US2477244A - Stabilized organic sulfur-containing composition and method of preparing same - Google Patents

Stabilized organic sulfur-containing composition and method of preparing same Download PDF

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US2477244A
US2477244A US679593A US67959346A US2477244A US 2477244 A US2477244 A US 2477244A US 679593 A US679593 A US 679593A US 67959346 A US67959346 A US 67959346A US 2477244 A US2477244 A US 2477244A
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organic sulfur
hydrogen sulfide
oil
containing composition
alpha
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US679593A
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James W Gaynor
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Standard Oil Co
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Standard Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/044—Cyclic ethers having four or more ring atoms, e.g. furans, dioxolanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/08—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/20—Containing nitrogen-to-oxygen bonds
    • C10M2215/202—Containing nitrogen-to-oxygen bonds containing nitro groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041—Hydrocarbon polymers

Definitions

  • an object of the present invention toprovide animprovedmethod of inhibiting the evolution of hydrogen sulfide from organic sulfur-containing compounds which normally evolve hydrogen sulfide during serviceor stantially inhibit the evolution of hydrogen sulfide; suitably in concentrations of from about 0.001% to about 25.0%; and preferably from about 0.01% to about 5.0% by weight based upon the sulfur-containing compounds.
  • the alphabeta unsaturated ketone may be an alpha-beta unsaturated aliphatic, cycloaliphatic or aromatic ketone.
  • an alpha-beta unsaturated ketone as used herein and in the appended claims is meant a ketone containing at least one ethylene linkage I :2 attached *to the carbonyl group, as represented byrthei structuralrgroup Operable unsaturated ketone's include thoseihavinig one or two -"d'o'i'ible bonds "-conjugated with the carbonyl group.
  • the "ket'one group and/onthe double bond may "also be present "in a "cycloaliphatic ring.
  • aromatic nuclei in the alpha-beta unsaturated ketones may be alkylated or contain other substituents, such as, for example hydroxyl, amino and nitro groups.
  • the time required for 100 grams of the testmaterial to evolve 9 milligrams hydrogen sulfide was noted by the formation of PbS in the second vessel.
  • the control was a mineral lubricating oil additive composition containing a KOI-l neutralized product otPzSs and an isobutylene polymer, a sulfurized mineral oil and a sulfurized terpene.
  • Hydrogen Sulfide The above data show the stabilizing effect of alpha-beta unsaturated ketones on the evolution of hydrogen sulfide from organic sulfur-containing materials. While these data were obtained with a specific lubricant composition using a particular oil-soluble detergent, namely a KOI-I neutralized reaction product of P285 and an isobutylene polymer, and particular organic sulfur-containing compounds, namely a sulfurized mineral oil and a sulfurized terpene, other oil-soluble detergent-type additives and other organic-sulfurcontaining materials can be used.
  • the oil-soluble detergent additive may be a neutralized reaction product of a phosphorus sulfide and a hydrocarbon as described in U. S. 2,316,082.
  • lubricant compositions contain from about 0.01% to about 10% by weight of an oilsoluble detergent-type additive and an organic sulfur-containing additive, the former to impart varnish inhibiting or removing properties to the lubricant, and the latter to impart lubricating.
  • the oilsoluble detergent-type additive is frequently responsible for an increased rate of hydrogen sulfide evolution from the organic sulfur-containing additive. Under these conditions the addition of the herein-disclosed alpha-beta unsaturated ketones efiectively inhibits the evolution of hydrogen sulfide from such compositions.
  • oil-soluble detergent-type additive internal combustion engines and/or the property of removing varnish formed in such engines.
  • a lubricant composition comprising a major proportion of a hydrocarbon oil and an organic sulfur-containing compound which normally evolves hydrogen sulfide and from about 0.001% to about 25% by weight based upon the sulfurcontaining compound of an alpha-beta unsaturated aliphatic ketone.
  • a lubricant composition consisting essential- 1y of a major proportion of a hydrocarbon oil, an oil-soluble detergent type additive consistin essentially of a neutralized reaction product of a phosphorus sulfide and a hydrocarbon, an organic sulfur-containin compound, which normally evolves hydrogensulfide, and from about 0.001% to about 25% by weight, based upon the sulfurcontaining compound, of an alpha beta unsaturated aliphatic ketone;
  • the method ofinhibiting the evolution of hydrogen sulfide from an organic sulfur-containing compound which evolves hydrogen sulfide comprising adding to said compound from about 0.001% to about 25 by weight, based upon the sulfur-containing compound of an alpha-beta unsaturated aliphatic ketone to substantially inhibit theevolution of hydrogen sulfide from said organic sulfur-containing compound.

Description

Patented July 26, 1949 pairs s T ES " ORGANIC SULFUR-CONTAIN- 'ING omosrnon aunnerrnon or -rarraamesmn flames W.Gray-nor, flammond, lnd iassignorito Standard Oil aGon pany, Ghicago,..i ll.,.-a z'corpora- V .tion of Indiana Ndllrawing. Applicationilune26,1946,
*S'etial No. 679,593
6 Qlaims. (Cl. 252-148;?)
'to organic sulfur-containing compositions tstabilized against hydrogen sulfide evolution,
Many organic sulfur-containing compounds evolve ihydrogen sulfide in the course of their normal use or in storage. Because of the obnoxious odor pf hydrogen sulfide gas the evolu- "tion of .hydrogennulfidefrom such organic compounds ;is very objectionable. Examples of such organic compounds are ;sulfurized terp'enes,.;sul-
.furized olefins and olefin polymers, sulfurized fatty :oils :of :animal and vegetable -.origin, .asulfur- 1- ized :sperm oil, suliurized :mineral .oils and the like. Not only is the use of such organic :com-
pounds -.restricted because of the obnoxious odor of the evolved hydrogen sulfide, but the use i'o'i compositions .tcontaining various amounts of such organicsul'iur compounds is often .i-estricted because :of this :nuisance. For examplelubri'cants such :as hydrocarbon lubricating oils frequently contain .sulfurized materials to impart thereto various desired properties such as extreme pressure properties, :anticorrosion properties 'and'the like. However, such lubricants during service or in storage evolve hydrogen sulfide which 'is'found highly objectionable by the users of such lubricants. a
It is, therefore, an object of the present invention toprovide animprovedmethod of inhibiting the evolution of hydrogen sulfide from organic sulfur-containing compounds which normally evolve hydrogen sulfide during serviceor stantially inhibit the evolution of hydrogen sulfide; suitably in concentrations of from about 0.001% to about 25.0%; and preferably from about 0.01% to about 5.0% by weight based upon the sulfur-containing compounds. The alphabeta unsaturated ketone may be an alpha-beta unsaturated aliphatic, cycloaliphatic or aromatic ketone.
By an alpha-beta unsaturated ketone as used herein and in the appended claims is meant a ketone containing at least one ethylene linkage I :2 attached *to the carbonyl group, as represented byrthei structuralrgroup Operable unsaturated ketone's include thoseihavinig one or two -"d'o'i'ible bonds "-conjugated with the carbonyl group. The "ket'one group and/onthe double bond may "also be present "in a "cycloaliphatic ring.
The "following specific compounds are representative -of alpha beta unsaturated .ketone's:
CH3 HO Ill Coumarln H O CaHsC=- CaHs Benzal acetophenone The aromatic nuclei in the alpha-beta unsaturated ketones may be alkylated or contain other substituents, such as, for example hydroxyl, amino and nitro groups.
asused herein and in the appended claims means an organic compound having the'property of substantially inhibiting the formation of varnish in not to be implied that all are equivalents, since their specific activity varies to some'ex'ten't. v
The effectiveness of the alpha-beta unsaturated ketones in inhibiting the evolution of hydrogen sulfide from organic sulfur-containing c'ompounds is illustrated by thefollowing tabulated data. These data were obtained by diluting a composition containing an organic sulfur-con taining compound with an SAE 10 motor oil, placing the mixture in a container, and maintaining the mixture therein at a temperature of F. while passin nitrogen through the mixture at a rate of one liter per hour. Preformed hydrogen sulfide was firstremoved by passing'nitrogen through the mixture for one-half hour. he exit tube from the container was then connected to two vessels in series and containing lead acetate solution, the first of which had a known volume and concentration. The time required for 100 grams of the testmaterial to evolve 9 milligrams hydrogen sulfide was noted by the formation of PbS in the second vessel. The control was a mineral lubricating oil additive composition containing a KOI-l neutralized product otPzSs and an isobutylene polymer, a sulfurized mineral oil and a sulfurized terpene.
' Hours for 100 grams 0 i S a m p 1 e t 0 Y Evolve 9 mg. Hydrogen Sulfide The above data show the stabilizing effect of alpha-beta unsaturated ketones on the evolution of hydrogen sulfide from organic sulfur-containing materials. While these data were obtained with a specific lubricant composition using a particular oil-soluble detergent, namely a KOI-I neutralized reaction product of P285 and an isobutylene polymer, and particular organic sulfur-containing compounds, namely a sulfurized mineral oil and a sulfurized terpene, other oil-soluble detergent-type additives and other organic-sulfurcontaining materials can be used. For example, the oil-soluble detergent additive may be a neutralized reaction product of a phosphorus sulfide and a hydrocarbon as described in U. S. 2,316,082.
Many lubricant compositions contain from about 0.01% to about 10% by weight of an oilsoluble detergent-type additive and an organic sulfur-containing additive, the former to impart varnish inhibiting or removing properties to the lubricant, and the latter to impart lubricating.
and/or corrosion inhibiting properties. The oilsoluble detergent-type additive is frequently responsible for an increased rate of hydrogen sulfide evolution from the organic sulfur-containing additive. Under these conditions the addition of the herein-disclosed alpha-beta unsaturated ketones efiectively inhibits the evolution of hydrogen sulfide from such compositions.
The term oil-soluble detergent-type additive internal combustion engines and/or the property of removing varnish formed in such engines.
While I have described my invention by reference to specific embodiments thereof, these have been by way of illustration, and the invention is notto be limited thereby, but includes within its scope such modifications as come within the spirit of the appended claims.
I claim:
1. A lubricant composition comprising a major proportion of a hydrocarbon oil and an organic sulfur-containing compound which normally evolves hydrogen sulfide and from about 0.001% to about 25% by weight based upon the sulfurcontaining compound of an alpha-beta unsaturated aliphatic ketone.
2.' A lubricant composition as defined in claim 1 in which the alpha beta unsaturated aliphatic ketone is phorone.
3. A lubricant composition consisting essential- 1y of a major proportion of a hydrocarbon oil, an oil-soluble detergent type additive consistin essentially of a neutralized reaction product of a phosphorus sulfide and a hydrocarbon, an organic sulfur-containin compound, which normally evolves hydrogensulfide, and from about 0.001% to about 25% by weight, based upon the sulfurcontaining compound, of an alpha beta unsaturated aliphatic ketone;
4. The method ofinhibiting the evolution of hydrogen sulfide from an organic sulfur-containing compound which evolves hydrogen sulfide comprising adding to said compound from about 0.001% to about 25 by weight, based upon the sulfur-containing compound of an alpha-beta unsaturated aliphatic ketone to substantially inhibit theevolution of hydrogen sulfide from said organic sulfur-containing compound.
5. The method of claim 4 in which the ketone is phorone. 1
6. The method of inhibiting the evolution of hydrogen sulfide from a lubricant composition containing a major proportion of a hydrocarbon oil and a sulfurized organic compound which normally evolves-hydrogen sulfide comprisin employing with said, lubricant composition from about 0.001% to about 25% by weight based upon the sulfur-containing compound of an alpha-beta unsaturated aliphatic ketone'.
- JAMES 'W. GAYNOR.
REFERENCES CITED "The following references are of record in the file of this patent:
V UNITED STATES PATENTS N umber Fieser and Fieser, Organic Chemistry, D. C. Heath & 00., Boston, 1944, page 725.
Houben, Die Methoden der Organischen Chemie, vol. II, 3d edition, page 1008.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755193A (en) * 1952-11-12 1956-07-17 Marathon Corp Hydrocarbon wax containing a diaryl ketone
US2783205A (en) * 1950-05-12 1957-02-26 Socony Mobil Oil Co Inc Suppression of acidic gas evolution

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2130080A (en) * 1936-08-19 1938-09-13 Shell Dev Inhibition of peroxide formation in aliphatic ethers
US2158724A (en) * 1936-03-28 1939-05-16 Kilgore Dev Corp Stabilized composition
US2367344A (en) * 1941-01-08 1945-01-16 Wakefield & Co Ltd C C Lubricant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2158724A (en) * 1936-03-28 1939-05-16 Kilgore Dev Corp Stabilized composition
US2130080A (en) * 1936-08-19 1938-09-13 Shell Dev Inhibition of peroxide formation in aliphatic ethers
US2367344A (en) * 1941-01-08 1945-01-16 Wakefield & Co Ltd C C Lubricant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2783205A (en) * 1950-05-12 1957-02-26 Socony Mobil Oil Co Inc Suppression of acidic gas evolution
US2755193A (en) * 1952-11-12 1956-07-17 Marathon Corp Hydrocarbon wax containing a diaryl ketone

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