JP3141074B2 - Azeotropic and azeotropic compositions comprising fluorinated ethers and alcohols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an azeotropic or azeotropic composition comprising a fluorinated ether and an alcohol.

[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 fluorocarbon hydrocarbons and 1,1,1-trichloroethane containing chlorine 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, 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane 91.0-97.5% by weight and methanol 9.0-9.0.
An azeotropic or azeotrope-like composition is provided, characterized in that it comprises 2.5% by weight. According to the present invention, 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane is composed of 95.0-98.5% by weight and ethanol 1.5-5.0% by weight. An azeotropic or azeotrope-like composition is provided. Furthermore, according to the present invention, 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane 97.0-99.5% by weight and 2-propanol 0.5-3.0% by weight. An azeotropic or azeotrope-like composition 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) 3-difluoromethoxy 1,1,1,2,2-
An azeotropic liquid composition comprising 91.0-97.5% by weight of pentafluoropropane and 9.0-2.5% by weight of methanol, preferably 3-difluoromethoxy 1,
1,1,2,2-pentafluoropropane 95.68
An azeotropic liquid composition comprising, by weight, 4.3% by weight of methanol. The boiling point of this azeotropic liquid product is atmospheric pressure (76
01.5 mmHg). (2) 3-difluoromethoxy 1,1,1,2,2-
An azeotropic liquid composition comprising 95.0 to 98.5% by weight of pentafluoropropane and 1.5 to 5.0% by weight of ethanol, preferably 3-difluoromethoxy 1,
1,1,2,2-pentafluoropropane 97.34
An azeotropic liquid composition comprising, by weight, 2.66% by weight of ethanol. The boiling point of this azeotropic liquid composition is at atmospheric pressure (76
(0 mmHg). (3) 3-difluoromethoxy 1,1,1,2,2-
An azeotropic and azeotrope-like liquid composition comprising 97.0 to 99.5% by weight of pentafluoropropane and 0.5 to 3.0% by weight of 2-propanol, preferably 3-difluoromethoxy 1,1,1,2 An azeotropic composition comprising 98.12% by weight of 2,2-pentafluoropropane and 1.82% by weight of 2-propanol. The boiling point of this azeotropic composition is 45.93 ° C. at atmospheric pressure (760 mmHg).

3-Difluoromethoxy used in the present invention
1,1,1,2,2-pentafluoropropane is a known substance, for example, in the presence of potassium hydroxide, 2,2,2,2-pentafluoropropane
It is easily obtained by reacting 3,3,3-pentafluoropropanol with chlorodifluoromethane.

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; olefin alcohols such as allyl alcohol and 1-butene-3-ol; Methyl-1-butyn-3-o-
And acetylenic alcohols such as 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 3-Difluoromethoxy was measured using a vapor-liquid equilibrium measuring device.
The vapor-liquid equilibrium composition (x ₁ and y ₁ ) and boiling point of a mixture of 1,1,1,2,2-pentafluoropropane and methanol were measured. 3-difluoromethoxy 1,1,1,
A mixed sample having a constant composition of 2,2-pentafluoropropane and methanol 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. The solid line shown in FIGS. 1 and 2 is a calculated curve based on the Wilson equation determined so as to correlate a plurality of measured values obtained by experiments. The Wilson equation in this case is described in, for example, Am. Chem. Soc. , 86,127
(1964). Also, the solid line in FIGS.
It is a calculation curve by an on formula. From the above experimental results,
Difluoromethoxy 1,1,1,2,2-pentafluoropropane 91.0 to 97.5% by weight and methanol 9.0 to 2.5% by weight of the composition of the present invention have an azeotropic composition Things. Here, 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane
The composition consisting of 95.68% by weight and 4.32% by weight of methanol is an azeotropic composition having a boiling point of 41.53 ° C. at atmospheric pressure (760 mmHg).

Example 2 The composition of Example 1 was replaced with 3-difluoromethoxy
An experiment was performed in the same manner as in Example 1, except that 1,1,1,2,2-pentafluoropropane and ethanol were used. The results are shown in Table 2, FIG. 3 and FIG. From these results, the composition of the present invention in the range of 95.0 to 98.5% by weight of 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane and 1.5 to 5.0% by weight of ethanol. Is an azeotropic-like composition. Here, a composition comprising 97.34% by weight of 3-difluoromethoxy 1,1,1,2,2-pentafluoropropane and 2.66% by weight of ethanol is an azeotropic composition, and the boiling point of the composition is atmospheric pressure ( 760 mmHg).

Example 3 The composition of Example 1 was replaced with 3-difluoromethoxy
The measurement was performed using the same apparatus and procedure as in Example 1, except that 1,1,1,2,2-pentafluoropropane and 2-propanol were used. The results are shown in Table 3, FIG. 5 and FIG. From this result, 3-difluoromethoxy 1,1,
1,2,2-pentafluoropropane 97.0-9
Compositions of the invention in the range of 9.5% by weight and 0.5-3.0% by weight of 2-propanol are azeotrope-like compositions. Here, 3-difluoromethoxy 1,1,1,2,2
98.12% by weight of pentafluoropropane and 2-
The composition consisting of 1.82% by weight of propanol is an azeotropic composition, the boiling point of which is 45.93 ° C. at atmospheric pressure (760 mmHg).

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

The azeotropic and azeotropic compositions of the present invention have excellent properties such as detergency and low toxicity similar to those of chlorofluorocarbon and chlorohydrocarbons. By using the composition of the present invention, the environmental load can be significantly reduced as compared with conventional chlorofluorocarbons and chlorinated hydrocarbons. Further, since the composition of the present invention does not change or is negligibly small even when it is recycled and used by distillation or the like, the conventionally used CFC-113 or CF
It is effective as a substitute for C-11.

[Brief description of the drawings]

[1] _{CF 3 CF 2 CH 2 OCHF 2} / air-methanol system liquid equilibrium in the liquid phase in (760mmHg) CF ₃ CF ₂
CH ₂ OCHF ₂ concentration (x ₁ ) and CF ₃ CF ₂ CH _{2 in} gas phase
The relationship with the OCHF ₂ concentration (y ₁ ) is shown.

[Figure 2] _{CF 3 CF 2 CH 2 OCHF 2} / air-methanol system liquid equilibrium in the liquid phase in (760mmHg) CF ₃ CF ₂
The relationship between the CH ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

[Figure 3] _{CF 3 CF 2 CH 2 OCHF 2} / CF 3 CF 2 in the liquid phase in the ethanol-based gas-liquid equilibrium (760 mmHg)
CH ₂ OCHF ₂ concentration (x ₁ ) and CF ₃ CF ₂ CH _{2 in} gas phase
The relationship with the OCHF ₂ concentration (y ₁ ) is shown.

[4] _{CF 3 CF 2 CH 2 OCHF 2} / CF 3 CF 2 in the liquid phase in the ethanol-based gas-liquid equilibrium (760 mmHg)
The relationship between the CH ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

FIG. 5: CF in the liquid phase in a gas-liquid balance (760 mmHg) of the CF ₃ CF ₂ CH ₂ OCHF ₂ / 2-propanol system
₃ CF ₂ CH ₂ OCHF ₂ concentration (x ₁ ) and CF ₃ CF in gas phase
The relationship with the ₂ CH ₂ OCHF ₂ concentration (y ₁ ) is shown.

FIG. 6: CF in the liquid phase in a gas-liquid balance (760 mmHg) of a CF ₃ CF ₂ CH ₂ OCHF ₂ / 2-propanol system
The relationship between the ₃ CF ₂ CH ₂ OCHF ₂ concentration (x ₁ ) and the boiling point temperature (t) is shown.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C11D 7/28 C11D 7/28 7/50 7/50 (72) Inventor Takayuki Ishimura Hongo 2-40-17 Hongo, Bunkyo-ku, Tokyo Wakai Building 6F Global Environmental Industrial Technology Research Organization New refrigerant project room (72) Inventor Tetsuya Suzuda Hongo Wakai Building 6F Global Innovative Technology Research Institute 2-40-17 Hongo, Bunkyo-ku, Tokyo Structure New refrigerant project room (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref. Inspector, Institute of Materials Science and Engineering, Institute of Industrial Science and Technology Motohiro Okubo (56) References JP-A-6-220497 (JP, A) JP-A-4-227695 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/26 C11D 7/28 C11D 7/50

Claims (3)

(57) [Claims] (1) 3-difluoromethoxy 1,1,1,
2,2-pentafluoropropane 91.0-97.5
An azeotropic or azeotrope-like composition, characterized in that the composition consists of 9.0% to 2.5% by weight of methanol. 2. 3-Difluoromethoxy 1,1,1,
2,2-pentafluoropropane 95.0-98.5
An azeotropic or azeotrope-like composition, characterized in that it consists of 1.5% by weight and 1.5-5.0% by weight of ethanol. 3. 3-Difluoromethoxy 1,1,1,
2,2-pentafluoropropane 97.0-99.5
An azeotropic or azeotrope-like composition, characterized in that the composition consists of 0.5% by weight and 0.5-3.0% by weight of 2-propanol.