CA1048994A - Internal combustion engine lubricating oil composition - Google Patents
Internal combustion engine lubricating oil compositionInfo
- Publication number
- CA1048994A CA1048994A CA74214579A CA214579A CA1048994A CA 1048994 A CA1048994 A CA 1048994A CA 74214579 A CA74214579 A CA 74214579A CA 214579 A CA214579 A CA 214579A CA 1048994 A CA1048994 A CA 1048994A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- lubricating
- amount
- internal combustion
- carbon atoms
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 25
- 239000010687 lubricating oil Substances 0.000 title description 16
- 230000001050 lubricating effect Effects 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003599 detergent Substances 0.000 claims description 20
- 238000005461 lubrication Methods 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 abstract description 2
- -1 phenyl butyl Chemical group 0.000 description 26
- 239000000306 component Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002199 base oil Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000005024 alkenyl aryl group Chemical group 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 102200084471 c.4C>T Human genes 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
IMPROVED INTERNAL COMBUSTION ENGINE
LUBRICATING O L COMPOSITION
ABSTRACT OF DISCLOSURE
An improved lubricating composition comprising a major amount of oil of lubricating viscosity and minor amounts of at least one of certain sulfur-containing compounds and at least one of certain phenolic compounds which provide outstanding benefits, e.g., improved wear resistance to valve trains of internal combustion engines. These compositions may be used in an improved method of lubricating an internal combustion engine comprising at least one valve train.
LUBRICATING O L COMPOSITION
ABSTRACT OF DISCLOSURE
An improved lubricating composition comprising a major amount of oil of lubricating viscosity and minor amounts of at least one of certain sulfur-containing compounds and at least one of certain phenolic compounds which provide outstanding benefits, e.g., improved wear resistance to valve trains of internal combustion engines. These compositions may be used in an improved method of lubricating an internal combustion engine comprising at least one valve train.
Description
95~4 This invention relates to new and improved lubricating oil compositions. More particularly, it relates to lubricating oil compositions which have properties which provide improved resistance to internal combustion engine, e.g., valve train, wear.
When in use, many components of internal combustion engines may be subject to excessive wear. For example r internal combustion engines which have at least one valve train, e.g., cam system and hydraulic valve lifters for properly positioning valves during the engine cycle, may be one point where such excessive wear takes place.
Previous attempts to provide resistance to valve train wear have included using a lubricating oil composition containing zinc alkyl and aryl dithiophosphates. Although these metal salts are somewhat effective in improving the wear resistance of the valve train, their presence in the lubricating oil composition can cause problems elsewhere in the internal combustion engine system. For example, phosphorus may deactivate various platinum group metal catalysts which may be used to reduce hydrocarbon and carbon monoxide exhaust emissions from internal combustion engines. Also, the presence of these zinc salts often results in deposits upon combustion of the compounded oil. Therefore, it would be advantageous to have lubricating oil compositions having improved valve train antiwear properties without requiring the inclusion of alkyl and aryl dithiophosphates.
Therefore, one of the objects of the present invention is to provide an improved lubricating oil composition for lubri-cating internal combustion engines comprising at least one valve train to provide improved wear resistance to the valve train.
Another object of the present invention is to provide an improved method for lubricating an internal combustion engine comprising at least one valve train by which the valve train is provided with improved wear resistance. Other objects and advantages of the present invention will become apparent hereinafter.
An improved composition for lubricating internal combustion engines having at least one valve train has now been discovered. This composition comprises a major amount of oil of lubricating viscosity; a minor amount of at least one sulfur-containing compound having the following structure N N
R1 - SX - 1 1! sy R
\S/
wherein each Rl is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from 1 to about 30 carbon atoms, x and y each are integers from 1 to about 9, preferably from 1 to about 3, and the sum of x and y is at least 2, preferably from 2 to about 6; and a minor amount of at least one phenolic component having the following structure OH OH OH
~R2]p ~ a ~ R2]T
wherein each R is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from about 3 to about 20, preferably from about 8 to about 20, carbon atoms, each R2 is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from 1 to about 20 carbon 30 atoms, non-interferring non-hydrocarbon radicals, -C=O
1~4~9~34 and -C=O wherein each R3 is independently selected from the ~(R3)2 group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing from 1 to about 5 carbon atoms, a and b are each integers from l to about 6, n is an integer from zero to about 6, preferably from zero to about 3, P and T
are each integers from zero to 2, provided that the phenolic compo-nent contains at least one ortho hydrogen atom on at least one of the terminal phenyl groups, and C is an integer from zero to 3; the sulfur-containing compound and the phenolic component each being present in amounts sufficient to improve the wear resistance of the valve train or trains of the internal combustion engine.
It has been found that the combination of the sulfur-containing compound and phenolic component imparts significantly superior internal combustion engine valve train wear resistance to the lubricating oil composition than would be expected based upon the wear resistance achieved using only one of these materials.
It is preferred that the sulfur-containing compound be present 20 in an amount from about 0.005% to about 10%, more preferably from about 0.005% to about 2.0%, by weight of the total composi-tion. It is preferred that the phenolic component be present in a concentration from about 0.05% to about 15%, more preferably from about 0.1% to about 10%, by weight of the total composition.
The oils of lubricating viscosity which may be used in the compositions of the present invention include those conventionally used in lubricant manufacture. Typical examples of the suitable lubricating oils include those having a viscosity within the range of about 50 SUS to about 1200 SUS, preferably within the range of about 50 SUS to about 1~48~394 500 SUS, at 100F. These oils may be refined or otherwise processed to produce the desired quality. Although mineral oils are preferred, the base oil may be synthetic in nature.
Combinations or mixtures of two or more different base oils in a single lubricating composition are often used to provide the desired physical properties and these mixtures are, therefore, within the scope of the present invention. The base oil comprises a major portion, preferably at least about 70%, still more preferably at least about 85~, by weight of the total composition.
The general formula for the suitable sulfur-containing compounds is Rl SX ~ sy Rl wherein each Rl is the same or different monovalent essentially hydrocarbon radicals, x and y each are integers from 1 to about 9, preferably from 1 to 3, and the sum of x and y is at least
When in use, many components of internal combustion engines may be subject to excessive wear. For example r internal combustion engines which have at least one valve train, e.g., cam system and hydraulic valve lifters for properly positioning valves during the engine cycle, may be one point where such excessive wear takes place.
Previous attempts to provide resistance to valve train wear have included using a lubricating oil composition containing zinc alkyl and aryl dithiophosphates. Although these metal salts are somewhat effective in improving the wear resistance of the valve train, their presence in the lubricating oil composition can cause problems elsewhere in the internal combustion engine system. For example, phosphorus may deactivate various platinum group metal catalysts which may be used to reduce hydrocarbon and carbon monoxide exhaust emissions from internal combustion engines. Also, the presence of these zinc salts often results in deposits upon combustion of the compounded oil. Therefore, it would be advantageous to have lubricating oil compositions having improved valve train antiwear properties without requiring the inclusion of alkyl and aryl dithiophosphates.
Therefore, one of the objects of the present invention is to provide an improved lubricating oil composition for lubri-cating internal combustion engines comprising at least one valve train to provide improved wear resistance to the valve train.
Another object of the present invention is to provide an improved method for lubricating an internal combustion engine comprising at least one valve train by which the valve train is provided with improved wear resistance. Other objects and advantages of the present invention will become apparent hereinafter.
An improved composition for lubricating internal combustion engines having at least one valve train has now been discovered. This composition comprises a major amount of oil of lubricating viscosity; a minor amount of at least one sulfur-containing compound having the following structure N N
R1 - SX - 1 1! sy R
\S/
wherein each Rl is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from 1 to about 30 carbon atoms, x and y each are integers from 1 to about 9, preferably from 1 to about 3, and the sum of x and y is at least 2, preferably from 2 to about 6; and a minor amount of at least one phenolic component having the following structure OH OH OH
~R2]p ~ a ~ R2]T
wherein each R is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from about 3 to about 20, preferably from about 8 to about 20, carbon atoms, each R2 is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from 1 to about 20 carbon 30 atoms, non-interferring non-hydrocarbon radicals, -C=O
1~4~9~34 and -C=O wherein each R3 is independently selected from the ~(R3)2 group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing from 1 to about 5 carbon atoms, a and b are each integers from l to about 6, n is an integer from zero to about 6, preferably from zero to about 3, P and T
are each integers from zero to 2, provided that the phenolic compo-nent contains at least one ortho hydrogen atom on at least one of the terminal phenyl groups, and C is an integer from zero to 3; the sulfur-containing compound and the phenolic component each being present in amounts sufficient to improve the wear resistance of the valve train or trains of the internal combustion engine.
It has been found that the combination of the sulfur-containing compound and phenolic component imparts significantly superior internal combustion engine valve train wear resistance to the lubricating oil composition than would be expected based upon the wear resistance achieved using only one of these materials.
It is preferred that the sulfur-containing compound be present 20 in an amount from about 0.005% to about 10%, more preferably from about 0.005% to about 2.0%, by weight of the total composi-tion. It is preferred that the phenolic component be present in a concentration from about 0.05% to about 15%, more preferably from about 0.1% to about 10%, by weight of the total composition.
The oils of lubricating viscosity which may be used in the compositions of the present invention include those conventionally used in lubricant manufacture. Typical examples of the suitable lubricating oils include those having a viscosity within the range of about 50 SUS to about 1200 SUS, preferably within the range of about 50 SUS to about 1~48~394 500 SUS, at 100F. These oils may be refined or otherwise processed to produce the desired quality. Although mineral oils are preferred, the base oil may be synthetic in nature.
Combinations or mixtures of two or more different base oils in a single lubricating composition are often used to provide the desired physical properties and these mixtures are, therefore, within the scope of the present invention. The base oil comprises a major portion, preferably at least about 70%, still more preferably at least about 85~, by weight of the total composition.
The general formula for the suitable sulfur-containing compounds is Rl SX ~ sy Rl wherein each Rl is the same or different monovalent essentially hydrocarbon radicals, x and y each are integers from 1 to about 9, preferably from 1 to 3, and the sum of x and y is at least
2, preferably 2 to about 6. The radicals Rl can be aliphatic or aromatic including acyclic, alicyclic, aralkyl, aryl and alkaryl radicals and mixtures of such radicals. The essentially hydrocarbon radicals from which each Rl is independently chosen can contain from 1 to about 30 carbon atoms, and preferably from about 1 to about 18 carbon atoms. More preferably, each essentially hydrocarbon Rl is independently selected from the group consisting of alkyl, aralkyl and alkaryl containing up to about 18 carbon atoms. The most preferred sulfur-containing compounds are those in which each essentially hydrocarbon Rl is independently selected from the group consisting of alkyl and aralkyl containing up to about 18 carbon atoms and x and y 1048~4 each are integers from 1 to 3. Examples of suitable monovalent hydrocarbon radicals are ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl, cyclo-hexyl, phenyl ethyl, phenyl propyl, phenyl butyl, phenyl hexyl, phenyl decyl, phenyl, tolyl, benzyl, naphthyl, ethyl phenyl, propyl phenyl, butyl phenyl, hexyl phenyl, dodecyl phenyl and the like. These sulfur-containing compounds and methods for their preparation are described in United States Patent 2,719,126.
With regard to the phenolic component, the monovalent essentially hydrocarbon radicals from which each R is independently selected include alkyl and alkenyl groups containing from about
With regard to the phenolic component, the monovalent essentially hydrocarbon radicals from which each R is independently selected include alkyl and alkenyl groups containing from about
3 to about 20, preferably from about 8 to about 20, carbon atoms; and aryl, aralkyl, alkaryl, aryl alkenyl and alkenyl aryl groups containing from about 6 to about 20, preferably from ~out 8 to about 20 carbon atoms.
Typical examples of suitable alkyl groups include propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, stearyl and the like. Suitable alkenyl groups include propenyl, butenyl, pentenyl, octenyl, decenyl, dodecenylj tetradecenyl, oleic and the like. Suitable aryl, aralkyl, alkaryl, aryl alkenyl and alkenyl aryl groups include phenyl, naphthyl, phenyl ethyl, phenyl hexyl, phenyl octyl, phenyl tetradecyl, naphthyl hexyl, naphthyl octyl, ethyl phenyl, hexyl phenyl, octyl phenyl, tetra-decyl phenyl, hexyl naphthyl, octyl naphthyl, phenyl ethenyl, phenyl hexenyl, phenyl octenyl, phenyl tetradecenyl, naphthyl hexenyl, naphthyl octenyl, ethenyl phenyl, hexenyl phenyl, octenyl phenyl, tetradecenyl phenyl, hexenyl naphthyl, octenyl naphthyl and the like.
It is preferred that each R be an alkyl group, more preferably the same alkyl group, containing from about 8 to about 20 carbon atoms.
1~48994 In addition, at least one of the terminal phenyl groups of the phenolic component may be further substituted with R2, which include non-interferring monovalent essentially hydrocarbon radicals containing from 1 to about 20 carbon atoms, and non-interferring non-hydrocarbon radicals. By "non-interferring radicals" is meant radicals which do not materially interfere with the effectiveness of the phenolic component in the compositions of the present invention. Each R2 may be chosen from, for example, R and non-hydrocarbon radicals such as OH, -C=O, NH2, halide and the like radicals. In addition, a radical selected from the group consisting of -C=O and _f=o may form at 1R3 N ( R3 ) 2 least part of a substituent, R2, on at least one of the terminal phenyl groups. However, it is essential to the present invention that the phenolic component contain at least one ortho hydrogen atom on at least one terminal phenyl group, preferably at least one ortho hydrogen atom on both terminal phenyl groups. In other words, although P and T may be integers from zero to 2, it is preferred that P and T be zero or 1.
Each R3 is independently selected from the group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing from 1 to about 5 carbon atoms. Examples of such monovalent essentially hydrocarbon radicals include alkyl, such as methyl, ethyl, propyl butyl, pentyl; alkenyl, such as ethenyl, propenyl, butenyl, pentenyl; and the like radicals.
The above-described essentially hydrocarbon radicals include those hydrocarbon radicals which do not materially inter-fere with the effectiveness, e.g., anti-wear properties, of the 30 sulfur-containing compounds and phenolic components of the present 1~)48994 invention. In other words, these essentially hydrocarbon radicals include non-interferring hydrocarbon radicals. Also, these essentially hydrocarbon radicals may include non-hydro-carbonaceous substituents. Suitable non-hydrocarbonaceous substituents include those which do not materially interfer with the effectiveness, e.g., anti-wear properties, of the sulfur-containing compound and the phenolic component. Typical examples of such non-interferring substituents include OH, NH2, -C=O, halide and the like radicals.
It is preferred that the lubricating compositions of the present invention include at least one detergent. Both the ash-containing detergents, such as the conventional metal based detergents, and the ashless detergents are suitable for use.
However, it is preferred to use the ashless detergents in the compositions of the present invention. When these detergent~s are included in the compositions of this invention, they often comprise from about 1% to about 6~ by weight of the total composition.
In general, the ashless detergents preferred for use are compounds which comprise an oil solubilizing tail and a polar detergent head. Many ashless detergents fitting this general description are known to the art and are commercially available. For example, basic polyamines substituted with long chain hydrocarbons having from about 30 to about 250 carbon atoms to provide oleophilic character are suitable for use in the present invention. Specific examples of this type of ashless detergent include the polyamine-polyalkylene alkenyl succinimides in which the alkenyl group contains from about 30 to about 250 carbon atoms, and the divalent alkylene radicals, which number from about 2 to about 6, each contain from about 1 to about 3 carbon atoms; and the N-dialkylaminoalkyl alkenyl succinimides in which the alkenyl group contains from about 30 to about 250 1~48994 carbon atoms and the divalent alkylene radical along with the two alkyl radicals contain a total of less than about lO carbon atoms. The required polarity may be supplied by groups containing, for example, oxygen, sulfur, phosphorous as well as nitrogen and mixtures thereof. For example, an ashless detergent can be derived by reacting a hydrocarbon polymer containing from about 30 to about 250 carbon atoms with P2Ss. All of these suitable ashless detergents may be generally characterized as compounds comprising a hydrocarbon portion of sufficient size to render the compound oil soluble and at least one non-metallic polar portion which provides a substantial part of the detergent action.
In addition to the additives already described, lubricating oil compositions contemplated herein may contain other agents such as other detergents, anti-wear agents, antifoam agents, corrosion inhibitors, metal deactivators, pour point depressants, oiliness agents, compounds for enhancing the viscosity index of the lubricating oil, etc.
The lubricating compositions of the present invention may be prepared in any conventional manner. For example, the various components may be brought together and blended at a slightly elevated temperature, i.e., from about 100 to 130F., to insure a uniform composition.
In many instances, the additives incorporated into the present lubricating compositions are available as a mixture 11~48394 in a mineral oil or other solvent carrier. Unless otherwise noted, the weight proportions given above refer to the amount of additive material on a carrier or solvent free basis.
The lubricating compositions of the present invention can be used to lubricate internal combustion engines having at least one valve train. By the term "valve train" is meant those components of the engine, such as valve cam lobe and hydraulic valve lifter, which cooperate to properly position the valves associated with the internal combustion engine during the engine cycle. Maintaining (or causing to be maintained) a lubricating amount of the lubricating compositions of the present invention on the components of such valve train components requiring lubri-cation results in obtaining substantial benefits from the present invention.
The following examples illustrate clearly the present invention. However, these examples are not to be interpreted as specific limitations on the invention.
EXAMPLES 1 to 4 The following examples illustrate certain of the outstanding benefits of the present invention.
A series of four lubricating oil compositions were prepared by blending together individual components, noted below, at a slightly elevated temperature, i.e., from about 100F. to about 130F., to insure proper mixing. The final compositions were as follows:
_g_ 1~)4~994 Examples Component, Wt.% 1 2 3 4 .
Mineral Oil, 125 SUS
at 100F. 72.0 71.0 80.75 79.75 Viscosity Index Improver (1) 14.0 14.0 7.75 7.75 Succinimide-Type Ashless Dispersant (1)9~0 9 0 3 0 9 0 Ashless Rust Inhibitor (1) _ 0.5 0.5 0.5 10 Pour Point Depressant (1) 0.5 0.5 0.5 0.5 Di-T-Butyl Bis~henol Monosulfide(2 1.5 1.5 1.0 1.0 Phenolic Component (3) 3.0 3.0 - 1.0 Sulfur-Containing Compound(4) - 0.5 0.5 0.5 (1) These materials are commerically available and conventionally used in lubricating oil compositions.
The same material was used in each composition.
(2) This material has the following structural OH OH
formula: , ÇH3 1 ~ ÇH3 H3C C~H ~ - S ~ , ~ HC3H3 (3) This material is iso-octyl bisphenol monosul~ide and has the following structural formula:
,OH qH
~S~
30 (4) This material comprises primarily:
CH CH N - CH CH
1 3 1 3 ~ 3 1 3 H3C - f CH2 c s s c\ C - S - S - C - CH2 - C - CH3 1¢)48994 Each of these lubricating oil compositions was used to lubricate an internal combustion engine having valve trains which, in turn, was operated through a Reference Sequence III C
Test. This test, in which the engine is operated for 64 hours, is described in "Multicylinder Test Sequences for Evaluating Automotive Engine Oils--ASTM Special Technical Publication 315F", American Society for Testing and Materials (1973). The procedure as described in the above publication was modified as follows:
1. Although the cylinder bore exceeded test specifications, the piston ring to cylinder wall clearance met test specifications.
2. The engine was initially rebuilt according to test specifications. In subsequent tests, only the valve trains, i.e., cam shaft including cam lobes, valve lifters and push rods, were replaced.
The engine was again totally rebuilt only after oil consumption for a given test exceeded 9 quarts.
This revised procedure is known to produce data which can be used to make valid comparisons of the effects various lubricating oil compositions have on engine valve train wear.
Valve train wear was measured as follows. Using a micrometer, the length of each cam lobe (16 in all) is measured both before and after the test. The decrease in length of the cam lobe over the test period is indicative of the wear experienced by this component. An overall average cam lobe wear measurement results from averaging these 16 individual wear measurements.
In a similar manner the length of each valve lifter (16 in all) is measured both before and after the test. An overall average valve lifter wear measurement is determined by averaging 1~4~9~4 the changes in individual valve lifter lengths over the test period. The term "combined cam lobe and valve lifter wear" as used herein refers to the sum of the overall average cam lobe wear and the overall average valve lifter wear.
Valve train wear results using each of the four lubricating oil compositions in the modified Reference Sequence III C Test are as follows:
Combined Cam Lobe Ex. 1 Ex. 2 Ex. 3 Ex. 4 and Valve Lifter Wear, in. x 10-4/64 hours 32 11 56 20 These results demonstrate the outstanding improvement in valve train wear resistance obtained using the present compositions. For example, the compositions used in Examples 2 and 4 which contained both the phenolic component and sulfur-containing compound according to the present invention produce significantly improved valve train wear resistance relative to compositions which contain only the phenolic component (Example 1) or the sulfur-containing compound (Example 3).
Further, these examples also illustrate that it is essential that the phenolic compound include at least one ortho hydrogen atom.
For example, the composition in Example 3 includes a sulfur-containing compound according to the present invention and di-t-butyl bisphenol mono-sulfide (which compound contains no phenyl groups having ortho hydrogen atoms) and produces significantly poorer valve train wear resistance relative to, for example, composition 4 which includes a phenolic component according to the present invention which has ortho hydrogen atoms on both terminal phenyl groups.
In summary, these examples clearly show certain of the outstanding and unexpected benefits, e.g., improved valve 1~485~94 train wear resistance, achieved by the present compositions and methods of lubrication.
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the ~ollowing claims.
Typical examples of suitable alkyl groups include propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, stearyl and the like. Suitable alkenyl groups include propenyl, butenyl, pentenyl, octenyl, decenyl, dodecenylj tetradecenyl, oleic and the like. Suitable aryl, aralkyl, alkaryl, aryl alkenyl and alkenyl aryl groups include phenyl, naphthyl, phenyl ethyl, phenyl hexyl, phenyl octyl, phenyl tetradecyl, naphthyl hexyl, naphthyl octyl, ethyl phenyl, hexyl phenyl, octyl phenyl, tetra-decyl phenyl, hexyl naphthyl, octyl naphthyl, phenyl ethenyl, phenyl hexenyl, phenyl octenyl, phenyl tetradecenyl, naphthyl hexenyl, naphthyl octenyl, ethenyl phenyl, hexenyl phenyl, octenyl phenyl, tetradecenyl phenyl, hexenyl naphthyl, octenyl naphthyl and the like.
It is preferred that each R be an alkyl group, more preferably the same alkyl group, containing from about 8 to about 20 carbon atoms.
1~48994 In addition, at least one of the terminal phenyl groups of the phenolic component may be further substituted with R2, which include non-interferring monovalent essentially hydrocarbon radicals containing from 1 to about 20 carbon atoms, and non-interferring non-hydrocarbon radicals. By "non-interferring radicals" is meant radicals which do not materially interfere with the effectiveness of the phenolic component in the compositions of the present invention. Each R2 may be chosen from, for example, R and non-hydrocarbon radicals such as OH, -C=O, NH2, halide and the like radicals. In addition, a radical selected from the group consisting of -C=O and _f=o may form at 1R3 N ( R3 ) 2 least part of a substituent, R2, on at least one of the terminal phenyl groups. However, it is essential to the present invention that the phenolic component contain at least one ortho hydrogen atom on at least one terminal phenyl group, preferably at least one ortho hydrogen atom on both terminal phenyl groups. In other words, although P and T may be integers from zero to 2, it is preferred that P and T be zero or 1.
Each R3 is independently selected from the group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing from 1 to about 5 carbon atoms. Examples of such monovalent essentially hydrocarbon radicals include alkyl, such as methyl, ethyl, propyl butyl, pentyl; alkenyl, such as ethenyl, propenyl, butenyl, pentenyl; and the like radicals.
The above-described essentially hydrocarbon radicals include those hydrocarbon radicals which do not materially inter-fere with the effectiveness, e.g., anti-wear properties, of the 30 sulfur-containing compounds and phenolic components of the present 1~)48994 invention. In other words, these essentially hydrocarbon radicals include non-interferring hydrocarbon radicals. Also, these essentially hydrocarbon radicals may include non-hydro-carbonaceous substituents. Suitable non-hydrocarbonaceous substituents include those which do not materially interfer with the effectiveness, e.g., anti-wear properties, of the sulfur-containing compound and the phenolic component. Typical examples of such non-interferring substituents include OH, NH2, -C=O, halide and the like radicals.
It is preferred that the lubricating compositions of the present invention include at least one detergent. Both the ash-containing detergents, such as the conventional metal based detergents, and the ashless detergents are suitable for use.
However, it is preferred to use the ashless detergents in the compositions of the present invention. When these detergent~s are included in the compositions of this invention, they often comprise from about 1% to about 6~ by weight of the total composition.
In general, the ashless detergents preferred for use are compounds which comprise an oil solubilizing tail and a polar detergent head. Many ashless detergents fitting this general description are known to the art and are commercially available. For example, basic polyamines substituted with long chain hydrocarbons having from about 30 to about 250 carbon atoms to provide oleophilic character are suitable for use in the present invention. Specific examples of this type of ashless detergent include the polyamine-polyalkylene alkenyl succinimides in which the alkenyl group contains from about 30 to about 250 carbon atoms, and the divalent alkylene radicals, which number from about 2 to about 6, each contain from about 1 to about 3 carbon atoms; and the N-dialkylaminoalkyl alkenyl succinimides in which the alkenyl group contains from about 30 to about 250 1~48994 carbon atoms and the divalent alkylene radical along with the two alkyl radicals contain a total of less than about lO carbon atoms. The required polarity may be supplied by groups containing, for example, oxygen, sulfur, phosphorous as well as nitrogen and mixtures thereof. For example, an ashless detergent can be derived by reacting a hydrocarbon polymer containing from about 30 to about 250 carbon atoms with P2Ss. All of these suitable ashless detergents may be generally characterized as compounds comprising a hydrocarbon portion of sufficient size to render the compound oil soluble and at least one non-metallic polar portion which provides a substantial part of the detergent action.
In addition to the additives already described, lubricating oil compositions contemplated herein may contain other agents such as other detergents, anti-wear agents, antifoam agents, corrosion inhibitors, metal deactivators, pour point depressants, oiliness agents, compounds for enhancing the viscosity index of the lubricating oil, etc.
The lubricating compositions of the present invention may be prepared in any conventional manner. For example, the various components may be brought together and blended at a slightly elevated temperature, i.e., from about 100 to 130F., to insure a uniform composition.
In many instances, the additives incorporated into the present lubricating compositions are available as a mixture 11~48394 in a mineral oil or other solvent carrier. Unless otherwise noted, the weight proportions given above refer to the amount of additive material on a carrier or solvent free basis.
The lubricating compositions of the present invention can be used to lubricate internal combustion engines having at least one valve train. By the term "valve train" is meant those components of the engine, such as valve cam lobe and hydraulic valve lifter, which cooperate to properly position the valves associated with the internal combustion engine during the engine cycle. Maintaining (or causing to be maintained) a lubricating amount of the lubricating compositions of the present invention on the components of such valve train components requiring lubri-cation results in obtaining substantial benefits from the present invention.
The following examples illustrate clearly the present invention. However, these examples are not to be interpreted as specific limitations on the invention.
EXAMPLES 1 to 4 The following examples illustrate certain of the outstanding benefits of the present invention.
A series of four lubricating oil compositions were prepared by blending together individual components, noted below, at a slightly elevated temperature, i.e., from about 100F. to about 130F., to insure proper mixing. The final compositions were as follows:
_g_ 1~)4~994 Examples Component, Wt.% 1 2 3 4 .
Mineral Oil, 125 SUS
at 100F. 72.0 71.0 80.75 79.75 Viscosity Index Improver (1) 14.0 14.0 7.75 7.75 Succinimide-Type Ashless Dispersant (1)9~0 9 0 3 0 9 0 Ashless Rust Inhibitor (1) _ 0.5 0.5 0.5 10 Pour Point Depressant (1) 0.5 0.5 0.5 0.5 Di-T-Butyl Bis~henol Monosulfide(2 1.5 1.5 1.0 1.0 Phenolic Component (3) 3.0 3.0 - 1.0 Sulfur-Containing Compound(4) - 0.5 0.5 0.5 (1) These materials are commerically available and conventionally used in lubricating oil compositions.
The same material was used in each composition.
(2) This material has the following structural OH OH
formula: , ÇH3 1 ~ ÇH3 H3C C~H ~ - S ~ , ~ HC3H3 (3) This material is iso-octyl bisphenol monosul~ide and has the following structural formula:
,OH qH
~S~
30 (4) This material comprises primarily:
CH CH N - CH CH
1 3 1 3 ~ 3 1 3 H3C - f CH2 c s s c\ C - S - S - C - CH2 - C - CH3 1¢)48994 Each of these lubricating oil compositions was used to lubricate an internal combustion engine having valve trains which, in turn, was operated through a Reference Sequence III C
Test. This test, in which the engine is operated for 64 hours, is described in "Multicylinder Test Sequences for Evaluating Automotive Engine Oils--ASTM Special Technical Publication 315F", American Society for Testing and Materials (1973). The procedure as described in the above publication was modified as follows:
1. Although the cylinder bore exceeded test specifications, the piston ring to cylinder wall clearance met test specifications.
2. The engine was initially rebuilt according to test specifications. In subsequent tests, only the valve trains, i.e., cam shaft including cam lobes, valve lifters and push rods, were replaced.
The engine was again totally rebuilt only after oil consumption for a given test exceeded 9 quarts.
This revised procedure is known to produce data which can be used to make valid comparisons of the effects various lubricating oil compositions have on engine valve train wear.
Valve train wear was measured as follows. Using a micrometer, the length of each cam lobe (16 in all) is measured both before and after the test. The decrease in length of the cam lobe over the test period is indicative of the wear experienced by this component. An overall average cam lobe wear measurement results from averaging these 16 individual wear measurements.
In a similar manner the length of each valve lifter (16 in all) is measured both before and after the test. An overall average valve lifter wear measurement is determined by averaging 1~4~9~4 the changes in individual valve lifter lengths over the test period. The term "combined cam lobe and valve lifter wear" as used herein refers to the sum of the overall average cam lobe wear and the overall average valve lifter wear.
Valve train wear results using each of the four lubricating oil compositions in the modified Reference Sequence III C Test are as follows:
Combined Cam Lobe Ex. 1 Ex. 2 Ex. 3 Ex. 4 and Valve Lifter Wear, in. x 10-4/64 hours 32 11 56 20 These results demonstrate the outstanding improvement in valve train wear resistance obtained using the present compositions. For example, the compositions used in Examples 2 and 4 which contained both the phenolic component and sulfur-containing compound according to the present invention produce significantly improved valve train wear resistance relative to compositions which contain only the phenolic component (Example 1) or the sulfur-containing compound (Example 3).
Further, these examples also illustrate that it is essential that the phenolic compound include at least one ortho hydrogen atom.
For example, the composition in Example 3 includes a sulfur-containing compound according to the present invention and di-t-butyl bisphenol mono-sulfide (which compound contains no phenyl groups having ortho hydrogen atoms) and produces significantly poorer valve train wear resistance relative to, for example, composition 4 which includes a phenolic component according to the present invention which has ortho hydrogen atoms on both terminal phenyl groups.
In summary, these examples clearly show certain of the outstanding and unexpected benefits, e.g., improved valve 1~485~94 train wear resistance, achieved by the present compositions and methods of lubrication.
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the ~ollowing claims.
Claims (17)
1. A lubricating composition for internal combustion engines having at least one valve train comprising a major amount of oil of lubricating viscosity; a minor amount of at least one sulfur-containing compound having the following structure wherein each R1 is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from 1 to about 30 carbon atoms, and x and y each are integers from 1 to about 9; and a minor amount of at least one phenolic component having the following structure wherein each R is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from about 3 to about 20 carbon atoms, each R2 is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing up to about 20 carbon atoms, non-interferring non-hydrocarbon radicals, and wherein each R3 is independently selected from the group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing up to about 5 carbon atoms, a and b are each integers from 1 to about 6, n is an integer from zero to about 6, P and T are each integers from zero to 2 and C is an integer from zero to 3 provided that said phenolic component contains at least one ortho hydrogen atom on at least one of the terminal phenyl groups, said sulfur-containing compound and phenolic component each being present in amounts sufficient to improve the wear resistance of said valve train.
2. The composition of claim 1 wherein said sulfur-containing compound is present in an amount of from about 0.005%
to about 10% by weight of the total composition and said phenolic component is present in an amount of from about 0.05% to about 15% by weight of the total composition.
to about 10% by weight of the total composition and said phenolic component is present in an amount of from about 0.05% to about 15% by weight of the total composition.
3. The composition of claim 2 wherein x and y each are integers from 1 to 3 and the sum of x and y is from 2 to about 6 and each R1 contains from 1 to about 18 carbon atoms.
4. The composition of claim 2 wherein each R contains from about 8 to about 20 carbon atoms.
5. The composition of claim 3 wherein each R contains from about 8 to about 20 carbon atoms, n is an integer from zero to about 3, both P and T are integers from zero to 1, and said phenolic component contains at least one ortho hydrogen atom on both terminal phenyl groups.
6. The composition of claim 5 wherein each R1 is indepen-dently selected from the group consisting of alkyl, aralkyl, and alkaryl containing up to about 18 carbon atoms.
7. The composition of claim 5 wherein each R1 is independently selected from the group consisting of alkyl and aralkyl containing up to about 18 carbon atoms.
8. The composition of claim 5 wherein said sulfur-containing compound is present in an amount of from about 0.005%
to about 2% by weight of the total composition and said phenolic component is present in an amount of from about 0.1% to about 10%
by weight of the total composition.
to about 2% by weight of the total composition and said phenolic component is present in an amount of from about 0.1% to about 10%
by weight of the total composition.
9. The composition of claim 7 wherein said sulfur-containing compound is present in an amount of from about 0.005%
to about 2% by weight of the total composition and said phenolic component is present in an amount of from about 0.1% to about 10% by weight of the total composition.
to about 2% by weight of the total composition and said phenolic component is present in an amount of from about 0.1% to about 10% by weight of the total composition.
10. The composition of claim 7 wherein said composition further comprises from about 1% to about 6% by weight of at least one ashless detergent, said ashless detergent being a compound which comprises a hydrocarbon portion of sufficient size to render said compound oil soluble and at least one non-metallic polar portion which provides a substantial portion of the deter-gent action.
11. The composition of claim 9 wherein said composition further comprises from about 1% to about 6% by weight of at least one ashless detergent, said ashless detergent being a compound which comprises a hydrocarbon portion of sufficient size to render said compound oil soluble and at least one non-metallic polar portion which provides a substantial portion of the detergent action.
12. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 1 on the components of said engine requiring lubrication.
13. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 2 on the components of said engine requiring lubrication.
14. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 5 on the components of said engine requiring lubrication.
15. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 7 on the components of said engine requiring lubrication.
16. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 8 on the components of said engine requiring lubrication.
17. A method of lubricating an internal combustion engine having at least one valve train comprising components requiring lubrication which comprises maintaining a lubricating amount of the composition of claim 11 on the components of said engine requiring lubrication.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42137273A | 1973-12-03 | 1973-12-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048994A true CA1048994A (en) | 1979-02-20 |
Family
ID=23670239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA74214579A Expired CA1048994A (en) | 1973-12-03 | 1974-11-25 | Internal combustion engine lubricating oil composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1048994A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4904403A (en) * | 1989-06-12 | 1990-02-27 | R. T. Vanderbilt Company, Inc. | Polyalkylated 1,3,4-thiadiazoles and lubricating compositions containing same |
| US5102566A (en) * | 1987-10-02 | 1992-04-07 | Exxon Chemical Patents Inc. | Low ash lubricant compositions for internal combustion engines (pt-727) |
| US5141657A (en) * | 1987-10-02 | 1992-08-25 | Exxon Chemical Patents Inc. | Lubricant compositions for internal combustion engines |
| US5320765A (en) * | 1987-10-02 | 1994-06-14 | Exxon Chemical Patents Inc. | Low ash lubricant compositions for internal combustion engines |
-
1974
- 1974-11-25 CA CA74214579A patent/CA1048994A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102566A (en) * | 1987-10-02 | 1992-04-07 | Exxon Chemical Patents Inc. | Low ash lubricant compositions for internal combustion engines (pt-727) |
| US5141657A (en) * | 1987-10-02 | 1992-08-25 | Exxon Chemical Patents Inc. | Lubricant compositions for internal combustion engines |
| US5320765A (en) * | 1987-10-02 | 1994-06-14 | Exxon Chemical Patents Inc. | Low ash lubricant compositions for internal combustion engines |
| US4904403A (en) * | 1989-06-12 | 1990-02-27 | R. T. Vanderbilt Company, Inc. | Polyalkylated 1,3,4-thiadiazoles and lubricating compositions containing same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6114288A (en) | Lubricating oil composition for internal combustion engines | |
| US6010987A (en) | Enhancement of frictional retention properties in a lubricating composition containing a molybdenum sulfide additive in low concentration | |
| CA2168386C (en) | Lubricating oil composition for internal combustion engines | |
| US5888945A (en) | Method for enhancing and restoring reduction friction effectiveness | |
| CA1176624A (en) | Antioxidant combinations of molybdenum complexes and aromatic amine compounds | |
| JP3927724B2 (en) | Lubricating oil composition for internal combustion engines | |
| JPS588798A (en) | Lubricant oil blend | |
| JPH06313183A (en) | Lubricating oil composition | |
| US3385791A (en) | Lubricant oil composition | |
| RU2012122021A (en) | LUBRICATION AND COMPOSITIONS OF LUBRICANTS | |
| US3779920A (en) | Lubricating oil composition | |
| US3340190A (en) | Railway diesel oil | |
| US3798163A (en) | Lubricant composition for inhibiting valve recession | |
| CA1048994A (en) | Internal combustion engine lubricating oil composition | |
| US4764294A (en) | Lubricating oil (PNE-500) | |
| JP6466706B2 (en) | Gas engine lubricating oil composition | |
| KR950006559B1 (en) | Improved lubricating oil | |
| JP2000290677A (en) | Lubricating oil composition for diesel engine | |
| CA2397885C (en) | Lubricating oil compositions | |
| Gatto et al. | The antioxidant properties of organomolybdenum compounds in engine oils (C) | |
| CN105296062B (en) | A kind of preparation method of oxidation resistant natural gas engine oil | |
| KR100551808B1 (en) | Automotive Engine Oil Composition | |
| US2795547A (en) | Lubricating oil compositions | |
| US2417827A (en) | Lubricating composition | |
| US3007869A (en) | Improved diesel lubricants |