CN113549426A - Compositions comprising fluoroolefins - Google Patents

Compositions comprising fluoroolefins Download PDF

Info

Publication number
CN113549426A
CN113549426A CN202110841031.XA CN202110841031A CN113549426A CN 113549426 A CN113549426 A CN 113549426A CN 202110841031 A CN202110841031 A CN 202110841031A CN 113549426 A CN113549426 A CN 113549426A
Authority
CN
China
Prior art keywords
hfc
composition
weight percent
dimethyl ether
isobutane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110841031.XA
Other languages
Chinese (zh)
Other versions
CN113549426B (en
Inventor
B·H·米诺尔
V·N·M·劳
D·B·比文斯
D·珀蒂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Priority to CN202110841031.XA priority Critical patent/CN113549426B/en
Publication of CN113549426A publication Critical patent/CN113549426A/en
Application granted granted Critical
Publication of CN113549426B publication Critical patent/CN113549426B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/30Materials not provided for elsewhere for aerosols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028Liquid extinguishing substances
    • A62D1/0057Polyhaloalkanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials 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
    • C09K5/044Materials 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
    • C09K5/045Materials 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating 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
    • C10M171/008Lubricant compositions compatible with refrigerants
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/12Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/04Aerosol, e.g. polyurethane foam spray
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/106Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/11Ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • C09K2205/122Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • C09K2205/126Unsaturated fluorinated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/134Components containing sulfur
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06Well-defined aromatic compounds
    • C10M2203/065Well-defined aromatic compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04Macromolecular 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
    • C10M2209/043Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
    • C10N2020/097Refrigerants
    • C10N2020/101Containing Hydrofluorocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09Characteristics associated with water
    • C10N2020/097Refrigerants
    • C10N2020/103Containing Hydrocarbons
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/12Inflammable refrigerants
    • F25B2400/121Inflammable refrigerants using R1234

Abstract

Compositions comprising fluoroolefins. The present invention relates to compositions for use in refrigeration, air-conditioning and heat pump systems, wherein the compositions comprise a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing refrigeration or heat, as heat transfer liquids, blowing agents, atomizing propellants, and fire suppression and extinguishing agents.

Description

Compositions comprising fluoroolefins
Cross Reference to Related Applications
The present application is a divisional application of Chinese patent application 201910000638.8, the aforementioned Chinese patent application 201910000638.8 is a divisional application of Chinese patent application 201510623155.5, and the aforementioned Chinese patent application 201510623155.5 is a divisional application of an invention patent application having an international application number of PCT/US2006/008164, an international application date of 3.3.2006 and a title of "fluoroolefin-containing composition", the national application number of 200680015438.0 obtained at the stage of entering the China.
This application claims priority benefits from U.S. provisional application 60/658,543 filed on 3/4/2005, U.S. provisional application 60/710,439 filed on 8/23/2005, and U.S. provisional application 60/732,769 filed on 11/1/2005.
Technical Field
The present invention relates to compositions for use in refrigeration, air-conditioning and heat pump systems, wherein the compositions comprise a fluoroolefin and at least one other component. The compositions of the present invention are useful in processes for producing refrigeration or heat, as heat transfer fluids, blowing agents, aerosol propellants and extinguishing and fire extinguishing agents.
Background
The refrigeration industry has endeavored in the past for decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons (HCFCs), which require a gradual decommissioning due to the montreal protocol. The solution for most refrigerant producers has been to industrialize Hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants (HFC-134a being the most widely used at present) have zero ozone depletion potential and are therefore not affected by the current regulatory mandates of the montreal protocol requiring gradual stopping.
Other environmental regulations may ultimately lead to global outages of certain HFC refrigerants. Currently, the automotive industry is facing regulatory restrictions regarding global warming potential for refrigerants used in mobile air conditioning. Thus, there is currently a great need for the mobile air conditioning market to identify new refrigerants that reduce global warming potential. If this legislation is more widely applied in the future, there is an even more urgent need for refrigerants that can be used in all fields of the refrigeration and air conditioning industry.
Currently proposed refrigerants for replacing HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or "natural" refrigerants such as CO2. Many of these proposed alternatives are toxic, flammable, and/or have low energy efficiency. Therefore, new replacement refrigerants are being sought.
It is an object of the present invention to provide novel refrigerant compositions and heat transfer fluid compositions that provide unique characteristics to meet the requirements of low or zero ozone depletion potential and provide lower global warming potential compared to current refrigerants.
Summary of the invention
The present invention relates to a composition comprising HFC-1225ye and at least one compound selected from the group consisting of:
HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to compositions comprising HFC-1234ze and at least one compound selected from the group consisting of: HFC-1234yf, HFC-1234yeHFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to a composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to a composition comprising HFC-1234ye and at least one compound selected from the group consisting of: HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to a composition comprising HFC-1243zf and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The invention further relates to a composition comprising:
(a) at least one lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly (alpha) olefins; and
(b) a composition selected from the group consisting of:
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-1234 yf;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% trans-HFC-1234 ze;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-1243 zf;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-134 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-227 ea; and
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% CF3I。
The invention further relates to a composition comprising:
a) a refrigerant or heat transfer fluid composition selected from the group consisting of:
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-1234 yf;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% trans-HFC-1234 ze;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-1243 zf;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-134 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-227 ea; and
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% CF3I; and
a compatibilizer selected from the group consisting of:
i) from the general formula R1[(OR2)xOR3]y represents a polyoxyalkylene glycol ether wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; r1Selected from hydrogen and aliphatic hydrocarbon radicals containing from 1 to 6 carbon atoms and y bonding sites; r2Selected from aliphatic hydrocarbylene groups having from 2 to 4 carbon atoms; r3Selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals containing from 1 to 6 carbon atoms; r1And R3At least one is selected from the group consisting of said hydrocarbyl groups; and wherein the polyoxyalkylene glycol ether has a molecular weight of about 100 to about 300 atomic mass units;
ii) from the general formula R1C(O)NR2R3And ring- [ R4CON(R5)-]An amide of wherein R1、R2、R3And R5Independently selected from aliphatic and alicyclic hydrocarbon groups having 1 to 12 carbon atoms, and up to one aromatic group having 6 to 12 carbon atoms; r4Selected from aliphatic hydrocarbylene groups having from 3 to 12 carbon atoms; and wherein the amide has a molecular weight of about 100 to about 300 atomic mass units;
iii) from the general formula R1C(O)R2A ketone of formula (I), wherein R1And R2Independently selected from aliphatic, alicyclic, and aryl hydrocarbon radicals containing from 1 to 12 carbon atoms, and wherein said ketone has a molecular weight of from about 70 to about 300 atomic mass units;
iv) from the general formula R1A nitrile represented by CN, wherein R1Selected from aliphatic, alicyclic, or aryl hydrocarbon groups containing 5 to 12 carbon atoms and wherein said nitrile has a molecular weight of about 90 to about 200 atomic mass units;
v) chlorinated hydrocarbons represented by the general formula RClx, wherein: x is 1 or 2; r is selected from aliphatic and alicyclic hydrocarbon radicals containing 1 to 12 carbon atoms; and wherein the chlorinated hydrocarbon has a molecular weight of about 100 to about 200 atomic mass units;
vi) from the general formula R1OR2An aryl ether of the formula (I) wherein: r1Selected from arylalkyl groups containing from 6 to 12 carbon atoms; r2Selected from aliphatic hydrocarbon groups containing 1 to 4 carbon atoms; and wherein the aryl ether hasHaving a molecular weight of about 100 to about 150 atomic mass units;
vii) from the general formula CF3R11, l, 1-trifluoroalkane of the formula, wherein R1Selected from aliphatic and alicyclic hydrocarbon radicals containing from about 5 to about 15 carbon atoms;
viii) from the general formula R1OCF2CF2Fluoroether represented by H, wherein R1Selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals containing from about 5 to about 15 carbon atoms; or wherein the fluoroether is derived from a fluoroolefin and a polyol, wherein the fluoroolefin has CF2A form CXY wherein X is hydrogen, chloro or fluoro and Y is chloro, fluoro, CF3OR ORrWherein R isfIs CF3、C2F5Or C3F7(ii) a And the polyol is linear or branched, wherein the linear polyol has a HOCH2(CHOH)x(CRR′)yCH2OH form, wherein R and R' are hydrogen, CH3Or C2H5X is an integer of 0 to 4, y is an integer of 0 to 3, z is 0 or 1, and the branched polyol has C (OH) t (R) u (CH)2OH)v[(CH2)mCH2OH]w type, wherein R can be hydrogen, CH3Or C2H5M is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, further wherein t + u + v + w is 4; and
ix) a lactone represented by the structures [ B ], [ C ] and [ D ]:
Figure BDA0003177520160000051
wherein R is1-R8Independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups; and a molecular weight of about 100 to about 300 atomic mass units; and
x) from the general formula R1CO2R2An ester of wherein R1And R2Independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl; and wherein the ester has a molecule of from about 80 to about 550 atomic mass unitsAmount of the compound (A).
The invention further relates to a composition comprising:
(a) at least one ultraviolet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthrenes, xanthenes, thioxanthenes, benzoxanthenes, fluoresceins, derivatives of said dyes, and combinations thereof; and
(b) a composition selected from the group consisting of:
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-1234 yf;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% trans-HFC-1234 ze;
from about 1M% to about 99% by weight HFC-1225ye and from about 99% to about 1% by weight HFC-1243 zf;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-134 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-227 ea; and
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% CF3I。
The present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition in a refrigeration lubricant selected from the group consisting of mineral oil, alkylbenzene, synthetic paraffin, synthetic cycloalkane, and poly (alpha) olefin, wherein said method comprises contacting said lubricant with said refrigerant or heat transfer fluid composition in the presence of an effective amount of a compatibilizer, wherein said refrigerant or heat transfer fluid comprises a composition selected from the group consisting of:
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-1234 yf;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% trans-HFC-1234 ze;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-1243 zf;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-134 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-227 ea; and
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% CF 3I;
and wherein the compatibilizer is selected from:
a) from the general formula R1[(OR2)xOR3]y represents a polyoxyalkylene glycol ether wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; r1Selected from hydrogen and aliphatic hydrocarbon radicals containing from 1 to 6 carbon atoms and y bonding sites; r2Selected from aliphatic hydrocarbylene groups having from 2 to 4 carbon atoms; r3 is selected from the group consisting of hydrogen and aliphatic and alicyclic hydrocarbon groups containing 1 to 6 carbon atoms; r1And R3At least one is selected from the group consisting of said hydrocarbyl groups; and wherein the polyoxyalkylene glycol ether has a molecular weight of about 100 to about 300 atomic mass units;
b) from the general formula R1C(O)NR2R3And ring- [ R4CON(R5)-]An amide of wherein R1、R2、R3And R5Independently selected from aliphatic and alicyclic hydrocarbon groups having 1 to 12 carbon atoms, and up to one aromatic group having 6 to 12 carbon atoms; r4Selected from aliphatic hydrocarbylene groups having from 3 to 12 carbon atoms; and wherein the amide has a molecular weight of about 100 to about 300 atomic mass units;
c) from the general formula R1C(O)R2A ketone of formula (I), wherein R1And R2Independently selected from aliphatic, alicyclic, and aryl hydrocarbon radicals containing from 1 to 12 carbon atoms, and wherein said ketone has a molecular weight of from about 70 to about 300 atomic mass units;
d) free-flowing water pipeFormula R1A nitrile represented by CN, wherein R1Selected from aliphatic, alicyclic, or aryl hydrocarbon groups containing 5 to 12 carbon atoms and wherein said nitrile has a molecular weight of about 90 to about 200 atomic mass units;
e) a chlorinated hydrocarbon represented by the general formula RClx, wherein: x is 1 or 2; r is selected from aliphatic and alicyclic hydrocarbon radicals containing 1 to 12 carbon atoms; and wherein the chlorinated hydrocarbon has a molecular weight of about 100 to about 200 atomic mass units;
f) from the general formula R1OR2An aryl ether of the formula (I) wherein: r1Selected from arylalkyl groups containing from 6 to 12 carbon atoms; r2Selected from aliphatic hydrocarbon groups containing 1 to 4 carbon atoms; and wherein the aryl ether has a molecular weight of about 100 to about 150 atomic mass units;
g) from the general formula CF3R11, 1, 1-trifluoroalkane of the formula, wherein R1Selected from aliphatic and alicyclic hydrocarbon radicals containing from about 5 to about 15 carbon atoms;
h) from the general formula R1OCF2CF2Fluoroether represented by H, wherein R1Selected from aliphatic and alicyclic hydrocarbon radicals containing from about 5 to about 15 carbon atoms; or wherein the fluoroether is derived from a fluoroolefin and a polyol, wherein the fluoroolefin has CF2A form CXY wherein X is hydrogen, chloro or fluoro and Y is chloro, fluoro, CF3OR ORfWherein R isfIs CF3、C2F5Or C3F7(ii) a And the linear polyol has a HOCH2CRR′(CH2)z(CHOH)xCH2(CH2OH) y form wherein R and R' are hydrogen, CH3Or C2H5X is an integer from 0 to 4, y is an integer from 0 to 3, z is 0 or 1; and
i) a lactone represented by structures [ B ], [ C ] and [ D ]:
Figure BDA0003177520160000071
wherein R is1-R8Independently selected from hydrogen, linear, branched, cyclic, bicyclicSaturated and unsaturated hydrocarbon groups; and a molecular weight of about 100 to about 300 atomic mass units; and
j) from the general formula R1CO2R2An ester of wherein R1And R2Independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl; and wherein the ester has a molecular weight of from about 80 to about 550 atomic mass units.
The invention further relates to a method for replacing a high GWP refrigerant in a refrigeration, air-conditioning or heat pump apparatus, wherein the high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502 and R404A, the method comprising admixing a composition selected from the group consisting of
From about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% HFC1225ye and from about 99 wt% to about 1 wt% HFC-1234 yf;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% trans-HFC-1234 ze;
from about 1 wt% to about 99 wt% HFC-1225ye and from about 99 wt% to about 1 wt% HFC-1243 zf;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-134 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-152 a;
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% HFC-227 ea; and
from about 1 wt% to about 99 wt% trans-HFC-1234 ze and from about 99 wt% to about 1 wt% CF 3I;
to said refrigeration, air-conditioning or heat pump apparatus using, used for, or designed to use said high GWP refrigerant.
The invention further relates to a method for early detection of refrigerant leaks in refrigeration, air-conditioning or heat pump apparatus, said method comprising using a non-azeotropic composition in said apparatus and monitoring the reduction in cooling performance.
Detailed description of the invention
The present invention relates to compositions comprising at least one fluoroolefin. The compositions of the present invention further comprise at least one additional component which may be a second fluoroolefin, a Hydrofluorocarbon (HFC), a hydrocarbon, dimethyl ether, bis (trifluoromethyl) sulfide, CF3I or CO2. The fluoroolefin compounds and other components of the compositions of the present invention are listed in Table 1.
TABLE 1
Figure BDA0003177520160000091
Figure BDA0003177520160000101
The components listed in table 1 may be prepared by methods known in the art.
The fluoroolefin compounds (HFC-1225ye, HFC-1234ze and HFC-1234ye) used in the compositions of the present invention may exist as isomers or stereoisomers in different configurations. The present invention is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture thereof. For example, 1, 3, 3, 3-tetrafluoropropene (HFC-1234ze) is meant to indicate the cis isomer, the trans isomer, or any combination or mixture of these two isomers in any ratio. Another example is HFC-1225ye, which is represented by the cis isomer, the trans isomer, or any combination or mixture of the two isomers in any ratio.
The compositions of the present invention comprise the following: HFC-1225ye and at least one compound selected from the group consisting of: HFC-1234ze, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I;
HFC-1234ze and at least one compound selected from the group consisting of: HFC-1225ye, HFC-1234yf, HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I;
HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I; and
HFC-1243zf and at least one compound selected from the group consisting of: HFC-1234ye, HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I; and
HFC-1234ye and at least one compound selected from the group consisting of: HFC-32, HFC-125, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, dimethyl ether, CF3SCF3、CO2And CF3I。
The compositions of the present invention may generally be useful when the fluoroolefin is present at a concentration of from about 1 wt% to about 99 wt%, preferably from about 20 wt% to about 99 wt%, more preferably from about 40 wt% to about 99 wt%, still more preferably from 50 wt% to about 99 wt%.
The present invention further provides the compositions listed in table 2.
TABLE 2
Figure BDA0003177520160000121
Figure BDA0003177520160000131
Figure BDA0003177520160000141
Figure BDA0003177520160000151
Figure BDA0003177520160000161
Figure BDA0003177520160000171
The most preferred compositions of the present invention listed in Table 2 are generally expected to maintain the desired properties and functionality when the components are present at a concentration of +/-2 wt% as listed. When CO is present2CO, when present at the concentrations listed +/-0.2 wt.%2The composition of (a) will be expected to maintain the desired properties and functionality.
The compositions of the present invention may be azeotropic or near-azeotropic compositions. By azeotropic composition is meant a constant boiling mixture of two or more substances that behaves as a single substance. One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it was evaporated or distilled, i.e., the mixture distills/refluxes without compositional change. Constant boiling compositions are characterized as azeotropic compositions in that they exhibit a maximum or minimum boiling point as compared to the boiling point of a non-azeotropic mixture of the same compounds. Azeotropic compositions do not fractionate within the refrigeration or air conditioning system during operation, which can reduce the efficiency of the system. In addition, the azeotropic composition does not fractionate from the refrigeration or air conditioning system in the event of a leak. Where one component of the mixture is a flammable component, fractionation during a leak may produce a flammable composition within the system or outside the system.
Near-azeotropic compositions (also commonly referred to as "azeotrope-like compositions") are substantially constant boiling point liquid mixtures of two or more substances that behave essentially as a single substance. One way to characterize a near azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, i.e., the mixture distills/refluxes without significant compositional change. Another way to characterize a near-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same. Herein, a composition is near azeotropic if, after 50 weight percent of the composition is removed (e.g., by evaporation or boiling off), the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
The azeotropic compositions of the present invention at the specified temperatures are shown in table 3.
TABLE 3
Figure BDA0003177520160000181
Figure BDA0003177520160000191
In addition, ternary azeotrope compositions as listed in table 4 have been found.
TABLE 4
Figure BDA0003177520160000192
Figure BDA0003177520160000201
Figure BDA0003177520160000211
Figure BDA0003177520160000221
The near azeotropic compositions of the present invention at the specified temperatures are listed in table 5.
TABLE 5
Figure BDA0003177520160000222
Figure BDA0003177520160000231
Figure BDA0003177520160000241
Ternary and higher order near azeotrope compositions comprising fluoroolefins as set forth in Table 6 have also been identified.
TABLE 6
Figure BDA0003177520160000242
Figure BDA0003177520160000251
Figure BDA0003177520160000261
Figure BDA0003177520160000271
Certain compositions of the present invention are non-azeotropic compositions. Those compositions of the present invention falling within the preferred ranges of table 2, but outside the near azeotropic ranges of tables 5 and 6, may be considered to be non-azeotropic.
Non-azeotropic compositions may have certain advantages over azeotropic or near-azeotropic mixtures. A non-azeotropic composition is a mixture of two or more substances that behaves as a mixture rather than as a single substance. One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a significantly different composition than the liquid from which it was evaporated or distilled, i.e., the mixture distills/refluxes under a substantial change in composition. Another way to characterize a non-azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are significantly different. Herein, a composition is non-azeotropic if, after 50 weight percent of the composition has been removed (e.g., by evaporation or boiling), the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent.
The compositions of the present invention may be prepared by mixing the required amounts of the components by any suitable method. A preferred method is to weigh the amounts of the desired components and then mix the components in a suitable container. Stirring may be used if desired.
An alternative means of preparing the composition of the present invention may be a method of preparing a refrigerant blend composition, wherein the refrigerant blend composition comprises a composition disclosed herein, the method comprising: (i) recovering a substantial amount of one or more components of the refrigerant composition from at least one refrigerant vessel, (ii) removing impurities sufficient to enable reuse of said one or more recovered components, (iii) and optionally, mixing all or part of said recovered amount of components with at least one additional refrigerant composition or component.
The refrigerant container may be any container in which a refrigerant blend composition has been stored that has been used in a refrigeration apparatus, an air conditioning apparatus or a heat pump apparatus. The refrigerant container may be a refrigeration apparatus, an air conditioning apparatus or a heat pump apparatus in which the refrigerant blend is used. Further, the refrigerant container may be a reservoir for collecting the recovered refrigerant blend components, including but not limited to a pressurized gas cylinder.
Residual refrigerant refers to any quantity of refrigerant blend or refrigerant blend components that may be removed from the refrigerant container by any known method for delivering a refrigerant blend or refrigerant blend components.
The impurities may be any component in the refrigerant blend or refrigerant blend component due to its use in a refrigeration, air conditioning or heat pump apparatus. These impurities include, but are not limited to, refrigeration lubricants, which are those described earlier herein, including, but not limited to, particulates of metal, metal salts or elastomer particles, which may be from refrigeration, air conditioning or heat pump equipment, and any other impurities that may adversely affect the performance of the refrigerant blend composition.
These impurities may be removed sufficiently to allow reuse of the refrigerant blend or refrigerant blend components without adversely affecting the performance of the device in which the refrigerant blend or refrigerant blend components are to be used.
In order to produce a composition that meets the desired specifications for a given product, it may be necessary to provide additional refrigerant blend or refrigerant blend components to the residual refrigerant blend or refrigerant blend components. For example, if a refrigerant blend has 3 components in a particular weight percent range, it may be necessary to add one or more components in a given amount to bring the composition back within specification limits.
The compositions of the present invention have zero or low ozone depletion potential and low Global Warming Potential (GWP). In addition, the compositions of the present invention will have a lower global warming potential than many hydrofluorocarbon refrigerants currently in use. One aspect of the present invention is to provide a refrigerant having a global warming potential of less than 1000, less than 500, less than 150, less than 100, or less than 50. Another aspect of the invention is to reduce the net GWP of the refrigerant mixture by adding a fluoroolefin to the mixture.
The compositions of the present invention may be used as low Global Warming Potential (GWP) replacements for currently used refrigerants, including, but not limited to: r134a (or HFC-134a, 1, 1, 1, 2-tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R123 (or HFC-123, 2, 2-dichloro-1, 1, 1-trifluoroethane), R11(CFC-11, monofluorotrichloromethane), R12(CFC-12, dichlorodifluoromethane), R245fa (or HFC-245fa, 1, 1, 1, 3, 3-pentafluoropropane), R114 (or CFC-114, 1, 2-dichloro-1, 1, 2, 2-tetrafluoroethane), R236fa (or HFC-236fa, 1, 1, 1, 3, 3, 3-hexafluoropropane), R124 (or HCFC-124, 2-chloro-1, 1, 1, 2-tetrafluoroethane), R407C (52 wt% HRAE 134a, 25 wt% R125 (pentafluoroethane), and 23 wt% R32 (difluoromethane), R410A (ASHRAE designation for a blend of 50 wt% R125 and 50 wt% R32), R417A (ASHRAE designation for a blend of 46.6 wt% R125, 50.0 wt% R134a, and 3.4 wt% n-butane), R422A (ASHRAE designation for a blend of 85.1 wt% R125, 11.5 wt% R134a, and 3.4 wt% isobutane), R404A (ASHRAE designation for a blend of 44 wt% R125, 52 wt% R143a (1, 1, 1-trifluoroethane), and 4.0 wt% R134 a), and R507A (ASHRAE designation for a blend of 50 wt% R125 and 50 wt% R143 a). In addition, the compositions of the invention may be used as a replacement for R12(CFC-12, dichlorodifluoromethane) or R502 (ASHRAE nomenclature for blends of 51.2 wt% CFC-115 (chloropentafluoroethane) and 48.8 wt% HCFC-22).
In general, a replacement refrigerant is most useful if it can be used with an original refrigeration unit designed for a different refrigerant. The composition of the present invention may be used as a replacement for the above-mentioned refrigerants in the original equipment. Furthermore, the composition of the present invention can be used as a substitute for the above-mentioned refrigerant in a device designed to use the above-mentioned refrigerant.
The composition of the present invention may further comprise a lubricant.
The lubricants of the present invention comprise refrigeration lubricants, i.e. are suitable for useLubricants such as those used in refrigeration, air conditioning or heat pump equipment. These lubricants include those commonly used in compression refrigeration equipment using chlorofluorocarbon refrigerants. These Lubricants and their properties are discussed in 1990 ASHRAEH Handbook, refining Systems and Applications, Chapter 8, entitled "Lubricants in refining Systems", pages 8.1 to 8.21. Lubricants of the present invention may include those commonly referred to in the field of compression refrigeration lubrication as "mineral oils". Mineral oils include paraffins (i.e., straight and branched carbon chains, saturated hydrocarbons), naphthalenes (i.e., cyclic paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). The lubricants of the present invention further include those commonly referred to in the field of compression refrigeration lubrication as "synthetic oils". Synthetic oils include alkylaryl compounds (i.e., linear and branched alkyl alkylbenzenes), synthetic paraffins and naphthenes, and poly (alpha olefins). Representative of conventional lubricants of the present invention are commercially available BVM 100N (paraffinic mineral oil sold by BVA Oils),
Figure BDA0003177520160000301
3GS and
Figure BDA0003177520160000302
5GS (naphthenic mineral oil sold by Crompton Co.),
Figure BDA0003177520160000303
372LT (naphthenic mineral oil sold by Pennzoil),
Figure BDA0003177520160000304
RO-30 (naphthenic mineral oil sold by Calumet Lubricants),
Figure BDA0003177520160000305
75、
Figure BDA0003177520160000306
150 and
Figure BDA0003177520160000307
500 (sold by Shrieve Chemicals)Linear alkylbenzenes) and HAB22 (branched alkylbenzenes sold by Nippon Oil).
Lubricants of the present invention further include those that have been designed for use with hydrofluorocarbon refrigerants and are miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration, air conditioning or heat pump apparatus. These Lubricants and their properties are discussed in "Synthetic Lubricants and High-Performance Fluids", R.L. Shunkin, editor, Marcel Dekker, 1993. These lubricants include, but are not limited to, polyol esters (POEs) such as
Figure BDA0003177520160000308
100(Castrol, United Kingdom), polyalkylene glycols (PAG) such as RL-488A from Dow (Dow Chemical, Midland, Michigan), and polyvinyl ethers (PVE). These lubricants are readily available from various commercial sources.
The lubricant of the present invention is selected by taking into account the requirements of a given compressor and the environment to which the lubricant will be exposed. The lubricants of the present invention preferably have a kinematic viscosity at 40 ℃ of at least about 5cs (centistokes).
Conventional refrigeration system additives may optionally be added to the compositions of the present invention as needed to enhance lubricity and system stability. These additives are known in the field of refrigeration compressor lubrication and include, anti-wear agents, extreme lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, foaming and defoaming control agents, leak detection agents, and the like. Typically, these additives are present in only small amounts relative to the total lubricant composition. Typically, they are used at concentrations of from less than about 0.1% up to about 3% of each additive. These additives are selected according to the respective system requirements. Some representative examples of such additives may include, but are not limited to, lubricity enhancing additives such as alkyl or aryl esters of phosphoric acid and thiophosphates. Additionally, metal dialkyldithiophosphates (e.g., zinc dialkyldithiophosphate or ZDDP, Lubrizol1375) and other members of such chemicals may be used in the compositions of the present invention. Other antiwear additives include natural product oils and asymmetric polyhydroxy lubricity additives such as Synergol TMS (International Lubricants). Similarly, stabilizers such as antioxidants, radical scavengers, and water scavengers may be used. Compounds in this class may include, but are not limited to, Butylated Hydroxytoluene (BHT) and epoxides.
The composition of the present invention may further comprise from about 0.01 wt% to about 5 wt% of additives, for example, stabilizers, radical scavengers, and/or antioxidants. These additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites or lactones. Single additives or combinations may be used.
The compositions of the present invention may further comprise from about 0.01 wt% to about 5 wt% of a water scavenger (drying compound). These water scavengers may include orthoesters such as trimethyl-, triethyl-or tripropylorthoformate.
The composition of the invention may further comprise a tracer selected from Hydrofluorocarbons (HFCs), deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, dinitrogen monoxide (N)2O) and combinations thereof. The tracer compound is added to the composition in a predetermined amount to allow detection of any dilution, contamination or other change in the composition as described in U.S. patent application serial No. 11/062044 filed on day 2, 18, 2005.
Typical tracer compounds for use in the compositions of the invention are listed in table 7.
TABLE 7
Figure BDA0003177520160000321
Figure BDA0003177520160000331
Figure BDA0003177520160000341
Figure BDA0003177520160000351
The compounds listed in table 7 are commercially available (from chemical suppliers) or may be prepared by methods known in the art.
A single tracer compound may be used in combination with a refrigeration/heating fluid in the compositions of the present invention or multiple tracer compounds may be mixed in any proportion to act as a tracer blend. The tracer blend may comprise multiple tracer compounds from the same class of compounds or multiple tracer compounds from different classes of compounds. For example, the tracer blend can comprise 2 or more deuterated hydrofluorocarbons, or one deuterated hydrofluorocarbon and in combination therewith one or more perfluorocarbons.
In addition, some of the compounds in table 7 exist as multiple isomers (structural isomers or optical isomers). Single isomers or multiple isomers of the same compound may be used in any proportion to prepare the tracer compound. Furthermore, single or multiple isomers of a given compound may be combined in any proportion with a number of other compounds to serve as tracer blends.
The tracer compound or tracer blend can be present in the composition at a total concentration of from about 50 parts by weight per million parts by weight (ppm) to about 1000 ppm. Preferably, the tracer compound or tracer blend is present at a total concentration of from about 50ppm to about 500ppm, most preferably, the tracer compound or tracer blend is present at a total concentration of from about 100ppm to about 300 ppm.
The composition of the present invention may further comprise a compatibilizer selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorohydrocarbons, esters, lactones, aryl ethers, fluoroethers and 1, 1, 1-trifluoroalkanes. The compatibilizers are used to improve the solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants. Refrigeration lubricants are required to lubricate compressors of refrigeration, air conditioning or heat pump equipment. The lubricant must move with the refrigerant throughout the apparatus and, in particular, it must return to the compressor from the non-compressor zone to continue to function as a lubricant and avoid compressor failure.
Hydrofluorocarbon refrigerants are generally not compatible with conventional refrigeration lubricants such as mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes and poly (alpha) olefins. Many alternative lubricants have been proposed, however, the polyalkylene glycols, polyol esters and polyvinyl ethers suggested for use with hydrofluorocarbon refrigerants are expensive and readily absorb water. Water in refrigeration, air conditioning systems or heat pumps can cause corrosion and the formation of particles that can plug capillaries and other small holes in the system, ultimately leading to system failure. Furthermore, in existing equipment, time consuming and expensive cleaning procedures are required to make changes to the new lubricant. It is therefore desirable to continue using the original lubricant if possible.
The compatibilizers of the present invention improve the solubility of hydrofluorocarbon refrigerants in conventional refrigeration lubricants and thus improve oil return to the compressor.
The polyoxyalkylene glycol ether compatibilizer of the present invention is represented by the general formula R1[(OR2)xOR3]y represents, wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; r1Selected from hydrogen and aliphatic hydrocarbon radicals containing from 1 to 6 carbon atoms and y bonding sites; r2Selected from aliphatic hydrocarbylene groups having from 2 to 4 carbon atoms; r3Selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals containing from 1 to 6 carbon atoms; r1And R3At least one is selected from the group consisting of said hydrocarbyl groups; and wherein the polyoxyalkylene glycol ether has a molecular weight of about 100 to about 300 atomic mass units. As used herein, a bonding site refers to a site that can be used to form a covalent bond with other groups. Alkylene means divalent hydrocarbon groups. In the present invention, the preferred polyoxyalkylene glycol ether compatibilizers are represented by the general formula R1[(OR2)xOR3]y represents, x is preferably 1 to 2; y is preferably 1; r1And R3Preferably independently selected from hydrogen and aliphatic hydrocarbon groups containing 1 to 4 carbon atoms; r2Preferably selected from aliphatic hydrocarbylene groups containing 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether preferably has a large molecular weightFrom about 100 to about 250 atomic mass units, and most preferably from about 125 to about 250 atomic mass units. R containing 1-6 carbon atoms1And R3The hydrocarbyl groups may be linear, branched or cyclic. Representative R1 and R3 hydrocarbyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. When the free hydroxyl groups on the polyoxyalkylene glycol ether compatibilizer are likely to be associated with certain compression refrigeration equipment materials of construction (e.g., the polypropylene glycol ether compatibilizer
Figure BDA0003177520160000371
) When incompatible, R1And R3Preferably an aliphatic hydrocarbon group containing 1 to 4 carbon atoms, most preferably 1 carbon atom. R containing 2-4 carbon atoms2The aliphatic alkylene groups forming repeating oxyalkylene groups- (OR)2) x-, the latter including oxyethylene groups, oxypropylene groups, and oxybutylene groups. Containing R in one polyoxyalkylene glycol ether compatibilizer molecule2The oxyalkylene groups of (a) may be the same, or one molecule may contain different R2An alkylene oxide. The polyoxyalkylene glycol ether compatibilizer of the present invention preferably comprises at least one oxypropylene group. When R is1When it is an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms and y bonding sites, the group may be linear, branched or cyclic. Representative of R containing two bonding sites1The aliphatic hydrocarbon group includes, for example, ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene and cyclohexylene. Representative R having 3 or 4 bonding sites1The aliphatic hydrocarbon group includes residues derived from polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, 1, 2, 3-trihydroxycyclohexane and 1, 3, 5-trihydroxycyclohexane by removing their hydroxyl groups.
Representative polyoxyalkylene glycol ether compatibilizers include, but are not limited to: CH (CH)3OCH2CH(CH3) O (H or CH)3) (propylene glycol methyl (or dimethyl) ether), CH3O[CH2CH(CH3)O]2(H or CH)3) (Dipropyleneglycol methyl group(or dimethyl) ether), CH3O[CH2CH(CH3)O]3(H or CH)3) (tripropylene glycol methyl (or dimethyl) ether) C2H5OCH2CH(CH3) O (H or C)2H5) (propylene glycol ethyl (or diethyl) ether), C2H5O[CH2CH(CH3)O]2(H or C)2H5) (dipropylene glycol ethyl (or diethyl) ether), C2H5O[CH2CH(CH3)O]3(H or C)2H5) (tripropylene glycol ethyl (or diethyl) ether) C3H7OCH2CH(CH3) O (H or C)3H7) (propylene glycol n-propyl (or di-n-propyl) ether), C3H7O[CH2CH(CH3)O]2(H or C)3H7) (dipropylene glycol n-propyl (or di-n-propyl) ether), C3H7O[CH2CH(CH3)O]3(H or C)3H7) (tripropylene glycol n-propyl (or di-n-propyl) ether), C4H9OCH2CH(CH3) OH (propylene glycol n-butyl ether), C4H9O[CH2CH(CH3)O]2(H or C)4H9) (dipropylene glycol n-butyl (or di-n-butyl) ether), C4H9O[CH2CH(CH3)O]3(H or C)4H9) (tripropylene glycol n-butyl (or di-n-butyl) ether), (CH)3)3COCH2CH(CH3) OH (propylene glycol tert-butyl ether), (CH)3)3CO[CH2CH(CH3)O]2(H or (CH)3)3) (dipropylene glycol t-butyl (or di-t-butyl) ether), (CH)3)3CO[CH2CH(CH3)O]3(H or (CH)3)3) (tripropylene glycol t-butyl (or di-t-butyl) ether) C5H11OCH2CH(CH3) OH (propylene glycol n-amyl ether), C4H9OCH2CH(C2H5) OH (butanediol n-butyl ether), C4H9O[CH2CH(C2H5)O]2H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C)2H5C(CH2O(CH2)3CH3)3) And trimethylolpropane di-n-butyl ether (C)2H5C(CH2OC(CH2)3CH3)2CH2OH)。
The amide compatibilizer of the present invention comprises a compound represented by the general formula R1C(O)NR2R3And ring- [ R4C(O)N(R5)]Those represented, wherein: r1、R2、R3And R5Independently selected from aliphatic and alicyclic hydrocarbon radicals containing from 1 to 12 carbon atoms; r4Selected from aliphatic hydrocarbylene groups having from 3 to 12 carbon atoms; and wherein the amide has a molecular weight of about 100 to about 300 atomic mass units. The molecular weight of the amide is preferably from about 160 to about 250 atomic mass units. R1,R2,R3And R5Substituted hydrocarbyl groups, i.e., groups containing non-hydrocarbon substituents selected from halo (e.g., fluoro, chloro) and alkoxy (e.g., methoxy), may optionally be included. R1,R2,R3And R5Heteroatom-substituted hydrocarbyl groups may optionally be included, i.e., groups containing the atom nitrogen (aza-), oxygen (oxa-), or sulfur (thia-) in a chain of groups otherwise composed of carbon atoms. Generally, for in R1-3Will have no more than three non-hydrocarbon substituents and heteroatoms per 10 carbon atoms, and preferably no more than one, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered when applying the molecular weight limitations described above. Preferred amide compatibilizers are composed of carbon, hydrogen, nitrogen and oxygen. Representative of R1,R2,R3And R5Aliphatic and alicyclic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of the amide solubilizer is one wherein the ring- [ R ] is in the above formula4C(O)N(R5)-]R in (1)4May be prepared from alkylene (CR)6R7) n, in other words, of the general formula: cyclo- [ (CR)6R7)nC(O)N(R5)-]Wherein: the same applies for the previously stated values for molecular weight; n is an integer of 3 to 5; r5Is a saturated hydrocarbon group containing 1 to 12 carbon atoms; r6And R7From the foregoing for the definition of R1-3Is selected independently (for each n). In a composition represented by the general formula: cyclo- [ (CR)6R7)nC(O)N(R5)-]In the lactam represented, all R6And R7Preferably hydrogen, or a single saturated hydrocarbon group containing among n methylene units, R5Is a saturated hydrocarbon group having 3 to 12 carbon atoms. For example, 1- (saturated hydrocarbon group) -5-methylpyrrolidin-2-one.
Representative amide solubilizing agents include, but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperidin-2-one, 1-pentyl-5-methylpiperidin-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperidin-2-one, 1, 3-dimethylpiperidin-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1, 5-dimethylpiperidin-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolidin-2-one, N, N-dibutylformamide and N, N-diisopropylacetamide.
The ketone compatibilizers of the present invention comprise a copolymer represented by the general formula R1C(O)R2A ketone of formula (I), wherein R1And R2Independently selected from aliphatic, alicyclic, and aromatic hydrocarbon radicals containing from 1 to 12 carbon atoms, and wherein said ketone has a molecular weight of from about 70 to about 300 atomic mass units. R in said ketone1And R2Preferably independently selected from aliphatic and alicyclic hydrocarbon radicals containing from 1 to 9 carbon atoms. The molecular weight of the ketone is preferably about 100-200 atomic mass units. R1And R2Together, alkylene groups can be formed which link and form five-, six-, or seven-membered cyclic ketones, such as cyclopentanone, cyclohexanone, and cycloheptanone. R1,R2,R3And R5Can be used forOptionally included are substituted hydrocarbyl groups, i.e., groups containing non-hydrocarbon substituents selected from halo (e.g., fluoro, chloro) and alkoxy (e.g., methoxy). R1And R2Heteroatom-substituted hydrocarbon radicals, i.e. radicals which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain otherwise composed of carbon atoms, may optionally be included. Generally, for in R1And R2Will have no more than three non-hydrocarbon substituents and heteroatoms per 10 carbon atoms, and preferably no more than one, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered when applying the molecular weight limitations described above. In the general formula R1COR2R is a representative of1And R2Aliphatic, alicyclic and aryl hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, 2, 4, 6-trimethylphenyl, tolyl, dimethylphenyl and phenethyl.
Representative ketone solubilizers include, but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanoylbenzene, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, methylhexyl ketone (2-octanone), 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone, and dicyclohexyl ketone.
The nitrile compatibilizers of the present invention comprise a copolymer represented by the general formula R1A nitrile represented by CN, wherein R1Selected from aliphatic, alicyclic, or aryl hydrocarbon groups containing 5 to 12 carbon atoms, and wherein said nitrile has a molecular weight of about 90 to about 200 atomic mass units. R in the nitrile compatibilizer1Preferably selected from aliphatic and alicyclic hydrocarbon radicals having from 8 to 10 carbon atoms. The molecular weight of the nitrile compatibilizer is preferably about 120 to about 140 atomic mass units. R1May optionally include substituted hydrocarbyl, i.e., radicals containing non-hydrocarbon substituents selected from halo (e.g., fluoro, chloro) and alkoxy (e.g., methoxy)And (4) clustering. R1Heteroatom-substituted hydrocarbon radicals, i.e. radicals which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in the radical chain otherwise composed of carbon atoms, may optionally be included. Generally, for in R1Will have no more than three non-hydrocarbon substituents and heteroatoms per 10 carbon atoms, and preferably no more than one, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered when applying the molecular weight limitations described above. In the general formula R1Representative R in CN1Aliphatic, alicyclic and aryl hydrocarbon groups include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, 2, 4, 6-trimethylphenyl, tolyl, dimethylphenyl and phenethyl.
Representative nitrile compatibilizers include, but are 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 chlorinated hydrocarbon compatibilizers of the present invention include chlorinated hydrocarbons represented by the general formula RClx, wherein: x is an integer selected from 1 or 2; r is selected from aliphatic and alicyclic hydrocarbon radicals containing 1 to 12 carbon atoms; and wherein the chlorinated hydrocarbon has a molecular weight of about 100 to about 200 atomic mass units. The molecular weight of the chlorinated hydrocarbon compatibilizer is preferably about 120-150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RClx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.
Representative chlorinated hydrocarbon compatibilizers include, but are not limited to: 3- (chloromethyl) pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1, 6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1, 1, 1-trichlorodecane.
The ester of the present inventionThe solvent comprises a compound represented by the general formula R1CO2R2An ester of wherein R1And R2Independently selected from linear and cyclic, saturated and unsaturated alkyl and aryl groups. Preferred esters consist essentially of elements C, H and O and have a molecular weight of about 80 to about 550 atomic mass units.
Representative esters include, but are not limited to: (CH)3)2CHCH2OOC(CH2)2-4OCOCH2CH(CH3)2(diisobutyl dibasic acid), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, ethoxyethyl benzoate, dipropyl carbonate, "Exxate 700" (commercial acetic acid C)7Alkyl esters), "Exxate 800" (commercial acetic acid C)8Alkyl esters), dibutyl phthalate, and tert-butyl acetate.
The lactone compatibilizers of the present invention include lactones represented by the structures [ a ], [ B ], and [ C ]:
Figure BDA0003177520160000411
these lactones contain a functional group-CO in a six-atom ring (A), or preferably a five-atom ring (B)2-, wherein for the structure [ A]And [ B],R1To R8Independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups. R1To R8Each of which may be with R1To R8The other of which is connected to form a ring. The lactone may have the structure [ C ]]In which R is an exocyclic alkylidene group1To R6Independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl groups. R1To R6Each of which may be with R1To R6The other of which is connected to form a ring. The lactone compatibilizers have a molecular weight of from about 80 to about 300 atomic mass units, preferably from about 80 to about 200 atomic mass units.
Representative lactone compatibilizers include, but are not limited to, the compounds listed in table 8.
TABLE 8
Figure BDA0003177520160000412
Figure BDA0003177520160000421
Figure BDA0003177520160000431
The lactone compatibilizers generally have a kinematic viscosity of less than about 7 centistokes at 40 ℃. For example, at 40℃, gamma undecalactone has a kinematic viscosity of 5.4 centistokes and cis (3-hexyl-5-methyl) dihydrofuran-2-one has a viscosity of 4.5 centistokes. The lactone compatibilizers may be commercially available or prepared by methods such as described in U.S. patent application 10/910,495 filed on 8/3/2004, which is incorporated herein by reference.
The aryl ether compatibilizers of the present invention further comprise a copolymer represented by the general formula R1OR2An aryl ether of the formula (I) wherein: r1Selected from aryl hydrocarbons containing 6 to 12 carbon atoms; r2Selected from aliphatic hydrocarbon groups containing 1 to 4 carbon atoms; and wherein the aryl ether has a molecular weight of about 100 to about 150 atomic mass units. In the general formula R1OR2R is a representative of1Aryl groups include phenyl, biphenyl, cumyl, 2, 4, 6-trimethylphenyl, tolyl, dimethylphenyl, naphthyl and pyridyl. In the general formula R1OR2Representative of R in (1)2Aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizing agents include, but are not limited to: methyl phenyl ether (anisole), 1, 3-dimethoxybenzene, ethyl phenyl ether and butyl phenyl ether.
The fluoroether compatibilizers of the present invention comprise a blend represented by the formula R1OCF2CF2H, wherein R is1Selected from largeAliphatic, alicyclic and aromatic hydrocarbon groups of from about 5 to about 15 carbon atoms, preferably primary, linear, saturated alkyl groups. Representative fluoroether compatibilizers include, but are not limited to: c8Hi7OCF2CF2H and C6H13OCF2CF2H. It should be noted that if the refrigerant is a fluoroether, the compatibilizer may not be the same fluoroether.
The fluoroether compatibilizer may further comprise an ether derived from a fluoroolefin and a polyol. The fluoroolefin may have CF2A form CXY wherein X is hydrogen, chloro or fluoro and Y is chloro, fluoro, CF3OR ORfWherein R isfIs CF3、C2F5Or C3F7. Representative fluoroolefins are tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and perfluoromethyl vinyl ether. The polyols may be linear or branched. The linear polyol may have a HOCH2(CHOH)x(CRR′)yCH2OH form, wherein R and R' are hydrogen, CH3Or C2H5And wherein x is an integer from 0 to 4 and y is an integer from 0 to 4. The branched polyol has C (OH) t (R) u (CH)2OH)v[(CH2)mCH2OH]w type, wherein R can be hydrogen, CH3Or C2H5M is an integer from 0 to 3, t and u can be 0 or 1, V and w are integers from 0 to 4, and further wherein t + u + V + w is 4. Representative polyols are trimethylolpropane, pentaerythritol, butanediol and ethylene glycol.
The 1, 1, 1-trifluoroalkane compatibilizers of the present invention comprise a copolymer represented by the general formula CF3R11, 1, 1-trifluoroalkane of the formula, wherein R1Selected from aliphatic and alicyclic hydrocarbon groups containing from about 5 to about 15 carbon atoms, preferably primary, linear, saturated alkyl groups. Representative 1, 1, 1-trifluoroalkane compatibilizers include, but are not limited to: 1, 1, 1-trifluorohexane and 1, 1, 1-trifluorododecane.
An effective amount of a compatibilizer refers to an amount of compatibilizer that causes the lubricant to effectively solubilize in the composition and thus provide sufficient oil return to optimize the operation of the refrigeration, air conditioning or heat pump apparatus.
The compositions of the present invention will generally comprise from about 0.1 to about 40 weight percent, preferably from about 0.2 to about 20 weight percent, and most preferably from about 0.3 to about 10 weight percent of the composition of the present invention of a compatibilizer.
The present invention further relates to a method of solubilizing a refrigerant or heat transfer fluid composition comprising a composition of the present invention in a refrigeration lubricant selected from the group consisting of mineral oil, alkylbenzene, synthetic paraffin, synthetic cycloalkane, and poly (alpha) olefin, wherein said method comprises contacting said lubricant with said composition in the presence of an effective amount of a compatibilizer, wherein said compatibilizer is selected from the group consisting of polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1, 1, 1-trifluoroalkanes.
The invention further relates to a method for improving oil return to a compressor in a compression refrigeration, air-conditioning or heat pump apparatus, said method comprising using a composition comprising a compatibilizer in said apparatus.
The composition of the present invention may further comprise an Ultraviolet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component that allows one to observe the fluorescence of the dye in a composition at or near the point of leakage in refrigeration, air conditioning or heat pump equipment to detect leakage from the composition. One can observe the fluorescence of the dye under ultraviolet light. Solubilizers are desirable due to the poor solubility of such UV dyes in some compositions.
"ultraviolet" dye refers to a UV fluorescent composition that can absorb light in the ultraviolet or "near" ultraviolet region of the electromagnetic spectrum. Fluorescence generated by UV fluorescent dyes emitting radiation having any wavelength from 10 nm to 750 nm under the irradiation of UV light can be detected. Thus, if a composition containing such a UV fluorescent dye leaks at a given point in a refrigeration, air conditioning or heat pump apparatus, the fluorescence can be detected at that leak point. Such UV fluorescent dyes include, but are not limited to, naphthalimides, perylenes, coumarins, anthracenes, phenanthrenes, xanthenes, thioxanthenes, benzoxanthenes, fluoresceins, and derivatives or combinations thereof.
The solubilizing agent of the present invention may comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, arylhydrocarbons, fluoroethers and 1, 1, 1-trifluoroalkanes. The polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1, 1, 1-trifluoroalkane solubilizing agents have been previously defined herein as compatibilizers for conventional refrigeration lubricants.
The hydrocarbon solubilizing agents of the present invention include hydrocarbons including straight chain, branched chain or cyclic paraffins or olefins containing 5 or less carbon atoms and having only hydrogen but no other functional groups. Representative hydrocarbon solubilizers include propane, propylene, cyclopropane, n-butane, isobutane, 2-methylbutane and n-pentane. It should be noted that if the composition comprises a hydrocarbon, the solubilizer may not be the same hydrocarbon.
The hydrocarbon ether solubilizing agents of the present invention include ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).
The solubilizing agent of the present invention may be present as a single compound or may be present as a mixture of more than one solubilizing agent. The mixture of solubilizers may contain two solubilizers belonging to the same class of compounds, for example two lactones, or two solubilizers belonging to different classes of compounds, for example lactones and polyoxyalkylene glycol ethers.
In the composition of the present invention comprising a refrigerant and a UV fluorescent dye or comprising a heat transfer fluid and a UV fluorescent dye, about 0.001 wt% to about 1.0 wt% of the composition is the UV dye, preferably about 0.005 wt% to about 0.5 wt%, most preferably 0.01 wt% to about 0.25 wt%.
Solubilizers such as ketones have undesirable odors that can be masked by the addition of odor masking agents or fragrances. Typical examples of odor masking agents or fragrances may include Evergreen (Evergreen), fresh lemon, cherry, cinnamon, mint, flower or orange peel, all of which are commercially available, as well as carvone and pinene. Such odor masking agents may be used at concentrations of about 0.001 wt% up to about 15 wt%, based on the total weight of the odor masking agent and the solubilizing agent.
The solubility of these UV fluorescent dyes in the compositions of the present invention may be poor. Therefore, the methods of introducing these dyes into refrigeration, air conditioning or heat pump equipment are awkward, expensive and time consuming. U.S. patent No. RE36,951 describes a process that uses dye powders, solid pellets or dye slurries that can be inserted into components of refrigeration, air conditioning or heat pump equipment. As the refrigerant and lubricant circulate in the device, the dye dissolves or disperses throughout the device. Many other methods of introducing dyes into refrigeration or air conditioning equipment are described in the literature.
Ideally, the UV fluorescent dye may be dissolved in the refrigerant itself, thus not requiring any special method of introduction into refrigeration, air conditioning or heat pumps. The present invention relates to compositions comprising UV fluorescent dyes that can be introduced into a system as a solution in a refrigerant. The compositions of the invention may allow storage and delivery of dye-containing compositions even at low temperatures while maintaining the dye in a dissolved state.
In the composition of the present invention comprising a refrigerant, a UV fluorescent dye and a solubilizing agent or comprising a heat transfer fluid and a UV fluorescent dye and a solubilizing agent, about 1 to about 50 wt%, preferably about 2 to about 25 wt%, most preferably about 5 to about 15 wt% of the total composition is a solubilizing agent. In the compositions of the present invention, the UV fluorescent dye is present at a concentration of about 0.001 wt% to about 1.0 wt%, preferably 0.005 wt% to about 0.5 wt%, and most preferably 0.01 wt% to about 0.25 wt%.
The present invention further relates to a method of using a composition further comprising an ultraviolet fluorescent dye, and optionally a solubilizing agent, in refrigeration, air-conditioning or heat pump apparatus. The method comprises introducing the composition into a refrigeration, air-conditioning or heat pump apparatus. This can be achieved by dissolving the UV fluorescent dye in the composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be accomplished by combining a solubilizing agent and a UV fluorescent dye and introducing the combination into a refrigeration or air conditioning apparatus containing a refrigerant and/or heat transfer fluid. The resulting compositions may be used in refrigeration, air-conditioning or heat pump equipment.
The invention further relates to methods of detecting leaks using compositions comprising ultraviolet fluorescent dyes. The presence of the dye in the composition allows for detection of leaking refrigerant in refrigeration, air conditioning or heat pump equipment. Leak detection helps to counter, address, or prevent inefficient operation of the device or system or device failure. Leak detection also helps it contain chemicals used in the operation of the device.
The method comprises providing a composition comprising a refrigerant, an ultraviolet fluorescent dye as described herein and optionally a solubilizing agent as described herein to a refrigeration, air conditioning or heat pump apparatus and using suitable means for detecting the refrigerant containing the UV fluorescent dye. Suitable devices for detecting dyes include, but are not limited to, ultraviolet lamps, often referred to as "black light" or "blue light". These ultraviolet lamps are commercially available from a number of sources specifically designed for this purpose. Once the composition containing the UV fluorescent dye has been introduced into the refrigeration, air-conditioning or heat pump apparatus and circulated through the system, leaks can be discovered by illuminating the UV lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak points.
The present invention further relates to a method of replacing a high GWP refrigerant in a refrigeration, air-conditioning or heat pump apparatus, wherein said high GWP refrigerant is selected from the group consisting of R134a, R22, R245fa, R114, R236fa, R124, R410A, R407C, R417A, R422A, R507A and R404A, said method comprising providing a composition of the present invention to said refrigeration, air-conditioning or heat pump apparatus used, used or designed to use said high GWP refrigerant. A vapor compression refrigeration, air conditioning or heat pump system includes an evaporator, a compressor, a condenser, and an expansion device. The vapor compression cycle reuses refrigerant in multiple steps, creating a cooling effect in one step and a heating effect in a different step. This cycle can be described briefly as follows. The liquid refrigerant enters the evaporator through an expansion device where it then boils at a low temperature to form a gas and produce a cooling effect. The low pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher pressure (compressed) gaseous refrigerant then enters the condenser where it condenses and rejects its heat to the environment. The refrigerant is returned to the expansion device, through which the liquid is expanded from a higher pressure level in the condenser to a lower pressure level in the evaporator, thus repeating the cycle.
As used herein, a sports refrigeration or sports air conditioning refers to any refrigeration or air conditioning apparatus incorporated into a transportation unit for roads, tracks, oceans or the sky. In addition, equipment used to provide refrigeration or air conditioning for systems that do not rely on any moving carriers (called "intermodal" systems) is also included in the present invention. Such intermodal systems include "containers" (combined marine/land transport) and "exchanges" (combined road and rail transport). The invention is particularly useful for road transport refrigeration or air conditioning apparatus, such as automotive air conditioning apparatus or refrigerated road transport vehicles.
The invention further relates to a method of refrigeration comprising evaporating a composition of the invention in the vicinity of the body to be cooled and thereafter condensing said composition.
The invention further relates to a method for generating heat, comprising condensing a composition according to the invention in the vicinity of a body to be heated, and thereafter evaporating said composition.
The present invention further relates to a refrigeration, air-conditioning or heat pump apparatus comprising the composition of the present invention, wherein the composition comprises at least one fluoroolefin.
The present invention further relates to a sports air conditioning unit comprising the composition of the present invention, wherein said composition comprises at least one fluoroolefin.
The invention further relates to a method for early detection of refrigerant leaks in refrigeration, air-conditioning or heat pump apparatus, said method comprising using a non-azeotropic composition in said apparatus and monitoring the reduction in cooling performance. The non-azeotropic composition will fractionate from the refrigeration, air conditioning or heat pump equipment in the event of a leak and the lower boiling (higher vapor pressure) component will leak out of the equipment first. When this occurs, if the lower boiling components in the composition provide the majority of the refrigeration capacity, a significant reduction in refrigeration capacity and hence equipment performance occurs. In an automotive air conditioning system, a passenger in an automobile, for example, will detect a reduction in the cooling capacity of the system. This reduction in cooling capacity may be interpreted to mean that the refrigerant is leaking and the system needs to be repaired.
The invention further relates to a method of using the composition of the invention as a heat transfer fluid composition comprising transporting the composition from a heat source to a heat sink.
The heat transfer fluid is utilized to transfer, migrate or separate heat from one space, location, object or body to a different space, location, object or body by radiation, conduction or convection. The heat transfer fluid may be used as a secondary coolant by providing a transfer device that cools (or heats) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may be maintained at a constant state (i.e., not vaporized or condensed) throughout the process. Alternatively, the evaporative cooling process may likewise utilize a heat transfer fluid.
A heat source may be defined as any space, location, object or body from which it is desirable to transfer, migrate or remove heat. Examples of heat sources may be spaces (open or closed) that require refrigeration or cooling, such as refrigerator or freezer cabinets in supermarkets, building spaces that require air conditioning, or the passenger compartment of a car that requires air conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.
In another embodiment, the present invention relates to a blowing agent composition for preparing a foam comprising the fluoroolefin-containing composition described herein. In other embodiments, the present invention provides foamable compositions, preferably polyurethane and polyisocyanate foam compositions, and methods of making foams. In these foam embodiments, one or more fluoroolefin-containing compositions of the present invention are included as blowing agents in foamable compositions that preferably include one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure. Any of the methods well known in the art, such as those described in "Polyurethanes Chemistry and Technology", volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y. (which is incorporated herein by reference), may be used or adapted for use in accordance with foam embodiments of the present invention.
The invention further relates to a method of forming a foam comprising: (a) adding the fluoroolefin-containing composition of the present invention to a foamable composition; and (b) reacting the foamable composition under conditions effective to form a foam.
Another embodiment of the present invention relates to the use of the fluoroolefin-containing compositions described herein as propellants in sprayable compositions. Further, the present invention relates to sprayable compositions comprising fluoroolefin-containing compositions described herein. The active ingredients to be sprayed, as well as inert ingredients, solvents, and other materials may also be present in the sprayable composition. Preferably, the sprayable composition is an aerosol. Suitable active materials to be sprayed include, but are not limited to, cosmetic materials such as deodorants, fragrances, hair sprays, cleansers and polishes, and medicinal materials such as anti-asthma and anti-halitosis medications.
The invention further relates to a method for the production of an aerosol product comprising the steps of: the fluoroolefin-containing compositions described herein are added to an active ingredient in an aerosol container, wherein the composition functions as a propellant.
Another aspect provides a method of suppressing a flame comprising contacting a flame with a fluid comprising a fluoroolefin-containing composition of the present disclosure. Any suitable method of contacting the flame with the composition of the present invention may be used. For example, the fluoroolefin-containing composition of the present disclosure may be sprayed, poured, etc. onto the flame, or at least a portion of the flame may be immersed in the flame inhibiting composition. Various conventional apparatus and methods of flame suppression will be readily adapted by those skilled in the art for use in the present disclosure in view of the teachings herein.
Another embodiment provides a method of suppressing or suppressing a fire in a total-flood application comprising: providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the reagent in a pressurized discharge system; and discharging the agent into a region to extinguish or suppress a fire in that region. Another embodiment provides a method of inerting an area to prevent a fire or explosion, comprising: providing an agent comprising a fluoroolefin-containing composition of the present disclosure; disposing the reagent in a pressurized discharge system; and discharging the agent into the area to prevent a fire or explosion from occurring.
The term "extinguishment" is commonly used to mean complete elimination of a fire; while "suppression" is generally used to mean a reduction, but not necessarily a complete elimination of a fire or explosion. As used herein, the terms "extinguishment" and "inhibition" will be used interchangeably. There are four general types of halocarbon fire and explosion protection applications. (1) In total flood fire suppression and/or suppression applications, the agent is discharged into a space to achieve a concentration sufficient to suppress or suppress an existing fire. Total flooding applications include the protection of enclosed, potentially occupied spaces such as computer rooms as well as dedicated, often vacant spaces such as aircraft engine nacelles and nacelles in carriers. (2) In jet (streaming) applications, the reagent is applied directly onto or into the area of a fire. This is typically accomplished using manually operated wheels or a portable device. A second method, included as a spray application, uses a "localized" system that discharges an agent from one or more fixed nozzles toward a fire. The localization system may be activated manually or automatically. (3) In explosion suppression, fluoroolefin-containing compositions of the present disclosure are discharged to suppress an explosion that has been initiated. The term "suppression" is commonly used in this application because explosions are generally self-limiting. However, the use of this term does not necessarily mean that the agent does not extinguish the explosion. In this application, a detector is typically used to detect an expanding fireball resulting from an explosion and rapidly discharge the agent to suppress the explosion. Explosion suppression is primarily, but not exclusively, used in defense applications. (4) In inerting, the fluoroolefin-containing compositions of the present disclosure are discharged into a space to prevent an explosion or fire from being initiated. Typically, a system similar or identical to that used for total flooding fire suppression or suppression is used. Typically, the presence of a hazardous condition (e.g., a hazardous concentration of flammable or explosive gas) is detected, and the fluoroolefin-containing composition of the present disclosure is discharged to prevent the explosion or fire from occurring until the condition can be remedied.
The extinguishing process may be carried out by introducing the composition into an enclosed area around the fire. Any known method of introduction may be used so long as the appropriate amount of the composition is metered into the enclosed area at the appropriate intervals. For example, the composition may be introduced as follows: spraying, for example using conventional portable (or fixed) fire extinguishing equipment; atomizing; or flooding, e.g., to release (using appropriate piping, valves, and controls) the composition into an enclosed area surrounding the fire. The composition may optionally be combined with an inert propellant, such as nitrogen, argon, decomposition products of glycidyl azide polymers, or carbon dioxide, to increase the rate at which the composition is discharged from the spraying or flooding device in use.
Preferably, the extinguishing method comprises introducing the fluoroolefin-containing composition of the present disclosure into a fire or flame in an amount sufficient to extinguish the fire or flame. Those skilled in the art will recognize that the amount of flame suppressant required to suppress a particular fire will depend on the nature and extent of the hazard. When flame suppressants are to be introduced by flooding, cup burner test data can be used to determine the amount or concentration of flame suppressant required to extinguish a particular type and size of fire.
Laboratory tests useful for determining effective concentration ranges for fluoroolefin-containing compositions when combined with extinguishing or suppressing a fire in a total flood application or fire inerting manner are described, for example, in U.S. Pat. No. 5,759,430, which is incorporated herein by reference.
Examples
Example 1
Influence of steam leakage
The initial composition is charged to a container at-25 ℃ or, if specified, at a temperature of 25 ℃ and the initial vapor pressure of the composition is measured. The composition is allowed to leak from the container while maintaining the temperature until 50 wt% of the initial composition is removed, at which time the vapor pressure of the composition remaining in the container is measured. The results are shown in table 9.
TABLE 9
Figure BDA0003177520160000521
Figure BDA0003177520160000531
Figure BDA0003177520160000541
Figure BDA0003177520160000551
Figure BDA0003177520160000561
Figure BDA0003177520160000571
Figure BDA0003177520160000581
Figure BDA0003177520160000591
Figure BDA0003177520160000601
Figure BDA0003177520160000611
Figure BDA0003177520160000621
Figure BDA0003177520160000631
Figure BDA0003177520160000641
Figure BDA0003177520160000651
Figure BDA0003177520160000661
Figure BDA0003177520160000671
Figure BDA0003177520160000681
For the compositions of the present invention, the difference in vapor pressure between the original composition and the composition remaining after 50 wt% removal is less than about 10%. This indicates that the compositions of the present invention may be azeotropic or near azeotropic.
Example 2
Refrigeration performance data
Table 10 shows the performance of various refrigerant compositions of the present invention compared to HFC-134 a. In table 10, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor outlet temperature, COP is energy efficiency, and CAP is capacity (capacity). The data are based on the following conditions.
Figure BDA0003177520160000682
Figure BDA0003177520160000691
Note that superheat is taken into account in the cooling capacity calculation.
Watch 10
Figure BDA0003177520160000692
Figure BDA0003177520160000701
Several compositions have even higher energy efficiency (COP) than HFC-134a while maintaining lower discharge pressures and temperatures. The capacity of the compositions of the present invention is also similar to that of R134a, indicating that they may be used as a replacement refrigerant for R134a in refrigeration and air conditioning, especially sports air conditioning applications. Those compositions containing hydrocarbons may also improve oil solubility with conventional mineral oils and alkylbenzene lubricants.
Example 3
Refrigeration performance data
Table 11 shows the performance of various refrigerant compositions of the present invention compared to R404A and R422A.
In Table 11, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor outlet temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Figure BDA0003177520160000711
Note that superheat is taken into account in the cooling capacity calculation.
TABLE 11
Figure BDA0003177520160000712
Figure BDA0003177520160000721
Figure BDA0003177520160000731
Figure BDA0003177520160000741
Figure BDA0003177520160000751
Several compositions have similar energy efficiencies (COPs) as R404A and R422A. The discharge temperature is also lower than R404A and R507A. The capacity of the compositions of the present invention is also similar to that of R404A, R507A and R422A, indicating their potential use as replacement refrigerants in refrigeration and air conditioning. Those compositions containing hydrocarbons may also improve oil solubility with conventional mineral oils and alkylbenzene lubricants.
Example 4
Refrigeration performance data
Table 12 shows the performance of various refrigerant compositions of the present invention compared to HCFC-22, R410A, R407C, and R417A. In Table 12, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor outlet temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Figure BDA0003177520160000761
Note that superheat is taken into account in the cooling capacity calculation.
TABLE 12
Figure BDA0003177520160000762
Figure BDA0003177520160000771
The compositions have Energy Efficiencies (EERs) similar to R22, R407C, R417A, and R410A, while maintaining low discharge temperatures. The capacity of the compositions of the present invention is also similar to that of R22, R407C and R417A, indicating their potential use as replacement refrigerants in refrigeration and air conditioning. Those compositions containing hydrocarbons may also improve oil solubility with conventional mineral oils and alkylbenzene lubricants.
Example 5
Refrigeration performance data
Table 13 shows the performance of various refrigerant compositions of the present invention compared to HCFC-22 and R410A. In Table 13, Evap Pres is evaporator pressure, Cond Pres is condenser pressure, Comp Disch T is compressor outlet temperature, EER is energy efficiency, and CAP is capacity. The data are based on the following conditions.
Figure BDA0003177520160000772
Note that superheat is taken into account in the cooling capacity calculation.
Watch 13
Figure BDA0003177520160000773
Figure BDA0003177520160000781
The compositions have Energy Efficiencies (EERs) similar to R22 and R410A while maintaining reasonable discharge temperatures. The capacity of the compositions of the present invention was also similar to that of R22, indicating their potential use as replacement refrigerants in refrigeration and air conditioning.
Example 6
Combustibility
The combustible compounds can be determined by Testing using an electronic ignition source under ASTM (American Society of Testing and materials) E681-01. Such flammability tests were conducted at various concentrations in air at 101kPa (14.7psia), 100 ℃ (212 ° F), and 50% relative humidity on HFC-1234yf, HFC-1225ye, and mixtures of the present disclosure to determine a Lower Flammability Limit (LFL) and an Upper Flammability Limit (UFL). The results are given in table 14.
TABLE 14
Figure BDA0003177520160000791
The results show that the addition of HFC-1225ye reduces flammability when HFC-1234yf is flammable. Thus, compositions comprising from about 1 wt% to about 49 wt% HFC-1234yf and from about 99 wt% to about 51 wt% HFC-1225ye are preferred.

Claims (24)

1. A composition comprising HFC-1234yf and at least one compound selected from the group consisting of: HFC-1234ve, HFC-1243zf, HFC-125, HFC-134, HFC-143a, HFC-161, HFC-227ea, HFC-236fa, HFC-245fa, HFC-365mfc, CF3SCF3、CO2And CF3I。
2. The composition of claim 1 selected from the group consisting of:
HFC-1234yf, HFC-125, and n-butane;
HFC-1234yf, HFC-125, and isobutane;
HFC-1234yf, HFC-32 and HFC-143 a;
HFC-1234yf, HFC-125 and HFC-143 a;
HFC-1234yf, HFC-125, and isobutane;
HFC-1234yf, HFC-134, and propane;
HFC-1234yf, HFC-134, and dimethyl ether;
HFC-1234yf, HFC-143a and propane;
HFC-1234yf, HFC-143a and dimethyl ether;
HFC-1234yf, HFC-227ea and propane;
HFC-1234yf, HFC-227ea and n-butane;
HFC-1234yf, HFC-227ea and isobutane;
HFC-1234yf, HFC-227ea and dimethyl ether;
HFC-1234yf, dimethyl ether and CF3I; and
HFC-1234yf, dimethyl ether and CF3SCF3
3. The composition of claim 1 selected from the group consisting of:
from 0.1% to 98% by weight of HFC-125, from 0.1% to 98% by weight of HFC-1234yf and from 0.1% to 98% by weight of n-butane; and
0.1 wt% -98 wt% of HFC-125, 0.1 wt% -98 wt% of HFC-1234yf and 0.1 wt% -98 wt% of isobutane;
1 to 50 weight percent HFC-1234yf, 1 to 98 weight percent HFC-32 and 1 to 98 weight percent HFC-143 a;
1 wt% -60 wt% of HFC-1234yf, 1 wt% -98 wt% of HFC-125 and 1 wt% -98 wt% of HFC-143 a;
1-40 wt% HFC-1234yf, 59-98 wt% HFC-125 and 1-20 wt% isobutane;
1 wt% to 80 wt% HFC-1234yf, 1 wt% to 70 wt% HFC-134 and 19 wt% to 90 wt% propane;
1 wt% -70 wt% of HFC-1234yf, 1 wt% -98 wt% of HFC-134 and 29 wt% -98 wt% of dimethyl ether;
1 wt% -80 wt% of HFC-1234yf, 1 wt% -98 wt% of HFC-143a and 1 wt% -98 wt% of propane;
1 to 40 weight percent HFC-1234yf, 59 to 98 weight percent HFC-143a and 1 to 20 weight percent dimethyl ether;
1 wt% to 80 wt% HFC-1234yf, 1 wt% to 70 wt% HFC-227ea and 29 wt% to 98 wt% propane;
40 to 98 wt% HFC-1234yf, 1 to 59 wt% HFC-227ea and 1 to 20 wt% n-butane;
30 wt% -98 wt% of HFC-1234yf, 1 wt% -69 wt% of HFC-227ea and 1 wt% -30 wt% of isobutane;
1 to 98 weight percent HFC-1234yf, 1 to 80 weight percent HFC-227ea and 1 to 98 weight percent dimethyl ether;
1 to 98 wt% of HFC-1234yf, 1 to 98 wt% of dimethyl ether and 1 to 98 wt% of CF3I; and
1 to 98 weight percent HFC-1234yf, 1 to 40 weight percent dimethyl ether and 1 to 98 weight percent CF3SCF3
4. The composition of claim 1 selected from the group consisting of:
5 to 70 weight percent HFC-125, 5 to 70 weight percent HFC-1234yf and 1 to 20 weight percent n-butane;
5 wt% -70 wt% of HFC-125, 5 wt% -70 wt% of HFC-1234yf and 1 wt% -20 wt% of isobutane;
15 wt% to 50 wt% HFC-1234yf, 20 wt% to 80 wt% HFC-32 and 5 wt% to 60 wt% HFC-143 a;
10 wt% to 60 wt% HFC-1234yf, 20 wt% to 70 wt% HFC-125 and 20 wt% to 70 wt% HFC-143 a;
10 wt% -40 wt% HFC-1234yf, 59 wt% -90 wt% HFC-125 and 1 wt% -10 wt% isobutane;
20 wt% to 80 wt% HFC-1234yf, 10 wt% to 70 wt% HFC-134 and 19 wt% to 50 wt% propane;
20 to 70 weight percent HFC-1234yf, 10 to 70 weight percent HFC-134 and 29 to 50 weight percent dimethyl ether;
10 wt% to 80 wt% HFC-1234yf, 10 wt% to 80 wt% HFC-143a and 1 wt% to 50 wt% propane;
5 to 40 weight percent HFC-1234yf, 59 to 90 weight percent HFC-143a and 1 to 10 weight percent dimethyl ether;
10 wt% to 60 wt% HFC-1234yf, 10 wt% to 60 wt% HFC-227ea and 29 wt% to 50 wt% propane;
50 to 98 wt% of HFC-1234yf, 10 to 49 wt% of HFC-227ea and 1 to 10 wt% of n-butane;
50 to 98 weight percent of HFC-1234yf, 10 to 49 weight percent of HFC-227ea and 1 to 10 weight percent of isobutane;
10 wt% to 80 wt% HFC-1234yf, 10 wt% to 80 wt% HFC-227ea and 1 wt% to 20 wt% dimethyl ether;
10 wt% to 80 wt% HFC-1234yf, 1 wt% to 20 wt% dimethyl ether and 10 wt% to 80 wt% CF3I; and
10 wt% to 80 wt% HFC-1234yf, 1 wt% to 20 wt% dimethyl ether and 10 wt% to 70 wt% CF3SCF3
5. The composition of claim 1 selected from the group consisting of:
67 wt% HFC-125, 32 wt% HFC-1234yf and 1 wt% n-butane; and
87.1% by weight of HFC-125, 11.5% by weight of HFC-1234yf and 1.4% by weight of isobutane.
6. The composition of claim 1 comprising an azeotropic or near-azeotropic composition selected from the group consisting of:
1 to 51 wt% of HFC-1234yf and 99 to 49 wt% of HFC-125;
1 wt% to 99 wt% HFC-1234yf and 99 wt% to 1 wt% HFC-134;
1 to 99 wt% HFC-1234yf and 99 to 1 wt% HFC-161;
1 to 60 wt% HFC-1234yf and 40 to 1 wt% HFC-143 a;
29 to 99 wt% HFC-1234vf and 71 to 1 wt% HFC-227 ea;
from 66 wt% to 99 wt% HFC-1234yf and from 34 wt% to 1 wt% HFC-236 fa;
1 wt% -99 wt% HFC-1234yf and 99 wt% -1 wt% HFC-1243 zf;
80-98 wt% of HFC-125, 1-19 wt% of HFC-1234yf and 1-10 wt% of isobutane;
80 wt% to 98 wt% HFC-125, 1 wt% to 19 wt% HFC-1234yf and 1 wt% to 10 wt% n-butane;
1 to 50 weight percent HFC-1234yf, 1 to 98 weight percent HFC-32 and 1 to 98 weight percent HFC-143 a;
1 wt% -60 wt% of HFC-1234yf, 1 wt% -98 wt% of HFC-125 and 1 wt% -98 wt% of HFC-143 a;
1-40 wt% HFC-1234yf, 59-98 wt% HFC-125 and 1-20 wt% isobutane;
1 wt% to 80 wt% HFC-1234yf, 1 wt% to 70 wt% HFC-134 and 19 wt% to 90 wt% propane;
1-70 Wt% HFC-1234yf, 1-98 Wt% HFC-134 and 29-98 Wt% dimethyl ether;
1 wt% -80 wt% of HFC-1234yf, 1 wt% -98 wt% of HFC-143a and 1 wt% -98 wt% of propane;
1 to 40 weight percent HFC-1234yf, 59 to 98 weight percent HFC-143a and 1 to 20 weight percent dimethyl ether;
1 wt% to 80 wt% HFC-1234yf, 1 wt% to 70 wt% HFC-227ea and 29 wt% to 98 wt% propane;
40 to 98 wt% HFC-1234yf, 1 to 59 wt% HFC-227ea and 1 to 20 wt% n-butane;
30 wt% -98 wt% of HFC-1234yf, 1 wt% -69 wt% of HFC-227ea and 1 wt% -30 wt% of isobutane;
1 to 98 weight percent HFC-1234yf, 1 to 80 weight percent HFC-227ea and 1 to 98 weight percent dimethyl ether;
1 to 98 wt% of HFC-1234yf, 1 to 98 wt% of dimethyl ether and 1 to 98 wt% of CF3I; and
1 to 98 weight percent HFC-1234yf, 1 to 40 weight percent dimethyl ether and 1 to 98 weight percent CF3SCF3
7. The composition of claim 1 comprising an azeotropic composition selected from the group consisting of:
10.9 wt% HFC-1234yf and 89.1 wt% HFC-125 having a vapor pressure of 40.7psia (281kPa) at a temperature of-25 ℃;
17.3 wt% HFC-1234yf and 82.7 wt% HFC-143a having a vapor pressure of 29.5psia (272kPa) at a temperature of-25 ℃;
84.6 wt% HFC-1234yf and 15.4 wt% HFC-227ea having a vapor pressure of 18.0psia (124kPa) at a temperature of-25 ℃;
89.1 wt% HFC-125, 9.7 wt% HFC-1234yf, and 1.2 wt% isobutane having a vapor pressure of 40.8psia (281kPa) at a temperature of-25 ℃;
3.9 wt% HFC-1234yf, 74.3 wt% HFC-32 and 21.8 wt% HFC-143a having a vapor pressure of 50.0psia (345kPa) at a temperature of-25 ℃;
14.4 wt% HFC-1234yf, 43.5 wt% HFC-125, and 42.1 wt% HFC-143a having a vapor pressure of 38.6psia (266kPa) at a temperature of-25 ℃;
4.3 wt% HFC-1234yf, 39.1 wt% HFC-134 and 56.7 wt% propane having a vapor pressure of 34.3psia (236kPa) at a temperature of-25 ℃;
15.2 wt% HFC-1234yf, 67.0 wt% HFC-134 and 17.8 wt% dimethyl ether having a vapor pressure of 10.4psia (71.6kPa) at a temperature of-25 ℃;
17.7 wt% HFC-1234yf, 71.0 wt% HFC-143a and 11.3 wt% propane having a vapor pressure of 40.4psia (279kPa) at a temperature of-25 ℃;
5.7 wt% HFC-1234yf, 93.0 wt% HFC-143a and 1.3 wt% dimethyl ether having a vapor pressure of 39.1psia (269kPa) at a temperature of-25 ℃;
35.6 wt% HFC-1234yf, 17.8 wt% HFC-227ea and 46.7 wt% propane having a vapor pressure of 33.8psia (233kPa) at a temperature of-25 ℃;
81.9 wt% HFC-1234yf, 16.0 wt% HFC-227ea and 2.1 wt% n-butane having a vapor pressure of 18.1psia (125kPa) at a temperature of-25 ℃;
70.2 wt% HFC-1234yf, 18.2 wt% HFC-227ea and 11.6 wt% isobutane having a vapor pressure of 19.3psia (133kPa) at a temperature of-25 ℃;
28.3 wt% HFC-1234yf, 55.6M% HFC-227ea and 16.1 wt% dimethyl ether having a vapor pressure of 15.0psia (104kPa) at a temperature of-25 ℃;
16.3 wt% HFC-1234yf, 10.0 wt% dimethyl ether and 73.7 wt% CF having a vapor pressure of 15.7psia (108kPa) at a temperature of-25 deg.C3I; and
34.3 wt% HFC-1234yf, 10.5 wt% dimethyl ether and 55.2 wt% CF having a vapor pressure of 14.6psia (100kPa) at a temperature of-25 deg.C3SCF3
8. The composition of any of claims 1-7, further comprising a lubricant selected from the group consisting of polyol esters, polyalkylene glycols, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly (alpha) olefins.
9. The composition of any of claims 1-7, further comprising a tracer selected from the group consisting of hydrofluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide (N)2O) and combinations thereof.
10. The composition of any of claims 1-7, further comprising at least one ultraviolet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthrenes, xanthenes, thioxanthenes, benzoxanthenes, fluoresceins, derivatives of said dyes, and combinations thereof.
11. The composition of claim 10 further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethyl ethers, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorinated hydrocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and 1, 1, 1-trifluoroalkanes.
12. The composition of any of claims 1-7, further comprising a stabilizer, a water scavenger, or an odor masking agent.
13. The composition of claim 12, wherein the stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, and lactones.
14. A method of refrigeration, the method comprising: evaporating the composition of any one of claims 1 to 7 in the vicinity of the body to be cooled, after which the composition is condensed.
15. A method of generating heat, the method comprising: condensing the composition of any one of claims 1 to 7 in the vicinity of the body to be heated, after which the composition is evaporated.
16. A method of replacing a high GWP refrigerant in a refrigeration, air-conditioning or heat pump apparatus, wherein the high GWP refrigerant is selected from the group consisting of R134a, R22, R123, R11, R245fa, R114, R236fa, R124, R12, R410A, R407C, R417A, R422A, R507A, R502 and R404A, the method comprising: providing a composition according to any of claims 1 to 7 to said refrigeration, air-conditioning or heat pump apparatus used, used or designed to use said high GWP refrigerant.
17. A method of using the composition of any of claims 1-7 as a heat transfer fluid composition, the method comprising transporting the composition from a heat source to a heat sink.
18. A method of making the composition of any one of claims 1-7, the method comprising:
(i) recovering an amount of one or more components of the refrigerant composition from at least one refrigerant container, (ii) removing impurities sufficient to enable reuse of the one or more recovered components, (iii) and optionally, mixing all or a portion of the recovered amount of components with at least one additional refrigerant composition or component.
19. A refrigeration, air-conditioning or heat pump apparatus comprising a composition according to any of claims 1 to 7.
20. A refrigeration, air-conditioning or heat pump apparatus according to claim 19, which comprises a vehicle air-conditioning apparatus.
21. A blowing agent comprising the composition of any of claims 1-7.
22. A method of forming a foam comprising:
(a) adding the composition of any of claims 1-7 to a foamable composition; and
(b) the foamable composition is reacted under conditions effective to form a foam.
23. A sprayable composition comprising the composition of any of claims 1 to 7.
24. A method of producing an aerosol product comprising the steps of: adding a composition according to any one of claims 1 to 7 to an active ingredient in an aerosol container, wherein the composition acts as a propellant.
CN202110841031.XA 2005-03-04 2006-03-03 Compositions comprising fluoroolefins Active CN113549426B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110841031.XA CN113549426B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US65854305P 2005-03-04 2005-03-04
US60/658543 2005-03-04
US60/710439 2005-08-23
US60/732769 2005-11-01
US11/369227 2006-03-02
CNA2006800154380A CN101297016A (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
CN202110841031.XA CN113549426B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNA2006800154380A Division CN101297016A (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin

Publications (2)

Publication Number Publication Date
CN113549426A true CN113549426A (en) 2021-10-26
CN113549426B CN113549426B (en) 2023-11-14

Family

ID=40066557

Family Applications (10)

Application Number Title Priority Date Filing Date
CN201910001475.5A Pending CN109971431A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN201910001471.7A Pending CN110003859A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN202110841031.XA Active CN113549426B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CNA2006800154380A Pending CN101297016A (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
CN201910001116.XA Active CN109897605B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910000638.8A Pending CN109897604A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN201910000605.3A Pending CN110003858A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN202111244244.0A Active CN113845884B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910001095.1A Active CN109971428B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910881175.0A Pending CN110564372A (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins

Family Applications Before (2)

Application Number Title Priority Date Filing Date
CN201910001475.5A Pending CN109971431A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN201910001471.7A Pending CN110003859A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin

Family Applications After (7)

Application Number Title Priority Date Filing Date
CNA2006800154380A Pending CN101297016A (en) 2005-03-04 2006-03-03 Compositions comprising a fluoroolefin
CN201910001116.XA Active CN109897605B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910000638.8A Pending CN109897604A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN201910000605.3A Pending CN110003858A (en) 2005-03-04 2006-03-03 Composition comprising fluoroolefin
CN202111244244.0A Active CN113845884B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910001095.1A Active CN109971428B (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins
CN201910881175.0A Pending CN110564372A (en) 2005-03-04 2006-03-03 Compositions comprising fluoroolefins

Country Status (1)

Country Link
CN (10) CN109971431A (en)

Families Citing this family (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7569170B2 (en) * 2005-03-04 2009-08-04 E.I. Du Pont De Nemours And Company Compositions comprising a fluoroolefin
US8574451B2 (en) * 2005-06-24 2013-11-05 Honeywell International Inc. Trans-chloro-3,3,3-trifluoropropene for use in chiller applications
GB201002625D0 (en) * 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
DE202009019199U1 (en) * 2008-11-19 2018-10-15 The Chemours Company Fc, Llc Tetrafluoropropene compositions and their uses
US8871112B2 (en) * 2008-11-19 2014-10-28 E I Du Pont De Nemours And Company Compositions comprising 2,3,3,3-tetrafluoropropene and hydrocarbons and uses thereof
FR2938551B1 (en) * 2008-11-20 2010-11-12 Arkema France METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
FR2938550B1 (en) * 2008-11-20 2010-11-12 Arkema France COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
BRPI0922124A2 (en) * 2008-12-02 2016-01-05 Mexichem Amanco Holding Sa heat transfer composition and device, use of a composition, blowing agent, foamable composition, foam, spray composition, methods for cooling and heating an article, for extracting a substance from biomass, a material from an aqueous solution, and a particulate solid matrix material, to clean an article, to retrofit a heat transfer device, to reduce the environmental impact arising from the operation of a product, and to generate greenhouse gas emission credit, and, generation device of mechanical energy.
FR2942237B1 (en) * 2009-02-13 2013-01-04 Arkema France METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
GB0915004D0 (en) * 2009-08-28 2009-09-30 Ineos Fluor Holdings Ltd Heat transfer composition
FR2950066B1 (en) * 2009-09-11 2011-10-28 Arkema France LOW AND MEDIUM TEMPERATURE REFRIGERATION
FR2950067B1 (en) * 2009-09-11 2011-10-28 Arkema France HEAT TRANSFER FLUID IN REPLACEMENT OF R-410A
CN101665578B (en) * 2009-09-28 2011-08-17 关志强 Foaming agent used for thermal-insulating polyurethane plastics
CN101671542A (en) * 2009-09-29 2010-03-17 山东东岳化工有限公司 Refrigerant composition
CN102311719A (en) * 2009-10-13 2012-01-11 天津大学 Organic Rankine cycle mixed working fluid containing HFO-1234yf(CF3CF=CH2)
CN102732220A (en) * 2009-10-13 2012-10-17 天津大学 Organic Rankine cycle mixed refrigerant containing HFO-1234yf(CF3CF=CH2)
CN102712838A (en) * 2009-12-21 2012-10-03 纳幕尔杜邦公司 Compositions comprising tetrafluoropropene and difluoromethane and uses thereof
GB201002615D0 (en) * 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
US8951431B2 (en) * 2010-05-06 2015-02-10 E I Du Pont De Nemours And Company Azeotrope-like compositions of pentafluoropropene and water
FR2959997B1 (en) * 2010-05-11 2012-06-08 Arkema France HEAT TRANSFER FLUIDS AND THEIR USE IN COUNTER-CURRENT HEAT EXCHANGERS
FR2959999B1 (en) * 2010-05-11 2012-07-20 Arkema France HEAT TRANSFER FLUIDS AND THEIR USE IN COUNTER-CURRENT HEAT EXCHANGERS
CN101864277A (en) * 2010-06-03 2010-10-20 集美大学 Refrigerant composition with low GWP (Global Warming Potential) value
GB2481443B (en) * 2010-06-25 2012-10-17 Mexichem Amanco Holding Sa Heat transfer compositions
EP2603569B1 (en) * 2010-08-13 2018-07-18 Carrier Corporation Fluorinated hydrocarbon composition
FR2964976B1 (en) * 2010-09-20 2012-08-24 Arkema France COMPOSITION BASED ON 1,3,3,3-TETRAFLUOROPROPENE
US20120119136A1 (en) * 2010-11-12 2012-05-17 Honeywell International Inc. Low gwp heat transfer compositions
FR2968009B1 (en) * 2010-11-25 2012-11-16 Arkema France REFRIGERANT FLUIDS CONTAINING (E) -1,1,1,4,4,4-HEXAFLUOROBUT-2-ENE
US8889031B2 (en) * 2010-11-30 2014-11-18 Jx Nippon Oil & Energy Corporation Working fluid composition for refrigerator machine and refrigerating machine oil
CN102229794A (en) * 2011-05-06 2011-11-02 山东东岳化工有限公司 Refrigerant composition with low GWP (Global Warming Potential) value
US9169427B2 (en) * 2011-07-13 2015-10-27 Honeywell International Inc. Low GWP heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene
US20130075063A1 (en) * 2011-09-26 2013-03-28 Ryan Hulse Azeotrope-like compositions of cis-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane
WO2013079458A1 (en) * 2011-12-01 2013-06-06 Solvay Sa Novel use for compositions comprising hfc-134a and hfo-1234yf and an azeotropic composition thereof
CN102676121B (en) * 2012-05-24 2014-01-29 浙江大学 Refrigerant capable of improving environmental performance and preparation method for refrigerant
MX2015002083A (en) * 2012-08-20 2015-05-11 Honeywell Int Inc Low gwp heat transfer compositions.
US8940180B2 (en) * 2012-11-21 2015-01-27 Honeywell International Inc. Low GWP heat transfer compositions
CN104955916A (en) * 2012-12-04 2015-09-30 霍尼韦尔国际公司 Low GWP heat transfer compositions
CN111925775A (en) * 2013-03-14 2020-11-13 霍尼韦尔国际公司 Low GWP fluids for high temperature heat pump applications
US9394469B2 (en) * 2013-03-14 2016-07-19 Honeywell International Inc. Low GWP fluids for high temperature heat pump applications
WO2014139146A1 (en) * 2013-03-15 2014-09-18 Honeywell International Inc. Compositions and method for refrigeration
CN104277765B (en) 2013-07-05 2017-12-08 中化蓝天集团有限公司 A kind of environment-friendly type near azeotropic mixed refrigerant
FR3010415B1 (en) * 2013-09-11 2015-08-21 Arkema France HEAT TRANSFER FLUIDS COMPRISING DIFLUOROMETHANE, PENTAFLUOROETHANE, TETRAFLUOROPROPENE AND POSSIBLY PROPANE
WO2016059698A1 (en) * 2014-10-16 2016-04-21 三菱電機株式会社 Refrigeration cycle device
CN112940683A (en) * 2015-01-05 2021-06-11 浙江省化工研究院有限公司 Environment-friendly refrigeration composition
FR3061906B1 (en) * 2017-01-19 2019-03-15 Arkema France COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE
FR3061905B1 (en) * 2017-01-19 2019-05-17 Arkema France COMPOSITION COMPRISING 2,3,3,3-TETRAFLUOROPROPENE
CN107936925A (en) * 2017-02-22 2018-04-20 唐建 A kind of ternary mixed refrigerant being applied in air-conditioning/heat pump system
FR3064264B1 (en) * 2017-03-21 2019-04-05 Arkema France COMPOSITION BASED ON TETRAFLUOROPROPENE
FR3064275B1 (en) * 2017-03-21 2019-06-07 Arkema France METHOD FOR HEATING AND / OR AIR CONDITIONING A VEHICLE
CN107213576A (en) * 2017-07-17 2017-09-29 九江中船化学科技有限公司 A kind of clean efficient gas extinguishing agent composition
TW202317734A (en) * 2017-10-12 2023-05-01 美商科慕Fc有限責任公司 Compositions containing difluoromethane, tetrafluoropropene, and carbon dioxide and uses thereof
JP6555315B2 (en) * 2017-10-16 2019-08-07 ダイキン工業株式会社 Refrigerant composition containing HFO-1234ze (E) and HFC-134 and use thereof
US10731066B2 (en) * 2017-11-17 2020-08-04 Honeywell International Inc. Heat transfer compositions, methods and systems
US20190161662A1 (en) * 2017-11-30 2019-05-30 Honeywell International Inc. Heat transfer compositions, methods, and systems
WO2019208722A1 (en) * 2018-04-25 2019-10-31 ダイキン工業株式会社 Refrigerant-containing composition, use thereof, refrigerating method using same, and refrigerator comprising same
CN109810674B (en) * 2019-01-19 2020-05-19 珠海格力电器股份有限公司 Novel refrigerant replacing R134a
US20220041911A1 (en) * 2019-03-04 2022-02-10 The Chemours Company Fc, Llc Heat transfer compositions comprising r-1225ye(e) and r-32
MX2021010196A (en) * 2019-03-04 2021-09-21 Chemours Co Fc Llc Heat transfer compositions comprising r-1225ye(e), hfo-1234yf, r-32, r-125 and co2.
WO2020180839A1 (en) * 2019-03-04 2020-09-10 The Chemours Company Fc, Llc Heat transfer compositions comprising r-1225ye(e), hfo-1234yf, r-32, r-125, and co2
CN113891925A (en) * 2019-03-08 2022-01-04 科慕埃弗西有限公司 Process and method for regenerating flammable and non-flammable hydrofluoroolefin-containing refrigerants
CN109971433B (en) * 2019-04-08 2021-04-13 中国科学院理化技术研究所 Multi-component mixed refrigerant
CN110655909B (en) * 2019-09-12 2020-11-27 珠海格力电器股份有限公司 Environment-friendly mixed refrigerant suitable for automobile air conditioner
CN110628390B (en) * 2019-09-12 2020-12-15 珠海格力电器股份有限公司 Environment-friendly mixed refrigerant, composition and heat exchange system
CN110669479B (en) * 2019-09-12 2020-10-30 珠海格力电器股份有限公司 Safe and environment-friendly heat transfer medium and refrigeration system adopting centrifugal compressor
CN110628388B (en) * 2019-09-12 2021-01-15 珠海格力电器股份有限公司 Mixed working medium suitable for scroll compressor and automobile air conditioning system
CN110628387B (en) * 2019-09-12 2020-12-11 珠海格力电器股份有限公司 Low-flammability heat transfer composition and heat exchange system
CN110746936B (en) * 2019-10-11 2021-05-04 金华永和氟化工有限公司 Environment-friendly mixed refrigerant
CN110878197B (en) * 2019-10-16 2020-12-22 珠海格力电器股份有限公司 Mixed working medium and heat exchange system
CN110845997B (en) * 2019-10-16 2020-12-22 珠海格力电器股份有限公司 Heat transfer medium and composition suitable for cooler
CN110878194B (en) * 2019-10-16 2020-11-17 珠海格力电器股份有限公司 R13I 1-containing environment-friendly mixed refrigerant and heat exchange system
CN110878196B (en) * 2019-10-16 2020-12-22 珠海格力电器股份有限公司 Quaternary mixed environment-friendly refrigerant and composition
CN110699043B (en) * 2019-10-18 2020-11-27 天津大学 Environment-friendly mixed refrigeration working medium
CN111004610B (en) * 2019-12-18 2021-06-25 湖北绿冷高科节能技术有限公司 Refrigerant replacing R134a and preparation method and application thereof
CN113528091B (en) * 2020-04-09 2023-03-24 浙江省化工研究院有限公司 HFC-161-containing environment-friendly refrigeration composition
CN111944489B (en) * 2020-07-21 2021-10-29 浙江衢化氟化学有限公司 Composition containing fluorohydrocarbon and preparation method thereof
CN112552876B (en) * 2020-12-10 2021-11-16 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN112680193B (en) * 2021-01-04 2021-07-23 珠海格力电器股份有限公司 Mixed refrigerant, heat exchange system and household appliance
CN113025279B (en) * 2021-02-09 2023-07-25 浙江衢化氟化学有限公司 Composition containing fluoroolefin and preparation method thereof
CN113025280B (en) * 2021-03-12 2022-11-15 冰轮环境技术股份有限公司 Mixed refrigerant replacing R507A
CN113388370B (en) * 2021-06-07 2022-06-21 湖北瑞能华辉能源管理有限公司 Ternary mixed refrigerant capable of replacing R134a and application thereof
CN113388371B (en) * 2021-06-07 2022-06-24 湖北瑞能华辉能源管理有限公司 Quaternary mixed refrigerant capable of replacing R22 or R410a and application thereof
CN113480978A (en) * 2021-07-07 2021-10-08 国节新辉科技(浙江)有限公司 Refrigerant replacing R22, and preparation method and application thereof
CN113563847B (en) * 2021-07-27 2022-04-15 珠海格力电器股份有限公司 Quaternary environment-friendly mixed refrigerant, preparation method thereof and refrigeration system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1166479A (en) * 1996-05-13 1997-12-03 埃勒夫阿托化学有限公司 Synthesis of 1-chloro-3,3,3-trifluoropropene and its fluorination to 1,1,1,3,3-pentafluoropropane
CN1304395A (en) * 1998-06-02 2001-07-18 纳幕尔杜邦公司 Process for production of hexafluoropropene and optionally other halogenated hydrocarbons containing fluorine
US20040167366A1 (en) * 2002-12-13 2004-08-26 Rao Velliyur Nott Mallikarjuna Process for purifying hydrofluoropropanes
US20040236161A1 (en) * 2003-05-23 2004-11-25 Rao Velliyur Nott Mallikarjuna Process for the reduction of acidic contaminates in fluorinated hydrocarbons
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
CN103396766A (en) * 2004-04-29 2013-11-20 霍尼韦尔国际公司 Azeotrope-like composition of tetrafluoropropene and hydrofluorocarbons

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3884828A (en) * 1970-10-15 1975-05-20 Dow Corning Propellants and refrigerants based on trifluoropropene
US3723318A (en) * 1971-11-26 1973-03-27 Dow Corning Propellants and refrigerants based on trifluoropropene
MX9203904A (en) * 1991-07-03 1993-01-01 Du Pont AZEOTROPIC OR AZEOTROPE TYPE COMPOSITION OF PENTAFLUOROETHANE AND PROPANE OR ISOBUTANE AND PROCEDURES FOR PRODUCING REFRIGERATION AND HEAT WHEN CONDENSING SUCH COMPOSITION.
EP1028152A3 (en) * 1993-02-05 2005-06-15 E.I. Du Pont De Nemours And Company Compositions of a hydrofluorocarbon and a hydrocarbon
ID21960A (en) * 1996-11-04 1999-08-19 Du Pont HYDROFLUOROKARBON COMPOSITIONS
US6031141A (en) * 1997-08-25 2000-02-29 E. I. Du Pont De Nemours And Company Fluoroolefin manufacturing process
US5811603A (en) * 1997-12-01 1998-09-22 Elf Atochem North America, Inc. Gas phase fluorination of 1230za
US6124510A (en) * 1998-07-21 2000-09-26 Elf Atochem North America, Inc. 1234ze preparation
JP4356149B2 (en) * 1999-08-23 2009-11-04 旭硝子株式会社 Method for treating 1,1,1,3,3-pentafluoropropane
EP2277942A3 (en) * 2002-10-25 2014-07-09 Honeywell International, Incorporated. Compositions containing fluorine substituted olefins
US7230146B2 (en) * 2003-10-27 2007-06-12 Honeywell International Inc. Process for producing fluoropropenes
US7592494B2 (en) * 2003-07-25 2009-09-22 Honeywell International Inc. Process for the manufacture of 1,3,3,3-tetrafluoropropene
US7655610B2 (en) * 2004-04-29 2010-02-02 Honeywell International Inc. Blowing agent compositions comprising fluorinated olefins and carbon dioxide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1166479A (en) * 1996-05-13 1997-12-03 埃勒夫阿托化学有限公司 Synthesis of 1-chloro-3,3,3-trifluoropropene and its fluorination to 1,1,1,3,3-pentafluoropropane
CN1304395A (en) * 1998-06-02 2001-07-18 纳幕尔杜邦公司 Process for production of hexafluoropropene and optionally other halogenated hydrocarbons containing fluorine
US20040256594A1 (en) * 2002-10-25 2004-12-23 Honeywell International, Inc. Compositions containing fluorine substituted olefins
US20040167366A1 (en) * 2002-12-13 2004-08-26 Rao Velliyur Nott Mallikarjuna Process for purifying hydrofluoropropanes
US20040236161A1 (en) * 2003-05-23 2004-11-25 Rao Velliyur Nott Mallikarjuna Process for the reduction of acidic contaminates in fluorinated hydrocarbons
WO2004106272A2 (en) * 2003-05-23 2004-12-09 E.I. Dupont De Nemours And Company Process for the reduction of acidic contaminantes in fluorinated hydrocarbons
CN103396766A (en) * 2004-04-29 2013-11-20 霍尼韦尔国际公司 Azeotrope-like composition of tetrafluoropropene and hydrofluorocarbons

Also Published As

Publication number Publication date
CN110003858A (en) 2019-07-12
CN113845884B (en) 2024-02-02
CN109971428A (en) 2019-07-05
CN109971428B (en) 2021-08-10
CN109897605B (en) 2021-09-10
CN113549426B (en) 2023-11-14
CN109971431A (en) 2019-07-05
CN109897605A (en) 2019-06-18
CN110003859A (en) 2019-07-12
CN110564372A (en) 2019-12-13
CN113845884A (en) 2021-12-28
CN109897604A (en) 2019-06-18
CN101297016A (en) 2008-10-29

Similar Documents

Publication Publication Date Title
CN109971429B (en) Compositions comprising fluoroolefins
CN109897605B (en) Compositions comprising fluoroolefins
JP5980272B2 (en) Compositions containing fluoroolefins
DK2749623T3 (en) COMPOSITIONS CONTAINING A FLUOROLEFINE
RU2418027C2 (en) Coolant or heat carrier composition, method of using said composition, method of cooling or heating, installations containing said composition, method of detecting said composition in installation, foaming agent containing said composition, method of obtaining foam, sprayed composition, method of obtaining aerosol products, method of suppressing flame or extinction, as well as method of treating area with inert gas in order to prevent burning
AU2016200229B2 (en) Compositions comprising a fluoroolefin

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant