CN102206535A

CN102206535A - Lubricating oil composition

Info

Publication number: CN102206535A
Application number: CN2011100796898A
Authority: CN
Inventors: R·D·波特莱姆; D·怀特; M·D·欧文
Original assignee: Infineum International Ltd
Current assignee: Infineum International Ltd
Priority date: 2010-03-31
Filing date: 2011-03-31
Publication date: 2011-10-05
Anticipated expiration: 2031-03-31
Also published as: EP2371934B1; BRPI1101393B1; BRPI1101393A2; JP5738054B2; CA2735498A1; CA2735498C; JP2011214004A; EP2371934A1; CN102206535B; US20110245120A1

Abstract

A lubricating oil composition having a phosphorus content of up to 0.12 wt%, a sulfated ash content of up to 1.2 wt% comprising (a) a major amount of an oil of lubricating viscosity; (b) an alkali metal or alkaline earth metal alkyl salicylate lubricating oil detergent providing from 7-15 mmol salicylate soap per kilogram of lubricating oil composition; (c) one or more dispersants providing the lubricating oil composition with from at least 0.12 wt% to 0.20 wt% atomic nitrogen, based on the weight of the lubricating oil composition, and (d) a dispersant-viscosity modifier.

Description

Lubricating oil composition

Technical field

The present invention relates to lubricating oil composition.The present invention relates more specifically to be used in the lubricating oil composition in the engine that comprises emission control systems.

Background technology

Environmental concern has caused constantly making great efforts CO, hydrocarbon and the oxynitride (NO of reduction ignition (is fuel with diesel oil) and spark ignition (is fuel with gasoline) light internal combustion engine _x) discharging.In addition, constantly make great efforts to reduce the particulate emission of ignition light internal combustion engine.For the emission standard that meets the existing of vehicle and be about to come into force, Original equipment manufacturers (OEMs) depends on the use exhaust gas aftertreatment.Such exhaust gas aftertreatment can comprise exhaust gas recirculation layout and cooling exhaust recirculation layout, catalytic converter, and it can contain one or more oxide catalysts, NO _xStorage catalyst and/or NH ₃Reducing catalyst; And/or particle trapper.OEM ' s is also just considering to use SCR (SCR) system further to reduce NO _xDischarging.

Oxide catalyst is owing to be exposed to some elements that exists in the engine exhaust, particularly owing to be exposed to by the degraded of phosphorous lubricating oil additive and introduce phosphorus in the waste gas and phosphorus compound and can be poisoned with effect and reduce.Sulphur and the sulphur compound sensitivity of reducing catalyst to introducing by the degraded of the lubricating oil additive of base oil that is used to allocate lubricant and sulfur-bearing in the engine exhaust.Particle trapper can be stopped up by the metal ash content, and this metal ash content is the product of the metallic lubricating oil additive of degraded.Therefore, except that designed engines comprising the various emission control systems, OEM ' s also requires lubricating oil composition is formulated as the existence that reduces hazardous material in the exhaust flow.Simultaneously, selected lubricating oil composition must provide competent lubricant properties, comprises competent resistance to abrasion and peace and quiet power.

European patent application 1167497A2 disclose have limited sulphur, the lubricating oil composition of p and s acidifying ash oontent, zinc dialkyl dithiophosphate and oxidation retarder that it comprises the ashless dispersant with certain nitrogen content, the containing metal purification agent (basic metal or alkaline earth salt that described metal salts of organic acids is selected from the basic metal or the alkaline earth salt of the alkyl salicylate that certain sulfate ash content is provided and has the alkylphenol derivative of Mannich base structure) that contains metal salts of organic acids, the phosphorus content of regulation is provided.Although the sulphur of said composition, p and s acidifying ash oontent are lower, it is said the peace and quiet power of good high-temperature that shows according to the lubricating oil of this patent application preparation.

Brief summary of the invention

According to a first aspect of the invention, provide a kind of lubricating oil composition, it has the phosphorus content that reaches 0.12 weight % most, the sulfate ash content that reaches 1.2 weight % most, comprises: (a) oil of the lubricant viscosity of main amount; (b) basic metal or alkaline-earth metal alkylsalicylate detergent for lubricating oil, it provides 7 to 15 mmole salicylate soaps for every kilogram of lubricating oil composition; (c) one or more dispersion agents, based on the weight of described lubricating oil composition, it provides the Nitrogen Atom of at least 0.12 weight % to 0.20 weight % and (d) dispersion agent-viscosity modifier for described lubricating oil composition.

According to a second aspect of the invention, provide the lubricated method that comprises the vehicular engine of exhaust gas recirculation (EGR) system, be included in the lubricating oil composition that uses in this engine according to a first aspect of the invention.

According to a third aspect of the invention we, provide the method according to second aspect, wherein this engine further comprises SCR (SCR) system.

Unless indicate separately, all amounts of additive are all reported with weight % on activeconstituents (" a.i. ") basis, and are promptly irrelevant with diluent or carrier oil.

The oil of lubricant viscosity

The oil of lubricant viscosity can be selected from I, II, III, IV or V class oil base stock, synthetic ester base plinth oil plant or its mixture.At American Petroleum Institute (API) publication " Engine Oil Licensing and Certification System ", Industry Services Department, the 14 edition, in December, 1996, appendix has defined the classification of oil base stock in 1,1998 year 12 months.Oil base stock has preferred 3 to 12, more preferably 4 to 10, most preferably 4.5 to 8mm at 100 ℃ ²The viscosity of/s (cSt.).

(a) use the test method of stipulating in the Table A down, I class mineral oil basis oil plant contains and is less than 90% saturates and/or more than 0.03% sulphur, and has more than or equal to 80 and less than 120 viscosity index.

(b) use the test method of stipulating in the Table A down, II class mineral oil basis oil plant contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and has more than or equal to 80 and less than 120 viscosity index.

(c) use the test method of stipulating in the Table A down, III class mineral oil basis oil plant contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and has the viscosity index more than or equal to 120.

(d) IV class oil base stock is polyalphaolefin (PAO).

(e) the ester base oil material package that available is suitable contains the ester of dicarboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid, alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc.) and various alcohol (for example butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol etc.).The specific examples of these esters comprises the own diester of 2-ethyl of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two (larane base) ester, linoleic acid dimer, by making 1 mole of sebacic acid and 2 moles of TEGs and 2 moles of complex ester that the 2 ethyl hexanoic acids reaction forms, or the like.

The ester that can be used as the synthetic base oil material also comprises by C ₅To C ₁₂Those that monocarboxylic acid and polyvalent alcohol and polyol ethers (for example neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and tripentaerythritol etc.) are made.

In an embodiment of the invention, the oil of lubricant viscosity comprises the Fischer-Tropsch base oil that is less than 50 weight %, be less than suitably 30 weight %, preferably be less than 10 weight %, most preferably do not have the Fischer-Tropsch base oil substantially; Wherein do not have the Fischer-Tropsch base oil substantially and be meant no more than impurity level.

Table A-be used to the test analytical procedure of oil base stock

Character	Test method
		Saturates	?ASTM?D2007
Viscosity index	?ASTM?D2270
		Sulphur	ASTM D2622, D4294, D4927 or D3120

Metal salicylate salt purification agent

The present invention requires to exist at least a basic metal or alkaline-earth metal lubricating oil salicylate purification agent.

This metal salicylate salt purification agent can be C ₈-C ₃₀Alkylsalicylate or its mixture, C ₁₀-C ₂₀Alkylsalicylate is particularly preferred.This salicylate purification agent is calcium and/or magnesium salicylate preferably, and has 10 to 1000, more preferably 20 to 850 the total basicnumber under 100% active mass (TBN).Being used for most preferably purification agent of the present invention is that TBN is one of high alkalinity alkyl sodium salicylate purification agent of 300 to 600 or its mixture.In one embodiment, this metal salicylate salt purification agent does not preferably contain the magnesium alkylsalicylate purification agent substantially.

In the present invention, the amount of used metal salicylate salt purification agent can change in wide region, but based on the gross weight of said composition, is typically about 0.1 to about 5 weight %, preferred 0.5 to 1.5 weight % is to provide 7 to 15 mmole metal salicylate salt purification agent/kilograms final oil compositions.Suitably, the amount of used metal salicylate salt purification agent provides at least 8 mmoles soap/kilogram final oil compositions for said composition among the present invention.Suitably, the amount of used metal salicylate salt purification agent provides no more than 11 mmoles soap/kilogram final oil compositions for said composition among the present invention.

Suitably, described metal salicylate salt purification agent provides in the metal of sulfate ash more than 0.3 quality %, preferred 0.4 quality % for lubricating oil composition at least.

This metal salicylate salt can be the unique metal lubrication oil purification agent that exists in the lubricating oil composition of the present invention.Perhaps, in lubricating composition, can there be other metallic purification agent, for example metal sulfonate or phenates.Advantageously, when lubricating oil composition comprised the mixture of purification agent type, this lubricating oil composition comprised the mixture of metal salicylate salt and metal sulphonate detergent suitably.Should additional purification agent can be calcium or magnesium metal-salt.In an embodiment of the invention, this additional purification agent is the calcium metal-salt, and this lubricating oil composition does not contain the magnesium metal-salt substantially.Preferably, the salicylate purification agent provides the most of detergent additives in this lubricating oil composition.

Substantially do not contain magnesium metal-salt purification agent and do not contain the magnesium alkylsalicylate purification agent substantially and be meant no more than impurity level, for example provide be less than 50ppm magnesium, preferably be less than 30ppm magnesium, most preferably be less than the amount of 10ppm magnesium.

The metal salts of organic acids that is commonly used for detergent for lubricating oil exists with the stable colloidal dispersion form of salt in oil.Usually by in the presence of processing aid with in the strong metal alkali and organic acid make these components.When this component is high alkalinity, in the presence of sour gas (being generally carbonic acid gas), use in the strong metal alkali and organic acid.As a result, organic acid and sour gas all change into metal-salt, and this component contains the metal that surpasses the required amount of this organic acid of neutralization.

The manufacturing of these components is extremely complicated, and the final composition of colloidal dispersion is not accurately known.For example, the metal sulphide phenates is described to contain two-sulfo-phenates of the sulfide linkage of all lengths usually.In fact, the quantity of the actual phenolic group that links together not is known really.Similarly, the amount that is considered to change into the phenol of metal-salt is assumed to be 100% usually.In fact, degree of neutralization depends on the acidity of phenol and the acidity of neutralization bases.In addition, if with this component with contain other material fusion of alkaline, the balance of setting up when making this component will move.For those reasons, the amount that exists in amount each component by the final lubricant of fusion manufacturing of the carbonate that exists in the lubricant, sulfonate and phenol formula oxyhydroxide is inferred.Again by the raw-material charge ratio that is used to make this purification agent or rely on to measure and to detect residue and infer this tittle so that infer the analytical procedure of all the other residues.

Therefore, the metal salts of organic acids mole number of existence can directly be measured in some cases, must derive in other cases.When this salt is calcium sulphonate, can use the liquid phase chromatography of describing among the ASTM 3712 to carry out direct analysis.For other organic acid, the salt mole number must be derived.When needs were done like this, titrimetry (comprising the diphasic titration method), total acid value (TAN), dialysis and other the known analytical technology of using ASTM D664 to record can be measured organic salt content.Therefore, for phenates and carboxylate salt (comprising salicylate), must measure total metal content and use metal than between organic acid and mineral acid, distributing.Passing through inductively coupled plasma atomic emission spectrometry--ASTM D4951 measures the total metal content of existence expediently.Metal than the total metal content that is meant existence divided by the amount of metal that surpasses the required amount of the existing any organic acid of neutralization, promptly in and the amount of mineral acid.The dated metal ratio of commercial purification agent manufacturers, and can measure by the manufacturers of the salt total amount of understanding existence and organic acid molecular-weight average.Can measure the amount of the metal-salt that exists in the purification agent by the amount of this purification agent of dialysis and quantification residue.If molecular-weight average the unknown of organic salt can be with strong acid treatment through the residue of the purification agent of dialysis,,, and connect with acid with known properties by chromatography, proton N MR and analytical reagent composition salt is changed into its sour form.More particularly, this purification agent of dialysis, then with the strong acid treatment residue any salt is changed into their sour forms separately.Can measure the hydroxide value of this mixture then by the method described in the ASTM D1957.If purification agent contains non-phenolic hydroxyl and (for example is used to make the pure formula derivative of the ethylene glycol of commercial phenates on phenolic compound, or the hydroxy-acid group on the Whitfield's ointment), must carry out separate analysis to quantize the amount of these hydroxyls, so that the hydroxide value that recoverable records by ASTM D1957.The technology that is applicable to the amount of measuring non-phenolic hydroxyl comprises by mass spectroscopy, liquid phase chromatography and proton N MR analysis, and connects with the compound with known properties.

Second method hypothesis of the metal salts of organic acids mole number that derive to exist in fact all transforms salify for making all organic acids that this component adds.In practice, these two kinds of methods can produce different slightly results, but the both is considered to enough accurate, thereby can be to implement the amount of precision determination salt required for the present invention.

The amount restriction of the soap that exists in being subjected to final oil compositions, existing purification agent total amount is subjected to the most nearly restriction of the sulfate ash content of 1.2 weight % of final oil compositions.

Total soap content of lubricating oil for being not more than 1.5 weight %, preferably is not more than 1.2 weight % suitably, more preferably no more than 1.0 weight %.Total soap content of this lubricating oil composition is suitably at least 0.7 weight %, preferably at least 0.75 weight %.

Ashless dispersant

Ashless dispersant comprises oil soluble polymeric hydrocarbon skeleton usually, its have can with want divided particles bonded functional group.Usually, this dispersion agent comprises with polymer backbone amine, alcohol, acid amides or the ester polar residues that is connected (connecting via bridging group usually).Ashless dispersant of the present invention can for example be selected from the monocarboxylic acid of long chain hydrocarbon replacement and oil soluble salt, ester, amino ester, acid amides, imide He the oxazoline of dicarboxylic acid or its acid anhydride; Dithionate/the ester derivative of long chain hydrocarbon; Long chain aliphatic hydrocarbon with direct connected polyamines; The Mannich condensation product that forms with condensation by long-chain substituted phenol and formaldehyde and polyalkylenepolyamines.The most frequently used dispersion agent is known succinimide dispersants, and it is the condensation product of hydrocarbyl substituted succinic acid anhydride and many (alkylene amines).List-succinimide and two-succinimide dispersants (and composition thereof) all be known.

The dispersion agent of preferred type comprises the poly-alpha olefins dispersion agent of polyamines derivation, particularly based on the dispersion agent of ethylene/butylene alpha-olefin and polyisobutene.Particularly preferably be the ashless dispersant that generates by polyisobutene, described polyisobutene is replaced by succinic anhydride group, and with polyethylene amine (for example polyethylene diamines, tetren) or many oxyalkylenes polyamines (for example polyoxy Pn, Tutofusin tris), oxy-compound (for example tetramethylolmethane) and composite reaction thereof.A kind of particularly preferred dispersion agent combination is following combination: (A) polyisobutene that is replaced by succinic anhydride group, and with (B) oxy-compound (for example tetramethylolmethane), (C) many oxyalkylenes polyamines (for example polyoxy Pn) or (D) polyalkylene diamines (for example polyethylene diamines and tetren) reaction, wherein every mole (A) uses about 0.3 to about 2 moles (B), (C) and/or (D).Another preferred dispersing agent combination comprises as U.S. Patent No. 3, (A) polyisobutenyl succinic anhydride described in 632,511 and (B) polyalkylenepolyamines (for example tetren) and (C) combination of the aliphatic primary amine (for example tetramethylolmethane or Tutofusin tris) that replaces of polyvalent alcohol or poly-hydroxy.

Another kind of ashless dispersant comprises mannich base condensation products.Usually, these products pass through as U.S. Patent No. 3, disclosedly in 442,808 make monohydroxy that about 1 mole of alkyl replaces or polyhydroxy-benzene and about 1 to 2.5 mole of carbonyl compound (for example formaldehyde and paraformaldehyde) and about 0.5 to 2 mole of polyalkylenepolyamines condensation like that and make.This class mannich base condensation products can comprise that the polymeric polymer product of metallocene catalyst is as the substituting group on the phenyl, or can with U.S. Patent No. 3, similar mode described in 442,808 and the compound reaction that contains substituted this polymkeric substance on succinyl oxide.The example that uses the functionalized and/or derivation olefin polymer of metallocene catalyst system synthetic has been described in indicated open source literature above.

This dispersion agent can pass through various conventional post treatment methods, as United States Patent(USP) Nos. 3,087, summarizes the boronation method of instruction in 936 and 3,254,025, further aftertreatment.The easy following realization of the boronation of dispersion agent: with boron compound (for example ester of the acid of the acid of boron oxide, halogenation boron, boron and boron), to be enough to providing 0.1 to handle the dispersion agent that contains acyl group nitrogen to the amount of about 20 atomic ratio boron for every mole of acylated nitrogen composition.The available dispersion agent contains about 0.05 to about 2.0 quality %, about 0.05 boron to about 0.7 quality % for example.In product, (mainly be (HBO with dehydration boric acid polymkeric substance ₂) ₃) boron that occurs of form is considered to combine with dispersion agent imide and imide with the form of amine salt, the metaborate of imide for example.Can followingly carry out boronation: in the acyl group nitrogen compound, add about 0.5 to about 4 quality %, for example about 1 the boron compound that is generally slurry form to about 3 quality % (based on the quality of acyl group nitrogen compound); preferred boric acid; and, carry out the nitrogen stripping then under agitation about 135 ℃ to about 190 ℃, for example 140 ℃ to 170 ℃ down heating about 1 to about 5 hours.Perhaps, can carry out the boron processing by in the thermal reaction mixture of dicarboxylic acid material and amine, adding boric acid and dewatering simultaneously.Also can use other afterreaction method as known in the art.

This dispersion agent also can be by coming further aftertreatment with so-called " end-capping reagent " reaction.Traditionally, with nitrogenous dispersion agent " end-blocking " to reduce the detrimental action of this class dispersion agent to the fluoroelastomer engine sealing.Many end-capping reagents and method are known.In known " end-capping reagent ", those that alkaline dispersing agent amino is changed into non-alkaline residue (for example amido or acylimino) are only.For example, at United States Patent(USP) Nos. 4,839, nitrogenous dispersion agent and Acetacetic acid alkyl ester (methyl aceto acetate for example, reaction EAA) have been described in 071,4,839,072 and 4,579,675.For example in U.S. Patent No. 3,185, the reaction of nitrogenous dispersion agent and formic acid has been described in 704.At United States Patent(USP) Nos. 4,663,064 (oxyacetic acid), 4,612,132,5,334,321,5,356,552,5,716,912,5,849,676,5,861,363 (alkyl carbonate and alkylene carbonates, ethylene carbonate for example), 5,328,622 (monoepoxides), 5,026,495,5,085,788,5,259,906,5,407, the reaction product of nitrogenous dispersion agent and other suitable end-capping reagent has been described in 591 (many (for example two)-epoxide) and 4,686,054 (maleic anhydride or the succinyl oxide).Aforementioned list is not an exhaustive, and other is well known by persons skilled in the art with the end capped method of nitrogenous dispersion agent.

This dispersion agent is the dispersion agent of hot maleinization preferably, the monocarboxylic acid that it replaces by polyalkenyl or dicarboxylic acid, acid anhydride or ester react with polyamines and form, for each polyalkenyl residue, have greater than about 1.3 to the residues that produce monocarboxylic acids or dicarboxylic acid less than about 1.7, and wherein said polyalkenyl residue has 1.5 to 2.0 molecular weight distribution (M _w/ M _n) and about 1800 to about 3000 number-average molecular weight (M _n).For example at United States Patent(USP) Nos. 6,734, this type of preferred dispersing agent has been described in 148 and 6,743,757.

On 100% actives basis, ashless dispersant exists with the amount of 4 to 10 weight %, preferably approximately 5 to 8 weight % suitably.This dispersion agent should provide the Nitrogen Atom of at least 0.12 weight % for lubricating oil composition.This dispersion agent provides the Nitrogen Atom that is not more than 0.2 weight % for lubricating oil composition suitably.This dispersion agent is preferably the Nitrogen Atom that lubricating oil composition provides 0.12 to 0.17 weight %.

Can be by the nitrogen content that this dispersion agent provides for lubricating oil composition according to the program determination of ASTM D5762.

Preferred dispersing agent is the polyisobutenyl succinimide dispersion agent of boration or non-boration, and wherein this polyisobutenyl has number-average molecular weight (Mn) about 400 to 3,000, preferably approximately 900 to 2,500.

The polyisobutenyl succinimide dispersion agent that an embodiment of the invention utilization uses polyisobutene to make, described polyisobutene is given birth to by pure iso-butylene stream or raffinate I miscarriage, contains the reactive isobutene polymer of terminal vinylidene alkene with preparation.Preferably, these polymkeric substance that are known as highly reactive polyisobutenes (HR-PIB) have at least 65%, for example 70%, more preferably at least 80%, most preferably at least 85% terminal vinylidene content.For example in U.S. Patent No. 4,152, the preparation of this base polymer has been described in 499.HR-PIB is known, and HR-PIB can be with trade(brand)name Glissopal ^TM(from BASF) and Ultravis ^TM(from BP-Amoco) buys.

This dispersion agent can comprise a kind of dispersion agent or dispersion agent combination.If this dispersion agent comprises the dispersion agent combination, then this mixture comprises lower molecular weight dispersion agent and high molecular weight dispersant suitably.The lower molecular weight dispersion agent is to have the dispersion agent of number-average molecular weight (Mn) for about 500 to 1750 polymeric hydrocarbon skeleton.High molecular weight dispersant is to have the dispersion agent of number-average molecular weight (Mn) for about 1800 to 3000 polymeric hydrocarbon skeleton.In one embodiment, the whole dispersion agents that exist in the lubricating oil composition comprise and are less than 40 quality %, are less than 35 quality % or are less than the lower molecular weight dispersion agent of 30 quality %.

Can measure polymericular weight by various known technologies, especially A kind of method easily is gel permeation chromatography (GPC), its provide in addition molecular weight distribution information (referring to W.W.Yau, J.J.Kirkland and D.D.Bly, " Modern Size Exclusion Liquid Chromatography ", John Wiley and Sons, New York, 1979).For the lower molecular weight polymkeric substance, another method that can be used for determining molecular weight is vapor-pressure osmometry (referring to for example ASTM D3592) especially.

Viscosity modifier

By in oil base stock, mixing some polymeric material that serves as viscosity modifier (VM) or viscosity index improver (VII), improve or increase the viscosity index of oil base stock.Usually, the polymeric material that can be used as viscosity modifier be number-average molecular weight (Mn) for about 5,000 to about 250,000, preferably approximately 15,000 to about 200,000, more preferably about 20,000 to about 150,000 those.Suitable viscosity modifier is the multipolymer of multipolymer, vinylbenzene and the acrylate of polyisobutene, olefin copolymer (for example ethene and propylene and the more multipolymer of high-grade alpha-olefin), polymethacrylate/salt, polyalkyl methacrylate, methacrylic ester/salt copolymer, unsaturated dicarboxylic acid and vinyl compound, with the partially hydrogenated multipolymer of styrene/isoprene, phenylethylene/butadiene and isoprene/butadiene, and the partially hydrogenated homopolymer of divinyl and isoprene, isoprene/Vinylstyrene.

Dispersion agent-viscosity modifier

Dispersion agent-viscosity modifier manufacturing as described below: make viscosity modifier (for example above-mentioned those) and graft materials (for example maleic anhydride) grafting, make then through grafted material and amine for example, acid amides, nitrogenous heterogeneous ring compound or alcohol reaction.

The example of dispersion agent-viscosity modifier comprises monocarboxylic acid or dicarboxylic acid the amine derivation, that replaced by alkyl, and wherein said hydrocarbyl substituent comprises length is enough to make this compound to have the chain that viscosity index is improved character.Usually, dispersion agent-viscosity modifier can be by for example following material manufacturing: the C of vinyl alcohol ₄To C ₂₄Unsaturated ester or C ₃To C ₁₀Unsaturated monocarboxylic or C ₄To C ₁₀The polymkeric substance of dicarboxylic acid, it is had the unsaturated nitrogen containing monomer derivation of 4 to 20 carbon atoms; C ₂To C ₂₀Alkene and unsaturated C ₃To C ₁₀The polymkeric substance of monocarboxylic acid or dicarboxylic acid, it is by amine, azanol or pure derivation; Or ethene and C ₃To C ₂₀The polymkeric substance of alkene, this polymkeric substance passes through grafting C thereon ₄To C ₂₀Unsaturated nitrogen containing monomer or by being grafted to unsaturated acid on the polymer backbone and making the hydroxy-acid group of this grafting acid then and amine, azanol or alcohol reaction and further reaction.

Preferred dispersing agent-viscosity modifier comprises the polymkeric substance arylamine derivation, maleic anhydride graft.Preferred arylamine is a N-phenyl-1, the 4-phenylenediamine.This polymkeric substance is ethylene-propylene copolymer suitably.This polymkeric substance preferably has at least 5,000, preferably at least 8, and 000, suitably at least 10,000 number-average molecular weight Mn.The Mn of this polymkeric substance can be up to 100,000, but are not more than 60,000 suitably, are preferably about 40,000.

Suitable commercial dispersants-viscosity modifier includes, but not limited to can be available from the HiTec 5777 of Afton Chemicals, or polyfunctional poly methacrylic ester viscosity modifier, for example can be available from the Viscoplex of Rohmax GmbH ^TMOr Acryloid ^TMThe product of series.

The present invention comprises dispersion agent-viscosity modifier.On the actives basis, it can exist with the amount of 0.05 to 5 weight %, preferably approximately 0.5 to 3 weight %.

Lubricating oil composition of the present invention can comprise one or more standard crankcase oil additives in addition; The example is discussed hereinafter.

Antioxidant

Antioxidant reduces the oil base stock trend of deterioration in use, and this deterioration can raise by oxidation products on the metallic surface (for example greasy filth and lacquer deposit) and viscosity and show.In the present invention, they exist with the amount of 0.1 to 5.0 weight % suitably.As U.S.4, described in 867,890, suitable oxidation retarder comprises hindered phenol, has preferred C ₅To C ₁₂The pentanoic that the alkaline earth salt of the alkylphenol thioesters of alkyl group side chain, nonyl phenol sulfurated lime, ashless oil soluble phenates and sulfurized phenates, phosphorus sulfuration or sulfurized hydrocarbon, alkyl replace, phenyl and ALPHA-NAPHTHYL AMINE, phosphide, metal thiocarbamate, ashless thiocarbamate and the oil-soluble copper compounds that alkyl replaces.The pentanoic that replaces of dialkyl group most preferably, wherein this alkyl is C ₄-C ₂₀, for example dinonyldiphenylamine, and hindered phenol, iso-octyl-3 for example, 5-two-tertiary butyl-4-hydroxy laurate and composition thereof.

The dialkyl zinc dithiophosphate

The dialkyl zinc dithiophosphate is the oil soluble salt of dialkyl phosphorodithioic acid, and can represent with following formula:

Wherein R and R ' identical or different contain 1 to 18, the alkyl of preferred 2 to 12 carbon atoms, and comprise for example group of alkyl, thiazolinyl, aryl, aralkyl, alkaryl and alicyclic group and so on.Preferred especially is the alkyl with 2 to 8 carbon atoms as R and R ' group.Therefore, this group can for example be ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.In order to obtain oil soluble, the total number of carbon atoms in this phosphorodithioic acid (being R and R ') is typically about 5 or bigger.This dialkyl zinc dithiophosphate (ZDDP) therefore can comprise zinc dialkyl dithiophosphate.ZDDP is mixed with the most frequently used antioxidant/anti-wear agent in the oil engine that satisfies existing European ACEA specification and the used lubricating oil composition of conventional passenger vehicle diesel engine.Lubricating oil composition of the present invention contains in oriented this lubricating oil composition about 0.02 to 0.12 weight %, preferred 0.02 to 0.1 weight %, the more preferably amount of the ZDDP of 0.05 to 0.08 quality % phosphorus (or other dialkyl phosphorodithioic acid metal-salt) introduced suitably.Phosphorus content according to this lubricating oil composition of program determination of ASTM D5185.

Molybdenum compound

For lubricating oil composition of the present invention, can use any suitable oil-soluble organo-molybdenum compound.This molybdenum compound is considered to serve as wear-resistant simultaneously and antioxidant addn.Preferably, use dimerization and trimerization molybdenum compound.The example of this type of oil-soluble organo-molybdenum compound is dialkyl dithiocarbamate, dialkyl dithiophosphate, dialkyl dithio phosphinate, xanthogenate, sulfo-xanthogenate, carboxylate salt and analogue, and composition thereof.Particularly preferably be the dialkyl thiocarbamic acid molybdenum.

Suitable molybdenum dialkyldithiocarbamacompositions comprises the dimerization molybdenum dialkyldithiocarbamacompositions, as has following formula those:

R ₁To R ₄Represent straight chain, side chain or aromatic hydrocarbyl independently; And X1 to X4 represents Sauerstoffatom or sulphur atom independently.Four alkyl R ₁To R ₄Can be same to each other or different to each other.

The another kind of organic molybdenum of available is three nuclear (trimerization) molybdenum compound, especially formula Mo in the lubricating composition of the present invention ₃S _kL _nQ _zThose and composition thereof, wherein L is the independent part of selecting, it contains carbonatoms and is enough to make the oil-soluble organic group of this compound, n is 1 to 4, and k 4 to 7 does not wait, and Q is selected from the neutral electron compound of giving, as water, amine, alcohol, phosphine and ether, z is 0 to 5 and comprises the nonstoichiometry value.In all part organic groups, should there be at least 21 carbon atoms altogether, for example at least 25, at least 30, or at least 35 carbon atoms.

This part is selected from:

——X——R 1，

And composition thereof, wherein X, X ₁, X ₂Be independently selected from oxygen and sulphur with Y, and R wherein ₁, R ₂Be independently selected from hydrogen and organic group with R, these organic groups can be identical or different.This organic group is preferably alkyl, for example the aryl and the ether group of alkyl (carbon atom that for example wherein is connected on this part rest part is primary carbon atom or secondary carbon(atom)), aryl, replacement.Each part more preferably has identical alkyl.

Term " alkyl " in this article refers to has carbon atom that directly links to each other with the part rest part and the substituting group that is mainly alkyl in nature.Such substituting group comprises following substituting group:

1, hydrocarbon substituent, be aliphatics (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl group) substituting group, the aromatic ring of aromatics, aliphatics and alicyclic replacement etc., and the cyclic substituents (that is, the substituting group shown in any two forms alicyclic radical together) finished by another part of part of ring wherein.

2, the hydrocarbon substituent of Qu Daiing promptly comprises and can not change those of non-hydrocarbons group that substituting group among the present invention is mainly the character of alkyl.Those skilled in the art understand suitable group (for example, halogeno-group, particularly chloro and fluoro base, amino, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group, sulphur oxygen base etc.).

Importantly, the part organic group has is enough to make the oil-soluble carbonatoms of compound.For example, the carbonatoms in each group is generally about 1 to about 100, and preferred about 1 to about 30, and more preferably from about 4 to about 20.Preferred part comprises the dialkyl dithiophosphoric acid root, alkyl xanthogenic acid root, carboxylate radical, dialkyldithiocarbamacompositions root and composition thereof.Dialkyldithiocarbamacompositions root most preferably.One skilled in the art will recognize that the formation of The compounds of this invention need be selected the part of suitable electric charge, with the electric charge (as described below) of balance nuclear.

Formula is Mo ₃S _kL _nQ _zCompound have the cationic core that is surrounded by anion ligand, wherein cationic core is represented with for example following structure:

Its net charge is+4.Therefore, in order to make these karyolysis, the total charge of all parts is necessary for-4.Preferred 4 single anion ligands.Do not wish to be bound by any theory, but believe that two or more three endorse to connect by one or more parts or to link.Part can be multiple tooth, and a plurality of connections that are connected with one or more nuclears are promptly arranged.Believe that oxygen and/or selenium can replace the sulphur in the nuclear.

Oil soluble three nuclear molybdenum compounds are preferred, and can be prepared as follows: make (NH ₄) ₂Mo ₃S ₁₃N (H ₂O) the suitable ligand sources of and so on molybdenum source and for example thiuram disulfide and so on reacts in suitable liquid and/or solvent, and wherein n changes between 0 to 2 and comprises the nonstoichiometry value.Other oil soluble three nuclear molybdenum compounds can generate in molybdenum source, ligand sources and the sulphur extraction agent reaction process in suitable solution, and wherein there is for example (NH in the molybdenum source ₄) ₂Mo ₃S ₁₃N (H ₂O), ligand sources has for example thiuram disulfide, dialkyl dithio amino formate/salt or dialkyl dithiophosphate/salt, and the sulphur extraction agent has for example phosphine of cyanide ion, sulfite ion or replacement.In addition, as [M '] ₂[Mo ₃S ₇A ₆] (wherein M ' is a gegenion, A for as the halogen of Cl, Br or I) and so on three nuclear molybdenum-sulfur halide salt can in suitable liquid and/or solvent, react with the ligand sources of for example dialkyl dithio amino formate/salt or dialkyl dithiophosphate/salt, examine molybdenum compounds to generate oil soluble three.Described suitable liquid and/or solvent can be for example water-containing solvent or organic solvent.

Selected part must have the carbon atom of enough numbers, so that compound dissolves in lubricating oil composition.Differ definiteness compound or additive of term used herein " oil-soluble " can any ratio be dissolved in oil, and refer to use, transportation and store in they are soluble.

The sulfurized molybdenum containing compositions is prepared as follows: acid molybdenum compound and basic nitrogen compound are reacted in the presence of polar accelerant, generate molybdenum complex, wherein basic nitrogen compound is selected from group or its mixture of being made up of succinimide, carboxylic acid amide, alkyl monoamine, phosphamide, thio-phosphamide, the strange alkali of Manny, dispersant viscosity index improvers, (ii) make the reaction of molybdenum complex and sulfocompound, thereby generate the composition of available sulfur-bearing and molybdenum in the context of the invention.The sulfurized molybdenum containing compositions can be characterized by the molybdenum/sulfide complex of basic nitrogen compound usually.The accurate molecular formula of these molybdenum compositions is also imprecise to be known.But believe that they are following compounds: wherein valency and oxygen or sulphur atom equilibrated molybdenum be by the one or more nitrogen-atoms coordinations in the basic nitrogen compound that uses in the process of these compositions of preparation, or their salt.

Lubricating oil composition of the present invention can contain a spot of soluble molybdenum compounds.If exist, the molybdenum from molybdenum compound of the amount of the extremely maximum about 600ppm of 10ppm can be present in the lubricating oil composition at least.The preferred molybdenum that uses about 10ppm to 300ppm from molybdenum compound.More preferably use the molybdenum that is not more than 100ppm from molybdenum compound.These values are benchmark with the weight of lubricating oil composition.

Friction improver

Lubricating oil composition can contain organic oil dissolubility friction improver.This friction improver can constitute about 0.02 to 2.0 weight % of lubricating oil composition usually.

Friction improver comprises following compound: the alphatic carboxylic acid ester of the aliphatic amine of aliphatic amine or ethoxylation, aliphatic fatty acid amide, aliphatic carboxylic acid, the polyvalent alcohol (glyceryl ester of lipid acid for example, olein for example, it is preferred), aliphatic carboxylic acid ester-acid amide, aliphatic phosphonic acid ester, aliphatic thiophosphatephosphorothioate etc., wherein aliphatic group contains usually more than about 8 carbon atoms, so that this compound suitably is oil-soluble.Same suitable be aliphatic substituted succinimide by one or more aliphatic amber acid or anhydrides and ammonia react are formed.

Pour point reducer is also referred to as the mobile improving agent of lubricating oil, reduces fluid and can flow or dumpable required minimum temperature.This class additive is known.The representative that improves those additives of fluidic low-temperature fluidity is fumaric acid C ₈To C ₁₈Dialkyl/vinyl acetate copolymer, polyalkyl methacrylate etc.They can use with the amount of 0.01 to 5.0 weight %, preferably approximately 0.1 to 3.0 weight %.When using mineral oil basis oil plant, preferably use them, but when oil base stock is PAO or synthetic ester, do not need them usually.

Can provide foam control by chemical compound lot, comprise polysiloxane type antifoams, for example silicone oil or polydimethylsiloxane.

Some above-mentioned additives can provide multiple action; For example, single additive can serve as dispersion agent-oxidation retarder.This method is known, and does not need to be described in further detail.

Each additive can mix in the oil base stock in any mode easily.For example, can be by each component is dispersed or dissolved in oil base stock or the base oil adulterant with the desired concn level and directly it is added in oil base stock or the base oil adulterant.This fusion can be carried out in the temperature of envrionment temperature or rising.Form lubricating oil composition by the binder component fusion and produce product of the present invention.

Preferably, all additives are blended together to form enriched material or additive suit, then it are mixed in the oil base stock to make final lubricant.This enriched material or additive suit can contain viscosity modifier, or this viscosity modifier can separate interpolation to form lubricating oil composition with this enriched material or additive suit.Usually this enriched material of preparation is to contain the additive that the appropriate amount of desired concn is provided in end formulation when the base lubricant with this enriched material and predetermined amount merges.

Final crankcase lubrication oil formulation can use enriched material or the additive suit of 10 to 50 quality %, preferred 15 to 40 quality %, and all the other are oil base stock.

Further describe the present invention referring now to following exemplary embodiment; Wherein all amounts are all based on 100% active substance (that is, not comprising any diluent oil).

Embodiment 1

Preparation lubricating oil composition as described below oil A: will comprise 4.8 quality % is the polyisobutenyl succinimide dispersion agent that 2225 polyisobutenyl is made by number-average molecular weight (Mn), 1.08 quality % is the polyisobutenyl succinimide dispersion agent that 950 polyisobutenyl is made by number-average molecular weight (Mn), 0.74 the 565TBN overbased calcium salicylate purification agent of the 321TBN overbased calcium salicylate purification agent of quality % and 0.34 quality %, 0.43 the 709TBN overbased magnesium sulphonates purification agent of quality %, 0.84 HiTec 5777 dispersion agents-viscosity modifier of quality %, with additional zinc dialkyl dithiophosphate, organic disulfide is for the carboxylamine molybdenum, be mixed in the oil base stock of the mixture that comprises I class and III class base oil with the additive suit of antioxidant.Oil A comprises atomic boron, 50ppm molybdenum, 0.153 quality % calcium and the 0.069 quality % magnesium of 0.96 weight % sulfate ash, 0.08 weight % phosphorus, 0.21 weight % sulphur, 130ppm.The salicylate soap content of oil A is that 8.8 mmoles and total soap content that should oil are 0.85 quality % soap.Described calcium salicylate purification agent provides the calcium in sulfate ash of 0.5 quality % for this lubricating oil composition.Described dispersion agent provides 0.135 quality % nitrogen for this lubricating oil composition, and wherein the N of 0.096 quality % is provided by described high molecular weight dispersant, and 0.039 quality % is provided by described lower molecular weight dispersion agent.

Oily then A moves in ASTM D7422 testing of engine (the more normal Mack T-12 that is called).Design this Mack T-12 test and will be furnished with the ability that the wearing and tearing in the engine of egr system minimize to evaluate and test oil.This Mack T-12 testing of engine is the part of API CJ-4 and ACEA E6 performance class.

Used engine is the Mack E7E-Tech 460 that has the modification of egr system, and its rated value is 460bhp and 1,800rpm.This test run surpasses 300 hours and evaluation and test piston ring scuffing, cylinder liner abrasion, plumbous bearing corrosion, oil consumption and oxidation when off-test.

In following table 1, list qualified/defective limit and result of oily A:

Table 1

Standard	Qualified/defective limit	Oil A
			Collar weight loss	＜105	73
Cylinder wear	≤21	5.9
			Lead corrosion	≤30	23
Oil consumption	≤80	56.8
			Estimate	1000	1342

Oil A clearly tests by Mack T-12 with required API CJ-4 and ACEA E6 performance level.

Embodiment 2

Preparation lubricating oil composition as described below oil B: will comprise 4.8 quality % is the polyisobutenyl succinimide dispersion agent that 2225 polyisobutenyl is made by number-average molecular weight (Mn), 1.08 quality % is the polyisobutenyl succinimide dispersion agent that 950 polyisobutenyl is made by number-average molecular weight (Mn), 0.84 the 565TBN overbased calcium salicylate purification agent of the 321TBN overbased calcium salicylate purification agent of quality % and 0.34 quality %, 0.43 the 709TBN overbased magnesium sulphonates purification agent of quality %, 0.84 HiTec 5777 dispersion agents-viscosity modifier of quality %, and zinc dialkyl dithiophosphate, the additive suit of molybdenum dithiocarbamate and antioxidant is mixed in the oil base stock of the mixture that comprises I class and III class base oil.Oil B comprises atomic boron and 50ppm molybdenum, 0.165 quality % calcium and the 0.069 quality % magnesium of 1.0 weight % sulfate ashes, 0.08 weight % phosphorus, 0.21 weight % sulphur, 130ppm.The salicylate soap content of oil B is that 9.8 mmoles and total soap content that should oil are 0.92 quality % soap.Described calcium salicylate purification agent provides the calcium in sulfate ash of 0.54 quality % for this lubricating oil composition.Described dispersion agent provides 0.135 quality % nitrogen for this lubricating oil composition, and wherein the N of 0.096 quality % is provided by described high molecular weight dispersant, and 0.039 quality % is provided by described lower molecular weight dispersion agent.

Oily then B moves in Mercedes-Benz OM646LA (CEC L-99-08) testing of engine, and it is the part of ACEA and Daimler specification.2.2L co-rail diesel OM646DE 22LA engine is used in test in this 300 hours, the performance of evaluation and test engine lubricant aspect engine scuffing and total degree of cleaning and piston cleanliness and ring bonding.

In following table 2, listed qualified/defective limit and result of oily B:

Table 2

Standard	Qualified/defective limit (ACEA E6)	Oil B
			Cam outlet wearing and tearing	≤140	87.3

Result from table 2 as can be seen, oily B has passed through the OM646LA testing of engine with the performance level that ACEA E6 requires.This test also realizes all call parameters of stricter MB 228.51 specification levels.

Claims

1. lubricating oil composition, it has the phosphorus content of 0.12 weight % the most nearly, the sulfate ash content of 1.2 weight % the most nearly, comprises:

(a) oil of the lubricant viscosity of main amount;

(b) basic metal or alkaline-earth metal alkylsalicylate detergent for lubricating oil, it provides 7 to 15 mmole salicylate soaps for every kilogram of lubricating oil composition;

(c) one or more ashless nitrogenous dispersion agents, based on the weight of described lubricating oil composition, described one or more ashless nitrogenous dispersion agents for described lubricating oil composition provide at least 0.12 weight % to 0.20 weight % Nitrogen Atom and

(d) dispersion agent-viscosity modifier.

2. according to the lubricating oil composition of claim 1, wherein phosphorus content is not more than 0.08 weight %.

3. according to the lubricating oil composition of claim 1 or 2, wherein sulfate ash content is not more than 1.0 weight %.

4. according to claim 1,2 or 3 lubricating oil composition, wherein said basic metal or alkaline-earth metal alkylsalicylate detergent for lubricating oil provide 8 to 11 mmole salicylate soaps for every kilogram of lubricating oil composition.

5. according to each lubricating oil composition of aforementioned claim, wherein based on the weight of this lubricating oil composition, described one or more dispersion agents provide the Nitrogen Atom of at least 0.12 weight % to 0.17 weight % for this lubricating oil composition.

6. according to each lubricating oil composition of aforementioned claim, wherein said basic metal or alkaline-earth metal alkylsalicylate are calcium salicylate or magnesium salicylate or their combination.

7. according to each lubricating oil composition of aforementioned claim, further comprise alkaline-earth metal alkylsulfonate detergent for lubricating oil.

8. according to each lubricating oil composition of aforementioned claim, wherein said dispersion agent is the polyisobutenyl succinimide dispersion agent.

9. according to each lubricating oil composition of aforementioned claim, it meets the requirement of API-CJ4 specification and ACEA E6 specification.

10. the lubricated method that comprises the vehicular engine of exhaust gas recirculation (EGR) system is included in and uses in this engine according to each lubricating oil composition of claim 1 to 9.

11. according to the method for claim 10, wherein said engine is a compression ignition engine.

12. according to the method for claim 11, wherein said engine is a large diesel engine.

13. according to each method of claim 10 to 12, wherein said engine further comprises selective catalytic reduction device.