JP3364640B2 - Azeotropic or azeotropic composition composed of fluorinated ethers and alcohols - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azeotropic composition or an azeotropic composition, and more particularly to flux cleaning, degreasing cleaning, draining drying, solvent and the like. Azeotropic compositions or azeotropic compositions used as Hitherto, halogenated hydrocarbons have been best known as solvents for cleaning electronic parts, precision machine parts, resin processed parts and the like. This has a characteristic as a hydrocarbon group in which a chlorine atom or a chlorine atom and a fluorine atom are substituted. These halogenated hydrocarbons are less toxic, show nonflammability when the number of halogen substitution is large,
It is widely used in various industrial fields because it is chemically and thermally stable and has a suitable solubility of dissolving wax and oils without eroding the surface of plastics and rubber. . 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.
-Freon-based hydrocarbons such as trifluoroethane (Freon 113) are known. In particular, the latter, which is less toxic, non-flammable, chemically and thermally stable, has a wide range of applications. Used in However, the serious disadvantage of destroying the stratospheric ozone layer has been pointed out because such chlorofluorocarbon-based hydrocarbons and 1,1,1-trichloroethane have chlorine atoms, and their production and use can be stopped. Internationally determined. Trichlorethylene and tetrachlorethylene have been classified as Class 2 Specified Chemical Substances since 1989, based on the results of surveys on environmental pollution and subsequent toxicological findings indicating that chronic toxicity, etc., have been raised for groundwater pollution problems. Cabinet order specified. Under such circumstances, the development of such chlorofluorocarbon-based hydrocarbons and substances that substitute for chlorinated hydrocarbons has been actively conducted. At present, fluorine compounds containing no chlorine atom are widely known as substitute substances. However, since such compounds do not contain chlorine atoms, they have poor solubility in waxes and fats. To solve this problem,
A general-purpose solvent such as alcohol is mixed with the substitute substance compound to improve the dissolving power.However, if such a mixture is used as a cleaning agent under heating, the concentration must be controlled because the vapor composition and the liquid composition are different. Is known to be. Among the mixed compositions, it is known that the azeotropic composition is a useful composition having the same vapor composition and liquid composition, and the azeotropic-like composition is a useful composition that does not require concentration control because they are almost the same ( JP-A-8-268944). However, the azeotropic composition does not always exist in the mixture, and its presence cannot be estimated. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent properties, such as chlorofluorocarbon-based hydrocarbons and chlorine-based hydrocarbons, such as detergency and low toxicity. Without deteriorating the properties of the ozone layer,
Another object of the present invention is to provide a novel azeotropic composition and an azeotropic composition having a small greenhouse effect. [0004] The inventors of the present invention 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, 1,1,1,2,3,3-hexafluoro- represented by the following formula (1) CF ₃ CHFCF ₂ OCH ₂ CF ₃ (1)
An azeotropic or azeotropic composition comprising 3- (2,2,2-trifluoroethoxy) propane and one alcohol selected from methanol, ethanol and 2-propanol is provided. [0005] 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) 1,1,1,2,3,3-hexafluoro-3-
(2,2,2-trifluoroethoxy) propane80.
An azeotropic composition consisting of 0-99.9% by weight and 0.1-20.0% by weight of methanol, preferably 1,1,1,1
An azeotropic composition comprising 85.93% by weight of 2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 14.07% by weight of methanol. The boiling point of this azeotropic composition is 5 at atmospheric pressure (760 mmHg).
7.52 ° C. (2) 1,1,1,2,3,3-hexafluoro-3-
(2,2,2-trifluoroethoxy) propane80.
An azeotropic composition comprising 0-99.9% by weight and 0.1-20.0% by weight of ethanol, preferably 1,1,1,1
An azeotropic composition comprising 89.14% by weight of 2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 10.86% by weight of ethanol. The boiling point of this azeotropic composition is 6 at atmospheric pressure (760 mmHg).
4.73 ° C. (3) 1,1,1,2,3,3-hexafluoro-3-
(2,2,2-trifluoroethoxy) propane80.
0 to 99.9% by weight and 2-propanol 0.1 to 2
An azeotropic composition comprising 0.0% by weight, preferably 1,
1,1,2,3,3-hexafluoro-3- (2,2,
2-trifluoroethoxy) propane 88.90% by weight
And an azeotropic composition comprising 11.10% by weight of 2-propanol. The boiling point of this azeotropic composition is at atmospheric pressure (760
68.08 ° C. in mmHg). According to the present invention, 1,1,1,2,3,3-
Hexafluoro-3- (2,2,2-trifluoroethoxy) propane is a known substance and is easily synthesized, for example, by reacting 2,2,2-trifluoroethanol with hexafluoropropene under basic conditions. Is done. 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, 1,2-dimethoxyethane, 1,4-dioxane, 1,4-dioxane, and the like. Ethers such as 3,5-trioxane, glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, epoxides such as 1,2-butylene oxide, cyclohexene oxide, epichlorohydrin, hexene, heptene, pentadiene, cyclopentene, cyclohexene, etc. Unsaturated hydrocarbons, allyl alcohol, 1
Olefinic alcohols such as -buten-3-ol,
3-methyl-1-butyn-3-ol, 3-methyl-1
Acetylenic alcohols such as -pentin-3-ol; and acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate. In order to further obtain a synergistic stabilization 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 type of the stabilizer and the like, but is set to such an extent that the azeotropic property is not hindered. The amount used is usually about 0.01 to 10% by weight of the composition of the present invention, and 0.1 to 5% by weight.
It is more preferable to set it to about weight%. [0007] In order to further improve the detergency and the interfacial action, various surfactants can be added to the composition of the present invention as needed. As a surfactant,
Sorbitan fatty acid esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as polyoxyethylene sorbite tetraoleate; polyethylene glycol fatty acid esters such as polyoxyethylene monolaurate; polyoxyethylene Nonionic surfactants such as polyoxyethylene alkyl ethers such as lauryl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, and polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic amide And 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 it is an amount which does not hinder the azeotropic property, and is usually 0.1% of the composition of the present invention.
About 20% by weight, 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 for resin-processed parts, optical lenses, clothing, and the like, and drainers and desiccants. 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 fluorocarbons. Now, the present invention will be described in further detail with reference to Examples. Example 1 A 1,1,1,2,3,3-
The vapor-liquid equilibrium and azeotropic point of hexafluoro-3- (2,2,2-trifluoroethoxy) propane and methanol were measured. 1,1,1,2,3,3-hexafluoro-3
-A mixed sample having a constant composition of (2,2,2-trifluoroethoxy) propane and methanol is placed in a sample container,
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. Table 1, FIG. 1 and FIG.
Shown in From the results, 80.0-99.9% by weight of 1,1,1,2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 0.1-20. Compositions of the invention in the range of 0% by weight are azeotrope-like compositions. Where 1,1,1,2,3,
85.93% by weight of 3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and methanol 1
The composition consisting of 4.07% by weight is an azeotropic composition having a boiling point of 57.52 ° C. at atmospheric pressure (760 mmHg). [Table 1] Example 2 The same procedure as in Example 1 was carried out except that ethanol was used instead of methanol. Table 2, FIG. 3 and FIG.
Shown in From these results, 80.0-99.9% by weight of 1,1,1,2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 0.1-20. Compositions of the invention in the range of 0% by weight are azeotropic-like compositions. Where 1,1,1,2,3,
89.14% by weight of 3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and ethanol 1
The composition consisting of 0.86% by weight is an azeotropic composition having a boiling point of 64.73 ° C. at atmospheric pressure (760 mmHg). [Table 2] Example 3 The procedure of Example 1 was repeated, except that 2-propanol was used instead of methanol. The measurement results are shown in Table 3, FIG. 5 and FIG. From these results, 1,1,1,2,3,3
The composition of the present invention in the range of 80.0 to 99.9% by weight of hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 0.1 to 20.0% by weight of 2-propanol; , An azeotropic composition. Where 1,1,1,
88.90% by weight of 2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane and 2-
A composition consisting of 11.10% by weight of propanol is an azeotropic composition and has a boiling point of 6 at atmospheric pressure (760 mmHg).
8.08 ° C. [Table 3] The composition of the present invention has excellent properties, such as detergency and low toxicity, similar to those of fluorocarbons and chlorine-based hydrocarbons. Compared with hydrocarbons, it can greatly reduce the environmental burden such as ozone depletion and global warming.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1: Liquid phase concentration (X1) / gas phase concentration (Y) in vapor-liquid equilibrium of a system of CF ₃ CHFCF ₂ OCH ₂ CF ₃ + methanol
1) Show the curve. FIG. 2 shows a liquid phase concentration (X1) / temperature (T) curve in a gas-liquid equilibrium of a CF ₃ CHFCF ₂ OCH ₂ CF ₃ + methanol system. FIG. 3 shows a liquid-phase concentration (X1) / gas-phase concentration (Y) in a gas-liquid equilibrium of a CF ₃ CHFCF ₂ OCH ₂ CF ₃ + ethanol system.
1) Show the curve. FIG. 4 shows a liquid phase concentration (X1) / temperature (T) curve in a gas-liquid equilibrium of a CF ₃ CHFCF ₂ OCH ₂ CF ₃ + ethanol system. FIG. 5 shows a liquid phase concentration (X1) / gas phase concentration (Y1) curve in a gas-liquid equilibrium of CF ₃ CHFCF ₂ OCH ₂ CF ₃ + 2-propanol system. FIG. 6 shows a liquid phase concentration (X1) / temperature (T) curve in a gas-liquid equilibrium of a CF ₃ CHFCF ₂ OCH ₂ CF ₃ + 2-propanol system.

──────────────────────────────────────────────────続 き Continuing from the front page (73) Patent holder 000157119 Kanto Denka Kogyo Co., Ltd. 1-2-1, Marunouchi, Chiyoda-ku, Tokyo (73) Patent holder 000002004 Showa Denko Co., Ltd. 1-113 Shiba-Daimon, Minato-ku, Tokyo No. 9 (73) patent holder 000002200 Central Glass Co., Ltd. 5253, Okibe, Oji, Ube City, Yamaguchi Prefecture (73) Patent holder 000002853 Daikin Industries, Ltd. 2-4-1 Nakazaki Nishi, Kita-ku, Osaka City, Osaka Umeda Center Building ( 73) Patent holder 000003034 Toagosei Co., Ltd. 1-14-1 Nishi-Shimbashi, Minato-ku, Tokyo (73) Patent holder 000174851 Mitsui-Dupont Fluorochemical Co., Ltd. 100074505 Patent Attorney Toshiaki Ikeura (72) Inventor Toshihiko Hijiaki 4-6-17 Okubo, Narashino City, Chiba Prefecture 72) Inventor Junji Murata 2-40-17 Hongo, Wakyo Building, Bunkyo-ku, Tokyo 6F Hongo Wakai Building Research Institute for Global Environmental Research, New Refrigerant Project Room (72) Inventor Shingo Urata 2-40- Hongo, Bunkyo-ku, Tokyo 17 Hongo Wakai Building 6F Research Institute for Innovative Technology for the Earth Global Research Institute for New Refrigerants (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (56) References JP Hei 4-273839 (JP, A) Fluid Phase Equilibria, 194-197 (2002) 969-979 (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/50 C11D 7/26 C11D 7 / 28 C23G 5/028 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims 1] 1,1,1,2,3,3-hexafluoro-3- (2,2,2-trifluoroethoxy) propane, methanol, ethanol and 2 -An azeotropic composition or an azeotrope-like composition comprising one alcohol selected from propanol