JP2881190B2 - Novel azeotropic and azeotropic compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to azeotropic or azeotropic compositions.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons are the most well-known 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. Hydrogen groups are used. 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. It is widely used in various industrial fields because it has an appropriate solubility of dissolving fats and oils. For example, as these halogenated hydrocarbons, trichloroethylene, tetrachloroethylene,
Chlorinated hydrocarbons such as 1,1,1-trichloroethane and CFCs such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC 113) are known. CFC-based hydrocarbons are 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, there is a strong demand for the development of a CFC-based hydrocarbon containing chlorine or a substance replacing the chlorine-based hydrocarbon.

[0003]

DISCLOSURE OF THE INVENTION The present invention has excellent properties such as detergency and low toxicity similar to those of chlorofluorocarbon and chlorofluorocarbon-based hydrocarbons, and also has a concern that the ozone layer may be destroyed. An object of the present invention is to provide a novel composition having no greenhouse effect and having no greenhouse effect.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, 1-difluoromethoxy 1,1,2-trifluoroethane represented by the following formula CH ₂ FCF ₂ OCHF ₂ (1) and ethanol, methanol, 2-propanol, acetone, cyclohexane, An azeotropic or azeotropic composition comprising at least one organic solvent selected from hexane and cyclopentane is provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the composition of the present invention are shown below. 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. In addition, an azeotropic-like composition has almost the same vapor composition and liquid composition,
It means that the composition change of the composition after repeated condensation changes only negligibly. (1) An azeotropic liquid composition comprising 97.64% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 2.36% by weight of ethanol. The azeotropic liquid composition has a boiling point of 42.45 ° C. at atmospheric pressure (760 mmHg). (2) An azeotropic liquid composition comprising 95.18% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 4.82% by weight of methanol. The azeotropic liquid composition has a boiling point of 40.02 ° C. at atmospheric pressure (760 mmHg). (3) 99.41% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 2-propanol
An azeotropic liquid composition consisting of 59% by weight. The boiling point of this azeotropic liquid composition is 43.01 ° C. at atmospheric pressure (760 mmHg).
It is. (4) An azeotropic liquid composition comprising 30 to 55% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 45 to 70% by weight of acetone, preferably 1-difluoromethoxy 1,1,2. -Trifluoroethane 41.6
An azeotropic liquid composition consisting of 6% by weight and 58.34% by weight of acetone. The boiling point of this azeotropic liquid composition is 57.37 ° C. at atmospheric pressure (760 mmHg). (5) 1-difluoromethoxy 1,1,2-trifluoroethane 40 to 95% by weight and cyclohexane 5 to 6
Azeotropic liquid composition consisting of 0% by weight, preferably 1-difluoromethoxy 1,1,2-trifluoroethane 8
6.79% by weight and 13.21% by weight of cyclohexane
An azeotropic liquid composition comprising: The boiling point of this azeotropic liquid composition is 39.55 ° C. at atmospheric pressure (760 mmHg). (6) An azeotropic liquid composition comprising 50 to 90% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 10 to 50% by weight of hexane, preferably 1-difluoromethoxy 1,1,2. -Trifluoroethane 83.2
An azeotropic liquid composition comprising 8% by weight and 16.72% by weight of hexane. The boiling point of this azeotropic liquid composition is at atmospheric pressure (7
37.60 ° C. at 60 mmHg). (7) 1-difluoromethoxy 1,1,2-trifluoroethane 50 to 75% by weight and cyclopentane 25 to 25% by weight
50% by weight azeotropic liquid composition, preferably 1-
Difluoromethoxy 1,1,2-trifluoroethane 6
5.10% by weight and 34.90% by weight of cyclopentane
An azeotropic liquid composition comprising: The boiling point of this azeotropic liquid composition is 30.78 ° C. at atmospheric pressure (760 mmHg).

1-difluoromethoxy used in the present invention
1,1,2-Trifluoroethane is a known substance, for example, commercially available 2-chloro 1-difluoromethoxy 1,2
It is easily obtained by reducing 1,2-trifluoroethane. 1-difluoromethoxy used in the present invention
1,1,2-Trifluoroethane has a boiling point of 43.1 ° C. and azeotropes with 1,1,1-trichloroethane, and its azeotropic composition is 1-difluoromethoxy 1,1,2-trifluoroethane. 94.93% by weight and 5.07% by weight of 1,1,1-trichloroethane. The boiling point of this azeotropic composition is 43.01 ° C. at atmospheric pressure (760 mmHg).

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,
Epoxides 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 Acetylenic alcohols such as -3-ol and 3-methyl-1-pentyn-3-ol; and acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate. 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 varies depending on the type of the stabilizer and the like, but is set to such an extent that the azeotropic property of the composition is not hindered.
The amount of use is usually about 0.01 to 10% by weight in the composition, 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. Esters, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide Nonionic surfactants may be used alone or in 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 to be used varies depending on the kind and the like, but is not so much as to hinder the azeotropic property of the composition, and is usually about 0.1 to 20% by weight in the composition, More preferably, it is about 5% by weight.

The composition of the present invention has excellent solubility and 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. CFC 113 and 1,1,1-
It is a very useful alternative to trichloroethane. Specific applications include flux, grease, oil, wax, and ink removers, electronic components (printed circuit boards, liquid crystal displays, magnetic recording components, semiconductor materials, etc.), electrical components, precision machinery components, and resin processing. Examples include cleaning agents for components, optical lenses, clothing, and the like, and draining and drying agents. As the cleaning method, a conventionally used method such as immersion, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning, or a combination thereof can be adopted. 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 chlorofluorocarbon.

[0010]

Next, the present invention will be described in more detail with reference to examples.

Example 1 1-Difluoromethoxy 1,
The vapor-liquid equilibrium composition and azeotropic point of a mixture of 1,2-trifluoroethane and ethanol were measured. A mixed sample having a fixed composition of 1-difluoromethoxy 1,1,2-trifluoroethane 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 experimental results are shown in Table 1, FIG. 1 and FIG. FIG.
The solid line shown in FIG. 2 is a calculated curve according to the Wilson equation determined so as to correlate a plurality of actually measured values obtained by experiments. For the Wilson expression in this case,
For example, J. Am. Chem. Soc. , 86,127
(1964). Also, the solid lines in FIGS. 3 to 8, 11, and 12 shown in connection with the examples described below are calculation curves based on the similar Wilson equation. From the above experimental results, 97.64% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and ethanol 2.
The composition consisting of 36% by weight is an azeotropic composition having a boiling point of 42.45 ° C. at atmospheric pressure (760 mmHg).

Example 2 In place of the composition of Example 1, 1-difluoromethoxy 1,
Except for using 1,2-trifluoroethane and methanol,
An experiment was performed in the same manner as in Example 1. Table 2 shows the results.
3 and 4. From these results, it was found that a composition comprising 95.18% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 4.82% by weight of methanol was an azeotropic composition, and its boiling point was at atmospheric pressure (760 mmH
g) is 40.02 ° C.

Example 3 The composition of Example 1 was replaced with 1-difluoromethoxy 1,
An experiment was performed in the same manner as in Example 1, except that 1,2-trifluoroethane and 2-propanol were used. The results are shown in Table 3, FIG. 5 and FIG. From this result, 1-difluoromethoxy 1,1,2-trifluoroethane 99.4
A composition consisting of 1% by weight and 0.59% by weight of 2-propanol is an azeotropic composition whose boiling point is at atmospheric pressure (7
43.01 ° C. at 60 mmHg).

Example 4 In place of the composition of Example 1, 1-difluoromethoxy 1,
An experiment was conducted in the same manner as in Example 1 except that 1,2-trifluoroethane and acetone were used. The results are shown in Table 4, FIG. 7 and FIG. From these results, 1-difluoromethoxy 1,1,2-trifluoroethane 30 to 55% by weight
And acetone in the range of 45-70% by weight are azeotrope-like compositions. Here, the composition comprising 41.66% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 58.34% by weight of acetone is an azeotropic composition, and the boiling point thereof is at atmospheric pressure (760 mmH
g) is 57.37 ° C.

Example 5 In place of the composition of Example 1, 1-difluoromethoxy 1,
An experiment was conducted in the same manner as in Example 1 except that 1,2-trifluoroethane and cyclohexane were used. The results of the experiment are shown in Table 5, FIG. 9 and FIG. The solid line shown in FIGS. 9 and 10 is a calculated curve according to the NRTL equation determined so as to correlate a plurality of measured values obtained by experiments. For the NRTL expression in this case, for example, I. Ch.
EJ. , 14, 135 (1968).
Further, solid lines in FIGS. 13 and 14 which are shown in connection with the examples described later are also calculated curves by the same NRTL equation.
From the above experimental results, 1-difluoromethoxy 1,1,
Compositions of the invention ranging from 40 to 95% by weight 2-trifluoroethane and 5 to 60% by weight cyclohexane comprise:
An azeotropic composition. Where 1-difluoromethoxy
A composition consisting of 86.79% by weight of 1,1,2-trifluoroethane and 13.21% by weight of cyclohexane is an azeotropic composition and has a boiling point at atmospheric pressure (760 mmH
g) is 39.55 ° C.

Example 6 1-Difluoromethoxy 1,1 was used in place of the composition of Example 1.
An experiment was performed in the same manner as in Example 1, except that 1,2-trifluoroethane and hexane were used. The results are shown in Table 6, FIG. 11 and FIG. From this result, the composition of the present invention in the range of 50 to 90% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 10 to 50% by weight of hexane is an azeotropic composition. Here, 1-difluoromethoxy 1,1,2-trifluoroethane 83.2
A composition consisting of 8% by weight and 16.72% by weight of hexane is an azeotropic composition whose boiling point is at atmospheric pressure (760 mm
Hg) 37.60 ° C.

Example 7 The composition of Example 1 was replaced with 1-difluoromethoxy 1,
An experiment was conducted in the same manner as in Example 1 except that 1,2-trifluoroethane and cyclopentane were used. The results are shown in Table 7, FIG. 13 and FIG. From these results, 1-difluoromethoxy 1,1,2-trifluoroethane 50 to 7
Compositions of the invention in the range of 5% by weight and 25-50% by weight of cyclopentane are azeotropic-like compositions. Here, the composition consisting of 65.10% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 34.90% by weight of cyclopentane is an azeotropic composition, and its boiling point is at atmospheric pressure (760 mmHg). 30.78 ° C.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

[Table 6]

[0024]

[Table 7]

[0025]

The azeotropic and azeotrope-like compositions of the present invention do not contain chlorine atoms, so there is no concern about destruction of the ozone layer. Also, since they contain hydrogen atoms, they can react with hydroxyl radicals in the atmosphere. Since it has high reactivity and is easily decomposed in the troposphere, it has the advantage that the greenhouse effect is small. Further, the composition of the present invention has no change in composition or is so small that it can be neglected even when recycled and used by distillation or the like. Therefore, it is a substitute for CFC-113 and CFC-11 which have been generally used in the past. Is effective as

[Brief description of the drawings]

FIG. 1 shows CH ₂ FC in a liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / ethanol system.
F ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ FCF _{2 in} gas phase
The relationship with the OCHF ₂ concentration (y ₁ ) is shown.

FIG. 2 CH ₂ FC in a liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / ethanol system
The relationship between the F ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

FIG. 3 CH ₂ FC in a liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / methanol system
F ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ FCF _{2 in} gas phase
The relationship with the OCHF ₂ concentration (y ₁ ) is shown.

FIG. 4 CH ₂ FC in the liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / methanol system
The relationship between the F ₂ CHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

FIG. 5: CH in liquid phase in gas-liquid equilibrium (760 mmHg) of CH ₂ FCF ₂ OCHF ₂ / 2-propanol system
₂ FCF ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ F in gas phase
The relationship with the CF ₂ OCHF ₂ concentration (y ₁ ) is shown.

FIG. 6: CH in a liquid phase in a gas-liquid equilibrium (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / 2-propanol system
₂ shows the relationship between the FCF ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t).

[7] _{CH 2 FCF 2 OCHF 2 / CH} 2 FCF in the liquid phase in a gas of acetone-based liquid equilibrium (760 mmHg)
₂ OCHF ₂ concentration (x ₁ ) and CH ₂ FCF ₂ O in gas phase
The relationship with the CHF ₂ concentration (y ₁ ) is shown.

[8] _{CH 2 FCF 2 OCHF 2 / CH} 2 FCF in the liquid phase in a gas of acetone-based liquid equilibrium (760 mmHg)
₂ shows the relationship between the OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t).

[9] _CH 2 _FCF 2 OCHF ₂ / cyclohexane system of the gas-liquid equilibrium CH ₂ in the liquid phase in (760 mmHg)
FCF ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ FC in gas phase
The relationship with the F ₂ OCHF ₂ concentration (y ₁ ) is shown.

FIG. 10: CH in the liquid phase in a gas-liquid equilibrium (760 mmHg) of the CH ₂ FCF ₂ OCHF ₂ / cyclohexane system
₂ shows the relationship between the FCF ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t).

FIG. 11: CH ₂ FC in a liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / hexane system
F ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ FCF _{2 in} gas phase
The relationship with the OCHF ₂ concentration (y ₁ ) is shown.

FIG. 12: CH ₂ FC in a liquid phase in a gas-liquid balance (760 mmHg) of a CH ₂ FCF ₂ OCHF ₂ / hexane system
The relationship between the F ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

FIG. 13: CH in the liquid phase in a gas-liquid equilibrium (760 mmHg) of the CH ₂ FCF ₂ OCHF ₂ / cyclopentane system
₂ FCF ₂ OCHF ₂ concentration (x ₁ ) and CH ₂ F in gas phase
The relationship with the CF ₂ OCHF ₂ concentration (y ₁ ) is shown.

FIG. 14: CH in the liquid phase in a gas-liquid equilibrium (760 mmHg) of the CH ₂ FCF ₂ OCHF ₂ / cyclopentane system
₂ shows the relationship between the FCF ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t).

Continued on the front page (72) Inventor Takayuki Ishimura 6F, Hongo Wakai Building, Hongo 2-40-17, Hongo, Bunkyo-ku, Tokyo New Refrigerant Project Room (72) Inventor Tetsuya Suzuda Tokyo 6F, Hongo Wakai Building, Hongo 2-40-17, Bunkyo-ku New Technology Project Room (72) Inventor Akira Sekiya 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Examiner in the laboratory Toshiro Fujimori (56) References JP-A-8-259995 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 43/12 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] 1. 97.64% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and ethanol
An azeotropic composition comprising 2.36% by weight. 2. An azeotropic composition comprising 99.41% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 0.59% by weight of 2-propanol. 3. 95% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and methanol
An azeotropic composition comprising 4.82% by weight. 4. 30-55% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 45 of acetone
An azeotropic or azeotrope-like composition comprising from about 70% by weight. 5. 1-Difluoromethoxy 1,1,2-trifluoroethane 41.66% by weight and acetone 5
The azeotropic composition according to claim 4, wherein the composition comprises 8.34% by weight. 6. An azeotropic or azeotrope-like composition comprising 40 to 95% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 5 to 60% by weight of cyclohexane. 7. The composition according to claim 6, comprising 86.79% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 13.21% by weight of cyclohexane.
An azeotropic composition as described. 8. 50% to 90% by weight of 1-difluoromethoxy 1,1,2-trifluoroethane and 10 parts of hexane.
An azeotropic or azeotrope-like composition, characterized by comprising up to 50% by weight. 9. 1-difluoromethoxy 1,1,2-trifluoroethane (83.28% by weight) and hexane (1)
9. The azeotropic composition according to claim 8, comprising 6.72% by weight. 10. 10-Difluoromethoxy 1,1,2-
An azeotropic or azeotropic composition comprising 50 to 75% by weight of trifluoroethane and 25 to 50% by weight of cyclopentane. 11. 1-Difluoromethoxy 1,1,2-
2. The composition according to claim 1, comprising 65.10% by weight of trifluoroethane and 34.90% by weight of cyclopentane.
0. The azeotropic composition according to 0.