JPH1180791A - Azeotropy and azeotropic mixture consisting of fluorine-containing ketone and organic solvent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new composition needing no worry about the depletion of ozone layer, having little greenhouse effect and keeping excellent properties such as cleaning activity and low toxicity which are characteristic to a chlorine- containing HCFC-based hydrocarbon or a chlorine-containing hydrocarbon. SOLUTION: This composition is composed of 3,3,4,4,5,5,6,6,6- nonafluorohexan-2-one expressed by the formula CF3 CF2 CF2 CF2 COCH3 and at least one kind of organic solvent selected from methanol, ethanol, 2-propanol, methylene chloride and trans-1,2-dichloroethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azeotropic composition and an azeotropic composition, and more particularly to an azeotropic composition and an azeotropic composition used as flux cleaning, degreasing cleaning, draining and drying, and a solvent. -Like compositions.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons are best known as solvents for cleaning electronic parts, precision machine parts, resin processed parts, etc., and chlorine atoms or carbon atoms obtained by substituting chlorine atoms for fluorine atoms. It has characteristics as a hydrogen group. These halogenated hydrocarbons are less toxic, show non-flammability when the number of substituted halogens is large, are chemically and thermally stable, and do not erode the surface of plastics or rubbers. Since it has an appropriate solubility for dissolving fats and oils, it is widely used in various industrial fields. For example, these halogenated hydrocarbons include chlorinated hydrocarbons such as trichloroethylene, tetrachloroethylene and 1,1,1-trichloroethane, and 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113). Such fluorocarbons are known, and in particular, the latter fluorocarbons have been used in a wide range of fields because of their low toxicity, nonflammability, and chemical and thermal stability. However, the serious disadvantage of destruction of the stratospheric ozone layer has been pointed out because such chlorofluorocarbon-based hydrocarbons and 1,1,1-trichloroethane have chlorine atoms. Is decided. In addition, trichlorethylene and tetrachlorethylene have been designated as Class 2 Specified Chemical Substances since 1989 based on the results of surveys on the status of environmental pollution and the findings of harmful effects of chronic toxicity, etc. Designated. Under such circumstances, the development of such chlorofluorocarbon-based hydrocarbons and substances that substitute for chlorinated hydrocarbons has been actively conducted.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides excellent properties such as chlorofluorocarbon-based hydrocarbons and chlorine-based hydrocarbons having excellent detergency and low toxicity. Without damaging, there is no worry of ozone layer destruction,
Another object of the present invention is to provide a novel composition having a small greenhouse effect.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, 3,3,4,4,5,5,6,6,6-nonafluoro represented by the following formula (1) CF ₃ CF ₂ CF ₂ CF ₂ COCH ₃ (1) Hexane-2-one, methanol, ethanol, 2-propanol, methylene chloride and trans-
An azeotropic and azeotropic composition comprising at least one organic solvent selected from 1,2-dichloroethylene is provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The composition of the present invention is specifically the following composition. The azeotropic composition means a composition having the same vapor composition and liquid composition and no change in the composition of the composition after repeated evaporation and condensation. Further, the azeotropic-like composition means a composition whose vapor composition and liquid composition are substantially the same and whose composition change after repeating evaporation and condensation changes to a negligible extent. (1) An azeotropic composition comprising 75 to 85% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexane-2-one and 15 to 25% by weight of ethanol, preferably 80.60% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and ethanol 1
An azeotropic composition consisting of 9.40% by weight. The boiling point of this azeotropic composition is 70.08 at atmospheric pressure (760 mmHg).
° C. (2) 3,3-, 4,4,5,5,6,6-6-nonafluorohexan-2-one An azeotropic composition comprising 75 to 85% by weight of ethanol and 20 to 30% by weight of ethanol, preferably 73.06% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and methanol 2
It is an azeotropic composition consisting of 6.94% by weight. The boiling point of this azeotropic composition is 62.10 at atmospheric pressure (760 mmHg).
° C. (3) an azeotropic composition comprising 75 to 85% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and 15 to 25% by weight of 2-propanol; Preferably, it is an azeotropic composition comprising 78.87% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and 21.13% by weight of 2-propanol.
The boiling point of this azeotropic composition is 72.37 ° C. at atmospheric pressure (760 mmHg). (4) An azeotropic composition comprising 1 to 10% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and 90 to 99% by weight of methylene chloride, preferably Is 4.53% by weight of 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one and methylene chloride 9
An azeotropic composition consisting of 5.46% by weight. The boiling point of this azeotropic composition is 39.70 at atmospheric pressure (760 mmHg).
° C. (5) 3,3,4,4,5,5,6,6,6-nonafluorohexan-2-one 5 to 15% by weight and trans
An azeotropic composition comprising 85-95% by weight of -1,2-dichloroethylene, preferably 3,3,4,4,5,5
6,6,6-Nonafluorohexane-2-one 12.6
2% by weight and trans-1,2-dichloroethylene 8
An azeotropic composition comprising 7.38% by weight. The boiling point of this azeotropic composition is 47.33 at atmospheric pressure (760 mmHg).
° C.

[0006] 3,3,4,4,5 used in the present invention
5,6,6,6-Nonafluorohexane-2-one is a known substance, for example, commercially available 2,2,3,3,4,4
It is easily obtained by reacting 5,5,5-nonafluorovaleric acid with methylmagnesium bromide.

The composition according to the present invention may further contain various stabilizers when used under severe conditions. As the stabilizer, those which are entrained by distillation or those which form an azeotropic mixture are desirable. Specific examples of such a stabilizer include aliphatic nitro compounds such as nitromethane and nitroethane; aromatic nitro compounds such as nitrobenzene and nitrostyrene; dimethoxymethane;
-Dimethoxyethane, 1,4-dioxane, 1,3,5
Ethers such as trioxane, glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 1,2-butylene oxide,
Epoxys such as cyclohexene oxide and epichlorohydrin; unsaturated hydrocarbons such as hexene, heptene, pentadiene, cyclopentene and cyclohexene; olefinic alcohols such as allyl alcohol and 1-buten-3-ol; 3-methyl-1-butyne -3-ol,
Acetylene alcohols such as 3-methyl-1-pentyn-3-ol and the like, and acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate are exemplified. In order to further obtain a synergistic stabilizing effect, phenols, amines and benzotriazoles may be used in combination. These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer used depends on the kind of the stabilizer and the like, but is set to such an extent that the azeotropic property of the composition of the present invention is not hindered. The amount used is usually from 0.01 to 1 of the composition of the present invention.
It is about 0% by weight, and more preferably about 0.1 to 5% by weight.

[0008] Various surfactants can be added to the composition of the present invention, if necessary, in order to further improve detergency, interfacial action and the like. Surfactants include sorbitan monooleate, sorbitan fatty acid esters such as sorbitan trioleate, polyoxyethylene sorbite fatty acid esters such as polyoxyethylene sorbit tetraoleate, and polyethylene glycol fatty acids such as polyoxyethylene monolaurate. Nonionic surfactants such as esters, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether, and polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide. Or a combination of two or more. For the purpose of synergistically improving the detergency and the interfacial action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. The amount of the surfactant used varies depending on the type and the like, but is set to such an extent that the azeotropic property of the composition of the present invention is not hindered. Usually, it is about 0.1 to 20% by weight of the composition of the present invention, more preferably about 0.3 to 5% by weight.

The composition of the present invention can be widely used for known washing and drying applications. In particular, it can be used as a flux detergent, a washing solvent, a degreasing detergent and a draining desiccant. It is extremely useful as a substitute for 1-trichloroethane. Specific applications include flux, grease, oil, wax, and ink removers, electronic components (printed boards, liquid crystal displays, magnetic recording components, semiconductor materials, etc.), electrical components, precision machinery components,
Examples include detergents and drainers for resin-processed parts, optical lenses, and clothing. As the cleaning method,
Conventional methods such as immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning and the like, or a combination thereof can be employed. Further, the composition of the present invention can be used for various uses such as a solvent for a paint, an extractant, a heating medium, and a foaming agent, similarly to the conventional fluorocarbons.

[0010]

The following examples are provided to further clarify the features of the present invention. Of course, the present invention is not limited by these examples.

Example 1 Using a vapor-liquid equilibrium measuring apparatus, 3,3,4,4,5,5,5
The vapor-liquid equilibrium and azeotropic point of 6,6,6-nonafluorohexan-2-one were measured. 3,3,4,4,5,5
A mixed sample having a constant composition of 6,6,6-nonafluorohexane-3-one and ethanol was placed in a sample container and heated. The heating was adjusted so that the dropping rate of the vapor-phase condensate became appropriate, and stable boiling was maintained for 40 minutes or more.
After ensuring that the pressure and boiling point were stable, they were measured. The liquid phase and the gas phase condensate were sampled, and the composition of the sampled solution was analyzed by gas chromatography. The measurement results are shown in Table 1, FIG. 1 and FIG. From these results, 3,3,4,4,5,5,6,
Compositions of the invention ranging from 75-85% by weight of 6,6-nonafluorohexan-2-one and 15-25% by weight of ethanol are azeotrope-like compositions. Where 3,3
4,4,5,5,6,6,6-nonafluorohexane-
The composition consisting of 80.60% by weight of 2-one and 19.40% by weight of ethanol is an azeotropic composition and has a boiling point of 70.08 ° C. at atmospheric pressure (760 mmHg).

[0012]

[Table 1]

Example 2 Instead of the composition of Example 1, 3,3,4,4,5,5
The measurement was carried out using the same apparatus and procedure as in Example 1, except that 6,6,6-nonafluorohexane-2-one and methanol were used. The measurement results are shown in Table 2, FIG. 3 and FIG. From this result, 3,3,4,4,5,5,6,6,6
6-nonafluorohexan-2-one 70-80% by weight
And the composition of the present invention in the range of 20 to 30% by weight of methanol is an azeotropic composition. Where 3,3,4
4,5,5,6,6,6-nonafluorohexane-2-
73.06% by weight and 26.94% by weight of methanol
Is an azeotropic composition having a boiling point of 62.10 ° C. at atmospheric pressure (760 mmHg).

[0014]

[Table 2]

Example 3 Instead of the composition of Example 1, 3,3,4,4,5,5
The measurement was carried out using the same apparatus and procedure as in Example 1, except that 6,6,6-nonafluorohexane-2-one and 2-propanol were used. Table 3, FIG. 5 and FIG.
Shown in From these results, 3,3,4,4,5,5,6,
Compositions of the invention in the range of 75-85% by weight of 6,6-nonafluorohexan-2-one and 15-25% by weight of 2-propanol are azeotrope-like compositions. Where 3,
78.87% by weight of 3,4,4,5,5,6,6,6-nonafluorohexan-2-one and 2-propanol 2
The composition consisting of 1.13% by weight is an azeotropic composition and its boiling point is 72.37 ° C. at atmospheric pressure (760 mmHg).

[0016]

[Table 3]

Example 4 In place of the composition of Example 1, 3,3,4,4,5,5
The measurement was performed using the same apparatus and procedure as in Example 1 except that 6,6,6-nonafluorohexane-2-one and methylene chloride were used. The measurement results are shown in Table 4, FIG. 7 and FIG. From this result, 3,3,4,4,5,5,6,6,6
Compositions of the present invention in the range of 1-10% by weight of 6-nonafluorohexan-2-one and 90-99% by weight of methylene chloride are azeotropic compositions. Where 3,3,4
4,5,5,6,6,6-nonafluorohexane-2-
4.54% by weight and 95.46% by weight of methylene chloride
Is an azeotropic composition having a boiling point of 39.70 ° C. at atmospheric pressure (760 mmHg).

[0018]

[Table 4]

Example 5 Instead of the composition of Example 1, 3,3,4,4,5,5
6,6,6-Nonafluorohexane-2-one and tra
The measurement was performed using the same device and procedure as in Example 1 except that ns-1,2-dichloroethylene was used. The measurement results are shown in Table 5, FIG. 9 and FIG. From these results,
3,4,4,5,5,6,6,6-nonafluorohexan-2-one 5 to 15% by weight and trans-1,2-
Compositions of the invention in the range of 85 to 95% by weight of dichloroethylene are azeotropic compositions. Where 3,3,4
4,5,5,6,6,6-nonafluorohexane-2-
A composition consisting of 12.62% by weight of ON and 87.38% by weight of trans-1,2-dichloroethylene is an azeotropic composition having a boiling point of 4 at atmospheric pressure (760 mmHg).
7.33 ° C.

[0020]

[Table 5]

[0021]

Since the composition of the present invention does not contain chlorine atoms, there is no fear of destruction of the ozone layer. Further, the composition of the present invention has an advantage that it has a small greenhouse effect because it contains a hydrogen atom and has high reactivity with hydroxyl radicals in the atmosphere and is easily decomposed in the troposphere.

[Brief description of the drawings]

FIG. 1: C ₄ F ₉ COCH ₃ -ethanol system (760 mm
Hg) shows a gas-liquid average curve (liquid-gas phase).

FIG. 2 C ₄ F ₉ COCH ₃ -ethanol system (760 mm
2 shows a gas-liquid average curve (liquid phase-boiling point) of Hg).

FIG. 3 shows a C ₄ F ₉ COCH ₃ -methanol system (760 mm
Hg) shows a gas-liquid average curve (liquid-gas phase).

FIG. 4 shows a C ₄ F ₉ COCH ₃ -methanol system (760 mm
2 shows a gas-liquid average curve (liquid phase-boiling point) of Hg).

[5] C ₄ F ₉ COCH ₃ -2- propanol system (76
1 shows a gas-liquid average curve (liquid phase-gas phase) of 0 mmHg).

6 C ₄ F ₉ COCH ₃ -2- propanol system (76
1 shows a gas-liquid average curve (liquid phase-boiling point) of 0 mmHg).

FIG. 7: C ₄ F ₉ COCH ₃ -methylene chloride system (760 m
2 shows a gas-liquid average curve (liquid phase-gas phase) of mHg).

FIG. 8: C ₄ F ₉ COCH ₃ -methylene chloride system (760 m
2 shows a gas-liquid average curve (liquid phase-boiling point) of mHg).

FIG. 9 shows a gas-liquid average curve (liquid-gas phase) of C ₄ F ₉ COCH ₃ -trans-1,2-dichloroethylene (760 mmHg).

FIG. 10 shows a gas-liquid average curve (liquid phase-boiling point) of a C ₄ F ₉ COCH ₃ -trans-1,2-dichloroethylene system (760 mmHg).

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[Procedure amendment]

[Submission date] October 9, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

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[0012]

[Table 1]

[Procedure amendment 2]

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[0014]

[Table 2]

[Procedure amendment 3]

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[0016]

[Table 3]

[Procedure amendment 4]

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[0018]

[Table 4]

[Procedure amendment 5]

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[0020]

[Table 5]

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

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[0021]

Since the composition of the present invention does not contain chlorine atoms, there is no fear of destruction of the ozone layer. Further, since the composition of the present invention contains a hydrogen atom, it has high reactivity with hydroxyl radicals in the atmosphere.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1: C ₄ F ₉ COCH ₃ -ethanol system (760 m
the vapor-liquid equilibrium curve (liquid phase of mHg) - shows the gas phase).

FIG. 2: C ₄ F ₉ COCH ₃ -ethanol system (760 m
the vapor-liquid equilibrium curve (liquid phase of mHg) - boiling point) is shown a.

FIG. 3 shows a C ₄ F ₉ COCH ₃ -methanol system (760 m
the vapor-liquid equilibrium curve (liquid phase of mHg) - shows the gas phase).

FIG. 4 shows a C ₄ F ₉ COCH ₃ -methanol system (760 m
the vapor-liquid equilibrium curve (liquid phase of mHg) - boiling point) is shown a.

[5] _C 4 _F 9 COCH ₃ -2- propanol system (7
The vapor-liquid equilibrium curve (liquid phase of 60mmHg) - shows the gas phase).

6 _C 4 _F 9 COCH ₃ -2- propanol system (7
The vapor-liquid equilibrium curve (liquid phase of 60mmHg) - boiling point) is shown a.

FIG. 7: C ₄ F ₉ COCH ₃ -methylene chloride system (760
the vapor-liquid equilibrium curve (liquid phase of mmHg) - shows the gas phase).

FIG. 8: C ₄ F ₉ COCH ₃ -methylene chloride system (760
the vapor-liquid equilibrium curve (liquid phase of mmHg) - boiling point) is shown a.

Gas-liquid equilibrium curve in FIG. 9 _{C 4 F 9 COCH 3 -trans-} 1,2 -dichloroethylene system (760 mmHg) - shows the (liquid vapor).

[10] _{C 4 F 9 COCH 3 -trans-} 1,2 -dichloroethylene vapor-liquid equilibrium curve of (760 mmHg) (liquid - boiling point) shows a.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C11D 7:20 7:30) (72) Inventor Seiji Takubo 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building 6th floor Foundation Research Institute of Innovative Technology for the Environment, New Refrigerant Project Room (72) Inventor Minoru Akiyama 6F, Hongo Wakai Building, Hongo 2-40-17, Bunkyo-ku, Tokyo New Project Room for Refrigerant, etc. (72) Invention Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref.

Claims (1)

[Claims] 1, 3, 4, 4, 5, 5, 6, 6, 6
Nonafluorohexan-2-one, methanol, ethanol, 2-propanol, methylene chloride and tran
An azeotropic and azeotrope-like composition comprising one kind of organic solvent selected from s-1,2-dichloroethylene.