USRE26025E - Stabilization of methyl chloroform - Google Patents
Stabilization of methyl chloroform Download PDFInfo
- Publication number
- USRE26025E USRE26025E US26025DE USRE26025E US RE26025 E USRE26025 E US RE26025E US 26025D E US26025D E US 26025DE US RE26025 E USRE26025 E US RE26025E
- Authority
- US
- United States
- Prior art keywords
- weight
- dioxolane
- aluminum
- stabilized
- stabilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-Trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 title description 7
- 238000011105 stabilization Methods 0.000 title description 2
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229960002415 trichloroethylene Drugs 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N triclene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic amines Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000000087 stabilizing Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- DQCMWCVJSOFDSA-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl.CC(Cl)(Cl)Cl DQCMWCVJSOFDSA-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-Di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 241001417515 Kuhliidae Species 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 241000054817 Lycaena dione Species 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N Nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- NGBFQHCMQULJNZ-UHFFFAOYSA-N Torsemide Chemical compound CC(C)NC(=O)NS(=O)(=O)C1=CN=CC=C1NC1=CC=CC(C)=C1 NGBFQHCMQULJNZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003413 degradative Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
Definitions
- This invention relates to the process of cleaning metal articles with methyl chloroform, and to a methyl chloroform solvent stabilized against decomposition when used in such process.
- MC methyl chloroform (1,1,1-trichloroethane) in the following called MC
- MC presents certain important advantages in degreasing operations, f.i. the relatively low degree of toxicity of this compound and also in the greater solvent economy, compared to carbon tetrachloride or trichloroethylene, due to the lower specific gravity.
- MC thus far has only enjoyed rather restricted commercial use, owing to insufiicient stabilization.
- MC has been used only in the relatively wasteful cleaning processes of dipping and spraying, and has secured almost no entry to the field of vapor degreasing which is more important from the economic viewpoint.
- MC stabilized for vapor degreasing should withstand prolonged contact of the boiling liquid and vapor with aluminum, and should also remain substantially unat tacked by other degradative influences encountered in degreasing practice, such as oxygen, moisture, and the presence of other metals particularly zinc, iron and copper. In the absence of aluminum, these influences are not damaging to MC, but in combination with aluminum, they represent a severe problem, as will be shown in the examples.
- the object is accomplished by the use as stabilizer of 0.55%, preferably about 13% by weight of 1,3-dioxolane, the cyclic formal of ethylene glycol.
- This compound has the formula:
- the compound has an excellent stabilizing effect. Its boiling point of 74 C. is extremely close to that of MC, maintaining complete stability when MC containing this stabilizer is vaporized or distilled.
- MC stabilized with 2% 1.3 dioxolane exhibited no decomposition in 10 days and an Al weight loss of 0.03%.
- EXAMPLE 3 Action of MC on metal combinations in the presence of oxygen and moisture In this test, the oxidation apparatus described in the Federal Specification OT634A, Trichloroethylene, technical was used. Each test run was performed with 230 ml. MC, 5 g. aluminum in the form of /4 inch pellets, and at least one other metal. The other metals used were mossy zinc, about 5 g. in a run, mild steel strips, 2 x /2 x A inch, and about 5 g. copper foil, 0.032 inch thick. Oxygen from a cylinder passed through a wash bottle and a bubble counter, both containing water, before entering the flask. The oxygen flow rate was about 30 bubbles per minute. A watt electric light bulb was used to illuminate and heat the flasks.
- the MC was analysed for chloride ion formed in the oxidation by the Volhard method.
- EXAMPLE 4 Formula Metals Pcr- Metals weight used cent C1 change, percent l ⁇ lC+1.S% 1,3-dioxcla1le+0.05% Al, Zn 0. 006 Al 0.0, Zn0.1.
- Ethyl Ari-33 is the trade mark for u. commercially available mixture 01 t-butyl substituted phenols.
- a stabilized composition consisting of methylchloroform having incorporated therein from 0.5 to by weight of 1,3-dioxolane,]
- a stabilized composition consisting of methylchloroform having incorporated therein from 1 to 3% by weight of 1,3-dioxolane.
- a stabilized composition consisting essentially of methylchloroform having incorporated therein from 0.5 to 5% by weight of 1,3-dioxo1ane and in addition thereto 0.01 to 0.1% by weight of a phenolic antioxidant.
- a stabilized composition consisting essentially of methyl-chloroform having incorporated therein from 0.5 to 5% by weight of 1,3-dioxolane and in addition thereto 0.01 to 0.1% by weight of 4,4'-thiobis-2-t-butyl-5-mcthylphenol.
- a stabilized composition consisting essentially of methylchloroforrn having incorporated therein from 0.5 to 5% by Weight of 1,3-dioxolane and in addition thereto a mixture of -t-butyl substituted phenols containing 2,6- di-t-butylphenol 2,4,6 tri4t-butylphenol l0-15%, and ortho-t-butylphenol 1015%.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Description
United States Patent No Drawing. Original No. 3,008,999, dated Nov. 14,
Application for 1961, Ser. No. 845,100, Oct. 8, 1959. reissue Nov. 7, 1963, Ser. No. 322,262
3 Claims. (Cl. 260-6525) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This invention relates to the process of cleaning metal articles with methyl chloroform, and to a methyl chloroform solvent stabilized against decomposition when used in such process.
The use of methyl chloroform (1,1,1-trichloroethane) in the following called MC, presents certain important advantages in degreasing operations, f.i. the relatively low degree of toxicity of this compound and also in the greater solvent economy, compared to carbon tetrachloride or trichloroethylene, due to the lower specific gravity. However, MC thus far has only enjoyed rather restricted commercial use, owing to insufiicient stabilization. Thus MC has been used only in the relatively wasteful cleaning processes of dipping and spraying, and has secured almost no entry to the field of vapor degreasing which is more important from the economic viewpoint.
The principal stability problem with MC arises in contact with aluminum. Unstabilized MC in contact with a freshly exposed or scratched aluminum surface turns dark and begins to decompose within a few minutes. Additives conventionally used with trichloroethylene, such as the epoxides, aliphatic amines, and pyrroles, are without appreciable effect in stabilizing MC. The use of 1,4-dioxane, as disclosed in US. Patent 2,811,252, provides a certain degree of protection to MC in contact with aluminum, and alfords a product of acceptable quality for the present use of metal cleaning by the cold dipping and spraying processes. However, MC stabilized with dioxane does not appear to be sutficiently stabilized for the more severe requirements of the vapor degreasing process, as will be shown in detail below.
MC stabilized for vapor degreasing should withstand prolonged contact of the boiling liquid and vapor with aluminum, and should also remain substantially unat tacked by other degradative influences encountered in degreasing practice, such as oxygen, moisture, and the presence of other metals particularly zinc, iron and copper. In the absence of aluminum, these influences are not damaging to MC, but in combination with aluminum, they represent a severe problem, as will be shown in the examples.
It is therefore the object of this invention to provide a degreasing solvent comprising stabilized MC.
The object is accomplished by the use as stabilizer of 0.55%, preferably about 13% by weight of 1,3-dioxolane, the cyclic formal of ethylene glycol. This compound has the formula:
(1 MFA. T12
The compound has an excellent stabilizing effect. Its boiling point of 74 C. is extremely close to that of MC, maintaining complete stability when MC containing this stabilizer is vaporized or distilled.
Yet more advantageous results are obtained by using along with the 1,3-dioxolane stabilizer a very small quan- "ice tity, 0.01-0.1%, of a material belonging to the class of phenolic antioxidants. In the absence of 1.3-dioxolane the phenolic antioxidants are totally without effect. Typical phenolic antioxidants are p-t-butyl phenol, 2,6-di-tbutyl-p-cresol, nonylphenol or 4,4'-thiobis-(t-butyl-mcresol).
The following examples serve to illustrate the invention, but it should be understood that they are not given by way of limitation and that many changes in the details may be made without departing from the spirit of the invention.
We describe first the removal of stabilizer from commercial MC, stabilized with dioxane, since unstabilized MC is not commercially available. Each of four separatory funnels was charged with 200 ml. water. One liter of commercial MC was shaken with the water in the first funnel, allowed to separate, and drained into the second funnel. This operation was repeated until the MC was taken from the fourth funnel and dried over sodium sulfate. The resulting material gave an immediate reaction with a freshly scratched piece of aluminum foil. In the following examples percentages are indicated by weight.
EXAMPLE 1 Action of boiling MC on aluminum rods Twenty-five ml. samples of MC were heated to reflux in a conical flask containing an aluminum Welding rod about 2 inches long and weighing approximately 1 gram. At the end of the reflux test, the rods were reweighed.
MC without stabilizer showed complete decomposition in 2 hours.
MC stabilized with 2% 1.3 dioxolane exhibited no decomposition in 10 days and an Al weight loss of 0.03%.
EXAMPLE 2 Action of MC and water on aluminum rods The reflux test of Example 1 was repeated, but the flasks were charged with 25 ml. MC and 25 ml. water. There was no visible decomposition of the solvent, but the aluminum rods were slowly attacked.
Al weight loss after 7 days: Percent MC containing 4% dioxane 50.0 MC containing 2% 1.3 dioxolane 14.1
A similar test was run by shaking the flasks containing water, MC, and aluminum rods at room temperature.
A] weight loss after 10 days: Percent MC containing 4% dioxane 14.6 MC containing 2% 1.3 dioxolane 5.2
EXAMPLE 3 Action of MC on metal combinations in the presence of oxygen and moisture In this test, the oxidation apparatus described in the Federal Specification OT634A, Trichloroethylene, technical was used. Each test run was performed with 230 ml. MC, 5 g. aluminum in the form of /4 inch pellets, and at least one other metal. The other metals used were mossy zinc, about 5 g. in a run, mild steel strips, 2 x /2 x A inch, and about 5 g. copper foil, 0.032 inch thick. Oxygen from a cylinder passed through a wash bottle and a bubble counter, both containing water, before entering the flask. The oxygen flow rate was about 30 bubbles per minute. A watt electric light bulb was used to illuminate and heat the flasks.
At the end of the test period, after 72 hours, the metals were removed, washed once with water and once with acetone, and weighed to determine the weight change.
The MC was analysed for chloride ion formed in the oxidation by the Volhard method.
Formula Metals Pcr- Metals weight used cent C1 change, percent MC+4% dioxano Al, Zn 0, 07 A100, Zn-T 6. MC+2% 1.3 dioxolane A1, Zn 0.03 A1 0.0, Zn- 8. MC+4% dioxmio Al, Fe 1), 000 Al-OA, Fe0,2. MC+2% 1,3 dioxolanc A1, Fe... 0. 01 rel-0.2, Fe[) 1. MC+4% dioxanc Al, Cu, 0.03 A1+l).3, (Eu-45.8. MC+2% 1,3 dioxolanc Al, Cu 0. 01 A1-[).3, Cu+1.1.
These figures and the results of Example 2, show the superiority of 1,3-dioxolane as stabilizer compared to dioxane.
EXAMPLE 4 Formula Metals Pcr- Metals weight used cent C1 change, percent l\lC+1.S% 1,3-dioxcla1le+0.05% Al, Zn 0. 006 Al 0.0, Zn0.1.
Tl1lobis-t-butyl-m cresol.
Do A1, Fe.-. 0.008 A100, Fe-D.05. Do -7 Al, Cu 0. 005 Al-l-(LOI, Cu+0.2.
These figures show the synergistic effect when a minute quantity of thiobis-t-butyl-m-cresol is being used together with 1,3-dioxo1ane.
1 Ethyl Ari-33 is the trade mark for u. commercially available mixture 01 t-butyl substituted phenols.
What is claimed is: [1. A stabilized composition consisting of methylchloroform having incorporated therein from 0.5 to by weight of 1,3-dioxolane,]
[2. A stabilized composition consisting of methylchloroform having incorporated therein from 1 to 3% by weight of 1,3-dioxolane.]
3. A stabilized composition consisting essentially of methylchloroform having incorporated therein from 0.5 to 5% by weight of 1,3-dioxo1ane and in addition thereto 0.01 to 0.1% by weight of a phenolic antioxidant.
4. A stabilized composition consisting essentially of methyl-chloroform having incorporated therein from 0.5 to 5% by weight of 1,3-dioxolane and in addition thereto 0.01 to 0.1% by weight of 4,4'-thiobis-2-t-butyl-5-mcthylphenol.
5. A stabilized composition consisting essentially of methylchloroforrn having incorporated therein from 0.5 to 5% by Weight of 1,3-dioxolane and in addition thereto a mixture of -t-butyl substituted phenols containing 2,6- di-t-butylphenol 2,4,6 tri4t-butylphenol l0-15%, and ortho-t-butylphenol 1015%.
References Cited by the Examiner The following references, cited by the Examiner, are of recomd in the patented lite of this patent or the original patent.
UNITED STATES PATENTS 2,155,723 4/1939 Levine et al. 260-6525 2,371,645 3/1945 Aitchison ct al. 260652.5 2,810,765 10/1957 Neuworth et a1. 260652.5 2,841,625 7/1958 Burch et al. 260652.5 2,852,572 9/1958 Shukys et a1. 260652.5 2,922,776 1/ 1960 Wultf et a1. 26045.8 2,978,518 4/1961 Daras 26065.5 2,999,887 9/1961 Furlay 260652.5 X 3,025,331 3/1962 Dial 260652.5
FOREIGN PATENTS 201,160 4/1955 Australia.
OTHER REFERENCES Rose et al.: Condensed Chemical Dictionary (Reinhold), 1961, page 456.
LEON ZITVER, Primary Examiner.
K. V. ROCKEY, Assistant Examiner.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE26025E true USRE26025E (en) | 1966-05-17 |
Family
ID=2095323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US26025D Expired USRE26025E (en) | Stabilization of methyl chloroform |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE26025E (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4418231A (en) | 1981-08-07 | 1983-11-29 | Ppg Industries, Inc. | Corrosion inhibited solvent compositions |
| US4466903A (en) | 1981-08-07 | 1984-08-21 | Ppg Industries, Inc. | Unsaturated 1,3-dioxolane stabilized with aliphatic aldehyde hydrazone |
-
0
- US US26025D patent/USRE26025E/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4418231A (en) | 1981-08-07 | 1983-11-29 | Ppg Industries, Inc. | Corrosion inhibited solvent compositions |
| US4466903A (en) | 1981-08-07 | 1984-08-21 | Ppg Industries, Inc. | Unsaturated 1,3-dioxolane stabilized with aliphatic aldehyde hydrazone |
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