CA2344490A1 - Lubricating oil compositions comprising phosphorous esters - Google Patents
Lubricating oil compositions comprising phosphorous esters Download PDFInfo
- Publication number
- CA2344490A1 CA2344490A1 CA002344490A CA2344490A CA2344490A1 CA 2344490 A1 CA2344490 A1 CA 2344490A1 CA 002344490 A CA002344490 A CA 002344490A CA 2344490 A CA2344490 A CA 2344490A CA 2344490 A1 CA2344490 A1 CA 2344490A1
- Authority
- CA
- Canada
- Prior art keywords
- lubricating oil
- acid ester
- oil composition
- range
- group
- 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.)
- Abandoned
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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- 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
- C10M129/95—Esters
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- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
- C10M133/56—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/08—Ammonium or amine salts
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
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- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/043—Mannich bases
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M2223/043—Ammonium or amine salts thereof
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- C10M2223/045—Metal containing thio derivatives
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- C10M2223/047—Thioderivatives not containing metallic elements
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- C10M2223/049—Phosphite
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- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10N2010/04—Groups 2 or 12
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
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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)
Abstract
The present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils.
In its broadest aspect, the present invention comprises a lubricating oil composition having a major amount of a base oil of lubricating viscosity and a minor, but effective amount, of A. at least one a compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. a phosphorus acid ester and/or an amine thereof; and C. at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance..
In its broadest aspect, the present invention comprises a lubricating oil composition having a major amount of a base oil of lubricating viscosity and a minor, but effective amount, of A. at least one a compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. a phosphorus acid ester and/or an amine thereof; and C. at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance..
Description
LUBRICATING OIL COMPOSITION HAVING EXCELLENT THERMAL STABILITY, EXTREME PRESSURE RESISTANCE AND ANTI-WEAR PERFORMANCE
The present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
BACKGROUND OF THE INVENTION
The technology that is normally responsible for separating the applications of lubricants is anti-wear or extreme pressure (EP) chemistry. The distinction between anti-wear and EP is difficult to define but anti-wear is in general based on the prevention of damage caused by moderate and intermittent loadings whereas EP is the protection from shock loadings and continually applied heavy or ;>liding loads. Two types of chemistry have evolved around these needs. EP and anti-wear protection are typically provided by "ash-containing" components such as zinc; dithiophosphates (ZnDTP).
ZnDTP are commonly employed as additives in lubricating oils primarily for their excellent extreme pressure and anti-wear properties. However, ZnDTP may decompose at high operating temperatures and produce sludge that can contribute to filter plugging and viscosity increase of the lubricating oil. The other type of chemistry involves "ashless" sulfur and phosphorus chemistry. The reference to ash containing or ashless chemistry is historical and there are now ashless alternatives to ZnDTP.
Generally, phosphorus-containing anti-wear agents have excellent thermal stability under conditions of high temperature operation as dernanded, for instance, in industrial oils such as hydraulic oil, bearing oil, industrial gear oil and sliding surface lubricating oil. But, extreme pressure and anti-wear performance: is relatively poor in comparison to ZnDTP. Thus, in practice ZnDTP-free lubricating oiils combining thermal stability, extreme pressure resistance and anti-wear performance are rare. It is not easy to produce lubricating oils having thermal stability at high temperatures with concomitant extreme pressure and anti-wear performance.
Japanese Patent Provisional Publication No. 9-11127'7 describes an ashless hydraulic oil composition comprising a base oil having a % CA (ipercentage that represents the number of carbon atoms in aromatic groups divided by total carbon atoms) 5 or less, (A) 0.01-5 wt % of an amine-type oxidation inhibitor, (B) 0.01-5 wt % of a phenolic oxidation inhibitor, (C) 0.01-5 wt % of a phosphoric acicl ester, and (D) 0.001-5 wt % of an aliphatic amide andlor a polyhydric alcohol ester.
Japanese Patent Provisional Publication No. 11-323365 describes a hydraulic oil using a mineral oil, a synthetic oil, or a mixture thereof, as a base oil, which further contains (A) 0.01-1 wt % of an alkenyl succinimide or its derivative, (B) 0.1-5 wt % of a phosphoric acid ester, (C) 0.05-0.5 wt % of an alkylated diphenylamine, and (D) 0.05-0.5 wt % of a hindered phenol.
SUMMARY OF THE INVENITION
The present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
In its broadest aspect, the present invention relates to .a lubricating oil composition comprising a major amount of a base oil of lubricating 'viscosity and A. 0.1 to 5.0 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 0.01 to 1.0 wt % of a phosphorus acid e;>ter andlor an amine thereof; and C. 0.01 to 2.0 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester and/or an amine thereof is in the range of 1:1 to 500:1.
The present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
BACKGROUND OF THE INVENTION
The technology that is normally responsible for separating the applications of lubricants is anti-wear or extreme pressure (EP) chemistry. The distinction between anti-wear and EP is difficult to define but anti-wear is in general based on the prevention of damage caused by moderate and intermittent loadings whereas EP is the protection from shock loadings and continually applied heavy or ;>liding loads. Two types of chemistry have evolved around these needs. EP and anti-wear protection are typically provided by "ash-containing" components such as zinc; dithiophosphates (ZnDTP).
ZnDTP are commonly employed as additives in lubricating oils primarily for their excellent extreme pressure and anti-wear properties. However, ZnDTP may decompose at high operating temperatures and produce sludge that can contribute to filter plugging and viscosity increase of the lubricating oil. The other type of chemistry involves "ashless" sulfur and phosphorus chemistry. The reference to ash containing or ashless chemistry is historical and there are now ashless alternatives to ZnDTP.
Generally, phosphorus-containing anti-wear agents have excellent thermal stability under conditions of high temperature operation as dernanded, for instance, in industrial oils such as hydraulic oil, bearing oil, industrial gear oil and sliding surface lubricating oil. But, extreme pressure and anti-wear performance: is relatively poor in comparison to ZnDTP. Thus, in practice ZnDTP-free lubricating oiils combining thermal stability, extreme pressure resistance and anti-wear performance are rare. It is not easy to produce lubricating oils having thermal stability at high temperatures with concomitant extreme pressure and anti-wear performance.
Japanese Patent Provisional Publication No. 9-11127'7 describes an ashless hydraulic oil composition comprising a base oil having a % CA (ipercentage that represents the number of carbon atoms in aromatic groups divided by total carbon atoms) 5 or less, (A) 0.01-5 wt % of an amine-type oxidation inhibitor, (B) 0.01-5 wt % of a phenolic oxidation inhibitor, (C) 0.01-5 wt % of a phosphoric acicl ester, and (D) 0.001-5 wt % of an aliphatic amide andlor a polyhydric alcohol ester.
Japanese Patent Provisional Publication No. 11-323365 describes a hydraulic oil using a mineral oil, a synthetic oil, or a mixture thereof, as a base oil, which further contains (A) 0.01-1 wt % of an alkenyl succinimide or its derivative, (B) 0.1-5 wt % of a phosphoric acid ester, (C) 0.05-0.5 wt % of an alkylated diphenylamine, and (D) 0.05-0.5 wt % of a hindered phenol.
SUMMARY OF THE INVENITION
The present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance.
In its broadest aspect, the present invention relates to .a lubricating oil composition comprising a major amount of a base oil of lubricating 'viscosity and A. 0.1 to 5.0 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 0.01 to 1.0 wt % of a phosphorus acid e;>ter andlor an amine thereof; and C. 0.01 to 2.0 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester and/or an amine thereof is in the range of 1:1 to 500:1.
The weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an allkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20.
The lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm.
In another aspect, the present invention relates to a lubricating oil concentrate containing a compatible organic diluent and A. 10 to 90 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 1 to 20 wt % of a phosphorus acid ester andlor an amine thereof; and C. 1 to 40 wt % of at least one compound ;>elected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The lubricating oil concentrate of the present invention has a total phosphorus content in the range of 5,000 to 80,000 mass ppm.
In a further aspect, the present invention relates to a rnethod of producing the lubricating oil composition of the present invention by blending the mixture of the components of the lubricating oil composition of the present invention. The resulting lubricating oil composition having excellent thermal stability, extreme pressure resistance and anti-wear pertormance.
In still a further aspect, the present invention relates to a method of lubricating hydraulic systems, bearing systems, gear systems, or sliding systems with the lubricating oil composition of the present invention.
The lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm.
In another aspect, the present invention relates to a lubricating oil concentrate containing a compatible organic diluent and A. 10 to 90 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 1 to 20 wt % of a phosphorus acid ester andlor an amine thereof; and C. 1 to 40 wt % of at least one compound ;>elected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The lubricating oil concentrate of the present invention has a total phosphorus content in the range of 5,000 to 80,000 mass ppm.
In a further aspect, the present invention relates to a rnethod of producing the lubricating oil composition of the present invention by blending the mixture of the components of the lubricating oil composition of the present invention. The resulting lubricating oil composition having excellent thermal stability, extreme pressure resistance and anti-wear pertormance.
In still a further aspect, the present invention relates to a method of lubricating hydraulic systems, bearing systems, gear systems, or sliding systems with the lubricating oil composition of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As mentioned above, the present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance. The lubricating oil composition of the present invention described herein having thermal stability will minimize sludge formation <~nd viscosity increase resulting from decomposition of the components in the present invention.
The base oil of lubricating viscosity used in the lubricating oil composition of the present invention may be mineral or synthetic base oil having a kinematic viscosity of 5 to 900 mm2ls, preferably 20 to 700 mm2ls at 40 °C. A mineral oil employable for the invention can be obtained from crude oil by distillation I;under atmospheric or reduced pressure) and purification such as solvent extraction, hydrocracking, solvent dewaxing or hydrogenation refining. Particularly preferred is a highly hydrogenation-refined base oil having a viscosity index of 100 to 150, an aromatic content of 5 wt % or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less.
The synthetic oil (i.e., synthetic lubricating base oil) can be poly-a-olefin which is a polymer of a-olefin having 3 to 12 carbon atoms; a dialkyl diester such as dioctyl sebacate, which is an ester of a dibasic acid (e.g., sebacic acid, azelaic acid, or adipic acid) and an alcohol having 4 to 12 carbon atoms; a polyol ester which is an ester of a monobasic acid having 3 to 18 carbon atoms and 1-trirnethylolpropane or pentaerythritol, or an alkylbenzene having an alkyl group which contains 9 to 40 carbon atoms.
The mineral oil and synthetic oil can be employed singly or blended in combination.
Blends of mineral oils with synthetic oils are also useful.
The lubricating oil composition of the present invention contains 0.1 to 5.0 wt %, preferably 0.1 to 3.0 wt %, more preferably 0.1 to 1.0 wt % and most preferably 0.1 to 0.5 wt %, of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine ;>alt thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
The phosphoric acid ester, thiophosphoric acid ester, and amine salt thereof functions to enhance the lubricating performances, and can be ;elected from known compounds conventionally employed as extreme pressure agents. Generally employed are a phosphoric acid ester, a thiophosphoric acid ester, or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
Examples of the phosphoric acid esters include aliphatic phosphoric acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; and aromatic phosphoric acid ester's such as benzyl phenyl phosphate, allyl Biphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl Biphenyl phosphate, cresyl Biphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl Biphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl Biphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl Biphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate. Preferably, the phosphoric acid ester is a trialkylphenyl phosphate.
Examples of the thiophosphoric acid esters include aliphatic thiophosphoric acid esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoric acid esters such as benzyl phenyl thiophosphate, allyl Biphenyl thiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyl Biphenyl thiophosphate, cresyl Biphenyl thiophosphate, dicresyl phenyl thiophosphate, ethylphenyl Biphenyl thiophosphate, diethylphenyl phenyl thiophosphate, propylphenyl Biphenyl thiophosphate, dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenyl thiophosphate, butylphenyl Biphenyl thiophosphate, dibutylphenyl phenyl thiophosphate, and tributylphenyl thiophosphate. Preferably, the thiophosphoric acid ester is a trialkylphenyl thiophosphate.
_5_ Also employable are amine salts of the above-mentioned phosphates and thiophosphates. Amine salts of acidic alkyl or aryl esters of the phosphoric acid and thiophosphoric acid are also employable. Preferably, the amine salt is an amine salt of trialkylphenyl phosphate or an amine salt of alkyl phosphate.
One or any combination of the compounds selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof may be used.
If the content of the phosphoric acid ester, thiophosphoric acid ester, and/or their amine salts in the lubricating oil is less than 0.1 wt %; the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is more than 5.0 wt.%, no further improvement is expected and' would not be cost-effective.
The lubricating oil composition of the present invention further contains 0.01 to 1.0 wt %, preferably 0.01 to 0.4 wt %, more preferably 0.01 toy 0.2 wt %, and most preferably 0.01 to 0.1 wt %, of a phosphorus acid ester andlor an amine salt thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
In the lubricating oil composition of the present invention, the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester andlor an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
The phosphorus acid ester and/or its amine salt function to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents. Generally employed are a phosphorus acid ester or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
Examples of the phosphorus acid esters include aliphatic phosphorus acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexylphosphite, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate;
and aromatic phosphorus acid esters such as benzyl phenyl phosphate, allyl diphenylphosphite, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate. Also favorably employed are dilauryl phosphate, dioleyl phosphate, dialkyl phosphates, and diphenyl phosphate.
Preferably, the phosphorus acid ester is a dialkyl phosphate or a trialkyl phosphate.
Amine salts of these phosphorus acid esters are also employable and can be used singly or together in combination.
If the content of the phosphorus acid ester andlor its amine salt in the lubricating oil is less than 0.01 wt %, the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is rnore than 1.0 wt %, no further improvement is expected and would not be cost-effective.
The lubricating oil composition of the present invention further contains 0.01 to 2.0 wt %, preferably 0.01 to 1.0 wt %, more preferably 0.01 to 0.4 wt %, and most preferably 0.01 to 0.2 wt %, of a compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
In the lubricating oil composition of the present invention, the weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyll succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
_7_ g ~ CA 02344490 2001-04-12 The alkenyl succinimide can be a monoimide or a bisimide, and can be prepared by reaction between a polybutenyl succinic anhydride and a polyamine. The polybutenyl succinic anhydride can be produced by reaction of a polybutene having a mean molecular weight of 800 to 8,000 or a chlorinated polybutene having a mean molecular weight of 800 to 8,000 with malefic anhydride at a temperature of 100 to 200 °C.
Examples of the polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, andl hexamethylene heptamine.
Examples of the alkenyl succinimide derivatives includE: borated derivatives, organic phosphonate derivatives, and derivatives which is produced by reacting an alkenyl succinimide with aldehyde, ketone, carboxylic acid, sulifonic acid, alkylene oxide, sulfur, or polyhydric alcohol. A preferred derivative is a borated derivative, which can be produced by reacting the polybutenyl succinic anhydride-polyamine reaction product with boric acid or a boric acid derivative.
The alkenyl succinic acid ester and its derivative can be an ester of the above-mentioned polybutenyl succinic anhydride which has been prepared by the reaction between a polybutene or a chlorinated polybutene and malefic anhydride, with a polyhydric alcohol such as pentaerythritol; and its derivative.
The benzylamine and its derivative can be prepared by reacting the above-mentioned polybutene with phenol, formaldehyde and polyamine.
One or any combination of the compounds selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof may be used.
If the content of the component in the lubricating oil is less than 0.01 wt %, sludge dispersing performance will be insufficient and, furthermore, the lubricating oil composition of the present invention will have poor water tolerance. If the content is more than 2.0 wt %, oxidation stability likely decreases..
_g_ The lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, preferably 50 to 2,500 mass ppm, and most preferably 50 to 1,000 mass ppm.
The lubricating oil composition of the present invention may contain a variety of other auxiliary additives that can be favorably employed in the present invention.
Examples of the auxiliary additives include extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers and pour point depressants. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
The lubricating oil composition of the present invention can be prepared by successively or simultaneously adding the additive components to a base oil of lubricating viscosity, or by beforehand preparing a lubi°icating oil concentrate, as herein described below, and then mixing it with a base oil of lubricating viscosity.
The components can be blended in any order and can be blended as combinations of components.
In a further aspect, the present invention also involves a lubricating oil concentrate comprising 1.0 to 30 wt % of a compatible organic diluent and A. 10 to 90 wt % of at least one compoundl selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 1 to 20 wt % of a phosphorus acid ester andlor an amine thereof; and C. 1 to 40 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The concentrates contain sufficient organic liquid diluent to make them easy to handle during shipping and storage. Typically, the concentrate will contain from 1.0 to 30.0 wt _g_ %, preferably 3.0 to 20.0 wt %, more preferably 5.0 to 10.0 wt %, of a compatible organic diluent.
Suitable compatible organic diluents which can be used include, for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 1001V, i.e., Chevron 100N, and the like. The organic diluent preferably has a viscosity of about from 1.0 to 20.0 cSt at 100°C.
In the lubricating oil concentrate of the present invention, the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and 'the phosphorus acid ester andlor an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
In the lubricating oil concentrate of the present invention, the weight ratio between the phosphoric acid ester andlor an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyl :>uccinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
The lubricating oil concentrate of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, more preferably 10,000 to 50,000 mass ppm, and most preferably 15,000 to 30,000 mass ppm.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it. 'This application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.
Examples 1-4 The components were blended in amounts (wt %) set forth in Table I to prepare lubricating oil compositions.
(A) Tricresyl phosphate solution: TCP (available from Daihachi Chemicals Co., Ltd.) (B) Triphenyl thiophosphate and its derivative solution (Irgalube 232, available from Ciba Specialty Chemicals, Inc.) (C) Dilauryl phosphite solution (JP 212, Johoku Chemicals Co., Ltd.) (D) Alkenylsuccinimide (OLOA 371, available from Chevron Oronite Japan Ltd.) (E) Zinc dithiophosphate (OLOA 2698, available from Chevron Oronite Japan Ltd.) Each of the components above were blended in a petroleum base oil having a viscosity @ 40°C of 36 cSt containing auxiliary additives, i.e., oxidation inhibitor, metal deactivator, demulsifier, anti-foaming agent, etc. The total phosphorus contents (mass ppm) were those set forth in Table I.
Comparative Examples A-G
The above-mentioned additive components were blended to prepare lubricating oil compositions as described in the Examples. The amounts of each of the components in the Comparative Examples are indicated in Table I.
Performance Evaluation The lubricating oil compositions of Examples and Connparative Examples were evaluated by the following tests. The results of the tests are set forth in Table II.
, CA 02344490 2001-04-12 Modified CM Thermal Stabilit~r Test The lubricating oil compositions were evaluated by a modified CM Thermal Stability Test that heated the composition at 150 °C rather than at 135 °C under the following conditions:
Test temperature: 150°C
Test period: 168 hours.
The test oil was then filtered over a filter (pore size: 0.8 Vim), washed with n-hexane, and dried. The dry residue on the filter was weighed to determine the amount of sludge. The lower the number (mg), the lower the sludge. The viscosity increase is also indicated. A viscosity increase lower than 5% is preferable.
Shell Four-Ball Test The lubricating oil compositions were evaluated by the Shell Four-Ball Tester, which operated at 1,800 r.p.m., to determine an initial seizure load (ISL).
The higher the number (kg), the better the extreme pressure resistance.
Vickers 35VQ25A (M-3952-5) The Vickers 35VQ25A (M-3952-5) vane pump fiest is a common wear test to evaluate the anti-wear characteristics of hydraulic oil by means of weight loss on the cam ring and the vanes of a 35VQ25A pump. Test duration is 50 hours per cartridge with a pump outlet pressure of 3,000 psi and an inlet oil temperature of 93.3 °C. A low number indicates low wear.
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Results of the three test evaluations are shown in Table II. In general, the lubricating oil composition of the present invention produces sludge and viscosity increase less than the Comparative lubricating oil compositions, while also providing excellent extreme pressure resistance. That is, the lubricating oil compositions of the present invention showed a high initial seizure load in the Shell Four-Ball Test, which means excellent extreme pressure resistance. While some of the Comparative Examples gave modified CM Thermal Stability Test results comparable to the Examples, they did not provide favorable viscosity increase or extreme pressure resistance. See for example, Comparative Example E.
Further, Comparative Examples C and D provided excellent extreime pressure resistance, but the thermal stability and viscosity increase were higher than t;he lubricating oil compositions of the present invention demonstrated by Examples 1-3. Additionally, the lubricating oil composition of the present invention (Example 4) also demonstrated excellent anti-wear performance in the Vicker 35VQ25A (M-3952-5) Test.
These results therefore provide support that the lubricating oil composition of the present invention has a broader scope of lubricating pertormance than the comparative lubricating oil compositions. The lubricating oil composition of the piresent invention provides an excellent combination of thermal stability, extreme pressure resistance and anti-wear performance all in one multi-functional package.
As mentioned above, the present invention relates to a lubricating oil composition for use in industrial oils such as hydraulic oils, bearing oils, industrial gear oils and sliding surface lubricating oils. The lubricating oil composition of the present invention provides excellent thermal stability, extreme pressure resistance and anti-wear performance. The lubricating oil composition of the present invention described herein having thermal stability will minimize sludge formation <~nd viscosity increase resulting from decomposition of the components in the present invention.
The base oil of lubricating viscosity used in the lubricating oil composition of the present invention may be mineral or synthetic base oil having a kinematic viscosity of 5 to 900 mm2ls, preferably 20 to 700 mm2ls at 40 °C. A mineral oil employable for the invention can be obtained from crude oil by distillation I;under atmospheric or reduced pressure) and purification such as solvent extraction, hydrocracking, solvent dewaxing or hydrogenation refining. Particularly preferred is a highly hydrogenation-refined base oil having a viscosity index of 100 to 150, an aromatic content of 5 wt % or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less.
The synthetic oil (i.e., synthetic lubricating base oil) can be poly-a-olefin which is a polymer of a-olefin having 3 to 12 carbon atoms; a dialkyl diester such as dioctyl sebacate, which is an ester of a dibasic acid (e.g., sebacic acid, azelaic acid, or adipic acid) and an alcohol having 4 to 12 carbon atoms; a polyol ester which is an ester of a monobasic acid having 3 to 18 carbon atoms and 1-trirnethylolpropane or pentaerythritol, or an alkylbenzene having an alkyl group which contains 9 to 40 carbon atoms.
The mineral oil and synthetic oil can be employed singly or blended in combination.
Blends of mineral oils with synthetic oils are also useful.
The lubricating oil composition of the present invention contains 0.1 to 5.0 wt %, preferably 0.1 to 3.0 wt %, more preferably 0.1 to 1.0 wt % and most preferably 0.1 to 0.5 wt %, of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine ;>alt thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
The phosphoric acid ester, thiophosphoric acid ester, and amine salt thereof functions to enhance the lubricating performances, and can be ;elected from known compounds conventionally employed as extreme pressure agents. Generally employed are a phosphoric acid ester, a thiophosphoric acid ester, or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
Examples of the phosphoric acid esters include aliphatic phosphoric acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate; and aromatic phosphoric acid ester's such as benzyl phenyl phosphate, allyl Biphenyl phosphate, triphenyl phosphate, tricresyl phosphate, ethyl Biphenyl phosphate, cresyl Biphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl Biphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl Biphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl Biphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate. Preferably, the phosphoric acid ester is a trialkylphenyl phosphate.
Examples of the thiophosphoric acid esters include aliphatic thiophosphoric acid esters such as triisopropyl thiophosphate, tributyl thiophosphate, ethyl dibutyl thiophosphate, trihexyl thiophosphate, tri-2-ethylhexyl thiophosphate, trilauryl thiophosphate, tristearyl thiophosphate, and trioleyl thiophosphate; and aromatic thiophosphoric acid esters such as benzyl phenyl thiophosphate, allyl Biphenyl thiophosphate, triphenyl thiophosphate, tricresyl thiophosphate, ethyl Biphenyl thiophosphate, cresyl Biphenyl thiophosphate, dicresyl phenyl thiophosphate, ethylphenyl Biphenyl thiophosphate, diethylphenyl phenyl thiophosphate, propylphenyl Biphenyl thiophosphate, dipropylphenyl phenyl thiophosphate, triethylphenyl thiophosphate, tripropylphenyl thiophosphate, butylphenyl Biphenyl thiophosphate, dibutylphenyl phenyl thiophosphate, and tributylphenyl thiophosphate. Preferably, the thiophosphoric acid ester is a trialkylphenyl thiophosphate.
_5_ Also employable are amine salts of the above-mentioned phosphates and thiophosphates. Amine salts of acidic alkyl or aryl esters of the phosphoric acid and thiophosphoric acid are also employable. Preferably, the amine salt is an amine salt of trialkylphenyl phosphate or an amine salt of alkyl phosphate.
One or any combination of the compounds selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and an amine salt thereof may be used.
If the content of the phosphoric acid ester, thiophosphoric acid ester, and/or their amine salts in the lubricating oil is less than 0.1 wt %; the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is more than 5.0 wt.%, no further improvement is expected and' would not be cost-effective.
The lubricating oil composition of the present invention further contains 0.01 to 1.0 wt %, preferably 0.01 to 0.4 wt %, more preferably 0.01 toy 0.2 wt %, and most preferably 0.01 to 0.1 wt %, of a phosphorus acid ester andlor an amine salt thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
In the lubricating oil composition of the present invention, the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and the phosphorus acid ester andlor an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
The phosphorus acid ester and/or its amine salt function to enhance the lubricating performances, and can be selected from known compounds conventionally employed as extreme pressure agents. Generally employed are a phosphorus acid ester or an amine salt thereof which has an alkyl group, an alkenyl group, an alkylaryl group, or an aralkyl group, any of which contains approximately 3 to 30 carbon atoms.
Examples of the phosphorus acid esters include aliphatic phosphorus acid esters such as triisopropyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri-2-ethylhexylphosphite, trilauryl phosphate, tristearyl phosphate, and trioleyl phosphate;
and aromatic phosphorus acid esters such as benzyl phenyl phosphate, allyl diphenylphosphite, triphenyl phosphate, tricresyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethylphenyl diphenyl phosphate, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phenyl phosphate, and tributylphenyl phosphate. Also favorably employed are dilauryl phosphate, dioleyl phosphate, dialkyl phosphates, and diphenyl phosphate.
Preferably, the phosphorus acid ester is a dialkyl phosphate or a trialkyl phosphate.
Amine salts of these phosphorus acid esters are also employable and can be used singly or together in combination.
If the content of the phosphorus acid ester andlor its amine salt in the lubricating oil is less than 0.01 wt %, the lubricating oil composition of the present invention will have insufficient lubricating performance. If the content is rnore than 1.0 wt %, no further improvement is expected and would not be cost-effective.
The lubricating oil composition of the present invention further contains 0.01 to 2.0 wt %, preferably 0.01 to 1.0 wt %, more preferably 0.01 to 0.4 wt %, and most preferably 0.01 to 0.2 wt %, of a compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof. The amount means a ratio based on the total amount of the lubricating oil, and each component of the indicated amount contains a small amount of hydrocarbon oil which is employed in the preparation of the component and remains in the component.
In the lubricating oil composition of the present invention, the weight ratio between the phosphoric acid ester and/or an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyll succinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
_7_ g ~ CA 02344490 2001-04-12 The alkenyl succinimide can be a monoimide or a bisimide, and can be prepared by reaction between a polybutenyl succinic anhydride and a polyamine. The polybutenyl succinic anhydride can be produced by reaction of a polybutene having a mean molecular weight of 800 to 8,000 or a chlorinated polybutene having a mean molecular weight of 800 to 8,000 with malefic anhydride at a temperature of 100 to 200 °C.
Examples of the polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, andl hexamethylene heptamine.
Examples of the alkenyl succinimide derivatives includE: borated derivatives, organic phosphonate derivatives, and derivatives which is produced by reacting an alkenyl succinimide with aldehyde, ketone, carboxylic acid, sulifonic acid, alkylene oxide, sulfur, or polyhydric alcohol. A preferred derivative is a borated derivative, which can be produced by reacting the polybutenyl succinic anhydride-polyamine reaction product with boric acid or a boric acid derivative.
The alkenyl succinic acid ester and its derivative can be an ester of the above-mentioned polybutenyl succinic anhydride which has been prepared by the reaction between a polybutene or a chlorinated polybutene and malefic anhydride, with a polyhydric alcohol such as pentaerythritol; and its derivative.
The benzylamine and its derivative can be prepared by reacting the above-mentioned polybutene with phenol, formaldehyde and polyamine.
One or any combination of the compounds selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzyl amine, and derivatives thereof may be used.
If the content of the component in the lubricating oil is less than 0.01 wt %, sludge dispersing performance will be insufficient and, furthermore, the lubricating oil composition of the present invention will have poor water tolerance. If the content is more than 2.0 wt %, oxidation stability likely decreases..
_g_ The lubricating oil composition of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, preferably 50 to 2,500 mass ppm, and most preferably 50 to 1,000 mass ppm.
The lubricating oil composition of the present invention may contain a variety of other auxiliary additives that can be favorably employed in the present invention.
Examples of the auxiliary additives include extreme pressure agents, corrosion inhibitors, rust inhibitors, friction modifiers, anti-foaming agents, viscosity index improvers and pour point depressants. These examples of additives are provided to illustrate the present invention, but they are not intended to limit it.
The lubricating oil composition of the present invention can be prepared by successively or simultaneously adding the additive components to a base oil of lubricating viscosity, or by beforehand preparing a lubi°icating oil concentrate, as herein described below, and then mixing it with a base oil of lubricating viscosity.
The components can be blended in any order and can be blended as combinations of components.
In a further aspect, the present invention also involves a lubricating oil concentrate comprising 1.0 to 30 wt % of a compatible organic diluent and A. 10 to 90 wt % of at least one compoundl selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 1 to 20 wt % of a phosphorus acid ester andlor an amine thereof; and C. 1 to 40 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
The concentrates contain sufficient organic liquid diluent to make them easy to handle during shipping and storage. Typically, the concentrate will contain from 1.0 to 30.0 wt _g_ %, preferably 3.0 to 20.0 wt %, more preferably 5.0 to 10.0 wt %, of a compatible organic diluent.
Suitable compatible organic diluents which can be used include, for example, solvent refined 100N, i.e., Cit-Con 100N, and hydrotreated 1001V, i.e., Chevron 100N, and the like. The organic diluent preferably has a viscosity of about from 1.0 to 20.0 cSt at 100°C.
In the lubricating oil concentrate of the present invention, the weight ratio between the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof and 'the phosphorus acid ester andlor an amine thereof is in the range of 1:1 to 500:1, preferably 1:1 to 50:1, more preferably 1:1 to 25:1, and most preferably 1:1 to 10:1.
In the lubricating oil concentrate of the present invention, the weight ratio between the phosphoric acid ester andlor an amine thereof and the compound selected from the group consisting of an alkenyl succinimide, an alkenyl :>uccinic acid ester, benzylamine, and derivatives thereof is in the range of 1:0.5 to 1:20, more preferably 1:1 to 1:3, and most preferably 1:1 to 1:2 wt %.
The lubricating oil concentrate of the present invention has a total phosphorus content in the range of 50 to 5,000 mass ppm, more preferably 10,000 to 50,000 mass ppm, and most preferably 15,000 to 30,000 mass ppm.
EXAMPLES
The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. While the Examples are provided to illustrate the present invention, they are not intended to limit it. 'This application is intended to cover those various changes and substitutions that may be made by those skilled in the art without departing from the spirit and scope of the appended claims.
Examples 1-4 The components were blended in amounts (wt %) set forth in Table I to prepare lubricating oil compositions.
(A) Tricresyl phosphate solution: TCP (available from Daihachi Chemicals Co., Ltd.) (B) Triphenyl thiophosphate and its derivative solution (Irgalube 232, available from Ciba Specialty Chemicals, Inc.) (C) Dilauryl phosphite solution (JP 212, Johoku Chemicals Co., Ltd.) (D) Alkenylsuccinimide (OLOA 371, available from Chevron Oronite Japan Ltd.) (E) Zinc dithiophosphate (OLOA 2698, available from Chevron Oronite Japan Ltd.) Each of the components above were blended in a petroleum base oil having a viscosity @ 40°C of 36 cSt containing auxiliary additives, i.e., oxidation inhibitor, metal deactivator, demulsifier, anti-foaming agent, etc. The total phosphorus contents (mass ppm) were those set forth in Table I.
Comparative Examples A-G
The above-mentioned additive components were blended to prepare lubricating oil compositions as described in the Examples. The amounts of each of the components in the Comparative Examples are indicated in Table I.
Performance Evaluation The lubricating oil compositions of Examples and Connparative Examples were evaluated by the following tests. The results of the tests are set forth in Table II.
, CA 02344490 2001-04-12 Modified CM Thermal Stabilit~r Test The lubricating oil compositions were evaluated by a modified CM Thermal Stability Test that heated the composition at 150 °C rather than at 135 °C under the following conditions:
Test temperature: 150°C
Test period: 168 hours.
The test oil was then filtered over a filter (pore size: 0.8 Vim), washed with n-hexane, and dried. The dry residue on the filter was weighed to determine the amount of sludge. The lower the number (mg), the lower the sludge. The viscosity increase is also indicated. A viscosity increase lower than 5% is preferable.
Shell Four-Ball Test The lubricating oil compositions were evaluated by the Shell Four-Ball Tester, which operated at 1,800 r.p.m., to determine an initial seizure load (ISL).
The higher the number (kg), the better the extreme pressure resistance.
Vickers 35VQ25A (M-3952-5) The Vickers 35VQ25A (M-3952-5) vane pump fiest is a common wear test to evaluate the anti-wear characteristics of hydraulic oil by means of weight loss on the cam ring and the vanes of a 35VQ25A pump. Test duration is 50 hours per cartridge with a pump outlet pressure of 3,000 psi and an inlet oil temperature of 93.3 °C. A low number indicates low wear.
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Results of the three test evaluations are shown in Table II. In general, the lubricating oil composition of the present invention produces sludge and viscosity increase less than the Comparative lubricating oil compositions, while also providing excellent extreme pressure resistance. That is, the lubricating oil compositions of the present invention showed a high initial seizure load in the Shell Four-Ball Test, which means excellent extreme pressure resistance. While some of the Comparative Examples gave modified CM Thermal Stability Test results comparable to the Examples, they did not provide favorable viscosity increase or extreme pressure resistance. See for example, Comparative Example E.
Further, Comparative Examples C and D provided excellent extreime pressure resistance, but the thermal stability and viscosity increase were higher than t;he lubricating oil compositions of the present invention demonstrated by Examples 1-3. Additionally, the lubricating oil composition of the present invention (Example 4) also demonstrated excellent anti-wear performance in the Vicker 35VQ25A (M-3952-5) Test.
These results therefore provide support that the lubricating oil composition of the present invention has a broader scope of lubricating pertormance than the comparative lubricating oil compositions. The lubricating oil composition of the piresent invention provides an excellent combination of thermal stability, extreme pressure resistance and anti-wear performance all in one multi-functional package.
Claims (36)
1. A lubricating oil composition comprising a major amount of a base oil of lubricating viscosity, and A. 0.1 to 5.0 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 0.01 to 1.0 wt % of a phosphorus acid ester and/or an amine thereof; and C. 0.01 to 2.0 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
B. 0.01 to 1.0 wt % of a phosphorus acid ester and/or an amine thereof; and C. 0.01 to 2.0 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
2. A lubricating oil composition comprising a major amount of base oil of lubricating viscosity, and A. 0.1 to 3.0 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric; acid ester, and amine salts thereof; and B. 0.01 to 0.4 wt % of a phosphorus acid ester and/or an amine thereof; and C. 0.01 to 1.0 wt % of the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
3. A lubricating oil composition comprising a major amount of a base oil of lubricating viscosity and A. 0.1 to 1.0 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 0.01 to 0.2 wt % of a phosphorus acid ester and/or an amine thereof; and C. 0.01 to 0.4 wt % of a compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
B. 0.01 to 0.2 wt % of a phosphorus acid ester and/or an amine thereof; and C. 0.01 to 0.4 wt % of a compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
4. A lubricating oil composition according to Claim 1, wherein the weight ratio of components A to B is in the range of 1:1 to 500:1.
5. A lubricating oil composition according to Claim 4, wherein the weight ratio of components A to B is in the range of 1:1 to 50:1.
6. A lubricating oil composition according to Claim 5, wherein the weight ratio of components A to B is in the range of 1:1 to 25:1.
7. A lubricating oil composition according to Claim 1, wherein the weight ratio of components B to C is in the range of 1:0.5 to 1:20.
8. A lubricating oil composition according to Claim 7, wherein the weight ratio of components B to C is in the range of 1:1 to 1:3.
9. A lubricating oil composition according to Claim 8, wherein the weight ratio of components B to C is in the range of 1:1 to 1:2.
10. A lubricating oil composition according to Claim 1, wherein the weight the total phosphorus content in the range of 50 to 5,000 mass ppm.
11. A lubricating oil composition according to Claim 10, wherein the weight the total phosphorus content in the range of 50 to 2,500 mass ppm.
12. A lubricating oil composition according to Claim 11, wherein the weight the total phosphorus content in the range of 50 to 1,000 mass ppm.
13. A lubricating oil composition according to Claim 1, wherein the base oil of lubricating viscosity has a kinematic viscosity of 5 to 900 mm2/s at 40 °C.
14. A lubricating oil composition according to Claim 1, wherein the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof is a phosphoric acid ester.
15. A lubricating oil composition according to Claim 14, wherein the phosphoric acid ester is a trialkylphenyl phosphate.
16. A lubricating oil composition according to Claim 1, wherein the phosphorus acid ester and/or an amine thereof is a dialkyl phosphite or a trialkyl phosphite.
17. The lubricating oil composition according to Claim 1, wherein the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is an alkyl succinic acid ester.
18. The lubricating oil composition according to Claim 17, wherein the alkyl succinic acid ester is a polybutenyl succinic acid ester.
19. A lubricating oil concentrate comprising 1.0 to 30 wt % of a compatible organic diluent and A. 10 to 90 wt % of at least one compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof;
B. 1 to 20 wt % of a phosphorus acid ester and/or an amine thereof; and C. 1 to 40 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
B. 1 to 20 wt % of a phosphorus acid ester and/or an amine thereof; and C. 1 to 40 wt % of at least one compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof.
20. A lubricating oil concentrate according to Claim 19, wherein the weight ratio of components A to B is in the range of 1:1 to 500:1.
21. A lubricating oil concentrate according to Claim 20, wherein the weight ratio of components A to B is in the range of 1:1 to 50:1.
22. A lubricating oil concentrate according to Claim 21, wherein the weight ratio of components A to B is in the range of 1:1 to 25:1.
23. A lubricating oil concentrate according to Claim 19, wherein the weight ratio of components B to C is in the range of 1:0.5 to 1:20.
24. A lubricating oil concentrate according to Claim 23, wherein the weight ratio of components B to C is in the range of 1:1 to 1:3.
25. A lubricating oil concentrate according to Claim 24, wherein the weight ratio of components B to C is in the range of 1:1 to 1:2.
26. A lubricating oil concentrate according to Claim 19, wherein the weight the total phosphorus content in the range of 5,000 to 80,000 mass ppm.
27. A lubricating oil concentrate according to Claim 19, wherein the weight the total phosphorus content in the range of 10,000 to 50,000 mass ppm.
28. A lubricating oil concentrate according to Claim 27, wherein the weight the total phosphorus content in the range of 15,000 to 30,000 mass ppm.
29. A lubricating oil concentrate according to Claim 19, wherein the compound selected from the group consisting of a phosphoric acid ester, a thiophosphoric acid ester, and amine salts thereof is a phosphoric acid ester.
30. A lubricating oil concentrate according to Claim 29, wherein the phosphoric acid ester is a trialkylphenyl phosphate.
31. A lubricating oil concentrate according to Claim 19, wherein the phosphorus acid ester and/or an amine thereof is a dialkyl phosphate or a trialkyl phosphate.
32. The lubricating oil concentrate according to Claim 19, wherein the compound selected from the group consisting of an alkenyl succinimide, an alkenyl succinic acid ester, benzylamine, and derivatives thereof is an alkenyl succinic acid ester.
33. The lubricating oil concentrate according to Claim 32, wherein the alkenyl succinic acid ester is a polybutenyl succinic acid ester.
34. A method for producing a lubricating oil composition comprising blending the components according to Claim 1.
35. A lubricating oil composition produced by the method according to Claim 34.
36. A method for lubricating hydraulic systems, bearing systems, gear systems, or sliding systems with the lubricating oil composition of Claim 1.
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JP2000116378A JP2001303086A (en) | 2000-04-18 | 2000-04-18 | Lubricating oil composition and additive composition |
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JP3175893B2 (en) * | 1994-03-25 | 2001-06-11 | 日石三菱株式会社 | Hydraulic oil composition for shock absorber |
TW291495B (en) * | 1994-08-03 | 1996-11-21 | Lubrizol Corp | |
US5759965A (en) * | 1995-10-18 | 1998-06-02 | The Lubrizol Corporation | Antiwear enhancing composition for lubricants and functional fluids |
US6613722B1 (en) * | 1997-03-07 | 2003-09-02 | Exxon Chemical Patents Inc. | Lubricating composition |
DE59813902D1 (en) * | 1997-09-18 | 2007-03-29 | Ciba Sc Holding Ag | Lubricant compositions with thiophosphoric acid esters and dithiophosphoric acid esters |
US5968880A (en) * | 1997-10-23 | 1999-10-19 | The Lubrizol Corporation | Lubricating compositions, functional fluids and greases containing thiophosphorus esters or their salts with a oxyalkylene group, and methods of using the same |
WO2000001790A1 (en) * | 1998-07-06 | 2000-01-13 | The Lubrizol Corporation | Mixed phosphorus compounds and lubricants containing the same |
AU760391B2 (en) * | 1998-10-19 | 2003-05-15 | Lubrizol Corporation, The | Lubricating compositions with improved thermal stability and limited slip performance |
JP4049916B2 (en) * | 1998-12-25 | 2008-02-20 | 出光興産株式会社 | High temperature lubricating oil composition |
US6573223B1 (en) * | 2002-03-04 | 2003-06-03 | The Lubrizol Corporation | Lubricating compositions with good thermal stability and demulsibility properties |
-
2000
- 2000-04-18 JP JP2000116378A patent/JP2001303086A/en active Pending
-
2001
- 2001-03-29 US US09/823,086 patent/US20020010103A1/en not_active Abandoned
- 2001-04-12 CA CA002344490A patent/CA2344490A1/en not_active Abandoned
- 2001-04-12 EP EP01303441A patent/EP1148114A3/en not_active Withdrawn
- 2001-04-17 SG SG200102166A patent/SG100670A1/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105164238A (en) * | 2013-03-29 | 2015-12-16 | 出光兴产株式会社 | Lubricating oil composition |
Also Published As
Publication number | Publication date |
---|---|
US20020010103A1 (en) | 2002-01-24 |
SG100670A1 (en) | 2003-12-26 |
EP1148114A3 (en) | 2002-12-04 |
EP1148114A2 (en) | 2001-10-24 |
JP2001303086A (en) | 2001-10-31 |
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