CN102876294B - Compositions comprising fluoroolefins and uses thereof - Google Patents

Compositions comprising fluoroolefins and uses thereof Download PDF

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Publication number
CN102876294B
CN102876294B CN201210340141.9A CN201210340141A CN102876294B CN 102876294 B CN102876294 B CN 102876294B CN 201210340141 A CN201210340141 A CN 201210340141A CN 102876294 B CN102876294 B CN 102876294B
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fluoro
composition
butylene
refrigerant
hfc
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CN102876294A (en
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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
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Chemours Co FC LLC
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EI Du Pont de Nemours and Co
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Priority claimed from US11/589,588 external-priority patent/US7708903B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
    • B60H1/00—Heating, cooling or ventilating [HVAC] devices
    • B60H1/32—Cooling devices
    • B60H1/3204—Cooling devices using compression
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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    • C09K2205/11—Ethers
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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    • C09K2205/112—Halogenated ethers
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/132—Components containing nitrogen
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/0206—Well-defined aliphatic compounds used as base material
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material

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  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

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

Description

Comprise the composition and use thereof of fluoroolefins
The divisional application that the application is international filing date is on October 31st, 2006, national applications number is 2006800488601.0 (international application no is PCT/US2006/042686), denomination of invention is the application of " composition and use thereof comprising fluoroolefins ".
The cross reference of related application
This application claims the right of priority of the U.S. Patent application 11/486,791 of the U.S. Provisional Application submission on July 13rd, 60/732,581 and 2006 submitted on November 1st, 2005.
Technical field
The present invention relates to for freezing, the composition of air-conditioning or heat pump, wherein said composition comprises at least one fluoroolefins.Composition of the present invention can be used as heat-transfer fluid in the method for freezing or heat, and also can be used for other purposes many.
Background technology
Refrigeration industry comes in the past few decades attempting to find the Chlorofluorocarbons (CFCs) (CFC) of depletion ozone and the alternative refrigerant of Hydrochlorofluorocarbons (HCFC) always, CFC and HCFC is just eliminated gradually because of the signing of Montreal Protocol (Montreal Protocol).The terms of settlement of most of refrigeration agent manufacturer is business promotion hydrogen fluorohydrocarbon (HFC) refrigeration agent.The ozone depletion potential of new HFC refrigeration agent (the most widely using HFC-134a at present) is zero, therefore not by the impact of the existing superseded control under Montreal Protocol.
Further environmental legislation may finally cause some HFC refrigeration agent to be eliminated in the whole world.At present, automobile industry is faced with the regulation relating to the global warming potential of refrigeration agent used for automobile air conditioning.Therefore, current pole is required to be automobile air-conditioning market and determines the novel refrigerant that global warming potential reduces.If these regulations scope of application in the future expands more, then more need be used for freezing and the refrigeration agent of all areas of air conditioner industry.
The alternative refrigerant of the HFC-134a of current proposition comprises HFC-152a, pure hydrocarbon as butane or propane, or " natural " refrigeration agent is as CO 2.Many these propose substitute be all poisonous, flammable and/or energy efficiency low.Therefore, new binary mixtures is being sought.
The object of this invention is to provide novel refrigerant composition and heat transfer fluid composition, these compositions can provide unique characteristic, low or for zero to meet ozone depletion potential; And global warming potential these requirements lower compared with existing refrigeration agent.
Summary of the invention
The present invention relates to and comprise refrigeration agent or the heat transfer fluid composition that at least one is selected from following compound:
(i) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group, and the carbon wherein in this compound adds up at least 5;
(ii) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5;
(iii) following fluoroolefins is selected from:
The fluoro-1-propylene (CHF of 2,3,3-tri- 2CF=CH 2); The fluoro-1-propylene (CH of 1,1,2-tri- 3CF=CF 2); The fluoro-1-propylene (CH of 1,2,3-tri- 2FCF=CF 2); The fluoro-1-propylene (CH of 1,1,3-tri- 2FCH=CF 2); The fluoro-1-propylene (CHF of 1,3,3-tri- 2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-butylene (CH of 1,1,1,2,4-five 2FCH=CFCF 3); The fluoro-2-butylene (CF of 1,1,1,3,4-five 3CH=CFCH 2F); The fluoro-1-butylene (CF of 3,3,4,4,4-five 3CF 2CH=CH 2); The fluoro-2-butylene (CHF of 1,1,1,4,4-five 2CH=CHCF 3); The fluoro-2-butylene (CH of 1,1,1,2,3-five 3CF=CFCF 3); The fluoro-1-butylene (CH of 2,3,3,4,4-five 2=CFCF 2CHF 2); The fluoro-2-butylene (CHF of 1,1,2,4,4-five 2CF=CHCHF 2); The fluoro-1-butylene (CH of 1,1,2,3,3-five 3CF 2CF=CF 2); The fluoro-2-butylene (CH of 1,1,2,3,4-five 2FCF=CFCHF 2);The fluoro-2-methyl-1-propylene (CF of 1,1,3,3,3-five 2=C (CF 3) (CH 3)); The fluoro-1-propylene (CH of 2-(difluoromethyl)-3,3,3-three 2=C (CHF 2) (CF 3)); The fluoro-1-butylene (CH of 2,3,4,4,4-five 2=CFCHFCF 3); The fluoro-1-butylene (CHF=CFCH of 1,2,4,4,4-five 2CF 3); The fluoro-1-butylene (CHF=CHCHFCF of 1,3,4,4,4-five 3); The fluoro-1-butylene (CHF=CHCF of 1,3,3,4,4-five 2CHF 2); The fluoro-1-butylene (CHF=CFCHFCHF of 1,2,3,4,4-five 2); The fluoro-1-butylene (CH of 3,3,4,4-tetra- 2=CHCF 2CHF 2); 1,1-bis-fluoro-2-(difluoromethyl)-1-propylene (CF 2=C (CHF 2) (CH 3)); The fluoro-2-methyl-1-propylene (CHF=C (CF of 1,3,3,3-tetra- 3) (CH 3)); 3,3-bis-fluoro-2-(difluoromethyl)-1-propylene (CH 2=C (CHF 2) 2); The fluoro-2-butylene (CF of 1,1,1,2-tetra- 3CF=CHCH 3); The fluoro-2-butylene (CH of 1,1,1,3-tetra- 3CF=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); 1,1,1-tri-fluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-amylene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C (CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-amylene (CH 2=CHCF 2CHFCF 3); 4,4,4-tri-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CH 2CF 3); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHCF 2CH 3); 4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylene (CH 2=C (CF 3) CH 2C 2F 5); The fluoro-2-Methyl-1-pentene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2C (CH 3)=CH 2); 4,4,5,5,6,6,The fluoro-2-hexene (CF of 6-seven 3CF 2CF 2CH=CHCH 3); The fluoro-1-hexene (CH of 4,4,5,5,6,6,6-seven 2=CHCH 2CF 2C 2F 5); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4-seven 3CF 2CF=CFC 2H 5); 4,5,5,5-tetra-fluoro-4-(trifluoromethyl)-1-amylene (CH 2=CHCH 2CF (CF 3) 2); 1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylene (CF 3CF=CHCH (CF 3) (CH 3)); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CFC 2H 5); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3And CF (PEVE) 2=CFOCF 3(PMVE).
The invention further relates to the composition comprising (i) at least one fluoroolefin compounds refrigeration agent flammable with (ii) at least one, wherein said fluoroolefins is selected from following:
(a) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group;
(b) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5; With
C () is selected from following fluoroolefins:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5) and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5).
The invention further relates to the method using refrigeration agent or heat transfer fluid composition in refrigeration, air-conditioning or thermal-pump unit, described method comprises described composition to be incorporated into and has (a) centrifugal compressor; B, in the described device of () multistage centrifugal compressor or (c) veneer (single slab)/one way (single pass) interchanger, wherein said refrigeration agent or heat transfer compositions are used for causing heating or cooling in said device; And wherein said refrigeration agent or heat transfer compositions comprise at least one is selected from following fluoroolefins:
(i) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group;
(ii) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5; Or
(iii) following fluoroolefins is selected from:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF 3CF=CH 2); 1,3,3,3-tetrafluoro-1-propene (CF 3CH=CHF); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1-propene (CHF 2CH=CF 2); The fluoro-1-propylene (CHF of 2,3,3-tri- 2CF=CH 2); The fluoro-1-propylene (CF of 3,3,3-tri- 3CH=CH 2); The fluoro-1-propylene (CH of 1,1,2-tri- 3CF=CF 2); The fluoro-1-propylene (CH of 1,1,3-tri- 2FCH=CF 2); The fluoro-1-propylene (CH of 1,2,3-tri- 2FCF=CHF); The fluoro-1-propylene (CHF of 1,3,3-tri- 2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-butylene (CH of 1,1,1,2,4-five 2FCH=CFCF 3); The fluoro-2-butylene (CF of 1,1,1,3,4-five 3CH=CFCH 2F); The fluoro-1-butylene (CF of 3,3,4,4,4-five 3CF 2CH=CH 2); The fluoro-2-butylene (CHF of 1,1,1,4,4-five 2CH=CHCF 3); The fluoro-2-butylene (CH of 1,1,1,2,3-five 3CF=CFCF 3); The fluoro-1-butylene (CH of 2,3,3,4,4-five 2=CFCF 2CHF 2); The fluoro-2-butylene (CHF of 1,1,2,4,4-five 2CF=CHCHF 2); The fluoro-1-butylene (CH of 1,1,2,3,3-five 3CF 2CF=CF 2); The fluoro-2-butylene (CH of 1,1,2,3,4-five 2FCF=CFCHF 2); The fluoro-2-methyl-1-propylene (CF of 1,1,3,3,3-five 2=C (CF 3) (CH 3)); The fluoro-1-propylene (CH of 2-(difluoromethyl)-3,3,3-three 2=C (CHF 2) (CF 3)); The fluoro-1-butylene (CH of 2,3,4,4,4-five 2=CFCHFCF 3); The fluoro-1-butylene (CHF=CFCH of 1,2,4,4,4-five 2CF 3);The fluoro-1-butylene (CHF=CHCHFCF of 1,3,4,4,4-five 3); The fluoro-1-butylene (CHF=CHCF of 1,3,3,4,4-five 2CHF 2); The fluoro-1-butylene (CHF=CFCHFCHF of 1,2,3,4,4-five 2); The fluoro-1-butylene (CH of 3,3,4,4-tetra- 2=CHCF 2CHF 2); 1,1-bis-fluoro-2-(difluoromethyl)-1-propylene (CF 2=C (CHF 2) (CH 3)); The fluoro-2-methyl-1-propylene (CHF=C (CF of 1,3,3,3-tetra- 3) (CH 3)); The fluoro-1-propylene (CH of 2-difluoromethyl-3,3-two 2=C (CHF 2) 2); The fluoro-2-butylene (CF of 1,1,1,2-tetra- 3CF=CHCH 3); The fluoro-2-butylene (CH of 1,1,1,3-tetra- 3CF=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); 1,1,1-tri-fluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-amylene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C (CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-amylene (CH 2=CHCF 2CHFCF 3); The fluoro-1-butylene (CH of 3-(trifluoromethyl)-4,4,4-three 2=C (CF 3) CH 2CF 3); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHCF 2CH 3); 4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylene (CH 2=C (CF 3) CH 2C 2F 5); The fluoro-2-Methyl-1-pentene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2C (CH 3)=CH 2); The fluoro-2-hexene (CF of 4,4,5,5,6,6,6-seven 3CF 2CF 2CH=CHCH 3); The fluoro-1-hexene (CH of 4,4,5,5,6,6,6-seven 2=CHCH 2CF 2C 2F 5); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4-seven 3CF 2CF=CFC 2H 5); The fluoro-4-Trifluoromethyl-1-amylene (CH of 4,5,5,5-tetra- 2=CHCH 2CF (CF 3) 2); 1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylene (CF 3CF=CHCH (CF 3) (CH 3)); 1,1,1,3-tetra-fluoro-2-trifluoromethyl-2-amylene ((CF 3) 2C=CFC 2H 5); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3(PEVE); CF 2=CFOCF 3And their combination (PMVE).
detailed Description Of The Invention
The present invention relates to the composition comprising at least one fluoroolefins.So-called fluoroolefins refers to any compound containing carbon, fluorine and optional hydrogen or oxygen and also containing at least one double bond.These fluoroolefins can be straight chain, side chain or ring-type.
These compositions serve many purposes in working fluid, comprise and are such as used as whipping agent (foaming agent), pore forming material (blowing agent), fire-fighting medium, heat-transfer medium (as the heat-transfer fluid of refrigeration system, refrigerator, air-conditioning system, heat pump, water cooler etc. and refrigeration agent).
Heat-transfer fluid (also claiming heat transfer compositions or heat transfer fluid composition in this article) is the working fluid in order to heat to be sent to heat sink from thermal source.
Refrigeration agent serves as the compound of heat-transfer fluid or the mixture of compound in the circulation that fluid experience liquid-gas and gas and liquid phase become wherein.
The invention provides and there is formula E-or Z-R 1cH=CHR 2the fluoroolefins of (formula I), wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group.R 1and R 2the example of group includes but not limited to CF 3, C 2f 5, CF 2cF 2cF 3, CF (CF 3) 2, CF 2cF 2cF 2cF 3, CF (CF 3) CF 2cF 3, CF 2cF (CF 3) 2, C (CF 3) 3, CF 2cF 2cF 2cF 2cF 3, CF 2cF 2cF (CF 3) 2, C (CF 3) 2c 2f 5, CF 2cF 2cF 2cF 2cF 2cF 3, CF (CF 3) CF 2cF 2c 2f 5with C (CF 3) 2cF 2c 2f 5.In one embodiment, have at least about 3 carbon atoms in the molecule of formula I fluoroolefins.In another embodiment, have at least about 4 carbon atoms in the molecule of formula I fluoroolefins.In still another embodiment, have at least about 5 carbon atoms in the molecule of formula I fluoroolefins.Table 1 provides exemplary non-limiting formula I.
table 1
Formula I can be prepared like this: make formula R 1the perfluoroalkyl iodides of I and formula R 2cH=CH 2perfluoroalkyl three hydrogen alkene carry out contact and form formula R 1cH 2cHIR 2three hydrogen iodo perfluoro alkane.Then this three hydrogen iodo perfluoro alkane can form R through dehydrogenation iodine (dehydroiodinated) 1cH=CHR 2.Or, alkene R 1cH=CHR 2can prepare like this: make formula R 2the perfluoroalkyl iodides of I and formula R 1cH=CH 2perfluoroalkyl three hydrogen olefine reaction form formula R 1cHICH 2r 2three hydrogen iodo perfluoro alkane, then dehydrogenation Iod R is carried out to the latter.
The contact of described perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene can in a batch manner, undertaken mixing occurring by the suitable reaction vessels that operated under the autogenous pressure that can produce under temperature of reaction at each reactant and product by each reactant.Suitable reaction vessel comprise by stainless steel (particularly austenitic stainless steel) and known Langaloy as nickel-copper alloy, nickel-base alloy and the reaction vessel that nickel-chromium alloy manufactures.
Or reaction can be carried out in semi-batch mode, in such a way, by suitable adding apparatus as perfluoroalkyl three hydrogen olefin reactant is joined perfluoroalkyl iodides reactant by pump at the reaction temperatures.
The ratio of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene should about 1: 1 to about between 4: 1, and preferably about 1.5: 1-2.5: 1.As the Journal of Fluorine Chemistry such as Jeanneaux, Vol.4, pages 261-270 (1974) reported, the ratio being less than 1.5: 1 easily causes producing a large amount of 2: 1 adductss (adduct).
The preferable temperature of the contact of described perfluoroalkyl iodides and described perfluoroalkyl three hydrogen alkene, preferably in the scope of about 150 DEG C-300 DEG C, preferably about 170 DEG C to about 250 DEG C, most preferably from about 180 DEG C to about 230 DEG C.
The appropriate contact time of the reaction of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene is about 0.5 hour-18 hours, preferably about 4 to about 12 hours.
The three hydrogen iodo perfluoro alkane prepared by the reaction of perfluoroalkyl iodides and perfluoroalkyl three hydrogen alkene can be directly used in dehydrogenation Iod R step, or preferably first carry out reclaiming and distillation purifying before for dehydrogenation Iod R step.
Dehydrogenation Iod R step carries out contacting performing with alkaline matter by making three hydrogen iodo perfluoro alkane.Suitable alkaline matter comprise alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide), alkalimetal oxide (such as sodium oxide), alkaline earth metal hydroxides (such as calcium hydroxide), alkaline earth metal oxide (such as calcium oxide), alkali metal alcoholates (such as sodium methylate or sodium ethylate), ammoniacal liquor, sodium amide or alkaline matter mixture as soda-lime.Preferred alkaline matter is sodium hydroxide and potassium hydroxide.
Three described hydrogen iodo perfluoro alkane and the contact of alkaline matter, can in the liquid phase, preferably occur under the solvent at least partially that can dissolve two kinds of reactants exists.The solvent being adapted to dehydrogenation Iod R step comprises one or more polar organic solvents as alcohol (such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol), nitrile (such as acetonitrile, propionitrile, butyronitrile, benzonitrile or adiponitrile), methyl-sulphoxide, N, dinethylformamide, N,N-dimethylacetamide or tetramethylene sulfone.The selection of solvent can be determined from the easy degree of product separation trace solvent according in the boiling point of product and purge process.Usually, ethanol or Virahol are the good solvents of reaction.
Usually, dehydrogenation Iod R is by being undertaken a kind of reactant (alkaline matter or three hydrogen iodo perfluoro alkane) the another kind of reactant be added in suitable reaction vessels.Described reaction vessel can by glass, pottery or metal manufacture, and preferred impeller or stirring mechanism stir.
The optimal temperature of dehydrogenation Iod R is about 10 DEG C to about 100 DEG C, preferably about 20 DEG C to about 70 DEG C.Dehydrogenation Iod R can carry out under ambient pressure, or carries out under decompression or boosting.It is worth mentioning that such dehydrogenation Iod R, in the reaction along with it distills from reaction vessel by the formation of formula I.
Or, dehydrogenation Iod R is undertaken by making the aqueous solution of described alkaline matter contact in the presence of a phase transfer catalyst with the solution of three hydrogen iodo perfluoro alkane in one or more lower polar organic solvents, described organic solvent is as alkane (such as hexane, heptane or octane), aromatic hydrocarbons (such as toluene), halohydrocarbon (such as methylene dichloride, chloroform, tetracol phenixin or tetrachloroethylene) or ether (such as diethyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, glycol dimethyl ether, diglyme or tetraethylene glycol dimethyl ether).Suitable phase-transfer catalyst comprises quaternary ammonium halides salt (such as Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride and three capryloyl ammonio methacrylates), halogenation season salt (such as triphenylmethylphosphonium bromide and tetraphenylphosphonichloride chloride ) or this area be called crown ether cyclic polyether compound (such as 18-hat-6 and 15-hat-5).
Or, dehydrogenation Iod R can solvent not in the presence of undertaken by three hydrogen iodo perfluoro alkane being added to solid-state or liquid alkaline material.
The suitable reactions time of dehydrogenation Iod R is about 15 minutes to about 6 hours or longer time, and this depends on the solubleness of reactant.Usually, dehydrogenation Iod R is fast, needs within about 30 minutes to about 3 hours, just complete.
Formula I is separated after adding water, by distilling or being reclaimed from dehydrogenation Iod R mixture by the combination of aforementioned two kinds of methods.
In another embodiment of the invention, fluoroolefins comprises ring-type fluoroolefins (ring-[CX=CY (CZW) n-] (formula II), wherein X, Y, Z and W are independently selected from H and F, and n is the integer of 2-5).Representational formula II ring-type fluoroolefins listed by table 2.
Table 2
In another embodiment, fluoroolefins can comprise those compounds listed by table 3.
table 3
Table 2 and the compound listed by table 3 are commercially available, or are prepared by method well known in the art or described herein.
1,1, Isosorbide-5-Nitrae, the fluoro-2-butylene of 4-five is by by 1,1,1,2,4,4-hexafluoro butane (CHF 2cH 2cHFCF 3) at room temperature carry out dehydrogenation fluorine reaction (dehydrofluorination) with gas phase state solid KOH and prepare.The synthesis of 1,1,1,2,4,4-hexafluoro butane is described in US6, and 066,768, this patent is incorporated herein by reference.
1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene by making 1,1 with phase-transfer catalyst, Isosorbide-5-Nitrae, 4,4-hexafluoro-sec.-butyl iodide (CF 3cHICH 2cF 3) carry out reacting preparing at about 60 DEG C with KOH.1,1, Isosorbide-5-Nitrae, the synthesis of 4,4-hexafluoro-sec.-butyl iodide is by making perfluoro-methyl iodine (CF 3and 3,3,3-trifluoro propene (CF I) 3cH=CH 2) react about 8 hours at autogenous pressures to carry out at about 200 DEG C.
3,4,4,5,5,5-hexafluoro-2-amylene by carrying out 1,1,1,2,2,3,3-seven amyl fluoride (CF with solid KOH or with C catalyst at 200-300 DEG C 3cF 2cF 2cH 2cH 3) dehydrogenation fluorine reaction prepare.1,1,1,2,2,3,3-seven amyl fluoride is by the fluoro-1-amylene of 3,3,4,4,5,5,5-seven (CF 3cF 2cF 2cH=CH 2) hydrogenation prepare.
1,1,1,2,3,4-hexafluoro-2-butylene is by carrying out 1,1,1,2,3,3,4-seven fluorine butane (CH with solid KOH 2fCF 2cHFCF 3) dehydrogenation fluorine reaction prepare.
1,1,1,2,4,4-hexafluoro-2-butylene is by carrying out 1,1,1,2,2,4,4-seven fluorine butane (CHF with solid KOH 2cH 2cF 2cF 3) dehydrogenation fluorine reaction prepare.
1,1,1,3,4,4-hexafluoro 2-butylene is by carrying out 1,1,1,3,3,4,4-seven fluorine butane (CF with solid KOH 3cH 2cF 2cHF 2) dehydrogenation fluorine reaction prepare.
The fluoro-2-butylene of 1,1,1,2,4-five is by carrying out 1,1,1,2,2,3-hexafluoro butane (CH with solid KOH 2fCH 2cF 2cF 3) dehydrogenation fluorine reaction prepare.
The fluoro-2-butylene of 1,1,1,3,4-five is by carrying out 1,1,1,3,3,4-hexafluoro butane (CF with solid KOH 3cH 2cF 2cH 2prepared by dehydrogenation fluorine reaction F).
The fluoro-2-butylene of 1,1,1,3-tetra-is by making 1,1,1,3,3-3-pentafluorobutane (CF 3cH 2cF 2cH 3) react to prepare at 120 DEG C with the KOH aqueous solution.
1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene is by making (CF with phase-transfer catalyst 3cHICH 2cF 2cF 3) react to prepare at about 60 DEG C with KOH.The synthesis of iodo-1,1,1,2,2,5,5, the 5-octafluoro pentane of 4-is by making perfluoro ethyl iodide (CF 3cF 2i) and 3,3,3-trifluoro propene react about 8 hours to carry out at autogenous pressures at about 200 DEG C.
1,1,1,2,2,5,5,6,6,6-ten fluoro-3-hexene is by making the fluoro-3-iodohexane of 1,1,1,2,2,5,5,6,6,6-ten (CF with phase-transfer catalyst 3cF 2cHICH 2cF 2cF 3) react to prepare at about 60 DEG C with KOH.The synthesis of the fluoro-3-iodohexane of 1,1,1,2,2,5,5,6,6,6-ten is by making perfluoro ethyl iodide (CF 3cF 2and the fluoro-1-butylene (CF of 3,3,4,4,4-five I) 3cF 2cH=CH 2) react about 8 hours at autogenous pressures to carry out at about 200 DEG C.
1,1, Isosorbide-5-Nitrae, the fluoro-4-of 5,5,5-seven (trifluoromethyl)-2-amylene by making the iodo-2-of the fluoro-4-of 1,1,1,2,5,5,5-seven (trifluoromethyl)-pentane (CF with KOH in Virahol 3cHICH 2cF (CF 3) 2) reaction of dehydrogenation fluorine occurs prepare.CF 3cHICH 2cF (CF 3) 2by making (CF 3) 2cFI and CF 3cH=CH 2react at high temperature according to appointment 200 DEG C and prepare.
1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene of 4,5,5,6,6,6-ten by 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (CF 3cH=CHCF 3) and tetrafluoroethylene (CF 2=CF 2) and antimony pentafluoride (SbF 5) reaction prepare.
The fluoro-1-butylene of 2,3,3,4,4-five is prepared by high temperature making 1,1,2,2,3,3-hexafluoro butane carry out the reaction of dehydrogenation fluorine by fluorided alumina.
2,3,3,4,4,5,5,5-octafluoro-1-amylene is prepared by making 2,2,3,3,4,4,5,5,5-nine amyl fluoride carry out the reaction of dehydrogenation fluorine with solid KOH.
1,2,3,3,4,4,5,5-octafluoro-1-amylene is prepared by high temperature making 2,2,3,3,4,4,5,5,5-nine amyl fluoride carry out the reaction of dehydrogenation fluorine by fluorided alumina.
Composition of the present invention can the single compound of contained I, formula II or table 3, or can comprise the combination of described compound.Or many formula I, formula II and table 3 compound can exist with the form of different configurational isomers or steric isomer.The invention is intended to comprise all single configurational isomers, single stereoisomers or their any combination.Such as, 1,3,3,3-tetrafluoeopropene (HFC-1234ze) means to represent E-isomer, Z-isomer or this two kinds of isomer with any combination of any ratio or mixture.Another example is F12E, and it represents E-isomer, Z-isomer or this two kinds of isomer with any combination of any ratio or mixture.
Composition of the present invention has zero or low-ozone depletion potential and low global warming potential (GWP).The mixture of fluoroolefins of the present invention or fluoroolefins of the present invention and other refrigeration agent, its global warming potential can be less than the many fluoroether refrigerants used at present.One aspect of the present invention be to provide global warming potential be less than 1000, be less than 500, be less than 150, be less than 100 or be less than 50 refrigeration agent.Another aspect of the present invention reduces the clean GWP of described mixture.
Each composition of aequum is undertaken mixing preparing by any method easily by the present composition as combination or mixture.Preferred method takes required each component amount, then mixed in suitable container by each composition.Stirring can be adopted to operate if needed.
The method preparing the present composition of alternative comprises: (i) reclaims one or more refrigerant composition compositions of certain volume from least one cryogen vessel, (ii) fully impurity is removed, the described composition that one or more reclaim is re-used, (iii) optionally, refrigerant composition other with at least one for each composition of the described recovery volume of all or part or composition are mixed.
Cryogen vessel can be any container wherein storing the refrigeration agent blend composition (refrigerant blend composition) being used to refrigeration plant, air-conditioning plant or thermal-pump unit.Described cryogen vessel can be the refrigeration plant, air-conditioning plant or the thermal-pump unit that wherein use this refrigeration agent adulterant (refrigerant blend).In addition, cryogen vessel can be the storage vessel for collecting reclaimed each refrigeration agent fusion composition (refrigerant blend components), includes but not limited to pressurized gas cylinder.
Refrigeration agent adulterant that residual refrigeration agent refers to any amount, that shift out from cryogen vessel by any method becoming known for diverted refrigerant adulterant or refrigeration agent fusion composition or refrigeration agent fusion composition.
Impurity can be any because of the use in refrigeration plant, air-conditioning plant or thermal-pump unit of refrigeration agent adulterant or refrigeration agent fusion composition and the composition be present in this refrigeration agent adulterant or refrigeration agent fusion composition.This impurity includes but not limited to refrigeration lubricant (those refrigeration lubricants as herein described); Particulate matter, as may from refrigeration plant, air-conditioning plant or thermal-pump unit metal out or elastomerics; With other pollutent that adversely may affect the performance of refrigeration agent blend composition any.
This impurity fully can be removed, be blended into allow refrigeration agent adulterant or refrigeration agent and point to be re-used, and don't disadvantageous effect can wherein use the performance of the equipment of refrigeration agent adulterant or refrigeration agent fusion composition.
May need to provide other refrigeration agent adulterant or refrigeration agent fusion composition, to produce the composition meeting given product and specify to the refrigeration agent adulterant of remnants or refrigeration agent fusion composition.Such as, if refrigeration agent adulterant has 3 kinds of compositions in specified weight percentage range, then may need to add one or more compositions with specified rate, return in regulation compass to make composition.
The present composition that can be used as refrigeration agent or heat-transfer fluid comprises at least one and is selected from following fluoroolefins:
(i) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group, and the carbon wherein in this compound adds up at least 5;
(ii) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5;
(iii) following fluoroolefins is selected from:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF 3CF=CH 2); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1-propene (CHF 2CH=CF 2); The fluoro-1-propylene (CHF of 2,3,3-tri- 2CF=CH 2); The fluoro-1-propylene (CF of 3,3,3-tri- 3CH=CH 2); The fluoro-1-propylene (CH of 1,1,2-tri- 3CF=CF 2); The fluoro-1-propylene (CH of 1,2,3-tri- 2FCF=CF 2); The fluoro-1-propylene (CH of 1,1,3-tri- 2FCH=CF 2); The fluoro-1-propylene (CHF of 1,3,3-tri- 2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-butylene (CH of 1,1,1,2,4-five 2FCH=CFCF 3); The fluoro-2-butylene (CF of 1,1,1,3,4-five 3CH=CFCH 2F); The fluoro-1-butylene (CF of 3,3,4,4,4-five 3CF 2CH=CH 2); The fluoro-2-butylene (CHF of 1,1,1,4,4-five 2CH=CHCF 3); The fluoro-2-butylene (CH of 1,1,1,2,3-five 3CF=CFCF 3); The fluoro-1-butylene (CH of 2,3,3,4,4-five 2=CFCF 2CHF 2); The fluoro-2-butylene (CHF of 1,1,2,4,4-five 2CF=CHCHF 2); The fluoro-1-butylene (CH of 1,1,2,3,3-five 3CF 2CF=CF 2); The fluoro-2-butylene (CH of 1,1,2,3,4-five 2FCF=CFCHF 2); The fluoro-2-methyl-1-propylene (CF of 1,1,3,3,3-five 2=C (CF 3) (CH 3)); The fluoro-1-propylene (CH of 2-(difluoromethyl)-3,3,3-three 2=C (CHF 2) (CF 3)); The fluoro-1-butylene (CH of 2,3,4,4,4-five 2=CFCHFCF 3); 1,The fluoro-1-butylene (CHF=CFCH of 2,4,4,4-five 2CF 3); The fluoro-1-butylene (CHF=CHCHFCF of 1,3,4,4,4-five 3); The fluoro-1-butylene (CHF=CHCF of 1,3,3,4,4-five 2CHF 2); The fluoro-1-butylene (CHF=CFCHFCHF of 1,2,3,4,4-five 2); The fluoro-1-butylene (CH of 3,3,4,4-tetra- 2=CHCF 2CHF 2); 1,1-bis-fluoro-2-(difluoromethyl)-1-propylene (CF 2=C (CHF 2) (CH 3)); The fluoro-2-methyl-1-propylene (CHF=C (CF of 1,3,3,3-tetra- 3) (CH 3)); 3,3-bis-fluoro-2-(difluoromethyl)-1-propylene (CH 2=C (CHF 2) 2); The fluoro-2-butylene (CF of 1,1,1,2-tetra- 3CF=CHCH 3); The fluoro-2-butylene (CH of 1,1,1,3-tetra- 3CF=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); 1,1,The fluoro-1-amylene (CF of 2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); 1,1,1-tri-fluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-amylene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C (CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-amylene (CH 2=CHCF 2CHFCF 3); 4,4,4-tri-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CH 2CF 3); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHCF 2CH 3); 4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylene (CH 2=C (CF 3) CH 2C 2F 5); The fluoro-2-Methyl-1-pentene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2C (CH 3)=CH 2); The fluoro-2-hexene (CF of 4,4,5,5,6,6,6-seven 3CF 2CF 2CH=CHCH 3); The fluoro-1-hexene (CH of 4,4,5,5,6,6,6-seven 2=CHCH 2CF 2C 2F 5); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4-seven 3CF 2CF=CFC 2H 5); 4,5,5,5-tetra-fluoro-4-(trifluoromethyl)-1-amylene (CH 2=CHCH 2CF (CF 3) 2); 1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylene (CF 3CF=CHCH (CF 3) (CH 3)); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CFC 2H 5); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3(PE VE) and CF 2=CFOCF 3(PMVE).
The invention still further relates to the composition comprising at least one fluoroolefins and the flammable refrigeration agent of at least one or heat-transfer fluid, wherein said fluoroolefins is selected from:
(i) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group, and the carbon wherein in this compound adds up at least 5;
(ii) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5;
(iii) following fluoroolefins is selected from:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF 3CF=CH 2); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1-propene (CHF 2CH=CF 2); The fluoro-1-propylene (CHF of 2,3,3-tri- 2CF=CH 2); The fluoro-1-propylene (CF of 3,3,3-tri- 3CH=CH 2); The fluoro-1-propylene (CH of 1,1,2-tri- 3CF=CF 2); The fluoro-1-propylene (CH of 1,2,3-tri- 2FCF=CF 2); The fluoro-1-propylene (CH of 1,1,3-tri- 2FCH=CF 2); The fluoro-1-propylene (CHF of 1,3,3-tri- 2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-butylene (CH of 1,1,1,2,4-five 2FCH=CFCF 3); The fluoro-2-butylene (CF of 1,1,1,3,4-five 3CH=CFCH 2F); The fluoro-1-butylene (CF of 3,3,4,4,4-five 3CF 2CH=CH 2); The fluoro-2-butylene (CHF of 1,1,1,4,4-five 2CH=CHCF 3); The fluoro-2-butylene (CH of 1,1,1,2,3-five 3CF=CFCF 3); The fluoro-1-butylene (CH of 2,3,3,4,4-five 2=CFCF 2CHF 2); The fluoro-2-butylene (CHF of 1,1,2,4,4-five 2CF=CHCHF 2); The fluoro-1-butylene (CH of 1,1,2,3,3-five 3CF 2CF=CF 2); The fluoro-2-butylene (CH of 1,1,2,3,4-five 2FCF=CFCHF 2); The fluoro-2-methyl-1-propylene (CF of 1,1,3,3,3-five 2=C (CF 3) (CH 3)); The fluoro-1-propylene (CH of 2-(difluoromethyl)-3,3,3-three 2=C (CHF 2) (CF 3)); The fluoro-1-butylene (CH of 2,3,4,4,4-five 2=CFCHFCF 3); 1,The fluoro-1-butylene (CHF=CFCH of 2,4,4,4-five 2CF 3); The fluoro-1-butylene (CHF=CHCHFCF of 1,3,4,4,4-five 3); The fluoro-1-butylene (CHF=CHCF of 1,3,3,4,4-five 2CHF 2); The fluoro-1-butylene (CHF=CFCHFCHF of 1,2,3,4,4-five 2); The fluoro-1-butylene (CH of 3,3,4,4-tetra- 2=CHCF 2CHF 2); 1,1-bis-fluoro-2-(difluoromethyl)-1-propylene (CF 2=C (CHF 2) (CH 3)); The fluoro-2-methyl-1-propylene (CHF=C (CF of 1,3,3,3-tetra- 3) (CH 3)); 3,3-bis-fluoro-2-(difluoromethyl)-1-propylene (CH 2=C (CHF 2) 2); The fluoro-2-butylene (CF of 1,1,1,2-tetra- 3CF=CHCH 3); The fluoro-2-butylene (CH of 1,1,1,3-tetra- 3CF=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); 1,1,The fluoro-1-amylene (CF of 2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); 1,1,1-tri-fluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-amylene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C (CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-amylene (CH 2=CHCF 2CHFCF 3); 4,4,4-tri-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CH 2CF 3); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro 1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHCF 2CH 3); 4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylene (CH 2=C (CF 3) CH 2C 2F 5); The fluoro-2-Methyl-1-pentene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2C (CH 3)=CH 2); The fluoro-2-hexene (CF of 4,4,5,5,6,6,6-seven 3CF 2CF 2CH=CHCH 3); The fluoro-1-hexene (CH of 4,4,5,5,6,6,6-seven 2=CHCH 2CF 2C 2F 5); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4-seven 3CF 2CF=CFC 2H 5); 4,5,5,5-tetra-fluoro-4-(trifluoromethyl)-1-amylene (CH 2=CHCH 2CF (CF 3) 2); 1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylene (CF 3CF=CHCH (CF 3) (CH 3)); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CFC 2H 5); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3And CF (PEVE) 2=CFOCF 3(PMVE).
Being specially adapted to the fluoroolefins of the composition comprising the flammable refrigeration agent of at least one and at least one fluoroolefins, is non-flammable fluoroolefins itself.The combustibility of fluoroolefins seems relevant with number of hydrogen atoms with the number of fluorine atoms in molecule.Following equation can calculate the flammable factor, is used as the flammable index of prediction.
In formula:
Number of fluorine atoms in F=molecule;
Number of hydrogen atoms in H=molecule.
Because the measuring of some compound is flammable, the cutoff value (cut-off) of the flammable factor of non-flammable fluoroolefins is determined.Fluoroolefins by with electronics ignition source in ASHRAE (U.S. heating, refrigeration and air-conditioning man IEEE, American Society ofHeating, Refrigerating and Air-Conditioning Engineers, carry out testing to determine to be that flammable also right and wrong are flammable under the condition of Inc.) standard 34-2001 (under ASTM (American Society Testing and Materials, American Society of Testing andMaterials) E681-01) defined.This flammability test uses test compounds under 101kPa (14.7psia) and specified temperature (usual 100 DEG C (212 °F)), carry out with concentration in different air, to determine the aerial lean flammability of this test compound (LFL) and/or upper limit of flammability (UFL).
Table 4 lists the flammable factor of several fluoroolefins and measuring result that is flammable or non-combustible.Therefore, in measurable other fluoroolefins disclosed by the invention, which is the in fact non-flammable fluoroolefins that combines of optimum and combustible refrigerant disclosed by the invention.
table 4
According to the numerical value of the flammable factor, can determine that the fluoroolefins listed by table 4 is that flammable right and wrong of going back are flammable.If show that the flammable factor is equal to or greater than 0.70, then can expect that these fluoroolefins right and wrong are flammable.If the flammable factor is less than 0.70, then can expect that this fluoroolefins is flammable.
In another embodiment of the invention, be selected from following fluoroolefins for becoming the fluoroolefins of composition with flammable refrigeration agent:
(a) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group;
(b) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5, and wherein the flammable factor is more than or equal to 0.70;
C () is selected from following fluoroolefins:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); 1,1,2,3,3,4,The fluoro-1-butylene (CF of 4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); The fluoro-2-amylene (CHF of 1,1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); The fluoro-1-butylene (CF of 1,1,3,3,5,5,5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); 4,4,4-tri-fluoro-3,Two (the trifluoromethyl)-1-butylene (CH of 3- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-3-methyl-2-butene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5) and 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5).
In still another embodiment, the fluoroolefins of the present invention that can be specially adapted to carry out combining with combustible refrigerant can be that at least one is selected from following fluoroolefins:
(a) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group, and wherein the flammable factor is more than or equal to 0.70;
(b) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5, and wherein the flammable factor is more than or equal to 0.70;
Although the flammable factor provides the flammable basis of some fluoroolefin compounds of prediction, but some variable may be had, as the position of hydrogen atom on molecule, some isomer that can cause given molecular formula is flammable, and other isomer then right and wrong is flammable.Therefore, the flammable factor is used as the instrument of prediction flammability properties only.
Combustible refrigerant of the present invention comprises any provable compound with making propagation of flame during air mixed under the temperature specified, pressure and composition condition.Combustible refrigerant by with electronics ignition source in ASHRAE (U.S. heating, refrigeration and air-conditioning man IEEE, AmericanSociety of Heating, Refrigerating and Air-Conditioning Engineers, carry out testing to identify under the condition of Inc.) standard 34-2001 (under ASTM (American Society Testing and Materials, American Society of Testingand Materials) E681-01) defined.This flammability test be with this refrigeration agent under 101kPa (14.7psia) and specified temperature (usual 100 DEG C (212 °F)) or room temperature (about 23 DEG C (73 °F)) with different air in concentration carry out, to determine the aerial lean flammability of this test compound (LFL) and/or upper limit of flammability (UFL).
With regard to practical situation, if certain refrigeration agent can cause catching fire when refrigeration plant or air-conditioning plant leak and touch ignition source, then combustible refrigerant can be classified as.Composition of the present invention causes the possibility of catching fire low in this leakage process.
Combustible refrigerant of the present invention comprises hydrogen fluorohydrocarbon (HFC), fluoroolefins, fluoroether, hydrocarbyl ether, hydrocarbon, ammonia (NH 3) and their combination.
Flammable HFC refrigeration agent includes but not limited to: methylene fluoride (HFC-32), fluoromethane (HFC-41), 1,1,1-Halothane (HFC-143a), 1,1,2-Halothane (HFC-143), 1,1-C2H4F2 C2H4F2 (HFC-152a), fluoroethane (HFC-161), 1,1,1-trifluoro propane (HFC-263fb), 1,1,1,3,3-pentafluoropropane (HFC-365mfc) and their combination.These are flammable, and HFC refrigeration agent available from the commercially available prod of multiple source as chemical Synesis Company, or can be prepared by synthetic method disclosed in this area.
Combustible refrigerant of the present invention also comprises and includes but not limited to following fluoroolefins: 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1-propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); The fluoro-1-propylene (HFC-1243yf) of 2,3,3-tri-; The fluoro-1-propylene (HFC-1243zf) of 3,3,3-tri-; The fluoro-1-propylene (HFC-1243yc) of 1,1,2-tri-; The fluoro-1-propylene (HFC-1243zc) of 1,1,3-tri-; The fluoro-1-propylene (HFC-1243ze) of 1,2,3-tri-fluoro-1-propylene (HFC-1243ye) and 1,3,3-tri-.
Combustible refrigerant of the present invention also comprises fluoroether, this compound and hydrogen fluorohydrocarbon similar, also containing at least one ether group Sauerstoffatom.Representational fluoroether refrigerant includes but not limited to C 4f 9oC 2h 5, it is commercially available.
Combustible refrigerant of the present invention also comprises hydrocarbon coolant.Representational hydrocarbon coolant includes but not limited to propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, 2-methylbutane (iso-pentane), tetramethylene, pentamethylene, 2,2-dimethylpropane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentanes, 2-methyl hexane, 3-methyl hexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, hexanaphthene, normal heptane, methylcyclopentane and normal hexane.Flammable hydrocarbon coolant can easily obtain from multiple commercial source.
Combustible refrigerant of the present invention also comprises hydrocarbyl ether, as dme (DME, CH 3oCH 3) and methyl tertiary butyl ether (MTBE, (CH 3) 3cOCH 3), both all can obtain from multiple commercial source.
Combustible refrigerant of the present invention also comprises ammonia (NH 3), this is a kind of compound be commercially available.
Combustible refrigerant of the present invention also can comprise the mixture exceeding a kind of refrigeration agent, as the mixture of two or more combustible refrigerants (such as two kinds of HFC or a kind of HFC and a kind of hydrocarbon), or comprise the mixture of combustible refrigerant and non-combustible refrigerant, a rear mixture carries out identifying or still can think combustible refrigerant generally with regard to practical situation under ASTM condition as herein described.
R-134a can be comprised with the example that other refrigeration agent of the present invention carries out the non-combustible refrigerant mixed, R-134, R-23, R125, R-236fa, (ASHRAE label is R401 or R-401A to R-245fa and HCFC-22/HFC-152a/HCFC-124 mixture, R-401B and R-401C), HFC-125/HFC-143a/HFC-134a mixture (ASHRAE label is R-404 or R-404A), (ASHRAE label is R407 or R-407A to HFC-32/HFC-125/HFC-134a mixture, R-407B and R-407C), HCFC-22/HFC-143a/HFC-125 mixture (ASHRAE label is R408 or R-408A), HCFC-22/HCFC-124/HCFC-142b mixture (ASHRAE label is R-409 or R-409A), HFC-32/HFC-125 mixture (ASHRAE label is R-410A) and HFC-125/HFC-143a mixture (ASHRAE label is R-507 or R507A) and carbonic acid gas.
The example exceeding a kind of mixture of combustible refrigerant comprises propane/Trimethylmethane mixture, HFC-152a/ Trimethylmethane mixture, R32/ propane mixture, R32/ Trimethylmethane mixture and HFC/ carbon dioxide mixture as HFC-152a/CO 2.
One aspect of the present invention provides global warming potential to be less than 150, is preferably less than the non-combustible refrigerant of 50.Another aspect of the present invention is by adding the combustibility that non-flammable fluoroolefins reduces described mixture to flammable mixture.
Can prove, although some refrigeration agent is flammable, non-combustible refrigerant composition can be produced by adding another kind of non-flammable compound to combustible refrigerant.The example of this non-combustible refrigerant adulterant comprises R-410A (HFC-32 is combustible refrigerant, and HFC-125 is then non-combustible) and R-407C (HFC-32 is combustible refrigerant, HFC-125 and HFC-134a is then non-combustible).
Can be used as comprising the refrigeration agent of at least one fluoroolefins and at least one combustible refrigerant or the present composition of heat-transfer fluid, non-flammable composition can be belonged to produce according to the result of ASTM E681-01 by the fluoroolefins containing significant quantity.
Comprise the present composition of at least one combustible refrigerant and at least one fluoroolefins, can containing the combustible refrigerant of 1 weight percent to the fluoroolefins of about 99 weight percents and about 99 weight percents extremely about 1 weight percent of having an appointment.
In another embodiment, the present composition can containing the combustible refrigerant of 10 weight percents to the fluoroolefins of about 80 weight percents and about 90 weight percents extremely about 20 weight percents of having an appointment.In still another embodiment, the present composition can containing the combustible refrigerant of 20 weight percents to the fluoroolefins of about 70 weight percents and about 80 weight percents extremely about 30 weight percents of having an appointment.
A what is worth mentioning embodiment of the present invention is, fluoroolefins comprises HFC-1225ye and combustible refrigerant comprises HFC-32 (methylene fluoride).Measure by ASTM 681-01 and know, the composition right and wrong comprising the HFC-32 of maximum 37 weight percents are flammable, and the composition comprising the HFC-32 of 38 weight percents or more is flammable.The invention provides and comprise the non-flammable composition of about 1.0 weight percents to the HFC-32 of about 37.0 weight percents and the about 99.0 weight percents extremely HFC-1225ye of about 63 weight percents.
An embodiment of the present invention of being worth mentioning equally is that composition comprises HFC-1225ye, HFC-32 and HFC-125.This composition of the present invention comprises about 20 weight percents to the HFC-1225ye of about 95 weight percents, about 1.0 weight percents to the HFC-32 of about 65 weight percents and about 1.0 weight percents to the HFC-125 of about 40 weight percents.In another embodiment, composition comprises about 30 weight percents to the HFC-1225ye of about 90 weight percents, about 5.0 weight percents to the HFC-32 of about 55 weight percents and about 1.0 weight percents to the HFC-125 of about 35 weight percents.In still another embodiment, composition comprises about 40 weight percents to the HFC-1225ye of about 85 weight percents, about 10 weight percents to the HFC-32 of about 45 weight percents and about 1.0 weight percents to the HFC-125 of about 28 weight percents.Containing the flammable composition of those compositions contemplated right and wrong of HFC-32 being less than about 40 weight percents.Depend on the relative proportion of HFC-1225ye and HFC-125 existed in composition, this limit of combustibility can change from the HFC-32 being less than about 45 weight percents to the HFC-32 being less than about 37 weight percents.
In another what is worth mentioning embodiment, combustible refrigerant comprises HFC-1243zf, and non-flammable fluoroolefins is intended to the combustibility reducing overall composition.Composition can comprise the HFC-1225ye of about 1.0 weight percents to the HFC-1243zf of about 99 weight percents and about 99 weight percents extremely about 1.0 weight percents.Or composition can comprise the HFC-1225ye of about 40 weight percents to the HFC-1243zf of about 70 weight percents and about 60 weight percents extremely about 30 weight percents.
In another what is worth mentioning embodiment, composition comprises the HFC-1243zf of about 1.0 weight percents to about 98 weight percents; About 1.0 weight percents are to the HFC-125 of the HFC-1225ye of about 98 weight percents and about 1.0 weight percents extremely about 50 weight percents.Or composition comprises about 40 weight percents to the HFC-1243zf of about 70 weight percents, about 20 weight percents to the HFC-1225ye of about 60 weight percents and about 1.0 weight percents to the HFC-125 of about 10 weight percents.
In another what is worth mentioning embodiment, composition comprises the HFC-1243zf of about 1.0 weight percents to about 98 weight percents; About 1.0 weight percents are to the HFC-1225ye of about 98 weight percents; About 1.0 weight percents are to the HFC-32 of about 50 weight percents.In still another embodiment, composition comprises about 40 weight percents to the HFC-1243zf of about 70 weight percents, about 20 weight percents to the HFC-1225ye of about 60 weight percents and about 1.0 weight percents to the HFC-32 of about 10 weight percents.
In another what is worth mentioning embodiment, composition comprises the HFC-1243zf of about 1.0 weight percents to about 97 weight percents; About 1.0 weight percents are to the HFC-1225ye of about 97 weight percents; About 1.0 weight percents are to the HFC-32 of the HFC-125 of about 50 weight percents and about 1.0 weight percents extremely about 50 weight percents.
Or composition comprises the HFC-1243zf of about 40 weight percents to about 70 weight percents; About 20 weight percents are to the HFC-1225ye of about 60 weight percents; About 1.0 weight percents are to about 10 weight percent HFC-125 and about 1.0 weight percents to the HFC-32 of about 10 weight percents.
The invention still further relates to the flammable method reducing combustible refrigerant, described method comprises and being mixed with at least one fluoroolefins by combustible refrigerant.The amount of the fluoroolefins added must be significant quantity, measures the non-flammable composition of genus to produce by ASTM 681-01.
Composition of the present invention can combinationally use with siccative, so that dry-off moisture in refrigeration, air-conditioning or heat pump.Siccative can comprise activated alumina, silica gel or zeolite-based molecular sieves.Representational molecular sieve comprises MOLSIV XH-7, XH-6, XH-9 and XH-11 (UOP LLC, Des Plaines, IL), for the less refrigeration agent of molecular size as HFC-32, preferred XH-11 siccative.
Composition of the present invention also can comprise at least one lubricant.Lubricant of the present invention comprises those lubricants being applicable to refrigeration or air-conditioning plant.In the middle of these lubricants, have conventional for adopting those lubricants of the compression refrigerating apparatus of chlorofluorocarbon refrigerant.This lubricant and their characteristic are at 1990ASHRAE Handbook, Refrigeration Systems andApplications (refrigeration system and application), 8th chapter, title " Lubricants in RefrigerationSystems (lubricant in refrigeration system) ", have discussion in 8.1-8.21 page, this section of document is incorporated herein by reference.Lubricant of the present invention can comprise those lubricants that compression refrigeration lubricating area is commonly referred to as " mineral oil ".Mineral oil comprises paraffin (i.e. straight chain and branched-chain saturated hydrocarbon), cycloalkanes (i.e. cyclic paraffins) and aromatic hydrocarbons (namely containing one or more with the unsaturated cyclic hydrocarbon replacing the ring that double bond is feature).Lubricant of the present invention also comprises those lubricants that compression refrigeration lubricating area is commonly referred to as " synthetic oil ".Synthetic oil comprises alkylaryl material (i.e. straight chain and branched-chain alkyl alkylbenzene), synthesis paraffin and cycloalkanes and poly-(alhpa olefin).Representative traditional lubrication agent of the present invention be commercially available BVM 100N (paraffinic mineral oil, BVA Oils sells), 3GS and 5GS (naphthenic mineral oil, Crompton Co. sells), 372LT (naphthenic mineral oil, Pennzoil sells), rO-30 (naphthenic mineral oil, CalumetLubricants sells), 75, 150 Hes 500 (linear alkylbenzenes, Shrieve Chemicals sells) and HAB 22 (branched alkylbenzene, Nippon Oil sells).
Lubricant of the present invention also comprise be designed to fluoroether refrigerant and with refrigeration agent of the present invention those lubricants mixable under the operational condition of compression refrigeration and air-conditioning plant.This lubricant and their character are at " Synthetic Lubricants and High-PerformanceFluids (synthetic lubricant and high efficiency fluid) ", R.L.Shubkin (editor), Marcel Dekker, has discussion in 1993.This lubricant include but not limited to polyol ester (POE) as 100 (Castrol, United Kingdom), polyalkylene glycol (PAG) are as RL-488A (DowChemical, Midland, Michigan) and polyvingl ether (PVE).
Lubricant of the present invention is that the environment that requirement by considering given compressor and lubricant will be exposed to carries out selecting.
Optionally can add conventional refrigeration system additives to composition of the present invention as required, to improve oilness and system stability.These additives are that refrigeration compressor lubricating area is known, comprise anti-wear agent, extreme pressure lubricant, corrosion and oxidation retarder, metal surface deactivators, foam and or anti-foaming control agent, leak detectants etc.In general, these additives are only a small amount of relative to overall lubricant composition exists.The working concentration of often kind of additive is normally from being less than about 0.1% to as high as about 3%.These additives carry out selecting on the basis that different system requires.Some representative instances of these additives can include but not limited to the additive strengthening lubrication, as alkyl ester or the aryl ester of phosphoric acid and thiophosphate.In addition, other member also composition used in the present invention of metal dialkyldithiophosphate (such as zinc dialkyl dithiophosphate or ZDDP, Lubrizol 1375) and this class chemical.Other anti-wear agent comprises natural product oil (natural product oil) and asymmetric poly-hydroxy slip additive as Synergol TMS (International Lubricants).Equally, the stablizers such as such as antioxidant, free-radical scavengers and dehydrating agent (drying compound) can also be adopted.This additive includes but not limited to Nitromethane 99Min., hindered phenol (as Butylated Hydroxytoluene or BHT), azanol, mercaptan, phosphite, epoxide or lactone.Dehydrating agent includes but not limited to that ortho ester is as trimethyl orthoformate, triethyl orthoformate or tripropyl orthoformate.The combination of single additive or additive can be used.
In one embodiment, the invention provides and comprise the composition that at least one fluoroolefins and at least one are selected from following stablizer: thiophosphatephosphorothioate, butylated triphenyl thiophosphatephosphorothioate, organophosphate, dialkylthiophosphate esters, terpene, terpenoid, soccerballene, functionalized perfluoropolyether, polyoxyalkylated aromatic substances (polyoxyalkylated aromatics), epoxide, fluorinated epoxide, trimethylene oxide, xitix, mercaptan, lactone, thioether, Nitromethane 99Min., alkyl silane, methanone derivatives, aromatic yl sulfide, terephthalic acid divinyl ester, terephthaldehyde's diphenyl phthalate, alkylamine, hindered amine antioxidant and phenol.Alkylamine can comprise other member of triethylamine, Tributylamine, Diisopropylamine, tri-isopropyl amine, tri-isobutylamine and this kind of alkyl ammonium compounds.
In another embodiment, stablizer of the present invention can comprise the concrete combination of each stablizer.A what is worth mentioning combination of stabilizers comprises at least one terpene or terpenoid.These terpenes or terpenoid can mix with the compound that at least one is selected from epoxide, fluorinated epoxide and trimethylene oxide.
Terpene is being the hydrocarbon compound of feature containing repeating the structure of isoprene (2-methyl isophthalic acid, 3-divinyl) unit more than one.Terpene can be acyclic or ring-type.Representational terpene includes but not limited to myrcene (pungent-1, the 7-diene of 2-methyl-6-methylene radical), alloocimene, β-ocimene, terebene, limonene (or (R)-4-isopropenyl-1-methyl-1-cyclohexene), retinene, firpene (or α-pinene), menthol, Geraniol, farnesol, phytol, vitamin A, terpinene, δ-3-carene, terpinolene, phellandrene, fenchene and their mixture.Terpene stablizer is commercially available, or prepares by method well known in the art or be separated from natural origin.
Terpenoid is with containing repeating natural product that the structure of isoprene unit is feature and related compound more than one and optional containing aerobic.Representational terpenoid comprises carotenoid as Lyeopene (CAS reg.no. [502-65-8]), β-carotene (CAS reg.no. [7235-40-7]) and xenthophylls and zeaxanthin (CAS reg.no. [144-68-3]); Retinoids is as vitamin A epoxide (CAS reg.no. [512-39-0]) and isotretinoin (CAS reg.no. [4759-48-2]); Abietane (CAS reg.no. [640-43-7]); Ambrosane (CAS reg.no. [24749-18-6]); Aristolane (CAS reg.no. [29788-49-6]); Ah 's alkane (CAS reg.no. [24379-83-7]); Beyerane (CAS reg.no. [2359-83-3]), bisabolane (CAS reg.no. [29799-19-7]); Camphane (CAS reg.no. [464-15-3]); Caryophyllane (CAS reg.no. [20479-00-9]); Cedrane (CAS reg.no. [13567-54-9]); Dammarane (CAS reg.no. [545-22-2]); Drimane (CAS reg.no. [5951-58-6]); Eremophilane (CAS reg.no. [3242-05-5]); Eudesmane (CAS reg.no. [473-11-0]); Fenchane (CAS reg.no. [6248-88-0]); Gammacerane (CAS reg.no. [559-65-9]); Germacrane (CAS reg.no. [645-10-3]); Gibberellane (CAS reg.no. [6902-95-0]); Grayanotoxane (CAS reg.no. [39907-73-8]); Guainane (CAS reg.no. [489-80-5]); Cedrane (CAS reg.no. [20479-45-2]); Humulane (CAS reg.no. [471-62-5]); Humulane (CAS reg.no. [430-19-3]); Kaurane (CAS reg.no. [1573-40-6]); Ladanum alkane (CAS reg.no. [561-90-0]); Lanostane (CAS reg.no. [474-20-4]); Lupinane (CAS reg.no. [464-99-3]); P-menthane (CAS reg.no. [99-82-1]); Volatile oil (CAS reg.no. [471-67-0]); Ophiobolane (CAS reg.no. [20098-65-1]); Picrasane (CAS reg.no. [35732-97-9]); Pimarane (CASreg.no. [30257-03-5]); Pinane (CAS reg.no. [473-55-2]); Podocarpane (CASreg.no. [471-78-3]); Protostane (CAS reg.no. [70050-78-1]); Rose alkane (CASreg.no. [6812-82-4]); Taxan (CAS reg.no. [1605-68-1]); Thujane (CASreg.no. [471-12-5]); Spore bacterium alkane (CAS reg.no. [24706-08-9]) and aromadendrane (CASreg.no. [464-93-7]).Terpenoid of the present invention is commercially available, or prepares by method well known in the art or can be separated from natural origin.
In one embodiment, terpene or terpenoid stablizer can be mixed with at least one epoxide.Representational epoxide comprises 1,2 epoxy prapane (CAS reg.no. [75-56-9]), 1,2-butylene oxide ring (CAS reg.no. [106-88-7]) or their mixture.
In another embodiment, terpene of the present invention or terpenoid stablizer can be mixed with at least one fluorinated epoxide.Fluorinated epoxide of the present invention can as shown in Equation 3, wherein R 2to R 5in each is the alkyl of H, 1-6 carbon atom or the fluoro-alkyl of 1-6 carbon atom, condition is R 2to R 5in at least one is fluoroalkyl group.
Formula 3
Representational fluorinated epoxide stablizer includes but not limited to trifluoromethyl oxyethane and two (trifluoromethyl) oxyethane of 1,1-.This compound is prepared by method well known in the art, such as, pass through journal of Fluorine Chemistry, 24 volumes, 93-104 page (1984), journal of Organic Chemistry, 56 volumes, 3187-3189 page (1991) and journal of fluorine Chemistry, 125 volumes, the method described in 99-105 page (2004) preparation.
In another embodiment, terpene of the present invention or terpenoid stablizer can be mixed with at least one trimethylene oxide.Trimethylene oxide stablizer of the present invention can be the compound with one or more oxetane groups, as shown in Equation 4, and wherein R 1-R 6identical or different, hydrogen, alkyl or substituted alkyl, aryl or substituted aryl can be selected from.
Formula 4
Representational trimethylene oxide stablizer includes but not limited to that 3-ethyl-3-methylol-trimethylene oxide is as OXT-101 (Toagosei Co., Ltd), 3-ethyl-3-((phenoxy group) methyl)-trimethylene oxide is as OXT-211 (Toagosei Co., Ltd) and 3-ethyl-3-((2-ethyl-hexyloxy) methyl)-trimethylene oxide as OXT-212 (Toagosei Co., Ltd).
Another what is worth mentioning embodiment is the combination of stabilizers comprising soccerballene.The compound that fullerene stabilizers and at least one can be selected from epoxide, fluorinated epoxide and trimethylene oxide mixes.Epoxide, fluorinated epoxide and the trimethylene oxide carrying out with soccerballene mixing is supplied to supply epoxide, fluorinated epoxide and the trimethylene oxide carrying out with terpene or terpenoid mixing as previously described.
Another what is worth mentioning embodiment is the combination of stabilizers comprising phenol.The compound that phenolic stabilizers and at least one can be selected from epoxide, fluorinated epoxide and trimethylene oxide combines.Epoxide, fluorinated epoxide and the trimethylene oxide carrying out with phenol combining is supplied to supply epoxide, fluorinated epoxide and the trimethylene oxide carrying out with terpene or terpenoid combining as previously described.
Phenolic stabilizers comprises any substituted or unsubstituted oxybenzene compound, described oxybenzene compound comprises and comprises one or more substituted or unsubstituted ring-type, the substituent phenol of straight or branched aliphatic series, as alkylation list phenol, comprise 2,6-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol, 2,4 dimethyl 6 tert butyl phenol, tocopherol etc., quinhydrones and alkvlated hvdroquinones, comprise tertiary butylated hydroquinone, other hydroquinone derivatives etc., Hvdroxvlated thiodiphenvl ether, comprises 4,4 '-thiobis (2-methyl-6-tert-butylphenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol) etc., alkylidene bisphenols, comprise 4, 4 '-methylene-bis (2, 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 '-methylene-bis(4-ethyl-6-t-butyl phenol), 2, 2 '-methylene-bis (4-methyl-6-tert-butylphenol), 4, 4-butylidene-bis(3-methyl-6-t-butyl phenol), 4, 4-isopropylidene two (2, 6-DI-tert-butylphenol compounds), 2, 2 '-methylene-bis(4-methyl-6-nonyl phenol), 2, 2 '-isobutylene two (4, 6-xylenol, 2, 2 '-methylene-bis (4-methyl-6-cyclohexylphenol, 2,2-or 4,4-'-biphenyl diphenol, comprise 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), Butylated Hydroxytoluene (BHT), comprise heteroatomic bis-phenol, comprise 2,6-, bis--uncle-alpha-alpha-dimethyl amino-p-cresol, 4,4-thiobiss (the 6-tertiary butyl-meta-cresol) etc., acyl aminophenols, 2,6-di-t-butyl-4 (N, N '-dimethyl amino methyl phenol), sulfide, comprises two (3-methyl-4-hydroxyl-5-t-butylbenzyl) sulfide, two (3,5-di-tert-butyl-4-hydroxyl benzyl) sulfide etc.
In one embodiment of the invention, these comprise terpene or terpenoid or soccerballene or phenol and at least one and are selected from epoxide, the combination of stabilizers of the compound of fluorinated epoxide and trimethylene oxide, also can comprise and be selected from following other stabilizer compounds: two (benzylidene hydrazine) (areoxalyl bis (benzylidene) hydrazide) (the CAS reg.no.6629-10-3) of oxalyl, N, N '-bis-(3, 5-di-t-butyl-4-hydroxyhydrocinnamoyl hydrazine) (CAS reg.no.32687-78-8), 2, 2 '-oxamidobis-ethyl-(3, 5-d-tertiary butyl-4-hydroxy hydrogenated cinnamate) (CAS reg.no.70331-94-1), N, N '-(two salicylidenes)-1, 2-propylene diamine (CAS reg.no.94-91-1) and ethylenediamine tetraacetic acid (EDTA) (CAS reg.no.60-00-4) and salt thereof.
In another embodiment of the invention, these comprise the combination of stabilizers that terpene or terpenoid or soccerballene or phenol and at least one are selected from the compound of epoxide, fluorinated epoxide and trimethylene oxide, also can comprise at least one and be selected from following alkylamine: triethylamine, Tributylamine, tri-isopropyl amine, diisobutylamine, tri-isopropyl amine, tri-isobutylamine and hindered amine antioxidant.
Composition of the present invention also can comprise compound as tracer agent or composition, and described compound or composition are selected from hydrogen fluorohydrocarbon (HFC), deuteroparaffin, deuterated hydrofluorocarbons, perfluoroparaffin, fluoroether, brominated compound, iodinated compounds, alcohol, aldehyde, ketone, nitrous oxide (N 2and their combination O).For the composition that tracer agent of the present invention is different from the composition being used as refrigeration agent or heat-transfer fluid, join in refrigeration agent and heat transfer fluid composition with predetermined amount, so that any dilution of detection composition, pollution or other changing conditions, this U.S. Patent Application Serial 11/062 submitted on February 18th, 2005, has description in 044.
The typical tracer compounds for the present composition listed by table 5.
table 5
Compound listed by table 5 is commercially available (chemically product supply firm), or prepares by method well known in the art.
Each single tracer compounds can use with the refrigerating/heating combination of fluids in the present composition, or multiple tracer compounds can combine with any ratio, as tracer agent adulterant.Tracer agent adulterant can containing from the multiple tracer compounds of similar compound, or from the multiple tracer compounds of inhomogeneity compound.Such as, tracer agent adulterant can contain 2 kinds or multiple deuterated hydrofluorocarbons, or the combination of a kind of deuterated hydrofluorocarbons and one or more perfluoroparaffins.
In addition, some compounds in table 4 exist with the form of various structures isomer or optically active isomer.The individual isomer of same compound or multiple isomer can use with any ratio, to prepare tracer compounds.In addition, given one or more isomer of compound list can combine with any ratio, as tracer agent adulterant with other compound any amount of.
Tracer compounds or tracer agent adulterant with about 50ppm (1,000,000/, the total concn by weight) to about 1000ppm is present in composition.Preferably, tracer compounds or tracer agent adulterant exist with the total concn of about 50ppm to about 500ppm, and most preferably tracer compounds or tracer agent adulterant exist with the total concn of about 100ppm to about 300ppm.
Composition of the present invention also can comprise ultraviolet (UV) dyestuff and optionally comprise solubilizing agent.UV dyestuff is the useful component of the leakage detecting refrigerant composition or heat-transfer fluid, and it is that fluorescence by allowing people can observe the refrigeration agent near leakage point in refrigeration, air-conditioning, thermal-pump unit or leakage point or the dyestuff in heat transfer fluid composition detects leakage.People can observe the fluorescence of dyestuff under ultraviolet lamp.Because the solubleness of this UV dyestuff in some refrigeration agents and heat-transfer fluid is low, solubilizing agent may be needed.
So-called " ultraviolet " dyestuff refers to can the UV fluorescent composition of light in the ultraviolet of electromagnetic wave absorption frequency spectrum or " closely " ultraviolet region.Can be detected by the fluorescence that ultra-violet fluorescent dye can produce under the ultra violet lamp of emission wavelength for the radiation between 10nm to 750nm.Therefore, if the refrigeration agent containing this ultra-violet fluorescent dye or heat-transfer fluid leak out from the set point refrigeration, air-conditioning or thermal-pump unit, fluorescence can be detected near this leakage point or this leakage point.This ultra-violet fluorescent dye includes but not limited to derivative or their combination of naphthalimide, perylene, tonka bean camphor, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein and described dyestuff.Solubilizing agent of the present invention comprises at least one and is selected from following compound: hydrocarbon, hydrocarbyl ether, polyoxyalkylene glycol ether, acid amides, nitrile, ketone, chlorocarbon, ester, lactone, aryl ethers, fluoroether and 1,1,1-trifluoroalkanes.
The hydrocarbon that hydrocarbon solubilizing agent of the present invention comprises comprises the carbon atom containing less than 16 or 16 and only has hydrogen and without the straight chain of other functional group, side chain or cyclic alkane or alkene.Representational hydrocarbon solubilizing agent comprises propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, octane, decane and n-Hexadecane.Be to be noted that then solubilizing agent can not be same hydrocarbon if refrigeration agent is certain hydrocarbon.
Hydrocarbon ether solubilizing agents of the present invention comprises the ether of a carbon containing, hydrogen and oxygen as dme (DME).
Polyoxyalkylene glycol ether solubilizing agent of the present invention is by formula R 1[(OR 2) xoR 3] yshown in, wherein: x is the integer of 1-3; Y is the integer of 1-4; R 1be selected from hydrogen and the aliphatic hydrocarbyl with 1-6 carbon atom and y bonding point; R 2be selected from the aliphatic hydrocarbylene with 2-4 carbon atom; R 3be selected from hydrogen and aliphatic hydrocarbyl and the alicyclic hydrocarbon radical with 1-6 carbon atom; R 1and R 3in at least one is described alkyl; And the molecular weight of wherein said polyoxyalkylene glycol ether is about 100 to about 300 atomic mass units.Bonding point used herein refers to the group site that can supply to form covalent linkage with other group.Alkylene refers to bivalent hydrocarbon radical.In the present invention, preferred polyoxyalkylene glycol ether solubilizing agent is by formula R 1[(OR 2) xoR 3] yshown in: x is preferably 1-2; Y is preferably 1; R 1and R 3the preferred aliphatic hydrocarbyl being independently selected from hydrogen and there is 1-4 carbon atom; R 2be preferably selected from the aliphatic hydrocarbylene with 2 or 3 carbon atoms, most preferably 3 carbon atoms; Described polyoxyalkylene glycol ether molecular weight is preferably about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units.There is the R of 1-6 carbon atom 1and R 3alkyl can be straight chain, side chain or ring-type.Representational R 1and R 3alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl and cyclohexyl.Free hydroxyl group on polyoxyalkylene glycol ether solubilizing agent of the present invention may with some compression refrigerating apparatus constituent material (such as ) in inconsistent situation, R 1and R 3preferably there is the aliphatic hydrocarbyl of 1-4 carbon atom, most preferably 1 carbon atom.There is the R of 2-4 carbon atom 2aliphatic hydrocarbylene forms the oxyalkylene group-(OR repeated 2) x-, described alkylidene oxide comprises oxy ethylene, oxypropylene and oxybutylene.R is comprised in a polyoxyalkylene glycol ether solubilizing agent molecule 2alkylidene oxide can be identical, or molecule can containing different R 2alkylidene oxide.Polyoxyalkylene glycol ether solubilizing agent of the present invention preferably comprises at least one oxypropylene.At R 1for having in 1-6 carbon atom and the aliphatic hydrocarbyl of y bonding point or the situation of alicyclic hydrocarbon radical, this group can be straight chain, side chain or ring-type.The representational R with two bonding points 1aliphatic hydrocarbyl comprises such as ethylidene, propylidene, butylidene, pentylidene, hexylidene, cyclopentylidene and cyclohexylidene.The representational R with three or four bonding points 1aliphatic hydrocarbyl comprises the residue by the hydroxyl of removing polyvalent alcohol from this polyol derivative, and described polyvalent alcohol is as TriMethylolPropane(TMP), glycerine, tetramethylolmethane, 1,2,3-trihydroxy-hexanaphthene and 1,3,5-trihydroxy-hexanaphthene.
Representational polyoxyalkylene glycol ether solubilizing agent includes but not limited to CH 3oCH 2cH (CH 3) O (H or CH 3) (propylene glycol methyl (or dimethyl) ether), CH 3o [CH 2cH (CH 3) O] 2(H or CH 3) (dipropylene glycol methyl (or dimethyl) ether), CH 3o [CH 2cH (CH 3) O] 3(H or CH 3) (tripropylene glycol methyl (or dimethyl) ether), C 2h 5oCH 2cH (CH 3) O (H or C 2h 5) (propylene glycol ethyl (or diethyl) ether), C 2h 5o [CH 2cH (CH 3) O] 2(H or C 2h 5) (dipropylene glycol ethyl (or diethyl) ether), C 2h 5o [CH 2cH (CH 3) O] 3(H or C 2h 5) (tripropylene glycol ethyl (or diethyl) ether), C 3h 7oCH 2cH (CH 3) O (H or C 3h 7) (propylene glycol n-propyl (or diη-propyl) ether), C 3h 7o [CH 2cH (CH 3) O] 2(H or C 3h 7) (dipropylene glycol n-propyl (or diη-propyl) ether), C 3h 7o [CH 2cH (CH 3) O] 3(H or C 3h 7) (tripropylene glycol n-propyl (or diη-propyl) ether), C 4h 9oCH 2cH (CH 3) OH (propylene glycol n-butyl ether), C 4h 9o [CH 2cH (CH 3) O] 2(H or C 4h 9) (dipropylene glycol normal-butyl (or di-n-butyl) ether), C 4h 9o [CH 2cH (CH 3) O] 3(H or C 4h 9) (tripropylene glycol normal-butyl (or di-n-butyl) ether), (CH 3) 3cOCH 2cH (CH 3) OH (propylene glycol t-butyl ether), (CH 3) 3cO [CH 2cH (CH 3) O] 2(H or (CH 3) 3) (the dipropylene glycol tertiary butyl (or di-t-butyl) ether), (CH 3) 3cO [CH 2cH (CH 3) O] 3(H or (CH 3) 3) (the tripropylene glycol tertiary butyl (or di-t-butyl) ether), C 5h 11oCH 2cH (CH 3) OH (propylene glycol n-pentyl ether), C 4h 9oCH 2cH (C 2h 5) OH (butyleneglycol n-butyl ether), C 4h 9o [CH 2cH (C 2h 5) O] 2h (dibutylene glycol n-butyl ether), trimethylolpropane tris n-butyl ether (C 2h 5c (CH 2o (CH 2) 3cH 3) 3) and TriMethylolPropane(TMP) di-n-butyl ether (C 2h 5c (CH 2oC (CH 2) 3cH 3) 2cH 2oH).
The contained R of Amide solubilizing agents of the present invention 1c (O) NR 2r 3with ring-[R 4c (O) N (R 5)] shown in those acid amides, wherein R 1, R 2, R 3and R 5independently be selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-12 carbon atom; R 4be selected from the aliphatic hydrocarbylene with 3-12 carbon atom; And the molecular weight of wherein said acid amides is about 100 to about 300 atomic mass units.The molecular weight of described acid amides is preferably about 160 to about 250 atomic mass units.R 1, R 2, R 3and R 5can optionally comprise the alkyl be substituted, namely containing the group of substituents being selected from halogen (such as fluorine, chlorine) and alkoxyl group (such as methoxyl group).R 1, R 2, R 3and R 5can optionally comprise by the alkyl of hybrid atom MCM-41, the group namely containing nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom in the original group chain be made up of carbon atom.In general, for R 1-3in every 10 carbon atoms, have and be no more than three, exist preferably more than a substituents and heteroatoms, and any this substituents and heteroatomic existence must be considered when using above-mentioned molecular weight limit.Preferred Amide solubilizing agents is made up of carbon, hydrogen, nitrogen and oxygen.Representational R 1, R 2, R 3and R 5aliphatic hydrocarbyl and alicyclic hydrocarbon radical comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer.The preferred embodiment of Amide solubilizing agents is above formula ring-[R 4c (O) N (R 5r in)-] 4can by (CR 6r 7) nin other words those acid amides shown in alkylene are formula ring-[(CR 6r 7) nc (O) N (R 5)-], wherein: the values for molecular weight specified above is suitable for; N is the integer of 3-5; R 5for the saturated hydrocarbyl containing 1-12 carbon atom; R 6and R 7independently by the definition R provided above 1-3rule carry out selecting (for each n).At formula ring-[(CR 6r 7) nc (O) N (R 5in lactan shown in)-], all R 6and R 7be preferably hydrogen, or containing single saturated hydrocarbyl in the middle of this n MU (methylene unit), R 5for the saturated hydrocarbyl containing 3-12 carbon atom.Such as, 1-(saturated hydrocarbyl)-5-methylpyrrolidin-2-ketone.
Representational Amide solubilizing agents includes but not limited to 1-octyl group pyrrolidin-2-one, 1-decyl pyrrolidine-2-ketone, 1-octyl group-5-methylpyrrolidin-2-ketone, 1-butyl hexanolactam, 1-cyclohexyl pyrrolidin-2-one, 1-butyl-5-methyl piperidine-2-ketone, 1-amyl group-5-methyl piperidine-2-ketone, 1-hexyl hexanolactam, 1-hexyl-5-methylpyrrolidin-2-ketone, 5-methyl-1-pentene phenylpiperidines-2-ketone, 1, 3-lupetidine-2-ketone, 1-methyl caprolactam, 1-Butyl-pyrrol alkane-2-ketone, 1, 5-lupetidine-2-ketone, 1-decyl-5-methylpyrrolidin-2-ketone, 1-dodecyl pyrrolidine-2-ketone, N, N-dibutyl formamide and N, N-di-isopropyl ethanamide.
The contained R of ketone solubilizing agent of the present invention 1c (O) R 2shown ketone, wherein R 1and R 2independently be selected from aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl with 1-12 carbon atom, and the molecular weight of wherein said ketone is about 70 to about 300 atomic mass units.R in described ketone 1and R 2preferably independently be selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-9 carbon atom.The molecular weight of described ketone is preferably about 100 to about 200 atomic mass units.R 1and R 2alkylene can be connected to form together, thus form five yuan, hexa-atomic or seven-membered ring cyclic ketone, such as cyclopentanone, pimelinketone and suberone.R 1and R 2can optionally comprise the alkyl be substituted, namely containing the group of substituents being selected from halogen (such as fluorine, chlorine) and alkoxyl group (such as methoxyl group).R 1and R 2can optionally comprise by the alkyl of hybrid atom MCM-41, the group namely containing nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom in the original group chain be made up of carbon atom.In general, for R 1and R 2in every 10 carbon atoms, have and be no more than three, exist preferably more than a substituents and heteroatoms, and any this substituents and heteroatomic existence must be considered when using above-mentioned molecular weight limit.General formula R 1c (O) R 2in representative R 1and R 2aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer, and phenyl, benzyl, cumenyl, Lai Ji, tolyl, xylyl and styroyl.
Representational ketone solubilizing agent includes but not limited to 2-butanone, 2 pentanone, methyl phenyl ketone, phenyl propyl ketone, benzene hexanone, pimelinketone, suberone, 2-heptanone, 3-heptanone, 5 methy 12 hexanone, methyln-hexyl ketone, 3-octanone, diisobutyl ketone, 4-ethyl cyclohexanone, methyl n-heptyl ketone, butyl ketone, 2-decanone, propyl hexyl ketone, 2-decalone, 2-ten triketone, two hexanones and two pimelinketone.
The contained R of nitrile solubilizing agent of the present invention 1nitrile shown in CN, wherein R 1be selected from aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl with 5-12 carbon atom, and the molecular weight of wherein said nitrile is about 90 to about 200 atomic mass units.R in described nitrile solubilizing agent 1be preferably selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 8-10 carbon atom.The molecular weight of described nitrile solubilizing agent is preferably about 120 to about 140 atomic mass units.R 1can optionally comprise the alkyl be substituted, namely containing the group of substituents being selected from halogen (such as fluorine, chlorine) and alkoxyl group (such as methoxyl group).R 1can optionally comprise by the alkyl of hybrid atom MCM-41, the group namely containing nitrogen (azepine), oxygen (oxa-) or sulphur (thia) atom in the original group chain be made up of carbon atom.In general, for R 1in every 10 carbon atoms, have and be no more than three, exist preferably more than a substituents and heteroatoms, and any this substituents and heteroatomic existence must be considered when using above-mentioned molecular weight limit.General formula R 1representative R in CN 1aliphatic hydrocarbyl, alicyclic hydrocarbon radical and aryl comprise amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer, and phenyl, benzyl, cumenyl, Lai Ji, tolyl, xylyl and styroyl.
Representational nitrile solubilizing agent includes but not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.
The contained RCl of chlorocarbon solubilizing agent of the present invention xshown chlorocarbon, wherein: x is selected from the integer of 1 or 2; R is selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with 1-12 carbon atom; And the molecular weight of wherein said chlorocarbon is about 100 to about 200 atomic mass units.The molecular weight of described chlorocarbon solubilizing agent is preferably about 120 to about 150 atomic mass units.General formula R Cl xin representative R aliphatic hydrocarbyl and alicyclic hydrocarbon radical comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their configurational isomer.
Representational chlorocarbon solubilizing agent includes but not limited to: the chloro-3-methylpentane of 3-(chloromethyl) pentane, 3-, 1-chlorohexane, 1,6-dichloro hexane, 1-chloroheptane, 1-chloro-octane, 1-chlorononane, 1-chlorodecane and 1,1,1-trichlorodecane.
Ester solubilizing agent of the present invention comprises general formula R 1cO 2r 2shown ester, wherein R 1and R 2independently be selected from straight chain and ring-type, saturated and undersaturated alkyl and aryl.Preferred ester is made up of Elements C, H and O substantially, and molecular weight is about 80 to about 550 atomic mass units.
Representational ester includes but not limited to (CH 3) 2cHCH 2oOC (CH 2) 2-4oCOCH 2cH (CH 3) 2(diisobutyl dibasic ester), ethyl hexanoate, oil of cognac, n-butyl propionate, n propyl propionate, ethyl benzoate, n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, " Exxate 700 " (commercially available acetic acid C 7alkyl ester), " Exxate 800 " (commercially available acetic acid C 8alkyl ester), dibutyl phthalate and tert.-butyl acetate.
Lactone solubilizing agents of the present invention comprises following structure [A], the lactone shown in [B] and [C]:
[A] [B] [C]
These lactones are at six atom rings (A) or preferably in pentatomic ring (B), contain functional group-CO 2-, wherein for structure [A] and [B], R 1to R 8independently be selected from hydrogen or straight chain, side chain, ring-type, dicyclo, saturated and undersaturated alkyl.R 1to R 8each can with R 1to R 8another is connected to form ring.As in structure [C], lactone can have ring outer alkylidene group, wherein R 1to R 6independently be selected from hydrogen or straight chain, side chain, ring-type, dicyclo, saturated and undersaturated alkyl.R 1to R 6each can with R 1to R 6another is connected to form ring.The molecular weight ranges of Lactone solubilizing agents is about 80 to about 300 atomic mass units, preferably about 80 to about 200 atomic mass units.
Representational Lactone solubilizing agents includes but not limited to the compound listed by table 6.
table 6
The kinematic viscosity of Lactone solubilizing agents at 40 DEG C is less than about 7 centistokes usually.Such as at 40 DEG C, the kinematic viscosity of γ-undecalactone is 5.4 centistokes, and the kinematic viscosity of cis-(3-hexyl-5-methyl) dihydrofuran-2-ketone is 4.5 centistokes.Lactone solubilizing agents is commercially available, or the U.S. Patent application 10/910 can submitted to by August 3rd, 2004, and the method preparation described by 495, this patent application is incorporated herein by reference.
Aryl ether solubilizing agents of the present invention is contained R also 1oR 2shown aryl ethers, wherein R 1be selected from the aryl with 6-12 carbon atom; R 2be selected from the aliphatic hydrocarbyl with 1-4 carbon atom; And the molecular weight of wherein said aryl ethers is about 100 to about 150 atomic mass units.General formula R 1oR 2in representative R 1aryl comprises phenyl, xenyl, cumenyl, Lai Ji, tolyl, xylyl, naphthyl and pyridyl.General formula R 1oR 2in representative R 2aliphatic hydrocarbyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl and the tertiary butyl.Representational Aryl ether solubilizing agents includes but not limited to methyl phenyl ether (phenylmethylether), 1,3-dimethoxy benzene, ethylphenyl ether and butyl phenylate.
Fluoroether solubilizing agents of the present invention comprises general formula R 1oCF 2cF 2those fluoroethers shown in H, wherein R 1be selected from aliphatic hydrocarbyl, alicyclic hydrocarbon radical and the aryl with about 5 to about 15 carbon atoms, preferred one-level, straight chain, saturated alkyl.Representational Fluoroether solubilizing agents includes but not limited to C 8h 17oCF 2cF 2h and C 6h 13oCF 2cF 2h.Be to be noted that then solubilizing agent can not be same fluoroether if refrigeration agent is certain fluoroether.
Fluoroether solubilizing agents also can comprise the ether spread out from fluoroolefins and polyvalent alcohol.Fluoroolefins can be CF 2=CXY type, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3or OR f, wherein R ffor CF 3, C 2f 5or C 3f 7.Representational fluoroolefins is tetrafluoroethylene, chlorotrifluoroethylene, R 1216 and perfluoro methyl vinyl ether.Polyvalent alcohol can be straight chain or side chain.Straight chain polyalcohols can be HOCH 2(CHOH) x(CRR ') ycH 2oH type, wherein R and R ' is hydrogen or CH 3or C 2h 5, and wherein x is the integer of 0-4, y is the integer of 0-4.Branched chain polyol can be C (OH) t(R) u(CH 2oH) v[(CH 2) mcH 2oH] wtype, wherein R can be hydrogen, CH 3or C 2h 5, m can be the integer of 0-3, t and u can be 0 or 1, v and w be the integer of 0-4, and wherein t+u+v+w=4.Representational polyvalent alcohol is TriMethylolPropane(TMP), tetramethylolmethane, butyleneglycol and ethylene glycol.
1,1,1-Trifluoroalkane solubilizing agents of the present invention comprises general formula CF 3r 11,1,1-shown trifluoroalkanes, wherein R 1be selected from the aliphatic hydrocarbyl and alicyclic hydrocarbon radical with about 5 to about 15 carbon atoms, preferred one-level, straight chain, saturated alkyl.Representational 1,1,1-Trifluoroalkane solubilizing agents includes but not limited to 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.
Solubilizing agent of the present invention can be used as single compound to be existed, or can be used as the mixture existence exceeding a kind of solubilizing agent.The mixture of solubilizing agent can contain two kinds of solubilizing agent from similar compound, for example two kinds of lactones, or contains two kinds of solubilizing agent from the different compounds of two classes, as lactone and polyoxyalkylene glycol ether.
Comprising refrigeration agent and ultra-violet fluorescent dye or comprising in the present composition of heat-transfer fluid and ultra-violet fluorescent dye, 0.001 weight percent to about 1.0 weight percents of having an appointment are UV dyestuffs, and preferably about 0.005 weight percent is UV dyestuff to about 0.5 weight percent, most preferably 0.01 weight percent to about 0.25 weight percent.
The solubleness of these ultra-violet fluorescent dye in refrigeration agent and heat transfer compositions may be poor.Therefore, the method these dyestuffs being incorporated into refrigeration, air-conditioning or thermal-pump unit is inconvenient, expensive and time-consuming always.United States Patent (USP) RE 36,951 (it is incorporated herein by reference) describes a method, and this method adopts the dye powder of certain assembly, solid particulate or the slurries that can put into refrigeration or air-conditioning plant.Along with refrigeration agent and lubricant cycle through this device, dyestuff occurs to dissolve or disperse and be carried through this device.Also describe in document many other in order to dyestuff to be incorporated into refrigeration or the method for air-conditioning plant.
Ideally, ultra-violet fluorescent dye can be dissolved in refrigeration agent, thus is incorporated in refrigeration, air-conditioning or thermal-pump unit without any need for special method.The present invention relates to the composition comprising ultra-violet fluorescent dye, this fluorescence dye can be dissolved in refrigeration agent and being introduced in apparatus system together with solubilizing agent.Even if the present composition can allow and also to store and transport at low temperatures containing the refrigeration agent of dyestuff and heat-transfer fluid, keep dyestuff to be in solution state simultaneously.
Comprising refrigeration agent, ultra-violet fluorescent dye and solubilizing agent or comprising in the present composition of heat-transfer fluid, ultra-violet fluorescent dye and solubilizing agent, 1 to about 50 weight percent of having an appointment in total composition, preferably about 2 to about 25 weight percents, most preferably from about 5 to about 15 weight percents are the solubilizing agent in refrigeration agent or heat-transfer fluid.In the present compositions, ultra-violet fluorescent dye in refrigeration agent or heat-transfer fluid with about 0.001 weight percent to about 1.0 weight percents, preferably 0.005 weight percent is to about 0.5 weight percent, and most preferably 0.01 weight percent exists to the concentration of about 0.25 weight percent.
The solubilizing agent of such as ketone may have makes us unhappy smell, by adding mask agent or perfume compound is covered.The representative instance of mask agent or perfume compound can comprise Chinese ilex, Fresh Lemon, cherry, Chinese cassia tree, Mentha arvensis L. syn.M.haplocalyxBrig, flower (Floral) or tangerine peel (they are all commercially available), and (R)-4-isopropenyl-1-methyl-1-cyclohexene and firpene.The working concentration of this mask agent is about 0.001% of mask agent and solubilizing agent gross weight to as high as about 15%.
The invention still further relates to use and comprise the refrigeration agent of ultra-violet fluorescent dye or heat transfer fluid composition to detect the method for the leakage in refrigeration plant, air-conditioning plant or thermal-pump unit.Dyestuff existence in the composition makes it possible to detect the leakage of refrigerant in refrigeration, air-conditioning or thermal-pump unit.Leak detection can help people to notice, solve and/or the fallback of anti-locking apparatus or system or equipment failure.Leak detection can also help people to install the chemical of the operation for device.
The method comprises to refrigeration, air-conditioning or thermal-pump unit providing package are containing refrigeration agent described herein, ultra-violet fluorescent dye or comprise heat-transfer fluid described herein and ultra-violet fluorescent dye and optionally comprise the composition of solubilizing agent described herein, and adopts suitable means to detect refrigeration agent containing ultra-violet fluorescent dye.The appropriate means detecting dyestuff includes but not limited to ultraviolet lamp, and it is often called " black lamp " or " blue-ray light ".This ultraviolet lamp can obtain from the source of multiple special detection ultra-violet fluorescent dye is commercially available.Once the composition containing ultra-violet fluorescent dye be incorporated in refrigeration, air-conditioning or thermal-pump unit and allow it cycle through this apparatus system, by by described ultra violet lamp on the apparatus and observe the fluorescence of the dyestuff near any leakage point, come locating leaks point or leakage point near zone.
Mechanical refrigeration mainly applies such thermodynamic process: heat-eliminating medium reuses as refrigeration agent is recyclable after a circulation.Conventional circulation comprise steam compressed, absorb, vapour injection (steam-jet) or vapor steam blaster (steam-ejector) and air.
Vapor compression refrigeration system comprises vaporizer, compressor, condenser and expansion gear, vapor-compression cycle reuses refrigeration agent in multiple steps, produces cooling effect in one step, and produce heat effect in other step.This circulation can be summarized as follows.Liquid refrigerant enters vaporizer by expansion gear, and this liquid refrigerant at low-temperature boiling at vaporizer, forms gas and produces cooling.Low-pressure gas enters compressor and is improved pressure and temperature by compressing.Then high pressure (compression) gaseous refrigerant enters condenser generation condensation, releases heat to environment.Refrigeration agent returns expansion gear, and this liquid expand into the low pressure level vaporizer by this expansion gear from its high-pressure horizontal within the condenser, thus repeats this circulation.
Polytype compressor is had to can be used for refrigeration application.Compressor generally can be divided into reciprocating, rotary, jet-type, centrifugal, vortex, spiral or axial-flow compressor according to the mechanical system of compressed fluid, or generally can be divided into positive-displacement compressor (such as reciprocating, vortex or screw compressor) or dynamic compressors (such as centrifugal or jet-type compressor) according to the mode that mechanical organ acts on fluid to be compressed.
The present composition comprising fluoroolefins can be used for any above-mentioned compressor type.For any given compressor, the selection of refrigeration agent will depend on many factors, comprises such as boiling point and vapor pressure requirement.
Positive-displacement compressor and dynamic compressors all can be used for the inventive method.Some is comprised to the refrigerant composition of at least one fluoroolefins, radial compressor is a kind of preferred device type.
Radial compressor uses spinner member that refrigeration agent radial direction is accelerated, and generally includes and is contained in impeller in casing and diffuser (diffuser).Radial compressor sucks fluid at central inlet (central inlet) place of impeller eye (impeller eye) or convolution impeller usually, and is radially outward accelerated by fluid.In impeller, there will be certain static pressure liter, but most of voltage rise appears in the diffuser part of casing, speed is converted into static pressure there.Often organize the one-level that impeller-diffuser is compressor.Depend on required resulting pressure and refrigerant volume to be dealt with, 1-12 level or more level made by radial compressor.
The pressure ratio of compressor or compression ratio are the ratios of absolute top hole pressure and absolute intake pressure.In fact the pressure that radial compressor is sent be constant in relatively wide containment.
Positive-displacement compressor by steam suction cavity, and makes cavity volume reduce thus compressed vapour.After steam compressed, reduce to zero or force steam to leave cavity close to zero further by making the volume of cavity.Positive-displacement compression chance accumulated pressure, this pressure only bears the restriction of the intensity of pressure by volumetric efficiency and each parts.
The formula different from positive-displacement compressor, radial compressor relies on the centrifugal force of quick runner to make steam compressedly to pass through impeller completely.There is not positive displacement, but there is so-called powered compressor.
The developable pressure of radial compressor depends on the tip speed of impeller.Tip speed is the speed measured at the tip of impeller, relevant with rotations per minute with the diameter of impeller.The capacity of radial compressor determined by the size of the passage by impeller.This makes the size of compressor more depend on required pressure instead of capacity.
Because radial compressor is high-speed cruising, it is high volume, low pressure machine substantially.Radial compressor low pressure refrigerant such as trichlorofluoromethane (CFC-11) or 1,2,2-Refrigerant R 113 (CFC-113) get into smooth best.Some low-pressure refrigerant liquid of the present invention are suitable for simple and easy alternative (the drop-in replacement) that make CFC-113 in existing centrifugation apparatus.
Large radial compressor is usually with the speed operation of 3000-7000 rpm (rpm).Little turbine centrifugal compressors (miniature centrifugal compressors) is designed to carry out about 40, the high speed operation of 000 to about 70,000 (rpm), and its impeller size is little, is usually less than 0.15 meter (about 6 inches).
Can multi-stage impeller be used in radial compressor, to improve compressor efficiency, thus need less power in use.For two-stage system, be in operation, the outlet thing of first step impeller enters the suction import of the second impeller.These two impellers can operate with single axle.Every grade of compression ratio that can accumulate about 4:1; That is, absolute top hole pressure can be four times of absolute suction pressure.US 5,065,990 and US 5,363,674 describes several examples of two-stage centrifugal compressor system (especially for automobile), and these two patents are incorporated herein by reference.
The invention still further relates to the method producing heating or cooling in refrigeration, air-conditioning or thermal-pump unit, described method comprises in described device refrigeration agent or heat transfer fluid composition being incorporated into and having (a) radial compressor, (b) multistage centrifugal compressor or (c) veneer/single-pass exchanger; Wherein said refrigeration agent or heat transfer fluid composition comprise at least one and are selected from following fluoroolefins:
(i) formula E-or Z-R 1cH=CHR 2fluoroolefins, wherein R 1and R 2independent is C 1-C 6perfluoro alkyl group;
(ii) formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5; Or
(iii) following fluoroolefins is selected from:
The fluoro-1-propylene (CF of 1,2,3,3,3-five 3CF=CHF); The fluoro-1-propylene (CF of 1,1,3,3,3-five 3CH=CF 2); The fluoro-1-propylene (CHF of 1,1,2,3,3-five 2CF=CF 2); 1,2,3,3-tetrafluoro-1-propene (CHF 2CF=CHF); 2,3,3,3-tetrafluoro-1-propene (CF 3CF=CH 2); 1,3,3,3-tetrafluoro-1-propene (CF 3CH=CHF); 1,1,2,3-tetrafluoro-1-propene (CH 2FCF=CF 2); 1,1,3,3-tetrafluoro-1-propene (CHF 2CH=CF 2); The fluoro-1-propylene (CHF of 2,3,3-tri- 2CF=CH 2); The fluoro-1-propylene (CF of 3,3,3-tri- 3CH=CH 2); The fluoro-1-propylene (CH of 1,1,2-tri- 3CF=CF 2); The fluoro-1-propylene (CH of 1,1,3-tri- 2FCH=CF 2); The fluoro-1-propylene (CH of 1,2,3-tri- 2FCF=CHF); The fluoro-1-propylene (CHF of 1,3,3-tri- 2CH=CHF); 1,1,1,2,3,4,4,4-octafluoro-2-butylene (CF 3CF=CFCF 3); 1,1,2,3,3,4,4,4-octafluoro-1-butylene (CF 3CF 2CF=CF 2); The fluoro-2-butylene (CF of 1,1,1,2,4,4,4-seven 3CF=CHCF 3); The fluoro-1-butylene (CHF=CFCF of 1,2,3,3,4,4,4-seven 2CF 3); The fluoro-2-butylene (CHF of 1,1,1,2,3,4,4-seven 2CF=CFCF 3); 1,3,3,3-tetra-fluoro-2-(trifluoromethyl)-1-propylene ((CF 3) 2C=CHF); The fluoro-1-butylene (CF of 1,1,3,3,4,4,4-seven 2=CHCF 2CF 3); The fluoro-1-butylene (CF of 1,1,2,3,4,4,4-seven 2=CFCHFCF 3); The fluoro-1-butylene (CF of 1,1,2,3,3,4,4-seven 2=CFCF 2CHF 2); 2,3,3,4,4,4-hexafluoro-1-butylene (CF 3CF 2CF=CH 2); 1,3,3,4,4,4-hexafluoro-1-butylene (CHF=CHCF 2CF 3); 1,2,3,4,4,4-hexafluoro-1-butylene (CHF=CFCHFCF 3); 1,2,3,3,4,4-hexafluoro-1-butylene (CHF=CFCF 2CHF 2); 1,1,2,3,4,4-hexafluoro-2-butylene (CHF 2CF=CFCHF 2); 1,1,1,2,3,4-hexafluoro-2-butylene (CH 2FCF=CFCF 3); 1,1,1,2,4,4-hexafluoro-2-butylene (CHF 2CH=CFCF 3); 1,1,1,3,4,4-hexafluoro-2-butylene (CF 3CH=CFCHF 2); 1,1,2,3,3,4-hexafluoro-1-butylene (CF 2=CFCF 2CH 2F); 1,1,2,3,4,4-hexafluoro-1-butylene (CF 2=CFCHFCHF 2); 3,3,3-tri-fluoro-2-(trifluoromethyl)-1-propylene (CH 2=C (CF 3) 2); The fluoro-2-butylene (CH of 1,1,1,2,4-five 2FCH=CFCF 3); 1,1,1,3,The fluoro-2-butylene (CF of 4-five 3CH=CFCH 2F); The fluoro-1-butylene (CF of 3,3,4,4,4-five 3CF 2CH=CH 2); The fluoro-2-butylene (CHF of 1,1,1,4,4-five 2CH=CHCF 3); The fluoro-2-butylene (CH of 1,1,1,2,3-five 3CF=CFCF 3); The fluoro-1-butylene (CH of 2,3,3,4,4-five 2=CFCF 2CHF 2); The fluoro-2-butylene (CHF of 1,1,2,4,4-five 2CF=CHCHF 2); The fluoro-1-butylene (CH of 1,1,2,3,3-five 3CF 2CF=CF 2); The fluoro-2-butylene (CH of 1,1,2,3,4-five 2FCF=CFCHF 2); The fluoro-2-methyl-1-propylene (CF of 1,1,3,3,3-five 2=C (CF 3) (CH 3)); The fluoro-1-propylene (CH of 2-(difluoromethyl)-3,3,3-three 2=C (CHF 2) (CF 3)); 2,3,4,4,The fluoro-1-butylene (CH of 4-five 2=CFCHFCF 3); The fluoro-1-butylene (CHF=CFCH of 1,2,4,4,4-five 2CF 3); The fluoro-1-butylene (CHF=CHCHFCF of 1,3,4,4,4-five 3); The fluoro-1-butylene (CHF=CHCF of 1,3,3,4,4-five 2CHF 2); The fluoro-1-butylene (CHF=CFCHFCHF of 1,2,3,4,4-five 2); The fluoro-1-butylene (CH of 3,3,4,4-tetra- 2=CHCF 2CHF 2); 1,1-bis-fluoro-2-(difluoromethyl)-1-propylene (CF 2=C (CHF 2) (CH 3)); The fluoro-2-methyl-1-propylene (CHF=C (CF of 1,3,3,3-tetra- 3) (CH 3)); The fluoro-1-propylene (CH of 2-difluoromethyl-3,3-two 2=C (CHF 2) 2); The fluoro-2-butylene (CF of 1,1,1,2-tetra- 3CF=CHCH 3); The fluoro-2-butylene (CH of 1,1,1,3-tetra- 3CF=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5,5-ten 3CF=CFCF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5,5-ten 2=CFCF 2CF 2CF 3); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCF 3); The fluoro-2-amylene (CF of 1,1,1,2,4,4,5,5,5-nine 3CF=CHCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,3,4,4,5,5,5-nine 3CH=CFCF 2CF 3); The fluoro-1-amylene (CHF=CFCF of 1,2,3,3,4,4,5,5,5-nine 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,3,3,4,4,5,5,5-nine 2=CHCF 2CF 2CF 3); The fluoro-1-amylene (CF of 1,1,2,3,3,4,4,5,5-nine 2=CFCF 2CF 2CHF 2); 1,The fluoro-2-amylene (CHF of 1,2,3,4,4,5,5,5-nine 2CF=CFCF 2CF 3); The fluoro-2-amylene (CF of 1,1,1,2,3,4,4,5,5-nine 3CF=CFCF 2CHF 2); The fluoro-2-amylene (CF of 1,1,1,2,3,4,5,5,5-nine 3CF=CFCHFCF 3); 1,2,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CHF=CFCF (CF 3) 2); 1,1,2,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CFCH (CF 3) 2); 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (CF 3CH=C (CF 3) 2); 1,1,3,4,4,4-hexafluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCF (CF 3) 2); 2,3,3,4,4,5,5,5-octafluoro-1-amylene (CH 2=CFCF 2CF 2CF 3); 1,2,3,3,4,4,5,5-octafluoro-1-amylene (CHF=CFCF 2CF 2CHF 2); 3,3,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CH 2=C (CF 3) CF 2CF 3); 1,1,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CF 2=CHCH (CF 3) 2); 1,3,4,4,4-five fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCF (CF 3) 2); 1,1,4,4,4-five fluoro-2-(trifluoromethyl)-1-butylene (CF 2=C (CF 3) CH 2CF 3); 3,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene ((CF 3) 2CFCH=CH 2); The fluoro-1-amylene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2CH=CH 2); The fluoro-1-amylene (CH of 2,3,3,4,4,5,5-seven 2=CFCF 2CF 2CHF 2); 1,1,3,3,5,5,The fluoro-1-butylene (CF of 5-seven 2=CHCF 2CH 2CF 3); The fluoro-3-methyl-2-butene (CF of 1,1,1,2,4,4,4-seven 3CF=C (CF 3) (CH 3)); 2,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CH 2=CFCH (CF 3) 2); 1,4,4,4-tetra-fluoro-3-(trifluoromethyl)-1-butylene (CHF=CHCH (CF 3) 2); 1,1,1,4-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 2FCH=C (CF 3) 2); 1,1,1,3-tetra-fluoro-2-(trifluoromethyl)-2-butylene (CH 3CF=C (CF 3) 2); 1,1,1-tri-fluoro-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=CHCH 3); 3,4,4,5,5,5-hexafluoro-2-amylene (CF 3CF 2CF=CHCH 3); 1,1,1,4,4,4-hexafluoro-2-methyl-2-butene (CF 3C (CH 3)=CHCF 3); 3,3,4,5,5,5-hexafluoro-1-amylene (CH 2=CHCF 2CHFCF 3); The fluoro-1-butylene (CH of 3-(trifluoromethyl)-4,4,4-three 2=C (CF 3) CH 2CF 3); The fluoro-1-hexene (CF of 1,1,2,3,3,4,4,5,5,6,6,6-12 3(CF 2) 3CF=CF 2); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4,5,5,6,6,6-12 3CF 2CF=CFCF 2CF 3); Two (trifluoromethyl)-2-the butylene ((CF of 1,1,1,4,4,4-hexafluoro-2,3- 3) 2C=C (CF 3) 2); 1,1,1,2,3,4,5,5,5-nine fluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CFCF 3); 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHC 2F 5); 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-amylene ((CF 3) 2CFCF=CHCF 3); The fluoro-1-hexene (CF of 3,3,4,4,5,5,6,6,6-nine 3CF 2CF 2CF 2CH=CH 2); Two (the trifluoromethyl)-1-butylene (CH of the fluoro-3,3-of 4,4,4-tri- 2=CHC (CF 3) 3); 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butylene ((CF 3) 2C=C (CH 3) (CF 3)); 2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-amylene (CH 2=CFCF 2CH (CF 3) 2); 1,1,1,2,4,4,5,5,5-nine fluoro-3-methyl-2-amylene (CF 3CF=C (CH 3) CF 2CF 3); 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-amylene (CF 3CH=CHCH (CF 3) 2); 3,4,4,5,5,6,6,6-octafluoro-2-hexene (CF 3CF 2CF 2CF=CHCH 3); 3,3,4,4,5,5,6,6-octafluoro-1-hexene (CH 2=CHCF 2CF 2CF 2CHF 2); 1,1,1,4,4-five fluoro-2-(trifluoromethyl)-2-amylene ((CF 3) 2C=CHCF 2CH 3); 4,4,5,5,5-five fluoro-2-(trifluoromethyl)-1-amylene (CH 2=C (CF 3) CH 2C 2F 5); The fluoro-2-Methyl-1-pentene (CF of 3,3,4,4,5,5,5-seven 3CF 2CF 2C (CH 3)=CH 2); The fluoro-2-hexene (CF of 4,4,5,5,6,6,6-seven 3CF 2CF 2CH=CHCH 3); The fluoro-1-hexene (CH of 4,4,5,5,6,6,6-seven 2=CHCH 2CF 2C 2F 5); The fluoro-3-hexene (CF of 1,1,1,2,2,3,4-seven 3CF 2CF=CFC 2H 5); The fluoro-4-Trifluoromethyl-1-amylene (CH of 4,5,5,5-tetra- 2=CHCH 2CF (CF 3) 2); 1,1,1,2,5,5,5-seven fluoro-4-methyl-2-amylene (CF 3CF=CHCH (CF 3) (CH 3)); 1,1,1,3-tetra-fluoro-2-trifluoromethyl-2-amylene ((CF 3) 2C=CFC 2H 5); The fluoro-2-heptene (CF of 1,1,1,2,3,4,4,5,5,6,6,7,7,7-14 3CF=CFCF 2CF 2C 2F 5); The fluoro-3-heptene (CF of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-14 3CF 2CF=CFCF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,3,4,4,5,5,6,6,7,7,7-13 3CH=CFCF 2CF 2C 2F 5); The fluoro-2-heptene (CF of 1,1,1,2,4,4,5,5,6,6,7,7,7-13 3CF=CHCF 2CF 2C 2F 5); 1,1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CH=CFCF 2C 2F 5); 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-3-heptene (CF 3CF 2CF=CHCF 2C 2F 5); CF 2=CFOCF 2CF 3(PEVE); CF 2=CFOCF 3And their combination (PMVE).
Method in order to produce heating or cooling can be used for fixed air-conditioning, heat pump or movable air conditioner and refrigeration system.Fixed air-conditioning and heat pump application comprise window, pipe free, have tubular type, sealed terminal, and refrigerator (chiller) and commercialization, comprise closed roof.Refrigeration application comprises family expenses or houshold refrigerator and reezer system (freezer), ice-making machine, free-standing water cooler (cooler) and reezer system, large built-in wardrobe type water cooler and reezer system and transport refrigeration system.
Composition of the present invention can be used for adopting in plate-fin and tubular heat exchanger, the air-conditioning of micro-channel type heat exchanger and horizontal or vertical one way pipe or plate type regenerator, heating and refrigeration system in addition.
Conventional micro-channel heat exchanger may be unsatisfactory for low pressure refrigerant composition of the present invention.Low operating pressure and density cause high flow rate and the high frictionloss at all parts.In these cases, evaporator designs can be changed.Can use veneer/single-pass exchanger arrangement, instead of several microchannel plate links together (relative to refrigerant path).Therefore, the preferred heat exchanger for refrigeration agent of the present invention or heat transfer fluid composition is veneer/single-pass exchanger.
The invention still further relates to the method producing cooling, described method is included in the neighbouring evaporation fluoroalkene composition of the present invention of object to be cooled, composition described in condensation afterwards.
The invention still further relates to the method producing heating, described method is included in the neighbouring condensation fluoroalkene composition of the present invention of object to be heated, is evaporated by described composition afterwards.
The invention still further relates to the method producing cooling, described method is included in compressed package in radial compressor and, containing the composition of at least one fluoroolefins, evaporates described composition, evaporate described composition afterwards near object to be cooled.In addition, the radial compressor of the inventive method can be multistage centrifugal compressor, preferably 2 grades of radial compressors.
The invention still further relates to the method producing cooling in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device comprises at least one veneer/single-pass exchanger, described method comprises condensation composition of the present invention, evaporates described composition afterwards near object to be cooled.
Composition of the present invention is particularly useful for little turbine centrifugal compressors (miniature centrifugal compressors can be used for automobile and window air-conditioning), heat pump or transport refrigeration and other application.These high-level efficiency miniature centrifugal compressors by motor drive, therefore can not rely on motor speed and operate.Constant compressor speed can allow system under all motor speed, all provide the cooling power of relative constancy.Compared to the R-134a automotive air-conditioning system of routine, this provide the chance of efficiency improvement, particularly at higher engine speeds.When considering conventional system circular flow at high driving speeds, the advantage of these lp systems becomes more outstanding.
Or, miniature centrifugal compressors can not use electric power, but the turbine driven by engine exhaust or the ratio type gear wheel driving device (ratioed geardrive assembly with a ratioed belt drive) with ratioed belt drive provide power.In existing Automobile Design, available electric power is about 14 volts, but new miniature centrifugal compressors needs the electric power of about 50 volts.Therefore, use substitute energy will be favourable.The U.S. Patent Application Serial 11/367 that the turbine driven by engine exhaust provides the refrigeration plant of power or air-conditioning plant to submit on March 3rd, 2006, has a detailed description in 517.The U.S. Patent Application Serial 11/378 providing the refrigeration plant of power or air-conditioning plant to submit on March 17th, 2006 by ratio type gear wheel driving device, has a detailed description in 832.
The invention still further relates to the method producing cooling, described method is included in the turbine driven by engine exhaust and provides distilled edition inventive composition in the miniature centrifugal compressors of power; Composition described in condensation; Described composition is evaporated afterwards near object to be cooled.
The invention still further relates to the method producing cooling, described method is included in provides distilled edition inventive composition in the miniature centrifugal compressors of power by the ratio type gear wheel driving device with ratioed belt drive; Composition described in condensation; Described composition is evaporated afterwards near object to be cooled.
The present invention relates to the method producing cooling in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device comprises at least one veneer/single-pass exchanger, described method is included in distilled edition inventive composition in radial compressor, composition described in condensation and evaporate described composition afterwards near object to be cooled.
The invention still further relates to that to substitute with the composition with lower GWP or replace GWP be the refrigerant composition of about 150 or higher or the method for high GWP refrigeration agent.A kind of method comprises the composition as an alternative product of providing package containing at least one fluoroolefins of the present invention.In another embodiment of the invention, the refrigeration agent of the present invention or heat transfer fluid composition compared with composition that is replaced or that replace with lower GWP are incorporated into and freeze, in air-conditioning or thermal-pump unit.In some cases, before the lower GWP composition of introducing, need from device, remove the high GWP refrigeration agent wherein existed.In other situation, fluoroalkene composition of the present invention can be incorporated in device simultaneously at high GWP refrigeration agent.
Global warming potential (GWP) is the index estimating that the relative Global warming of the airborne release of 1 kilogram of certain specific greenhouse gases compared with the discharge of 1 kilogram of carbonic acid gas is contributed.The GWP of different time scope can be calculated, to show the impact of the atmospheric lifetime of given gas.The numerical value of usual indication is the GWP of 100 year scopes.
High GWP refrigeration agent be anyly can serve as refrigeration agent or heat-transfer fluid, within 100 years its GWP be about 1000 or larger or 500 or larger, 150 or larger, 100 or larger or 50 or larger compound.According to inter-governmental climate change work group (Intergovernmental Panel on Climate Change, IPCC) the GWP calculation result announced needs the refrigeration agent that carries out substituting and heat-transfer fluid, include but not limited to HFC-134a (1,1,1,2-Tetrafluoroethane).
The present invention will provide the composition with zero or low-ozone depletion potential and low global warming potential (GWP).Its global warming potential of mixture of fluoroolefins of the present invention or fluoroolefins of the present invention and other refrigeration agent is by lower than the many fluoroether refrigerants used at present.Usually, fluoroolefins expection of the present invention has the GWP being less than about 25.One aspect of the present invention be to provide global warming potential be less than 1000, be less than 500, be less than 150, be less than 100 or be less than 50 refrigeration agent.Another aspect of the present invention reduces the clean GWP of described mixture.
The invention still further relates to the method for the GWP reducing refrigeration agent or heat-transfer fluid, described method comprises and described refrigeration agent or heat-transfer fluid and at least one fluoroolefins of the present invention being combined.In another embodiment, method in order to reduce global warming potential comprises and described first composition and the composition that comprises at least fluoroolefins being combined, to produce the second composition being suitable as refrigeration agent or heat-transfer fluid, and the global warming potential of wherein said second composition is lower than described first composition.What was certain was that the mixture of each compound or the GWP of combination can calculate by the weighted mean of the GWP of often kind of pure compound.
The invention still further relates to and use the present composition comprising at least one fluoroolefins to reduce the method for the global warming potential of original refrigerant or heat transfer fluid composition, described method comprises and described original refrigerant or heat transfer fluid composition and the present composition that comprises at least one fluoroolefins being combined, to produce second refrigerant or heat transfer fluid composition, the global warming potential of wherein said second refrigerant or heat transfer fluid composition than described original refrigerant or heat transfer fluid composition low.
The invention still further relates to the method for the GWP reducing original refrigerant in refrigeration, air-conditioning or thermal-pump unit or heat transfer fluid composition, the GWP of wherein said original refrigerant or heat-transfer fluid is about 150 or higher; Described method comprise to described refrigeration, air-conditioning or thermal-pump unit introduce second, the refrigeration agent of the present invention of lower GWP or heat transfer fluid composition.
The method of the GWP in order to reduce original refrigerant of the present invention also can be included in introducing second, before the refrigeration agent of lower GWP or heat-transfer fluid, first original refrigerant or heat transfer fluid composition are removed from described refrigeration, air-conditioning or thermal-pump unit.
The invention still further relates to the method substituting original refrigerant or heat transfer fluid composition by second refrigerant or heat transfer fluid composition, described method comprises provides composition of the present invention as second refrigerant or heat transfer fluid composition.Original refrigerant can be anyly to freeze, refrigeration agent that the needs that use in air-conditioning or thermal-pump unit substitute.
The original refrigerant that needs substitute or heat-transfer fluid can be any one in the adulterant of fluoroether refrigerant, chlorofluorocarbon refrigerant, hydrochlorofluorocarbon refrigerants, fluoroether refrigerant or refrigerant compound.
The fluoroether refrigerant of the present invention substituted may be needed to include but not limited to: CHF 3(HFC-23), CH 2f 2(HFC-32), CH 3f (HFC-41), CHF 2cF 3(HFC-125), CHF 2cHF 2(HFC-134), CH 2fCF 3(HFC-134a), CHF 2cH 2f (HFC 143), CF 3cH 3(HFC-143a), CHF 2cH 3(HFC-152a), CH 2fCH 3(HFC-161), CHF 2cF 2cF 3(HFC-227ca), CF 3cFHCF 3(HFC-227ea), CHF 2cF 2cHF 2(HFC-236ca), CH 2fCF 2cF 3(HFC-236cb), CHF 2cHFCF 3(HFC-236ea), CF 3cH 2cF 3(HFC-236fa), CH 2fCF 2cHF 2(HFC-245ca), CH 3cF 2cF 3(HFC-245cb), CHF 2cHFCHF 2(HFC-245ea), CH 2fCHFCF 3(HFC-245eb), CHF 2cH 2cF 3(HFC-245fa), CH 2fCF 2cH 2f (HFC-254ca), CH 3cF 2cHF 2(HFC-254cb), CH 2fCHFCHF 2(HFC-254ea), CH 3cHFCF 3(HFC-254eb), CHF 2cH 2cHF 2(HFC-254fa), CH 2fCH 2cF 3(HFC-254fb), CF 3cH 2cH 3(HFC-263fb), CH 3cF 2cH 2f (HFC-263ca), CH 3cF 2cH 3(HFC-272ca), CH 3cHFCH 2f (HFC-272ea), CH 2fCH 2cH 2f (HFC-272fa), CH 3cH 2cF 2h (HFC-272fb), CH 3cHFCH 3(HFC-281ea), CH 3cH 2cH 2f (HFC-281fa), CHF 2cF 2cF 2cF 2h (HFC-338pcc), CF 3cH 2cF 2cH 3(HFC-365mfa), CF 3cHFCHFCF 2cF 3(HFC-43-10mee).These fluoroether refrigerants are commercially available, or prepare by method well known in the art.
Fluoroether refrigerant of the present invention also can comprise azeotropic, the composition of azeotropic mixture sample (azeotrope-like) and non-azeotrope, these compositions comprise HFC-125/HFC-143a/HFC-134a (ASHRAE label is R404 or R404A), (ASHRAE label is R407 or R407A to HFC-32/HFC-125/HFC-134a, R407B or R407C), HFC-32/HFC-125 (R410 or R410A) and HFC-125/HFC-143a (ASHRAE label is R507 or R507A), R413A (adulterant of R134a/R218/ Trimethylmethane), R423A (adulterant of R134a/R227ea), R507A (adulterant of R125/R143a) and other.
The chlorofluorocarbon refrigerant of the present invention substituted may be needed to comprise R22 (CHF 2c1), R123 (CHCl 2cF 3), R124 (CHClFCF 3), R502 (CFC-115 (CClF 2cF 3) and the adulterant of R22), R503 (R23/R13 (CClF 3) adulterant) and other.
The Hydrochlorofluorocarbons of the present invention substituted may be needed to comprise R12 (CF 2cl 2), R11 (CCl 3f), R113 (CCl 2fCClF 2), R114 (CF 2clCF 2cl), R401A or R401B (adulterant of R22/R152a/R124), R408A (adulterant of R22/R125/R143a) and other.
The fluoroether refrigerant of the present invention substituted may be needed to comprise be similar to hydrogen fluorohydrocarbon but compound also containing at least one ether group Sauerstoffatom.Fluoroether refrigerant includes but not limited to C 4f 9oCH 3and C 4f 9oC 2h 5(being all commercially available).
The original refrigerant of the present invention that substitutes or heat transfer fluid composition may be needed optionally also can to comprise dme containing maximum 10 weight percents or at least one C 3-C 5the combination of the refrigeration agent of hydrocarbon (such as propane, propylene, cyclopropane, normal butane, Trimethylmethane, Skellysolve A, pentamethylene and neopentane (2,2-dimethylpropane)).Containing this C 3-C 5the example of the refrigeration agent of hydrocarbon is following azeotrope-like composition: HCFC-22/HFC-125/ propane composition (ASHRAE label is R402 or R402A and R402B), HCFC-22/ octafluoropropane/propane composition (ASHRAE label is R403 or R403A and R403B), octafluoropropane/HFC-134a/ Trimethylmethane composition (ASHRAE label is R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/ Trimethylmethane composition (ASHRAE label is R414 or R414A and R414B), HFC-134a/HCFC-124/ normal butane composition (ASHRAE label is R416 or R416A), HFC-125/HFC-134a/ normal butane composition (ASHRAE label is R417 or R417A), (ASHRAE label is R422 for HFC-125/HFC-134a/ dimethyl ether composition (ASHRAE label is R419 or R419A) and HFC-125/HFC-134a/ Trimethylmethane composition, R422A, R422B, R422C, R422D).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R134a (HFC-134a, HFA 134a, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 3cH 2f), wherein said method comprises and is selected from the second refrigerant of the compound of trifluoromethyl trifluoro vinyl ether (PMVE) or heat transfer fluid composition substitutes R134a with comprising at least one.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R152a (HFC-152a, 1,1-C2H4F2 C2H4F2, CHF in refrigeration plant, air-conditioning plant or thermal-pump unit 2cH 3), wherein said method comprises and is selected from E-1,3 with comprising at least one, 3,3-tetrafluoeopropene (E-HFC-1234ze), 1,2,3,3,3-five fluorine propylene (HFC-1225ye), 2,3,3, second refrigerant or the heat transfer fluid composition of the compound of 3-tetrafluoeopropene (HFC-1234yf), 3,3,3-trifluoro propenes (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE) substitute R152a.
The invention still further relates to R227ea (HFC-227ea, HFC-227ea, the CF in alternative refrigeration plant, air-conditioning plant or thermal-pump unit 3cHFCF 3) method, wherein said method comprises providing package containing at least one and is selected from E-1,3,3,3-tetrafluoeopropene (E-HFC-1234ze), 1,2,3,3,3-five fluorine propylene (HFC-1225ye), 2,3,3, the composition product as an alternative of the compound of 3-tetrafluoeopropene (HFC-1234yf), 3,3,3-trifluoro propenes (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R113 (chloro-1,2, the 2-Halothane of CFC-113,1,1,2-tri-, CFCl in refrigeration plant, air-conditioning plant or thermal-pump unit 2cF 2cl), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene (HFC-151-12mcy) of 1,1,1,2,2,3,4,5,5,6,6,6-12; The fluoro-2-butylene of 1,1,1,3-tetra-(HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 4,4-hexafluoro-2,3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene (HFC-1567fts) of 3,3,4,4,5,5,5-seven; The fluoro-1-hexene (PFBE) of 3,3,4,4,5,5,6,6,6-nine; The fluoro-2-hexene (HFC-1567szz) of 4,4,5,5,6,6,6-seven; 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene (F13E) of 4,5,5,6,6,6-ten; The fluoro-3-hexene (F22E) of the fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6-ten.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R43-10mee (HFC-43-10mee), 1,1 in refrigeration plant, air-conditioning plant or thermal-pump unit, 1,2,3,4,4,5,5,5-Decafluoropentane, CF 3cHFCHFCF 2cF 3), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene (HFC-151-12mcy) of 1,1,1,2,2,3,4,5,5,6,6,6-12; The fluoro-2-butylene of 1,1,1,3-tetra-(HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 4,4-hexafluoro-2,3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene (HFC-1567fts) of 3,3,4,4,5,5,5-seven; The fluoro-1-hexene (PFBE) of 3,3,4,4,5,5,6,6,6-nine; The fluoro-2-hexene (HFC-1567szz) of 4,4,5,5,6,6,6-seven; 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene (F13E) of 4,5,5,6,6,6-ten; The fluoro-3-hexene (F22E) of the fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6-ten.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the C in refrigeration plant, air-conditioning plant or thermal-pump unit 4f 9oCH 3(perfluorobutyl methyl ethers), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene (HFC-151-12mcy) of 1,1,1,2,2,3,4,5,5,6,6,6-12; The fluoro-2-butylene of 1,1,1,3-tetra-(HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 4,4-hexafluoro-2,3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene (HFC-1567fts) of 3,3,4,4,5,5,5-seven; The fluoro-1-hexene (PFBE) of 3,3,4,4,5,5,6,6,6-nine; The fluoro-2-hexene (HFC-1567szz) of 4,4,5,5,6,6,6-seven; 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene (F13E) of 4,5,5,6,6,6-ten; The fluoro-3-hexene (F22E) of the fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6-ten.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R365mfc (HFC-365mfc, 1,1,1,3,3-3-pentafluorobutane, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 3cH 2cF 2cH 3), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butylene (HFC-152-11mmyyz); 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-(trifluoromethyl)-2-amylene (HFC-152-11mmtz); The fluoro-3-hexene (HFC-151-12mcy) of 1,1,1,2,2,3,4,5,5,6,6,6-12; The fluoro-2-butylene of 1,1,1,3-tetra-(HFC-1354mzy); 1,1, Isosorbide-5-Nitrae, two (the trifluoromethyl)-2-butylene (HFC-151-12mmtt) of 4,4-hexafluoro-2,3-; 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y); The fluoro-2-Methyl-1-pentene (HFC-1567fts) of 3,3,4,4,5,5,5-seven; The fluoro-1-hexene (PFBE) of 3,3,4,4,5,5,6,6,6-nine; The fluoro-2-hexene (HFC-1567szz) of 4,4,5,5,6,6,6-seven; 1,1, Isosorbide-5-Nitrae, the fluoro-2-hexene (F13E) of 4,5,5,6,6,6-ten; The fluoro-3-hexene (F22E) of the fluoro-4-of 1,1,1,2,3,4,5,5,5-nine (trifluoromethyl)-2-amylene (HFC-151-12mmzz) and 1,1,1,2,2,5,5,6,6,6-ten.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R11 (CFC-11, trichlorofluoromethane, CFCl in refrigeration plant, air-conditioning plant or thermal-pump unit 3), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y) with comprising at least one; The fluoro-2-amylene (FC-141-10myy) of 1,1,1,2,3,4,4,5,5,5-ten; The fluoro-2-amylene (HFC-1429myz) of 1,1,1,2,4,4,5,5,5-nine; The fluoro-2-amylene (HFC-1429mzy) of 1,1,1,3,4,4,5,5,5-nine; The fluoro-1-amylene (HFC-1447fz) of 3,3,4,4,5,5,5-seven; 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (HFC-1429mzt) and 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene (F12E).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R123 (chloro-1,1, the 1-Halothane of HCFC-123,2,2-bis-, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 3cHCl 2), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y) with comprising at least one; The fluoro-2-amylene (FC-141-10myy) of 1,1,1,2,3,4,4,5,5,5-ten; The fluoro-2-amylene (HFC-1429myz) of 1,1,1,2,4,4,5,5,5-nine; The fluoro-2-amylene (HFC-1429mzy) of 1,1,1,3,4,4,5,5,5-nine; The fluoro-1-amylene (HFC-1447fz) of 3,3,4,4,5,5,5-seven; 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-(trifluoromethyl)-2-butylene (HFC-1429mzt) and 1,1, Isosorbide-5-Nitrae, 4,5,5,5-octafluoro-2-amylene (F12E).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R245fa (HFC-245fa, 1,1,1,3,3-pentafluoropropane, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 3cH 2cHF 2), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 2,3,3-trifluoro propene (HFC-1243yf) with comprising at least one; 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (F11E); 1,3,3,3-tetrafluoeopropene (HFC-1234ze); The fluoro-2-butylene of 1,1,1,2,4,4,4-seven (HFC-1327my); 1,2,3,3-tetrafluoeopropene (HFC-1234ye) and pentafluoroethyl group trifluoro vinyl ether (PEVE).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R114 (chloro-1,1,2, the 2-Tetrafluoroethane of CFC-114,1,2-bis-, CFCl in refrigeration plant, air-conditioning plant or thermal-pump unit 2cF 2cl), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 1,1,1,2,3,4,4,4-octafluoro-2-butylene (FC-1318my) with comprising at least one; 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butylene (HFC-1336yf) and the fluoro-1-butylene of 3,3,4,4,4-five (HFC-1345fz).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R236fa (HFC-236fa, 1,1,1,3,3,3-HFC-236fa, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 3cH 2cF 3), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 1,1,1,2,3,4,4,4-octafluoro-2-butylene (FC-1318my) with comprising at least one; 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc); 2,3,3,4,4,4-hexafluoro-1-butylene (HFC-1336yf) and the fluoro-1-butylene of 3,3,4,4,4-five (HFC-1345fz).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R401A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401A is HCFC-22 (chlorodifluoromethane, CHF containing 53 weight percents of having an appointment 2cl), HFC-152a (1,1-C2H4F2 C2H4F2, the CHF of about 13 weight percents 2cH 3) and HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 34 weight percents 3the ASHRAE label of refrigeration agent adulterant CHClF).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R401B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R401B is HCFC-22 (chlorodifluoromethane, CHF containing 61 weight percents of having an appointment 2cl), HFC-152a (1,1-C2H4F2 C2H4F2, the CHF of about 11 weight percents 2cH 3) and HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 28 weight percents 3the ASHRAE label of refrigeration agent adulterant CHClF).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R409A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409A is HCFC-22 (chlorodifluoromethane, CHF containing 60 weight percents of having an appointment 2cl), HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 25 weight percents 3and HCFC-142b (1-chlorine-1,1-difluoroethane, the CF of about 15 weight percents CHClF) 2clCH 3) the ASHRAE label of refrigeration agent adulterant.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R409B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R409B is HCFC-22 (chlorodifluoromethane, CHF containing 65 weight percents of having an appointment 2cl), HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 25 weight percents 3and HCFC-142b (1-chlorine-1,1-difluoroethane, the CF of about 10 weight percents CHClF) 2clCH 3) the ASHRAE label of refrigeration agent adulterant.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R414B in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R414B is HCFC-22 (chlorodifluoromethane, CHF containing 50 weight percents of having an appointment 2cl), HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 39 weight percents 3cHClF), Trimethylmethane (R600a, the CH of about 1.5 weight percents 3cH (CH 3) CH 3) and HCFC-142b (1-chlorine-1,1-difluoroethane, the CF of about 9.5 weight percents 2clCH 3) the ASHRAE label of refrigeration agent adulterant.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R416A in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: E-1 with comprising at least one, 3,3,3-tetrafluoeopropene (E-HFC-1234ze); 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf) and trifluoromethyl trifluoro vinyl ether (PMVE).R416A is HFC-134a (HFA 134a, CF containing 59 weight percents of having an appointment 3cH 2f)), HCFC-124 (the chloro-HFA 134a of 2-, the CF of about 39.5 weight percents 3and the normal butane (CH of about 1.5 weight percents CHClF) 3cH 2cH 2cH 3) the ASHRAE label of refrigeration agent adulterant.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is R12 (CFC-12, Refrigerant 12, CF in refrigeration plant, air-conditioning plant or thermal-pump unit 2cl 2), wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes: 1,2,3,3,3-five fluorine propylene (HFC-1225ye) with comprising at least one; 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf); With trifluoromethyl trifluoro vinyl ether (PMVE).
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, described original composition is the R500 in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said method comprises and is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,3-five fluorine propylene (HFC-1225ye); 2,3,3,3-tetrafluoeopropene (HFC-1234yf); 3,3,3-trifluoro propene (HFC-1243zf); With trifluoromethyl trifluoro vinyl ether (PMVE).R500 is R12 ((CFC-12, Refrigerant 12, CF containing 73.8 weight percents of having an appointment 2cl 2) and R152a (HFC-152a, 1,1-C2H4F2 C2H4F2, the CHF of about 26.2 weight percents 2cH 3) the ASHRAE label of azeotrope refrigerant adulterant.
The present invention relates to the method for alternative original refrigerant or heat transfer fluid composition, wherein said original refrigerant or heat transfer fluid composition are R134a or R12, and wherein said R134a or R12 is with comprising about 1.0 weight percents, and to the HFC-32 of about 37 weight percents and about 99 weight percents, extremely the second refrigerant of the HFC-1225ye of about 63 weight percents or heat transfer fluid composition substitute.In another embodiment, second refrigerant or heat transfer fluid composition can comprise the HFC-1225ye of about 1.0 weight percents to the HFC-32 of about 10 weight percents and about 99 weight percents extremely about 90 weight percents.
The present invention relates to the method for alternative original refrigerant or heat transfer fluid composition, wherein said original refrigerant or heat transfer fluid composition are R22, R404A or R410A, and wherein said R22, R404A or R410A substitute to the HFC-32 of about 37 weight percents and about 99 weight percents to the second refrigerant of the HFC-1225ye of about 63 weight percents or heat transfer fluid composition with comprising about 1.0 weight percents.In another embodiment, second refrigerant or heat transfer fluid composition can comprise the HFC-1225ye of about 20 weight percents to the HFC-32 of about 37 weight percents and about 80 weight percents extremely about 63 weight percents.
The invention still further relates to the method for alternative original refrigerant or heat transfer fluid composition, wherein said original refrigerant or heat transfer fluid composition are R22, R404A or R410A, and wherein said R22, R404A or R410A substitute to the HFC-32 of about 65 weight percents and about 1.0 weight percents to the second refrigerant of the HFC-125 of about 40 weight percents or heat transfer fluid composition to the HFC-1225ye of about 95 weight percents, about 1.0 weight percents with comprising about 20 weight percents.In another embodiment, second refrigerant or heat transfer fluid composition comprise about 30 weight percents to the HFC-1225ye of about 90 weight percents, about 5.0 weight percents to the HFC-32 of about 55 weight percents and about 1.0 weight percents to the HFC-125 of about 35 weight percents.In still another embodiment, second refrigerant or heat transfer fluid composition comprise about 40 weight percents to the HFC-1225ye of about 85 weight percents, about 10 weight percents to the HFC-32 of about 45 weight percents and about 1.0 weight percents to the HFC-125 of about 28 weight percents.
The present invention relates to the method for alternative original refrigerant or heat transfer fluid composition, wherein said original refrigerant or heat transfer fluid composition are R134a or R12, and wherein said R134a or R12 is with comprising following second refrigerant or heat transfer fluid composition substitutes:
HFC-1243zf and HFC-1225ye;
HFC-1243zf, HFC-1225ye and HFC-125;
HFC-1243zf, HFC-1225ye and HFC-32; Or
HFC-1243zf, HFC-1225ye, HFC-125 and HFC-32.
In the method for all aforesaid alternative refrigerants, all can carry out the refrigeration agent in alternative existing installation with fluoroolefins.In addition, alternate design can be carried out with fluoroolefins and use this refrigeration agent in the existing installation of certain refrigeration agent.In addition, can the refrigeration agent in alternative existing installation be carried out with fluoroolefins and need not change or alternative lubricant.
The present invention relates to the method for the fire hazard reduced in refrigeration plant, air-conditioning plant or thermal-pump unit, described method comprises and being incorporated in described refrigeration plant or air-conditioning plant by composition of the present invention.
When considering combustibility, the refrigeration agent that may leak from refrigeration plant, air-conditioning plant or thermal-pump unit is a large problem.Once leak in refrigeration plant or air-conditioning plant, refrigeration agent and possible a small amount of lubricant may discharge from apparatus system.If this leak materials touches ignition source, fire may be caused.So-called fire hazard to refer in the middle of refrigeration plant, air-conditioning plant or thermal-pump unit or near may the possibility of presence of fire.Reducing the fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit, carrying out measuring through previously described method and standard and discriminating is considered to non-flammable refrigeration agent or heat-transfer fluid realizes by using.In addition, non-flammable fluoroolefins of the present invention can be joined in a device or the combustible refrigerant that not yet adds in auto levelizer or heat-transfer fluid.Non-flammable fluoroolefins of the present invention can reduce just in case presence of fire when occurring leaking possibility and/or reduced the degree of fire hazard by the temperature of the flame that reduces any generation or size.
The invention still further relates to the method reducing fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit or neighbouring, described method comprises and non-at least one flammable fluoroolefins and combustible refrigerant being combined, and said composition is incorporated in refrigeration plant, air-conditioning plant or thermal-pump unit.
The invention still further relates to the method reducing fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit or neighbouring, described method comprises and non-at least one flammable fluoroolefins and lubricant being combined, and said composition is incorporated into combustible refrigerant is housed refrigeration plant, air-conditioning plant or thermal-pump unit in.
The invention still further relates to and reduce in refrigeration plant, air-conditioning plant or thermal-pump unit or the method for neighbouring fire hazard, described method comprises and being incorporated in described device by least one fluoroolefins.
The invention still further relates to the method using combustible refrigerant in refrigeration plant, air-conditioning plant or thermal-pump unit, described method comprises and described combustible refrigerant and at least one fluoroolefins being combined.
The invention still further relates to the flammable method reducing combustible refrigerant or heat-transfer fluid, described method comprises and combustible refrigerant and at least one fluoroolefins being combined.
The invention still further relates to method heat being transferred to heat sink from thermal source, wherein composition of the present invention serves as heat-transfer fluid.Described transfer of heat method comprises composition of the present invention is sent to heat sink from thermal source.
Heat-transfer fluid to be used to heat by radiation, conduction or convection current from a space, position, object or object transfer, mobile or move to another space, position, object or object.Heat-transfer fluid shifts the means of cooling (or heating) to serve as secondary coolant by providing by remote refrigeration (or heating) system.In some systems, heat-transfer fluid can remain on steady state (namely not evaporating or condensation) in whole transfer process.Or transpiration cooling process also can adopt heat-transfer fluid.
Thermal source may be defined as anyly to be needed to shift, mobile or move out of the space of heat, position, object or object.The example of thermal source can be need the space of refrigeration or cooling (open or enclosed space) as the refrigerator in supermarket or refrigerator, need the space of air-conditioning or need the automobile passenger compartment of air-conditioning.Heat sink can be defined as any can absorb heat space, position, object or object.Vapor compression refrigeration system is an example of this heat sink.
Embodiment
embodiment
embodiment 1
performance data
Table 7 shows the compounds of this invention and CFC-113, HFC-43-10mee, C 4f 9oCH 3the refrigeration performance compared with HFC-365mfc, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Supercooling temperature (subcool temperature) 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
table 7
embodiment 2
performance data
Table 8 shows the refrigeration performance that the compounds of this invention is compared with CFC-11 with HCFC-123, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Supercooling temperature 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
table 8
embodiment 3
performance data
Table 9 shows the refrigeration performance of the compounds of this invention compared with HFC-245fa, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Supercooling temperature 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
table 9
embodiment 4
performance data
Table 10 shows the refrigeration performance that the compounds of this invention is compared with CFC-114 with HFC-236fa, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Supercooling temperature 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
table 10
embodiment 5
performance data
Table 11 shows the refrigeration performance that the compounds of this invention is compared with HFC-227ea with HFC-134a, HFC-152a, as the pressure in vaporizer (Evap) and condenser (Cond), temperature out (Disch T), energy efficiency (COP) and capacity (Cap).These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Supercooling temperature 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
table 11
embodiment 6
flammable
Combustible cpd is by being undertaken testing identifying by ASTM (American Society Testing and Materials) E681-01 with electronics ignition source.This flammability test be to composition of the present invention under 101kPa (14.7psia), 50% relative humidity and the temperature of specifying with different air in concentration carry out, to determine that whether it is flammable, and flammable words find out lean flammability (LFL).Result provides in table 12.
table 12
Result shows that HFC-1234yf and E-HFC-1234ze is flammable, and HFC-1225ye, HFC-1429myz/mzy and F12E right and wrong are flammable.For the mixture of HFC-1225ye and HFC-32 (known be flammable under pure state), through determining that the HFC-32 of discovery 37 weight percent is the maximum amount for keeping non-flammable characteristic to exist.Those compositions comprising non-flammable fluoroolefins are more receivable refrigeration agent or heat transfer fluid composition candidate.
embodiment 7
Produce the tip speed of pressure
Tip speed uses the refrigeration equipment of radial compressor to set up some fundamental relations to estimate by giving.The torque that impeller gives gas is ideally defined as:
T=m* (v 2* r 2-v 1* r 1) equation 1
In formula
T=torque, Newton meter (n.m.)
M=mass flow rate, kg/sec
V 2=refrigeration agent leaves the tangential velocity (tip speed) of impeller, meter per second
R 2the radius of=outlet impeller, rice
V 1=refrigeration agent enters the tangential velocity of impeller, meter per second
R 1the radius of=impeller inlet, rice
Assuming that refrigeration agent enters impeller with the direction of substantial axial, the tangential component v of speed 1=0, then:
T=m*v 2* r 2equation 2
The power that axle place needs is the product of torque and speed of rotation.
P=T* ω equation formula 3
In formula
P=power, W
ω=circular frequency, radian/s
Then
P=T*w=m*v 2* r 2* ω equation formula 4
Under low refrigerant flow rates, the tip speed of impeller and the tangential velocity of refrigeration agent almost equal; Then
R 2* ω=v 2equation 5
With
P=m*v 2* v 2equation 6
Another expression formula of ideal power is the product of mass flow rate and isentropic compression work,
P=m*H i* (1000J/kJ) equation 7
In formula
H i=refrigeration agent by the saturated vapo(u)r under evaporation conditions to the enthalpy difference under saturated condensing condition, kJ/kg.
Merge equation 6 and 7 two expression formulas,
V 2* v 2=1000*H iequation 8
Although equation 8 is based on some basic hypothesis, it can be estimated the tip speed of impeller well and provide the important way of tip speed of more each refrigeration agent.
Following table 13 shows the theoretical tip speeds calculated 1,2,2-Refrigerant R 113 (CFC-113) and the present composition.This assumed conditions compared is:
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 110.0 °F (43.3 DEG C)
Liquid subcool temperature 10.0 °F (5.5 DEG C)
Reflux gas temperature 75.0 °F (23.8 DEG C)
Compressor efficiency is 70%
These are representative conditions of small sized turbine radial compressor operation.
table 13
The present embodiment shows, and the tip speed of the compounds of this invention differs with CFC-113 within about 15%, will be effective substitute of CFC-113, and required compressor design changes few.Its tip speed of most preferred composition differs within about 10% with CFC-113.
embodiment 8
refrigeration performance data
Table 14 shows the performance of various refrigerant composition of the present invention compared with HFC-134a.In table 14, Evap Pres refers to evaporator pressure, Cond Pres refers to condenser pressure, and CompDisch T refers to compressor exit temperature, COP refers to energy efficiency, and CAP refers to capacity.These data are based on following condition.
Evaporator temperature 40.0 °F (4.4 DEG C)
Condenser temperature 130.0 °F (54.4 DEG C)
Cross cold 10.0 °F (5.5 DEG C)
Reflux gas temperature 60.0 °F (15.6 DEG C)
Compressor efficiency is 100%
Note overheated being included in cooling capacity.
table 14
There is several composition to have than HFC-134a more energy-efficient (COP), also keep lower or suitable top hole pressure and temperature simultaneously.The capacity of the composition listed by table 14 is also similar to R134a, show these compositions can in refrigeration and air-conditioning particularly in automative air conditioning is applied as the alternative refrigerant of R134a.The cooling capacity that result also shows HFC-1225ye improves by adding other compound such as HFC-32.
embodiment 9
refrigeration performance data
Table 15 shows the performance that various refrigerant composition of the present invention is compared with R404A with R422A.In table 15, Evap Pres refers to evaporator pressure, Cond Pres refers to condenser pressure, and Comp Disch T refers to compressor exit temperature, EER refers to energy efficiency, and CAP refers to capacity.These data are based on following condition.
Evaporator temperature-17.8 DEG C
Condenser temperature 46.1 DEG C
Cross cold 5.5 DEG C
Reflux gas temperature 15.6 DEG C
Compressor efficiency is 70%
Note overheated being included in cooling capacity.
table 15
There is its energy efficiency of several composition (EER) suitable with R404A and R422A.Temperature out is also low than R404A and R507A.The capacity of the composition listed by table 15 is also similar with R422A to R404A, R507A, shows that these compositions can as the alternative refrigerant of R404A, R507A and R422A in refrigeration and air-conditioning.
embodiment 10
refrigeration performance data
Table 16 shows the performance that various refrigerant composition of the present invention is compared with HCFC-22 with R410A.In table 16, Evap Pres refers to evaporator pressure, Cond Pres refers to condenser pressure, and Comp Disch T refers to compressor exit temperature, EER refers to energy efficiency, and CAP refers to capacity.These data are based on following condition.
Evaporator temperature 4 DEG C
Condenser temperature 43 DEG C
Cross cold 6 DEG C
Reflux gas temperature 18 DEG C
Compressor efficiency is 70%
Note overheated being included in cooling capacity.
Table 16
These compositions have the energy efficiency (EER) suitable with R22 and R410A, keep rational temperature out simultaneously.The capacity of some composition listed by table 16 is also similar to R22, shows that these compositions can as the alternative refrigerant of R22 in refrigeration and air-conditioning.In addition, its capacity of the composition had in composition listed by table 16 is close or be equivalent to R410A, shows that these compositions can as the alternative refrigerant of R410A in refrigeration and air-conditioning.
embodiment 11
refrigeration performance data
Table 17 shows the performance that various refrigerant composition of the present invention is compared with R417A with HCFC-22, R410A, R407C.In table 17, Evap Pres refers to evaporator pressure, Cond Pres refers to condenser pressure, and Comp Disch T refers to compressor exit temperature, EER refers to energy efficiency, and CAP refers to capacity.These data are based on following condition.
Evaporator temperature 4.4 DEG C
Condenser temperature 54.4 DEG C
Cross cold 5.5 DEG C
Reflux gas temperature 15.6 DEG C
Compressor efficiency is 100%
Note overheated being included in cooling capacity.
table 17
These compositions have the energy efficiency (EER) suitable with R22, R407C, R417A and R410A, keep low temperature out simultaneously.The capacity of the composition listed by table 17 is also similar with R417A to R22, R407C, shows that these compositions can as the alternative refrigerant of R22, R407C and R417A in refrigeration and air-conditioning.

Claims (1)

1. refrigeration agent or a heat transfer fluid composition, described composition comprises at least one and is selected from following compound:
Formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, wherein X, Y, Z and W are independently H or F, and n is the integer of 2-5.
2. a composition, described composition comprises: (i) at least one fluoroolefin compounds; (ii) at least one combustible refrigerant; Wherein said fluoroolefins is selected from:
Formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, wherein X, Y, Z and W are independently H or F, and n is the integer of 2-5.
3. a method of cooling, described method comprises the composition of condensation claim 1 or 2, evaporates described composition afterwards near object to be cooled.
4. heating means, described method comprises the composition of evaporation claim 1 or 2, composition described in condensation near object to be heated afterwards.
5. in refrigeration, air-conditioning or thermal-pump unit, produce a method for heating or cooling, described method comprises in described device refrigeration agent or heat transfer fluid composition being incorporated into and having (a) radial compressor or (b) veneer/single-pass exchanger; Wherein said refrigeration agent or heat transfer fluid composition comprise at least one and are selected from following fluoroolefins: formula ring-[CX=CY (CZW) n-] ring-type fluoroolefins, the wherein integer of X, Y, Z and W to be independently H or F, n be 2-5.
6. the method for claim 5, wherein said radial compressor is multistage centrifugal compressor.
7. one kind uses the composition of claim 1 or 2 to reduce the method for the fire hazard in refrigeration plant, air-conditioning plant or thermal-pump unit, wherein said device is equipped with combustible refrigerant, described method comprises and being incorporated in described device by described composition, and optionally adds lubricant to added described composition.
8. use the refrigeration agent of claim 1 or heat transfer fluid composition to reduce a flammable method for combustible refrigerant, described method comprises: mixed with described composition by described combustible refrigerant.
9. substitute a method for the use of high global warming potential refrigeration agent, described method comprises: in refrigeration, air-conditioning or thermal-pump unit, provide the composition of claim 1 or 2 carry out the high global warming potential refrigeration agent in alternative described device or mix with this refrigeration agent.
10. use the composition of claim 1 to reduce the method for the global warming potential of original refrigerant or heat transfer fluid composition, described method comprises and described original refrigerant or heat transfer fluid composition being mixed with the composition of claim 1, to produce second refrigerant or heat transfer fluid composition, the global warming potential of wherein said second refrigerant or heat transfer fluid composition than described original refrigerant or heat transfer fluid composition low.
11. 1 kinds of methods reducing the GWP of original refrigerant in refrigeration, air-conditioning or thermal-pump unit or heat transfer fluid composition, the GWP of wherein said original refrigerant or heat-transfer fluid is 150 or higher; Described method comprise to described refrigeration, air-conditioning or thermal-pump unit introduce second, the refrigeration agent of the claim 1 or 2 of lower GWP or heat transfer fluid composition.
12. 1 kinds substitute the method for original refrigerant or heat transfer fluid composition by second refrigerant or heat transfer fluid composition, described method comprises: the composition containing at least one fluoroolefins being provided as second refrigerant or heat transfer fluid composition, and wherein said original refrigerant or heat transfer fluid composition are selected from following:
(i) 1,1,2-tri-chloro-1,2,2-Halothane (R113), wherein said R113 is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);
(ii) 1,1,1,2,3,4,4,5,5,5-Decafluoropentane (R43-10mee), wherein said R43-10mee is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);
(iii) C 4f 9oCH 3, wherein said C 4f 9oCH 3the second refrigerant of following compound is selected from or heat transfer fluid composition substitutes: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y) with comprising at least one;
(iv) 1,1,1,3,3-3-pentafluorobutane (R365mfc), wherein said R365mfc is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene (FC-C151-10y);
(v) fluoro trichloromethane (R11), wherein said R11 is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y);
(vi) 2,2 ,-two chloro-1,1,1-Halothane (R123), wherein said R123 is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4,5,5-octafluoro cyclopentenes (FC-C1418y);
(vii) 1,2-bis-chloro-1,1,2,2-Tetrafluoroethane (R124), wherein said R124 is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc);
(viii) 1,1,1,3,3,3-HFC-236fa (R236fa), wherein said R236fa is selected from the second refrigerant of following compound or heat transfer fluid composition substitutes with comprising at least one: 1,2,3,3,4,4-hexafluoro cyclobutene (FC-C1316cc).
13. 1 kinds of composition methods as heat transfer fluid composition using claim 1 or 2, described method comprises described composition is sent to heat sink from thermal source.
14. 1 kinds of methods preparing the composition of claim 1 or 2, described method comprises: (i) reclaims one or more refrigerant composition compositions of certain volume from least one cryogen vessel, (ii) fully impurity is removed, the described composition that one or more reclaim is re-used, (iii) optionally, refrigerant composition other with at least one for the composition of the described recovery volume of all or part or composition are mixed.
15. 1 kinds of refrigeration, air-conditioning or thermal-pump uniies, described device is equipped with the composition any one of claim 1 or 2.
16. 1 kinds of mobile refrigeratings or air-conditioning plant, described device is equipped with the composition any one of claim 1 or 2.
CN201210340141.9A 2005-11-01 2006-10-31 Compositions comprising fluoroolefins and uses thereof Expired - Fee Related CN102876294B (en)

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