[go: up one dir, main page]

WO2019117100A1 - Composition de type azéotrope contenant du z-1,2-dichloro-3,3,3-trifluoropropène - Google Patents

Composition de type azéotrope contenant du z-1,2-dichloro-3,3,3-trifluoropropène Download PDF

Info

Publication number
WO2019117100A1
WO2019117100A1 PCT/JP2018/045364 JP2018045364W WO2019117100A1 WO 2019117100 A1 WO2019117100 A1 WO 2019117100A1 JP 2018045364 W JP2018045364 W JP 2018045364W WO 2019117100 A1 WO2019117100 A1 WO 2019117100A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
azeotropic
composition according
mol
liquid
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.)
Ceased
Application number
PCT/JP2018/045364
Other languages
English (en)
Japanese (ja)
Inventor
井村　英明
覚 岡本
祥雄 西口
冬彦 佐久
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.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
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 Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP2019559634A priority Critical patent/JP7189448B2/ja
Publication of WO2019117100A1 publication Critical patent/WO2019117100A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • 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
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • 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
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • 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
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C11D7/30—Halogenated hydrocarbons
    • 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

Definitions

  • the present invention relates to an azeotrope-like composition
  • an azeotrope-like composition comprising Z-1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223 x d (Z)”) as a component.
  • Fluorinated saturated compounds such as chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been used in applications such as blowing agents, heat transfer media, solvents, detergents and the like. In these applications it is particularly desirable to use single component or azeotrope-like compositions, ie those which do not substantially fractionate upon boiling, evaporation.
  • HCFO hydrochlorofluoroolefins
  • Patent Document 1 the composition of a C3-C3 fluorine-containing olefin and a general purpose solvent is proposed.
  • Example 4 of Patent Document 1 a degreasing test example of 1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223xd") alone is disclosed.
  • Patent Documents 2 to 7 disclose buffing cleaning test examples of 1223xd alone, resist development test examples, resist peeling test examples, dry cleaning test examples, flux cleaning test examples, and adhesion water removal test examples.
  • the low-boiling component in the washing solution may decrease over time to cause poor washing.
  • the used washing solution is usually regenerated and reused by distillation, but in the case of a composition having different composition of liquid phase and composition of gas phase, it is necessary to adjust the liquid composition of the recovered composition. It is not efficient.
  • the present invention is a novel azeotrope (like) containing environmentally friendly (Z) -1,2-dichloro-3,3,3-trifluoropropene (1223xd (Z)) and whose composition does not change upon volatilization
  • the task is to propose a composition.
  • the present inventors diligently studied to solve the above problems. As a result, it was found that the composition of 1223 ⁇ d (Z) and the specific compound was an azeotrope-like composition having substantially the same composition of the gas phase part and the liquid phase part. Furthermore, it was also confirmed in the examples that the azeotrope-like composition of the present invention is suitable as a cleaner for articles to be cleaned, and the present invention has been completed.
  • the present invention includes the following inventions.
  • invention 2 The azeotropic (like) composition according to the invention 1, comprising 1 to 40 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 60 mol% of dichloromethane.
  • invention 4 The azeotrope (like) composition according to invention 1, comprising 80-99 mole% Z-1,2-dichloro-3,3,3-trifluoropropene and 20-1 mole% ethanol.
  • invention 5 The azeotropic (like) composition according to the invention 1, comprising 90-99 mole% Z-1,2-dichloro-3,3,3-trifluoropropene and 10-1 mole% n-propanol.
  • invention 6 The azeotropic (like) composition according to the invention 1, comprising 85 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 15 to 1 mol% of isopropanol.
  • invention 7 The azeotropic (like) composition according to the invention 1, comprising 75 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 25 to 1 mol% of n-hexane.
  • invention 8 The azeotropic (like) composition according to the invention 1, comprising 85 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 15 to 1 mol% of cyclohexane.
  • invention 9 The azeotropic (like) composition according to the invention 1, comprising 1 to 99 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 1 mol% of acetone.
  • invention 10 The azeotropic (like) composition according to the invention 1, comprising 1 to 60 mol% of Z-1,2-dichloro-3,3,3-trifluoropropene and 99 to 40 mol% of cyclopentane.
  • a liquid composition comprising at least the azeotropic (like) composition according to any of Inventions 1 to 10.
  • invention 14 An aerosol composition comprising the azeotropic (for) composition according to any of Inventions 1 to 10 or the liquid composition according to any of Inventions 11 to 13 and a propellant gas.
  • a cleaning agent comprising the azeotropic (like) composition according to any of the inventions 1 to 10, the liquid composition according to any of the inventions 11 to 13 or the aerosol composition according to the invention 14.
  • invention 16 The cleaning agent according to invention 15, which is for cleaning a vehicle, a vehicle or a transportation vehicle.
  • invention 17 The cleaning agent according to invention 15 or 16, which is for a vehicle, vehicle or vehicle brake cleaner.
  • a solvent comprising the azeotropic (like) composition according to any of the inventions 1 to 10, the liquid composition according to any of the inventions 11 to 13 or the aerosol composition according to the invention 14.
  • invention 20 An effervescent agent comprising the azeotropic (like) composition according to any of the inventions 1 to 10, the liquid composition according to any of the inventions 11 to 13 or the aerosol composition according to the invention 14.
  • a heat transfer medium comprising the azeotropic (like) composition according to any of the inventions 1 to 10, the liquid composition according to any of the inventions 11 to 13 or the aerosol composition according to the invention 14.
  • a lubricant solvent comprising the azeotropic (like) composition according to any of Inventions 1 to 10, the liquid composition according to any of Inventions 11 to 13 or the aerosol composition according to Invention 14.
  • Patent Documents 1 to 7 there is no description of detailed behavior when blending 1,2-dichloro-3,3,3-trifluoropropene (1223xd) with the specific compound described above. Furthermore, geometric isomers of E-form and Z-form exist in 1223xd, and since these geometric isomers each have an inherent boiling point and polarity, drying properties, washing properties, and the like differ. However, the above-mentioned patent documents do not disclose geometric isomers.
  • the present invention provides novel azeotropic (like) compositions.
  • This azeotropic (like) composition exerts an effect that the load on the environment is small, and the performance as a liquid whose composition does not easily change even when used under open conditions is easily maintained.
  • this azeotropic (like) composition is useful as a cleaning agent for an article (a to-be-cleaned article) to which a contaminant such as a foreign matter or a fat or oil adheres.
  • a binary liquid composition when placed in an ultrasonic cleaner and used as a cleaning agent, generally, low-boiling components with high volatility (components with a large vapor pressure) are volatilized preferentially, and the inside of the cleaning tank
  • the high volatility components with low volatility are concentrated.
  • the concentration of low boiling point components in the cleaning solution may decrease with time, which may cause cleaning failure.
  • the cleaning solution when a nonflammable solvent is blended with a flammable solvent to prepare a nonflammable composition, if the nonflammable component preferentially volatilizes, the cleaning solution may become a flammable composition.
  • thermodynamic cycle The same problem arises when used for working fluid of thermodynamic cycle. That is, even when used as a working fluid of the thermodynamic cycle, there is a possibility that the liquid composition may change in a long time. If the liquid composition changes, the heat capacity of the liquid, the viscosity, or the affinity with the lubricant may change, and the operation performance of the thermodynamic cycle may be reduced.
  • liquid composition control can be a heavy task load.
  • azeotropic refers to the thermodynamically strict meaning of azeotrope.
  • azeotrope azeotropic mixture
  • “Azeotropic-like” is also called “pseudo-azeotropic”, and is not thermodynamically strictly azeotropic, but for a liquid of a range of composition, its liquid composition and the composition of the gas in equilibrium are , Which may be substantially equal, refers to such a phenomenon. Even if the compositions of the gas phase part and the liquid phase part do not match completely, if the compositions of the gas phase part and the liquid phase substantially match, one skilled in the art can handle the same as the azeotropic composition. At this time, the smaller the gas-liquid equilibrium composition difference between the gas phase part and the liquid phase part, the better. Thus, the phenomenon in which the vapor-liquid equilibrium composition of the vapor phase part and the liquid phase part substantially match is called azeotropic or quasi azeotropic, and the composition is called azeotropic or pseudo azeotropic composition .
  • azeotropic phenomena and pseudo-azeotropic phenomena should be distinguished, but in practice such as washing, they distinguish between azeotropic phenomena and azeotrope-like phenomena (or quasi-azeotropic reactions)
  • the azeotropic phenomenon and the azeotrope-like phenomenon are collectively referred to as "azeotrope" in the present specification because they are not necessary and can be handled in exactly the same way.
  • the composition at that time is called "azeotropic (like) composition". In the azeotropic (like) manner, the presence or absence of the azeotropic point does not matter. It is sufficient if the vapor-liquid equilibrium composition of the gas phase part and the liquid phase part substantially match.
  • “Azeotropic (like)” is not theoretically derived, and the vapor-liquid equilibrium is experimentally investigated for various liquid types and composition ratios, and accidentally, the composition of the gas phase and the composition of the liquid phase are substantially It can only be found when it matches.
  • vapor-liquid equilibrium experiments of 1223xd (Z) and a specific compound were conducted, and it was found that the azeotropic point at which the vapor-liquid composition completely matched and / or that the vapor-liquid composition was substantially identical. The boiling (like) composition could be found.
  • E- and Z-forms exist in 1,2-dichloro-3,3,3-trifluoropropene (1223xd), and a method for selectively producing Z-form is disclosed in the patent document (WO2014 / 046250, WO2014 / 046251).
  • High purity Z form (1223 x d (Z)) is available by precision distillation.
  • the composition of the present invention comprising the first component 1223xd (Z) and the second component specific compound has a specific composition An azeotropic (like) composition in which the compositions of the gas phase part and the liquid phase part are substantially the same.
  • composition containing the first component 1223xd (Z) and the second component dichloromethane 1 to 40% by mole of 1223xd (Z) and 99 to 60% by mole of dichloromethane It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, when the composition of 1223 ⁇ d (Z) is 1 to 30 mol% and dichloromethane is 99 to 70 mol%, the compositions of the gas phase part and the liquid phase part are further closer, and composition fluctuation is further less likely to occur.
  • composition containing 1223 x d (Z) which is the first component and methanol which is the second component in the case of 67 to 77 mol% of 1223 x d (Z) and 33 to 23 mol% of methanol, It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Further, 70 to 74 mol% of 1223 ⁇ d (Z) and 30 to 26 mol% of methanol are particularly preferable because the compositions of the gas phase part and the liquid phase part are closer to each other and composition fluctuation is less likely to occur.
  • composition containing 1223 x d (Z) as the first component and ethanol as the second component 80 to 99 mol% of 1223 x d (Z) and 20 to 1 mol% of ethanol It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, in the case of 85 to 99 mol% of 1223 ⁇ d (Z) and 15 to 1 mol% of ethanol, the compositions of the gas phase part and the liquid phase part are closer to each other.
  • composition containing 1223 x d (Z) as the first component and n-propanol as the second component 90 to 99 mol% of 1223 x d (Z) and 10 to 1 mol of n-propanol %
  • the risk of ignition and the risk of fire in the composition usage environment is low.
  • the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation hardly occurs. preferable.
  • composition containing 1223 x d (Z) which is the first component and isopropanol which is the second component in the case of 85 to 99 mol% of 1223 x d (Z) and 15 to 1 mol% of isopropanol, It is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Furthermore, in the case of 90 to 99 mol% of 1223 ⁇ d (Z) and 10 to 1 mol% of isopropanol, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is further less likely to occur.
  • composition containing 1223 x d (Z) as the first component and n-hexane as the second component 75 to 99 mol% of 1223 x d (Z) and 25 to 1 mol of n-hexane %, It is an azeotropic (like) composition in which the composition of the gas phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Further, when 80 to 99 mol% of 1223 x d (Z) and 20 to 1 mol% of n-hexane, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is further less likely to occur. preferable.
  • composition containing 1223 x d (Z) which is the first component and cyclohexane which is the second component when 85 to 99 mol% of 1223 x d (Z) and 15 to 1 mol% of cyclohexane, it is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Also, with this composition, the risk of ignition and the risk of fire in the composition usage environment is low. Further, 90 to 99 mol% of 1223 x d (Z) and 10 to 1 mol% of cyclohexane are particularly preferable because the compositions of the gas phase part and the liquid phase part are closer to each other and composition fluctuation hardly occurs.
  • composition containing 1223 x d (Z) which is the first component and acetone which is the second component when 1-99 mol% of 1223 x d (Z) and 99-1 mol% of acetone, it is an azeotropic (like) composition in which the composition of the phase part and the liquid phase part is substantially the same. Furthermore, in 45 to 99 mol% of 1223 x d (Z) and 55 to 1 mol% of acetone, the compositions of the gas phase part and the liquid phase part are closer to each other, and composition fluctuation is further less likely to occur. Particularly preferred because of the low risk of fire and fire hazard in the use environment.
  • composition containing 1223 x d (Z) which is the first component and cyclopentane which is the second component 1 to 60 mol% of 1223 x d (Z) and 99 to 40 mol% of cyclopentane
  • the value of the mole% is the mole of each component when the total value of the number of moles of the first component 1223 x d (Z) and the number of moles of the specific compound as the second component is 100. Represents the% of number (ie, the relative mole% between the two components). If it is a composition of this range, even if it handles a liquid composition by an open system in practice, even if it performs collection operation by distillation, composition change hardly occurs.
  • the azeotropic (like) composition of the present invention can be produced, for example, by mixing 1223 x d (Z) as the first component and the specific compound as the second component in a specific amount.
  • the azeotropic (like) composition of the present invention is one that is substantially free of impurities (consisting essentially of the first component and the second component) and is of high purity in a preferred embodiment. is there.
  • the azeotropic (like) composition of the present invention may be used as a starting material for synthesizing them, Small amounts of by-products etc. (Each component is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1% by mass, with respect to the azeotropic (like) composition Or less) may remain.
  • the azeotropic (like) composition of the present invention may contain, in addition to the first component and the second component, the following compounds: 1-chloro-3,3,3-trifluoropropene (1233zd), 2-chloro-3,3,3-trifluoropropene (1233xf), 2,3-dichloro-3,3-difluoropropene (1232xf), 1,2,3-Trichloro-3,3-difluoropropene (1222xd), 2,3,3-trichloro-3-fluoropropene (1231xf), E-1,2-dichloro-3,3,3-trile HCFOs such as fluoropropene (1223xd (E)), 1,1-dichloro-3,3,3-trifluoropropene (1223za); 1,3,3,3-tetrachloropropene (1230zd), 1,1,2,3-tetrachloropropene (1230xa), 1,1,3,3-tetrachloroprop
  • additional components can also be added to improve the performance of the azeotropic (like) composition.
  • additional components include, but are not limited to, detergency enhancers (surfactants), stabilizers (acid acceptors, antioxidants) and the like.
  • detergency enhancers include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbit fatty acid esters such as polyoxyethylene sorbit tetraoleate; Polyethylene glycol fatty acid esters such as laurate; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxy acids such as polyoxyethylene oleic acid amide
  • Nonionic surfactants such as ethylene alkyl amine fatty acid amides, are mentioned. These detergency enhancers may be used alone or in combination of two or more.
  • cationic surfactants and anionic surfactants are added to the azeotropic (like) composition of the present invention for the purpose of synergistically improving the detergency and the surface action. It is also good.
  • the stabilizer is not particularly limited, but it is more desirable to carry out co-distillation by distillation operation or to form an azeotrope-like mixture.
  • Specific examples of such stabilizers include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like.
  • nitro compound known compounds may be used, and aliphatic and / or aromatic derivatives and the like can be mentioned.
  • aliphatic nitro compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like.
  • aromatic nitro compound for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o And m- or p-nitroanisole and the like.
  • Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Monoepoxy compounds such as 2-ethylhexyl glycidyl ether, diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, polyepoxy such as trimethylolpropane tolglycidyl ether Compounds etc. may be mentioned.
  • the phenols also include phenols containing various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group and a halogen in addition to a hydroxyl group.
  • Monohydric phenols such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or t-butylcatechol, bivalents such as 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone Phenol and the like.
  • imidazoles 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1 having 1 to 18 carbon atoms and having an alkyl group, cycloalkyl group or aryl group as a substituent at the N-position -Benzylimidazole, 1- ( ⁇ -oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole, 1 2,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2-methylimidazole and the like. These compounds may be used alone, or two or more compounds may be used in combination.
  • amines pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, ⁇ -methyl Benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, dibutylamine, tributylamine, dibenzylamine, triphenthylamine, 2-ethylhexylamine, aniline N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetra Renpentamin, benzylamine, dibenzyl
  • hydrocarbons examples include ⁇ -methylstyrene, p-isopropenyltoluene, isoprenes, propadienes and terpenes. These may be used alone or two or more compounds may be used in combination.
  • the azeotropic (like) composition of the present invention may contain, as additional components, lubricants, flame retardants, metal passivators, corrosion inhibitors and the like.
  • the addition amount of the additional component in the azeotropic (like) composition of the present invention may vary depending on the component, but may be an extent that does not affect the azeotropic (like) properties of the azeotropic (like) composition. For example, it is 30% by mass or less, preferably 10% by mass or less, particularly preferably 5% by mass or less, and more preferably 3% by mass or less, based on the azeotropic (like) composition. Further, it may be 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more with respect to the azeotropic (like) composition.
  • the additional components may be added in the following amounts based on the azeotropic (like) composition: 0.001 to 30% by mass; 0.001 to 10% by mass; 0.001 to 5% by mass 0.001 to 3% by mass; 0.001 to 1% by mass; 0.001 to 0.01% by mass; 0.001 to 0.1% by mass; 0.01 to 30% by mass; 0.01 to 10 0.01% to 5% by mass; 0.01 to 3% by mass; 0.01 to 1% by mass; 0.01 to 0.1% by mass; 0.1 to 30% by mass; 0.1 to 10% 0.1% to 5% by mass; 0.1 to 3% by mass; 0.1 to 1% by mass; 1 to 30% by mass; 1 to 10% by mass; 1 to 5% by mass; 1 to 3% by mass 3 to 30% by mass; 3 to 10% by mass; 3 to 5% by mass; 5 to 30% by mass; 5 to 10% by mass; 10 to 30% by mass.
  • the azeotropic (like) composition of the present invention may be mixed with a propellant gas to form an aerosol composition.
  • liquefied gas or compressed gas can be used as the injection gas.
  • the above gases such as LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide gas, fluorocarbon gas, nitrogen gas, compressed air and the like, mixtures of LPG and DME, mixtures of LPG and carbon dioxide, etc.
  • LPG liquefied petroleum gas
  • DME dimethyl ether
  • carbon dioxide gas fluorocarbon gas
  • nitrogen gas compressed air and the like
  • mixtures of LPG and DME mixtures of LPG and carbon dioxide, etc.
  • species or combinations it is not limited to this.
  • the aerosol composition of the present invention can be produced by mixing the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) and the above-mentioned propellant gas, Moreover, it can be filled and provided in a pressure-resistant can.
  • the azeotropic (like) composition (or liquid composition containing the azeotropic (like) composition) of the present invention is a precision machine part, an electronic material (printed substrate, liquid crystal display, magnetic recording part, semiconductor material, etc.) ), Resin-processed parts, optical lenses, clothing articles, etc. are suitable for removing foreign substances, fats and oils, greases, waxes, fluxes, inks and the like. Since the azeotropic (like) composition of the present invention has appropriate fluidity and solubility, foreign substances (such as particles) can be washed away or dissolved and removed.
  • the azeotropic (like) composition (or liquid composition containing the azeotropic (like) composition) of the present invention has a suitable boiling point and can wet and wash away dirt. It is suitable for such cleaning.
  • the cleaning method is not particularly limited, but the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is dipped in the article to be cleaned to wash away dirt, with a waste Methods such as wiping off and spray washing may be mentioned, and these may be used in combination.
  • azeotropic (like) composition Placing the azeotropic (like) composition in an ultrasonic cleaner, immersing the article to be cleaned in the liquid and subjecting it to ultrasonic cleaning is one of the particularly preferred embodiments.
  • spray cleaning for example, the azeotropic (like) composition of the present invention (or a liquid composition containing the azeotropic (like) composition) is mixed with a propellant gas and aerosolized to produce various articles to be cleaned
  • the method of spraying on is also one of the preferred embodiments.
  • the azeotropic (like) composition of the present invention exerts a stable detergency even if the composition is not frequently controlled, because the composition hardly changes even when used in an open system. . This is a great merit in practice.
  • a general distillation regenerator for detergents is a simple distillation system, and in the case of an azeotropic (like) composition comprising a first component 1223xd (Z) and a second component specific compound, it is commercially available. Can be regenerated substantially without composition change.
  • use of a high-stage distillation column is preferable because there is no change in the composition.
  • the two liquid components of 1223xd (Z) and the specific compound maintain their properties as an azeotropic (like) composition, and the recovered liquid then undergoes extensive compositional adjustment Without, it can be used again as a washing solvent.
  • the "additional component” may be removed by distillation when the said "additional component” is used, it is desirable to supplement separately in that case.
  • the azeotropic (like) composition of the present invention is also suitable as a drainage agent, a foaming agent, a heat transfer medium, and a lubricant solvent.
  • Example 1-1 In a 50 mL three-necked flask equipped with a septum, a stirrer, and a Dimroth capable of flowing a ⁇ 10 ° C. refrigerant, Z-1, 2-Dichloro-3,3,3-trifluoropropene was brought to the molar concentration shown in Table 1. It was charged 25mL combined (1223xd (Z)) and dichloromethane (CH 2 Cl 2). A synthetic zeolite tube was attached to the upper part of Jimroth. The flask was immersed in an oil bath and heated to reflux with stirring.
  • the gas phase part was sampled from the septum with a gas tight syringe and analyzed by gas chromatography.
  • the liquid phase was similarly sampled with about 1 mL using a polypropylene syringe equipped with an injection needle, transferred to a 2 mL vial previously cooled with ice water, and then subjected to gas chromatography analysis.
  • Table 1 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the vapor phase composition of 1223 ⁇ d (Z)
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 1 to 40 mol% of the first component 1223 ⁇ d (Z) and 99 to 60 mol% of the second component dichloromethane. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Embodiment 1-2 The same operation as in Example 1-1 was performed except that methanol (MeOH) was used instead of dichloromethane.
  • Table 2 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z), and the ordinate represents the vapor phase composition of 1223 ⁇ d (Z), and the results of Table 2 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 67 to 77 mol% of the first component 1223 ⁇ d (Z) and 33 to 23 mol% of the second component methanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Embodiment 1-3 The same operation as in Example 1-1 was performed except that ethanol (EtOH) was used instead of dichloromethane.
  • EtOH ethanol
  • Table 3 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the vapor phase composition of 1223 ⁇ d (Z)
  • the results of Table 3 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 80 to 99 mol% of the first component 1223 ⁇ d (Z) and 20 to 1 mol% of the second component ethanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Embodiment 1-4 The same operation as in Example 1-1 was performed except that n-propanol (n-PrOH) was used instead of dichloromethane.
  • Table 4 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z), and the ordinate represents the gas phase composition of 1223 ⁇ d (Z), and the results of Table 4 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 90 to 99 mol% of the first component 1223 ⁇ d (Z) and 10 to 1 mol% of the second component n-propanol. It became clear that it was an azeotropic composition or an azeotrope-like composition which does not change as it is.
  • Example 1-5 The same operation as in Example 1-1 was performed except that isopropanol (IPA) was used instead of dichloromethane.
  • Table 5 the calibration curve prepared in advance was used to indicate mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the gas phase composition of 1223 ⁇ d (Z)
  • the results of Table 5 were plotted.
  • the composition of the gas phase portion and the liquid phase portion is substantially in the range of 85 to 99 mol% of the first component 1223 ⁇ d (Z) and 15 to 1 mol% of the second component isopropanol. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Example 1-6 The same operation as in Example 1-1 was performed except that n-hexane was used instead of dichloromethane.
  • Table 6 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the gas phase composition of 1223 ⁇ d (Z)
  • the results of Table 6 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 75 to 99 mol% of the first component 1223 ⁇ d (Z) and 25 to 1 mol% of the second component n-hexane. It became clear that it was an azeotropic composition or an azeotrope-like composition which does not change as it is.
  • Example 1-7 The same operation as in Example 1-1 was performed except that cyclohexane was used instead of dichloromethane.
  • Table 7 the calibration curve prepared in advance was used to indicate mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the vapor phase composition of 1223 ⁇ d (Z)
  • the results of Table 7 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 85 to 99 mol% of the first component 1223 ⁇ d (Z) and 15 to 1 mol% of the second component cyclohexane. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Example 1-8 The same operation as in Example 1-1 was performed except that acetone was used instead of dichloromethane.
  • Table 8 the calibration curve prepared in advance was used to indicate mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z)
  • the ordinate represents the gas phase composition of 1223 ⁇ d (Z)
  • the results in Table 8 were plotted.
  • the composition of the gas phase portion and the liquid phase portion is substantially in the range of 1 to 99 mol% of the first component 1223 ⁇ d (Z) and 99 to 1 mol% of the second component acetone. It turned out to be an unchanged azeotropic or azeotrope-like composition.
  • Example 1-9 The same operation as in Example 1-1 was performed except that cyclopentane was used instead of dichloromethane.
  • Table 9 using the calibration curve prepared in advance, it is indicated by mol%.
  • the abscissa represents the liquid phase composition of 1223 ⁇ d (Z), and the ordinate represents the vapor phase composition of 1223 ⁇ d (Z), and the results of Table 9 were plotted.
  • the composition of the gas phase part and the liquid phase part is substantially in the range of 1 to 60 mol% of the first component 1223 ⁇ d (Z) and 99 to 40 mol% of the second component cyclopentane. It turned out that it is an azeotropic composition or an azeotrope-like composition which does not change.
  • Example 2-1 The flash point of the mixed liquid of 1223xd (Z) and dichloromethane (CH 2 Cl 2 ) was measured in accordance with Japanese Industrial Standard JIS K 2265-1 "How to determine the flash point-Part 1: Tag sealing method". .
  • JIS K 2265-1 Japanese Industrial Standard JIS K 2265-1 "How to determine the flash point-Part 1: Tag sealing method".
  • an automatic flash point measuring device atg-8l (Tanaka Scientific Instruments Co., Ltd.) was used. As a result, it was observed that there was no flash point under atmospheric pressure conditions in the range of the azeotropic or azeotrope-like composition of 1223 ⁇ d (Z) and dichloromethane described in Example 1-1.
  • Example 2-2 to [Example 2-7]
  • the same operation as in Example 2-1 was carried out except using methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), isopropanol (IPA), n-hexane or cyclohexane instead of dichloromethane.
  • MeOH methanol
  • EtOH ethanol
  • n-propanol n-PrOH
  • IPA isopropanol
  • n-hexane or cyclohexane instead of dichloromethane.
  • each composition was observed to have no flash point under atmospheric pressure conditions in the range of the azeotropic or azeotrope-like composition described in Examples 1-2 to 1-7.
  • Example 2-8 The same operation as in Example 2-1 was performed except that acetone was used instead of dichloromethane. The measurement results for each composition are shown in Table 10.
  • Example 3-1 A commercially available 25 mL graduated cylinder was cut at an 11 mL scale. Diameter: about 7.2 mm ⁇ length: After measuring the weight of a clean glass rod of about 40 mm, it was immersed in the oil described in Table 11 for 2 minutes, and it was allowed to stand for 10 minutes to drain (remove excess oil) Then, after measuring the mass (glass rod + initial adhesion oil), it was put into the above-mentioned measuring cylinder. A mixture of 1223 x d (Z) and dichloromethane (CH 2 Cl 2 ) (pre-test composition shown in Table 11) was charged to 10 mL and filled with water at 20 ° C.
  • 1223 x d (Z) and dichloromethane (CH 2 Cl 2 ) pre-test composition shown in Table 11
  • the glass rod is dried and the mass (total mass of the glass rod and the remaining oil) is measured to determine the oil removal rate (the mass of the remaining oil / the mass of the initial adhering oil ⁇ 100 [%]),
  • the surface of the glass was visually observed with a magnifying glass.
  • the oil removal rate was 100% in all the examples, and in the observation result of the magnifying glass, it was judged to be good since no oil component remained.
  • Table 11 The results of each example are shown in Table 11 below.
  • Example 3-2 to [Example 3-9] Instead of using dichloromethane (methanol), ethanol (EtOH), n-propanol (nPrOH), isopropanol (IPA), n-hexane (nHex), cyclohexane (cHex), acetone or cyclopentane (cPen) instead of dichloromethane
  • EtOH ethanol
  • nPrOH n-propanol
  • IPA isopropanol
  • nHex n-hexane
  • cHex cyclohexane
  • acetone or cyclopentane (cPen) instead of dichloromethane
  • the liquid composition before and after the washing was substantially the same despite the volatilization of 2 mL.
  • each mixed liquid was an azeotropic (like) composition which does not substantially change the composition of the residual liquid even if it partially evaporates.
  • results of the respective examples are shown in the following Tables 12 to 19 with respect to the oil removal rate and the observation result of the magnifying glass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une nouvelle composition azéotropique (de type azéotrope) respectueuse de l'environnement. Cette composition contient du Z-1,2-dichloro-3,3,3-trifluoropropène (1223xd(Z)) en tant que premier constituant, et du dichlorométhane, du méthanol, de l'éthanol, du n-propanol, de l'isopropanol, du n-hexane, du cyclohexane, de l'acétone ou du cyclopentane en tant que second constituant. Cette composition a un faible impact sur l'environnement global et présente des propriétés azéotropiques ou de type azéotrope.
PCT/JP2018/045364 2017-12-15 2018-12-10 Composition de type azéotrope contenant du z-1,2-dichloro-3,3,3-trifluoropropène Ceased WO2019117100A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019559634A JP7189448B2 (ja) 2017-12-15 2018-12-10 Ｚ－１，２－ジクロロ－３，３，３－トリフルオロプロペンを構成成分とする共沸様組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017240099 2017-12-15
JP2017-240099 2017-12-15

Publications (1)

Publication Number Publication Date
WO2019117100A1 true WO2019117100A1 (fr) 2019-06-20

Family

ID=66820383

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/045364 Ceased WO2019117100A1 (fr) 2017-12-15 2018-12-10 Composition de type azéotrope contenant du z-1,2-dichloro-3,3,3-trifluoropropène

Country Status (2)

Country Link
JP (1) JP7189448B2 (fr)
WO (1) WO2019117100A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020031962A1 (fr) * 2018-08-10 2020-02-13 ダイキン工業株式会社 Composition contenant du 1,2-dichloro-3,3,3-trifluoropropène
JP2021116323A (ja) * 2020-01-23 2021-08-10 セントラル硝子株式会社 共沸様組成物及び液体組成物

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02221388A (ja) * 1989-02-23 1990-09-04 Asahi Glass Co Ltd 脱脂洗浄剤
JPH02222702A (ja) * 1989-02-23 1990-09-05 Asahi Glass Co Ltd 付着水除去用溶剤
US20050096246A1 (en) * 2003-11-04 2005-05-05 Johnson Robert C. Solvent compositions containing chlorofluoroolefins
JP2013504655A (ja) * 2009-09-11 2013-02-07 スリーエム イノベイティブ プロパティズ カンパニー １，１，１，２，２，３，４，５，５，５−デカフルオロ−３−メトキシ−４−（トリフルオロメチル）−ペンタンを含有する三元共沸混合物及びそれから作製される組成物
JP2016194377A (ja) * 2015-03-31 2016-11-17 三菱重工業株式会社 冷媒循環装置、冷媒循環方法、冷媒充填方法および冷媒循環装置の運転方法
JP2017075313A (ja) * 2015-10-13 2017-04-20 積水化学工業株式会社 フェノール樹脂発泡板
WO2017104738A1 (fr) * 2015-12-18 2017-06-22 株式会社トクヤマＭｅｔｅｌ Composition d'agent de nettoyage, composition d'agent de rinçage et procédé de nettoyage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6575526B2 (ja) 2014-10-02 2019-09-18 セントラル硝子株式会社 ２−クロロ−１，３，３，３−テトラフルオロプロペン及び１−クロロ−３，３，３−トリフルオロプロペンを含有する共沸様組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02221388A (ja) * 1989-02-23 1990-09-04 Asahi Glass Co Ltd 脱脂洗浄剤
JPH02222702A (ja) * 1989-02-23 1990-09-05 Asahi Glass Co Ltd 付着水除去用溶剤
US20050096246A1 (en) * 2003-11-04 2005-05-05 Johnson Robert C. Solvent compositions containing chlorofluoroolefins
JP2013504655A (ja) * 2009-09-11 2013-02-07 スリーエム イノベイティブ プロパティズ カンパニー １，１，１，２，２，３，４，５，５，５−デカフルオロ−３−メトキシ−４−（トリフルオロメチル）−ペンタンを含有する三元共沸混合物及びそれから作製される組成物
JP2016194377A (ja) * 2015-03-31 2016-11-17 三菱重工業株式会社 冷媒循環装置、冷媒循環方法、冷媒充填方法および冷媒循環装置の運転方法
JP2017075313A (ja) * 2015-10-13 2017-04-20 積水化学工業株式会社 フェノール樹脂発泡板
WO2017104738A1 (fr) * 2015-12-18 2017-06-22 株式会社トクヤマＭｅｔｅｌ Composition d'agent de nettoyage, composition d'agent de rinçage et procédé de nettoyage

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020031962A1 (fr) * 2018-08-10 2020-02-13 ダイキン工業株式会社 Composition contenant du 1,2-dichloro-3,3,3-trifluoropropène
JP2020026481A (ja) * 2018-08-10 2020-02-20 ダイキン工業株式会社 １，２−ジクロロ−３，３，３−トリフルオロプロペンを含む組成物
US11981883B2 (en) 2018-08-10 2024-05-14 Daikin Industries, Ltd. Composition containing 1,2-dichloro-3,3,3-trifluoropropene
JP2021116323A (ja) * 2020-01-23 2021-08-10 セントラル硝子株式会社 共沸様組成物及び液体組成物
JP7417066B2 (ja) 2020-01-23 2024-01-18 セントラル硝子株式会社 共沸様組成物及び液体組成物

Also Published As

Publication number Publication date
JP7189448B2 (ja) 2022-12-14
JPWO2019117100A1 (ja) 2020-12-24

Similar Documents

Publication Publication Date Title
JPWO2020022474A1 (ja) 共沸（様）組成物
CN107001997B (zh) 以含氟烯烃为构成成分的类共沸组合物
JP7656166B2 (ja) 溶剤組成物、エアゾール組成物、洗浄剤、物品の洗浄方法、塗膜形成用組成物、塗膜付き物品の製造方法、水切り剤、リンス剤及び潤滑剤溶液
JP6503765B2 (ja) 含フッ素オレフィンを構成成分とする共沸様組成物
EP2935555A1 (fr) Compositions ternaires ininflammables et utilisation de ces compositions
JPWO2004005445A1 (ja) 溶剤組成物
KR20160145620A (ko) 용매 증기상 디그리싱 및 디플럭싱 조성물, 방법, 장치 및 시스템
JP7189448B2 (ja) Ｚ－１，２－ジクロロ－３，３，３－トリフルオロプロペンを構成成分とする共沸様組成物
EP2970835A1 (fr) Compositions ininflammables et utilisation de ces compositions
JP6520178B2 (ja) 含フッ素オレフィンを構成成分とする共沸様組成物
KR100346677B1 (ko) 혼합용매조성물
EP2876153A1 (fr) Compositions ininflammables et utilisation de ces compositions
JP6896991B2 (ja) 組成物、液体組成物、洗浄用溶剤、およびこれらの製造方法と回収方法、ならびに洗浄用溶剤を用いる洗浄方法
JP2001509533A (ja) １−ブロモプロパンと高度フッ素化炭化水素の共沸混合物および共沸混合物様組成物
JP2004075910A (ja) 共沸溶剤組成物および溶剤組成物
JPH06220497A (ja) フッ素化エーテルを含む組成物およびそれらの組成物の使用
US20230399591A1 (en) Cleaning solvent blends of low global warming potential exhibiting azeotrope-like behavior and their use
JP7417066B2 (ja) 共沸様組成物及び液体組成物
EP4200389B1 (fr) Compositions de solvant de nettoyage faisant preuve d'un comportement de type azéotrope et leur utilisation
EP2746380A1 (fr) Compositions ternaires ininflammables et utilisation de ces compositions
JP2010001319A (ja) 共沸溶剤組成物、擬共沸溶剤組成物および混合溶剤組成物
WO2024182748A1 (fr) Mélanges de solvants de type azéotrope présentant un faible potentiel de réchauffement planétaire et procédés d'utilisation
JP2023158659A (ja) 溶液の調製方法、物品の洗浄方法、溶剤組成物、及びその用途
WO1993016215A2 (fr) Compositions analogues a des azeotropes contenant du 1,1-dichloro-1-fluoroethane, du dichloroethylene, de l'alcane possedant 6 atomes de carbone ou du cyclopenthane, de l'alcanol, et eventuellement du nitromethane
HK1139431A (en) Nonflammable compositions comprising fluorinated compounds and use of these compositions

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18887612

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019559634

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18887612

Country of ref document: EP

Kind code of ref document: A1