferably 1-2；Y is preferred It is 1；R¹And R³It is preferred that being independently selected from hydrogen and the aliphatic hydrocarbyl with 1-4 carbon atom；R²Being preferably selected from has 2 or 3 carbon originals The aliphatic hydrocarbylene of son, most preferably 3 carbon atoms；The polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 Atomic mass unit, most preferably from about 125 to about 250 atomic mass units.R with 1-6 carbon atom¹And R³Alkyl can be It is straight chain, branch or cricoid.Representative R¹And R³Alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta and cyclohexyl.In polyoxyalkylene two of the present invention Free hydroxyl group on alcohol ether solubilizer may with certain compression refrigerating apparatus constituent materials (such as) incompatible In situation, R¹And R³The preferably aliphatic hydrocarbyl with 1-4 carbon atom, most preferably 1 carbon atom.With 2-4 carbon atom R²Aliphatic hydrocarbylene forms duplicate oxyalkylene group-(OR²)_x, the alkylidene oxide includes oxy ethylene, oxypropylene And oxybutylene.That in one polyoxyalkylene glycol ether solubilizing agent molecule includes R²Alkylidene oxide can be it is identical Or molecule contain different R²Alkylidene oxide.Polyoxyalkylene glycol ether solubilizer of the present invention preferably wraps Containing at least one oxypropylene.In R¹For the feelings of aliphatic hydrocarbyl or alicyclic hydrocarbon radical with 1-6 carbon atom and y bonding point In condition, which can be straight chain, branch or cricoid.There are two the R of bonding point for representative tool¹Aliphatic hydrocarbyl includes Such as ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylene and cyclohexylidene.Representative tool there are three or The R of four bonding points¹Aliphatic hydrocarbyl include by remove polyalcohol hydroxyl derived from the polyalcohol residue, it is described polynary Alcohol such as trimethylolpropane, glycerol, pentaerythrite, 1,2,3- trihydroxy hexamethylenes and 1,3,5- trihydroxy hexamethylenes.

Representative polyoxyalkylene glycol ether solubilizer includes but is not limited to CH₃OCH₂CH(CH₃) O (H or CH₃) (propylene glycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropylene glycol methyl (or dimethyl) ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃) (tripropylene glycol methyl (or dimethyl) ether), C₂H₅OCH₂CH(CH₃) O (H or C₂H₅) (propylene glycol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₂(H or C₂H₅) (dipropylene glycol ethyl (or diethyl) Ether), C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅) (tripropylene glycol ethyl (or diethyl) ether), C₃H₇OCH₂CH(CH₃) O (H or C₃H₇) (propylene glycol n-propyl (or diη-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇) (dipropylene glycol n-propyl (or diη-propyl) ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇) (tripropylene glycol n-propyl (or diη-propyl) ether), C₄H₉OCH₂CH(CH₃) OH (propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉) (dipropylene glycol normal-butyl (or Di-n-butyl) ether), C₄H₉O[CH₂CH(CH₃)O]₃(H or C₄H₉) (tripropylene glycol normal-butyl (or di-n-butyl) ether), (CH₃)₃COCH₂CH(CH₃) OH (propylene glycol t-butyl ether), (CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃) (the tertiary fourth of dipropylene glycol Base (or di-t-butyl) ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃) (tripropylene glycol tert-butyl (or di-t-butyl) Ether), C₅H₁₁OCH₂CH(CH₃) OH (propylene glycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅) OH (butanediol n-butyl ether), C₄H₉O [CH₂CH(C₂H₅)O]₂H (dibutylene glycol n-butyl ether), trimethylolpropane tris n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) With trimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH)。

Amide solubilizing agents of the invention include formula R¹C(O)NR²R³With ring-[R⁴C(O)N(R⁵)] shown in those of amide, Middle R¹、R²、R³And R⁵It is independently selected from aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-12 carbon atom；R⁴Selected from former with 3-12 carbon The aliphatic hydrocarbylene of son；And wherein the molecular weight of the amide is about 100 to about 300 atomic mass units.Point of the amide Son amount is preferably from about 160 to about 250 atomic mass units.R¹、R²、R³And R⁵It can optionally include substituted alkyl, i.e., containing choosing From the group of halogen (such as fluorine, chlorine) and the substituents of alkoxy (such as methoxyl group).R¹、R²、R³And R⁵Can optionally include The alkyl being exchanged for heteroatoms contains nitrogen (azepine), oxygen (oxa-) or sulphur that is, in the group chain being made of originally carbon atom The group of (thia) atom.Generally, for R^1-3In every 10 carbon atoms, have no more than three, preferably more than one A substituents and hetero atom exist, and must be taken into consideration when with above-mentioned molecular weight limit any this substituents with Heteroatomic presence.Preferred Amide solubilizing agents are made of carbon, hydrogen, nitrogen and oxygen.Representative R¹、R²、R³And R⁵Aliphatic hydrocarbyl and Alicyclic hydrocarbon radical includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, new penta Base, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configuration isomery Body.The preferred embodiment of Amide solubilizing agents is above formula ring-[R⁴C(O)N(R⁵R in) -]⁴It can be by (CR⁶R⁷)_nShown in alkylene Those of amide, be in other words formula ring-[(CR⁶R⁷)_nC(O)N(R⁵) -], wherein：Values for molecular weight as defined in front is applicable in； N is the integer of 3-5；R⁵For the saturated hydrocarbyl containing 1-12 carbon atom；R⁶And R⁷The definition R independently provided by front^1-3's Rule is selected (for each n).In formula ring-[(CR⁶R⁷)_nC(O)N(R⁵In lactams shown in) -], all R⁶And R⁷It is excellent It is selected as hydrogen, or contains single saturated hydrocarbyl, R in the n methylene units⁵For the saturated hydrocarbons containing 3-12 carbon atom Base.For example, 1- (saturated hydrocarbyl) -5- methylpyrrolidin- 2- ketone.

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

Ketone solubilizer of the invention includes formula R¹C(O)R²Shown in ketone, wherein R¹And R²It is independently selected from 1-12 carbon Aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl of atom, and wherein the molecular weight of the ketone is about 70 to about 300 atomic mass lists Position.R in the ketone¹And R²It is preferred that being independently selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-9 carbon atom.Point of the ketone Son amount is preferably from about 100 to about 200 atomic mass units.R¹And R²It can connect to form alkylene together, to form five yuan, six Member or heptatomic ring cyclic ketone, such as cyclopentanone, cyclohexanone and cycloheptanone.R¹And R²It can include optionally substituted alkyl, that is, contain The group of substituents selected from halogen (such as fluorine, chlorine) and alkoxy (such as methoxyl group).R¹And R²It can optionally include miscellaneous The alkyl that atom replaces contains nitrogen (azepine), oxygen (oxa-) or sulphur (thia) that is, in the group chain being made of originally carbon atom The group of atom.Generally, for R¹And R²In every 10 carbon atoms, have no more than three, preferably more than one Substituents and hetero atom exist, and any this substituents and miscellaneous must be taken into consideration when with above-mentioned molecular weight limit The presence of atom.General formula R¹C(O)R²In representative R¹And R²Aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl include methyl, ethyl, Propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, hexamethylene Base, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomer and phenyl, benzyl, cumene Base,Base, tolyl, xylyl and phenethyl.

Representative ketone solubilizer includes but is not limited to 2- butanone, 2 pentanone, acetophenone, phenyl propyl ketone, benzene hexanone, hexamethylene Ketone, cycloheptanone, 2-HEPTANONE, 3- heptanone, 5 methy 12 hexanone, 2- octanone, 3- octanone, diisobutyl ketone, 4- ethyl cyclohexanone, 2- Nonanone, butyl ketone, 2- decanone, 4- decanone, 2- decalone, ten triketone of 2-, two hexanones and two cyclohexanone.

Nitrile solubilizer of the invention includes formula R¹Nitrile shown in CN, wherein R¹Selected from the aliphatic hydrocarbon with 5-12 carbon atom Base, alicyclic hydrocarbon radical and aryl, and wherein the molecular weight of the nitrile is about 90 to about 200 atomic mass units.The nitrile solubilising R in agent¹It is preferably selected from aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 8-10 carbon atom.The molecular weight of the nitrile solubilizer is excellent It is selected as about 120 to about 140 atomic mass units.R¹Can optionally include substituted alkyl, i.e., containing selected from halogen (such as fluorine, Chlorine) and alkoxy (such as methoxyl group) substituents group.R¹It can include optionally the alkyl being exchanged for heteroatoms, that is, exist Originally contain the group of nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom in the group chain being made of carbon atom.In general, For R¹In every 10 carbon atoms, have and exist no more than three, preferably more than a substituents and hetero atom, and Any this substituents and heteroatomic presence must be taken into consideration when with above-mentioned molecular weight limit.General formula R¹Generation in CN Table R¹Aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl include amyl, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptan Base, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomer and phenyl, benzyl, cumenyl, Base, tolyl, xylyl and phenethyl.

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

Chlorocarbon solubilizer of the invention includes formula RCl_xShown in chlorocarbon, wherein：X is selected from an integer of 1 or 2；R is selected from tool There are the aliphatic hydrocarbyl and alicyclic hydrocarbon radical of 1-12 carbon atom；And wherein the molecular weight of the chlorocarbon is about 100 to about 200 atom matter Measure unit.The molecular weight of the chlorocarbon solubilizer is preferably from about 120 to about 150 atomic mass units.General formula R Cl_xIn representative Property R aliphatic hydrocarbyl and alicyclic hydrocarbon radical include methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, penta Base, isopentyl, neopentyl, tertiary pentyl, cyclopenta, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and Their configurational isomer.

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

Ester solubilizer of the invention includes general formula R¹CO₂R²Shown in ester, wherein R¹And R²Be independently selected from straight chain and it is cricoid, Saturation and unsaturated alkyl and aryl.Preferred ester is substantially made of Elements C, H and O, and molecular weight is about 80 to about 550 originals Protonatomic mass unit.

Representative ester includes but is not limited to (CH₃)₂CHCH₂OOC(CH₂)_2-4OCOCH₂CH(CH₃)₂(diisobutyl binary Ester), ethyl hexanoate, cognac oil, n-butyl propionate, n propyl propionate, ethyl benzoate, n-propyl phthalate, benzene Formic acid ethoxy ethyl ester, dipropyl carbonate, " Exxate 700 " (commercially available acetic acid C₇Arrcostab), " Exxate 800 " it is (commercially available Acetic acid C₈Arrcostab), dibutyl phthalate and tert-butyl acetate.

Lactone solubilizing agents of the invention include with lactone shown in flowering structure [A], [B] and [C]：

These lactones contain functional group-CO in six-membered ring (A) or preferably in pentatomic ring (B)₂, wherein for knot Structure [A] and [B], R₁To R₈It is independently selected from hydrogen or straight chain, branch, ring-type, bicyclic, saturation and undersaturated alkyl.R₁To R₈Each It all can be with R₁To R₈Another connection forms ring.Such as in structure [C], lactone can have the outer alkylidene group of ring, wherein R¹Extremely R⁶It is independently selected from hydrogen or straight chain, branch, ring-type, bicyclic, saturation and undersaturated alkyl.R¹To R⁶Each can be with R¹To R⁶It is another A connection forms ring.The molecular weight ranges of Lactone solubilizing agents are about 80 to about 300 atomic mass units, preferably from about 80 to about 200 Atomic mass unit.

Representative Lactone solubilizing agents include but is not limited to compound listed by table 6.

Table 6

Kinematic viscosity of the Lactone solubilizing agents at 40 DEG C is generally less than about 7 centistokes.Such as at 40 DEG C, gamma-undecalactone Kinematic viscosity be 5.4 centistokes, the kinematic viscosity of cis--(3- hexyl -5- methyl) dihydrofuran -2- ketone is 4.5 centistokes.Lactone Solubilizer is commercially available, or the U.S. Patent application 10/910 that can be submitted for 3rd by Augusts in 2004, side described in 495 Method preparation, the patent application are incorporated herein by reference.

Aryl ether solubilizing agents of the invention also include formula R¹OR²Shown in aryl ether, wherein R¹Selected from former with 6-12 carbon The aryl of son；R²Selected from the aliphatic hydrocarbyl with 1-4 carbon atom；And wherein the molecular weight of the aryl ether be about 100 to About 150 atomic mass units.General formula R¹OR²In representative R¹Aryl include phenyl, xenyl, cumenyl,Base, tolyl, Xylyl, naphthalene and pyridyl group.General formula R¹OR²In representative R²Aliphatic hydrocarbyl include methyl, ethyl, propyl, isopropyl, Butyl, isobutyl group, sec-butyl and tert-butyl.Representative Aryl ether solubilizing agents include but is not limited to methyl phenyl ether (fennel Ether), 1,3- dimethoxy benzene, ethylphenyl ether and butyl phenylate.

Fluoroether solubilizing agents of the invention include general formula R¹OCF₂CF₂Fluoro-ether those of shown in H, wherein R¹Selected from having Aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl of about 5 to about 15 carbon atoms, the preferably alkyl of level-one, straight chain, saturation.It is representative Fluoroether solubilizing agents include but is not limited to C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H.It should be pointed out that if refrigerant is certain Kind fluoro-ether, then solubilizer can not be same fluoro-ether.

Fluoroether solubilizing agents also may include the ether to spread out from fluoroolefin and polyalcohol.Fluoroolefin can be CF₂=CXY class Type, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF₃Or OR_f, wherein R_fFor CF₃、C₂F₅Or C₃F₇.Representative fluoroolefin is Tetrafluoroethene, chlorotrifluoroethylene, hexafluoropropene and perfluoro methyl vinyl ether.Polyalcohol can be straight chain or branch.Directly Chain polyalcohol can be HOCH₂(CHOH)_x(CRR’)_yCH₂OH type, wherein R and R ' is hydrogen or CH₃Or C₂H₅, and wherein x is 0- 4 integer, y are the integer of 0-4.Branched chain polyol can be C (OH)_t(R)_u(CH₂OH)_v[(CH₂)_mCH₂OH]_wType, wherein R can For hydrogen, CH₃Or C₂H₅, m can be the integer of 0-3, and t and u can be 0 or 1, the integer that v and w are 0-4, and wherein t+u+v+w= 4.Representative polyalcohol is trimethylolpropane, pentaerythrite, butanediol and ethylene glycol.

Of the invention 1,1,1- Trifluoroalkane solubilizing agents include general formula CF₃R¹Shown in 1,1,1- trifluoroalkanes, wherein R¹Choosing From aliphatic hydrocarbyl and alicyclic hydrocarbon radical with about 5 to about 15 carbon atoms, the preferably alkyl of level-one, straight chain, saturation.It is representative 1,1,1- Trifluoroalkane solubilizing agents include but is not limited to 1,1,1- trifluorohexane and 1,1,1- trifluorododecane.

Solubilizer of the invention can be used as single compound presence, or the mixture that can be used as more than a kind of solubilizer is deposited ?.The mixture of solubilizer can contain there are two types of the solubilizer from similar compound, for example two kinds of lactones, or there are two types of containing Solubilizer from two class difference compounds, such as lactone and polyoxyalkylene glycol ether.

In the present invention combination comprising refrigerant and ultra-violet fluorescent dye or comprising heat-transfer fluid and ultra-violet fluorescent dye In object, about 0.001 weight percent to about 1.0 weight percent is UV dyestuff, and preferably from about 0.005 weight percent is to about 0.5 weight percent, most preferably 0.01 weight percent to about 0.25 weight percent are UV dyestuffs.

Solubility of these ultra-violet fluorescent dyes in refrigerant and heat transfer compositions may be poor.Therefore, by these dyestuffs The method for being introduced into refrigeration, air-conditioning or heat pump assembly is always inconvenient, expensive and time-consuming.36,951 (its of United States Patent (USP) RE It is incorporated herein by reference) method is described, method use can be put into some component of refrigeration or air-conditioning device Dye powder, solid particle or slurries.As refrigerant and lubricant cycle through the device, dissolution or dispersion occur for dyestuff simultaneously It is carried through the device.Many other sides dyestuff to be introduced into refrigeration or air-conditioning device are also described in document Method.

It is desirable that ultra-violet fluorescent dye can be dissolved in refrigerant, system is introduced into without any special method In cold, air-conditioning or heat pump assembly.The present invention relates to the composition including ultra-violet fluorescent dye, which can be with solubilizer one It rises and is dissolved in refrigerant and is introduced in apparatus system.The present composition can allow refrigerant containing dyestuff and heat-transfer fluid i.e. Make also to store and transport at low temperature, while dyestuff being kept to be in solution state.

Comprising refrigerant, ultra-violet fluorescent dye and solubilizer or including heat-transfer fluid, ultra-violet fluorescent dye and solubilising There are about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, most in the present composition of agent, in total composition Preferably from about 5 to about 15 weight percent are the solubilizer in refrigerant or heat-transfer fluid.In the present compositions, ultraviolet glimmering Photoinitiator dye is in refrigerant or heat-transfer fluid with about 0.001 weight percent to about 1.0 weight percent, preferably 0.005 weight Percentage to about 0.5 weight percent, the concentration of most preferably 0.01 weight percent to about 0.25 weight percent exists.

The solubilizer of such as ketone may have unpleasant smell, can be covered by the way that mask agent or aromatic is added Lid.The representative instance of mask agent or aromatic may include Chinese ilex, Fresh Lemon, cherry, cortex cinnamomi, peppermint, flower (Floral) Or tangerine peel (they are commercially available) and (R)-4-isopropenyl-1-methyl-1-cyclohexene and firpene.The use concentration of this mask agent is mask agent and increasing About the 0.001% up to about 15% of solvent total weight.

The invention further relates to use the refrigerant comprising ultra-violet fluorescent dye or heat transfer fluid composition to detect refrigeration dress It sets, the method for leakage in air-conditioning device or heat pump assembly.The presence of dyestuff in the composition allows to detect refrigeration, sky Leakage of refrigerant in tune or heat pump assembly.Leak detection can help people to notice, solve and/or prevent the low of device or system Effect operation or equipment fault.Leak detection can also help people to install the chemicals of operation for device.

This method include provided to refrigeration, air-conditioning or heat pump assembly comprising refrigerant described herein, ultra-violet fluorescent dye or Comprising heat-transfer fluid described herein and ultra-violet fluorescent dye and optionally comprising the composition of solubilizer described herein, and using suitable Means detect the refrigerant containing ultra-violet fluorescent dye.The appropriate means for detecting dyestuff include but is not limited to ultraviolet lamp, are often claimed For " black light lamp " or " blue-ray light ".This ultraviolet lamp can be obtained from the source of multiple special detection ultra-violet fluorescent dyes is commercially available.One Composition containing ultra-violet fluorescent dye is introduced into refrigeration, air-conditioning or heat pump assembly and it is allowed to cycle through the device by denier System, can be by irradiating the ultraviolet lamp on the apparatus and observing the fluorescence of the dyestuff near any leakage point, to position Leakage point or leakage point near zone.

Mechanical refrigeration mainly applies such thermodynamic process：Cooling medium such as refrigerant can after a circulation Recycling is reused.Common circulation includes steam compressed, absorption, vapour injection (steam-jet) or vapor steam blaster (steam-ejector) and air.

Vapor compression refrigeration system includes evaporator, compressor, condenser and expansion device, vapor-compression cycle multiple Refrigerant is reused in step, generates cooling effect in one step, and generates heat effect in other step.This is followed Ring can be summarized as follows.Liquid refrigerant enters evaporator by expansion device, the liquid refrigerant in evaporator in low-temperature boiling, It forms gas and generates cooling.Low-pressure gas enters compressor and improves pressure and temperature by compression.High pressure (compression) gaseous state Refrigerant is condensed subsequently into condenser, releases heat to environment.Refrigerant returns to expansion device, and the liquid is swollen by this Swollen device is expanded into the low voltage level in evaporator from its high-pressure horizontal within the condenser, to repeat the circulation.

There are many compressors of type can be used for refrigeration application.Compressor can generally divide according to the mechanical system of compression fluid For reciprocating, rotary, injecting type, centrifugal, vortex, spiral or Axial Flow Compressor, or made according to mechanical organ Mode for fluid to be compressed generally can be divided into positive-displacement compressor (such as reciprocating, vortex or screw compressor) or Dynamic compressors (such as centrifugal or injecting type compressor).

The present composition comprising fluoroolefin can be used for any of above type of compressor.For any given compression The selection of machine, refrigerant will depend on many factors, including such as boiling point and vapor pressure requirement.

Positive-displacement compressor and dynamic compressors can be used in the method for the present invention.Include at least one fluoro for certain For the refrigerant composition of alkene, centrifugal compressor is a kind of preferred device type.

Centrifugal compressor makes refrigerant radially accelerated using rotating element, generally include impeller in the cabinet and Diffuser (diffuser).Centrifugal compressor is usually in impeller eye (impeller eye) or the central inlet for the impeller that circles round Fluid is sucked at (central inlet), and fluid is radially outward accelerated.It will appear certain static pressure liter in impeller, but Most of pressure rises from the diffuser part of present cabinet, and speed is converted into static pressure there.Every group of impeller-diffuser is pressure The level-one of contracting machine.Depending on required final pressure and refrigerant volume to be dealt with, centrifugal compressor has made 1-12 grades Or more grade.

The pressure ratio or compression ratio of compressor are the ratio between absolute outlet pressure and absolute inlet pressure.Centrifugal compressor institute The pressure of delivering is constant actually in relatively wide range of capacity.

Steam is pumped into cavity by positive-displacement compressor, and reduces cavity volume to compressed vapour.After steam compressed, lead to Crossing makes the volume of cavity be further reduced zero or near zero and steam is forced to leave cavity.Positive-displacement compression chance accumulation pressure Power, the pressure are only limited by the intensity that volume efficiency and each component bear pressure.

The formula different from positive-displacement compressor, centrifugal compressor fully rely on the centrifugal force of quick runner to make vapour pressure Contracting passes through impeller.There is no positive displacements, but there are so-called powered compressors.

The developable pressure of centrifugal compressor depends on the tip speed of impeller.Tip speed is surveyed at the tip of impeller The speed of amount, it is related with the diameter of impeller and revolutions per minute.The capacity of centrifugal compressor is big by the channel by impeller It is small to be determined.This makes the size of compressor be more dependent upon required pressure rather than capacity.

Since centrifugal compressor is high-speed cruising, it is substantially high volume, low-pressure machine.Centrifugal compressor With low pressure refrigerant such as trichlorofluoromethane (CFC-11) or 1,2,2- trichorotrifluoroethanes (CFC-113) get into smooth best.One A little low-pressure refrigerant liquids of the present invention are suitable for the simple substitution (drop-in of CFC-113 in existing centrifugation apparatus replacement)。

Big centrifugal compressor is usually operated with 3000-7000 rpms (rpm) of speed.Small turbo-centrifugal Compressor (miniature centrifugal compressors) is designed for about 40,000 to about 70,000 (rpm) high speed operation, impeller ruler It is very little small, usually less than 0.15 meter (about 6 inches).

Multi-stage impeller can be used in centrifugal compressor, to improve compressor efficiency, to need when in use less Power.For two-stage system, in operation, the outlet object of first order impeller enters the sucking import of the second impeller.The two Impeller can be used single axis to be operated.Every grade can accumulate about 4: 1 compression ratio；That is, absolutely outlet pressure can be absolutely To four times of suction pressure.US 5,065,990 and US 5,363,674 describe two-stage centrifugal compressor system (especially For automobile) several examples, the two patents are incorporated herein by reference.

The invention further relates to generating the method being heated or cooled in refrigeration, air-conditioning or heat pump assembly, the method includes Refrigerant or heat transfer fluid composition, which are introduced into, has (a) centrifugal compressor, (b) multistage centrifugal compressor or (c) single In plate/single-pass exchanger described device；Wherein the refrigerant or heat transfer fluid composition include at least one selected from following Fluoroolefin：

(iii) fluoroolefin selected from the following：

1,2,3,3,3- five fluoro- 1- propylene (CF₃CF=CHF)；1,1,3,3,3- five fluoro- 1- propylene (CF₃CH=CF₂)； 1,1,2,3,3- five fluoro- 1- propylene (CHF₂CF=CF₂)；1,2,3,3- tetra- fluoro- 1- propylene (CHF₂CF=CHF)；2,3,3,3- Tetrafluoro-1-propene (CF₃CF=CH₂)；1,3,3,3- tetrafluoro-1-propene (CF₃CH=CHF)；1,1,2,3- tetrafluoro-1-propene (CH₂FCF=CF₂)；1,1,3,3- tetrafluoro-1-propene (CHF₂CH=CF₂)；2,3,3- tri- fluoro- 1- propylene (CHF₂CF=CH₂)； 3,3,3- tri- fluoro- 1- propylene (CF₃CH=CH₂)；1,1,2- tri- fluoro- 1- propylene (CH₃CF=CF₂)；1,1,3- tri- fluoro- 1- propylene (CH₂FCH=CF₂)；1,2,3- tri- fluoro- 1- propylene (CH₂FCF=CHF)；1,3,3- tri- fluoro- 1- propylene (CHF₂CH=CHF)；1, 1,1,2,3,4,4,4- octafluoro -2- butylene (CF₃CF=CFCF₃)；1,1,2,3,3,4,4,4- octafluoro -1- butylene (CF₃CF₂CF =CF₂)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (CF₃CF=CHCF₃)；1,2,3,3,4,4,4- seven fluoro- 1- butylene (CHF =CFCF₂CF₃)；1,1,1,2,3,4,4- seven fluoro- 2- butylene (CHF₂CF=CFCF₃)；1,3,3,3- tetra- fluoro- 2- (fluoroform Base) -1- propylene ((CF₃)₂C=CHF)；1,1,3,3,4,4,4- seven fluoro- 1- butylene (CF₂=CHCF₂CF₃)；1,1,2,3,4,4, The fluoro- 1- butylene (CF of 4- seven₂=CFCHFCF₃)；1,1,2,3,3,4,4- seven fluoro- 1- butylene (CF₂=CFCF₂CHF₂)；2,3,3, 4,4,4- hexafluoro -1- butylene (CF₃CF₂CF=CH₂)；1,3,3,4,4,4- hexafluoro -1- butylene (CHF=CHCF₂CF₃)；1,2,3, 4,4,4- hexafluoro -1- butylene (CHF=CFCHFCF₃)；1,2,3,3,4,4- hexafluoro -1- butylene (CHF=CFCF₂CHF₂)；1,1, 2,3,4,4- hexafluoro -2- butylene (CHF₂CF=CFCHF₂)；1,1,1,2,3,4- hexafluoro -2- butylene (CH₂FCF=CFCF₃)；1, 1,1,2,4,4- hexafluoro -2- butylene (CHF₂CH=CFCF₃)；1,1,1,3,4,4- hexafluoro -2- butylene (CF₃CH=CFCHF₂)； 1,1,2,3,3,4- hexafluoro -1- butylene (CF₂=CFCF₂CH₂F)；1,1,2,3,4,4- hexafluoro -1- butylene (CF₂= CFCHFCHF₂)；3,3,3- tri- fluoro- 2- (trifluoromethyl) -1- propylene (CH₂=C (CF₃)₂)；1,1,1,2,4- five fluoro- 2- butylene (CH₂FCH=CFCF₃)；1,1,1,3,4- five fluoro- 2- butylene (CF₃CH=CFCH₂F)；3,3,4,4,4- five fluoro- 1- butylene (CF₃CF₂CH=CH₂)；1,1, Isosorbide-5-Nitrae, the fluoro- 2- butylene (CHF of 4- five₂CH=CHCF₃)；1,1,1,2,3- five fluoro- 2- butylene (CH₃CF=CFCF₃)；2,3,3,4,4- five fluoro- 1- butylene (CH₂=CFCF₂CHF₂)；1,1,2,4,4- five fluoro- 2- butylene (CHF₂CF=CHCHF₂)；1,1,2,3,3- five fluoro- 1- butylene (CH₃CF₂CF=CF₂)；1,1,2,3,4- five fluoro- 2- butylene (CH₂FCF=CFCHF₂)；1,1,3,3,3- five fluoro- 2- methyl-1-propylene (CF₂=C (CF₃)(CH₃))；2- (difluoromethyl) -3, 3,3- tri- fluoro- 1- propylene (CH₂=C (CHF₂)(CF₃))；2,3,4,4,4- five fluoro- 1- butylene (CH₂=CFCHFCF₃)；1,2, 4,4,4- five fluoro- 1- butylene (CHF=CFCH₂CF₃)；1,3,4,4,4- five fluoro- 1- butylene (CHF=CHCHFCF₃)；1,3,3, 4,4- five fluoro- 1- butylene (CHF=CHCF₂CHF₂)；1,2,3,4,4- five fluoro- 1- butylene (CHF=CFCHFCHF₂)；3,3,4, The fluoro- 1- butylene (CH of 4- tetra-₂=CHCF₂CHF₂)；1,1- bis- fluoro- 2- (difluoromethyl) -1- propylene (CF₂=C (CHF₂)(CH₃))； 1,3,3,3- tetra- fluoro- 2- methyl-1-propylene (CHF=C (CF₃)(CH₃))；The fluoro- 1- propylene (CH of 2- difluoromethyl -3,3- bis-₂= C(CHF₂)₂)；1,1,1,2- tetra- fluoro- 2- butylene (CF₃CF=CHCH₃)；1,1,1,3- tetra- fluoro- 2- butylene (CH₃CF= CHCF₃)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (CF₃CF=CFCF₂CF₃)；1,1,2,3,3,4,4,5,5,5- Ten fluoro- 1- amylene (CF₂=CFCF₂CF₂CF₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- butylene ((CF₃)₂C= CHCF₃)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (CF₃CF=CHCF₂CF₃)；1,1,1,3,4,4,5,5,5- nine is fluoro- 2- amylene (CF₃CH=CFCF₂CF₃)；1,2,3,3,4,4,5,5,5- nine fluoro- 1- amylene (CHF=CFCF₂CF₂CF₃)；1,1,3, 3,4,4,5,5,5- nine fluoro- 1- amylene (CF₂=CHCF₂CF₂CF₃)；1,1,2,3,3,4,4,5,5- nine fluoro- 1- amylene (CF₂= CFCF₂CF₂CHF₂)；1,1,2,3,4,4,5,5,5- nine fluoro- 2- amylene (CHF₂CF=CFCF₂CF₃)；1,1,1,2,3,4,4,5, The fluoro- 2- amylene (CF of 5- nine₃CF=CFCF₂CHF₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 2- amylene (CF₃CF= CFCHFCF₃)；1,2,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CHF=CFCF (CF₃)₂)；1,1,2,4,4,4- Hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CFCH (CF₃)₂)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- (trifluoromethyl) -2- fourths Alkene (CF₃CH=C (CF₃)₂)；1,1,3,4,4,4- hexafluoro -3- (trifluoromethyl) -1- butylene (CF₂=CHCF (CF₃)₂)；2,3, 3,4,4,5,5,5- octafluoro -1- amylene (CH₂=CFCF₂CF₂CF₃)；1,2,3,3,4,4,5,5- octafluoro -1- amylene (CHF= CFCF₂CF₂CHF₂)；3,3,4,4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CH₂=C (CF₃)CF₂CF₃)；1, Isosorbide-5-Nitrae, 4,4- Five fluoro- 3- (trifluoromethyl) -1- butylene (CF₂=CHCH (CF₃)₂)；1,3,4,4,4- five fluoro- 3- (trifluoromethyl) -1- butylene (CHF=CHCF (CF₃)₂)；1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- (trifluoromethyl) -1- butylene (CF₂=C (CF₃)CH₂CF₃)；3,4,4, Tetra- fluoro- 3- (trifluoromethyl) -1- butylene ((CF of 4-₃)₂CFCH=CH₂)；3,3,4,4,5,5,5- seven fluoro- 1- amylenes (CF₃CF₂CF₂CH=CH₂)；2,3,3,4,4,5,5- seven fluoro- 1- amylene (CH₂=CFCF₂CF₂CHF₂)；1,1,3,3,5,5,5- Seven fluoro- 1- butylene (CF₂=CHCF₂CH₂CF₃)；1,1,1,2,4,4,4- seven fluoro- 3- methyl-2-butene (CF₃CF=C (CF₃) (CH₃))；2,4,4,4- tetra- fluoro- 3- (trifluoromethyl) -1- butylene (CH₂=CFCH (CF₃)₂)；Isosorbide-5-Nitrae, 4,4- tetra- fluoro- 3- (trifluoros Methyl) -1- butylene (CHF=CHCH (CF₃)₂)；1,1, fluoro- 2- (the trifluoromethyl) -2- butylene of Isosorbide-5-Nitrae-four (CH₂FCH=C (CF₃)₂)；1,1,1,3- tetra- fluoro- 2- (trifluoromethyl) -2- butylene (CH₃CF=C (CF₃)₂)；1,1,1- tri- fluoro- 2- (fluoroform Base) -2- butylene ((CF₃)₂C=CHCH₃)；3,4,4,5,5,5- hexafluoro -2- amylene (CF₃CF₂CF=CHCH₃)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- methyl-2-butene (CF₃C(CH₃)=CHCF₃)；3,3,4,5,5,5- hexafluoro -1- amylene (CH₂= CHCF₂CHFCF₃)；3- (trifluoromethyl) -4,4,4- tri- fluoro- 1- butylene (CH₂=C (CF₃)CH₂CF₃)；1,1,2,3,3,4,4, 5,5,6,6,6- ten two fluoro- 1- hexene (CF₃(CF₂)₃CF=CF₂)；1,1,1,2,2,3,4,5,5,6,6,6- ten two fluoro- 3- oneself Alkene (CF₃CF₂CF=CFCF₂CF₃)；1,1, Isosorbide-5-Nitrae, bis- (trifluoromethyl) -2- the butylene ((CF of 4,4- hexafluoros -2,3-₃)₂C=C (CF₃)₂)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene ((CF₃)₂CFCF=CFCF₃)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- amylene ((CF₃)₂C=CHC₂F₅)；1,1,1,3,4,5,5,5- octafluoro -4- (three Methyl fluoride) -2- amylene ((CF₃)₂CFCF=CHCF₃)；3,3,4,4,5,5,6,6,6- nine fluoro- 1- hexenes (CF₃CF₂CF₂CF₂CH=CH₂)；4,4,4- tri- fluoro- bis- (the trifluoromethyl) -1- butylene (CH of 3,3-₂=CHC (CF₃)₃)；1,1,1, 4,4,4- hexafluoro -3- methyl -2- (trifluoromethyl) -2- butylene ((CF₃)₂C=C (CH₃)(CF₃))；2,3,3,5,5,5- hexafluoros- 4- (trifluoromethyl) -1- amylene (CH₂=CFCF₂CH(CF₃)₂)；1,1,1,2,4,4,5,5,5- nine fluoro- 3- methyl -2- amylene (CF₃CF=C (CH₃)CF₂CF₃)；1,1,1,5,5,5- hexafluoro -4- (trifluoromethyl) -2- amylene (CF₃CH=CHCH (CF₃)₂)； 3,4,4,5,5,6,6,6- octafluoro -2- hexene (CF₃CF₂CF₂CF=CHCH₃)；3,3,4,4,5,5,6,6- octafluoro -1- hexenes (CH₂=CHCF₂CF₂CF₂CHF₂)；1,1, Isosorbide-5-Nitrae, five fluoro- 2- (trifluoromethyl) -2- amylene ((CF of 4-₃)₂C=CHCF₂CH₃)；4, 4,5,5,5- five fluoro- 2- (trifluoromethyl) -1- amylene (CH₂=C (CF₃)CH₂C₂F₅)；3,3,4,4,5,5,5- seven fluoro- 2- first Base -1- amylene (CF₃CF₂CF₂C(CH₃)=CH₂)；4,4,5,5,6,6,6- seven fluoro- 2- hexene (CF₃CF₂CF₂CH=CHCH₃)； 4,4,5,5,6,6,6- seven fluoro- 1- hexene (CH₂=CHCH₂CF₂C₂F₅)；1,1,1,2,2,3,4- seven fluoro- 3- hexene (CF₃CF₂CF=CFC₂H₅)；4,5,5,5- tetra- fluoro- 4- Trifluoromethyl-1-amylene (CH₂=CHCH₂CF(CF₃)₂)；1,1,1,2, 5,5,5- seven fluoro- 4- methyl -2- amylene (CF₃CF=CHCH (CF₃)(CH₃))；1,1,1,3- tetra- fluoro- 2- trifluoromethyl -2- penta Alkene ((CF₃)₂C=CFC₂H₅)；1,1,1,2,3,4,4,5,5,6,6,7,7,7- ten four fluoro- 2- heptene (CF₃CF= CFCF₂CF₂C₂F₅)；1,1,1,2,2,3,4,5,5,6,6,7,7,7- ten four fluoro- 3- heptene (CF₃CF₂CF=CFCF₂C₂F₅)；1, 1,1,3,4,4,5,5,6,6,7,7,7- ten three fluoro- 2- heptene (CF₃CH=CFCF₂CF₂C₂F₅)；1,1,1,2,4,4,5,5,6, 6,7,7,7- ten three fluoro- 2- heptene (CF₃CF=CHCF₂CF₂C₂F₅)；1,1,1,2,2,4,5,5,6,6,7,7,7- ten three fluoro- 3- Heptene (CF₃CF₂CH=CFCF₂C₂F₅)；1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene (CF₃CF₂CF= CHCF₂C₂F₅)；CF₂=CFOCF₂CF₃(PEVE)；CF₂=CFOCF₃(PMVE) and their combination.

It can be used for fixed air conditioning, heat pump or movable air conditioner and refrigeration system to generate the method being heated or cooled. Fixed air conditioning and heat pump application include window, and pipe free has tubular type, sealed terminal, freezer unit (chiller) and commercialization, Including closed roof.Refrigeration application includes that household or houshold refrigerator and reezer system (freezer), ice machine, stand alone type are cooling Device (cooler) and reezer system, big built-in wardrobe type cooler and reezer system and transport refrigeration system.

Composition of the invention may be additionally used for using plate-fin and pipe heat exchanger, micro-channel type heat exchanger and it is vertical or In the air-conditioning of horizontal single pass pipe or plate type regenerator, heating and refrigeration system.

Conventional micro-channel heat exchanger may be unsatisfactory for low pressure refrigerant composition of the invention.Low operating pressure Lead to high flow rate with density and in the high friction loss of all components.In these cases, evaporator design can be changed.It can make It is arranged with veneer/single-pass exchanger, rather than several microchannel plates are connected in series together (relative to refrigerant path).Cause This, the preferred heat exchanger for refrigerant of the present invention or heat transfer fluid composition is veneer/single-pass exchanger.

The invention further relates to cooling method is generated, the method includes the present invention is evaporated near object to be cooled Fluoroalkene composition, condense the composition later.

The invention further relates to the methods for generating heating, and the method includes the present invention is condensed near object to be heated Fluoroalkene composition, the composition is evaporated later.

It include at least one the method includes being compressed in centrifugal compressor the invention further relates to cooling method is generated The composition of kind fluoroolefin, evaporates the composition, evaporates the composition near object to be cooled later.Separately Outside, the centrifugal compressor of the method for the present invention can be multistage centrifugal compressor, preferably 2 grades of centrifugal compressors.

The invention further relates to cooling method is generated in refrigerating plant, air-conditioning device or heat pump assembly, wherein the dress It sets including at least one veneer/single-pass exchanger, the method includes condensing composition of the invention, later in object to be cooled The composition is evaporated near body.

Composition of the invention is particularly useful for small turbine centrifugal compressors, and (miniature centrifugal compressors can be used for Automobile and window air-conditioning), heat pump or transport with refrigeration and other application.These high efficiency miniature centrifugal compressors can be by electricity Motivation driving, therefore can be operated independent of engine speed.Constant compressor speed can allow system to be started all Relative constant cooling capacity is all provided under machine revolving speed.Compared to conventional R-134a automotive air-conditioning system, this provides efficiency Improved chance, especially at higher engine speeds.When the circulation fortune in view of conventional system at high driving speeds When row, the advantages of these low-pressure systems, becomes more prominent.

Alternatively, miniature centrifugal compressors can not use electric power, but by engine exhaust driving turbine or have than Ratio type gear wheel driving device (the ratioed gear drive assembly with a ratioed of example formula belt drive Belt drive) power is provided.Available electric power is about 14 volts in existing Automobile Design, but new Miniature centrifugal compression Machine needs about 50 volts of electric power.It therefore, will be advantageous using alternative energy source.Power is provided by the turbine of engine exhaust driving Refrigerating plant or air-conditioning device have in the U.S. Patent Application Serial 11/367,517 that on March 3rd, 2006 submits retouches in detail It states.The refrigerating plant or air-conditioning device for providing power by ratio type gear wheel driving device are in the U.S. submitted on March 17th, 2006 It is had a detailed description in patent application Ser. No 11/378,832.

The invention further relates to cooling method is generated, the method includes providing to move in the turbine driven by engine exhaust Composition of the invention is compressed in the miniature centrifugal compressors of power；Condense the composition；Later in object to be cooled Near evaporate the composition.

The invention further relates to cooling method is generated, the method includes by the ratio with ratioed belt drive Composition of the invention is compressed in the miniature centrifugal compressors of formula gear assembly offer power；Condense the composition； The composition is evaporated near object to be cooled later.

The present invention relates to cooling method is generated in refrigerating plant, air-conditioning device or heat pump assembly, wherein described device It is cold the method includes compressing composition of the invention in centrifugal compressor including at least one veneer/single-pass exchanger It coagulates the composition and evaporates the composition near object to be cooled later.

The invention further relates to substituted with the composition with lower GWP or GWP is replaced to be about 150 or higher refrigerant The method of composition or high GWP refrigerant.A kind of method include provide include at least one fluoroolefin of the present invention combination Object is as substitute.In another embodiment of the present invention, will have compared with the composition for being substituted or being replaced lower The refrigerant of the present invention or heat transfer fluid composition of GWP is introduced into refrigeration, air-conditioning or heat pump assembly.In some cases, exist Before introducing lower GWP composition, need to remove high GWP refrigerant present in it from device.It in other situations, can be by this The fluoroalkene composition of invention is introduced into device in the case where high GWP refrigerant exists simultaneously.

Global warming potential (GWP) is to estimate that the atmosphere of 1 kilogram of certain specific greenhouse gases discharges and 1 kilogram of dioxy The index for the opposite global warming contribution that the discharge of change carbon is compared.The GWP of different time range can be calculated, to show given gas The influence of the atmospheric lifetime of body.The numerical value of usually meaning is the GWP of 100 year ranges.

High GWP refrigerant is any to potentially act as that refrigerant or heat-transfer fluid, its GWP is within 100 years About 1000 or bigger or 500 or bigger, 150 or bigger, 100 or bigger or 50 or bigger compound.According to government Between climate change work group (Intergovernmental Panel on Climate Change, IPCC) announce GWP The refrigerant and heat-transfer fluid that calculated result is substituted, including but not limited to HFC-134a (1,1,1,2- tetrafluoro second Alkane).

The present invention will provide the composition with zero or low-ozone depletion potential and low global warming potential (GWP).This hair Its global warming potential will be than used at present with the mixture of other refrigerants for bright fluoroolefin or fluoroolefin of the present invention Many fluoroether refrigerants want low.In general, the expected GWP having less than about 25 of fluoroolefin of the invention.Of the invention one Aspect be to provide global warming potential less than 1000, less than 500, less than the 150, refrigerant less than 100 or less than 50.This hair Bright is to reduce the net GWP of the mixture by the way that fluoroolefin is added to refrigerant mixture on the other hand.

The invention further relates to the method for the GWP for reducing refrigerant or heat-transfer fluid, the method includes by the refrigerant Or heat-transfer fluid is combined at least one fluoroolefin of the present invention.In another embodiment, to reduce global change The method of warm potential includes being combined the first chamber and the composition comprising at least fluoroolefin, is suitble to generating Second chamber as refrigerant or heat-transfer fluid, and wherein the global warming potential of the second chamber than described first Composition is low.It is ensured that the mixture of each compound or combined GWP can be by the weightings of the GWP of every kind of pure compound Averagely calculated.

The invention further relates to use the present composition comprising at least one fluoroolefin reduce original refrigerant or The method of the global warming potential of heat transfer fluid composition, the method includes combining the original refrigerant or heat-transfer fluid Object is combined with the present composition comprising at least one fluoroolefin, to generate second refrigerant or heat-transfer fluid combination Object, wherein the second refrigerant or the global warming potential of heat transfer fluid composition are than the original refrigerant or heat-transfer fluid Composition is low.

The invention further relates to reduce refrigeration, the original refrigerant in air-conditioning or heat pump assembly or heat transfer fluid composition The method of GWP, wherein the GWP of the original refrigerant or heat-transfer fluid is about 150 or higher；The method includes to described Refrigeration, air-conditioning or heat pump assembly introduce second, lower GWP refrigerant of the present invention or heat transfer fluid composition.

The method of GWP to reduce original refrigerant of the invention may additionally include the system of introducing second, lower GWP Before cryogen or heat-transfer fluid, first original refrigerant or heat transfer fluid composition are removed from the refrigeration, air-conditioning or heat pump assembly It goes.

The invention further relates to combined with second refrigerant or heat transfer fluid composition substitution original refrigerant or heat-transfer fluid The method of object, the method includes providing composition of the invention as second refrigerant or heat transfer fluid composition.Original system Cryogen can be any refrigerant for freezing, needing to substitute used in air-conditioning or heat pump assembly.

The original refrigerant or heat-transfer fluid for needing to substitute can be fluoroether refrigerant, chlorofluorocarbon refrigerant, hydrogen chlorine fluorine Any one of hydrocarbon coolant, fluoroether refrigerant or admixture of refrigerant compound.

The fluoroether refrigerant of the present invention that substitutes may be needed to include but is not limited to：CHF₃ (HFC-23)、CH₂F₂(HFC- 32)、CH₃F(HFC-41)、CHF₂CF₃(HFC-125)、 CHF₂CHF₂(HFC-134)、CH₂FCF₃(HFC-134a)、CHF₂CH₂F (HFC143)、 CF₃CH₃(HFC-143a)、CHF₂CH₃(HFC-152a)、CH₂FCH₃(HFC-161)、 CHF₂CF₂CF₃(HFC- 227ca)、CF₃CFHCF₃(HFC-227ea)、CHF₂CF₂CHF₂ (HFC-236ca)、CH₂FCF₂CF₃(HFC-236cb)、 CHF₂CHFCF₃(HFC-236ea)、 CF₃CH₂CF₃(HFC-236fa)、CH₂FCF₂CHF₂(HFC-245ca)、CH₃CF₂CF₃ (HFC-245cb)、CHF₂CHFCHF₂(HFC-245ea)、CH₂FCHFCF₃ (HFC-245eb)、CHF₂CH₂CF₃(HFC- 245fa)、CH₂FCF₂CH₂F(HFC-254ca)、 CH₃CF₂CHF₂(HFC-254cb)、CH₂FCHFCHF₂(HFC-254ea)、 CH₃CHFCF₃ (HFC-254eb)、CHF₂CH₂CHF₂(HFC-254fa)、CH₂FCH₂CF₃(HFC-254fb)、 CF₃CH₂CH₃ (HFC-263fb)、CH₃CF₂CH₂F(HFC-263ca)、CH₃CF₂CH₃ (HFC-272ca)、CH₃CHFCH₂F(HFC-272ea)、 CH₂FCH₂CH₂F (HFC-272fa)、CH₃CH₂CF₂H(HFC-272fb)、CH₃CHFCH₃(HFC-281ea)、 CH₃CH₂CH₂F (HFC-281fa)、CHF₂CF₂CF₂CF₂H(HFC-338pcc)、 CF₃CH₂CF₂CH₃(HFC-365mfc)、CF₃CHFCHFCF₂CF₃ (HFC-43-10mee).These fluoroether refrigerants are commercially available, or can be prepared by methods known in the art.

Fluoroether refrigerant of the invention also may include azeotropic, azeotropic mixture sample (azeotrope-like) and non- The composition of azeotropic, these compositions include HFC-125/HFC-143a/HFC-134a (ASHRAE marked as R404 or R404A), HFC-32/HFC-125/HFC-134a (ASHRAE is marked as R407 or R407A, R407B or R407C), HFC- 32/HFC-125 (R410 or R410A) and HFC-125/HFC-143a (ASHRAE is marked as R507 or R507A), R413A (admixture of R134a/R218/ iso-butane), R423A (admixture of R134a/R227ea), (R125/R143a's mixes R507A Close object) and it is other.

May need the chlorofluorocarbon refrigerant of the present invention substituted includes R22 (CHF₂Cl)、R123 (CHCl₂CF₃)、R124 (CHClFCF₃)、R502(CFC-115(CClF₂CF₃) and R22 admixture), R503 (R23/R13 (CClF₃) admixture) and It is other.

May need the hydrochlorofluorocarbons of the present invention substituted includes R12 (CF₂Cl₂)、R11(CCl₃F)、 R113 (CCl₂FCClF₂)、R114(CF₂ClCF₂Cl), R401A or R401B (admixture of R22/R152a/R124), R408A (R22/ The admixture of R125/R143a) and it is other.

May need the fluoroether refrigerant of the present invention substituted may include being similar to hydrofluorocarbon but also containing at least one ether The compound of group oxygen atom.Fluoroether refrigerant includes but is not limited to C₄F₉OCH₃And C₄F₉OC₂H₅(being commercially available).

It may need the original refrigerant of the present invention substituted or heat transfer fluid composition can optionally further include containing most 10 The dimethyl ether or at least one C of weight percent₃-C₅Hydrocarbon (such as propane, propylene, cyclopropane, normal butane, iso-butane, pentane, Pentamethylene and neopentane (2,2- dimethylpropane)) refrigerant combination.Contain this C₃-C₅The example of the refrigerant of hydrocarbon is Following azeotrope-like composition：HCFC-22/HFC-125/ propane composition (ASHRAE marked as R402 or R402A and R402B), HCFC-22/ octafluoropropane/propane composition (ASHRAE is marked as R403 or R403A and R403B), octafluoropropane/ HFC-134a/ iso-butane composition (ASHRAE is marked as R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/ Iso-butane composition (ASHRAE is marked as R414 or R414A and R414B), HFC-134a/HCFC-124/ normal butane composition (ASHRAE is marked as R416 or R416A), HFC-125/HFC-134a/ normal butane composition (ASHRAE marked as R417 or R417A), HFC-125/HFC-134a/ dimethyl ether composition (ASHRAE is marked as R419 or R419A) and HFC-125/ HFC-134a/ iso-butane composition (ASHRAE is marked as R422, R422A, R422B, R422C, R422D).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R134a (HFC-134a, HFA 134a, CF in device, air-conditioning device or heat pump assembly₃CH₂F), wherein it is described Method includes with second refrigerant or biography comprising at least one compound selected from trifluoromethyl trifluoro vinyl ether (PMVE) Hot fluid composition substitutes R134a.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R152a (HFC-152a, 1,1- Difluoroethane, CHF in device, air-conditioning device or heat pump assembly₂CH₃), wherein the method Including being selected from E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze), 1,2,3,3,3- pentafluoropropenes with comprising at least one (HFC-1225ye), 2,3,3,3- tetrafluoropropenes (HFC-1234yf), 3,3,3- trifluoro propenes (HFC-1243zf) and fluoroform The second refrigerant or heat transfer fluid composition of the compound of base trifluoro vinyl ether (PMVE) substitute R152a.

The invention further relates in substitution refrigerating plant, air-conditioning device or heat pump assembly R227ea (HFC-227ea, 1,1, 1,2,3,3,3- heptafluoro-propane, CF₃CHFCF₃) method, wherein the method includes providing to be selected from E-1 comprising at least one, 3, 3,3- tetrafluoropropenes (E-HFC-1234ze), 1,2,3,3,3- pentafluoropropenes (HFC-1225ye), 2,3,3,3- tetrafluoropropenes (HFC-1234yf), 3, the compound of 3,3- trifluoro propenes (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE) Composition as substitute.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration In device, air-conditioning device or heat pump assembly R113 (CFC-113,1,1,2- tri- chloro- 1,2,2- trifluoroethane, CFCl₂CF₂Cl), wherein the method includes with second refrigerant or heat transfer stream comprising at least one compound selected from the following Body 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- amylenes (HFC-152-11mmtz)；1,1,1,2,2,3,4,5,5, 6,6,6- ten two fluoro- 3- hexenes (HFC-151-12mcy)；1,1,1,3- tetra- fluoro- 2- butylene (HFC-1354mzy)；1,1, Isosorbide-5-Nitrae, Bis- (the trifluoromethyl) -2- butylene (HFC-151-12mmtt) of 4,4- hexafluoros -2,3-；1,2,3,3,4,4,5,5,6,6- ten fluorine ring Hexene (FC-C151-10y)；3,3,4,4,5,5,5- seven fluoro- 2- Methyl-1-pentenes (HFC-1567fts)；3,3,4,4,5,5, 6,6,6- nine fluoro- 1- hexenes (PFBE)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (HFC-1567szz)；1,1, Isosorbide-5-Nitrae, 4,5, 5,6,6,6- ten fluoro- 2- hexenes (F13E)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene (HFC-151- 12mmzz) and 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- hexene (F22E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R43-10mee (HFC-43-10mee), 1,1,1,2,3,4,4,5,5,5- ten fluorine in device, air-conditioning device or heat pump assembly Pentane, CF₃CHFCHFCF₂CF₃), wherein the method includes being freezed with second comprising at least one compound selected from the following Agent or heat transfer fluid composition are 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- amylenes (HFC-152-11mmtz)；1,1,1,2,2, 3,4,5,5,6,6,6- ten two fluoro- 3- hexenes (HFC-151-12mcy)；1,1,1,3- tetra- fluoro- 2- butylene (HFC-1354mzy)； 1,1, Isosorbide-5-Nitrae, bis- (the trifluoromethyl) -2- butylene (HFC-151-12mmtt) of 4,4- hexafluoros -2,3-；1,2,3,3,4,4,5,5,6,6- Decafluorocyclohexene (FC-C151-10y)；3,3,4,4,5,5,5- seven fluoro- 2- Methyl-1-pentenes (HFC-1567fts)；3,3,4, 4,5,5,6,6,6- nine fluoro- 1- hexenes (PFBE)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (HFC-1567szz)；1,1, Isosorbide-5-Nitrae, 4,5,5,6,6,6- ten fluoro- 2- hexenes (F13E)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- hexene (F22E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration C in device, air-conditioning device or heat pump assembly₄F₉OCH₃(perfluorobutyl methyl ethers), wherein the method includes with comprising at least The second refrigerant or heat transfer fluid composition of a kind of compound selected from the following are substituted：1,1,1,3,4,5,5,5- eight Fluoro- 4- (trifluoromethyl) -2- butylene (HFC-152-11mmyyz)；1,1, Isosorbide-5-Nitrae, 4,5,5,5- octafluoro -2- (trifluoromethyl) -2- Amylene (HFC-152-11mmtz)；1,1,1,2,2,3,4,5,5,6,6,6- ten two fluoro- 3- hexene (HFC-151-12mcy)；1, 1,1,3- tetra- fluoro- 2- butylene (HFC-1354mzy)；1,1, Isosorbide-5-Nitrae, bis- (the trifluoromethyl) -2- butylene (HFC- of 4,4- hexafluoros -2,3- 151-12mmtt)；1,2,3,3,4,4,5,5,6,6- decafluorocyclohexene (FC-C151-10y)；3,3,4,4,5,5,5- seven fluoro- 2- Methyl-1-pentene (HFC-1567fts)；3,3,4,4,5,5,6,6,6- nine fluoro- 1- hexenes (PFBE)；4,4,5,5,6,6,6- Seven fluoro- 2- hexenes (HFC-1567szz)；1,1, Isosorbide-5-Nitrae, 4,5,5,6,6,6- ten fluoro- 2- hexenes (F13E)；1,1,1,2,3,4, 5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylenes (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- Hexene (F22E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration In device, air-conditioning device or heat pump assembly R365mfc (HFC-365mfc, 1,1,1,3,3- 3-pentafluorobutane, CF₃CH₂CF₂CH₃), wherein the method includes with the second refrigerant comprising at least one compound selected from the following 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- amylenes (HFC-152-11mmtz)；1,1,1,2,2, 3,4,5,5,6,6,6- ten two fluoro- 3- hexenes (HFC-151-12mcy)；1,1,1,3- tetra- fluoro- 2- butylene (HFC-1354mzy)； 1,1, Isosorbide-5-Nitrae, bis- (the trifluoromethyl) -2- butylene (HFC-151-12mmtt) of 4,4- hexafluoros -2,3-；1,2,3,3,4,4,5,5,6,6- Decafluorocyclohexene (FC-C151-10y)；3,3,4,4,5,5,5- seven fluoro- 2- Methyl-1-pentenes (HFC-1567fts)；3,3,4, 4,5,5,6,6,6- nine fluoro- 1- hexenes (PFBE)；4,4,5,5,6,6,6- seven fluoro- 2- hexenes (HFC-1567szz)；1,1,1, 4,4,5,5,6,6,6- ten fluoro- 2- hexenes (F13E)；1,1,1,2,3,4,5,5,5- nine fluoro- 4- (trifluoromethyl) -2- amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6- ten fluoro- 3- hexene (F22E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R11 (CFC-11, trichlorofluoromethane, CFCl in device, air-conditioning device or heat pump assembly₃), wherein the method includes with packet Second refrigerant or heat transfer fluid composition containing at least one compound selected from the following are substituted：1,2,3,3,4,4,5, 5- octafluoro cyclopentene (FC-C1418y)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (FC-141-10myy)；1,1,1, 2,4,4,5,5,5- nine fluoro- 2- amylenes (HFC-1429myz)；1,1,1,3,4,4,5,5,5- nine fluoro- 2- amylene (HFC- 1429mzy)；3,3,4,4,5,5,5- seven fluoro- 1- amylenes (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- eight Fluoro- 2- amylene (F12E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration In device, air-conditioning device or heat pump assembly R123 (HCFC-123,2,2- bis- chloro- 1,1,1- trifluoroethane, CF₃CHCl₂), Described in method include being carried out with the second refrigerant comprising at least one compound selected from the following or heat transfer fluid composition Substitution：1,2,3,3,4,4,5,5- octafluoro cyclopentene (FC-C1418y)；1,1,1,2,3,4,4,5,5,5- ten fluoro- 2- amylene (FC-141-10myy)；1,1,1,2,4,4,5,5,5- nine fluoro- 2- amylene (HFC-1429myz)；1,1,1,3,4,4,5,5,5- Nine fluoro- 2- amylenes (HFC-1429mzy)；3,3,4,4,5,5,5- seven fluoro- 1- amylenes (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- amylenes (F12E).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R245fa (HFC-245fa, 1,1,1,3,3- pentafluoropropane, CF in device, air-conditioning device or heat pump assembly₃CH₂CHF₂), Described in method include being carried out with the second refrigerant comprising at least one compound selected from the following or heat transfer fluid composition Substitution：2,3,3- trifluoro propenes (HFC-1243yf)；1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene (F11E)；1,3,3,3- tetrafluoro third Alkene (HFC-1234ze)；1,1,1,2,4,4,4- seven fluoro- 2- butylene (HFC-1327my)；1,2,3,3- tetrafluoropropene (HFC- 1234ye) and pentafluoroethyl group trifluoro vinyl ether (PEVE).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration In device, air-conditioning device or heat pump assembly R114 (CFC-114,1,2- bis- chloro- 1,1,2,2- tetrafluoroethane, CFCl₂CF₂Cl), wherein the method includes with second refrigerant or heat transfer stream comprising at least one compound selected from the following Body composition is substituted：1,1,1,2,3,4,4,4- octafluoro -2- butylene (FC-1318my)；1,2,3,3,4,4- hexafluoro ring fourth Alkene (FC-C1316cc)；2,3,3,4,4,4- hexafluoro -1- butylene (HFC-1336yf) and 3,3,4,4,4- five fluoro- 1- butylene (HFC-1345fz)。

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R236fa (HFC-236fa, 1,1,1,3,3,3- hexafluoropropane, CF in device, air-conditioning device or heat pump assembly₃CH₂CF₃), Wherein the method includes with the second refrigerant comprising at least one compound selected from the following or heat transfer fluid composition into Row substitution：1,1,1,2,3,4,4,4- octafluoro -2- butylene (FC-1318my)；1,2,3,3,4,4- hexafluoro cyclobutane (FC- C1316cc)；2,3,3,4,4,4- hexafluoro -1- butylene (HFC-1336yf) and 3,3,4,4,4- five fluoro- 1- butylene (HFC- 1345fz)。

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R401A in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401A is the HCFC-22 (chlorine two containing about 53 weight percent Fluoromethane, CHF₂Cl), HFC-152a (1,1- Difluoroethane, the CHF of about 13 weight percent₂CH₃) and about 34 weight percent HCFC-124 (the chloro- HFA 134a of 2-, CF₃CHClF the ASHRAE label of refrigerant admixture).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R401B in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401B is the HCFC-22 (chlorine two containing about 61 weight percent Fluoromethane, CHF₂Cl), HFC-152a (1,1- Difluoroethane, the CHF of about 11 weight percent₂CH₃) and about 28 weight percent HCFC-124 (the chloro- HFA 134a of 2-, CF₃CHClF the ASHRAE label of refrigerant admixture).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R409A in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409A is the HCFC-22 (chlorine two containing about 60 weight percent Fluoromethane, CHF₂Cl), HCFC-124 (the chloro- HFA 134a of 2-, the CF of about 25 weight percent₃) and about 15 CHClF HCFC-142b (1- chlorine-1,1-difluoroethane, the CF of weight percent₂ClCH₃) refrigerant admixture ASHRAE label.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R409B in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409B is the HCFC-22 (chlorine two containing about 65 weight percent Fluoromethane, CHF₂Cl), HCFC-124 (the chloro- HFA 134a of 2-, the CF of about 25 weight percent₃) and about 10 CHClF HCFC-142b (1- chlorine-1,1-difluoroethane, the CF of weight percent₂ClCH₃) refrigerant admixture ASHRAE label.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R414B in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R414B is the HCFC-22 (chlorine two containing about 50 weight percent Fluoromethane, CHF₂Cl), HCFC-124 (the chloro- HFA 134a of 2-, the CF of about 39 weight percent₃CHClF), about 1.5 Iso-butane (R600a, the CH of weight percent₃CH(CH₃)CH₃) and about 9.5 weight percent HCFC-142b (1- chloro- 1,1- Difluoroethane, CF₂ClCH₃) refrigerant admixture ASHRAE label.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R416A in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：E-1,3,3,3- tetrafluoropropenes (E-HFC-1234ze)；1,2, 3,3,3- pentafluoropropenes (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propene (HFC- 1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R416A be containing about 59 weight percent HFC-134a (1,1, 1,2- tetrafluoroethane, CF₃CH₂F)), about 39.5 weight percent HCFC-124 (the chloro- HFA 134a of 2-, CF₃) and the normal butane (CH of about 1.5 weight percent CHClF₃CH₂CH₂CH₃) refrigerant admixture ASHRAE label.

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R12 (CFC-12, dicholorodifluoromethane, CF in device, air-conditioning device or heat pump assembly₂Cl₂), wherein the method includes with Second refrigerant or heat transfer fluid composition comprising at least one compound selected from the following are substituted：1,2,3,3,3- five Fluoropropene (HFC-1225ye)；2,3,3,3- tetrafluoropropenes (HFC-1234yf)；3,3,3- trifluoro propenes (HFC-1243zf)； With trifluoromethyl trifluoro vinyl ether (PMVE).

The invention further relates to substitution original refrigerant or the method for heat transfer fluid composition, the original composition is refrigeration R500 in device, air-conditioning device or heat pump assembly, wherein the method includes with including at least one chemical combination selected from the following The second refrigerant or heat transfer fluid composition of object are substituted：1,2,3,3,3- pentafluoropropene (HFC-1225ye)；2,3,3, 3- tetrafluoropropene (HFC-1234yf)；3,3,3- trifluoro propenes (HFC-1243zf)；With trifluoromethyl trifluoro vinyl ether (PMVE).R500 is R12 ((CFC-12, dicholorodifluoromethane, CF containing about 73.8 weight percent₂Cl₂) and about 26.2 weights Measure R152a (HFC-152a, 1,1- Difluoroethane, the CHF of percentage₂CH₃) azeotrope refrigerant admixture ASHRAE label.

The present invention relates to substitution original refrigerant or the methods of heat transfer fluid composition, wherein the original refrigerant or biography Hot fluid composition is R134a or R12, and wherein the R134a or R12 with including about 1.0 weight percent to about 37 weight The second refrigerant of the HFC-1225ye of the HFC-32 of percentage and about 99 weight percent to about 63 weight percent or heat transfer Fluid composition is substituted.In another embodiment, second refrigerant or heat transfer fluid composition can include about 1.0 weights Percentage is measured to the HFC-32 of about 10 weight percent and the HFC- of about 99 weight percent to about 90 weight percent 1225ye。

The present invention relates to substitution original refrigerant or the methods of heat transfer fluid composition, wherein the original refrigerant or biography Hot fluid composition is R22, R404A or R410A, and wherein described R22, R404A or R410A with including about 1.0 weight percents Than the second of the HFC-1225ye of HFC-32 and about 99 weight percent to about 63 weight percent to about 37 weight percent Refrigerant or heat transfer fluid composition are substituted.In another embodiment, second refrigerant or heat transfer fluid composition It can include about the HFC-32 and about 80 weight percent to about 63 weight percent of 20 weight percent to about 37 weight percent HFC-1225ye.

The invention further relates to substitution original refrigerant or heat transfer fluid composition method, wherein the original refrigerant or Heat transfer fluid composition is R22, R404A or R410A, and wherein described R22, R404A or R410A with including about 20 weight percents Than HFC-1225ye, about 1.0 weight percent to the HFC-32 of about 65 weight percent and about 1.0 to about 95 weight percent Weight percent to about 40 weight percent HFC-125 second refrigerant or heat transfer fluid composition substituted.Another In one embodiment, second refrigerant or heat transfer fluid composition include about 30 weight percent to about 90 weight percent HFC-1225ye, the HFC-32 of about 5.0 weight percent to about 55 weight percent and about 1.0 weight percent to about 35 weight The HFC-125 of percentage.In yet another embodiment, second refrigerant or heat transfer fluid composition include about 40 weight percents Than HFC-1225ye, about 10 weight percent to the HFC-32 of about 45 weight percent and about 1.0 to about 85 weight percent Weight percent to about 28 weight percent HFC-125.

The present invention relates to substitution original refrigerant or the methods of heat transfer fluid composition, wherein the original refrigerant or biography Hot fluid composition is R134a or R12, and wherein the R134a or R12 with including second refrigerant below or heat transfer stream Body 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 alternative refrigerants above-mentioned, the refrigeration in existing equipment can be all substituted with fluoroolefin Agent.In addition, can with fluoroolefin come alternate design come the refrigerant in the existing equipment using certain refrigerant.In addition, available Fluoroolefin need not change or substitute lubricant to substitute the refrigerant in existing equipment.

The present invention relates to the method for reducing the fire hazard in refrigerating plant, air-conditioning device or heat pump assembly, the methods Including composition of the invention is introduced into the refrigerating plant or air-conditioning device.

It may be one from the refrigerant that refrigerating plant, air-conditioning device or heat pump assembly leak when in view of flammable A big problem.Once leaking in refrigerating plant or air-conditioning device, refrigerant and possible a small amount of lubricant may be from It is released in apparatus system.If this leak materials touches incendiary source, fire may result in.So-called fire hazard is A possibility that fire may occur for finger in refrigerating plant, air-conditioning device or heat pump assembly or nearby.Reduction refrigerating plant, Fire hazard in air-conditioning device or heat pump assembly can be measured and identify by using through previously described method and standard It is considered non-flammable refrigerant or heat-transfer fluid to realize.In addition, non-flammable fluoroolefin of the invention can be added to Through in a device or be not yet added to combustible refrigerant or heat-transfer fluid in device.Non-flammable fluoroolefin of the invention can drop It is low just in case reduced a possibility that generation fire and/or by the temperature of the flame of any generation of reduction or size when leak The degree of fire hazard.

The invention further relates to reducing refrigerating plant, in air-conditioning device or heat pump assembly or the method for neighbouring fire hazard, The method includes at least one non-flammable fluoroolefin to be combined with combustible refrigerant, and the composition is introduced into system In device for cooling, air-conditioning device or heat pump assembly.

The invention further relates to reducing refrigerating plant, in air-conditioning device or heat pump assembly or the method for neighbouring fire hazard, It is introduced into the method includes at least one non-flammable fluoroolefin to be combined with lubricant, and by the composition equipped with can It fires in refrigerating plant, air-conditioning device or the heat pump assembly of refrigerant.

The invention further relates to reducing refrigerating plant, in air-conditioning device or heat pump assembly or the method for neighbouring fire hazard, The method includes at least one fluoroolefin is introduced into described device.

It is described the invention further relates to the method for using combustible refrigerant in refrigerating plant, air-conditioning device or heat pump assembly Method includes being combined the combustible refrigerant and at least one fluoroolefin.

The invention further relates to the flammable methods for reducing combustible refrigerant or heat-transfer fluid, and the method includes will be flammable Refrigerant is combined at least one fluoroolefin.

The invention further relates to the methods that heat is transferred to thermoreceptor from heat source, wherein composition of the invention serves as heat transfer Fluid.The heat transfer method includes that composition of the invention is transmitted to thermoreceptor from heat source.

Heat-transfer fluid is used to turn heat from a space, position, object or object by radiation, conduction or convection current Shifting, movement move to another space, position, object or object.Heat-transfer fluid can by provide by remote refrigeration (or add Heat) means of system transfer cooling (or heating) serve as secondary coolant.In some systems, heat-transfer fluid is entirely shifting It is positively retained at steady state (do not evaporate or condense) in the process.Alternatively, heat-transfer fluid can also be used in evaporation cooling procedure.

Heat source may be defined as any required transfer, space, position, object or object mobile or that migrate out heat.Heat source Example can be and need to freeze or the refrigerator in cooling space (open or confined space) such as supermarket or refrigerating box, need sky The space of tune or the automobile passenger compartment for needing air-conditioning.Thermoreceptor can be defined as any sky that can absorb heat Between, position, object or object.Vapor compression refrigeration system is an example of this thermoreceptor.

Specific embodiment

Embodiment

Embodiment 1

Performance data

Table 7 shows the compounds of this invention and CFC-113, HFC-43-10mee, C₄F₉OCH₃The system compared with HFC-365mfc Cold performance, pressure, outlet temperature (Disch T), energy efficiency such as in evaporator (Evap) and condenser (Cond) (COP) and capacity (Cap).These data are based on the following conditions.

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of supercooling temperature (subcooltemperature) (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

Table 7

Embodiment 2

Performance data

Table 8 shows refrigeration performance of the compounds of this invention compared with CFC-11 and HCFC-123, such as at evaporator (Evap) With pressure, outlet temperature (Disch T), energy efficiency (COP) and the capacity (Cap) in condenser (Cond).These data are Based on the following conditions.

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of supercooling temperature (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

Table 8

Embodiment 3

Performance data

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

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of supercooling temperature (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

Table 9

Embodiment 4

Performance data

Table 10 shows refrigeration performance of the compounds of this invention compared with CFC-114 and HFC-236fa, such as in evaporator (Evap) and the pressure in condenser (Cond), outlet temperature (Disch T), energy efficiency (COP) and capacity (Cap).These Data are based on the following conditions.

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of supercooling temperature (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

Table 10

Embodiment 5

Performance data

Table 11 shows refrigeration performance of the compounds of this invention compared with HFC-134a, HFC-152a and HFC-227ea, such as Pressure, outlet temperature (Disch T), energy efficiency (COP) and capacity in evaporator (Evap) and condenser (Cond) (Cap).These data are based on the following conditions.

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of supercooling temperature (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

Table 11

Embodiment 6

It is flammable

Combustible cpd can be by being tried with electronics incendiary source by ASTM (American Society Testing and Materials) E681-01 It tests to identify.This flammability test in 101 kPa (14.7psia), 50% relative humidity and is referred to composition of the invention Carried out at a temperature of fixed with concentration in different air, it is flammable to determine if, and it is flammable if find out lean flammability (LFL).As a result it is provided in table 12.

Table 12

The result shows that HFC-1234yf and E-HFC-1234ze are flammable, and HFC-1225ye, HFC-1429myz/ Mzy and F12E is non-flammable.For the mixture of HFC-1225ye and HFC-32 (known is flammable under pure state), Being determined the HFC-32 of 37 weight percent of discovery is to keep maximum amount existing for non-flammable characteristic institute energy.Those include it is non-can The composition of the fluoroolefin of combustion is more receivable refrigerant or heat transfer fluid composition candidate.

Embodiment 7

Generate the tip speed of pressure

Tip speed can be by being estimated to some fundamental relations are established using the refrigeration equipment of centrifugal compressor. The torque that impeller ideally gives gas is defined as：

T=m* (v₂*r₂-v₁*r₁) equation 1

In formula

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

M=mass flowrate, kg/sec

v₂=refrigerant leaves the tangential velocity (tip speed) of impeller, meter per second

r₂The radius of=outlet impeller, rice

v₁=refrigerant enters the tangential velocity of impeller, meter per second

r₁The radius of=impeller inlet, rice

It is assumed that refrigerant enters impeller, the tangential component v of speed with substantial axial direction₁=0, then：

T=m*v₂*r₂Equation 2

The power needed at axis is the product of torque and rotation speed.

P=T* ω equation formula 3

In formula

P=power, W

ω=angular speed, radian/s

Then

P=T*w=m*v₂*r₂* ω equation formula 4

Under low refrigerant flow rates, the tip speed of impeller and the tangential velocity of refrigerant are almost equal；Then

r₂* ω=v₂Equation 5

With

P=m*v₂*v₂Equation 6

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

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

In formula

H_i=refrigerant is by the enthalpy difference under the saturated vapor under evaporation conditions to saturation condensing condition, kJ/kg.

Merge equation 6 and 7 two expression formula, obtain,

v₂*v₂=1000*H_iEquation 8

Although equation 8 is based on some basic assumptions, it can estimate tip speed and the offer of impeller well The important way of the tip speed of more each refrigerant.

The following table 13 shows theoretical leaf calculated to 1,2,2- trichorotrifluoroethane (CFC-113) and the present composition Sharp speed.This hypothesis condition compared is：

40.0 °F of evaporator temperature (4.4 DEG C)

110.0 °F of condenser temperature (43.3 DEG C)

10.0 °F of liquid supercooling temperature (5.5 DEG C)

75.0 °F of reflux gas temperature (23.8 DEG C)

Compressor efficiency is 70%

These are the representative conditions of small sized turbine centrifugal compressor operation.

Table 13

The present embodiment shows that the tip speed of the compounds of this invention is differed with CFC-113 within about 15%, it will is CFC- 113 effective substitute, required compressor design change few.Most preferred its tip speed of composition and CFC-113 phase Within difference about 10%.

Embodiment 8

Refrigeration performance data

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

40.0 °F of evaporator temperature (4.4 DEG C)

130.0 °F of condenser temperature (54.4 DEG C)

Cross 10.0 °F of cooling capacity (5.5 DEG C)

60.0 °F of reflux gas temperature (15.6 DEG C)

Compressor efficiency is 100%

Notice that overheat is included in cooling capacity.

Table 14

Have several compositions have than HFC-134a higher energy efficiency (COP), while also keep it is lower or it is comparable go out Mouth pressure and temperature.The capacity of composition listed by table 14 is also similar to R134a, show these compositions can refrigeration and Alternative refrigerant in air-conditioning especially in air conditioning for automobiles application as R134a.As a result the cooling of HFC-1225ye is also shown Capacity can be improved by the way that other compound such as HFC-32 are added.

Embodiment 9

Refrigeration performance data

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

- 17.8 DEG C of evaporator temperature

46.1 DEG C of condenser temperature

Cross 5.5 DEG C of cooling capacity

15.6 DEG C of reflux gas temperature

Compressor efficiency is 70%

Notice that overheat is included in cooling capacity.

Table 15

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

Embodiment 10

Refrigeration performance data

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

4 DEG C of evaporator temperature

43 DEG C of condenser temperature

Cross 6 DEG C of cooling capacity

18 DEG C of reflux gas temperature

Compressor efficiency is 70%

Notice that overheat is included in cooling capacity.

Table 16

These compositions have with the comparable energy efficiency of R22 and R410A (EER), while keeping reasonable outlet temperature. The capacity of certain compositions listed by table 16 is also similar to R22, shows that these compositions can be in refrigeration and air-conditioning as R22 Alternative refrigerant.In addition, its capacity of the composition having in composition listed by table 16 is close or is equivalent to R410A, show these Composition can be in refrigeration and the alternative refrigerant in air-conditioning as R410A.

Embodiment 11

Refrigeration performance data

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

4.4 DEG C of evaporator temperature

54.4 DEG C of condenser temperature

Cross 5.5 DEG C of cooling capacity

15.6 DEG C of reflux gas temperature

Compressor efficiency is 100%

Notice that overheat is included in cooling capacity.

Table 17

These compositions have with the comparable energy efficiency of R22, R407C, R417A and R410A (EER), while keeping low Outlet temperature.The capacity of composition listed by table 17 is also similar to R22, R407C and R417A, shows that these compositions can be with Alternative refrigerant in refrigeration and air-conditioning as R22, R407C and R417A.

Claims

1. a kind of refrigerant or heat transfer fluid composition, it includes 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and at least one are flammable Refrigerant, the combustible refrigerant are selected from difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1- trifluoroethane (HFC- 143a), 1,1,2- trifluoroethane (HFC-143), 1,1- Difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1- tri- Fluoro-propane (HFC-263fb), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 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 (HFC-1243zf) of 3,3,3- tri-, the fluoro- 1- propylene (HFC-1243yc) of 1,1,2- tri-, 1,1, The fluoro- 1- propylene (HFC-1243zc) of 3- tri-, the fluoro- 1- propylene (HFC-1243ye) of 1,2,3- tri-, the fluoro- 1- propylene of 1,3,3- tri- (HFC-1243ze)、C₄F₉OC₂H₅, propane, propylene, cyclopropane, normal butane, iso-butane, 2- methybutane, 2,2- dimethyl propylene Alkane, pentamethylene, cyclobutane, 2,2- dimethylbutane, 2,3- dimethylbutane, 2,3- dimethyl pentane, 2- methyl hexane, 3- first Base hexane, 2- methylpentane, 3- ethylpentane, 3- methylpentane, hexamethylene, normal heptane, methyl cyclopentane, n-hexane, diformazan Ether, methyl tertiary butyl ether(MTBE), ammonia and their combination.

2. the composition of claim 1, further includes lubricant, the lubricant is selected from mineral oil, paraffin, cycloalkanes, alkane Base benzene, poly-alpha-olefin, polyalkylene glycol, polyvingl ether, polyol ester and its mixture.

3. the composition of claim 2, wherein the paraffin is synthesis paraffin.

4. a kind of cooling means evaporates institute the method includes condensing a kind of composition near object to be cooled later Composition is stated, wherein it includes 1,1 that the composition, which is, Isosorbide-5-Nitrae, the refrigerant or heat transfer fluid composition of 4,4- hexafluoro -2- butylene, It either include the composition of 1,1,1,4,4,4- hexafluoro -2- butylene and at least one combustible refrigerant.

5. a kind of heating means condense institute the method includes evaporating a kind of composition near object to be heated later Composition is stated, wherein it includes 1,1 that the composition, which is, Isosorbide-5-Nitrae, the refrigerant or heat transfer fluid composition of 4,4- hexafluoro -2- butylene, It either include the composition of 1,1,1,4,4,4- hexafluoro -2- butylene and at least one combustible refrigerant.

6. a kind of generate the method being heated or cooled in refrigeration, air-conditioning or heat pump assembly, the method includes by refrigerant or Heat transfer fluid composition is introduced into (a) centrifugal compressor, (b) multistage centrifugal compressor or (c) veneer/one way heat exchange In the described device of device；Wherein the refrigerant or heat transfer fluid composition include a kind of -2- fourth of hexafluoro containing 1,1,1,4,4,4- The composition of alkene, or comprising one kind contain 1,1, Isosorbide-5-Nitrae, the composition of 4,4- hexafluoro -2- butylene and at least one combustible refrigerant.

7. method for claim 6, wherein the method includes being compressed described in the composition, condensation in centrifugal compressor Composition evaporates the composition near object to be heated or cooling later.

8. method for claim 6, wherein the centrifugal compressor is multistage centrifugal compressor.

9. method for claim 6, wherein the centrifugal compressor is two-stage centrifugal compressor.

10. a kind of method for the GWP for reducing refrigeration, air-conditioning or original refrigerant or heat transfer fluid composition in heat pump assembly, Wherein the GWP of the original refrigerant or heat-transfer fluid is 150 or higher；The method includes to the refrigeration, air-conditioning or heat The refrigerant or heat transfer fluid composition of pump installation introducing second, lower GWP, wherein the composition includes 1,1, Isosorbide-5-Nitrae, 4, 4- hexafluoro -2- butylene, or comprising 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and at least one combustible refrigerant.

11. method for claim 10, wherein the original refrigerant or heat transfer fluid composition are：

(i) fluoro trichloromethane (R11), wherein second refrigerant of the R11 comprising at least one compound selected from the following Or heat transfer fluid composition is substituted：1,2,3,3,4,4,5,5- octafluoro cyclopentene (FC-C1418y), 1,1,1,2,3,4,4, The fluoro- 2- amylene (FC-141-10myy) of 5,5,5- ten, the fluoro- 2- amylene (HFC-1429myz) of 1,1,1,2,4,4,5,5,5- nine, 1, The fluoro- 2- amylene (HFC-1429mzy) of 1,1,3,4,4,5,5,5- nine, the fluoro- 1- amylene (HFC- of 3,3,4,4,5,5,5- seven 1447fz), 1,1,1,4,4,4- hexafluoro -2- butylene (F11E), 1,1,1,4,4,4- hexafluoro -2- (trifluoromethyl) -2- butylene (HFC-1429mzt) and 1,1,1,4,4,5,5,5- octafluoro -2- amylene (F12E)；

(ii) 2,2 ,-two chloro- 1,1,1- trifluoroethane (R123), wherein the R123 is with comprising at least one selected from the following The second refrigerant or heat transfer fluid composition of compound are substituted：1,2,3,3,4,4,5,5- octafluoro cyclopentene (FC- C1418y), the fluoro- 2- amylene (FC-141-10myy) of 1,1,1,2,3,4,4,5,5,5- ten, 1,1,1,2,4,4,5,5,5- nine are fluoro- 2- amylene (HFC-1429myz), the fluoro- 2- amylene (HFC-1429mzy) of 1,1,1,3,4,4,5,5,5- nine, 3,3,4,4,5,5,5- Seven fluoro- 1- amylenes (HFC-1447fz), 1,1,1,4,4,4- hexafluoro -2- butylene (F11E), 1,1,1,4,4,4- hexafluoro -2- (three Methyl fluoride) -2- butylene (HFC-1429mzt) and 1,1,1,4,4,5,5,5- octafluoro -2- amylene (F12E)；Or

(iii) 1,1,1,3,3- pentafluoropropane (R245fa), wherein the R245fa is with including at least one selected from the followingization The second refrigerant or heat transfer fluid composition for closing object are substituted：2,3,3- trifluoro propene (HFC-1243yf), 1,1,1,4, 4,4- hexafluoro -2- butylene (F11E), 1,3,3,3- tetrafluoropropene (HFC-1234ze), the fluoro- 2- butylene of 1,1,1,2,4,4,4- seven (HFC-1327my), 1,2,3,3- tetrafluoropropene (HFC-1234ye) and pentafluoroethyl group trifluoro vinyl ether (PEVE).

12. a kind of composition of use comprising 1,1,1,4,4,4- hexafluoro -2- butylene includes 1,1,1,4,4,4- hexafluoro -2- fourth Method of the composition of alkene and at least one combustible refrigerant as heat transfer fluid composition, the method includes by the combination Object is transmitted to thermoreceptor from heat source.

13. a kind of refrigeration, air-conditioning or heat pump assembly, described device is equipped with a kind of composition, and the composition includes 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, or comprising 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and at least one combustible refrigerant.

14. a kind of mobile refrigerating or air-conditioning device, described device is equipped with a kind of composition, and the composition includes 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, or comprising 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene and at least one combustible refrigerant.