US3025331A - Stabilization of liquid halogenated aliphatic hydrocarbons - Google Patents
Stabilization of liquid halogenated aliphatic hydrocarbons Download PDFInfo
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- US3025331A US3025331A US770921A US77092158A US3025331A US 3025331 A US3025331 A US 3025331A US 770921 A US770921 A US 770921A US 77092158 A US77092158 A US 77092158A US 3025331 A US3025331 A US 3025331A
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- US
- United States
- Prior art keywords
- tetrahydrothiophene
- trichloroethylene
- stabilization
- aliphatic hydrocarbons
- oxide
- 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 - Lifetime
Links
- 230000006641 stabilisation Effects 0.000 title description 10
- 238000011105 stabilization Methods 0.000 title description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 title description 6
- 239000007788 liquid Substances 0.000 title description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 30
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 30
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 28
- 230000000087 stabilizing effect Effects 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 238000005238 degreasing Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic halogenated hydrocarbons Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals 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
- 238000013112 stability test Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- SNAUWGUVQBOHMZ-UHFFFAOYSA-N 2-methyl-3-pentyloxirane Chemical compound CCCCCC1OC1C SNAUWGUVQBOHMZ-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- ZYEMGPIYFIJGTP-UHFFFAOYSA-N Eugenol methyl ether Natural products COC1=CC=C(CC=C)C=C1OC ZYEMGPIYFIJGTP-UHFFFAOYSA-N 0.000 description 1
- NNWHUJCUHAELCL-SNAWJCMRSA-N Methyl isoeugenol Natural products COC1=CC=C(\C=C\C)C=C1OC NNWHUJCUHAELCL-SNAWJCMRSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- NNWHUJCUHAELCL-UHFFFAOYSA-N cis-Methyl isoeugenol Natural products COC1=CC=C(C=CC)C=C1OC NNWHUJCUHAELCL-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- PRHTXAOWJQTLBO-UHFFFAOYSA-N methyleugenol Natural products COC1=CC=C(C(C)=C)C=C1OC PRHTXAOWJQTLBO-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000003351 photoxidation Effects 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 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
- Halogenated hydrocarbons such as trichloroethylene and perchloroethylene evidence strong decomposition tendencies during storage, use and shipment. In the presence of metallic surfaces such as iron, copper, zinc, aluminum and the alloys of such metals, this decomposition is often pronounced. Often the decomposition negates practical usefulness of the halogenated hydrocarbon. Frequently the commercial value of thehalogenated hydrocarbon depends largely upon minimizing or avoiding serious decomposition. 7
- liquid aliphatic halogenated hydrocarbons and especially chlorinated aliphatic hydrocarbons useful as degreasing solvents may be stabilized by the use of small amounts of tetrahydrothiophene.
- trichloroethylene in which a small amount of tetrahydrothiophene has been dissolved manifests substantial resistance to decomposition.
- tetrahydrothiophene While the stabilizing eifects of tetrahydrothiophene is realized in trichloroethylene containing about 0.01 percent tetrahydrothiophene by weight, somewhat larger tetrahydrothiophene concentrations, notably at least 0.02 percent by weight of tetrahydrothiophene are preferable.
- additives may be used along with tetrahydrothiophene. Such additives may even augment the stabilizing effect of tetrahydrothiophene or retard other undesirable effects.
- Anti-oxidants and stabilizers useful for retarding decomposition caused by photoxidation may be included in the trichloroethylene without detracting from the stabilizing effect of tetrahydrothiophene.
- Aromatic compounds containing a phenolic hydroxyl group linked directly to a ring carbon such as phenol, thymol, catechol, para-cresol, guaicol, methyl salicylate, eugenol, isoeugenol and the like may be included in the trichloroethylene when tetrahydrothiophene is present. As a rule, these phenols generally have normal boiling points on the order of C. to 250 C.
- amines may be included along with tetrahydrothiophene in trichloroethylene.
- Amines as a general class have been recognized to impart certain stabilizing qualities to the trichloroethylene. Their use in conjunction with tetrahydrothiophene does not interfere with the stabilizing effect of tetrahydrothiophene.
- amines which may be used are diethylamine, triethylamine, dipropylamine, tripropylamine, triisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, diisopropylamine, diethanolamine, triethanolamine, N-methylmorpholine, methylpyrrole, beta-picoline, pyr'idine, aniline and the like.
- the concentration in trichloroethylene of these various additives does not exceed 1 or 2 percent by weight.
- the individual concentration in which each each additive may be present is Widely variable, but usually ranges between 0.001 and 0.5 percent by weight. Even then, judicious selection of the additives concentration is advisable. For example, amine concentration of about 0.5 percent by weight or more is not advised because amines in such concentrations are corrosive to zinc and zinc is a material of construction in many degreasers.
- ploying thiophene in lieu of tetrahydrothiophene in conjunction with butylene oxide indicates the stabilizing ac- Table I Concentra- Acidity tion Per- Alkalinity Standard Stability cent by HCl Stabilizer Composition Weight oi Evolved Triehloroethylene pH Titer Hours pH Titer Color Tetrahydrothiophene 0.01 6.7 0.1 72 7. 4 0.6 light nil.
- This test consists of placing a milliliter trichloroethylene sample in a beaker containing 25 milliliters of neutral distilled water and stirring while reading the pH with a meter in a glass ealornel electrode. The material was titrated with 0.01 N-hydrochlorie acid or 0.01 N sodium hydroxide until the neutral pH is reached.
- the standard stability test is designed to evaluate the efficiency of the stabilizer under especially rigorous conditions comparable to those found in shop usage. Procedurally, it involves placing 250 milliliter solution of 87.5 percent by volume of the trichloroethylene including the stabilizer in 12.5 volume percent Houghton H3105 drawing oil (sold by E. F. Houghton and Company) in a narrow mouth flask. Five grams of zinc and 5 grams of aluminum chips are added and the solution refluxed for the reported time period passing one bubble per second of air at 25 C. saturated with water through the solution.
- test data reported in Table I above indicates extremely effective stabilization of trichloroethylene under conditions representative of the most vigorous encountered in the normal use of trichloroethylene.
- the pH and titer of the trichloroethylene remains surprisingly constant despite the severity of the test conditions.
- tetrahydrothiophene alone or in conjunction :with other additives is of general applicability respecting the stabilization of all normally liquid halogenated hydrocarbons of 1 to 3 carbon atoms.
- Tetrahydrothiophene is particularly useful for stabilizing trichloroethylene, particularly when trichloroethylene is used as a degreasing Nevertheless, tetrahydrothiophene may be used to impart stabilizing qualities to various other chlorinated aliphatic hydrocarbons including methyl chloride, ethylene chloride, perchloroethylene, and 1,1,1-trichloropropane.
- a liquid composition comprising trichloroethylene containing in cooperative stabilizing concentration tetrahydrothiophene and butylene oxide.
- Stabilizer Composition Tetrahydrothiophene Butylene Oxide Tetrahydrothiophene Thymol Glycidol Ethyl Acetate DiiSObutyIene Mixed Butylene Oxides-- Thiophene Butylene Oxide Signed and sealed this 25th day of December 1962.
Description
United States Patent 3,025,331 Patented Mar. 13, 1952 ice 3,025,331 STABILIZATION F LKQUHD HALOGENATED ALHPHATIC HYDROCARBONS William R. Dial, Akron, Ohio, assignor, by mesne assignments, to Pittsburgh Plate Glass Company No Drawing. Filed Oct. 31, 1958, Ser. No. 770,921 1 Claim. (Cl. 260-6525) This invention deals with the stabilization of liquid halogenated aliphatic hydrocarbons, especially chlorinated aliphatic hydrocarbons. It is more particularly concerned with the stabilization of chlorinated aliphatic hydrocarbon degreasing solvents.
Halogenated hydrocarbons such as trichloroethylene and perchloroethylene evidence strong decomposition tendencies during storage, use and shipment. In the presence of metallic surfaces such as iron, copper, zinc, aluminum and the alloys of such metals, this decomposition is often pronounced. Often the decomposition negates practical usefulness of the halogenated hydrocarbon. Frequently the commercial value of thehalogenated hydrocarbon depends largely upon minimizing or avoiding serious decomposition. 7
Particularly acute decomposition problems arise in the use of trichloroethylene for degreasing of metals, especially aluminum. Unless adequately stabilized, trichloroethylene decomposes With alarming rapidity during degreasing usages. Not only does this decomposition destroy the usefulness of trichloroethylene as a degreasing solvent, but decomposition often is accompanied by the appearance of a tarry black intolerable residue that clogs and otherwise interferes with continued operation of the degreaser.
Effective stabilization of degreasing solvents, moreover, is complicated by the nature of degreasing operations. Degreasing entails utilizing a solvent in both liquid and vapor phases. In addition, .commercial degreasers are operated for extended periods of time, often several months .or longer, with asingle charge ;of solvent except for some addition of makeup solvent. Solvent is thus repeatedly vaporized and condensed. Adequate stabilization must protect trichloroethylene against detrimental decomposition both in vapor and liquid phases and should continue to exert astabilizing effect even after repeated distillations of trichloroethylene.
Now it has been discovered that liquid aliphatic halogenated hydrocarbons and especially chlorinated aliphatic hydrocarbons useful as degreasing solvents, notably trichloroethylene, may be stabilized by the use of small amounts of tetrahydrothiophene. Trichloroethylene containing as little as about 0.01 percent tetrahydrothiophene by weight or even less, accordingly, evidences substantial resistance to decomposition. Even under conditions of use encountered during degreasing of metals, trichloroethylene in which a small amount of tetrahydrothiophene has been dissolved manifests substantial resistance to decomposition.
While the stabilizing eifects of tetrahydrothiophene is realized in trichloroethylene containing about 0.01 percent tetrahydrothiophene by weight, somewhat larger tetrahydrothiophene concentrations, notably at least 0.02 percent by weight of tetrahydrothiophene are preferable.
pentene oxide.
erable. Costs rather than operability usually dictate use of the lower concentrations herein enumerated.
Since it may be expeditious to protect trichloroethylene againstany and all detrimental effects, other additives may be used along with tetrahydrothiophene. Such additives may even augment the stabilizing effect of tetrahydrothiophene or retard other undesirable effects. Anti-oxidants and stabilizers useful for retarding decomposition caused by photoxidation may be included in the trichloroethylene without detracting from the stabilizing effect of tetrahydrothiophene.
Aromatic compounds containing a phenolic hydroxyl group linked directly to a ring carbon such as phenol, thymol, catechol, para-cresol, guaicol, methyl salicylate, eugenol, isoeugenol and the like may be included in the trichloroethylene when tetrahydrothiophene is present. As a rule, these phenols generally have normal boiling points on the order of C. to 250 C.
Also a wide variety of amines may be included along with tetrahydrothiophene in trichloroethylene. Amines as a general class have been recognized to impart certain stabilizing qualities to the trichloroethylene. Their use in conjunction with tetrahydrothiophene does not interfere with the stabilizing effect of tetrahydrothiophene. Among the typical amines which may be used are diethylamine, triethylamine, dipropylamine, tripropylamine, triisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, diisopropylamine, diethanolamine, triethanolamine, N-methylmorpholine, methylpyrrole, beta-picoline, pyr'idine, aniline and the like.
Other additives may be incorporated in trichloroethylene along with the tetrahydrothiophene. Organic 1,2- epoxides (or oxiranes) may be included. Typical of such epoxides are =thylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2 ,3-butylene oxide, butadiene monoxide, butadiene dioxide, epichlorohydrin, glycidol, isobutylene oxide, 1,2-octylene oxide, 2,3-octylene oxide, 2,3-diisobutylene oxide, styrene oxide, cyclohexene oxide and cyclo- Ethyl acetate or like organic esters of monocarboxylic acids, alcohols such as propynyl alcohol, methanol, ethanol, etc., olefinically unsaturated compounds such as diisobutylene and the like may be included.
As a general rule, the concentration in trichloroethylene of these various additives does not exceed 1 or 2 percent by weight. The individual concentration in which each each additive may be present is Widely variable, but usually ranges between 0.001 and 0.5 percent by weight. Even then, judicious selection of the additives concentration is advisable. For example, amine concentration of about 0.5 percent by weight or more is not advised because amines in such concentrations are corrosive to zinc and zinc is a material of construction in many degreasers.
The following example illustrates the stabilizing effect of tetrahydrothiophene on halogenated hydrocarbons:
EXAMPLE Trichloroethylene containing tetrahydrothiophene was tested by accepted procedures to obtain the following data which demonstrates the stability imparted by the presence of tetrahydrothiophene:
ploying thiophene in lieu of tetrahydrothiophene in conjunction with butylene oxide indicates the stabilizing ac- Table I Concentra- Acidity tion Per- Alkalinity Standard Stability cent by HCl Stabilizer Composition Weight oi Evolved Triehloroethylene pH Titer Hours pH Titer Color Tetrahydrothiophene 0.01 6.7 0.1 72 7. 4 0.6 light nil.
amber. Butylene Oxide 0.25 'letrahydrothiophene 0. 01 6.2 0.5 2 72 7.35 0.3 do nil. Thym 0.01 Glycidol 0.05 Ethyl Acetate.-. 0.25 Diisobutylene 0.20 Mixed Butylene Oxides 0.25 Thiophene 0.01 6. 7 0. 4 72 3. 7 4. very nil.
dark Butylene Oxide 0.25
1 This test consists of placing a milliliter trichloroethylene sample in a beaker containing 25 milliliters of neutral distilled water and stirring while reading the pH with a meter in a glass ealornel electrode. The material was titrated with 0.01 N-hydrochlorie acid or 0.01 N sodium hydroxide until the neutral pH is reached. The
milliliters of hydrochloric acid or sodium hydroxide required is the titer.
2 Turned black only after 187-235 hours of continuous testing.
The standard stability test is designed to evaluate the efficiency of the stabilizer under especially rigorous conditions comparable to those found in shop usage. Procedurally, it involves placing 250 milliliter solution of 87.5 percent by volume of the trichloroethylene including the stabilizer in 12.5 volume percent Houghton H3105 drawing oil (sold by E. F. Houghton and Company) in a narrow mouth flask. Five grams of zinc and 5 grams of aluminum chips are added and the solution refluxed for the reported time period passing one bubble per second of air at 25 C. saturated with water through the solution.
The solution is observed for color. At the end of the 72 hours, a 25 milliliter portion of the trichloroethylene is titrated for acidity-alkalinity as described heretofore. The evolution of any HCl is determined by passing uncondensed gases leaving the refluxing condenser into a nitric acid acidulated silver nitrate fluid.
The test data reported in Table I above indicates extremely effective stabilization of trichloroethylene under conditions representative of the most vigorous encountered in the normal use of trichloroethylene. The pH and titer of the trichloroethylene remains surprisingly constant despite the severity of the test conditions.
Additionally, the fact that the stabilized samples, see footnote (2) of the table above, turned black only after some 200 hours of continuous testing under the standard stability test conditions is indicative of the highly efiective stabilization of trichloroethylene achieved by the stabilizing compositions including tetrahydrothiophene.
Moreover, the data in Table I demonstrates the unexpected and important stabilizing qualities of tetrahydrothiophene. Thus, comparison of the data obtained emsolvent.
tion of tetrahydrothiophene. When thiophene was employed in lieu of tetrahydrothiophene, trichloroethylene tested under standard stability test conditions rapidly developed a highly acidic pH and showed an increased titer. Increased acidity titer indicates inefiective stabilization of trichloroethylene.
Use of tetrahydrothiophene alone or in conjunction :with other additives is of general applicability respecting the stabilization of all normally liquid halogenated hydrocarbons of 1 to 3 carbon atoms. Tetrahydrothiophene is particularly useful for stabilizing trichloroethylene, particularly when trichloroethylene is used as a degreasing Nevertheless, tetrahydrothiophene may be used to impart stabilizing qualities to various other chlorinated aliphatic hydrocarbons including methyl chloride, ethylene chloride, perchloroethylene, and 1,1,1-trichloropropane.
Although this invention has been described by reference to specific details of certain embodiments, it is not intended that the invention be construed as limited to such specific details except insofar as such details appear in the appended claim.
I claim:
A liquid composition comprising trichloroethylene containing in cooperative stabilizing concentration tetrahydrothiophene and butylene oxide.
References Cited in the file of this patent UNITED STATES PATENTS 2,371,645 Aitchison et a1 Mar. 20, 1945 2,440,100 Klabunde Apr. 20, 1948 2,621,215 Cooper Dec. 9, 1952 2,797,250 Copelin June 25, 1957 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,025,331 March 13, 1962 William R. Dial It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as Corrected below.
Column 2, line 53, strike out "each"; columns 3 and 4, Table I column 1 of the table should appear as shown below instead of as in the patent:
Stabilizer Composition Tetrahydrothiophene Butylene Oxide Tetrahydrothiophene Thymol Glycidol Ethyl Acetate DiiSObutyIene Mixed Butylene Oxides-- Thiophene Butylene Oxide Signed and sealed this 25th day of December 1962.
(SEAL) Attest:
ERNEST W. SWIDER
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US770921A US3025331A (en) | 1958-10-31 | 1958-10-31 | Stabilization of liquid halogenated aliphatic hydrocarbons |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3152191A (en) * | 1960-08-08 | 1964-10-06 | Pittsburgh Plate Glass Co | Liquid halogenated hydrocarbon stabilized with a primary alkanol and an alkyl aldehyd hydrazone |
US5380449A (en) * | 1991-04-05 | 1995-01-10 | Alliedsignal Inc. | Stabilized dichlorotrifluoroethane refrigeration compositions |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2371645A (en) * | 1943-09-16 | 1945-03-20 | Westvaco Chlorine Products Cor | Degreasing process |
US2440100A (en) * | 1945-08-24 | 1948-04-20 | Du Pont | Solvent for degreasing iron and aluminum |
US2621215A (en) * | 1950-05-18 | 1952-12-09 | Diamond Alkali Co | Tetrachloroethylene stabilized by 2-halothiophene |
US2797250A (en) * | 1954-05-13 | 1957-06-25 | Du Pont | Stabilization of chlorinated hydrocarbons |
-
1958
- 1958-10-31 US US770921A patent/US3025331A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2371645A (en) * | 1943-09-16 | 1945-03-20 | Westvaco Chlorine Products Cor | Degreasing process |
US2440100A (en) * | 1945-08-24 | 1948-04-20 | Du Pont | Solvent for degreasing iron and aluminum |
US2621215A (en) * | 1950-05-18 | 1952-12-09 | Diamond Alkali Co | Tetrachloroethylene stabilized by 2-halothiophene |
US2797250A (en) * | 1954-05-13 | 1957-06-25 | Du Pont | Stabilization of chlorinated hydrocarbons |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3152191A (en) * | 1960-08-08 | 1964-10-06 | Pittsburgh Plate Glass Co | Liquid halogenated hydrocarbon stabilized with a primary alkanol and an alkyl aldehyd hydrazone |
US5380449A (en) * | 1991-04-05 | 1995-01-10 | Alliedsignal Inc. | Stabilized dichlorotrifluoroethane refrigeration compositions |
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