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Publication numberUS3767585 A
Publication typeGrant
Publication dateOct 23, 1973
Filing dateOct 12, 1971
Priority dateOct 12, 1971
Publication numberUS 3767585 A, US 3767585A, US-A-3767585, US3767585 A, US3767585A
InventorsY Genda, K Masuyama, S Sawabe, M Takebayashi, T Yamamoto
Original AssigneeNippon Soda Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Stable solvent composition
US 3767585 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent O 3,767,585 STABLE SOLVENT COMPOSITION Shigeji Sawabe, Takaoka, Yoshikazu Genda, Higashi, Takeo Yamamoto, Takaoka, Kazuyoshi Masuyama, Tonami, and Michinori Takebayashi, Takaoka, Japan, assignors to Nippon Soda Co., Ltd., Tokyo, Japan No Drawing. Filed Oct. 12, 1971, Ser. No. 188,527 Int. Cl. Clld 7/50 US. Cl. 252-171 14 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a new stabilizing mixture of additives for chlorinated aliphatic hydrocarbons to guard against decomposition, and more particularly, to a new stable solvent composition composed of chlorinated aliphatic hydrocarbons containing mixtures of stabilizing additives.

BACKGROUND OF THE INVENTION Chlorinated aliphatic hydrocarbons such as 1,1,l-t1ichloroethane, trichloroethylene, perchloroethylene are useful as solvents because they have a high solvency for oils and greases, a low flammability, and can be used for a dry cleaning, the degreasing of metals and for many other purposes. Unfortunately, however, the chlorinated aliphatic hydrocarbons have a tendency to decompose in the presence of moisture, air, a trace of acid, metal salts, and under radiation of light. Further, the decomposition is especially accelerated by the presence of aluminum, zinc, iron or their alloys.

THE PRIOR ART Many kinds of stabilizers or stabilizing mixtures have been reported for stabilization purposes. However, very few stabilizers or stabilizing mixtures have an elfect in the vapor phase, as well as in the liquid phase, or will not deteriorate the inflammability of the composition.

OBJECTS OF THE INVENTION SUMMARY OF THE INVENTION It has now been found that the 1,1,1-trichloroethane can be stabilized by a stabilizing mixture of saturated aliphatic primary alcohols having 1 to 4 carbon atoms, aliphatic keto-alcohols having 6 to 10 carbon atoms and nitro alkanes having 1 to 3 carbon atoms.

In accordance with the practice of this invention, 0.5 to 5.0%, preferably 1.0 to 3.0%, of saturated aliphatic primary alcohols, 0.1 to 5.0%, preferably 0.2 to 2.0% of aliphatic keto-alcohols and 0.1 to 4%, preferably 0.3 to 2.0% of nitro alkanes are added to a chlorinated aliphatic hydrocarbon such as 1,1,1-trichloroethane. Thus, a stable solvent composition composed of chlorinated aliphatic hydrocarbon containing a stabilizing additive can be obtained. The total amount of the stabilizin mixture is preferably 1.5 to 5.0% by weight, based on the sum total weight of the stabilized chlorinated aliphatic hydrocarbon.

As examples of saturated aliphatic primary alcohols, methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol, amyl alcohol, etc., can be used.

3,767,585 Patented Oct. 23, 1973 As examples of aliphatic keto-alcohols, acetonyl dimethyl carbinol, 1,1 diethyl 1-hydroxy-4-oxo-hexane, phenacyl alcohol, S-hydroxy-S-methylhexane-3-on, 5-hydroxy 5 methylheptane-3-on, S-methyl-S-hydroxyheptane-S-on, can be used.

As examples of nitro alkanes, nitro methane, nitro ethane, l-nitro propane, Z-nitro propane, etc., can be used.

When the amount of the stabilizing mixture is less than 1.5%, a suflicient stabilizing effect is not expected, and when the amount of the stabilizing mixture is more than 6%, inflammability of the stabilized solvent is deteriorated, thus, the amount of the stabilizing mixture should be from about 1.5 to 6.0% by weight, based on the sum total weight of the stabilized chlorinated aliphatic hydrocarbon.

In this invention, all or a part of the nitro alkanes can be replaced by epoxides having 3 to 5 carbon atoms and when all of the nitro alkanes are replaced by epoxides, 0.1 to 4.0%, preferably 0.2 to 3.0% of an epoxide having 3 to 5 carbon atoms by weight, based on the sum total weight of the stabilized solvent, may be employed.

As examples of epoxides, propylene oxide, epichlorohydrin, glycidol, a,;8, or iso-butylene oxide can be employed.

A three component mixture of saturated aliphatic primary alcohols, aliphatic keto-alcohols and a compound seelcted from a group of nitro alkanes and epoxides is required in order to stabilize the solvent, and only when the three components are used together, can a sufficient stabilizing effect be obtained.

The stable solvent composition in this invention is stabilized to the extent that decomposition of the chlorinated aliphatic hydrocarbon, or corrosion of metal does not occur under conditions of 200 hours of continuous refluxing in the presence of aluminum, zinc or iron and the effect of stabilizing is not decreased by the refining of the solvent by means of distillation or adsorption of activated carbon.

The following examples are illustrative of the invention. The invention is not limited to the examples or to the material, proportions, conditions, and procedures set forth therein, and all percentages are in weight units except as otherwise specified.

EXAMPLE 1 Polished aluminum workpieces being 10 mm. x 20 mm. x 2 mm. in size were Washed with ether and dried. Then one of the test pieces was dipped in g. of the stable solvent composition in a 150 ml. flask with a reflux condenser and another of the test pieces was hung in the vapor phase and then the reflux was continued for 200 hours.

Stable solvent compositions, corrosion of the test pieces and pH and appearance of the solvent are listed in Table 1.

EXAMPLE 2 100 g. of the stable solvent composition, listed in Table 1, run numbers 1 through 12, were respectively mixed with 10 g. of machine oil having a flash point higher than C. in a ml. flask with a reflux condenser and reflux was continued for 1 hour. Aluminum workpieces being 10 mm. x 20 mm. x 2 mm. in size were washed with ether, dried and then one of the test pieces was dipped in each solvent composition and one of the test pieces was hung in the vapor phase and then the reflux was continued for 10 hours. After the reflux, each stable solvent was distilled in order to refine and separate the stable solvent from the machine oil until the distilling temperature rose to 85 C. Then, 10 g. of machine oil was added to the stable composition, and refluxed for 100 hours in the presence of aluminum workpieces and distillation, as shown above, was repeated. Stabilities of the cycled stable solvent composition was tested in accordance with Example 1, and almost the same results as shown in Example 1, were obtained and it was confirmed that the stabilities of the cycled stable solvent composition did not deteriorate.

7. A stable solvent as claimed in claim 3, wherein the saturated aliphatic primary alcohol is ethanol.

8. A stable solvent as claimed in claim 3, wherein the saturated aliphatic primary alcohol is methanol.

9. A stable solvent as claimed in claim 3, wherein the saturated aliphatic primary alcohol in n-propyl alcohol.

TABLE 1 Stable solvent composition {l00,."g.)

Reflux Corrosion of test piece Solvent Run Solvent Stabilizing mixture (percent) time (hours) In vapor In solvent Appearence pH Thls mventwn"" n-Propytaloohol lacetonyldimethylcarbinol JNitroethane 2 ..do n-Prcpylalcohol [Acetonyldimethylcarblno Nitromet-hanenfl ethane.

Acetcnyldimeth 1 .ca 2-ni tropropane. 4 do Ethylalcohol 1,1-(licthyl-Lhydroxy-4- oxohexane.

Q-nitropi'o pane 5 do E thylalcohol lhl-diethylbhydroxy-- oxohexane Q-nitropropane Methylalcohol Ethyl alxohol 7 do .{l,2-butylene oxide Acctonyldiniethylcarbino Methyl alcohol. 8 .do 1,2-butylene oxide.

.Acetonyl dimethylcarbino [Methyl alcohol 9 .do -l,2-bt1tylene oxide lAoetonyl dirnethylcarbrnol- Ethyl alcohol 2methyl-2,3-epoxybutane Ethylalcohol 2-rnethyl-2,3epoxybu tane 11 "{Ll-diothyl-l-hydroxy-k oxohexane.

Ethyl alcohol 1.

l. l1,ldiotnyl-l-hydroxyorohexane 3.

1 1 1,itriehlorolliitmmctmm 200 None- None Transparence Withoutc or.

200 do d .d0

200 .do do d0 6.8

N 9 FF? PFP'PE NFPPNP F coo con: mocnoocotooooc oooa cacao MOONQOOOCOQW MWWMWWMWWW MW 200 do ..do.- ......do 6.8

200 do .do ..d.o 6. 8

Control 1,1,l-trichloroethane.

.do 1,2-butylene oxide.

Nitromet-hane 1,2-butylene 0Xide. do n-PropylalcohoL.

Acetyl acetone 1,2'bnt-yleneoxide do.- Acetylacetone.

Dioxarie 1 1 Lusterless. Corroded. Black tar 1.

7 None Corr0ded Yellow turbid 5. 12 .d do rovrn l? Corroded "do." White ttlrbid 8 do do-.-

I Lusterless do Transparence 1 Minute.

What is claimed is:

1. A stable solvent composition consisting essentially of 1,1,l-trichloroethane containing from about 1.5 to 5.0% of saturated aliphatic primary alcohol having 1 to 4 carbon atoms, 0.1 to 5.0% of aliphatic keto-alcohol having 6 to carbon atoms and 0.1 to 4% of a compound selected from the group consisting of nitro alkanes having 1 to 3 carbon atoms and epoxides having 3 to 5 carbon atoms, by Weight based on the sum total Weight of the stable solvent composition.

2. A stable solvent composition consisting essentially of 1,1,l-trich1oroethane containing from about 1.5 to 5.0% of saturated aliphatic primary alcohol having 1 to 4 carbon atoms, 0.1 to 5.0% of aliphatic keto-alcohol having 6 to 10 carbon atoms and 0.1 to 4.0% of nitro alkane having 1 to 3 carbon atoms, by weight based on the sum total weight of the stable solvent composition.

3. A stable solvent as claimed in claim 2, wherein the total weight of the said aliphatic primary alcohol, aliphatic keto-alcohol and nitro alkane is from 1.5 to 6.0% by weight based on the sum total weight of the stable solvent composition.

4. A stable solvent as claimed in claim 3, wherein the nitro alkane is nitro methane.

5. A stable solvent as claimed in claim 3, wherein the nitro alkane is nitro ethane.

6. A stable solvent as claimed in claim 3, wherein the nitro alkane is nitro propane.

10. A stable solvent as claimed in claim 3, wherein the aliphatic keto-alcohol is acetonyl dimethyl carbinol.

11. A stable solvent composition consisting essentially of 1,1,1-trichloroethane containing from about 1.5 to 5.0% of saturated aliphatic primary alcohol having 1 to 4 carbon atoms, 0.1 to 5.0% of aliphatic keto-alcohol having 6 to 10 carbon atoms and 0.1 to 4% of epoxide having 4 to 5 carbon atoms, by Weight based on the sum total weight of the stable solvent composition.

12. A stable solvent as claimed in claim 11, wherein the epoxide is propylene oxide.

13. A stable solvent as claimed in claim 11, wherein the epoxide is epichlorohydrin.

14-. A stable solvent as claimed in claim 11, wherein the epoxide is butylene oxide.

References Cited UNITED STATES PATENTS 3,499,047 3/1970 Cormany et al. 260652.5 3,546,305 12/1970 Archer et al. 260652.5 3,564,063 2/1971 Cormany et a1. 260-6525 WILLIAM E. SCHULZ, Primary Examiner US. Cl. X.R. 260652.5

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3932297 *Jan 14, 1974Jan 13, 1976Imperial Chemical Industries LimitedSolvent compositions for cleaning
US4023984 *Aug 19, 1975May 17, 1977Imperial Chemical Industries LimitedAzeotropic solvent composition for cleaning
US4052328 *Nov 16, 1976Oct 4, 1977Allied Chemical CorporationAzeotrope-like compositions of trichlorotrifluoroethane, ethanol, isopropanol and nitromethane
US4062794 *Nov 16, 1976Dec 13, 1977Allied Chemical CorporationAzeotrope-like compositions of trichlorotrifluoroethane, methanol, ethanol, isopropanol and nitromethane
US4086179 *Dec 10, 1976Apr 25, 1978Alpha Metals, Inc.Improved cleaning solvent containing non-azeotropic mixtures of 1,1,1-trichloroethane and n-propanol
US4231968 *Jan 22, 1979Nov 4, 1980Chemische Werke Huls AktiengesellschaftStabilization of 1,1,1-trichloroethane
EP0035268A1 *Mar 2, 1981Sep 9, 1981ADEKA ARGUS CHEMICAL CO., Ltd.Chlorinated organic compounds having their resistance to deterioration enhanced by 1,3-dicarbonyl compounds
EP0044111A1 *Jul 6, 1981Jan 20, 1982SOLVAY & Cie (Société Anonyme)Stabilised 1,1,1-trichloro-ethane compositions
Classifications
U.S. Classification252/364, 510/266, 510/285, 510/258, 570/116, 570/118, 510/412, 510/255, 570/117, 570/110
International ClassificationC07C17/42, C11D7/28, C11D7/26, C11D7/50, C23G5/028
Cooperative ClassificationC07C17/42, C11D7/5018, C11D7/28, C23G5/0288, C23G5/02887, C11D7/264, C11D7/261
European ClassificationC11D7/26A, C07C17/42, C23G5/028P2E, C23G5/028P3D, C11D7/50A6