US2944088A - Stabilization of chlorinated solbents - Google Patents

Stabilization of chlorinated solbents Download PDF

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Publication number
US2944088A
US2944088A US770942A US77094258A US2944088A US 2944088 A US2944088 A US 2944088A US 770942 A US770942 A US 770942A US 77094258 A US77094258 A US 77094258A US 2944088 A US2944088 A US 2944088A
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United States
Prior art keywords
solvent
product
decomposition
test
stabilizer
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US770942A
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English (en)
Inventor
Otto S Kauder
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Argus Chemical Corp
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Argus Chem
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Priority to BE584163D priority Critical patent/BE584163A/xx
Application filed by Argus Chem filed Critical Argus Chem
Priority to US770942A priority patent/US2944088A/en
Priority to GB32244/59A priority patent/GB894045A/en
Priority to FR808209A priority patent/FR1251255A/fr
Application granted granted Critical
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
    • C23G5/02883—Nitrogen-containing compounds
    • C23G5/0289—N-heterocyclics
    • 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

  • the second type decomposition is observed when the solvent is exposed to strong light in the presence of air, and much more severely when the solvent or its vapor comes in contact With metals at elevated temperatures, such as in a vapor-degreasing operation.
  • metals most active in promoting this oxidation-decomposition are iron, copper, and alloys of these metals. This decomposition leads to formation of HCl and acid chlorides and is less severe with methylchloroform than with triand perchloroethylene.
  • An acceptable stabilizer should-in addition to providing the necessary degree of stabilization-have about the same volatility as the solvent to be stabilized. It should not be so strongly alkaline that its volatility is appreciably reduced in the presence of acidic materials. It should not be removed from the solvent by water extraction. It should not promote the formation of corrosion products or insoluble sludges. It should also afford the possibility to the user to ascertain the concentration of available stabilizer during use.
  • Still another object of the invention is a method of preparing in situ a concentrate of the stabilizer in the solvent suitable for. dilution with unstabilized solvent for the final use.
  • stabilizer a condensation product obtained by reaction of formaldehyde or acetaldehyde with a primary amine having not more than three carbon atoms.
  • the amount of the stabilizer to be used is from 0.01 to 2% by weight of the solvent.
  • the condensation products to be used. as stabilizers according to the invention are known per se.
  • the originally formed Schiifs bases trimerize spontaneously to cyclic compounds.
  • the formula. of the cyclic compound is the following:
  • Trimethyl-1,3,5-hexahydrotriazine These cyclic trimers are generally considered to be stable compounds.
  • the above-mentioned compound for instance, is described as a liquid boiling at 166 C. at normal pressure, the ethyl homologue boiling at 250 C.
  • all efforts to prepare the monomeric Schifis bases from an aldehyde with one to two carbon atoms and an amine of not more than three: carbon atoms have furnished only the cyclic trimers.
  • the prep aration of monomeric N-methylmethylene imine by pyrolysis of the trimer under special rather severe temperature conditions has been disclosed in US. Patents 2,729,- 679 and 2,729,680.
  • a stabilizer concentrate (a) To a stirred mixture of 50 ml. trichloroethylene and 75 ml. (1 mol) 40% formaldehyde solution, 63.4 g. of a 71.7% aqueous ethylamine solution (1 mol) were addedslowly with cooling in a pan of water to keep the temperature from rising above 45 C. One hour after the end of the addition, the layers were separated, and the aqueous layer was extracted with two 50 ml. portions of trichloroethylene, combining the extracts with the first solvent layer. Titration showed a 91% yield of the condensation product in the trichloroethylene solution. The final product contains about 34 g. condensation product in 100 ml. solvent.
  • the metal-catalyzed oxidation is allowed to proceed for 48 hours; at the end of this time the solvent is cooled to room temperature and a sample titrated with 0.01 11 NaOH solution in order to determine the amount of acid formed in the oxidation.
  • Federal Specification requires a maximum of 0.02% hydrochloric acid after the stability test.
  • Table No. 1 illustrates the stability of trichloroethylene stabilized with various stabilizers.
  • test I the solvent samples were immediately submitted to the test as described above.
  • test II the solvent samples were distilled and a center cut submitted to the test.
  • test III 300 ml. portions of solvent were mixed with 30 ml. oleic acid and distilled until 240 ml. had been collected. These distillates were then submitted to the test.
  • the quantity of the various stabilizers is expressed in weight percent for g. solvent.
  • the stabilizers according to the invention are being used in a quantity of 0.001 mol per 100 g. solvent, so that their alkalinity is equivalent to 0.04 g. NaOI-I.
  • the product of Example 1 was applied in a concentration of 0.071 g. in 100 g. solvent and the products of Example 2 (a), (b), c), and (d) in the concentration determined by titration to beequivalent.
  • tylene oxide 0.05. Pyridine, 0.1 0. 025 dark red sludge. O. 04 dark red sludge. 0. 04 dark red sludge. Aniline, 0.05-l-Epichl0r0hy- 0.003 deep yellow, some 0.1 yellow 0. 1 yellow.
  • EXAMPLE 7 Stabilization against condensation-decomposition of methylchlaroform kept in contact with aluminum for 10 days without evidence of decomposition.
  • a stabilized chlorinated aliphatic solvent having a boiling point below 130 C. containing per g. solvent 0.01 to 2 g. of a condensation product of an aidehyde of the group consisting of formaldehyde and acetaldehyde with a primary amine containing 1-3 carbon atoms.
  • Stabilized trichloroethylene containing per 100 g. thereof 0.01-2 g. of a stabilizer consisting of a condensation product of an aldehyde of the group consisting of formaldehyde and acetaldehyde with a primary amine containing 1-3 carbon atoms.
  • Stabilized perchloroethylene containing per 100 g. thereof 0.01-2 g. of a stabilizer consisting of a condensation product of an aldehyde of the group consisting of formaldehyde and acetaldehyde with a primary amine containing 1-3 carbon atoms.
  • Stabilized methylchloroform containing per 100 g. thereof 0.01-2 g. of a stabilizer consisting of a condensation product of an aldehyde of the group consisting of formaldehyde and acetaldehyde with a primary amine containing 1-3 carbon atoms.
  • Stabilized chlorinated aliphatic solvent having a boiling point below C. containing per 100 g. solvent 0.01 to 2 g. of a condensation product of ethylamine and formaldehyde.
  • Stabilized chlorinated aliphatic solvent having a boiling point below 130 C. containing per 100 g. solvent 0.01 to 2 g. of a condensation product of methyl amine and acetaldehyde.
  • Stabilized chlorinated aliphatic solvent having a boiling point below 130 C. containing per 100 g. solvent 0.01-2 g. of a mixture of condensation products of an aldehyde selected from the group consisting of formaldehyde and acetaldehy'de with a primary amine containing 1-3 carbon atoms.
  • a method for making a stabilized chlorinated aliphatic solvent having a boiling point below 130 C. which comprises preparing a stabilizer concentrate by condensing in said solvent an aldehyde of the group consisting of formaldehyde and acetaldehyde and a primary amine containing 1-3 carbon atoms, allowing the mixture to react at temperatures below 450 C. until the condensation is completed, using the aldehyde and the amine in equimolecular proportions and such quantities that the final product contains from 10-50 g. per 100 ml. solvent, and subsequently diluting it to the concentration desired for use with unstabilized solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US770942A 1958-10-31 1958-10-31 Stabilization of chlorinated solbents Expired - Lifetime US2944088A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE584163D BE584163A (enrdf_load_html_response) 1958-10-31
US770942A US2944088A (en) 1958-10-31 1958-10-31 Stabilization of chlorinated solbents
GB32244/59A GB894045A (en) 1958-10-31 1959-09-22 Stabilized chlorinated hydrocarbon solvent
FR808209A FR1251255A (fr) 1958-10-31 1959-10-22 Procédé de stabilisation de solvants chlorés

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US770942A US2944088A (en) 1958-10-31 1958-10-31 Stabilization of chlorinated solbents

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US2944088A true US2944088A (en) 1960-07-05

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BE (1) BE584163A (enrdf_load_html_response)
GB (1) GB894045A (enrdf_load_html_response)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291745A (en) * 1963-04-29 1966-12-13 Du Pont Stabilization of trichlorethylene
US3546305A (en) * 1967-12-01 1970-12-08 Dow Chemical Co Stabilization of 1,1,1-trichloroethane
US3676355A (en) * 1967-12-22 1972-07-11 Ugine Kuhlmann Stabilization of 1,1,1,trichloroethane with oxazole

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113109473B (zh) * 2021-04-13 2022-01-14 长沙晨辰医药科技有限公司 一种甲醛衍生测试方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2043257A (en) * 1933-10-09 1936-06-09 Stauffer Chemical Co Preservation of chlorinated hydrocarbons
US2094367A (en) * 1933-10-09 1937-09-28 Stauffer Chemical Co Stabilized carbon tetrachloride
US2190776A (en) * 1937-01-27 1940-02-20 Du Pont Composition of matter
US2407405A (en) * 1943-02-15 1946-09-10 Du Pont Stabilization of tetrafluoroethylene
GB617572A (en) * 1945-11-27 1949-02-08 Mathieson Alkali Works A method of stabilizing halogeno-organic compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2043257A (en) * 1933-10-09 1936-06-09 Stauffer Chemical Co Preservation of chlorinated hydrocarbons
US2094367A (en) * 1933-10-09 1937-09-28 Stauffer Chemical Co Stabilized carbon tetrachloride
US2190776A (en) * 1937-01-27 1940-02-20 Du Pont Composition of matter
US2407405A (en) * 1943-02-15 1946-09-10 Du Pont Stabilization of tetrafluoroethylene
GB617572A (en) * 1945-11-27 1949-02-08 Mathieson Alkali Works A method of stabilizing halogeno-organic compounds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291745A (en) * 1963-04-29 1966-12-13 Du Pont Stabilization of trichlorethylene
US3546305A (en) * 1967-12-01 1970-12-08 Dow Chemical Co Stabilization of 1,1,1-trichloroethane
US3676355A (en) * 1967-12-22 1972-07-11 Ugine Kuhlmann Stabilization of 1,1,1,trichloroethane with oxazole

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BE584163A (enrdf_load_html_response)
GB894045A (en) 1962-04-18

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