JPH0374339A - Method for stabilizing fluorinated hydrocarbon based pseudoazeotropic composition - Google Patents

Abstract

PURPOSE:To suppress corrosion of a metal by adding a specific compound as a stabilizer to a pseudoazeotropic composition consisting of two or more compounds of 1,1-dichloro-2,2,3,3,3-pentafluoropropane, etc., and alcohols to stabilize the composition. CONSTITUTION:At least one compound selected from nitro compounds, phenols, amines, ethers, amylenes, esters, organophosphites, epoxides, furans, alcohols, ketones and triazoles as a stabilizer is added to a pseudoazeotropic composition consisting of either two or more compounds of 1,1-dichloro-2,2,3,3,3- pentafluoropropane, 1,3-dichloro-1,2,2,3,3-pentafluoropropane and 1-chloro-2,2,3,3- tetrafluoropropane to stabilize the above-mentioned composition. The stabilizer is used at an amount of 1ppm to 10wt.% based on the above-mentioned composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for stabilizing a fluorinated hydrocarbon-based pseudoazeotropic composition.

[Prior Art and Problems to be Solved by the Invention] Applicant Mizu has already developed 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R225ca), 1,3dichloro-1,2, 2,3,3-pentafluoropropane (R2
25cb) 1-chloro-2,2,3,3-tetrafluoroethane (R244ca) and one of methanol, ethanol, and isopropyl alcohol. These pseudo-azeotropic compositions keep the liquid composition and vapor composition almost constant, so they can be used for IC parts,
It is suitable for steam cleaning of precision mechanical parts and various other articles, but it is 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 of R225ca and R225cb.

A pseudoazeotropic composition consisting of any two or more of R244ca and any one of alcohols such as methanol, ethanol, and impropanol, including nitro compounds, phenols, amines, ethers, amylenes, esters, Organic phosphites, epoxides, furans,
The present invention relates to a method for stabilizing a pseudoazeotropic composition, characterized by adding at least one selected from the group of alcohols, ketones, and triazoles. A pseudoazeotropic composition stabilized according to the present invention Examples are as follows.

0 indicates the composition by weight% R225ca/R225cb/methanol (l-98
/1~98/1~16) R225ca/R244ca/
Methanol (45-98/1-54/1-16) R2
25cb/R244ca/methanol (30-98/
l~6971~16) R225ca/R225cb/R
244ca/methanol (14~96/2~84/l~
83/1~16) R225ca/R225cb/ethanol (1~98/1~98/1~24) R225ca
/R244ca#Knorr (45~98/1~54/
l~24) R225cb/R244ca/ethanol
(30-98/l-69/1-24) R225ca/R
225cb/R244ca/ethanol (14-96/
2-84/1-83/1-24) R225ca/R22
5cb/isopropanol (1~98/1~98/1~
35) R225ca/R244ca/Isofuropanol (45-98/1-54/1-35) R225cb/R
244ca/Isofushinor (30-98/1-69/
1-35) R225ca/R225cb/R244ca
/Isopropanol 14-96/2-84/1-83/
l~35) This azeotropic composition can be used as a solvent for various purposes, but when used in flux cleaning agents, degreasing cleaning agents, dry cleaning cleaning agents, etc., steam cleaning may be performed and thermal need to be stabilized. Especially washing?
If the object to be disputed or the material of the cleaning equipment is metal (iron, zinc, aluminum, copper, brass, various alloys, etc.), the effects of this metal will make it even more unstable.

The present invention provides nitro compounds, phenols, amines,
It is better stabilized by adding at least one member selected from the group of ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones, and triazoles to the azeotropic composition. can be converted into These stabilizers can be used alone or as a mixture of two or more, and when the use conditions of the azeotropic composition are severe and a high stabilizing effect is required, stabilizing agents can be used. Mixed use of agents is effective. The amount of the stabilizer added is not particularly limited, but is 11) pm to 0% by weight based on the present azeotropic composition.
, preferably IQppm ~ 5%, more preferably 10
0 ppm to 3%. As the nitro compounds, those represented by the general formula R-NO7 (R: a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms and a saturated or unsaturated bond) are preferred, and include nitromethane, nitroethane, 1-nitropropane. , 2-nitrofuropane, nitrobenzene, etc. More preferred are nitromethane and nitroethane. As the phenols, those represented by the following general formula are preferable, (where R, R', R'',
R"' is OH or a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms and having a saturated or unsaturated bond.) Phenol, 0-cresol, m-cresyl, p-cresol, thymol, p-tert-butylphenol , tertiary-butylcatechol, catechol, isoeugenol, 〇-methoxyphenol, 4,4°-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,
It is selected from 6-di-t-butyl-p-cresol and the like. More preferably, phenol, 4,4-dihydroxyphenyl-2,2-propane, 2,6-di-t
-butyl-p-cresol.

The amines are preferably those represented by the following general formula: RN(R')2. (R)2-NCR')2,
(R)2-NR'(R) 2N-R'-N-(R'')
2R-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''' 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-normalpropyl amine,
Diallylamine, triethylamine, N-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, Propylamine, butylamine, isobutylamine, sec-butylamine, tertiary-butylamine, dibutylamine, tributylamine,
Dibenzylamine, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline,
It is selected from N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamyl, and the like. More preferred are diisopropylamine and diallylamine.

The ethers are preferably those represented by the following general formula, HO-R-0-R', HO-R-0-R'-0-R''
, HO-R-OH.

R-0-R'-CH-R''R-0-R'-0-
R"L-1℃ J R-0-CH-R', R-0-R'-(OR
″) 2′-0J (Here, R, R′, and R″ are chain or cyclic hydrocarbon groups having 1 to 10 carbon atoms and having a saturated or unsaturated bond.) 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 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 mono Butyl ether, ethylene glycol monobenzyl ether, diallyl ether, allyl ethyl ether, diisopentyl ether, diallyl ether, butyl glycidyl ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether, vinyl glycidyl ether,
It is selected from dimethyl ether, diethyl ether, di-normal propyl ether, dibutyl ether, 12-dimethoxyethane, trimethoxyethane, triethoxyethane and the like.

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

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

As the esters, those represented by the following general formula are preferred, and those represented by the following are preferred: (RO)3P, (R-R'-0), P(RO)2
po+t RO-R'-C:OOR'' (where R, R', R'' are hydrogen atoms or carbon atoms 1 to 6
(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 meccrylate, 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.

Organic phosphites have the following general formula (where R
, R′, R″, R″′ are hydrogen atoms or carbon atoms 1 to 18
(chain or cyclic hydrocarbon group with saturated or unsaturated bonds) 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 dibrobylene glycol pentaerythritol tetraphosphite, trilauryl trithiophosphite, bis(tridecyl)
Pentaerythritol diphosphite, bis(norylphenyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-ditertiary)
butylphenyl) bosphite, etc.

More preferred are triphenyl phosphite and tributyl phosphite.

The eboxides are preferably those represented by the following general formula: RO, XRO (wherein, R is a chain or cyclic hydrocarbon group having 1 to 8 carbon atoms and having a saturated or unsaturated bond).

2 X is a halogen atom) It is selected from 1.2-butylene oxide, epichlorohydrin, propylene oxide, 2.3-butylene oxide, styrene oxide, etc., and 1.2-butylene oxide and epichlorohydrin are more preferable.

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

As alcohols, those represented by the following general formula are preferable, R-OH, NH2-R-DH, R-0-R'-OH, R
-R'-OH (Here, R, R' are chain or cyclic hydrocarbon groups having saturated and/or unsaturated bonds having 1 to 6 carbon atoms.) sec-butanol tert-butanol, allyl alcohol, benzyl Alcohol tert-amyl alcohol 1-amino-2-probanol, propargyl alcohol, inbutanol, butanol, 3-methyl-pentyn-3-ol, 1-methoxy-2-propanol,
3-methyl-1-butyl-3-ol, 2-methyl-3
-butyn-3-ol, etc., and more preferably sec-butanol and propargyl alcohol.

As the ketones, those represented by the following general formula are preferable, (R)2GO,R-GO-R', (RNCO)2゜(
Here, R, R', R'', R''' are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms and saturated and/or unsaturated bonds) Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, maleic acid Hydrazide, hydrazine phthalate, formamide N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylpropionamide, 2-pyrrolidone, N,N,N',N'-tetramethylurea, N -Methylpyrrolidone, etc., and more preferably methylisobutylketone and 2-pyrrolidone.

As triazoles, those represented by the following general formula are preferable, and A chain or cyclic hydrocarbon group having ~16 saturated or unsaturated bonds. -3'-tert-butyl-5'methylphenyl)-5-chloro-benzotriazole, L, 2,3-benzotriazole, 1-[(N,N-bis-2-ethylhexyl)aminomethylcobenzotriazole, etc. Among them, 1,2,3-benzotriazole is more preferable.

[Example] For the purpose of confirming the effect of the method for stabilizing an azeotropic composition of the present invention, a Fukiage 6 test was conducted on the compositions shown in Table 1.

According to JIS-1600, mild steel pieces were placed in each of the liquid phase and gas phase of the stabilizing composition shown in Table 1 below, and 48
The corrosion status of the copper pieces was observed after the passage of time.

The results are shown in Tables 3-15. Although the attached examples show some of the results of the present invention, similarly good stabilizing effects are obtained for all of the pseudoazeotropic composition systems A to L.

Table 1 1 Table 3 0: No corrosion, △: Slight corrosion, ○: No corrosion ×: Corrosion Table 2 0 Table 4 0: No corrosion, ○: No corrosion △ Slight corrosion , ×: Corrosion Table 5 0: No corrosion, ○: No corrosion △: Slight corrosion, ×: Corrosion 3 Table 7 0: No corrosion, ○: No corrosion △: Slight corrosion, ×: Corrosion Table 6 0: No corrosion, ○ No corrosion △: Slight corrosion, ×: Corrosion 4 Table 8 0: No corrosion, ○: No corrosion △: Slight corrosion, ×; Corrosion Table 9 0: No corrosion, △: Slight corrosion, ○: No corrosive corrosion ×; Corrosion 7 Table 11 0: No corrosion, △: Slightly corroded, ○: No corrosive corrosion ×; Corrosion Yes Table 10 0: No corrosion, ○: No corrosion △: Slight corrosion, ×: Corrosion 8 Table 12 0: No corrosion, ○: No corrosion △: Slight corrosion, ×: Corrosion Table 13 0: No corrosion, ○: No corrosion △: Slight corrosion, ×: Corrosion Table 15 △: Slight corrosion, ; Corrosion Table 14 0: No corrosion, ○: No corrosion △: Slightly corroded, ×: Corrosion 2 [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, if corrosion occurs during cleaning of electronic parts, electrical parts, etc. with a pseudo-azeotropic composition, the problem of contact failure occurs, but the stabilization method of the pseudo-azeotropic composition of the present invention is effective as a countermeasure against such problems. .

Claims (2)

[Claims] (1) 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,2,2,3
, 3-pentafluoropropane, 1-chloro-2,2,
Nitro compounds, phenols, amines, ethers, amylenes, esters, organic phosphites are added to the pseudoazeotropic composition consisting of any two or more of 3,3-tetrafluoropropanes and one alcohol. A method for stabilizing a fluorinated hydrocarbon-based pseudoazeotropic composition, which comprises adding at least one member selected from the group consisting of epoxides, epoxides, furans, alcohols, ketones, and triazoles. (2) The stabilization method according to claim 1, wherein the alcohol is methanol, ethanol, or isopropanol.