WO2017144018A1 - 一种包含含氟酮的组合物 - Google Patents

一种包含含氟酮的组合物 Download PDF

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Publication number
WO2017144018A1
WO2017144018A1 PCT/CN2017/074814 CN2017074814W WO2017144018A1 WO 2017144018 A1 WO2017144018 A1 WO 2017144018A1 CN 2017074814 W CN2017074814 W CN 2017074814W WO 2017144018 A1 WO2017144018 A1 WO 2017144018A1
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Prior art keywords
compound
cfc
phosphite
chfcf
composition
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PCT/CN2017/074814
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English (en)
French (fr)
Inventor
倪航
罗霞
Original Assignee
中化蓝天集团有限公司
浙江省化工研究院有限公司
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Application filed by 中化蓝天集团有限公司, 浙江省化工研究院有限公司 filed Critical 中化蓝天集团有限公司
Priority to JP2018515114A priority Critical patent/JP6730428B2/ja
Priority to EP17755847.5A priority patent/EP3421105A4/en
Priority to KR1020187022301A priority patent/KR102096201B1/ko
Priority to RU2018133670A priority patent/RU2701535C1/ru
Priority to MYPI2018701834A priority patent/MY187284A/en
Priority to SG11201804498WA priority patent/SG11201804498WA/en
Publication of WO2017144018A1 publication Critical patent/WO2017144018A1/zh
Priority to US15/923,870 priority patent/US10953256B2/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0092—Gaseous extinguishing substances, e.g. liquefied gases, carbon dioxide snow
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-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
    • C08J9/14—Working-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
    • C08J9/143—Halogen containing compounds
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/284—Esters of aromatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
    • C10M2211/042—Alcohols; Ethers; Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/60—Electro rheological properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/14—Electric or magnetic purposes
    • C10N2040/16—Dielectric; Insulating oil or insulators
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/04—Aerosols

Definitions

  • the present invention relates to a composition comprising a fluoroketone.
  • the fluoroketone compound can be used singly or in combination as a working fluid.
  • fluoroketone compounds are unstable under extreme conditions. For example, when exposed to air, they are prone to degradation or decomposition when exposed to moisture, oxygen or other compounds that may react with them, and may be in natural light or ultraviolet light. This degradation or decomposition is accelerated in the presence of a metal.
  • a fluoroketone compound When a fluoroketone compound is used as a working fluid for refrigeration equipment or other similar applications, it may also be unstable under extreme conditions, especially at high temperatures. This degradation or decomposition can be attributed to different situations, in some cases due to instability of the fluoroketone compound under extreme operating conditions, and in other cases due to unintentional leakage into the air. The degradation or decomposition of the fluoroketone compound is increased by any reason.
  • the stability of the alkane, olefin and ketone compound is compared from the structure of the compound.
  • propane, propylene and acetone as examples, the pKa is 45, 43 and 26.5, respectively.
  • Propane is very stable.
  • Propylene is basically the same as propane. It is also stable because acetone contains carbonyl groups. The carbonyl group easily binds to protons, so that the entire acetone molecule is electrically charged. Positive, leading to an increase in acidity, is not as stable as propane and propylene.
  • 1-bromopropane, 3-bromopropene and bromoacetone as examples, 1-bromopropane easily forms HBr after heating, and 3-bromopropene easily desorbs bromine radicals to form allyl radicals.
  • Bromoacetone is very unstable. After being placed, the color of the liquid will change from colorless to purple. When placed in the air for a long time, it will become a black resinous substance.
  • fluoroketones In order to avoid possible instability of fluoroketones under extreme conditions, it has been found that the addition of specific compounds to fluoroketones, ie selected from epoxy compounds, nitro compounds, hindered phenolic compounds, beta-diketones At least one of a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound Can improve its stability.
  • specific compounds to fluoroketones ie selected from epoxy compounds, nitro compounds, hindered phenolic compounds, beta-diketones
  • At least one of a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound Can improve its stability.
  • a composition comprising: A, at least one fluoroketone; and B, An effective amount of a stabilizer selected from the group consisting of an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, and a hydroxyl group At least one of a benzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • a stabilizer selected from the group consisting of an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, and a hydroxyl group At least one of a benzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • Also provided is a method of stabilizing a composition comprising at least one fluoroketone comprising comprising an effective amount comprising at least one member selected from the group consisting of an epoxy compound, a nitro compound, a hindered phenol compound, and a beta-diketone Compounds, phosphite compounds, salicylate compounds, cinnamate compounds, hydroxybenzophenone compounds, hydroxybenzoic acid compounds, alkoxymethane compounds, and compounds in organic thio compounds
  • a stabilizer is added to the composition comprising at least one fluoroketone.
  • a compound stabilizer selected from the group consisting of hindered phenol compounds, ⁇ -diketone compounds, phosphite compounds, hydroxybenzophenone compounds, and alkoxymethane compounds
  • At least one compound stabilizer selected from the group consisting of a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a hydroxybenzophenone compound, an alkoxymethane compound, and an organic thio compound is added to the inclusion In a composition of at least one fluoroketone.
  • an effective amount comprising at least one compound selected from the group consisting of hindered phenolic compounds, beta-diketones, a compound stabilizer in a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, and an alkoxymethane compound is added to at least one type In a composition of a
  • a method of reducing the reaction of a composition comprising at least one fluoroketone with oxygen comprising comprising an effective amount comprising at least one member selected from the group consisting of epoxy compounds, nitro compounds, hindered phenolic compounds, beta-two Ketones, phosphites a compound stabilizer in a compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, and an alkoxymethane compound is added to at least one fluoroketone In the composition.
  • Also provided is a method of inhibiting a flame comprising applying at least one composition to at least a portion of the flame or to a fuel source of the flame, the composition comprising at least one fluoroketone and an effective amount a stabilizer comprising an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, At least one of a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • a method of extinguishing a fire comprising applying at least one composition in a confined space containing air to prevent ignition or deflagration of the flammable material, the composition comprising at least one fluoroketone and an effective amount a stabilizer comprising an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, and a hydroxyl group.
  • a benzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound At least one of a benzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • composition as a fire suppressant, heat transfer medium, magnesium alloy melt protectant, solvent, cleaning agent, blowing agent, aerosol propellant, insulating medium or electronically etched gas.
  • the present invention provides a composition
  • a composition comprising: A, at least one fluoroketone; and B, an effective amount of a stabilizer selected from the group consisting of an epoxy compound, a nitro compound, a hindered phenol compound, and a ⁇ -diketone compound At least one of a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound .
  • compositions have a variety of uses, and by way of example, can be used as fire extinguishing agents, heat transfer media, magnesium alloy melt protectants, solvents, cleaning agents, blowing agents, aerosol propellants, insulating media, or electronically etched gases.
  • a fire extinguishing agent it may be, for example, a pipe network fire extinguishing system, a cabinet fire extinguishing system, a suspended fire extinguishing system, a fire detector fire extinguishing system, or a portable fire extinguisher.
  • a heat transfer medium it may be, for example, used in a refrigerator, a cooler, an organic Rankine cycle device, a heat pump or a container.
  • Extinguishing agents also known as flame retardants, are volatile compositions that extinguish or inhibit flames.
  • a heat transfer medium also known as a heat transfer fluid, heat transfer composition or heat transfer fluid composition, is a working fluid for transferring heat from a heat source to a heat sink.
  • the blowing agent is a volatile composition that expands the polymer matrix to form a porous structure.
  • a solvent is a fluid that removes dirt from a substrate or deposits material onto or onto a substrate.
  • An aerosol propellant is a volatile composition of one or more components that applies a pressure greater than one atmosphere to push the material out of the container.
  • fluoroketone as used in the present invention describes a compound containing a carbon atom, a fluorine atom and optionally a hydrogen atom and having a carbonyl group in its molecular structure.
  • the fluoroketone used in the present invention has the following molecular structure:
  • R 1 f and R 2 f are independently selected from C a H b F c Cl d Br e , a is selected from an integer from 1 to 7, and b, d and e are independently selected from an integer from 0 to 15, c is selected From an integer from 1 to 15, b+c+d+e ⁇ 2a+1.
  • the fluoroketone is selected from at least one of the following compounds:
  • the fluoroketone is selected from at least one of the following compounds:
  • the fluoroketone is selected from at least one of the following compounds:
  • the fluoroketone is selected from at least one of the following compounds:
  • the fluoroketone is selected from at least one of the following compounds:
  • Representative fluoroketones include, but are not limited to, the compounds listed in Table 1.
  • the stabilizer of the present invention is selected from the group consisting of an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, and a hydroxydiphenyl group. At least one of a ketone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • the epoxy compound is an epoxy compound understood by those skilled in the art, and is generally a chain compound containing the following structure (I), wherein R 1 , R 2 , R 3 , R 4 may be a single substituent or A cyclic substituent such as 1,2-epoxycyclopentane or a compound having a similar structure thereto.
  • the epoxy compound is selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxycyclopentane, 1,2-ring Oxycyclohexane, 1,2-epoxy isobutane, 1,2-epoxyethylene, 4-vinyl-1-cyclohexene diepoxide and 1-tert-butoxy-2,3 At least one of propylene oxide.
  • the epoxy compound is selected from the group consisting of 1,2-epoxypropane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxyisobutylene At least one of an alkane and a 1,2-epoxyethylbenzene.
  • the epoxy compound is selected from at least one of 1,2-epoxypropane, 1,2-epoxycyclohexane, and 1,2-epoxyethylene.
  • the nitro compound which is a nitro compound understood by those skilled in the art, is usually a compound containing a nitro group (-NO 2 ).
  • the nitro compound is selected from at least one of nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, and p-dinitrobenzene.
  • the nitro compound is at least one of nitromethane and nitrobenzene.
  • the nitro compound is nitromethane.
  • the hindered phenolic compound is a hindered phenolic compound which is understood by those skilled in the art and is usually a phenolic compound having an antioxidant action.
  • the hindered phenolic compound is selected from the group consisting of bisphenol A, p-nonylphenol, thymol, p-methoxyphenol, p-benzyloxyphenol, catechol, resorcinol, uncle Butyl catechol, 4,4'-butylene bis(6-tert-butylm-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), 2,6-di-tert Butyl p-cresol, 2,6-di-tert-butylphenol, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, 3-(3 , octadecyl 5-di-tert-butyl-4-hydroxyphenyl)propy
  • the hindered phenolic compound is selected from the group consisting of thymol, catechol, resorcinol, p-tert-butyl At least one of catechol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butylphenol.
  • the hindered phenolic compound is selected from at least one of thymol, catechol, resorcinol, and p-tert-butyl catechol.
  • the ⁇ -diketone compound is selected from at least one of xylyl methane and stearyl benzoylmethane.
  • the beta-diketone compound is xylyl methane.
  • the phosphite compound a phosphite compound understood by those skilled in the art, is generally a compound having a P(OR 1 )(OR 2 )OR 3 structure, wherein R1, R2, and R3 are chained. Or a substituent of a cyclic structure.
  • the phosphite compound is selected from the group consisting of trimethyl phosphate, diethyl phosphite, diisopropyl phosphite, triisopropyl phosphite, tributyl phosphite, diphenyl phosphite.
  • Ester triphenyl phosphite, dibenzyl phosphite, tribenzyl phosphite, decyl diphenyl phosphite, tridecyl phosphite, dioctadecyl pentaerythritol diphosphite, tris( ⁇ ) At least one of phenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and tris(2,4-di-tert-butylphenyl)phosphite.
  • the phosphite compound is selected from the group consisting of trimethyl phosphite, diethyl phosphite, diisopropyl phosphite, tributyl phosphite, diphenyl phosphite, and phosphorous triphosphate At least one of phenyl ester, dibenzyl phosphite, triphenyl phosphite, triphenyl phosphite, tridecyl phosphite, and dioctadecyl pentaerythritol bisphosphite.
  • the phosphite compound is selected from the group consisting of trimethyl phosphite, diisopropyl phosphite, dibenzyl phosphite, tribenzyl phosphite, triphenyl phosphite, and phosphorous acid At least one of the trialkyl esters.
  • the salicylate compound which is a salicylate compound understood by those skilled in the art, is usually a compound having the following structure (II), wherein R is a substituent having a chain or cyclic structure.
  • the salicylate compound is selected from the group consisting of methyl salicylate, ethyl salicylate, butyl salicylate, isooctyl salicylate, and 4-tert-butyl salicylate. At least one of phenyl ester and phenyl salicylate. In another embodiment, the salicylate compound is at least one of methyl salicylate, butyl salicylate, isooctyl salicylate, and phenyl salicylate. In another embodiment, the salicylate compound is at least one of methyl salicylate and phenyl salicylate.
  • the cinnamate compound is selected from the group consisting of ethyl 3-diphenylacrylate, benzyl 3-phenylacrylate, ethyl 2-cyano-3,3-diphenylacrylate, and 2- At least one of cyano-3,3-diphenylacrylate-2-ethylhexyl ester.
  • the cinnamate compound is at least one of ethyl 3-diphenylacrylate, benzyl 3-phenylacrylate, and ethyl 2-cyano-3,3-diphenylacrylate.
  • the cinnamate compound is at least one of benzyl 3-diphenylacrylate and ethyl 2-cyano-3,3-diphenylacrylate.
  • hydroxybenzophenone compound a 2-hydroxybenzophenone compound understood by those skilled in the art, is generally a compound having the following structure (III), wherein R 1 and R 2 are chained or The substituent of the cyclic structure, the substituent may be at any position of the benzene ring.
  • the hydroxybenzophenone compound is selected from the group consisting of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- 4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2 At least one of -hydroxy-4-n-octyloxybenzophenone.
  • the hydroxybenzophenone compound is selected from the group consisting of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2',4, At least one of 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
  • the hydroxybenzophenone compound is selected from the group consisting of 2-hydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxy At least one of benzophenone.
  • hydroxybenzoic acid compound a 4-hydroxybenzoic acid and a carboxylic acid ester compound thereof, which are understood by those skilled in the art, are generally a compound having the following structure (IV) wherein R 1 and R 2 are A substituent having a chain or cyclic structure, and the R 1 substituent may be at any position of the benzene ring.
  • the hydroxybenzoic acid compound is selected from the group consisting of 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl- At least one of n-hexadecyl 4-hydroxybenzoate.
  • the hydroxybenzoic acid compound is n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • alkoxymethane compound an alkoxymethane compound understood by those skilled in the art, is generally a compound having a structure of HC(OR 1 )(OR 2 )OR 3 wherein R1, R2 and R3 have A substituent of a chain or cyclic structure.
  • the alkoxymethane compound is selected from the group consisting of trimethoxymethane, triethoxymethane, tri-n-propoxymethane, tri-n-butoxymethane, tripentyloxymethane, trimethoxy At least one of phenylmethane, diethoxybenzyloxymethane, diethoxyalkenyloxymethane, and tris(chloroethoxy)methane.
  • the alkoxymethane compound is selected from the group consisting of trimethoxymethane, triethoxymethane, tri-n-propoxymethane, tri-n-butoxymethane, trimethoxyphenylmethane, and tri At least one of chloroethoxy)methane.
  • the alkoxymethane compound is selected from the group consisting of trimethoxymethane, triethoxymethane, tri-n-propoxymethane, trimethoxyphenylmethane, and tris(chloroethoxy)methane. At least one of them.
  • the organothio compound is selected from the group consisting of dilauryl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, and 3,3'-thio At least one of dimyristyl dipropionate.
  • the organothio compound is dilauryl 3,3'-thiodipropionate.
  • Representative stabilizers include, but are not limited to, the compounds listed in Table 2.
  • the present invention provides stabilizers in which some of the stabilizer compounds are present as a plurality of configurational isomers or stereoisomers.
  • a single isomer or multiple isomers of the same compound can be used in any ratio to prepare a stabilizer blend.
  • a single or how many isomers of a given compound can be combined with many other compounds in any ratio to act as a stabilizer blend.
  • the invention is intended to include all single configuration isomers, single stereoisomers, or any combination or mixture thereof.
  • any suitable effective amount of stabilizer can be used in the compositions of the present invention.
  • Effective amount means the amount of the stabilizer of the present invention which, when added to a composition comprising at least one fluoroketone, does not degrade to be as large as compared to a composition without a stabilizer. Performance is reduced when in use.
  • the mass ratio of the stabilizer to the fluoroketone is from 0.1:1000 to 50:1000.
  • the mass ratio of the stabilizer to the fluoroketone is from 0.5:1000 to 10:1000.
  • the mass ratio of the stabilizer to the fluoroketone is from 0.5:1000 to 5:1000.
  • the invention further relates to a method of stabilizing a composition comprising at least one fluoroketone, the method comprising comprising an effective amount comprising at least one member selected from the group consisting of epoxy compounds, nitro compounds, hindered phenolic compounds, ⁇ - Diketones, sub a phosphate stabilizer, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and a compound stabilizer in an organic thio compound are added to A composition comprising at least one fluoroketone.
  • the invention further relates to a method of reducing degradation of a composition comprising at least one fluoroketone, the degradation being caused by the presence of moisture in a fire extinguishing, cleaning, refrigeration, air conditioning or heat pump system, the method comprising including at least an effective amount a compound stabilizer selected from the group consisting of a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a hydroxybenzophenone compound, and an alkoxymethane compound, and added to at least one fluoroketone In the composition.
  • a compound stabilizer selected from the group consisting of a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a hydroxybenzophenone compound, and an alkoxymethane compound
  • the invention further relates to a method of reducing degradation of a composition comprising at least one fluoroketone, the degradation being caused by the presence of moisture and metals in a fire extinguishing, cleaning, refrigeration, air conditioning or heat pump system, the method comprising an effective amount Adding at least one compound stabilizer selected from the group consisting of a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a hydroxybenzophenone compound, an alkoxymethane compound, and an organic thio compound To a composition comprising at least one fluoroketone.
  • a compound stabilizer selected from the group consisting of a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a hydroxybenzophenone compound, an alkoxymethane compound, and an organic thio compound
  • the invention further relates to a method of reducing degradation of a composition comprising at least one fluoroketone, the degradation being caused by the presence of moisture, metals and acids in a fire extinguishing, cleaning, refrigeration, air conditioning or heat pump system, the method comprising An effective amount comprising at least one selected from the group consisting of a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone
  • the compound stabilizer in the compound, the hydroxybenzoic acid compound, the alkoxymethane compound, and the organic thio compound is added to the composition containing at least one fluoroketone.
  • the invention further relates to a method of reducing degradation of a composition comprising at least one fluoroketone under moisture and light, the method comprising comprising an effective amount comprising at least one selected from the group consisting of hindered phenolic compounds, beta-diketones a compound stabilizer in a compound, a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, and an alkoxymethane compound is added to at least A fluoroketone composition.
  • the invention further relates to a method of reducing the reaction of a composition comprising at least one fluoroketone with oxygen, the method comprising comprising an effective amount comprising at least one member selected from the group consisting of epoxy compounds, nitro compounds, hindered phenolic compounds, beta - a compound stabilizer in a diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, and an alkoxymethane compound Add to the composition comprising at least one fluoroketone.
  • an effective amount comprising at least one member selected from the group consisting of epoxy compounds, nitro compounds, hindered phenolic compounds, beta - a compound stabilizer in a diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, and an al
  • the invention further relates to a method of inhibiting a flame, the method comprising applying at least one composition to at least a portion of the flame or to a fuel source of the flame, the composition comprising at least one fluoroketone and An effective amount of a stabilizer comprising an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, and a phosphorous acid At least one of an ester compound, a salicylate compound, a cinnamate compound, a hydroxybenzophenone compound, a hydroxybenzoic acid compound, an alkoxymethane compound, and an organic thio compound.
  • the invention further relates to a method of extinguishing a fire comprising applying at least one composition in a confined space containing air to prevent ignition or deflagration of a flammable material, said composition comprising at least one fluoroketone and being effective
  • a stabilizer comprising an epoxy compound, a nitro compound, a hindered phenol compound, a ⁇ -diketone compound, a phosphite compound, a salicylate compound, a cinnamate compound
  • the invention further relates to the use of the composition as a fire extinguishing agent, a heat transfer medium, a magnesium alloy melt protectant, a solvent, a cleaning agent, a foaming agent, an aerosol propellant, an insulating medium, and an arc extinguishing agent.
  • Medium or electronically etched gas When the composition is used as a fire extinguishing agent, it is particularly suitable for use in a pipe network fire extinguishing system, a cabinet fire extinguishing system, a suspended fire extinguishing system or a portable fire extinguisher.
  • the composition is used as a heat transfer medium, it is particularly suitable for use in refrigerators, coolers, organic Rankine cycle units, heat pumps or containers.
  • the composition is used as an insulating medium or an arc extinguishing medium, it is particularly suitable for medium voltage, high voltage, ultra high voltage electric equipment.
  • the principle of the test method of the following examples refers to the refrigerant test standard ASHRAE 97:2007, using a pressure-resistant container, adding a fluoroketone composition under normal pressure or under a negative pressure, and then introducing nitrogen or air to maintain a certain temperature at a certain temperature. Days, then according to different test conditions such as shelter from light or in the presence of light. After reaching the set number of days, it is reduced to normal temperature and sampled for analysis.
  • the filling factor is referred to ISO 14520-5:2005.
  • the moisture unit is mg/kg, and the following is expressed in ppm.
  • the acidity is expressed in HCl, in mg/kg, and is expressed in ppm below.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 1.
  • the composition and amount of the stabilizer are shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 7.
  • the composition and amount of the stabilizer are shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 10.
  • the composition and amount of the stabilizer are shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 13.
  • the composition and amount of the stabilizer are shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 14.
  • the composition and amount of the stabilizer were shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 17.
  • the composition and amount of the stabilizer are shown in Table 3. Samples were taken for analysis at 10 days, 30 days, and 60 days. The results are shown in Table 4.
  • composition and amount of the stabilizer were changed, and the rest of the operation was the same as in Example 21.
  • the composition and amount of the stabilizer are shown in Table 5. Yu Sample analysis was performed for 30 days and 60 days, and the results are shown in Table 6.
  • composition and amount of the fluoroketone and the stabilizer were changed, and the rest of the operation was the same as in Example 21, and the composition and amount of the fluoroketone and the stabilizer were shown in Table 5.
  • the samples were sampled at 30 days and 60 days, and the results are shown in Table 6.

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Abstract

本发明公开了一种组合物，所述组合物包含：A、至少一种含氟酮；和B、有效量的稳定剂，其选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。本发明提供的组合物性能稳定，能够用作灭火剂、传热介质等。

Description

一种包含含氟酮的组合物 技术领域
本发明涉及一种包含含氟酮的组合物。
背景技术
含氟酮化合物由于不破坏臭氧层(ODP＝0)、温室效应低(GWP<150)，有望在灭火、制冷、发泡和清洗等多个领域替代现有的HCFCs和HFCs。
含氟酮化合物可单独或混配使用为工作流体。但含氟酮化合物在极端条件下存在不稳定的现象，例如暴露在空气中时，与湿气、氧气或其他可能与其发生反应的化合物接触时易发生降解或分解,并可能在自然光、紫外光或金属存在下加速这种降解或分解。当含氟酮化合物作为制冷设备的工作流体或其他相近用途时，其在极端条件下(尤其在高温下)也可能存在不稳定的现象。这种降解或分解可归因于不同的情形，一些情况下是由于含氟酮化合物在极端工作条件下的不稳定性引起的，在另一些情况下是由于无意泄漏到空气中所致。无论何种原因导致降解或分解，均增加了含氟酮化合物的应用难度。
为探寻含氟酮化合物的稳定性，从化合物结构出发，比较烷烃、烯烃和酮类化合物的稳定性。以丙烷、丙烯和丙酮为例，其pKa分别为45、43和26.5，丙烷十分稳定，丙烯基本和丙烷一样，也较稳定，丙酮由于含有羰基，羰基容易结合质子，从而使整个丙酮分子呈电正性，导致酸性的加强，在稳定性上就不如丙烷和丙烯。再以1-溴代丙烷、3-溴代丙烯和溴代丙酮为例，1-溴代丙烷在加热后易生成HBr，3-溴代丙烯易离去溴自由基生成烯丙基自由基，溴代丙酮很不稳定，放置后液体颜色会由无色变成紫色，长时间在空气中放置会成为黑色树脂状物质。
综上所知，为了利用含氟酮化合物的许多其他属性，需要寻找降低其降解或分解的手段。
发明内容
为避免含氟酮在极端条件下的可能的不稳定性，已经发现，向含氟酮中加入特定化合物，即选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种，能够提高其稳定性。
因此，根据本发明，提供了一种组合物，所述组合物包含：A、至少一种含氟酮；和B、 有效量的稳定剂，其选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
还提供了使包含至少一种含氟酮的组合物稳定化的方法，所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了降低包含至少一种含氟酮的组合物降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了降低包含至少一种含氟酮的组合物的降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分和金属的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了降低包含至少一种含氟酮的组合物的降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分、金属和酸的存在引起，所述方法包括将有效量的包含至少一种选自硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了降低包含至少一种含氟酮的组合物在水分和光照下发生降解的方法，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了减少包含至少一种含氟酮的组合物与氧反应的方法，所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯 类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
还提供了一种抑制火焰的方法，所述方法包括向所述火焰的至少一部分或向所述火焰的燃料源施用至少一种组合物，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
还提供了一种灭火的方法，所述方法包括在含有空气的密闭空间内施用至少一种组合物以防止可燃性材料起火或爆燃，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
还提供了所述组合物的应用，所述组合物用作灭火剂、传热介质、镁合金熔融保护剂、溶剂、清洗剂、发泡剂、气溶胶推进剂、绝缘介质或电子蚀刻气体。
具体实施方式
本发明提供一种组合物，包含：A、至少一种含氟酮；和B、有效量的稳定剂，其选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
这些组合物具有多种用途，作为示例，可以是用作灭火剂、传热介质、镁合金熔融保护剂、溶剂、清洗剂、发泡剂、气溶胶推进剂、绝缘介质或电子蚀刻气体。当所述组合物作为灭火剂使用时，作为示例，可以是用于管网式灭火系统、柜式灭火系统、悬挂式灭火系统、探火管式灭火系统或手提式灭火器。当所述组合物作为传热介质使用时，作为示例，可以是用于冷藏机、冷却器、有机兰金循环装置、热泵或集装箱。
灭火剂，亦称为火焰抑制剂，是熄灭或抑制火焰的挥发性组合物。
传热介质，亦称为传热流体、传热组合物或传热流体组合物，是用于将热从热源传向散热器的工作流体。
发泡剂是使聚合物基质膨胀形成多孔结构的挥发性组合物。
溶剂是从基材上除去污物或将材料沉积到基材上或负载材料的流体。
气溶胶推进剂是施加大于一大气压的压力以将材料从容器中推出的一种或多种组分的挥发性组合物。
本发明所用的术语含氟酮描述了包含碳原子、氟原子和任选氢原子且分子结构中含有羰基的化合物。在一个实施方案中，本发明使用的含氟酮具有以下的分子结构：
R1 f-C(＝O)-R2 f，
其中：R1 f和R2 f独立地选自CaHbFcCldBre，a选自1～7的整数，b、d和e独立地选自0～15的整数，c选自1～15的整数，b+c+d+e≤2a+1。
在另一个实施方案中，所述含氟酮选自以下化合物中的至少一种：
CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF2CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF2CF2CF3、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF2CF3、CF3C(＝O)CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF3、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF2CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF3、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)C(CF3)2CF2CF2CF3、CF3C(＝O)CF2CF(CF3)CF2CF2CF3、CF3C(＝O)CF(i-C3F7)CF2CF3、CF3C(＝O)CF(CF3)CF2CF(CF3)2、CF3C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CH(CF3)CHFBr、CF3C(＝O)CH2CFClCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH2CHFCF3、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CH2CF2CF3、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CHFCHFCF3、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CF2CHF2、CF3C(＝O)CClFCF3、CF3C(＝O)CF2CF2Cl、CF3C(＝O)CBrFCF3、CF3C(＝O)CF2CF2Br、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF2CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF2CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2C(＝O)CF2CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF(CF3)2、CF3CF2C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CH(CF3)CHFBr、CF3CF2C(＝O)CH2CFClCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、 CF3CF2C(＝O)CH2CHFCF3、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CH2CF2CF3、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CHFCHFCF3、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CF2CHF2、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CF2CF2Cl、CF3CF2C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF2Br、
CF3CF2CF2C(＝O)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CFCF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFBr、CF3CF2CF2C(＝O)CH2CFClCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH2CHFCF3、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CH2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CHFCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CF2CHF2、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CF2CF2Cl、CF3CF2CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF2CF2Br、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF3、(CF3)2CFC(＝O)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)C(CF3)2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF(CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF(i-C3F7)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF(CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFBr、(CF3)2CFC(＝O)CH2CFClCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH2CHFCF3、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CH2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CHFCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CF2CHF2、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CF2CF2Cl、(CF3)2CFC(＝O)CBrFCF3、(CF3)2CFC(＝O)CF2CF2Br。
在另一个实施方案中，所述含氟酮选自以下化合物中的至少一种：
CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF3、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF(CF3)CF2CF2CF2CF3、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)C(CF3)2CF2CF2CF3、CF3C(＝O)CF(i-C3F7)CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CH(CF3)CHFBr、CF3C(＝O)CH2CFClCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CF2CHF2、CF3C(＝O)CClFCF3、CF3C(＝O)CF2CF2Cl、CF3C(＝O)CBrFCF3、CF3C(＝O)CF2CF2Br、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、F3CF2C(＝O)CH(CF3)CHFBr、CF3CF2C(＝O)CH2CFClCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CF2CHF2、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CF2CF2Cl、CF3CF2C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF2Br、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFBr、CF3CF2CF2C(＝O)CH2CFClCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CF2CHF2、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CF2CF2Cl、CF3CF2CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF2CF2Br、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF3、 (CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)C(CF3)2CF2CF2CF3、(CF3)2CFC(＝O)CF(i-C3F7)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFBr、(CF3)2CFC(＝O)CH2CFClCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CF2CHF2、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CF2CF2Cl、(CF3)2CFC(＝O)CBrFCF3、(CF3)2CFC(＝O)CF2CF2Br。
在另一个实施方案中，所述含氟酮选自以下化合物中的至少一种：
CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CClFCF3、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、 (CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CBrFCF3。
在另一个实施方案中，所述含氟酮选自以下化合物中的至少一种：
CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CHFCF3、CF3C(＝O)CClFCF3、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CBrFCF3。
在另一个实施方案中，所述含氟酮选自以下化合物中的至少一种：
CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CBrFCF3。
在另一个实施方案中，所述含氟酮选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种。当所述含氟酮选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种时，四种含氟酮之间可以以任何质量配比混合。优选的是， 所述CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2的质量配比为0～30:0～50:0～70:0～65,且选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种的质量配比大于0。进一步优选的是，所述CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2的质量配比为0～20:0～40:0～35:0～65,且选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种的质量配比大于0。
代表性的含氟酮包括但不限于表1中所列的化合物。
表1
Figure PCTCN2017074814-appb-000001
Figure PCTCN2017074814-appb-000002
本发明所述稳定剂选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
其中所述环氧化合物，为本领域技术人员理解的环氧化合物，通常为含有以下结构(I)的链式化合物，其中R1、R2、R3、R4可以为单独的取代基或环状取代基，例如1,2-环氧环戊烷或者与其有类似结构的化合物。
Figure PCTCN2017074814-appb-000003
在一个实施方案中，所述环氧化合物选自环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷、1,2-环氧环戊烷、1,2-环氧环己烷、1,2-环氧异丁烷、1,2-环氧苯乙烷、4-乙烯基-1-环己烯二环氧化物和1-叔丁氧基-2,3-环氧丙烷中的至少一种。在另一个实施方案中，所述环氧化合物选自1,2-环氧丙烷、1,2-环氧环戊烷、1,2-环氧环己烷、1,2-环氧异丁烷和1,2-环氧苯乙烷中的至少一种。在另一个实施方案中，所述环氧化合物选自1,2-环氧丙烷、1,2-环氧环己烷和1,2-环氧苯乙烷中的至少一种。
其中所述硝基化合物，为本领域技术人员理解的硝基化合物，通常为含有硝基(-NO2)的化合物。在一个实施方案中，所述硝基化合物选自硝基甲烷、硝基乙烷、1-硝基丙烷、2-硝基丙烷、硝基苯和对二硝基苯烷中的至少一种。在另一个实施方案中，所述硝基化合物为硝基甲烷和硝基苯中的至少一种。在另一个实施方案中，所述硝基化合物为硝基甲烷。
其中所述受阻酚类化合物，为本领域技术人员理解的受阻酚类化合物，通常为具有抗氧化作用的酚类化合物。在一个实施方案中，所述受阻酚类化合物选自双酚A、对壬基酚、百里酚、对甲氧基苯酚、对苄氧基苯酚、儿茶酚、间苯二酚、对叔丁基邻苯二酚、4,4'-亚丁基双(6-叔丁基间甲酚)、2,2'-亚甲基双(6-叔丁基对甲酚)、2,6-二叔丁基对甲酚、2,6-二叔丁基苯酚、2,4,6-三(3',5'-二叔丁基-4'-羟基苄基)均三甲苯、3-(3,5-二叔丁基-4-羟苯基)丙酸十八烷酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮和2,2'-硫代二乙基双(3-(3,5-二叔丁基-4-羟苯基)丙酸酯中的至少一种。在另一个实施方案中，所述受阻酚类化合物选自百里酚、儿茶酚、间苯二酚、对叔丁 基邻苯二酚、2,6-二叔丁基对甲酚和2,6-二叔丁基苯酚中的至少一种。在另一个实施方案中，所述受阻酚类化合物选自百里酚、儿茶酚、间苯二酚和对叔丁基邻苯二酚中的至少一种。
其中所述β-二酮类化合物，为本领域技术人员理解的β-二酮类化合物，通常为在羰基的β位有另一个羰基的化合物，亦即含有(-C(＝O)-CH2-C(＝O)-)基团的化合物。在一个实施方案中，所述β-二酮类化合物选自二甲苯酰基甲烷和硬脂酰基苯甲酰甲烷中的至少一种。在另一个实施方案中，所述β-二酮类化合物为二甲苯酰基甲烷。
其中所述亚磷酸酯类化合物，为本领域技术人员理解的亚磷酸酯类化合物，通常为具有P(OR1)(OR2)OR3结构的化合物，其中R1、R2、R3为具有链式或环状结构的取代基。在一个实施方案中，所述亚磷酸酯类化合物选自磷酸三甲酯、亚磷酸二乙酯、亚磷酸二异丙酯、亚磷酸三异丙酯、亚磷酸三丁酯、亚磷酸二苯酯、亚磷酸三苯酯、亚磷酸二苄酯、亚磷酸三苄酯、亚磷酸癸基二苯基酯、亚磷酸十三烷酯、双十八烷基季戊四醇双亚磷酸酯、三(壬苯基)亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯和亚磷酸三(2,4-二叔丁苯基)酯中的至少一种。在另一个实施方案中，所述亚磷酸酯类化合物选自亚磷酸三甲酯、亚磷酸二乙酯、亚磷酸二异丙酯、亚磷酸三丁酯、亚磷酸二苯酯、亚磷酸三苯酯、亚磷酸二苄酯、亚磷酸三苄酯亚磷酸三苯酯、亚磷酸十三烷酯和双十八烷基季戊四醇双亚磷酸酯中的至少一种。在另一个实施方案中，所述亚磷酸酯类化合物选自亚磷酸三甲酯、亚磷酸二异丙酯、亚磷酸二苄酯、亚磷酸三苄酯、亚磷酸三苯酯和亚磷酸十三烷酯中的至少一种。
其中所述水杨酸酯类化合物，为本领域技术人员理解的水杨酸酯类化合物，通常为具有以下结构(II)的化合物，其中R为具有链式或环状结构的取代基。
Figure PCTCN2017074814-appb-000004
在一个实施方案中，所述水杨酸酯类化合物选自水杨酸甲酯、水杨酸乙酯、水杨酸丁酯、水杨酸异辛酯、水杨酸-4-叔丁基苯酯和水杨酸苯酯中的至少一种。在另一个实施方案中，所述水杨酸酯类化合物为水杨酸甲酯、水杨酸丁酯、水杨酸异辛酯和水杨酸苯酯中的至少一种。在另一个实施方案中，所述水杨酸酯类化合物为水杨酸甲酯和水杨酸苯酯中的至少一种。
其中所述肉桂酸酯类化合物，为本领域技术人员理解的肉桂酸酯类化合物,通常为具有PhCH＝CHCO2R结构的化合物，其中R为具有链式或环状结构的取代基。在一个实施方案中，所述肉桂酸酯类化合物选自3-二苯基丙烯酸乙酯、3-苯基丙烯酸苄酯、2-氰基-3,3-二苯基丙烯酸乙酯和2-氰基-3,3-二苯基丙烯酸-2-乙基己酯中的至少一种。在另一个实施方案中，所 述肉桂酸酯类化合物为3-二苯基丙烯酸乙酯、3-苯基丙烯酸苄酯和2-氰基-3,3-二苯基丙烯酸乙酯中的至少一种。在另一个实施方案中，所述肉桂酸酯类化合物为3-二苯基丙烯酸苄酯和2-氰基-3,3-二苯基丙烯酸乙酯中的至少一种。
其中所述羟基二苯甲酮类化合物，为本领域技术人员理解的2-羟基二苯甲酮类化合物,通常为具有以下结构(III)的化合物，其中R1和R2为具有链式或环状结构的取代基，取代基可在苯环任意位置。
Figure PCTCN2017074814-appb-000005
在一个实施方案中，所述羟基二苯甲酮类化合物选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2,2'-二羟基-4-甲氧基二苯甲酮、2,2',4，4'-四羟基二苯甲酮、2,2'-二羟基-4,4'-二甲氧基二苯甲酮和2-羟基-4-正辛氧基二苯甲酮中的至少一种。在另一个实施方案中，所述羟基二苯甲酮类化合物选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2,2',4,4'-四羟基二苯甲酮和2,2'-二羟基-4,4'-二甲氧基二苯甲酮中的至少一种。在另一个实施方案中，所述羟基二苯甲酮类化合物选自2-羟基-4-甲氧基二苯甲酮和2,2'-二羟基-4,4'-二甲氧基二苯甲酮中的至少一种。
其中所述羟基苯甲酸类化合物，为本领域技术人员理解的4-羟基苯甲酸类及其衍生的羧酸酯类化合物，通常为具有以下结构(IV)的化合物，其中R1和R2为具有链式或环状结构的取代基，R1取代基可在苯环任意位置。
Figure PCTCN2017074814-appb-000006
在一个实施方案中，所述羟基苯甲酸类化合物选自3,5-二叔丁基-4-羟基苯甲酸-2,4-二叔丁基苯酯和3,5-二叔丁基-4-羟基苯甲酸正十六酯中的至少一种。在另一个实施方案中，所述羟基苯甲酸类化合物为3,5-二叔丁基-4-羟基苯甲酸正十六酯。
其中所述烷氧基甲烷类化合物，为本领域技术人员理解的烷氧基甲烷类化合物，通常为具有HC(OR1)(OR2)OR3结构的化合物，其中R1、R2、R3为具有链式或环状结构的取代基。在一个实施方案中，所述烷氧基甲烷类化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷、三正丁氧基甲烷、三戊氧基甲烷、三甲氧基苯甲烷、二乙氧基苯甲氧基甲烷、二乙氧基烯氧基甲烷和三(氯代乙氧基)甲烷中的至少一种。在另一个实施方案中，所述烷氧基甲烷类 化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷、三正丁氧基甲烷、三甲氧基苯甲烷和三(氯代乙氧基)甲烷中的至少一种。在另一个实施方案中，所述烷氧基甲烷类化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷、三甲氧基苯甲烷和三(氯代乙氧基)甲烷中的至少一种。
其中所述有机硫代化合物，为本领域技术人员理解的有机硫代二丙酸化合物，通常为具有(R1-OC(＝O)-CH2CH2-S-CH2CH2-C(＝O)O-R2)结构的化合物，其中R1、R2为具有链式或环状结构的取代基。在一个实施方案中，所述有机硫代化合物选自3,3'-硫代二丙酸二月桂酯、3,3'-硫代二丙酸双十八酯和3,3'-硫代二丙酸二肉豆蔻基酯中的至少一种。在另一个实施方案中，所述有机硫代化合物为3,3'-硫代二丙酸二月桂酯。
代表性的稳定剂包括但不限于表2中所列的化合物。
表2
Figure PCTCN2017074814-appb-000007
Figure PCTCN2017074814-appb-000008
本发明提供的稳定剂，其中一些稳定剂化合物作为多种构型异构体或立体异构体存在。相同化合物的单一异构体或多种异构体可以以任何比例使用以制备稳定剂共混物。此外，给定化合物的单一或多少异构体可以与许多其他化合物以任何比例组合以充当稳定剂共混物。本发明拟包括所有单一的构型异构体、单一的立体异构体或其任何组合或混合物。
本发明所述组合物可以使用任何合适的有效量的稳定剂。“有效量”是指本发明的稳定剂的量，其在添加到包含至少一种含氟酮的组合物中时产生的组合物不会降解造成与无稳定剂的组合物相比一样大的在使用时的性能降低。在一个实施方案中，所述稳定剂与含氟酮的质量比为0.1:1000～50:1000。在另一个实施方案中，所述稳定剂与含氟酮的质量比为0.5:1000～10:1000。在另一个实施方案中，所述稳定剂与含氟酮的质量比为0.5:1000～5:1000。
本发明进一步的涉及使包含至少一种含氟酮的组合物稳定化的方法，所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚 磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及降低包含至少一种含氟酮的组合物降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及降低包含至少一种含氟酮的组合物的降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分和金属的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及降低包含至少一种含氟酮的组合物的降解的方法，所述降解由灭火、清洗、制冷、空调或热泵系统中水分、金属和酸的存在引起，所述方法包括将有效量的包含至少一种选自硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及降低包含至少一种含氟酮的组合物在水分和光照下发生降解的方法，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及减少包含至少一种含氟酮的组合物与氧反应的方法，所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
本发明进一步的涉及一种抑制火焰的方法，所述方法包括向所述火焰的至少一部分或向所述火焰的燃料源施用至少一种组合物，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸 酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
本发明进一步的涉及一种灭火的方法，所述方法包括在含有空气的密闭空间内施用至少一种组合物以防止可燃性材料起火或爆燃，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
本发明进一步的涉及所述组合物的应用，所述组合物用作灭火剂、传热介质、镁合金熔融保护剂、溶剂、清洗剂、发泡剂、气溶胶推进剂、绝缘介质、灭弧介质或电子蚀刻气体。当所述组合物作为灭火剂使用时，特别适合用于管网式灭火系统、柜式灭火系统、悬挂式灭火系统或手提式灭火器。当所述所述组合物作为传热介质使用时，特别适合用于冷藏机、冷却器、有机兰金循环装置、热泵或集装箱。当所述所述组合物作为绝缘介质或灭弧介质使用时，特别适用于中压、高压、特高压电力电气设备。
以下实施例的测试方法原理参照制冷剂测试标准ASHRAE 97:2007，使用耐压容器，在常压下或负压下加入含氟酮组合物，然后通入氮气或空气，在一定温度下保持若干天，再根据不同测试条件如避光或在有光线的条件下放置。到达设定天数后，降至常温，取样分析。充装系数参考ISO 14520-5：2005。水分单位为mg/kg，以下以ppm表示。酸度以HCl计，单位mg/kg，以下以ppm表示。
实施例
实施例1
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物，稳定剂组成及加入量见表3。20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例2～6
改变稳定剂的组成和用量，其余操作与实施例1一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
实施例7
使用100mL碳钢钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物，稳定剂组成及加入量见表3。20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例8～9
改变稳定剂的组成和用量，其余操作与实施例7一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
实施例10
使用100mL碳钢钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物及0.01g五氟丙酸，稳定剂组成及加入量见表3。20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例11～12
改变稳定剂的组成和用量，其余操作与实施例10一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
实施例13
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物及0.5g水，稳定剂组成及加入量见表3。20℃下通入未干燥的压缩空气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例14
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物及0.5g水，稳定剂组成及加入量见表3。20℃下通入氧气至5bar，继续通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例15
改变稳定剂的组成和用量，其余操作与实施例13一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
实施例16
改变稳定剂的组成和用量，其余操作与实施例14一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
实施例17
使用10mL耐压玻璃试管，负压吸入10.5g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮组合物及0.5g水，稳定剂组成及加入量见表3。20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表4。
实施例18～20
改变稳定剂的组成和用量，其余操作与实施例17一致，稳定剂的组成和用量见表3。于10天、30天、60天取样分析，结果见表4。
表3
Figure PCTCN2017074814-appb-000009
Figure PCTCN2017074814-appb-000010
表4
Figure PCTCN2017074814-appb-000011
实施例21
使用100mL内衬四氟的不锈钢瓶，负压吸入105g含氟酮组合物，含氟酮名称、稳定剂组成及加入量见表5。20℃下通入干燥的高纯氮气(水分＜10ppm)至25bar，密封，升温至60℃静置，于30天、60天取样分析，结果见表6。
实施例22～39
改变稳定剂的组成和用量，其余操作与实施例21一致，稳定剂的组成和用量见表5。于 30天、60天取样分析，结果见表6。
实施例40-45
改变含氟酮和稳定剂的组成和用量，其余操作与实施例21一致，含氟酮和稳定剂的组成和用量见表5。于30天、60天取样分析，结果见表6。
表5
Figure PCTCN2017074814-appb-000012
Figure PCTCN2017074814-appb-000013
Figure PCTCN2017074814-appb-000014
表6
Figure PCTCN2017074814-appb-000015
Figure PCTCN2017074814-appb-000016
比较例1
使用100mL内衬四氟的不锈钢釜，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮，20℃下通入未干燥的普通工业氮气至25bar，密封，常温下静置，于10天、30天、60天取样分析，结果见表7。
比较例2
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮，20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
比较例3
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮及0.5g水，20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
比较例4
使用100mL碳钢钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮，20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
比较例5
使用100mL碳钢钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮及0.01g五氟丙酸，20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静 置，于10天、30天、60天取样分析，结果见表7。
比较例6
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮及0.5g水，20℃下通入未干燥的压缩空气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
比较例7
使用100mL内衬四氟的不锈钢瓶，负压吸入105g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮及0.5g水，20℃下通入氧气至5bar，继续通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
比较例8
使用10mL耐压玻璃试管，负压吸入10.5g的1,1,1,2,2,4,5,5,5-九氟-4-(三氟代甲基)-3-戊酮及0.5g水，20℃下通入未干燥的普通工业氮气至25bar，密封，升温至60℃静置，于10天、30天、60天取样分析，结果见表7。
表7
Figure PCTCN2017074814-appb-000017

Claims (26)

  1. 一种组合物，其特征在于所述组合物包含：
    A、至少一种含氟酮；和
    B、有效量的稳定剂，其选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种，所述硝基化合物不包括硝基甲烷；
    当含氟酮为CF3CF2C(＝O)CF(CF3)2时，所述稳定剂不包括硝基甲烷、受阻酚类化合物和亚磷酸酯类化合物。
  2. 按照权利要求1所述的组合物，其特征在于所述含氟酮具有以下的分子结构：
    R1 f-C(＝O)-R2 f，
    其中：R1 f和R2 f独立地选自CaHbFcCldBre，a选自1～7的整数，b、d和e独立地选自0～15的整数，c选自1～15的整数，b+c+d+e≤2a+1。
  3. 按照权利要求2所述的组合物，其特征在于所述含氟酮选自以下化合物中的至少一种：CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF2CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF2CF2CF3、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF2CF3、CF3C(＝O)CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF3、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF2CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF3、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)C(CF3)2CF2CF2CF3、CF3C(＝O)CF2CF(CF3)CF2CF2CF3、CF3C(＝O)CF(i-C3F7)CF2CF3、CF3C(＝O)CF(CF3)CF2CF(CF3)2、CF3C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CH(CF3)CHFBr、CF3C(＝O)CH2CFClCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH2CHFCF3、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CH2CF2CF3、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CHFCHFCF3、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CF2CHF2、CF3C(＝O)CClFCF3、CF3C(＝O)CF2CF2Cl、CF3C(＝O)CBrFCF3、CF3C(＝O)CF2CF2Br、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF2CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF2CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、 CF3CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2C(＝O)CF2CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF(CF3)2、CF3CF2C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CH(CF3)CHFBr、CF3CF2C(＝O)CH2CFClCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CH2CHFCF3、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CH2CF2CF3、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CHFCHFCF3、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CF2CHF2、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CF2CF2Cl、CF3CF2C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF2Br、CF3CF2CF2C(＝O)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CFCF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF2CF2CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFBr、CF3CF2CF2C(＝O)CH2CFClCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH2CHFCF3、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CH2CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CHFCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CF2CHF2、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CF2CF2Cl、CF3CF2CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF2CF2Br、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF3、(CF3)2CFC(＝O)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)C(CF3)2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF(CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF(i-C3F7)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF(CF3)2、(CF3)2CFC(＝O)CF2CF2CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、 (CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFBr、(CF3)2CFC(＝O)CH2CFClCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH2CHFCF3、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CH2CF2CF3、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CHFCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CF2CHF2、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CF2CF2Cl、(CF3)2CFC(＝O)CBrFCF3、(CF3)2CFC(＝O)CF2CF2Br。
  4. 按照权利要求3所述的组合物，其特征在于所述含氟酮选自以下化合物中的至少一种：CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF3、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF(CF3)CF2CF2CF2CF3、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)C(CF3)2CF2CF2CF3、CF3C(＝O)CF(i-C3F7)CF2CF3、CF3C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CH(CF3)CHFBr、CF3C(＝O)CH2CFClCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CF2CHF2、CF3C(＝O)CClFCF3、CF3C(＝O)CF2CF2Cl、CF3C(＝O)CBrFCF3、CF3C(＝O)CF2CF2Br、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、F3CF2C(＝O)CH(CF3)CHFBr、CF3CF2C(＝O)CH2CFClCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CF2CHF2、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CF2CF2Cl、CF3CF2C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF2Br、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)C(CF3)2CF2CF2CF3、CF3CF2CF2C(＝O)CF(i-C3F7)CF2CF3、CF3CF2CF2C(＝O)CF(CF3)CF2CF2CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFBr、CF3CF2CF2C(＝O)CH2CFClCF3、 CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CF2CHF2、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CF2CF2Cl、CF3CF2CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF2CF2Br、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF3、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)C(CF3)2CF2CF2CF3、(CF3)2CFC(＝O)CF(i-C3F7)CF2CF3、(CF3)2CFC(＝O)CF(CF3)CF2CF2CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFBr、(CF3)2CFC(＝O)CH2CFClCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CF2CHF2、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CF2CF2Cl、(CF3)2CFC(＝O)CBrFCF3、(CF3)2CFC(＝O)CF2CF2Br。
  5. 按照权利要求4所述的组合物，其特征在于所述含氟酮选自以下化合物中的至少一种：CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF2CF3)2、CF3C(＝O)CF(CF2CF3)CF2CF2CF3、CF3C(＝O)CF2CF2CF＝CF2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CHClCHFCF3、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CH(CF3)CH2F、CF3C(＝O)CF(CF3)CH2F、CF3C(＝O)CH(CF3)CHF2、CF3C(＝O)CHFCF3、CF3C(＝O)CClFCF3、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF2CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF2CF3、CF3CF2C(＝O)CF(CF2CF3)2、CF3CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2C(＝O)CF2CF2CF＝CF2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CHClCHFCF3、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CH(CF3)CH2F、CF3CF2C(＝O)CF(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHF2、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF2CF3)2、CF3CF2CF2C(＝O)CF(CF2CF3)CF2CF2CF3、CF3CF2CF2C(＝O)CF2CF2CF＝CF2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、 CF3CF2CF2C(＝O)CHClCHFCF3、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CH(CF3)CH2F、CF3CF2CF2C(＝O)CF(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHF2、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF2CF3)2、(CF3)2CFC(＝O)CF(CF2CF3)CF2CF2CF3、(CF3)2CFC(＝O)CF2CF2CF＝CF2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CHClCHFCF3、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CH(CF3)CH2F、(CF3)2CFC(＝O)CF(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHF2、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CBrFCF3。
  6. 按照权利要求5所述的组合物，其特征在于所述含氟酮选自以下化合物中的至少一种：CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CF(CF3)CF＝CF2、CF3C(＝O)CH(CF3)CHFCF3、CF3C(＝O)CH2CFBrCF3、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CHBrCHFCF3、CF3C(＝O)CCl(CF3)CH2F、CF3C(＝O)CH(CF3)CHFCl、CF3C(＝O)CHFCF3、CF3C(＝O)CClFCF3、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2C(＝O)CH(CF3)CHFCF3、CF3CF2C(＝O)CH2CFBrCF3、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CHBrCHFCF3、CF3CF2C(＝O)CCl(CF3)CH2F、CF3CF2C(＝O)CH(CF3)CHFCl、CF3CF2C(＝O)CHFCF3、CF3CF2C(＝O)CClFCF3、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF＝CF2、CF3CF2CF2C(＝O)CH(CF3)CHFCF3、CF3CF2CF2C(＝O)CH2CFBrCF3、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CHBrCHFCF3、CF3CF2CF2C(＝O)CCl(CF3)CH2F、CF3CF2CF2C(＝O)CH(CF3)CHFCl、CF3CF2CF2C(＝O)CHFCF3、CF3CF2CF2C(＝O)CClFCF3、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CF(CF3)CF＝CF2、(CF3)2CFC(＝O)CH(CF3)CHFCF3、(CF3)2CFC(＝O)CH2CFBrCF3、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CHBrCHFCF3、(CF3)2CFC(＝O)CCl(CF3)CH2F、(CF3)2CFC(＝O)CH(CF3)CHFCl、(CF3)2CFC(＝O)CHFCF3、(CF3)2CFC(＝O)CClFCF3、(CF3)2CFC(＝O)CBrFCF3。
  7. 按照权利要求6所述的组合物，其特征在于所述含氟酮选自以下化合物中的至少一种：CF3C(＝O)CF3、CF3C(＝O)CF2CF3、CF3C(＝O)CF(CF3)2、CF3C(＝O)CF2CF(CF3)2、CF3C(＝O)CBr(CF3)CH2F、CF3C(＝O)CBrFCF3、CF3CF2C(＝O)CF2CF3、CF3CF2C(＝O)CF(CF3)2、CF3CF2C(＝O)CBr(CF3)CH2F、CF3CF2C(＝O)CBrFCF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF2CF(CF3)2、CF3CF2CF2C(＝O)CBr(CF3)CH2F、CF3CF2CF2C(＝O)CBrFCF3、(CF3)2CFC(＝O)CF(CF3)2、(CF3)2CFC(＝O)CF2CF(CF3)2、(CF3)2CFC(＝O)CBr(CF3)CH2F、(CF3)2CFC(＝O)CBrFCF3。
  8. 按照权利要求7所述的组合物，其特征在于所述含氟酮选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种。
  9. 按照权利要求8所述的组合物，其特征在于所述CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2的质量配比为0～30:0～50:0～70:0～65,且选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种的质量配比大于0。
  10. 按照权利要求9所述的组合物，其特征在于所述CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2的质量配比为0～20:0～40:0～35:0～65,且选自CF3C(＝O)CF(CF3)CF3、CF3CF2CF2C(＝O)CF(CF3)2、CF3CF2CF2C(＝O)CF(CF3)CF3和(CF3)2CFC(＝O)CF(CF3)2中的至少一种的质量配比大于0。
  11. 按照权利要求1所述的组合物，其特征在于：
    所述环氧化合物选自环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷、1,2-环氧环戊烷、1,2-环氧环己烷、1,2-环氧异丁烷、1,2-环氧苯乙烷、4-乙烯基-1-环己烯二环氧化物和1-叔丁氧基-2,3-环氧丙烷中的至少一种；
    所述硝基化合物选自硝基乙烷、1-硝基丙烷、2-硝基丙烷、硝基苯和对二硝基苯中的至少一种；
    所述受阻酚类化合物选自双酚A、对壬基酚、百里酚、对甲氧基苯酚、对苄氧基苯酚、儿茶酚、间苯二酚、对叔丁基邻苯二酚、4,4'-亚丁基双(6-叔丁基间甲酚)、2,2'-亚甲基双(6-叔丁基对甲酚)、2,6-二叔丁基对甲酚、2,6-二叔丁基苯酚、2,4,6-三(3',5'-二叔丁基-4'-羟基苄基)均三甲苯、3-(3,5-二叔丁基-4-羟苯基)丙酸十八烷酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮和2,2'-硫代二乙基双(3-(3,5-二叔丁基-4-羟苯基)丙酸酯中的至少一种；
    所述β-二酮类化合物选自二甲苯酰基甲烷和硬脂酰基苯甲酰甲烷中的至少一种；
    所述亚磷酸酯类化合物选自亚磷酸三甲酯、亚磷酸二乙酯、亚磷酸二异丙酯、亚磷酸三异丙酯、亚磷酸三丁酯、亚磷酸二苯酯、亚磷酸三苯酯、亚磷酸二苄酯、亚磷酸三苄酯、亚磷酸癸基二苯基酯、亚磷酸十三烷酯、双十八烷基季戊四醇双亚磷酸酯、三(壬苯基)亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯和亚磷酸三(2,4-二叔丁苯基)酯中的至少一 种；
    所述水杨酸酯类化合物选自水杨酸甲酯、水杨酸乙酯、水杨酸丁酯、水杨酸异辛酯、水杨酸-4-叔丁基苯酯和水杨酸苯酯中的至少一种；
    所述肉桂酸酯类化合物选自3-二苯基丙烯酸乙酯、3-苯基丙烯酸苄酯、2-氰基-3,3-二苯基丙烯酸乙酯和2-氰基-3,3-二苯基丙烯酸-2-乙基己酯中的至少一种；
    所述羟基二苯甲酮类化合物选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2,2'-二羟基-4-甲氧基二苯甲酮、2,2',4，4'-四羟基二苯甲酮、2,2'-二羟基-4,4'-二甲氧基二苯甲酮和2-羟基-4-正辛氧基二苯甲酮中的至少一种；
    所述羟基苯甲酸类化合物选自3,5-二叔丁基-4-羟基苯甲酸-2,4-二叔丁基苯酯和3,5-二叔丁基-4-羟基苯甲酸正十六酯中的至少一种；
    所述烷氧基甲烷类化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷、三正丁氧基甲烷、三戊氧基甲烷、三甲氧基苯甲烷、二乙氧基苯甲氧基甲烷、二乙氧基烯氧基甲烷和三(氯代乙氧基)甲烷中的至少一种；
    所述有机硫代化合物选自3,3'-硫代二丙酸二月桂酯、3,3'-硫代二丙酸双十八酯和3,3'-硫代二丙酸二肉豆蔻基酯中的至少一种。
  12. 按照权利要求11所述的组合物，其特征在于：
    所述环氧化合物选自1,2-环氧丙烷、1,2-环氧环戊烷、1,2-环氧环己烷、1,2-环氧异丁烷和1,2-环氧苯乙烷中的至少一种；
    所述硝基化合物为硝基苯；
    所述受阻酚类化合物选自百里酚、儿茶酚、间苯二酚、对叔丁基邻苯二酚、2,6-二叔丁基对甲酚和2,6-二叔丁基苯酚中的至少一种；
    所述β-二酮类化合物为二甲苯酰基甲烷；
    所述亚磷酸酯类化合物选自亚磷酸三甲酯、亚磷酸二乙酯、亚磷酸二异丙酯、亚磷酸三丁酯、亚磷酸二苯酯、亚磷酸三苯酯、亚磷酸二苄酯、亚磷酸三苄酯亚磷酸三苯酯、亚磷酸十三烷酯和双十八烷基季戊四醇双亚磷酸酯中的至少一种；
    所述水杨酸酯类化合物为水杨酸甲酯、水杨酸丁酯、水杨酸异辛酯和水杨酸苯酯中的至少一种；
    所述肉桂酸酯类化合物为3-二苯基丙烯酸乙酯、3-苯基丙烯酸苄酯和2-氰基-3,3-二苯基丙烯酸乙酯中的至少一种；
    所述羟基二苯甲酮类化合物选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、 2,2',4,4'-四羟基二苯甲酮和2,2'-二羟基-4,4'-二甲氧基二苯甲酮中的至少一种；
    所述羟基苯甲酸类化合物为3,5-二叔丁基-4-羟基苯甲酸正十六酯；
    所述烷氧基甲烷类化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷、三正丁氧基甲烷、三甲氧基苯甲烷和三(氯代乙氧基)甲烷中的至少一种；
    所述有机硫代化合物为3,3'-硫代二丙酸二月桂酯。
  13. 按照权利要求12所述的组合物，其特征在于：
    所述环氧化合物选自1,2-环氧丙烷、1,2-环氧环己烷和1,2-环氧苯乙烷中的至少一种；
    所述受阻酚类化合物选自百里酚、儿茶酚、间苯二酚和对叔丁基邻苯二酚中的至少一种；
    所述β-二酮类化合物为二甲苯酰基甲烷；
    所述亚磷酸酯类化合物选自亚磷酸三甲酯、亚磷酸二异丙酯、亚磷酸二苄酯、亚磷酸三苄酯、亚磷酸三苯酯和亚磷酸十三烷酯中的至少一种；
    所述水杨酸酯类化合物为水杨酸甲酯和水杨酸苯酯中的至少一种；
    所述肉桂酸酯类化合物为3-苯基丙烯酸苄酯和2-氰基-3,3-二苯基丙烯酸乙酯中的至少一种；
    所述羟基二苯甲酮类化合物选自2-羟基-4-甲氧基二苯甲酮和2,2'-二羟基-4,4'-二甲氧基二苯甲酮中的至少一种；
    所述羟基苯甲酸类化合物为3,5-二叔丁基-4-羟基苯甲酸正十六酯；
    所述烷氧基甲烷类化合物选自三甲氧基甲烷、三乙氧基甲烷、三正丙氧基甲烷和三甲氧基苯甲烷和三(氯代乙氧基)甲烷中的至少一种。
    所述有机硫代化合物为3,3'-硫代二丙酸二月桂酯。
  14. 按照权利要求1所述的组合物，其特征在于所述稳定剂与含氟酮的质量比为0.1:1000～50:1000。
  15. 按照权利要求14所述的组合物，其特征在于所述稳定剂与含氟酮的质量比为0.5:1000～10:1000。
  16. 按照权利要求15所述的组合物，其特征在于所述稳定剂与含氟酮的质量比为0.5:1000～5:1000。
  17. 使包含至少一种含氟酮的组合物稳定化的方法，其特征在于所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化 合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  18. 降低包含至少一种含氟酮的组合物降解的方法，其特征在于所述降解由灭火、清洗、制冷、空调或热泵系统中水分的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  19. 降低包含至少一种含氟酮的组合物的降解的方法，其特征在于所述降解由灭火、清洗、制冷、空调或热泵系统中水分和金属的存在引起，所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、羟基二苯甲酮类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  20. 降低包含至少一种含氟酮的组合物的降解的方法，其特征在于所述降解由灭火、清洗、制冷、空调或热泵系统中水分、金属和酸的存在引起，所述方法包括将有效量的包含至少一种选自硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  21. 降低包含至少一种含氟酮的组合物在水分和光照下发生降解的方法，其特征在于所述方法包括将有效量的包含至少一种选自受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  22. 减少包含至少一种含氟酮的组合物与氧反应的方法，其特征在于所述方法包括将有效量的包含至少一种选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类 化合物和烷氧基甲烷类化合物中的化合物稳定剂添加到包含至少一种含氟酮的组合物中。
  23. 一种抑制火焰的方法，其特征在于所述方法包括向所述火焰的至少一部分或向所述火焰的燃料源施用至少一种组合物，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
  24. 一种灭火的方法，其特征在于所述方法包括在含有空气的密闭空间内施用至少一种组合物以防止可燃性材料起火或爆燃，所述组合物包含至少一种含氟酮和有效量的稳定剂，所述稳定剂包含选自环氧化合物、硝基化合物、受阻酚类化合物、β-二酮类化合物、亚磷酸酯类化合物、水杨酸酯类化合物、肉桂酸酯类化合物、羟基二苯甲酮类化合物、羟基苯甲酸类化合物、烷氧基甲烷类化合物和有机硫代化合物中的至少一种。
  25. 一种组合物的应用，其特征在于所述组合物用作灭火剂、传热介质、镁合金熔融保护剂、溶剂、清洗剂、发泡剂、气溶胶推进剂、绝缘介质、灭弧介质或电子蚀刻气体。
  26. 按照权利要求25所述的组合物的应用，其特征在于所述组合物作为灭火剂用于管网式灭火系统、柜式灭火系统、悬挂式灭火系统、探火管式灭火系统或手提式灭火器，或者所述组合物作为传热介质用于冷藏机、冷却器、有机兰金循环装置、热泵或集装箱。或者所述组合物作为绝缘介质或灭弧介质用于中压、高压、特高压电力电气设备。
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