EP0907698B1 - Die Verwendung einer funktionalisierten Viskositätsverbesserer in Schmiermittel für Dieselmotoren - Google Patents

Die Verwendung einer funktionalisierten Viskositätsverbesserer in Schmiermittel für Dieselmotoren Download PDF

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Publication number
EP0907698B1
EP0907698B1 EP97925182A EP97925182A EP0907698B1 EP 0907698 B1 EP0907698 B1 EP 0907698B1 EP 97925182 A EP97925182 A EP 97925182A EP 97925182 A EP97925182 A EP 97925182A EP 0907698 B1 EP0907698 B1 EP 0907698B1
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EP
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Prior art keywords
lubricant
vinyl
graft copolymer
soot
functionalised
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English (en)
French (fr)
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EP0907698A1 (de
Inventor
Irwin Goldblatt
Michael Mchenry
Kenneth Henderson
Danny Carlisle
Niall Ainscough
Myron Brown
Richard Tittel
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Castrol Ltd
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Castrol Ltd
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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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M129/95—Esters
    • 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
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
    • C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086—Imides [having hydrocarbon substituents containing less than thirty 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—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
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—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
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • the present invention concerns the use of a functionalised viscosity improver in a lubricant for use in diesel engines, including passenger car and heavy duty commercial diesel engines.
  • Diesel engines produce soot as a by-product of the combustion process.
  • the soot increases the viscosity of lubricants used in the diesel engines and eventually the lubricants become too thick to be workable.
  • the soot therefore reduces the working life of the lubricants, and money and time are wasted in early replacement of the unworkable lubricant.
  • the soot also causes wear of the diesel engines, which reduces their working life.
  • Lubricants currently on the market for diesel engines typically comprise: 65-80% by weight of base oil; 5-15% by weight of viscosity index improver(s) (VII); and 10-22% by weight of a detergent inhibitor (Dl) package.
  • the viscosity index improver(s) (VII) may be a non-dispersant viscosity index improver (NDVII) and/ or a dispersant viscosity index improver (DVII).
  • NDVII non-dispersant viscosity index improver
  • DVII dispersant viscosity index improver
  • One function of the detergent inhibitor (DI) package is to provide a dispersant to disperse the soot and thereby prevent soot related viscosity increase of the lubricant and wear on the engine.
  • VVII viscosity index improver(s)
  • DVII detergent inhibitor package
  • increasing the amount of dispersant can cause the following negative effects: it can increase the wear on the engine by interfering with the anti-wear additives in the formulation; it can cause damage to seals in contact with the lubricant; it negatively impacts low temperature viscometrics; and it can increase the cost of the lubricant.
  • DI detergent inhibitor
  • the inventors of the present invention are therefore concerned with the problem of increasing the amount of soot that is dispersed by a lubricant without increasing the amount of dispersant, which is normally provided by the detergent inhibitor (DI) package, present in the finished lubricant.
  • the inventors are also concerned with the problem of controlling soot related viscosity increase with lower levels of dispersant, which is normally provided by the DI package, than conventionally used by those skilled in the art.
  • a method of controlling viscosity changes of a lubricant in a diesel engine that are caused by build-up of soot comprising using the lubricant defined above as the lubricant in the diesel engine.
  • the inventors have found a lubricant that allows an increased amount of soot to be dispersed without increasing the amount of dispersant, which is normally provided by the detergent inhibitor (DI), present in the lubricant.
  • DI detergent inhibitor
  • the inventors have also found a highly functionalised graft copolymer, which, when incorporated into a lubricant, allows the lubricant to disperse soot produced as a by-product of a diesel engine without adversely affecting the viscosity of the lubricant.
  • the lubricants of the present invention can comprise lower than conventional amounts (e.g. 4% or less) of dispersant, which is normally provided by the detergent inhibitor (DI), and still meet the current industry soot handling tests for passenger car and heavy duty commercial diesel engines.
  • DI detergent inhibitor
  • Highly functionalised graft copolymers suitable for use in the present invention may be prepared using either a solution grafting process or a melt grafting process.
  • Preferred solution graft copolymers suitable for use in the present invention are disclosed in WO 96/12746, which was published on 2nd May 1996.
  • Suitable graft copolymers may be prepared by grafting maleic anhydride on to the polyolefin copolymer and reacting the resulting succinic anhydride with an appropriate nitrogen containing moiety such as polyamine.
  • Polyolefins grafted to the appropriate level may be prepared by following the practices disclosed in, for example, US-A-4,144,181; US-A-4,507,515; US-A-4,557,847; US-A-4,632,769; US-A-4,693,838; US-A-4,707,285; and US-A-5,350,532.
  • Suitable solution graft copolymers may be comprised of Mannich Base condensates.
  • WO 96/12746 discloses the reaction materials and reaction conditions that are needed to produce a preferred graft copolymer for use in the present invention.
  • this document discloses the reaction materials and the reaction conditions that are needed to produce the graft copolymer reaction product and the viscosity index improving agent which can be used in the preferred lubricant of the present invention.
  • WO 96/12746 discloses: examples of preferred polyolefins that are suitable for use as a backbone for grafting; preferred graftable monomers that are suitable for being grafted on to the polyolefin backbone; and preferred initiators, solvents and inhibitors that are suitable for the grafting reaction.
  • WO 96/12746 also discloses suitable melt reaction conditions for producing the preferred grafted polyolefin by a melt reaction process.
  • WO 96/12746 also discloses test methods for determining: the proportions of nitrogen on the grafted copolymer and the process fluid (assuming the reaction is carried out in a process solvent); the amount of residual unreacted graftable monomer in a graft copolymer; the dispersancy of the graft copolymer; the UV/RI ratio; and the aromatic content of solvent or process fluid used in the solution grafting reactions.
  • WO 96/12746 also discloses details of the preferred: base oils; graft copolymers; non-grafted polyolefins; other dispersants; detergents; anti-wear agents; anti-oxidants; pour point depressants; and minor ingredients.
  • a preferred melt grafted copolymer for use in the present invention is PARATONE 8500®, available from Exxon Chemical Company.
  • US-A-5,427,702 also discloses suitable melt grafted copolymers for use in the present invention.
  • WO 96/12746 also discloses details of melt grafted copolymers for use in the present invention.
  • graft copolymer reaction product we preferably mean a graft copolymer reaction product that has at least 13 mole percent (based on a polymer having a molecular weight of 100,000) of monomer grafted on to the polyolefin copolymer. More preferably, 20 to 30 mole percent or greater of monomer is grafted on to the polyolefin copolymer.
  • the highly functionalised graft copolymer reaction product preferably has either:
  • the highly functionalised graft copolymer preferably has the property of increasing the viscosity index of a lubricating base oil stock by at least 20 points when present at a level of 1% by weight of solids in the base oil stock.
  • the highly functionalised graft copolymer preferably comprises at least one of the following monomers grafted on to the polymer backbone:
  • the highly functionalised graft copolymer preferably comprises at least 1.2% by weight of N-vinylimidazole, grafted on to the polymer backbone.
  • the highly functionalised graft copolymer preferably comprises at least 1.2% by weight of suitable grafted monomers such as succinic anhydride or acid functionality such as fumaric acid which, after functionalizing the polymer backbone, is derivatised with morpholines, tetra pentamine, triethyl tetramine or other suitable amines or nitrogen containing moieties.
  • suitable grafted monomers such as succinic anhydride or acid functionality such as fumaric acid which, after functionalizing the polymer backbone, is derivatised with morpholines, tetra pentamine, triethyl tetramine or other suitable amines or nitrogen containing moieties.
  • the highly functionalised graft copolymer reaction product preferably comprises a graft copolymer backbone having a weight average molecular weight of from 20,000 to 500,000 and a polydispersivity of less than 10.
  • the lubricating oil preferably comprises: lubricant base stock(s) (mineral, synthetic and mixtures thereof); a detergent inhibitor (Dl) package; and the highly functionalised graft copolymer defined above.
  • lubricant base stock(s) mineral, synthetic and mixtures thereof
  • Dl detergent inhibitor
  • VI standard commercial viscosity index improver
  • the lubricating oil preferably comprises:
  • the lubricant may comprise the usual optional additives such as detergents, extreme pressure antiwear inhibitors, oxidation inhibitors, rust inhibitors, friction modifiers, foam inhibitors and other minor additives. Suitable additives can be found in WO 96/12746.
  • WO 96/12746 discloses the details of the highly functionalised graft copolymers that are suitable for use in the present invention to disperse the soot in diesel engines.
  • WO 96/12746 discloses: specific examples of laboratory preparations of preferred grafted polyolefins; specific examples of pilot plant preparations of preferred graft copolymers; a specific example of a pilot plant preparation of a comparative graft copolymer; specific examples of preparations of preferred graft copolymers and a comparative graft copolymer; and specific examples of preparation of a preferred graft copolymer by extrusion.
  • US-A-5,427,702 also provides details for the preparation of preferred graft copolymers by extrusion. The person skilled in the art is therefore directed to WO 96/12746 and US-A-5,427,702.
  • the BMW TDS test was carried out using a new type M51 engine for each series of tests.
  • the engine was a 2.5 litre, 6 cylinder, turbocharged and intercooled indirect injection diesel engine.
  • the engine was adapted for engine test bed operation. The modifications were made to the fuel system, the oil cooling system and the engine cooling system.
  • the detergent inhibitor (Dl) package was constant, with the exception of the type and amount of dispersant present.
  • a 15W50 oil was blended in Exxon base stocks with a NDVII (an unfunctionalised olefin copolymer, Paratone 8002®, available from Exxon Chemical Company).
  • NDVII an unfunctionalised olefin copolymer, Paratone 8002®, available from Exxon Chemical Company.
  • the level of dispersant (LZ6420®, available from Lubrizol Corp.) present in the lubricant formulation was 6.5%.
  • Example A1 As for Example A1 except that the dispersant level was reduced to 1.5% in the finished lubricant and over half of the NDVII was replaced with a highly functionalised graft copolymer (0.88% weight by solids).
  • the highly functionalised graft copolymer was the graft copolymer prepared in Example 10 of WO 96/12746.
  • Example A2 The results from Examples A1 and A2 were very similar, despite the fact that the level of dispersant in the finished lubricant was 6.5% in Example A1 but only 1.5% in Example A2.
  • Test ends at 80 hours plus the power curve time (approx. 25 mins) plus the oil levelling times.
  • the XUD11ATE engine test (CEC L-56-T-95) is a recently established European test for determining the ability of a lubricant to control viscosity changes caused by soot that is produced as a by-product from the combustion process of modern passenger car diesel engines.
  • the XUD11ATE engine test is an integral part of the Association des Constructeurs Europeens D'Automobiles European Oil Sequences For Light Duty Diesel Engines.
  • the test also evaluates sludge and piston cleanliness.
  • a critical parameter is the viscosity increase in the lubricant at 3.0% soot in oil. The required level of soot must be achieved before the end of the test.
  • a formulation similar to A2 was assessed in the XUD11ATE test as a 15W50 in BP stocks.
  • the highly functionalised graft copolymer was PARATONE 8500® (available from Exxon Chemical Company) at 0.88% solids, with an additional 5% of NDVII (PARATONE 8002®, an unfunctionalised olefin copolymer) to adjust the viscometrics.
  • the Dl package treat rate was 7.07%, which gave a dispersant level in the finished lubricant of 1.75%.
  • the dispersant used in this Example was TLA1605X®, available from The Texaco Additive Company.
  • the test results meet the European ACEA B2-96 requirements for this engine test.
  • the viscosity increase at 3% soot was 182.8%, the piston merit 43.2 and the sludge rating was 9.50.
  • the test results meet the European ACEA B2-96 requirements for this engine test.
  • the viscosity increase at 3% soot was 195.1%, the piston merit 51.8 and the sludge rating was 9.57.
  • lubricant comprising the highly functionalised graft copolymer controls the soot related viscosity increase and allows the lubricant to meet the industry specification at unexpectedly low dispersant treat rates (1.75%).
  • the Mack T8 engine test is an established test for determining the ability of a lubricant to control viscosity changes caused by soot that is produced as a by-product from the combustion process of modern heavy duty truck diesel engines.
  • the Mack T8 engine test is an integral part of the American Petroleum Institute's CG4 lubricant specification for on-highway trucks.
  • the test also evaluates sludge and oil consumption.
  • the critical parameter is the viscosity increase in the lubricant at 3.8% soot in oil, measured by Thermogravimetric analysis (TGA). The required level of soot may be achieved before the end of the test (250 hours). At the end of the test, the soot and viscosity increase are measured. These measurements are used as a measure of oil performance.
  • the detergent inhibitor package was constant and the amount of dispersant derived from the Dl package was varied.
  • a 15w40 was blended in Sun HPO® Group 2 base stocks with a NDVII (an unfunctionalised olefin copolymer, Paratone 8011®, available from Exxon Chemical Company).
  • the level of dispersant used in the lubricant formulation was 4%.
  • a 15w40 was blended in Sun HPO® Group 2 base stocks with the highly functionalised graft copolymer obtained by following Example 10 of WO 96/12746.
  • the level of dispersant derived from the Dl package present in the lubricant formulation was 1%.
  • Example C2 shows good viscosity control throughout the test.
  • the average soot particle size is maintained at a relatively low value, which accounts for the lower viscosity increase.
  • Example C2 also shows better sludge control.

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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)
  • Graft Or Block Polymers (AREA)

Claims (9)

  1. Verwendung eines funktionalisierten Viskositätsverbesserers in einem Schmiermittel in einem Dieselmotor, um durch den Dieselmotor erzeugten Ruß zu dispergieren, wobei der Ruß ohne nachteilige Beeinflussung der Viskosität des Schmiermittels dispergiert wird; das Schmiermittel zusätzlich einen Dispersant umfasst; wobei der funktionalisierte Viskositätsindexverbesserer ein stark funktionalisiertes Pfropfcopolymerreaktionsprodukt von einem Stickstoff oder einem Sauerstoff und Stickstoff enthaltenden, ethylenisch ungesättigten, aliphatischen oder aromatischen Monomer mit 2 bis 50 Kohlenstoffatomen, gepfropft auf ein Polyolefincopolymer, umfasst.
  2. Verwendung nach Anspruch 1, wobei das Pfropfcopolymer mindestens 13 Molprozent (bezogen auf ein Polymer mit einem Molekulargewicht von 100 000) des auf das Polyolefincopolymer gepfropften Monomers umfasst.
  3. Verwendung nach Ansprüchen 1 oder 2, wobei das Monomer ein Mitglied, ausgewählt aus der nachstehenden Liste, umfasst: 1-Vinyl-2-pyrrolidinon; N-Vinylimidazol; N-Allylimidazol; 1-Vinylpyrrolidon; 2-Vinylpyridin; 4-Vinylpyridin; N-Methyl-N-vinylacetamid; Diallyformamid; N-Methyl-N-allylformamid; N-Ethyl-N-allylformamid; N-Cyclohexyl-N-allylformamid; 4-Methyl-5-vinylthiazol; N-Allyldi-iso-octylphenothiazin; 2-Methyl-1-vinylimidazol; 3-Methyl-1-vinylpyrazol; N-Vinylpurin; N-Vinylpiperazine; N-Vinylsuccinimid; Vinylpiperidine; Vinylmorpholine und Kombinationen von jenen Materialien.
  4. Verwendung nach Anspruch 3, wobei das Pfropfcopolymer mindestens 1,2 Gewichtsprozent von auf das Polymergerüst gepfropftem N-Vinylimidazol umfasst.
  5. Verwendung nach Ansprüchen 1 oder 2, wobei das Pfropfcopolymer mindestens 1,2 Gewichtsprozent von geeigneten Monomeren, wie Bernsteinsäureanhydrid, oder Säurefunktionalität, wie Fumarsäure, umfasst, welche nach Funktionalisieren des Polymergerüstes mit Morpholinen, Tetrapentamin, Triethyltetramin oder anderen geeigneten Aminen oder Stickstoff enthaltenden Einheiten derivatisiert ist.
  6. Verwendung nach einem der vorangehenden Ansprüche, wobei das Pfropfcopolymerreaktionsprodukt aufweist, entweder: a) einen ADT-Wert von mindestens 8, bevorzugter mindestens 16, wenn es unter Verwendung eines Lösungspfropfverfahrens hergestellt wurde, oder b) einen ADT-Wert von mindestens 1, wenn es unter Verwendung eines Schmelzpfropfverfahrens hergestellt wurde.
  7. Verwendung nach einem der vorangehenden Ansprüche, wobei das Pfropfcopolymergerüst ein gewichtsmittleres Molekulargewicht von 20 000 bis 500 000 und eine Polydispersität von weniger als 10 aufweist.
  8. Verwendung nach einem der vorangehenden Ansprüche, wobei das Schmiermittel 0,1% bis weniger als 10%, vorzugsweise 0,2% bis weniger als 7%, bevorzugter 0,2% bis weniger als 4%, stärker bevorzugt 0,2% bis weniger als 2 Gewichtsprozent Dispersant, normalerweise bereitgestellt mit einer Detergentinhibitor-(DI)-Packung, umfasst.
  9. Verfahren zum Bekämpfen von Viskositätsänderungen eines Schmiermittels in einem Dieselmotor, die durch Ansammeln von Ruß verursacht werden, wobei das Verfahren Anwenden eines funktionalisierten Viskositätsverbesserers in einem Schmiermittel, wie in einem der Ansprüche 1 bis 8 definiert, als das Schmiermittel in dem Dieselmotor umfasst.
EP97925182A 1996-06-12 1997-06-10 Die Verwendung einer funktionalisierten Viskositätsverbesserer in Schmiermittel für Dieselmotoren Revoked EP0907698B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9612278 1996-06-12
GBGB9612278.3A GB9612278D0 (en) 1996-06-12 1996-06-12 A lubricant for use in diesel engines
PCT/GB1997/001556 WO1997047709A1 (en) 1996-06-12 1997-06-10 A lubricant for use in diesel engines

Publications (2)

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EP0907698A1 EP0907698A1 (de) 1999-04-14
EP0907698B1 true EP0907698B1 (de) 2003-09-03

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EP (1) EP0907698B1 (de)
JP (1) JP2000512668A (de)
AR (1) AR007562A1 (de)
AT (1) ATE248903T1 (de)
AU (1) AU729492B2 (de)
BR (1) BR9709571A (de)
DE (1) DE69724615T2 (de)
GB (1) GB9612278D0 (de)
MY (1) MY120935A (de)
TR (1) TR199802568T2 (de)
TW (1) TW476787B (de)
WO (1) WO1997047709A1 (de)
ZA (1) ZA975163B (de)

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AU2003239878A1 (en) 2002-05-24 2003-12-12 Castrol Limited Preparation of monomers for grafting to polyolefins, and lubricating oil compositions containing grafted copolymer
US7514393B2 (en) 2003-11-21 2009-04-07 Castrol Limited Preparation of functional monomers for grafting to low molecular weight polyalkenes and their use in the preparation of dispersants and lubricating oil compositions containing dispersant polyalkenes
US20050124509A1 (en) * 2003-12-04 2005-06-09 Antonio Gutierrez Lubricating oil compositions
US8703872B2 (en) * 2005-03-11 2014-04-22 Castrol Limited Multiple function graft polymer
EP1874837A1 (de) 2005-04-28 2008-01-09 Castrol Limited Multifunktionelles dispergierend wirkendes pfropfpolymer
WO2025126063A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions containing silicon for reduced pre-ignition in hydrogen fueled engines
WO2025126133A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions containing phosphorus for use in hydrogen fueled engines
WO2025125892A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions containing molybdenum for reduced pre-ignition in hydrogen fueled engines
WO2025126134A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions containing detergent for reduced abnormal combustion events in hydrogen fueled engines
WO2025125894A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions containing magnesium detergent for reduced pre-ignition in hydrogen fueled engines
WO2025125893A1 (en) 2023-12-14 2025-06-19 Infineum International Limited Lubricant compositions for reduced pre-ignition in hydrogen fueled engines

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Publication number Priority date Publication date Assignee Title
CA1088694A (en) * 1975-07-31 1980-10-28 Robert L. Stambaugh Polyolefin grafted with polymers of nitrogen containing monomers and lubricants and fuel compositions containing same
US4699723A (en) * 1986-08-20 1987-10-13 Texaco Inc. Dispersant-antioxidant multifunction viscosity index improver
US5427702A (en) * 1992-12-11 1995-06-27 Exxon Chemical Patents Inc. Mixed ethylene alpha olefin copolymer multifunctional viscosity modifiers useful in lube oil compositions
US5663126A (en) * 1994-10-21 1997-09-02 Castrol Limited Polar grafted polyolefins, methods for their manufacture, and lubricating oil compositions containing them

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JP2000512668A (ja) 2000-09-26
WO1997047709A1 (en) 1997-12-18
TW476787B (en) 2002-02-21
AR007562A1 (es) 1999-11-10
EP0907698A1 (de) 1999-04-14
TR199802568T2 (xx) 1999-03-22
BR9709571A (pt) 1999-08-10
AU3041497A (en) 1998-01-07
DE69724615D1 (de) 2003-10-09
DE69724615T2 (de) 2004-03-25
ZA975163B (en) 1998-01-05
AU729492B2 (en) 2001-02-01
ATE248903T1 (de) 2003-09-15
GB9612278D0 (en) 1996-08-14
MY120935A (en) 2005-12-30

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