JPH02157234A - Stabilization of azeotropic composition - Google Patents

Abstract

PURPOSE:To increase the heat stability of an azeotropic composition composed of 1,1,2-trichlorotrifluoroethane, 1,1-dichlorethane, and/or methanol, etc., by adding a nitro compound, a phenol compound, or an amine to the composition. CONSTITUTION:A fluorocarbon azeotropic composition which is composed of at least one selected from 1,1,2-trichlorotrifluoroethane, 1,1-dichloroethane or additionally methanol, ethanol, 2,2-dimethylbutane is mixed with a stabilizer in an amount of 100ppm to 3% whereby the thermal stability is increased. The stabilizer is, for example, a nitro compound such as nitromethane, a phenol, an amine such as diisopropylamine, an ether such as 1,4-dioxan, an amylene, an ester, an organic phosphite or an epoxide. The azeotropic composition is used in vapor-washing of IC parts or precision machine parts without metal corrosion.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for stabilizing a fluorocarbon azeotropic composition.

[Prior art and problems to be solved by the invention] Japanese Patent Publication No. 46-40601 and U.S. Patent No. 3539462
According to the specification etc., 1,1,2-trichlorotrifluoroethane (hereinafter referred to as R113), 1,1-dichloroethane, methanol, ethanol, improper tool,
tert-butanol, 22-dimethylbutane or 2.
Azeotropic compositions comprising one or two of 3-dimethylbutane and the like are known.

These azeotropic compositions have constant liquid and vapor compositions and are therefore suitable for steam cleaning of IC parts, precision machine parts, and various other articles, but they are not necessarily sufficient in terms of thermal stability.

[Means for Solving the Problems] The present invention has been made to improve the above-mentioned stability, and includes 1,1,2-trichlorotrifluoroethane and 1.
an azeotropic group acid consisting of 1-dichloroethane, or one selected from methanol, ethanol, isopropanol, tert-butanol, 2,2-dimethylbutane or 2,3-dimethylbutane, 1,1,2-trichlorotri An azeotropic composition consisting of fluoroethane and 1,1-dichloroethane is combined with nitro compounds, phenols, amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, and ketones. The present invention relates to a method for stabilizing an azeotropic composition, which comprises adding at least one member selected from the group consisting of triazoles and triazoles.

The azeotropic compositions stabilized according to the invention are as follows.

Figures in parentheses indicate composition (wt%) R113/1.1-dichloroethane
(77/23) R113/1.1-nkuoxtan/methanol (90,1/4.215/7) R113
/1.1-jik oaxkun/ex/-4 (86,4/8
．． 615.0) R113/1.1-dichloroethane/isopropanol (85.7/l 1.4/2.9) R1
13/1.1-dichloroethane/1ert-7tanol (84,8/1.0/14.21R113/1.1-dichloroethane/2,2-dimethyl1k (65,6/1
5.5/18.9) R113/1.1-dichloroethane 72.3-dimethyl 1kun (78.9/15.215.9) The azeotropic composition can be used for various purposes as a solvent, but it is Cleaning agent, degreasing agent.

When used as a detergent for dry cleaning, etc., steam cleaning may be performed and it is necessary to thermally stabilize it. In particular, if the object to be cleaned or the cleaning equipment is made of metal (iron, zinc,
Aluminum, copper, brass.

various alloys, etc.), it becomes even more unstable due to the influence of this metal.

The present invention relates to nitro compounds and phenols.

Good stability can be obtained by adding at least one member selected from the group of amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, and triazoles to the azeotropic composition to be stabilized. can be converted into These stabilizers can be used singly or as a mixture of two or more types, and when the use conditions of the azeotropic composition are severe and a high stabilizing effect is required, the stabilizer can be used. Mixed use is effective. The amount of the stabilizer added is not particularly limited, but is 1 ppm = 10%, based on parts by weight based on the azeotropic composition.
Preferably 1091m to 5%, more preferably 110m
It is 0 pp to 3%.

As the nitro compounds, those represented by the general formula R-NO, (R, a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms and a saturated or unsaturated bond) are preferable, including nitromethane,
It is selected from nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene and the like. More preferred are nitromethane and nitroethane.

The phenols are preferably those represented by the following general formula, where R, R', R", and R"' are OH or a chain or cyclic group having saturated or unsaturated bonds having 1 to 6 carbon atoms. ) Phenol, 0-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, ineugenol, 〇-methoxyphenol, 4.4-dihydroxyphenyl- 2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate.

2.6-di-t-butyl-p-cresol and the like. More preferably phenol, 4,4-
It is dihydroxyphenyl-2,2-propane.

As the amines, those represented by the following general formula are preferable, R-N (R') x , (R) i-N (R'
) *, (R) 2-NR'(R), NR' -
N-(R″).

R-CHN(R'), -R"-N-(R"")2(R)
, N-R-NH-R''-N-(R''').

(R)2N-(R'NH)--R", R-NH-R
' , (R)2-N-OR' [where R, R
', R'', R''' are hydrogen atoms or chain or cyclic hydrocarbon groups having saturated or unsaturated bonds having 1 to 8 carbon atoms] Pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine ,
Diallylamine, triethylamine, N-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine.

Triallylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine butylamine, isobutylamine, sec-butylamine, tertiary-butylamine, dibutylamine, tributylamine , dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N, N-dimethylaniline, N,
It is selected from N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamyl, and the like. More preferably diisopropylamine,
It is diallylamine.

The ethers are preferably those represented by the following general formula, lo-R-0-R', 110-R-0-R'-0-
R”+1O-R-011.

R-0-R-CH-R''R-0-R'-0-R
"-1stEdition"R-0-CH-R'R-0-R'-(OR"
)z'-n-' [Here, R, R', and R'' are chain or cyclic hydrocarbon groups having saturated or unsaturated bonds and having a carbon number of 1 to IO.] 1.4-dioxane, 1, 2-butanediol, isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether ethyl isobutyl ether, ethyl isopropyl ether ethyl isopentyl ether ethyl naphthyl ether, ethyl vinyl ether,
Ethyl phenyl ether, anisole anethole, ethyl propargyl ether.

Ethyl propyl ether, ethyl methyl ether, ethylene glycol, methyl glycidyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether.

Ethylene glycol dimethyl ether Ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Dipentyl ether, allyl ethyl ether Diisopentyl ether, diallyl ether, butyl glycidyl ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether.

Vinyl glycidyl ether is selected from dimethyl ether, diethyl ether, di-normal propyl ether, dibutyl ether, 1,2-dimethoxyethane, trimethoxyethane, triethoxyethane and the like.

More preferred are 1,4-dioxane, butyl glycidyl ether, and 1,2-dimethoxyethane.

Amicins are preferably selected from α-amylene, β-amylene, γ-amylene, α-isoamylene, β-isoamylene, etc., and β-amylene is more preferable.

The esters are preferably those represented by the following general formula, (RO)iP, (R-R'-0), P, (1
10) 2POR'.

RO-R'-(OOR" [Here, R, R', R" are hydrogen atoms or have 1 to 6 carbon atoms.
Chain or cyclic hydrocarbon group having a saturated or unsaturated bond] Methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid It is selected from methyl, butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, ethyl carbamate, methyl carbamate, methyl salicylate, etc., and methyl acetate and methyl salicylate are more preferred.

As the organic phosphites, those represented by the following general formula are preferable, [where R, R', R", and R"' are hydrogen atoms or chains having 1 to 18 carbon atoms and having saturated or unsaturated bonds. or cyclic hydrocarbon group cotriphenylphosphite, tris(nonylphenyl)
Phosphite, triethyl phosphite, tris(2-
ethylhexyl) phosphite, tridecyl phosphite, tributyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl monotridecyl phosphite,
Dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dibrobylene glycol bentaerythritol tetraphosphite, trilauryl trithiophosphite, bis(tridecyl)
Pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-ditertiary)
butylphenyl) phosphite, etc.

More preferably triphenyl phosphite.

It is tributyl phosphite.

As the epoxides, those represented by the following general formula are preferred: RO, XRO.

[Here, R is a chain or cyclic hydrocarbon group having 1 to 8 carbon atoms and having a saturated or unsaturated bond. X is a halogen atom. ] Preferred epoxides include 1,2-butylene oxide, epichlorohydrin, propylene oxide, and 2,3-butylene oxide.

It is selected from styrene oxide, etc., and 1,2-butylene oxide is more preferable.

It is epichlorohydrin.

As the furans, those represented by the following general formula are preferable, [where R, R', R'' are hydrocarbon groups having 1 to 2 carbon atoms and saturated and/or unsaturated bonds] Tetrahydrofuran , N-methylvirol.

It is selected from 2-methylpyrrole, 3-methylpyrrole, etc., and N-methylpyrrole is more preferred.

As alcohols, those represented by the following general formula are preferable:
-R'-OH, R-R'-OH [where R, R' are chain or cyclic hydrocarbon groups having 1 to 6 carbon atoms and a saturated or unsaturated bond] 5ec-butanol, allyl alcohol, Benzyl alcohol, propatool, tert-amyl alcohol, l-amino-2-propertool, propargyl alcohol, isobutanol, butanol, 3-methyl-pentyn-3-ol, l-methoxy-2-propertool, 3
-Methyl-1-butyl-3-ol, 2-methyl-3-
It is selected from butyn-3-ol and the like, and more preferably propargyl alcohol.

Preferably, the ketones are those represented by the following general formula, (R)*CO, R-CO-R', (RNCO)2
Hydrocarbon group having a saturated/unsaturated bond with a number of degrees from 1 to 4] Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, maleic acid hydrazide, phthalic acid hydrazine, formamide, N-methylformamide, N,N-dimethyl Formamide, N,N-diethylformamide, N-methylpropionamide, 2
-pyrrolidone, N,N.

It is selected from N', N''-tetramethylurea, N-methylpyrrolidone, etc., and more preferably methylisobutylketone and 2-pyrrolidone.

As triazoles, those represented by the following general formula are preferred, where R, R', R", R" are hydrogen atoms or carbon atoms R
-N, -R'-N-R" [Here, R, R', R", R"' is a hydrogen atom or a chain or cyclic hydrocarbon having 1-16 carbon atoms and a saturated or unsaturated bond. group. X is a halogen atom.]2-(2°-
Hydroxy-5°-methyl-phenyl)benzotriazole, 2-(2°-hydroxy-3°-tertiary)
Butyl-5°-methylphenyl)-5-chloro-benzotriazole, 1,2.3-benzotriazole, 1
-[(N,N-bis-2-ethylhexyl)aminomethyl]benzotriazole, etc., and 1,2.3-benzotriazole is more preferred.

[Examples] Examples 1 to 91 The following tests were conducted for the purpose of confirming the effects of the method for stabilizing an azeotropic composition of the present invention.

According to JIS-1600, mild steel pieces are placed in each of the liquid phase part and the gas phase part of the stabilizing composition shown in Tables 1 to 7 below,
The corrosion status of the mild steel piece was observed after 48 hours had elapsed.

The results are shown in Tables 1 to 7.

Table 1 (): Mixing ratio [wt%] 0: No corrosion, ○: No corrosion.

△: Slightly corroded, x: Considerably corroded. table ) is the mixing ratio [wt%] 0: No corrosion, ○: No corrosion.

Δ: Slight corrosion.

×; Significant corrosion No. table ) is the mixing ratio [wt%] 0: No corrosion, ○: No corrosion.

△・Slightly corroded, ×; Considerably corroded. table ) is the mixing ratio [wt%] 0: No corrosion, ○: No corrosion.

△: Slightly corroded, ×: Significantly corroded. table (): Mixing ratio [gravity M%] 0: No corrosion, ○: No corrosion Δ: Slightly corroded, ×: Significantly corroded. table (): Mixing ratio [wt%] (): Mixing ratio [%] 0: No corrosion, ○: No corrosion.

△: Slight corrosion, X: Considerable corrosion 0: No corrosion, ○: No corrosion.

△: Slightly corroded, ×: Significantly corroded [Effects of the invention] As is clear from the examples, the method for stabilizing an azeotropic composition of the present invention has an excellent metal corrosion inhibiting effect, and a high stabilizing effect can be obtained. . In particular, when corrosion occurs during cleaning of electronic parts, electrical parts, etc. with an azeotropic composition, a problem of contact failure occurs, but the method for stabilizing an azeotropic composition of the present invention is effective as a countermeasure against such problems.

Claims (1)

[Claims] (1) Azeotropic composition consisting of 1,1,2-trichlorotrifluoroethane and 1,1-dichloroethane, or methanol, ethanol, isopropanol, tert-
An azeotropic composition consisting of one selected from butanol, 2,2-dimethylbutane or 2,3-dimethylbutane, 1,1,2-trichlorotrifluoroethane and 1,1-dichloroethane, nitro compounds and phenol. amines 2 ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols,
A method for stabilizing an azeotropic composition, comprising adding at least one member selected from the group of ketones and triazoles.