JPH0334943A - Method for stabilizing azeotropic composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized azeotropic composition capable of exhibiting excellent inhibitory effects on metal corrosion and high stabilizing effects by adding nitro compound, etc., used as a stabilizer to an azeotropic composition composed of a specific fluorocarbon-based composition and methanol and stabilizing the aforementioned composition. CONSTITUTION:A fluorocarbon-based azeotropic composition is stabilized by adding at least one selected from nitro compounds, phenols, amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones and triazoles as a stabilizer in an amount of 1ppm to 10% (on the pts.wt. basis) based on an azeotropic composition composed of 1,1-dichloro-2,2,2-trifluoroethane (R123) and methanol thereto. The above-mentioned azeotropic composition is used as a solvent and especially effective in solving problems of defective contact when corrosion occurs in cleaning electronic, electrical parts, etc.

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] Applicant Mizu has already proposed an azeotropic composition consisting of 1,1-dichloro-2,2,2-trifluoroethane (R123) and methanol. There is. This azeotropic composition has a constant liquid composition and vapor composition, so it is suitable for steam cleaning of IC parts, precision machine parts, and various other products, but it is not always sufficient in terms of thermal stability under harsh conditions. I found out that there may not be any.

[Means for Solving the Problems] The present invention has been made to improve the above-mentioned stability, and includes adding nitro compounds, phenols, amines, and ethers to an azeotropic composition consisting of R123 and methanol. ,
A method for stabilizing an azeotropic composition, which comprises adding at least one member selected from the group consisting of amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones, and triazoles. It is something.

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

The numbers in parentheses indicate the composition by weight. When used in agents, etc., steam cleaning may be performed and it is necessary to thermally stabilize it. In particular, if the object to be cleaned or the material of the cleaning device is made of metal (iron, zinc, aluminum, copper, brass, various alloys, etc.), the effects of this metal will make it even more unstable.

The present invention relates to nitro compounds and phenols.

Good stabilization by adding at least one member selected from the group of amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, and triazoles to the present azeotropic composition. I can do it. These stabilizers can be used singly or as a mixture of two or more types, and when the use conditions of the present azeotropic composition are severe and a high stabilizing effect is required,
Mixed use of stabilizers is effective. The amount of the stabilizer added is not particularly limited, but is 1 ppm-10%, preferably ]O
ppm to 5%, more preferably 20 ppm to 3%.

As nitro compounds, general formula R-No2 (R carbon number 1
A chain or cyclic hydrocarbon group having 6 to 6 saturated or unsaturated bonds) is preferred, and is selected from nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene and the like. More preferred are nitromethane and nitroethane.

As the phenols, those represented by the following general formula are preferable, (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). Hydrocarbon group.) Phenol, O-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol catechol, isoeugenol.

0-methoxyphenol, 4,4°-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate.

It is selected from 2.6-di-t-butyl-p-cresol and the like. More preferably phenol, 4.4-
They are dihydroxyphenyl-2,2-propane and 2,6-di-t-butyl-p-cresol.

As the amines, those represented by the following general formula are preferable, RN (R') 2 , (R) 2-N CR' )
2, (R) 2-NR'(R)2N-R'-N-
(R″)2 R-CHN (R′) 2-R″-N-(R″′) 2
(R)2N-R'-NH-R"-N-(R"')2(
R)2N-(R'NH)4-R'', R-NH-R'
, (R)2-N-OR' [where R, R', R
", R"' is a hydrogen atom or a chain or cyclic hydrocarbon group having 1 to 8 carbon atoms and having a saturated or unsaturated bond] Pentylamine, hexylamine, diisopropylamine, diisobutylamine di-n-propylamine,
Diallylamine, triethylamine, N-methylaniline pyridine picoline, morpholine, N-methylaniline.

Triallylamine, allylamine, α-methylbenzylamine, methylamine dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine isopropylamine, dipropylamine, butylamine, isobutylamine, sec-butylamine, tertiary-butylamine, dibutylamine, tributylamine, Dibentylamine, tripentylamine 2-edelhexylamine, 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: HO-R-0-R'HO-R-0-R'-0-R''
HO-R-OHR-0-R'-C:HR"
R-0-R"O-R'L-勺"R-0-CH-R',R-0-R'-(OR"
)zHe(4)" [Here, R, R', R" are chain or cyclic hydrocarbon groups having 1 to 10 carbon atoms and having a saturated or unsaturated bond.] 14-dioxane 12-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 propagyl 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 monobenzyl ether, dipentyl ether, allyl ethyl ether, diisopentyl ether, diallyl ether, butyl glycidyl ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether .

It is selected from vinyl glycidyl ether, 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.

The amylenes 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-R'-COOR' [where R2 R', R'' is a hydrogen atom or a chain having 1 to 6 carbon atoms and a saturated or unsaturated bond. or cyclic hydrocarbon group] Methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, butyl acrylate, phenyl acrylate, It is selected from 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, (RO)SP, (R-R'-0)3P, (R
O)2POR'.

[Here, R, R', R'', and R'' are hydrogen atoms or chain or cyclic hydrocarbon groups having 1 to 18 carbon atoms and having a saturated or unsaturated bond] Triphenylphosphite, 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 dipropylene glycol pentaerythritol tetraphosphite, trilauryl trithiophosphite, bis(tridecyl)
Pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-ditertiary)
butylphenyl) phosphite, etc.

More preferred is triphenylbosphite and tributylphosphite.

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. ] Epoxides are preferably selected from 1,2-butylene oxide, epichlorohydrin, propylene oxide, 2,3-butylene oxide, styrene oxide, etc., and more preferably 1,2-butylene oxide.

It is epichlorohydrin.

As the furans, those represented by the following general formula are preferred, [where R, R', R'' are hydrocarbon groups having 1 to 2 carbon atoms and saturated and/or unsaturated bonds, cotetrahydrofuran, N -Methylvirol 2-Methylvirol, 3-
It is selected from methylpyrol and the like, and N-methylpyrol is more preferred.

As alcohols, those represented by the following general formula are preferable, R-OH, NH2-R-OHR-0-R'-
OH, R-R'-OH [where R, R' has 1 to 1 carbon atoms
Chain or cyclic hydrocarbon group having 6 saturated or unsaturated bonds] Ethanol, 5ec-butanol, tert-butanol, allyl alcohol, benzyl alcohol, propanol, isopropanol, tert-amyl alcohol, 1-amino-2-propanol, Propargyl alcohol, isobutanol.

It is selected from butanol, 3-methyl-pentyn-3-ol, 1-methoxy-2-propanol, 3-methyl-butyl-3-ol, 2-methyl-3-butyn-3-ol, and more. Preferred is 5ec-butanol propargyl alcohol.

As the ketones, those represented by the following general formula are preferable, and (R)ico, R-CO-R', (RN(:
0) 2゜ [Here, R, R', R", R"' are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms and having saturated/unsaturated bonds] Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonate Amide, maleic acid hydrazide, phthalic acid hydrazine formamide N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylpropionamide,
2-pyrrolidone, N,N.

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

The triazoles are preferably those represented by the following general formula: A chain or cyclic hydrocarbon group having a saturated or unsaturated bond. X is a halogen atom. ] 2- (2"
-Hydroxy-5°-methyl-phenyl)benzotriazole, 2-(2'hydroxy-3'-tertiary-
Butyl 5°-methylphenyl)-5-chloro-ben■ Citriazole 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 15 The following tests were conducted for the purpose of confirming the effects of the method for stabilizing an azeotropic composition of the present invention.

In accordance with JIS-K1600, mild steel pieces were placed in each of the liquid phase and gas phase of the stabilized compositions shown in Tables 1 and 2 below, and the corrosion status of the mild steel pieces was observed after 48 hours had elapsed.

The results are shown in Tables 1 and 2.

Note that A represents the R123/methanol azeotropic composition.

No. table 0: No corrosion, ○: No corrosion.

△・Slightly corroded, ×; Considerably corroded. table 0: No corrosion, ○: No corrosion.

△: Slightly corroded, ×: Significantly corroded [Effects of the invention]

Claims (1)

[Claims] (1) An azeotropic composition consisting of 1,1-dichloro-2,2,2-trifluoroethane and methanol is added with nitro compounds, phenols, amines, ethers, amylenes, esters, and organic phosphorus. 1. A method for stabilizing an azeotropic composition, which comprises adding at least one member selected from the group consisting of phytes, epoxides, furans, alcohols, ketones, and triazoles.