JP2001172683A - Composition comprising 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and alcohols - Google Patents

Abstract

(57) [Problem] To provide a greenhouse effect without deteriorating the ozone layer destruction without impairing the excellent properties such as detergency and low toxicity possessed by chlorofluorocarbon-based hydrocarbons and chlorine-based hydrocarbons. A new small composition is provided. SOLUTION: 1,1,2,2-tetrafluoro-3- represented by the following formula (1) CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ (1)
A composition comprising (1,1,2,2-tetrafluoroethoxy) -propane and at least one alcohol selected from methanol, ethanol and 2-propanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition comprising a fluorine-containing ether and an alcohol,
More specifically, flux cleaning, degreasing cleaning, draining drying,
It relates to a composition used as a solvent or the like.

[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. It has characteristics as a hydrogen group. These halogenated hydrocarbons are less toxic,
High substitution number of halogen shows nonflammability and is chemically and thermally stable, and has appropriate solubility to dissolve waxes and oils without eroding the surface of plastics and rubber. Therefore, 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). Are particularly known, and the latter is used in a wide range of fields because of its 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 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, 1,1,2,2-tetrafluoro-3- represented by the following formula (1) CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ (1)
There is provided a composition comprising (1,1,2,2-tetrafluoroethoxy) -propane and at least one alcohol selected from methanol, ethanol and 2-propanol. Further, according to the present invention, there is provided an azeotropic or azeotropic-like composition comprising the above composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The content of alcohol in the composition of the present invention is 1 to 50% by weight in the total solvent. Alcohols in the composition is a flammable compound, so if the content is more than the above range, the flammability of the solvent increases, so it is not preferable.
This is not preferable because the effect of the addition becomes insufficient. The azeotropic composition in the present invention means a composition in which the vapor composition and the liquid composition are the same, and there is 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. An azeotropic composition of the present invention,
The azeotropic composition specifically has the following composition. (1) 1,1,2,2-tetrafluoro-3- (1,
1,2,2-tetrafluoroethoxy) -propane 50
An azeotropic composition consisting of -60% by weight and 40-50% by weight of methanol, preferably 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane 56 0.08% by weight and methanol
An azeotropic composition comprising 92% by weight. The boiling point of this azeotropic composition is 64.11 ° C. at atmospheric pressure (760 mmHg). (2) 1,1,2,2-tetrafluoro-3- (1,
1,2,2-tetrafluoroethoxy) -propane 65
An azeotropic composition comprising -80% by weight and 20-35% by weight of ethanol, preferably 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane 70 0.96% by weight and ethanol 29.
It is an azeotropic composition consisting of 04% by weight. The boiling point of this azeotropic composition is 74.44 ° C. at atmospheric pressure (760 mmHg). (3) 1,1,2,2-tetrafluoro-3- (1,
1,2,2-tetrafluoroethoxy) -propane 60
An azeotropic composition comprising -75% by weight and 25-40% by weight of 2-propanol, preferably 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy)- An azeotropic composition comprising 66.45% by weight of propane and 33.55% by weight of 2-propanol. The boiling point of this azeotropic composition is 7 at atmospheric pressure (760 mmHg).
8.28 ° C. 1,1,2,2-tetrafluoro-3- according to the present invention
(1,1,2,2-Terafluoroethoxy) -propane is a known substance, for example, 2,2,2 in the presence of a base catalyst.
It is easily obtained by reacting 3,3-tetrafluoropropanol with tetrafluoroethylene.

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 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 more preferably about 0.1 to 5% by 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. 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 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 chlorofluorocarbon.

[0009]

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 The vapor-liquid equilibrium and azeotropic point of 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane were measured using a vapor-liquid equilibrium measuring apparatus. It was measured. A mixed sample having a constant composition of bis (2,2,2-trifluoroethyl) ether 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 measurement results are shown in Table 1, FIG. 1 and FIG. From this result, 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy)-
Compositions of the invention in the range of 50-60% by weight of propane and 40-50% by weight of methanol are azeotrope-like compositions. Here, 1,1,2,2-tetrafluoro-3-
The composition consisting of 56.08% by weight of (1,1,2,2-tetrafluoroethoxy) -propane and 43.92% by weight of methanol is an azeotropic composition and has a boiling point of 64.60 at atmospheric pressure (760 mmHg). 11 ° C.

[0011]

[Table 1] * 1: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in liquid phase * 2: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in gas phase

Example 2 The procedure of Example 1 was repeated, except that 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and ethanol were used. The measurement was performed using the same device and procedure as in Example 1. The measurement results are shown in Table 2, FIG. 3 and FIG. From these results, 1, 1, 2,
Compositions of the present invention in the range of 65-80% by weight of 2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and 20-35% by weight of ethanol are azeotrope-like compositions It is. Here, 70.96% by weight of 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and ethanol 2
The composition consisting of 9.04% by weight is an azeotropic composition having a boiling point of 74.44 ° C. at atmospheric pressure (760 mmHg).

[0013]

[Table 2] * 1: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in liquid phase * 2: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in gas phase

Example 3 In place of the composition of Example 1, 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and 2-propanol were used. Except for this, the measurement was performed using the same apparatus and procedure as in Example 1. The measurement results are shown in Table 3, FIG. 5 and FIG. From this result, 1,
1,2,2-tetrafluoro-3- (1,1,2,2-
Tetrafluoroethoxy) -propane 60-75% by weight
The compositions of the present invention in the range of 25-40% by weight and 2-propanol are azeotropic compositions. Where 1,1,
The composition consisting of 66.45% by weight of 2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and 33.55% by weight of 2-propanol is an azeotropic composition, Its boiling point is atmospheric pressure (760mmHg)
78.28 ° C.

[0015]

[Table 3] * 1: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in liquid phase * 2: CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ concentration in gas phase

[0016]

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 and is easily decomposed in the troposphere, so that the greenhouse effect is small.

[Brief description of the drawings]

FIG. 1 shows a liquid phase / gas phase concentration curve in gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + methanol system.

FIG. 2 shows a liquid phase concentration / temperature curve in a gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + methanol system.

FIG. 3 shows a liquid phase concentration / gas phase concentration curve in a gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + ethanol system.

FIG. 4 shows a liquid phase concentration / temperature curve in a gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + ethanol system.

FIG. 5 shows a liquid phase / gas phase concentration curve in a gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + 2-propanol system.

FIG. 6 shows a liquid phase concentration / temperature curve in a gas-liquid equilibrium of a CHF ₂ CF ₂ CH ₂ OCF ₂ CHF ₂ + 2-propanol system.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junji Murata 6F Hongo Wakai Building 2-40-17 Hongo, Bunkyo-ku, Tokyo New Technology Project Room for Global Recycling Technology Institute (72) Inventor Yuji Kurokawa 6F Hongo Wakai Building, Hongo 2-40-17, Hongo, Tokyo Metropolitan Institute for Environmental Science and Technology New refrigerant room (72) Inventor, Masahiro Iijima Hongo Wakai Building, 2-40-17 Hongo, Bunkyo-ku, Tokyo 6F Foundation for Research on Global Environmental Industry Technology New Refrigerants Project Room (72) Inventor Akira Sekiya 1-1-1, Higashi, Tsukuba, Ibaraki Pref. 1-Chome No. 1 F-term in the National Institute of Advanced Industrial Science and Technology 4H003 DA12 DA14 DA15 ED26 ED28 FA01 FA03 FA46

Claims (2)

[Claims] 1. 1,1,2,2-tetrafluoro-3-
A composition comprising (1,1,2,2-tetrafluoroethoxy) -propane and at least one alcohol selected from methanol, ethanol and 2-propanol. 2. It is preferably selected from 1,1,2,2-tetrafluoro-3- (1,1,2,2-tetrafluoroethoxy) -propane and methanol, ethanol and 2-propanol. An azeotropic or azeotrope-like composition comprising one type of alcohol.