US2154096A - Lubricating oil - Google Patents

Lubricating oil Download PDF

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Publication number
US2154096A
US2154096A US111034A US11103436A US2154096A US 2154096 A US2154096 A US 2154096A US 111034 A US111034 A US 111034A US 11103436 A US11103436 A US 11103436A US 2154096 A US2154096 A US 2154096A
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United States
Prior art keywords
alloys
bearings
cadmium
oils
mercapto
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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
Application number
US111034A
Inventor
Clarence M Loane
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Standard Oil Co
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Standard Oil Co
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Publication date
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Priority to US111034A priority Critical patent/US2154096A/en
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Publication of US2154096A publication Critical patent/US2154096A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/16Naphthenic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/06Groups 3 or 13
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • Clarence nut. minor is Standard Oil 'ompany, Chicago, Ill, a corporation of Indiana No Drawing; November 16, 198i,
  • This invention relates to lubricants and, in
  • This invention has particular utility in improving the lubricating properties 01' lubricating oils and/or in preventing or inhibiting the corro-. sion of hard metal alloy bearings such as copper-lead, ca-nickel and cadmiumsilver bearings which, to a large extent, have re- I m placed soft metal bearings, such as Babbitt metal,
  • lubricating oil means visco'us oils which have a minimum via-- cosity of S. A. E. oils, or higher, and'whlch have been subjected to such refining pr that the parafllniclty of the oil is markedly inlubricating oils cause corrosion to alloy bearings of the hard metal type such as cadmium-silver alloy bearings to the extent of about 5 mg/cm.
  • the motor oils may be highly refined ,lubricatin'goils as such or mixtures 01 highly refined lubricating oils with less highly *reflned lubricating oils, or stated in another way, mixtures of corrosive oils and non-corrosive oils, examples of the latter being lubricating oil fractions from Winkler Crude or crudes of the Winkler I have found that corrosion of alloybearings of the cadmium-silver type can'be inhibited and highly desired properties can be imparted to lubricating oils by adding thereto up to 2%, but preferably 0.05% to 0.75%, of certain organic materials, particularly monovalent radical substituted heterocyclic organic compounds selected from the group consisting oi thiazines having the general formula creased.
  • thiazole as used herein includes the thio monazoles, the '(1-2-3, 1-2-4, 1-2-5, and
  • sion inhibitors amounts, for example up to 2%. but preferably 005% to 0.75%, of the foregoing compoundsare comprises adding to said lubricating oils in a. small but suificient proportion to substantially retard said corrosion a monovalent radical substituted heterocyclic organic compound selected from the group consisting of thiazines having the general formula v iii" iii" Lei LJ" i. it it it and thiazoles having the general formula in which R is a radical selected from the group consisting of, alkyl, aryl, aralkyl, amino, amino alkyl, mercapto, alkyl mercapto and aryl mercapto radicals.
  • R is a radical selected from the group consisting of, alkyl, aryl, aralkyl, amino, amino alkyl, mercapto, alkyl mercapto and aryl mercapto radicals.

Description

Patented Apr. 11, 1939 UNITED STATES- wa t-2 1 GFFIC'E I 't m 1 nnnnijca rma 01!.
Clarence nut. minor is Standard Oil 'ompany, Chicago, Ill, a corporation of Indiana No Drawing; November 16, 198i,
Serial No. 111,684
This invention relates to lubricants and, in
particular, to addition agents imparting improved properties to lubricants.
This invention has particular utility in improving the lubricating properties 01' lubricating oils and/or in preventing or inhibiting the corro-. sion of hard metal alloy bearings such as copper-lead, ca-nickel and cadmiumsilver bearings which, to a large extent, have re- I m placed soft metal bearings, such as Babbitt metal,
in the trend toward internal combustion engines having high compression ratios and increased acceleration and increased, speed characteristics.
The use of the "hard metal" bearings has created l5 lubricating and corrosion problems, particularly in connection with highly refined oils, some oi which may be very corrosive to bearings oi the hard metal type. 1 I
As used herein highly refined" lubricating oil means visco'us oils which have a minimum via-- cosity of S. A. E. oils, or higher, and'whlch have been subjected to such refining pr that the parafllniclty of the oil is markedly inlubricating oils cause corrosion to alloy bearings of the hard metal type such as cadmium-silver alloy bearings to the extent of about 5 mg/cm.
and even greater, when such bearings are sub- 3o merged for 25 hours or less in an air agitated oil which has been preoxidized at about 340-F. tor
25 to 50 hours. The motor oils may be highly refined ,lubricatin'goils as such or mixtures 01 highly refined lubricating oils with less highly *reflned lubricating oils, or stated in another way, mixtures of corrosive oils and non-corrosive oils, examples of the latter being lubricating oil fractions from Winkler Crude or crudes of the Winkler I have found that corrosion of alloybearings of the cadmium-silver type can'be inhibited and highly desired properties can be imparted to lubricating oils by adding thereto up to 2%, but preferably 0.05% to 0.75%, of certain organic materials, particularly monovalent radical substituted heterocyclic organic compounds selected from the group consisting oi thiazines having the general formula creased. It has been found that highly refined and thlazoles having the general formula E N-t c=s s or 3-1 s 'c ==o i i i in which B may be substituted alkyl and/or aryl and/or aralkyl and/or amino and/or amino alkyl and/or alkyl substituted amino and/or mercapto and/or alkyl mercapto and/or aryl mercapto radical or radicals.
The term thiazole as used herein includes the thio monazoles, the '(1-2-3, 1-2-4, 1-2-5, and
' 1-3-4) thio diaaolesand the (1-2-3-4 and 1-2-3-5) Mu-phenyl-alpha dimethyl gamma methyl penthiazoline; Mu-mercapto-gamma-methyl penthiazoline Mu-mercapto-gamma-butyl penthlazoline Gamma-methyl-alpha-dimethyl penthiazoline Para thlazine 2,4 dibutyl thiazine Some of the foregoing compounds may not be completely soluble in the lubricant, in which case eil'ective results are obtained by suspending the inhibitor in the lubricant by means of small amounts 01' a peptizing agent such as aluminum naphthenate, aluminum stearate, etc.
When highly refined motor oils are used in internal combustion engines provided. with bearings of the cadmium-silver and copper-lead type the bearings, after a comparatively short time,
i'ail due to the corrosion of the bearing metal.
This is probably due to the removal of certain constituents from the oil which behave ascorroa I have found that when small.-.:
sion inhibitors. amounts, for example up to 2%. but preferably 005% to 0.75%, of the foregoing compoundsare comprises adding to said lubricating oils in a. small but suificient proportion to substantially retard said corrosion a monovalent radical substituted heterocyclic organic compound selected from the group consisting of thiazines having the general formula v iii" iii" Lei LJ" i. it it it and thiazoles having the general formula in which R is a radical selected from the group consisting of, alkyl, aryl, aralkyl, amino, amino alkyl, mercapto, alkyl mercapto and aryl mercapto radicals.
2. The method of preventing corrosion of bear-- ing metal alloys having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys andcopp er-lead alloys in the presence of-highly refined lubricating oils normally corrosive to said bearings which comprises adding to said lubricating oils about 0.05% to about 0.75% of a mono- I valent radical substituted heterocyclic organic compound selected from the group consisting of thiazines having the general formula and thiazoles having the general formula in which R is a radical selected from the group consisting of alkyl, aryl, aralkyl, amino, amino alkyl, mercapto, alkyl mercapto and aryl mercapto radicals.
3. The method of preventing corrosion of bearing metal alloys having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys in the presence of highly refined lubricating oils normally corrosive to said bearings which comprises adding to said lubricating oils an alkyl thiazole in a small but suflicient proportion to substantially retard said corrosion.
4. The method of preventing corrosion of bearing metal alloys having the corrosivefsusceptlbility 01 alloys of the group consi ti g 91 m, mium-silver alloys, cadmium-nickelfalloys" and copper-lead alloys in the presence of highly refined lubricating oils normally corrosivejtofsaid bearings which comprises adding to said lubricating 01] from about 0.05% to-about' 0;75%*of a tributyl thiazole.
5. The method of preventing corrosion or bear- Y ing metal alloys having the corrosive susceptibility 01' alloys of the group consisting of 'cadmium-silver alloys, cadmium-nickel alloys and.
copper-lead alloys in the presence of highly refined lubricating oils normally corrosive tojsaid bearings which comprises adding to said lubricating oils an aryl thiazole in a small but suflicient proportion to substantially'retard said corrosion.
6. The method of preventing corrosion ot'bearing metal alloys having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys in the'presence of highly refined lubricating oils normally corrosive to said bearings which comprises adding tosaid lubricating oil from about 0.05% to about 0.75% of a triphenyl thiazole.
'I.- The method of preventing corrosion of hearing metal alloys having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys in the presence of highly refined lubricating oils normally corrosive to said bearings which comprises adding to said lubrieating oil from about 0.05% to about 0.75% of a mercapto thiazole.
CLARENCE M.
US111034A 1936-11-16 1936-11-16 Lubricating oil Expired - Lifetime US2154096A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2492632A (en) * 1946-12-03 1949-12-27 Socony Vacuum Oil Co Inc Alkyl thienyl ketimine from acylthiophene and primary amine reaction
US2518351A (en) * 1947-05-28 1950-08-08 Socony Vacuum Oil Co Inc N (thiophenalkyl) arylamines in mineral oil
US2528785A (en) * 1947-09-26 1950-11-07 Socony Vacuum Oil Co Inc Mineral oil compositions containing alkyl aminobenzothiophenes
US2607737A (en) * 1949-07-09 1952-08-19 California Research Corp Condensation product of a 2-thiothiazole, formaldehyde, and alkyl phenol to inhibit sulfur corrosive lubricants
US2620303A (en) * 1949-07-09 1952-12-02 California Research Corp Mercaptothiazines as sulfur-corrosion inhibiting agents
US2703785A (en) * 1953-02-27 1955-03-08 Standard Oil Co Soluble compositions containing a 2, 5-dimercapto-1, 3, 4-thiadiazole derivative
US2719125A (en) * 1952-12-30 1955-09-27 Standard Oil Co Oleaginous compositions non-corrosive to silver
US2719827A (en) * 1951-12-05 1955-10-04 California Research Corp Lubricating oil compositions containing sulfur corrosive to silver
US2796403A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2796402A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2796404A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2964471A (en) * 1959-06-26 1960-12-13 Cities Service Res & Dev Co Method of inhibiting corrosion
US3192225A (en) * 1961-04-24 1965-06-29 Geigy Chem Corp 2-substituted aminothiazoles
US3228888A (en) * 1960-05-13 1966-01-11 Geigy Chem Corp Method of stabilization with substituted thiazole stabilizers and stabilized compositions thereof
US3467666A (en) * 1966-11-07 1969-09-16 Geigy Chem Corp 2-substituted aminothiazoles
US3896050A (en) * 1974-07-05 1975-07-22 Texaco Inc Lubricating oil additives
US4446056A (en) * 1979-12-10 1984-05-01 Petrolite Corporation Preparation of mixture of nitrogen and sulfur-nitrogen heterocyclics and use in corrosion inhibiting
US4485022A (en) * 1983-08-24 1984-11-27 Phillips Petroleum Company Lubricating compositions containing normal-alkyl substituted 2-thiazoline disulfide antioxidants

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2492632A (en) * 1946-12-03 1949-12-27 Socony Vacuum Oil Co Inc Alkyl thienyl ketimine from acylthiophene and primary amine reaction
US2518351A (en) * 1947-05-28 1950-08-08 Socony Vacuum Oil Co Inc N (thiophenalkyl) arylamines in mineral oil
US2528785A (en) * 1947-09-26 1950-11-07 Socony Vacuum Oil Co Inc Mineral oil compositions containing alkyl aminobenzothiophenes
US2607737A (en) * 1949-07-09 1952-08-19 California Research Corp Condensation product of a 2-thiothiazole, formaldehyde, and alkyl phenol to inhibit sulfur corrosive lubricants
US2620303A (en) * 1949-07-09 1952-12-02 California Research Corp Mercaptothiazines as sulfur-corrosion inhibiting agents
US2719827A (en) * 1951-12-05 1955-10-04 California Research Corp Lubricating oil compositions containing sulfur corrosive to silver
US2719125A (en) * 1952-12-30 1955-09-27 Standard Oil Co Oleaginous compositions non-corrosive to silver
US2703785A (en) * 1953-02-27 1955-03-08 Standard Oil Co Soluble compositions containing a 2, 5-dimercapto-1, 3, 4-thiadiazole derivative
US2796403A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2796402A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2796404A (en) * 1953-11-16 1957-06-18 Texas Co Extreme pressure lubricant compositions
US2964471A (en) * 1959-06-26 1960-12-13 Cities Service Res & Dev Co Method of inhibiting corrosion
US3228888A (en) * 1960-05-13 1966-01-11 Geigy Chem Corp Method of stabilization with substituted thiazole stabilizers and stabilized compositions thereof
US3192225A (en) * 1961-04-24 1965-06-29 Geigy Chem Corp 2-substituted aminothiazoles
US3201409A (en) * 1961-04-24 1965-08-17 John D Spivack 2-substituted aminothiazoles
US3467666A (en) * 1966-11-07 1969-09-16 Geigy Chem Corp 2-substituted aminothiazoles
US3896050A (en) * 1974-07-05 1975-07-22 Texaco Inc Lubricating oil additives
US4446056A (en) * 1979-12-10 1984-05-01 Petrolite Corporation Preparation of mixture of nitrogen and sulfur-nitrogen heterocyclics and use in corrosion inhibiting
US4485022A (en) * 1983-08-24 1984-11-27 Phillips Petroleum Company Lubricating compositions containing normal-alkyl substituted 2-thiazoline disulfide antioxidants

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