EP0788535B1 - Novel cobalt containing deposit control additives - Google Patents
Novel cobalt containing deposit control additives Download PDFInfo
- Publication number
- EP0788535B1 EP0788535B1 EP95938911A EP95938911A EP0788535B1 EP 0788535 B1 EP0788535 B1 EP 0788535B1 EP 95938911 A EP95938911 A EP 95938911A EP 95938911 A EP95938911 A EP 95938911A EP 0788535 B1 EP0788535 B1 EP 0788535B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cobalt
- oil
- composition
- formulated
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010941 cobalt Substances 0.000 title claims description 34
- 229910017052 cobalt Inorganic materials 0.000 title claims description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 31
- 239000000654 additive Substances 0.000 title claims description 15
- 239000003921 oil Substances 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 230000001050 lubricating effect Effects 0.000 claims description 10
- 239000010687 lubricating oil Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 7
- 230000002708 enhancing effect Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000003599 detergent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical class [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 239000010705 motor oil Substances 0.000 claims 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims 1
- 235000019198 oils Nutrition 0.000 description 34
- 239000002199 base oil Substances 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229940035422 diphenylamine Drugs 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- -1 cobalt naphthenates Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BIQHBUMGFWTXCW-UHFFFAOYSA-J methanethioate;molybdenum(4+) Chemical compound [Mo+4].[O-]C([S-])=S.[O-]C([S-])=S BIQHBUMGFWTXCW-UHFFFAOYSA-J 0.000 description 1
- JXASPOITXHFJLW-UHFFFAOYSA-N nonylsulfanylbenzene Chemical compound CCCCCCCCCSC1=CC=CC=C1 JXASPOITXHFJLW-UHFFFAOYSA-N 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/24—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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
- C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/56—Acids of unknown or incompletely defined constitution
- C10M129/58—Naphthenic acids
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
- C10M129/92—Carboxylic acids
- C10M129/93—Carboxylic acids having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix 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
- C10M2207/126—Carboxylix 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 monocarboxylic
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
Definitions
- the present invention relates to novel lube oil base stock compositions containing deposit control additives.
- Copper is a common lube oil antioxidant additive. However, it forms deposits at higher temperatures. As a result additives and methods for increasing the lifetime of copper antioxidants and for retarding their degradation and resulting deposit formation would be desirable. The present invention addresses these needs.
- FR-A-2 372 222 and GB-A-772 029 disclose the use of copper and cobalt as lubricating oil additives.
- the present invention provides for formulated lubricating oil compositions, comprising a base stock of lubricating viscosity, a copper containing antioxidant and a deposit control enhancing amount of an oil soluble or oil dispersible cobalt containing compound.
- the present invention also provides for a method of controlling deposit formation in an engine lubricating system, comprising adding a deposit control enhancing amount of an oil soluble or oil dispersible cobalt containing compound to a base oil of lubricating viscosity formulated with a copper containing antioxidant.
- the present invention may suitably comprise, consist or consist essentially of the elements disclosed herein and may be practiced in the absence of any element not disclosed herein as required.
- the present invention provides for a method of controlling deposits, i.e. retarding deposit formation and buildup, in internal combustion engines by enhancing the performance of a certain base stocks containing copper containing antioxidants, with the addition of cobalt containing compounds as disclosed in claim 1.
- the invention also provides for novel formulated oil and additive compositions related thereto. As a benefit the life of the copper containing antioxidant and the formulated oil can be extended, as disclosed in claim 7 and the use of cobalt and copper soluble compound to enhance the control of deposit formation disclosed in claim 8.
- the starting materials disclosed herein may be made by methods known in the art or obtained from commercial sources.
- copper containing compounds and the cobalt containing compounds are individually present in a minor amount by weight percent of the compound to a major amount of the oil.
- minor amount as used herein is intended to mean that amount is less than 50% by weight of the composition.
- major amount is intended to mean that amount is more than 50% by weight of the composition.
- the copper antioxidant should be present in a hydrocarbon, preferably oil soluble or dispersible form. These antioxidants are of the type and are present in amounts typically used as lube additives for internal combustion engines as these represent an economical and readily available source of the materials. Suitable examples include copper naphthenates, oleates and polyisobutylene succinic anhydride (“PIBSA”) compounds. Thus, these amounts may vary with the particular formulation without affecting the present invention.
- PIBSA polyisobutylene succinic anhydride
- cobalt containing compounds that produce the synergistic effect of enhancing deposit control in formulated oils having copper containing antioxidants therein should be present in a hydrocarbon, preferably oil soluble or dispersible form.
- any source of cobalt is acceptable provided that it is oil soluble or dispersible.
- oil soluble cobalt salts such as cobalt naphthenates, or cobalt stearates and inorganic cobalt salts in combination with suitable dispersants or surfactants, for example cobalt PIBSA or cobalt acetylacetonate ("acac").
- the cobalt containing compound be compatible with the copper containing compound as well as the base stock or formulated oil to which it is added in order to achieve the synergistic effect of retarding deposit formation and extending the life of the copper antioxidant and formulated oil.
- the cobalt is present in an amount sufficient to enhance deposit control performance, i.e., to retard deposit formation and, thus, extend the life of the lube oil containing the copper antioxidant.
- This amount typically is a minor amount of cobalt metal, from about 10-1000 ppm, preferably about 50-500 ppm, more preferably about 75-200 ppm, as determined on the basis of the amount of the metal present in the formulated compositions.
- hydrocarbon or oil “soluble” and “dispersible” means that the material is soluble or stably dispersible in hydrocarbons, preferably oils of lubricating viscosity, that are liquid at temperatures found in the environments at which the formulated oils are typically used.
- stably dispersible means that the material is capable of being dispersed in the hydrocarbon or oil to an extent that allows it to function in its intended manner.
- a copper antioxidant or the cobalt antioxidant is hydrocarbon or oil soluble or dispersible if it is capable of being dissolved, dispersed or otherwise suspended in the oil in a manner sufficient to allow the oil to function as a lubricant.
- Detergents such as neutral and/or overbased blends of calcium sulfonated detergents and dispersants such as borated PIBSA-PAM may be used to achieve oil solubility or dispersibility.
- the base oils employed in the lubricant compositions according to the invention may be any base oil suitable for the intended use of the lubricant.
- the base oil may be, for example, a conventionally refined mineral oil, an oil derived from coal tar or shale, a vegetable oil, an animal oil, a hydrocracked oil, or a synthetic oil, or a mixture of two or more of these types of oils.
- synthetic oils include hydroisomerised paraffins, polyalpha-olefins, polybutenes, alkylbenzenes, polyglycols, esters such as polyol esters or dibasic carboxylic acid esters, alkylene oxide polymers, and silicone oils.
- the viscosity of the base oil depends upon the intended use, but generally is in the range of from 3 to 20cSt at 100°C.
- the present invention also permits the use of other additives in the oil compositions.
- additives include such conventional additive types as viscosity modifiers, extreme pressure agents, corrosion-inhibiting agents, pour point depressants, color stabilizing agents, anti-foam agents, and other such additive materials known generally to those skilled in the art of formulating lubricants.
- IPDT Inclined Panel Deposit Test
- the IPDT is a bench test that simulates piston deposit formation during engine operation. 35 ml of oil was heated to 150°C and run down a metal panel heated to 308°C at a 2 degree angle. The oil was then pumped through a sump back onto the panel. The oil was exposed to a synthetic blow-by gas throughout the 2 hour duration of the test. The panel was cooled and washed with heptane. The rating figure (demerit) value indicates the amount of deposition on the plate. A higher number (greater demerit) indicates greater deposit formation, with 10 being the highest and zero the lowest.
- Table 1 shows the results of the IPDT using a commercially available mineral oil base stock formulated with commercially available additive package containing copper PIBSA and a monofunctional olefin copolymer VI improver, borated PIBSA pour point depressant, calcium sulfonate overbased detergent, neutral calcium sulfonate detergent, nonyl phenyl sulfide antioxidant, ZDDP antiwear, molybdenum dithiocarbonate antiwear additive alone (Run 1) and in the presence of cobalt additive (Run 2) demonstrating the synergistic effect of adding cobalt in copper antioxidant systems.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
The present invention relates to novel lube oil base stock
compositions containing deposit control additives.
Copper is a common lube oil antioxidant additive. However,
it forms deposits at higher temperatures. As a result additives and
methods for increasing the lifetime of copper antioxidants and for
retarding their degradation and resulting deposit formation would be
desirable. The present invention addresses these needs.
FR-A-2 372 222 and GB-A-772 029 disclose the use
of copper and cobalt as lubricating oil additives.
The present invention provides for formulated lubricating
oil compositions, comprising a base stock of lubricating viscosity, a
copper containing antioxidant and a deposit control enhancing amount
of an oil soluble or oil dispersible cobalt containing compound.
The present invention also provides for a method of controlling
deposit formation in an engine lubricating system, comprising
adding a deposit control enhancing amount of an oil soluble or oil
dispersible cobalt containing compound to a base oil of lubricating
viscosity formulated with a copper containing antioxidant.
The present invention may suitably comprise, consist or
consist essentially of the elements disclosed herein and may be
practiced in the absence of any element not disclosed herein as
required.
The present invention provides for a method of controlling
deposits, i.e. retarding deposit formation and buildup, in internal
combustion engines by enhancing the performance of a certain base
stocks containing copper containing antioxidants, with the addition of
cobalt containing compounds as disclosed in claim 1. The invention also provides for novel
formulated oil and additive compositions related thereto. As a
benefit the life of the copper containing antioxidant and the
formulated oil can be extended, as disclosed in claim 7 and the
use of cobalt and copper soluble compound to enhance the control of deposit formation disclosed in claim 8.
The starting materials disclosed herein may be made by
methods known in the art or obtained from commercial sources.
Generally copper containing compounds and the cobalt
containing compounds are individually present in a minor amount by
weight percent of the compound to a major amount of the oil. The term
"minor amount" as used herein is intended to mean that amount is less
than 50% by weight of the composition. The term "major amount" is
intended to mean that amount is more than 50% by weight of the
composition.
The copper antioxidant should be present in a hydrocarbon,
preferably oil soluble or dispersible form. These antioxidants are of
the type and are present in amounts typically used as lube additives
for internal combustion engines as these represent an economical and
readily available source of the materials. Suitable examples include
copper naphthenates, oleates and polyisobutylene succinic anhydride
("PIBSA") compounds. Thus, these amounts may vary with the particular
formulation without affecting the present invention.
The cobalt containing compounds that produce the synergistic
effect of enhancing deposit control in formulated oils having copper
containing antioxidants therein should be present in a hydrocarbon,
preferably oil soluble or dispersible form. Thus, any source of
cobalt is acceptable provided that it is oil soluble or dispersible.
Examples include oil soluble cobalt salts such as cobalt naphthenates,
or cobalt stearates and inorganic cobalt salts in combination with
suitable dispersants or surfactants, for example cobalt PIBSA or
cobalt acetylacetonate ("acac"). It is desirable that the cobalt
containing compound be compatible with the copper containing compound
as well as the base stock or formulated oil to which it is added in
order to achieve the synergistic effect of retarding deposit formation
and extending the life of the copper antioxidant and formulated oil.
The cobalt is present in an amount sufficient to enhance deposit
control performance, i.e., to retard deposit formation and, thus,
extend the life of the lube oil containing the copper antioxidant.
This amount, for lube applications, typically is a minor amount of
cobalt metal, from about 10-1000 ppm, preferably about
50-500 ppm, more preferably about 75-200 ppm, as determined on the
basis of the amount of the metal present in the formulated
compositions.
The foregoing may be added to the base and formulated oils
by means well known in the art.
As used herein the term hydrocarbon or oil "soluble" and
"dispersible" means that the material is soluble or stably dispersible
in hydrocarbons, preferably oils of lubricating viscosity, that are
liquid at temperatures found in the environments at which the
formulated oils are typically used. The term "stably dispersible"
means that the material is capable of being dispersed in the
hydrocarbon or oil to an extent that allows it to function in its
intended manner. Thus, for example in lube oil formulations, a copper
antioxidant or the cobalt antioxidant is hydrocarbon or oil soluble or
dispersible if it is capable of being dissolved, dispersed or
otherwise suspended in the oil in a manner sufficient to allow the oil
to function as a lubricant. Detergents such as neutral and/or
overbased blends of calcium sulfonated detergents and dispersants
such as borated PIBSA-PAM may be used to achieve oil solubility or
dispersibility.
The base oils employed in the lubricant compositions
according to the invention may be any base oil suitable for the
intended use of the lubricant. Thus, the base oil may be, for
example, a conventionally refined mineral oil, an oil derived from
coal tar or shale, a vegetable oil, an animal oil, a hydrocracked oil,
or a synthetic oil, or a mixture of two or more of these types of
oils. Examples of synthetic oils include hydroisomerised paraffins,
polyalpha-olefins, polybutenes, alkylbenzenes, polyglycols, esters
such as polyol esters or dibasic carboxylic acid esters, alkylene
oxide polymers, and silicone oils. The viscosity of the base oil
depends upon the intended use, but generally is in the range of from 3
to 20cSt at 100°C.
The present invention also permits the use of other
additives in the oil compositions. These other additives include such
conventional additive types as viscosity modifiers, extreme pressure
agents, corrosion-inhibiting agents, pour point depressants, color
stabilizing agents, anti-foam agents, and other such additive
materials known generally to those skilled in the art of formulating
lubricants.
It is expected that the benefits described herein can be
achieved over the range of amounts and types of copper containing
antioxidants generally used as lube oil additives.
It is expected that similar benefits could be obtained in
fuels.
The present invention may be exemplified by reference to the
following examples:
The effect of the presence of cobalt containing compounds in
a lube oil formulated with a copper containing antioxidant was
evaluated using the Inclined Panel Deposit Test (IPDT). The
beneficial and synergestic effect on engine deposit formation of
adding cobalt containing compounds to base oils formulated with copper
containing antioxidants can be determined by measuring the buildup of
deposits during the course of the test. The beneficial effect of
cobalt addition is evidenced by smaller amounts of deposit formation.
The IPDT is a bench test that simulates piston deposit
formation during engine operation. 35 ml of oil was heated to 150°C
and run down a metal panel heated to 308°C at a 2 degree angle. The
oil was then pumped through a sump back onto the panel. The oil was
exposed to a synthetic blow-by gas throughout the 2 hour duration of
the test. The panel was cooled and washed with heptane. The rating
figure (demerit) value indicates the amount of deposition on the
plate. A higher number (greater demerit) indicates greater deposit
formation, with 10 being the highest and zero the lowest.
Table 1 shows the results of the IPDT using a commercially
available mineral oil base stock formulated with commercially
available additive package containing copper PIBSA and a
monofunctional olefin copolymer VI improver, borated PIBSA pour point
depressant, calcium sulfonate overbased detergent, neutral calcium
sulfonate detergent, nonyl phenyl sulfide antioxidant, ZDDP antiwear,
molybdenum dithiocarbonate antiwear additive alone (Run 1) and in the
presence of cobalt additive (Run 2) demonstrating the synergistic
effect of adding cobalt in copper antioxidant systems. A comparative
example demonstrating the deterioration of results upon addition of
cobalt to a commercially available diphenyl amine and hindered
phenolic antioxidant additive package is shown in Table 2.
| INCLINED PANEL DEPOSIT TEST | ||
| FORMULATED OIL | RESULT (DEMERITS) | |
| (1) | Lube base stock formulated with copper antioxidant | 6.4 |
| (2) | Lube base stock formulated with copper antioxidant + 100 ppm cobalt antioxidant | 3.4 |
| INCLINED PANEL DEPOSIT TEST (COMPARATIVE DATA) | ||
| FORMULATED OIL | RESULT (DEMERITS) | |
| (1) | Lube base stock formulated with diphenyl amine and hindered phenolic antioxidant | 2.4 |
| (2) | Lube base stock formulated with diphenyl amine and hindered phenolic antioxidant + 100 ppm cobalt | 4.0 |
Claims (8)
- A formulated internal combustion engine lubricating oil composition, comprising a base engine oil of lubricating viscosity, a copper containing antioxidant, and a deposit control enhancing amount of an oil soluble or oil dispersible cobalt containing compound, which provides from 10 to 1000 ppm by weight of cobalt metal in the formulated lubricant composition.
- The composition of claim 1 wherein the amount of the cobalt containing compound is from 50 to 500 ppm by weight based on the amount of cobalt metal in the formulated lubricant composition.
- The composition of claim 1 or 2 wherein the cobalt containing compound is selected from cobalt naphthenates, cobalt stearates, cobalt polyisobutylene succinic anhydrides and cobalt acetylacetonates.
- The composition of any preceding claim wherein the copper containing antioxidant is selected from copper naphthenates, oleates, stearates and polyisobutylene succinic anhydrides.
- The composition of any preceding claim further comprising at least one agent selected from a dispersant and a detergent.
- The composition of any preceding claim further comprising at least one additive selected from antiwear agents, viscosity modifiers, extreme pressure agents, antifoam agents, pour point depressants, and colour stabilizing agents.
- A method of controlling deposit formation in an internal combustion engine lubricating system, comprising: combining a deposit control enhancing amount of from 10 to 1000 ppm by weight based on the amount of cobalt metal in the formulated lubricant composition of an oil soluble or oil dispersible cobalt containing compound with a base engine oil of lubricating viscosity formulated with a copper containing antioxidant.
- Use of an oil soluble or oil dispersible cobalt containing compound to enhance the control of deposit formation in an internal combustion engine lubricating system, which lubricating system comprises a base engine oil of lubricating viscosity and a copper containing antioxidant.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US328209 | 1981-12-07 | ||
| US32820994A | 1994-10-25 | 1994-10-25 | |
| PCT/US1995/013840 WO1996012779A1 (en) | 1994-10-25 | 1995-10-25 | Novel cobalt containing deposit control additives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0788535A1 EP0788535A1 (en) | 1997-08-13 |
| EP0788535B1 true EP0788535B1 (en) | 2000-05-03 |
Family
ID=23279994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95938911A Expired - Lifetime EP0788535B1 (en) | 1994-10-25 | 1995-10-25 | Novel cobalt containing deposit control additives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0788535B1 (en) |
| JP (1) | JPH10508053A (en) |
| CA (1) | CA2201960A1 (en) |
| DE (1) | DE69516710T2 (en) |
| WO (1) | WO1996012779A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7648949B2 (en) | 2005-01-27 | 2010-01-19 | The Lubrizol Corporation | Low phosphorus cobalt complex-containing engine oil lubricant |
| US10000721B2 (en) | 2014-12-30 | 2018-06-19 | Exxonmobil Research And Engineering Company | Lubricating oil compositions with engine wear protection |
| US10781397B2 (en) | 2014-12-30 | 2020-09-22 | Exxonmobil Research And Engineering Company | Lubricating oil compositions with engine wear protection |
| WO2016184842A1 (en) * | 2015-05-18 | 2016-11-24 | Shell Internationale Research Maatschappij B.V. | Lubricating composition |
| JP6480324B2 (en) * | 2015-12-28 | 2019-03-06 | Ｊｘｔｇエネルギー株式会社 | Lubricating oil composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB772029A (en) * | 1954-12-07 | 1957-04-10 | Shell Res Ltd | Lubricating oil compositions |
| US3360467A (en) * | 1965-03-29 | 1967-12-26 | Monsanto Res Corp | Functional fluid |
| US3412028A (en) * | 1966-12-13 | 1968-11-19 | Texaco Inc | Synthetic ester base lubricating composition containing a copper or cobalt acetylacetonate |
| US4122033A (en) * | 1976-11-26 | 1978-10-24 | Black James F | Oxidation inhibitor and compositions containing the same |
| EP0444830A1 (en) * | 1990-02-26 | 1991-09-04 | Ethyl Petroleum Additives Limited | Succinimide composition |
-
1995
- 1995-10-25 WO PCT/US1995/013840 patent/WO1996012779A1/en active IP Right Grant
- 1995-10-25 DE DE69516710T patent/DE69516710T2/en not_active Expired - Fee Related
- 1995-10-25 CA CA002201960A patent/CA2201960A1/en not_active Abandoned
- 1995-10-25 JP JP8514140A patent/JPH10508053A/en active Pending
- 1995-10-25 EP EP95938911A patent/EP0788535B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69516710T2 (en) | 2000-08-31 |
| JPH10508053A (en) | 1998-08-04 |
| EP0788535A1 (en) | 1997-08-13 |
| DE69516710D1 (en) | 2000-06-08 |
| CA2201960A1 (en) | 1996-05-02 |
| WO1996012779A1 (en) | 1996-05-02 |
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