JP2717090B2 - Method for stabilizing hydrogen-containing chlorofluoropropanes - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for stabilizing hydrogen-containing chlorofluoropropanes.

[Problems to be Solved by the Prior Art and the Invention] The present applicant has already reported that CF ₃ CF ₂ CHCl ₂ (R225ca) and / or CCLF ₂ CF ₂ CHClF
(R225cb) has been proposed for various applications of hydrogen-containing chloropropanes.

Among these various uses, it has been found that, in particular, when steam cleaning is repeatedly performed, thermal stability may not always be sufficient.

[Means for Solving the Problems] The present invention has been made to improve the above-mentioned stability. The present invention relates to a method for converting a hydrogen-containing chloropropane compound comprising R225ca and / or R225cb into a nitro compound, a phenol, and an amine. The present invention relates to a method for stabilizing by using at least one selected from the group consisting of phenols, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones and triazoles.

R225ca and / or R225cb can be used for various purposes as a solvent. However, when used in flux detergents, degreasing detergents, dry cleaning detergents, etc., they may be subjected to steam cleaning and must be thermally stabilized. There is. Especially,
If the object to be cleaned or the material of the cleaning device is a metal (iron, zinc, aluminum, copper, brass, various alloys, etc.), it becomes more unstable due to the influence of the metal.

The present invention relates to nitro compounds, phenols, amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols,
By adding at least one member selected from the group consisting of ketones and triazoles to the above-mentioned hydrogen-containing fluorinated chloropropane to be stabilized, it can be well stabilized. These stabilizers can be used singly or as a mixture of two or more kinds. When the conditions for using hydrogenated chlorofluoropropanes are severe and a high stabilizing effect is required, a stable It is effective to use a mixture of agents. The amount of the stabilizer added is not particularly limited, but is 1 ppm to 10%, preferably 10 ppm to 5%, and more preferably 100 ppm to 3% by weight based on the weight of the hydrogen-containing chlorofluoropropane. %.

As the nitro compounds, a compound represented by the general formula R-NO ₂ (R;
(Chain or cyclic hydrocarbon group having a saturated or unsaturated bond of 6 to 6), and is selected from nitromethane, 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 hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms). Phenol, o-cresol, m-cresol, p -Cresol, thymol, p-tert-butylphenol,
It is selected from tertiary butyl catechol, catechol, isoeugenol, o-methoxyphenol, bisphenol A, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-t-butyl-p-cresol, and the like. More preferred are phenol and bisphenol A.

As the amines, those represented by the following general formula are preferable: RN (R ') ₂ , (R) _2- N (R') ₂ , (R) _2- N
R ′, (R) ₃ N, RN, _{(R) 2 N-R'-} N- (R ") 2 R-CHN (R ') 2 -R" -N- (R) 2 (R) 2 N-R'-NH-R "-N- _{(R) 2 (R) 2} N- (R'NH) 4 -R ", R-NH-R ', (R) 2
-N-OR '[where R, R', R ", R is a hydrogen atom or a carbon atom of 1 to 8
A chain or cyclic hydrocarbon group having a saturated or unsaturated bond of: pentylamine, hexylamine, diisopropylamine, diisobutylamine, diallylamine, triethylamine, N-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine, tri Allylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, secondary butylamine, tertiary butylamine, dibutylamine, tributylamine , Dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N, N
-Dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine and the like. More preferably,
Diisopropylamine and diallylamine.

As the ethers, those represented by the following general formula are preferable: R—O—R ′, HO-R-O-R ', HO-R-O-R'-OR ", R—O—R′—O—R ″, R-O-R '-(OR ") ₂ [where R, R' and R" are a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 10 carbon atoms. 1,4-dioxane, 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 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, diglycol Propyl ether,
Ethyl glycidyl ether, vinyl glycidyl ether, dimethyl ether, diethyl ether, dibutyl ether, 1,2-dimethoxyethane, trimethoxyethane,
It is selected from triethoxyethane and the like.

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

Amylenes are preferably selected from α-amylene, β-amylene, γ-amylene, α-isoamylene, β-isoamylene, and more preferably β-amylene.
Amylene.

As the esters, those represented by the following general formula are preferable, (R ') _2- N-COO-R', RO-R'-COOR "[where R, R ', R" is a hydrogen atom or a chain having a saturated or unsaturated bond having 1 to 6 carbon atoms or Cyclic hydrocarbon group] Methyl acetate, ethyl acetate, propyl acetate, normal butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, butyl acrylate, phenyl acrylate, acrylic It is selected from allyl acid, caprolactam, ethyl carbamate, methyl carbamate, methyl salicylate and the like, and more preferably methyl acetate and methyl salicylate.

As the organic phosphites, those represented by the following general formula are preferable: (RO) ₃ , (R—R′—O) ₃ P, (RO) ₂ POR ′, [Where R, R ', R ", R are a hydrogen atom or a linear or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 18 carbon atoms] triphenyl phosphite, 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 Phyte, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol pentaerythritol tetraphosphite, trilauryl trithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaeryth Litol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-ditert-butylphenyl) phosphite, and the like.

More preferred are triphenyl phosphite and tributyl phosphite.

The epoxides are preferably those represented by the following general formula: RO, XRO, wherein R is a linear or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 8 carbon atoms. X is a halogen atom. The epoxides are preferably selected from 1,2-butylene oxide, epichlorohydrin, propylene oxide, 2,3-butylene oxide, styrene oxide and the like, and more preferably 1,2-butylene oxide and epichlorohydrin. .

As the furans, those represented by the following general formula are preferable, [Where R, R ', R "are a hydrocarbon group having a saturated and / or unsaturated bond having 1 to 2 carbon atoms] selected from tetrahydrofuran, N-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole and the like. Is
More preferably, it is N-methylpyrrole.

As the alcohols, those represented by the following general formula are preferable, and R-OH, NH ₂ -R-OH, R-O-R'-OH, R-
R'-OH [where R and R 'are a chain or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 6 carbon atoms] methanol, sec-butanol, tert-butanol, allyl alcohol, benzyl alcohol , Propanol,
Isopropanol, tert-amyl alcohol, 1-amino-2-propanol, propargyl alcohol, isobutanol, butanol, 3-methyl-1-pentyne-3-
All, 1-methoxy-2-propanol, 3-methyl-1
-Butyn-3-ol and the like, and more preferably, sec-butanol and propargyl alcohol.

As the ketones, those represented by the following general formula are preferable, and (R) ₂ CO, R-CO-R ', , R-CO-NH-R ', R-CON- (R') 2, (R) 2 NCON
(R ') ₂ , [Where R, R ′, R ″, and R are a hydrogen atom or
A hydrocarbon group having a saturated / unsaturated bond of 4] acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, maleic hydrazide,
Phthalic acid hydrazide, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylpropionamide, 2-pyrrolidone, N,
It is selected from N, N ', N'-tetramethylurea, N-methylpyrrolidone and the like, and more preferably methyl isobutyl ketone, 2-pyrrolidone.

As the triazoles, those represented by the following general formula are preferable: R—N ₃ —R ′, RN ₃ -R'-NR ", wherein R, R ', R", and R are a hydrogen atom or a linear or cyclic hydrocarbon group having a saturated or unsaturated bond having 1 to 16 carbon atoms. . X is a halogen atom. 2- (2'-hydroxy-5'-methyl-phenyl)
Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 1,2,3-benzotriazole, 1
-[(N, N-bis-2-ethylhexyl) aminomethyl] benzotriazole and the like, and more preferably 1,2,3-benzotriazole.

[Examples] Examples 1 to 26 The following tests were conducted for the purpose of confirming the effect of the method for stabilizing hydrogen-containing chlorofluoropropanes of the present invention.

According to JIS-K1600, mild steel slabs were placed in each of the liquid phase part and the gas phase part of the stabilizing composition shown in Table 1 below, and the corrosion state of the mild steel slab after 48 hours had elapsed was observed.

 The results are shown in Table 1.

[Effects of the Invention] As is clear from the examples, the method for stabilizing hydrogen-containing chlorofluoropropanes of the present invention is excellent in the effect of suppressing metal corrosion and a high stabilizing effect is obtained. In particular, when corrosion occurs during cleaning of electronic parts, electric parts, and the like with hydrogen-containing chlorofluoropropanes, the problem of defective contacts occurs. As a countermeasure, the method of stabilizing hydrogen-containing chlorofluoropropanes of the present invention is used. Is valid.

Claims (1)

(57) [Claims] Claims: 1. CF ₃ CF ₂ CHCl ₂ and / or CClF ₂ CF ₂ CHClF
Of chloropropanes containing nitro compounds, phenols, amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones and triazoles A method for stabilizing hydrogen-containing chlorofluoropropanes, comprising adding at least one member selected from the group.