JP2003165998A - Ternary azeotropic composition and ternary azeotrope- like composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a 1,1,2,2,3,3,4-heptafluorocyclopentane (HFCPA)-containing composition which does not suffer from changes in this liquid composition by repeated evaporation and condensation, causes no separation into two layers at room temperature and exhibits excellent liquid manageability. <P>SOLUTION: The ternary azeotropic composition or the ternary azeotrope-like composition comprises (A) 1,1,2,2,3,3,4-heptafluorocyclopentane; (B) one selected from 2-5C alcohols not containing a fluorine atom; and (C) one selected from the group consisting of a 6-9C saturated hydrocarbon, a 2-3C fluorinated alcohol and a fluorinated aromatic hydrocarbon. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 1, 1, 2, 2,
It relates to novel ternary azeotropic and ternary azeotrope-like compositions containing 3,3,4-heptafluorocyclopentane.

[0002]

BACKGROUND OF THE INVENTION 1,1,2-Trichloro-1,2,2-
Chlorofluoroethane compounds typified by trifluoroethane (CFC-113) are nonflammable and selectively dissolve fats, greases, waxes, etc. without attacking polymeric materials such as plastics and rubber. Since it is also excellent in solubility, it has been widely used as a solvent, a cleaning agent or the like alone or in the form of a mixture with another organic solvent or an azeotropic composition.

However, in recent years, chlorofluorocarbon compounds such as CFC-113 in which all the hydrogen in the hydrocarbon is replaced by chlorine and fluorine destroys the ozone layer surrounding the earth, causing environmental pollution. Their production is discontinued and their use is regulated. Therefore, from the viewpoint of preventing the global warming without destroying the ozone layer, it is strongly desired to develop an alternative material having a short atmospheric life, and various studies have been conducted.

One example of such an investigation is based on a fluorohydrocarbon compound containing no chlorine atom. For example, International Publication WO98 / 51651 discloses a fluorinated hydrocarbon containing 95% by weight or more of a trihydrofluorocarbon compound having 4 to 6 carbon atoms, a cleaning agent and a cleaning method, a polymer-containing liquid and a polymer coating. Have been proposed.

In the publication, if the trihydrofluorocarbon compound is 1,1,2,2,3,3,4-heptafluorocyclopentane (hereinafter also referred to as HFCPA), hydrocarbons, It is described to form an azeotropic composition with alcohols, esters, halogenated hydrocarbons, ethers, ketones and the like. Further, in the application of the compound to a detergent, the azeotropic composition, particularly HFCPA and 1-butanol, 2-butanol, n-octane, 2,2,4-trimethylpentane, n-heptane and the like are used together. It is also stated that boiling compositions are preferred.

However, the binary azeotropic composition of HFCPA and hydrocarbons cannot be used as a single liquid solvent because the two layers are separated at room temperature, and it has the disadvantage of poor usability. It was Further, although the binary azeotropic composition of HFCPA and alcohols gives good results with respect to the dewatering detergency, it may not show a sufficiently satisfactory detergency in flux cleaning and the like.

By the way, when using a mixed solvent as a solvent such as a cleaning agent, it is important that the liquid can be easily controlled during use and that the used liquid can be recovered and reused. Furthermore, it is preferable that it can be used in liquid form or vapor form (for example, steam cleaning). A mixed solvent satisfying such requirements is
It is preferably an azeotropic mixture, but for example, 3
It is not easy to obtain an azeotropic composition or an azeotrope-like composition which is uniform at room temperature and easy to control the liquid from different kinds of liquid substances.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is that liquid composition remains the same or hardly changes even if evaporation and condensation are repeated, and liquid management is excellent in 1, 1, 2, 2, 3, 3.
3,4-heptafluorocyclopentane (HFCPA)
There is provided a composition comprising:

[0009]

The present invention which solves the above-mentioned problems includes (A) 1,1,2,2,3,3,4-heptafluorocyclopentane; and (B) fluorine having 2 to 5 carbon atoms. 1 selected from an alcohol containing no atom; and (C) selected from the group consisting of a saturated hydrocarbon having 6 to 9 carbon atoms, a fluorinated alcohol having 2 to 3 carbon atoms and a fluorinated aromatic hydrocarbon 1 A ternary azeotropic composition or a ternary azeotropic composition. The ternary azeotropic composition or ternary azeotrope-like composition is preferably uniform at 20 ° C. without layer separation.

In the present invention, the "azeotropic composition" means that the vapor composition and the liquid composition in the equilibrium state are the same,
It means that there is no change in composition of the composition after repeated condensation. The term "azeotrope-like composition" means that the vapor composition and the liquid composition are almost the same, and the composition change of the composition after repeated evaporation and condensation changes to a negligible level.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The ternary azeotropic composition or ternary azeotrope-like composition of the present invention comprises (A) HFCPA; (B) 2 carbon atoms.
1 to 5 selected from alcohols not containing a fluorine atom; and (C) a saturated hydrocarbon having 6 to 9 carbon atoms, a fluorinated alcohol having 2 to 3 carbon atoms, and a fluorinated aromatic hydrocarbon. One selected;

The above-mentioned (A) HFCPA is a known colorless and transparent compound having a boiling point of 82 ° C. under normal pressure. HFCPA is
The ozone depletion potential and global warming potential are significantly smaller than those of conventional chlorofluorocarbon compounds.
In addition, its atmospheric life is reported to be about 3.4 years, and it is a fluorinated hydrocarbon that has very little effect on the global environment.

The method of obtaining such HFCPA is not particularly limited, and it may be produced by a known method and used. For example, according to the method described in WO98 / 51651 related to the application of the present applicants, a dihydro body obtained by hydrogenating octafluorocyclopentene is used as a raw material, and this is subjected to alkali treatment and then hydrogenated. HFCPA having a purity of 95% by weight or more can be prepared.

One type selected from the above (B) C2-C5 fluorine atom-free alcohol forms an azeotropic composition or an azeotrope-like composition together with the above-mentioned (A) and (C). There is no particular limitation as long as it does. The alcohol may be primary, secondary or tertiary. Further, it may be chain-like or cyclic, but a chain-like one is preferable. It may be saturated or unsaturated, but saturated one is preferred. Monoalcohols or polyhydric alcohols may be used, but monoalcohols are preferred. Further, it may have a substituent such as a nitro group and a halogen group other than fluorine. However, the alcohol is not a fluorinated alcohol.

Examples of the alcohol (B) include ethanol, 2-chloroethanol, 2-nitroethanol, ethylene glycol, 1-propanol, 2
-Propanol, allyl alcohol, 1-butanol,
2-butanol, isobutyl alcohol, t-butyl alcohol, cyclobutanol, 1-pentanol, 2-
Pentanol, 3-pentanol, isoamyl alcohol, sec-isoamyl alcohol, t-amyl alcohol, cyclopentanol and the like can be mentioned.

Among these alcohols, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 2-pentanol and t-amyl alcohol are preferable.

The alcohol (B) is industrially widely used, and a commercially available alcohol can be obtained and used in the composition of the present invention. The purity is not particularly limited, and commercially available products for industrial use can be used.

The saturated hydrocarbon having 6 to 9 carbon atoms (C) is particularly limited as long as it forms an azeotropic composition or an azeotrope-like composition together with (A) and (B). Not done. The saturated hydrocarbon may be chain (straight chain and branched chain) or cyclic, for example, n-hexane, isohexane, 2,3-dimethylbutane, cyclohexane,
n-heptane, isoheptane, cycloheptane, methylcyclohexane, norbornane, n-octane, isooctane, cyclooctane, ethylcyclohexane, 1,
2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, n-nonane, isononane, cyclononane, dimethylnorbornane, ethylnorbornane and the like can be mentioned.

Examples of the fluorinated alcohol having 2 to 3 carbon atoms (C) include, for example, 2,2-difluoroethanol, 2,2,2-trifluoroethanol, 2,2,2.
3,3-tetrafluoropropanol, 2,2,3
3,3-pentafluoropropanol, 1,1,1-trifluoro-2-propanol, 1,1,1,3,3,3
3-hexafluoro-2-propanol etc. are mentioned. Preferably 2,2,2-trifluoroethanol,
2,2,3,3-tetrafluoropropanol, 2,
2,3,3,3-pentafluoropropanol,
More preferred is 2,2,2-trifluoroethanol.

Examples of the fluorinated aromatic hydrocarbon (C) include fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene. Fluorobenzene,
Fluorinated benzenes such as 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene and hexafluorobenzene; Fluorinated toluenes such as monofluoromethylbenzene and trifluoromethylbenzene;
-Fluorinated xylenes such as bis (trifluoromethyl) benzene, 1,3-bis (trifluoromethyl) benzene and 1,4-bis (trifluoromethyl) benzene;
And so on. Preferably, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, trifluoromethylbenzene, 1,3-
It is bis (trifluoromethyl) benzene.

The ternary azeotropic composition or ternary azeotrope-like composition of the present invention contains the above-mentioned components (A), (B) and (C), and its vapor composition and liquid composition are the same or almost the same. There is no particular limitation as long as there is no change in composition of the composition after repeated evaporation and condensation, or a change that is negligible.

Examples of such a ternary azeotropic composition or ternary azeotrope-like composition include (a) HFCPA 51.6 to 57.6% by weight, ethanol 8.4 to 14.4% by weight and cyclohexane. 31.
0-37.0% by weight under normal pressure 62.5-64.5
Ternary azeotrope-like composition having a boiling point of ℃, preferably HFC
Consists of PA 54.6% by weight, ethanol 11.4% by weight and cyclohexane 34.0% by weight under normal pressure 63.5%.
A ternary azeotropic composition having a boiling point of ° C;

(A) HFCPA 63.5 to 69.5% by weight, ethanol 9.8 to 15.8% by weight and n-heptane 17.7 to 23.7% by weight, and 67 to 6 under normal pressure.
Ternary azeotrope-like composition having a boiling point of 9 ° C, preferably HF
A ternary azeotropic composition consisting of 66.5% by weight of CPA, 12.8% by weight of ethanol and 20.7% by weight of n-heptane and having a boiling point of 68 ° C. under normal pressure;

(C) HFCPA 64.8 to 70.8% by weight, 2-propanol 9.8 to 15.8% by weight and n
-Heptane from 16.4 to 22.4% by weight under normal pressure 7
A ternary azeotrope-like composition having a boiling point of 0.5 to 72.5 ° C.,
A ternary azeotropic composition comprising 67.8% by weight of HFCPA, 12.8% by weight of 2-propanol and 19.4% by weight of n-heptane and having a boiling point of 71.5 ° C. under normal pressure;

(D) HFCPA 60.2 to 66.2% by weight, ethanol 12.2 to 18.2% by weight and isooctane 18.6 to 24.6% by weight.
Ternary azeotrope-like composition having a boiling point of 6 to 22.6 ° C., preferably HFCPA 63.2% by weight, ethanol 15.2
Ternary azeotropic composition having a boiling point of 69 ° C. under normal pressure, consisting of 1% by weight and 21.6% by weight of isooctane;

(E) HFCPA 70.8 to 76.8% by weight, 1-propanol 3.0 to 9.0% by weight, and isooctane 17.2 to 23.2% by weight, and 7 at normal pressure.
A ternary azeotrope-like composition having a boiling point of 4.5-76.5 ° C.,
A ternary azeotropic composition comprising 73.8% by weight of HFCPA, 6.0% by weight of 2-propanol and 20.2% by weight of isooctane and having a boiling point of 75.5 ° C. under normal pressure;

(F) HFCPA consisting of 63.6 to 69.6% by weight, 2-propanol 11.0 to 17.0% by weight and isooctane 16.4 to 22.4% by weight and having a boiling point of 71 to 73 ° C. under normal pressure. Ternary azeotrope-like composition having, preferably 66.6 wt% HFCPA, 2-propanol 1
A ternary azeotropic composition consisting of 4.0% by weight and 19.4% by weight of isooctane and having a boiling point of 72 ° C. under normal pressure;

(G) HFCPA consisting of 64.0 to 70.0% by weight, ethanol 10.4 to 16.4% by weight and methylcyclohexane 16.6 to 22.6% by weight and having a boiling point of 67 to 69 ° C. under normal pressure. Ternary azeotrope-like composition, preferably 67.0 wt% HFCPA, ethanol 13.4
A ternary azeotropic composition having a boiling point of 68 ° C. under normal pressure, which comprises 1% by weight of methylcyclohexane and 19.6% by weight of methylcyclohexane;

(H) Consists of 75.5 to 81.5% by weight of HFCPA, 12.5 to 18.5% by weight of ethanol and 3.0 to 9.0% by weight of n-octane, and 70 to 72 under normal pressure.
Ternary azeotrope-like composition having a boiling point of ℃, preferably HFC
A ternary azeotropic composition consisting of PA 78.5% by weight, ethanol 15.5% by weight and n-octane 6.0% by weight and having a boiling point of 71 ° C. under normal pressure;

(X) HFCPA 87.6 to 93.6% by weight, isobutyl alcohol 1.1 to 7.1% by weight and ethylcyclohexane 2.3 to 8.3% by weight, and 80.5 to 82.5 under normal pressure. Ternary azeotrope-like composition having a boiling point of ° C, preferably consisting of 90.6% by weight of HFCPA, 4.1% by weight of isobutyl alcohol and 5.3% by weight of ethylcyclohexane and having a boiling point of 81.5 ° C under normal pressure. Azeotropic composition;

(Co) HFCPA 79.8 to 85.8% by weight, 2-propanol 4.4 to 10.4% by weight and 2,2,2-trifluoroethanol 6.8 to 12.8
A ternary azeotrope-like composition, preferably HFCPA 82.8, consisting of 10% by weight and having a boiling point of 75.5-77.5 ° C under normal pressure.
% By weight, 7.4% by weight of 2-propanol and 2,2,2.
A ternary azeotropic composition consisting of 9.8% by weight of 2-trifluoroethanol and having a boiling point of 76.5 ° C. under normal pressure;

(F) HFCPA 78.0 to 84.0% by weight, 2-butanol 4.1 to 10.1% by weight and 1,
A ternary azeotrope-like composition consisting of 8.9-14.9% by weight of 4-difluorobenzene and having a boiling point of 79.5-81.5 ° C. under normal pressure, preferably 81.0% by weight of HFCPA, 2-
A ternary azeotropic composition comprising 7.1% by weight of butanol and 11.9% by weight of 1,4-difluorobenzene and having a boiling point of 80.5 ° C. under normal pressure; and the like. Such a composition is uniform at 20 ° C. without layer separation and is preferably used.

The method for preparing the composition of the present invention is not particularly limited, but the components (A), (B) and (C) may be mixed in an azeotropic composition ratio or an azeotrope-like composition ratio. It can also be prepared by mixing the three components in arbitrary proportions and distilling the mixture with a distillation apparatus that is usually used industrially.

The composition of the present invention exhibits high stability, but a stabilizer may be added if necessary. It is preferable that the stabilizer be distilled together with the stabilizer by a distillation operation. Specific examples of the stabilizer include nitro compounds such as nitroethane, nitropropane and nitrobenzene; acetylene alcohols such as 2-butyn-1ol and 3-hexyne-1-ol; epoxides such as glycidol, methylglycidyl ether and cyclohexene oxide. Kinds; dimethoxymethane,
1,2-dimethoxyethane, 1,4-dioxane, 1,
Ethers such as 3,5-trioxane;

Hexene, heptene, octene, 2,4
Unsaturated hydrocarbons such as 4-trimethyl-1-pentene, cyclopentene and cyclohexene; olefinic alcohols such as allyl alcohol, 2-buten-1-ol and 3-hexen-1-ol; methyl acrylate, acrylic acid Acrylic acid or methacrylic acid esters such as ethyl and vinyl methacrylate; Carboxylic acid esters such as chloroacetic acid methyl ester and bromoacetic acid ethyl ester;

Nitrile compounds such as chloroacetonitrile, bromoacetonitrile, α-chloropropionitrile, β-chloropropionitrile, α-bromopropionitrile; 1-chloroacetone, 1,3-dichloroacetone, 1-bromoacetone Carbonyl compounds such as 1,1-dibromoacetone; phenols such as phenol, trimethylphenol, thymol, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole and isoeugenol;

Dipropylamine, diisopropylamine, diisobutylamine, triethylamine, tributylamine, pyridine, N-ethylmorpholine, 2,2,2
Amines such as 6,6-tetramethylpiperidine and N, N'-diallyl-p-phenylenediamine; benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, chlorobenzotriazole and other triazoles And the like.

These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer to be used varies depending on its type, but is not particularly limited as long as it does not hinder the properties of the azeotrope-like composition of the present invention, and is usually 0.01 to 10 by weight of the azeotropic composition. %, And more preferably about 0.1 to 5%.

In addition, various surfactants can be added to the composition of the present invention, if necessary, in order to improve the detergency and the interfacial action. As the surfactant, sorbitan monooleate, sorbitan trioleate and other sorbitan fatty acid esters; polyoxyethylene sorbit tetraoleate and other polyoxyethylene sorbit fatty acid esters; polyoxyethylene monolaurate and other polyethylene glycol fatty acids Esters;

Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene polyoxypropylene cetyl ether; polyoxyethylene nonylphenyl ether and the like One or more nonionic surfactants such as polyoxyethylene alkyl phenyl ethers; polyoxyethylene oleyl amine, polyoxyethylene oleic acid amide and other polyoxyethylene alkyl amine fatty acid amides;

Further, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. Cationic surfactants and anionic surfactants are difficult to dissolve in an azeotropic composition, but when used in combination with a nonionic surfactant, the solubility is improved,
It is possible to synergistically improve detergency, interfacial action and the like.
The amount of surfactant used varies depending on its type,
Usually, it is about 0.1 to 20% by weight of the azeotropic composition,
About 0.3 to 5% is more preferable.

Although the composition of the present invention can be widely used for known washing and drying applications, it can be preferably used as a draining desiccant, a flux detergent, a washing solvent and a degreasing detergent.
The draining desiccant is, for example, an electronic component after washing with water,
By contacting various members such as optical parts with the azeotrope-like composition of the present invention, water adhering to the article can be dissolved and peeled off to facilitate drying.

More specifically, flux, grease,
Removers for oil, wax, ink, etc., electronic parts (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.), electrical parts, precision machine parts, resin processed parts, optical lenses, detergents for clothing, etc. A draining desiccant etc. can be mentioned. As the cleaning method, a conventionally used method such as dipping, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning or a combination thereof can be adopted. Also,
The composition of the present invention can be used for various applications such as a solvent for paints, an extractant, a heat medium and a foaming agent as well as a conventional chlorofluoroethane compound.

[0044]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The composition analysis of the distillate is
Gas chromatography (GC) method (apparatus: HITAC
HI-5000 company, column: FRONTIER L
AB Ultra ALLOY-1 or -CW).

Examples 1 to 19 (distillation experiment of ternary composition) Fractionation tower with reflux condenser corresponding to 7 theoretical plates (K, manufactured by Toshina Seiki Co., Ltd.)
A 100 mL glass distillation still equipped with a stirrer was set in the S-type rectification column). Component A shown in Table 1 below (HFCP
The predetermined amounts of A), B component (alcohols) and C component (saturated hydrocarbons, fluorinated alcohols or fluorinated aromatic hydrocarbons) were charged into a distillation pot so that the total amount became 100 g. 1 using an oil bath while stirring the contents
Heated to 10-140 ° C. About 30 minutes after the heating was started, the steam started to reflux at the top of the rectification column. In addition, 30
If the steam does not return after one minute, set the oil bath temperature to 1
The temperature was raised step by step at 0 ° C. The mixture was completely refluxed for 2 hours, and the temperature at the top of the column was stabilized. Then, the reflux ratio 2 /
At 40, withdraw 3-5 fractions of 5 mL each,
The composition of each fraction was analyzed by GC to determine the composition ratio. The composition of the third fraction was used to determine the azeotropic composition ratio.

The results of this distillation experiment are shown in Table 1. In addition,
"Temperature" in Table 1 is the temperature at the top of the column when the third fraction is withdrawn. “Liquid state” is the observation result of the liquid after the third fraction was extracted and left at 20 ° C. for a while.

[0047]

[Table 1]

Comparative Examples 1 to 3 (HFCPA and Distillation Experiment of Saturated Hydrocarbons) Using the same distillation apparatus as in Examples 1 to 19, HFCPA was used.
A binary azeotrope composition was prepared by distilling a mixed liquid in which each of 3 and 3 types of saturated hydrocarbons (cyclohexane, n-heptane, and n-octane) was combined. The azeotropic composition ratio determined by GC analysis was HFCPA 66.8% by weight, cyclohexane 33.2% by weight; HFCPA 87.2% by weight, n-heptane 12.8% by weight; HFCPA 92.2% by weight, n
-Octane 7.8% by weight; Both binary azeotropic compositions separated into two layers at 20 ° C.

Example 20 (Confirmation test by simple distillation) HF was determined by the composition ratio obtained by the precision distillation in Example 6 above.
CPA, 1-propanol and isooctane were charged into a flask so that the total amount was 100 g, and simple distillation was performed. As shown in Table 2, the distillate was separated into 7 fractions to stop the distillation. Table 2 shows the composition ratio charged and the composition ratio determined by GC analysis of each fraction.

[Table 2]

As is clear from Table 2, it was confirmed that the composition ratios of the test composition before and after distillation were almost the same.

Example 21 (Confirmation test by simple distillation) At the composition ratio obtained by precision distillation in Example 17, H
FCPA, 1-butanol and 1,2-difluorobenzene were charged into a flask so that the total amount was 100 g, and simple distillation was performed. As shown in Table 3, the distillate was divided into 6 fractions to stop the distillation. Table 3 shows the composition ratios of the charged materials and the composition ratios obtained by GC analysis of each fraction and the residue in the flask.
Shown in.

[0052]

[Table 3]

As is clear from Table 3, it was confirmed that the composition ratio before distillation, the composition ratio of each fraction and the composition ratio of the residue in the flask were almost the same.

[0054]

The effects of the present invention include 1, 1, 2,
2,3,3,4-heptafluorocyclopentane has no danger of ozone layer depletion or global warming. Further, the composition of the present invention has the effect of facilitating liquid management, recovery, regeneration treatment and the like without changing the composition during use as a cleaning agent or a desiccant desiccant.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 17/00 C11D 17/00 F term (reference) 4H003 DA15 DC03 ED03 ED21 ED26 ED28 FA46

Claims (2)

[Claims] 1. A type selected from (A) 1,1,2,2,3,3,4-heptafluorocyclopentane; (B) an alcohol having 2 to 5 carbon atoms and containing no fluorine atom; (C) Saturated hydrocarbon having 6 to 9 carbon atoms, 2 to 3 carbon atoms
A ternary azeotropic composition or a ternary azeotrope-like composition consisting of one selected from the group consisting of fluorinated alcohols and fluorinated aromatic hydrocarbons; 2. The ternary azeotropic composition or ternary azeotrope-like composition according to claim 1, which is uniform at 20 ° C. without layer separation.