CN1872969A - Lubricating oil compositions - Google Patents

Abstract

A method of improving the seal compatibility and/or copper corrosion performance of lubricating oil compositions for the lubrication of the crankcases of an internal combustion engine, which method includes the step of adding to the lubricating oil compositions a minor amount of a non-hydrogenated (unsaturated) olefin polymer. Also described are lubricating oil compositions for engines and transmissions, which compositions contain sulphur and/or a salicylate soap and a minor amount of a non-hydrogenated (unsaturated) polymer, which compositions are compatible with nitrile rubber engine and transmission seals and copper-containing engine and transmission components.

Description

Lubricating oil composition

Invention field

The present invention relates to a kind of improvement and be used for the sealing material consistency of the lubricating oil composition of base chamber and wheel box, especially have a method of sealing material consistency of the lubricating oil composition of significant sulphur content and/or Whitfield's ointment soap (salicylate soap) content, and relate to the lubricating oil composition that in engine that contains acrylonitrile butadiene packing material and wheel box, shows the sealing material consistency that improves with remarkable sulphur content and/or Whitfield's ointment soap content.The invention further relates to a kind of improvement and be used for the copper corrosion performance of the lubricating oil composition of base chamber and wheel box, especially have a method of copper corrosion performance of the lubricating oil composition of remarkable sulphur content, and relate to and show the sealing material consistency that improves and the lubricating oil composition with remarkable sulphur content of copper corrosion performance.

Background of invention

Base oil or this type of the oily mixture and being used to that the lubricating oil composition that is used for lubricated I. C. engine and wheel box comprises the lubricant viscosity of main amount improves the additive that described oiliness can characteristic.For example, additive is used to improve peace and quiet ability, reduces engine scuffing, and the stability of opposing heat and oxidation is provided, and reduces oil consumption, suppresses corrosion, serves as dispersion agent, and the loss of reducing friction.Some additives can provide multiple benefit, for example dispersion agent-viscosity modifier.Many base oils contain sulphur, and many extremely effective additives that are usually used in engine and the gear-box lubricating oil composition also contain sulphur, described additive comprises zinc dialkyl dithiophosphate (ZDDP), some molybdenum-sulphur compound, ashless dithiocar-bamate (ester) and sulfonate and some phenates purification agents, and the overall sulfur content of described preparation lubricating oil is had contribution.

Modern Internal-Combustion Engine and wheel box comprise many packing ring and other sealing materials that formed by nitrile rubber.The sulphur that has been found that lubricating oil can impel material degradation.Before the crankcase oil that is used for its engine was up to the standards, manufacturers of engines (being called " original equipment manufacturer " or " OEMs " often) required to comprise the compatibility test with the engine sealing material by many performance tests.Suspect in addition and high-loadly may impel the deterioration of acrylonitrile butadiene packing material, especially in " low ash content " lubricating oil from the Whitfield's ointment soap of salicylate purification agent.Therefore, be desirable to provide and improve lubricating oil composition, especially have the method for sealing material consistency of the lubricating oil composition of remarkable sulphur content and/or high-content Whitfield's ointment soap and a lubricating oil composition that the sealing material consistency that possesses raising is provided with remarkable sulphur content and/or high-content Whitfield's ointment soap.

Have been found that the sulphur in the lubricating oil can cause copper corrosion.Authorize be up to the standards before, OEMs also requires lubricating oil composition to test by copper corrosion.Therefore, be desirable to provide and improve lubricating oil composition, especially have a method of copper corrosion performance of the lubricating oil composition of remarkable sulphur content, and the lubricating oil composition with remarkable sulphur content that possesses improved copper corrosion performance is provided.

Summary of the invention

Have been found that now in lubricating oil composition add minor amount not hydrogenated olefins polymkeric substance (multipolymer) for example polyisobutene can improve consistency between this lubricating oil composition and paracril engine and the wheel box sealing material, especially for the sulphur that contains significant quantity, for example greater than about 0.10 quality %, as greater than about 0.15 quality %, particularly greater than the sulphur content of about 0.20 quality % and/or the Whitfield's ointment soap from the salicylate purification agent of significant quantity, for example in every kilogram of finished lube 9mmol or more, 18mmol or more particularly, the lubricating oil composition of 24mmol or more Whitfield's ointment soaps more particularly.Have been found that in addition in lubricating oil composition add minor amount not hydrogenated olefins polymkeric substance (multipolymer) for example polyisobutene can improve the copper corrosion performance of lubricating oil composition, especially improve contain the sulphur of significant quantity, for example greater than about 0.10 quality %, as greater than about 0.15 quality %, particularly greater than the copper corrosion performance of the lubricating oil composition of the sulphur content of about 0.20 quality %.

Therefore, in first aspect, the present invention relates to the method for sealing material consistency that a kind of improvement is used for the lubricating oil composition of lubricated oil engine or engine mission, this method comprises unhydrided (undersaturated) olefin polymer (multipolymer) that adds minor amount in above-mentioned lubricating oil composition.

In second aspect, the present invention relates to the method for first aspect, wherein said lubricating oil composition contains significant sulphur content, for example greater than about 0.10 quality %, especially greater than about 0.15 quality %, as greater than about 0.18 quality %, more particularly greater than the sulphur content of about 0.20 quality %, and the lubrication viscosity oil that comprises main amount; At least a sulfur-containing additive of minor amount; And the not hydrogenated olefins polymkeric substance (multipolymer) of the about 10.0 quality % of about 0.5 quality %-, wherein all mass percents are in the total mass of described lubricating oil composition.

In the third aspect, the present invention relates to the method for first aspect, wherein said lubricating oil composition comprises the lubrication viscosity oil of main amount; At least a salicylate purification agent of minor amount, its amount are introduced in described lubricating oil composition in every kilogram of lubricating oil composition 9mmol or more, 18mmol or more, more particularly 24mmol or more Whitfield's ointment soap especially; And the not hydrogenated olefins polymkeric substance (multipolymer) of the about 10.0 quality % of about 0.5 quality %-, wherein all mass percents are in the total mass of described lubricating oil composition.

In fourth aspect, the present invention relates to a kind of lubricating oil composition, it contains significant sulphur content, for example greater than about 0.10 quality %, especially greater than about 0.15 quality %, as greater than about 0.18 quality %, more particularly greater than the sulphur content of about 0.20 quality %, it comprises the lubrication viscosity oil of main amount; At least a sulfur-containing additive of minor amount; And the not hydrogenated olefins polymkeric substance (multipolymer) of the about 10.0 quality % of about 0.5 quality %-, wherein all mass percents are in the total mass of described lubricating oil composition.

In aspect the 5th, the present invention relates to a kind of lubricating oil composition, it comprises the lubrication viscosity oil of main amount; At least a salicylate purification agent of minor amount, its amount are introduced in described lubricating oil composition in every kilogram of lubricating oil composition (finished lube) 9mmol or more, 18mmol or more, more particularly 24mmol or more Whitfield's ointment soap especially; And the not hydrogenated olefins polymkeric substance (multipolymer) of the about 10.0 quality % of about 0.5 quality %-, wherein all mass percents are in the total mass of described lubricating oil composition.

In aspect the 6th, the present invention relates to the lubricating oil composition of the method or the fourth aspect of second aspect, wherein said sulfur-containing additive is one or more dialkyl phosphorodithioic acid metal-salts (as ZDDP), sulfonate detergent, sulfurized phenates purification agent, molybdenum-sulphur compound and ashless dithiocar-bamate (ester).

In aspect the 7th, the present invention relates to the lubricating oil composition of the method or the fourth aspect of second aspect, wherein said lubricating oil composition further comprises its amount to be introduced in described lubricating oil composition in the salicylate purification agent of every kilogram of finished lube at least about 9mmol Whitfield's ointment soap, and preferably have be not more than about 1.1 quality %, more preferably no more than the sulfate ash content of 1.05 quality %.

In eight aspect, the present invention relates to the lubricating oil composition of the method or the 5th aspect of the third aspect, wherein said lubricating oil composition contains significant sulphur content, for example greater than about 0.10 quality %, especially greater than about 0.15 quality %, as greater than about 0.18 quality %, more particularly greater than the sulphur content of about 0.20 quality %.

In aspect the 9th, the present invention relates to the method for copper corrosion performance that a kind of improvement is used for the lubricating oil composition of lubricated oil engine or engine speed change, this method comprises unhydrided (undersaturated) olefin polymer (multipolymer) that adds minor amount in above-mentioned lubricating oil composition.

In aspect the tenth, the present invention relates to the method for the 9th aspect, wherein said lubricating oil composition contains significant sulphur content, for example greater than about 0.10 quality %, especially greater than about 0.15 quality %, as greater than about 0.18 quality %, more particularly greater than the sulphur content of about 0.20 quality %, and the lubrication viscosity oil that comprises main amount; At least a sulfur-containing additive of minor amount; With the not hydrogenated olefins polymkeric substance (multipolymer) of the about 10.0 quality % of about 0.5 quality %-, wherein all mass percents are in the total mass of described lubricating oil composition.

In the tenth one side, the present invention relates to the method for the tenth aspect, wherein said sulfur-containing additive is one or more dialkyl phosphorodithioic acid metal-salts (as ZDDP), sulfonate detergent, sulfurized phenates purification agent, molybdenum-sulphur compound and ashless dithiocar-bamate (ester).

In aspect the 12, the present invention relates to a kind of enriched material that is used to prepare the lubricating oil composition of fourth aspect, it comprises oily carrier, not hydrogenated olefins polymkeric substance (multipolymer) and one or more sulfur-containing additives.

In aspect the 13, the present invention relates to a kind of enriched material that is used to prepare the lubricating oil composition of the 5th aspect, it comprises oily carrier, not hydrogenated olefins polymkeric substance (multipolymer) and one or more salicylate purification agents.

With reference to following detailed description will understand the present invention other and further purpose, advantage and feature.

Detailed Description Of The Invention

Lubricating oil composition of the present invention is used for lubricated oil engine, preferred compressed ignition type (diesel oil) engine, the more preferably crankcase of compression ignition type large diesel engine.Must prepare especially be used for diesel applications, particularly large diesel engine crankcase lubricating oil composition to satisfy the performance requriements of above-mentioned application.

The lubrication viscosity oil that can be used in the scope of the invention can be selected from natural lubricating oil, ucon oil and composition thereof.This lubricating oil can be from lighting end mineral oil to heavy grease aspect viscosity, for example petrol engine lubricating oil, mineral lubricating oils and heavy-duty diesel oil.Usually, described oil viscosity is measured as about 2 centistokes-Yue 40 centistokes under 100 ℃, especially about 4 centistokes-Yue 20 centistokes.

Natural oil comprises animal oil and vegetables oil (as Viscotrol C, lard); Kerosene and hydrofining, solvent treatment or acid-treated alkane type, cycloalkanes type and blended alkane-cycloalkanes type mineral oil.The lubrication viscosity oil that is derived from coal or shale also serves as the available base oil.

Ucon oil comprises hydrocarbon ils and halo hydrocarbon ils for example polymeric and poly-mutually alkene (as polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly-(1-hexene), poly-(1-octene), poly-(1-decene)); Alkylbenzene (as dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene); Poly benzene (as biphenyl, terphenyl, alkylation poly phenol); And alkylation phenyl ether and alkylated benzenes thioether and derivative, analogue and homologue.Available is to be derived from gas to the synthetic oil of liquid processes from the synthetic hydrocarbon of fischer-tropsch in addition, and its so-called gas is to liquid base oil or " GTL " base oil.

Make the alkylene oxide polymer of its terminal hydroxy group modification and interpretation and derivative thereof constitute another kind of known ucon oil by esterification, etherificate etc.The example is the polyoxyalkylene polymers of the polymerization preparation by oxyethane or propylene oxide, and the alkyl oxide of polyoxyalkylene polymers and aryl ethers (is that 1000 poly-Isopropanediol ether of methyl or molecular weight are the phenyl ether of the polyoxyethylene glycol of 1000-1500 as molecular weight); With and list and polycarboxylate, for example acetic ester of Tetraglycol 99, mixed C ₃-C ₈Fatty acid ester and C ₁₃The oxygen acid diester.

Another kind of suitable ucon oil comprises the ester of dicarboxylic acid (as phthalic acid, succsinic acid, alkyl succinic acid and 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) and multiple alcohol (as butanols, hexanol, dodecanol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol).The specific examples of above-mentioned ester comprises the 2-ethylhexyl diester of the two eicosyl esters 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, linoleic acid dimer and by making the complex ester of 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acids reaction formation.

The ester class that can be used as synthetic oil also comprises by C ₅-C ₁₂Monocarboxylic acid and polyvalent alcohol and polyol ester for example neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol and tripentaerythritol make those.

The for example poly-alkyl of silicon-based oil-, poly-aryl-, poly-alkoxyl group-or poly-aryloxy silicone oil and silicic acid ester oil constitute another kind of available ucon oil; Above-mentioned oil comprises tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four (2-ethylhexyl) ester, silicic acid four (4-methyl-2-ethylhexyl) ester, silicic acid four (to the tertiary butyl-phenyl) ester, six-(4-methyl-2-ethylhexyl) sily oxide, poly-(methyl) siloxanes and poly-(aminomethyl phenyl) siloxanes.Other ucon oils comprise the liquid ester (as the diethyl ester of Tritolyl Phosphate, trioctyl phosphate, decylphosphonic acid) and the polymeric tetrahydrofuran (THF) of phosphorous acids.

Other examples of base oil be gas to liquid (" GTL ") base oil, promptly this base oil can be the oil that is derived from the synthetic hydrocarbon made from Fischer-Tropsch catalyst from the synthesis gas that comprises hydrogen and carbon monoxide of fischer-tropsch.These hydrocarbon need further processing so that can be used as base oil usually.For example, can be by the known method in affiliated field with its hydroisomerization; Hydrocracking and hydroisomerization; Dewaxing; Or hydroisomerization and dewaxing.

Described lubrication viscosity oil can comprise the base oil mixture of I class, II class or III class basestocks or above-mentioned basestocks.Preferably, described lubrication viscosity oil is II class or III class basestocks, or its mixture, or the mixture of I class basestocks and one or more II classes and III class.Preferably, the described lubrication viscosity oil of main amount is II class, III class, IV class or V class basestocks, or its mixture.In a special embodiment, be preferably greater than 50 quality %, be mineral oil as lubrication viscosity oil as described in greater than 60 quality %.Described basestocks or basestocks mixture preferably have at least 65%, more preferably at least 75%, the saturates content as at least 85%.Most preferably, described basestocks or basestocks mixture have the saturates content greater than 90%.Preferably, described oil or oil mixt have be not more than 0.5 quality % (the about 0.5 quality % of for example about 0.001-), as being not more than 0.1 quality % (the about 0.1 quality % of for example about 0.001-), the preferred sulphur content of the about 0.05 quality % of about 0.005-.

Preferably the volatility of described oil that records by Noack volatility test (ASTM D5880) or oil mixt for be less than or equal to 30 quality %, preferably be less than or equal to 25 quality %, be more preferably less than or equal 20 quality %, most preferably be less than or equal to 16 quality %.Preferably, the viscosity index of described oil or oil mixt (VI) be at least 85, preferably at least 100, more preferably at least about 105-140.

The definition of basestocks and base oil and API (API) publication among the present invention " engine oil authorization and identification system (Engine Oil Licensing and Certification System) ", Industry Services Department, the 14th edition, in December, 1996, definition in the appendix 1,1998 year 12 months is identical.Described publication is classified as follows basestocks:

A) I class basestocks comprises less than 90% saturates and/or greater than 0.03% sulphur, and adopts the testing method that illustrates in the Table I to have more than or equal to 80 and less than 120 viscosity index.

B) II class basestocks comprises more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and adopts the testing method that illustrates in the Table I to have more than or equal to 80 and less than 120 viscosity index.

C) III class basestocks comprises more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and adopts the testing method that illustrates in the Table I to have viscosity index more than or equal to 120.

D) IV class basestocks is poly-alpha olefins (PAO).

E) V class basestocks comprises the every other basestocks that is not included in I, II, III or the IV class.

The analytical procedure of Table I-basestocks

Performance	Testing method
		Saturates	ASTM D 2007
Viscosity index	ASTM D 2270
		Sulphur	ASTM D 2622
	ASTM D 4294
			ASTM D 4927
	ASTM D 3120

Can be used for not hydrogenated olefins polymkeric substance (multipolymer) preferably one or more acyclic olefin polymer of monomers or multipolymers in the present invention practice.Generally speaking, the not hydrogenated olefins polymkeric substance (multipolymer) that can be used among the present invention has or on average has an about two key in every polymer chain.

Can or contain ethene and at least a C by polymerization of Alpha-olefin monomer or 'alpha '-olefin monomers mixture in the presence of the catalyst system that comprises at least a metallocene (being cyclopentadienyl-transistion metal compound) and aikyiaiurnirsoxan beta (alumoxane) compound ₃-C ₂₈The mixture of 'alpha '-olefin monomers and make described polymkeric substance (multipolymer).Adopt this method, can provide wherein 95% or the polymkeric substance of more polymer chain with end ethylidene fundamental mode (ethenylidene-type) degree of unsaturation.Can pass through FTIR spectroscopic analysis, titration or C ¹³NMR determines the per-cent of the polymer chain of display end ethidine degree of unsaturation.The interpretation of this back one class can be by formula POLY-C (R ¹)=CH ₂Characterize, wherein R ¹Be C ₁-C ₂₆Alkyl, preferred C ₁-C ₁₈Alkyl, more preferably C ₁-C ₈Alkyl and C most preferably ₁-C ₂Alkyl (as methyl or ethyl), and POLY representation polymer chain wherein.R ¹The chain length of alkyl can change according to selecting to be used for the polymeric monomer.The described polymer chain of minor amount can comprise end-vinyl degree of unsaturation, i.e. POLY-CH=CH ₂, and the described polymkeric substance of a part can comprise inner single degree of unsaturation, for example POLY-CH=CH (R ¹), R wherein ¹As defined above.Can pass through the unsaturated interpretation of known these ends of metallocene chemical preparation, also can be as U.S. patent 5,498,809; 5,663,130; 5,705,577; 5,814,715; 6,022,929 and 6,030, be prepared described in 930.

Another kind of available polymkeric substance (multipolymer) is the polymkeric substance of making by the cationoid polymerisation of iso-butylene, vinylbenzene etc. (multipolymer).The C that comprises the iso-butylene content of butene content by having the about 75wt% of about 35-and the about 60wt% of about 30-from this type of common polymkeric substance (multipolymer) making down of lewis acid catalyst such as aluminum chloride or boron trifluoride (preferred aluminum chloride) ₄Refiner streams polymerization and the polyisobutene that obtains.A kind of monomeric preferred source for preparing poly-n-butene is that petroleum feeding stream is as raffinate II.These chargings are disclosed in this area, for example disclosed in U.S. patent 4,952,739.Polyisobutene is a kind of most preferred polymkeric substance among the present invention because its be easy to by from the cationoid polymerisation of butene stream (as using AlCl ₃Or BF ₃Catalyzer) obtains.Above-mentioned polyisobutene comprises the residual degree of unsaturation in the two keys of every about ethylenic of polymer chain that is positioned on the described chain usually.One is preferred embodiment utilized the polyisobutene of making from pure iso-butylene materials flow or raffinate I materials flow to prepare the reactive isobutene polymer with end vinylidene (vinylidene) alkene.Preferably, these polymkeric substance that are called highly reactive polyisobutenes (HR-PIB) have at least 65%, the end vinylidene content as 70%, more preferably at least 80%, most preferably at least 85%.The preparation of above-mentioned polymkeric substance has for example been described in U.S. patent 4,152,499.HR-PIB is known, can trade(brand)name Glissopal ^TM(from BASF) and Ultravis ^TM(from BP-Amoco) commercially available acquisition HR-PIB.

In another embodiment, described not hydrogenated olefins polymkeric substance (multipolymer) for example polyisobutene have at the most 10%, as the polymer chain that has terminal double bond (or end ethylidene fundamental mode or end vinylidene degree of unsaturation) of 5-10%.Described polymkeric substance is considered to not to be hyperergy, and the example of the commercially available polymkeric substance that gets is to belong to trade(brand)name Napvis ^TM(from BP-Amoco's), and generally by obtaining as polymerization catalyst with aluminum chloride.

Preferably described polymkeric substance (multipolymer) is derived from one or more and has 2-10, as the polymerization of the alkene of 3-8 carbon atom.The particularly preferred alkene of one class is butylene, advantageously iso-butylene.

It is about 2300 to can be used for the preferably about 450-of number-average molecular weight of the not hydrogenated olefins polymkeric substance (multipolymer) among the present invention, and 450-is about 1300 according to appointment, preferably about 450-about 950.Can pass through some known technology determining molecular weights.A kind of proper method that is used for said determination is by gel permeation chromatography (GPC), it adds provides molecular weight distribution information (referring to W.W.Yau, J.J Kirkland and D.D Bly, " Modern Size Exclusion Liquid Chromatography ", JohnWiley and Sons, New York, 1979).In addition, preferably the kinematic viscosity of described not hydrogenated olefins polymkeric substance under 100 ℃ of measuring according to ASTM D445 is at least 9 or 15, as 100 or 150 to 3000, and advantageously 200 to 2500 or 2700mm ²s ^-1In an embodiment of the invention, find that number-average molecular weight is that kinematic viscosity under 450-2300 and 100 ℃ is about 200-2400mm ²s ^-1The polyisobutene polymkeric substance particularly advantageous performance can be provided.Lubricating oil composition of the present invention can comprise the about 10.0 quality % of about 0.2-, the about 5.0 quality % of 0.3-, the about 3.0 quality % of about 0.5-, the preferred not hydrogenated olefins polymkeric substance of the about 2.5 quality % of about 1.0-especially according to appointment.

Dispersion agent (or dispersing additive) is for example ashless (promptly not containing metal), and dispersion agent makes in use because solid and liquid impurity that oxidation produces are in suspended state, thereby prevents greasy filth flocculation and precipitation or be deposited on the metal parts; It comprises have can with the generate longer-chain hydrocarbons for the treatment of the associating polar head of discrete particles to give oil soluble.A noticeable class is the succinimide that hydrocarbon replaces.

Generally speaking, with metallic (thereby being to form ash content) purification agent contrast, do not form ash content during the ashless dispersant burning basically.Here also dispersion agent boronation, metal-free is considered as ashless dispersant." essentially no ash content " means that described dispersion agent can produce the trace ash content in when burning, but should amount can not produce actual to the performance of dispersion agent or remarkable influence.Also can use the dispersing additive composition that contains two or more dispersion agents.

Ashless dispersant comprise have can with the oil-soluble polymers long-chain skeleton for the treatment of the associating functional group of discrete particles.Usually, above-mentioned dispersion agent has amine, amine-alcohol or the acid amides polar structure that is connected on the polymer backbone, often via bridged group.Described ashless dispersant 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 polycarboxylic acid or its acid anhydrides; The carbothioic acid ester of long chain hydrocarbon (salt) derivative; Long chain aliphatic hydrocarbon with direct polyamine structure thereon; And Mannich condensation product by long-chain substituted phenol and formaldehyde and polyalkylene polyamine condensation are formed.Suitable dispersion agent for example comprises the derivative of the carboxylic acid that long chain hydrocarbon groups replaces, wherein this alkyl have tend to less than 15,000, as less than 5,000 number-average molecular weight; The example of said derivative is the derivative of the succsinic acid of high molecular alkyl replacement.The carboxylic acid that above-mentioned alkyl replaces can be for example with nitrogenous compound, advantageously polyalkylene polyamine or amine-alcohol or acid amides or ester are derived.Particularly preferred dispersion agent is the reaction product of polyalkylene amine and alkenyl succinic anhydride.The example that discloses the specification sheets of this dispersion agent of mentioning type at last is a U.S. patent 3,202,678; 3,154,560; 3,172,892; 3,024,195; 3,024,237; 3,219,666; 3,216,936; With BE-A-662 875.

(for example being single succinimide or double amber imide) that described dispersion agent is preferably non-polymeric.Dispersion agent of the present invention is boronation randomly.Can be by common method with described dispersion agent boronation, as usually in U.S. patent 3,087,936,3,254, instruction in 025 and 5,430,105.By handling the nitrogenous dispersion agent of acyl group with the amount of the boron that for the nitrogen compound of every mole of acidylate, is enough to provide about 20 atomic ratios of about 0.1-, thereby easily realize the boronation of dispersion agent with boron compound such as boron oxide, halogenation boron, boric acid class and borate ester.Also can use boronation and the not combination of the dispersion agent of boronation.

Ashless succinimide or derivatives thereof is a preferred dispersing agent, its can by from polybutene and maleic anhydride by thermal reaction method both without chlorine also need not chloride atom the polyisobutylene succinic anhydride for preparing of compound obtain.

Can provide dispersed by the polymkeric substance that can provide viscosity index to improve performance and dispersiveness, these compounds are called as decentralized viscosity index improving additives or multifunctional viscosity index improver.Above-mentioned polymkeric substance is with the difference of conventional viscosity index improver, and it goes back availability energy characteristic such as dispersiveness and/or oxidation-resistance (vide infra described in the viscosity modifier for the more details of multi-functional viscosity modifier) except the viscosity index improved action is provided.If, the decentralized viscosity index improving additives is used for lubricating oil composition of the present invention, preferably also there is dispersing additive.

Usually, one or more dispersion agents and/or decentralized viscosity index improver are used for heavy-duty diesel oil (HDD) engine oil composition, and its consumption provides the about 0.35 quality % of about 0.08 quality %-, the nitrogen content of the about 0.25 quality % of 0.09 quality %-, the preferred about 0.20 quality % of about 0.10 quality %-according to appointment for this lubricating oil composition.In passenger car diesel engine lubricant composition (PCDO), usually the addition of dispersion agent provides the about 0.10 quality % of about 0.04 quality %-, the nitrogen content of the about 0.09 quality % of 0.05 quality %-, the preferred about 0.085 quality % of about 0.065 quality %-according to appointment for this lubricating oil composition.Spark ignition engine with passenger car machine oil (PCMO) in, the dispersion agent addition provides the about 0.12 quality % of about 0.02 quality %-, the nitrogen content of the about 0.08 quality % of 0.03 quality %-, the preferred about 0.05 quality % of about 0.035 quality %-according to appointment for this lubricating oil composition usually.In manual gear box oil (MTF), usually the addition of dispersion agent provides the about 0.08 quality % of about 0.02 quality %-, the nitrogen of the about 0.06 quality % of 0.025 quality %-, the preferred about 0.05 quality % of about 0.03 quality %-according to appointment for this lubricating oil composition.In automatic transmission fluid (ATF), usually the addition of dispersion agent provides the about 0.14 quality % of about 0.02 quality %-, the nitrogen content of the about 0.11 quality % of 0.05 quality %-, the preferred about 0.08 quality % of about 0.06 quality %-according to appointment for this lubricating oil composition.

Purification agent (or detergent additive) is by making trickle solid keep suspended state to reduce the formation of piston deposit such as high temperature lacquer and lacquer deposit in engine; It also can have in the acid and performance.Purification agent comprises the organic acid metal-salt, and it is called as soap or tensio-active agent here.Purification agent has polar head, is the organic acid metal-salt, and has long hydrophobic tail and be used for oil soluble.Therefore, described organic acid has one or more and functional group such as OH or COOH or SO metal reaction usually ₃H, and hydrocarbyl substituent.Purification agent can be peralkaline, in this case this purification agent comprise with respect in and excess metal for the required stoichiometric quantity of organic acid.This excessive aqueous colloidal dispersion form that is, the normally carbonate of metal and/or oxyhydroxide, it has the metal salts of organic acids that is micellar structure.

The organic acid example comprises sulfonic acid, phenols and sulphurated derivatives thereof and the carboxylic-acid that comprises the aromatic carboxylic acid.

Phenols can be unvulcanized or sulfurized.In addition, the term " phenol " that is used for this paper comprises phenol (for example alkyl catechol) that contains a plurality of hydroxyls or the phenol (for example alkyl naphthol) that contains fused aromatic rings and passes through the phenol of chemical reaction modification, for example phenol of the phenol of alkylidene group bridging and Mannich base condensation; And salicyl alcohol glucoside type phenol (making in the reaction under the alkaline condition) by phenol and aldehyde.Usually use described phenol with sulfur form.The details of vulcanization process is that one of ordinary skill in the art are known, for example referring to U.S. patent 4,228,022 and 4,309,293.

As mentioned above, the term " phenol " that is used for this paper comprise by for example with the phenol of the chemical reaction modification of aldehyde and the phenol of Mannich base condensation.The aldehyde that can be used for modification phenol comprises for example formaldehyde, propionic aldehyde and butyraldehyde.Preferred aldehyde is formaldehyde.The aldehyde modification phenol that is suitable for according to the present invention using is for example in U.S. patent 5 259 967 and 6,310, is described in 009.The phenol of the prepared in reaction Mannich base condensation by phenol, aldehyde and amine.The example of the phenol of suitable Mannich base condensation is in U.S. patent 4,708,809 and 4,740, is described in 321.Generally speaking, described phenol can comprise and is different from above-mentioned those substituting group.These substituent examples are methoxyl group and halogen atom.

Usually the aromatic hydrocarbons sulfonation that replaces by aromatic hydrocarbons, the particularly alkyl that alkyl is replaced obtains sulfonic acid, and described aromatic hydrocarbons for example is those or by alkylating aromatic hydrocarbon is obtained those that oil carried out that classification obtains by distillation and/or extraction.Described alkyl aryl sulphonic acid comprises about 22-about 100 or more carbon atom usually.Described sulfonic acid can be replaced by a plurality of alkyl on the aromatics part, and for example it can be a di alkylaryl sulfonic acid.Preferably described sulfonic acid have 350 or bigger, more preferably 400 or bigger, particularly 500 or bigger, as 600 or bigger number-average molecular weight.Can measure number-average molecular weight by ASTM D3712.The sulfonic acid of operable other types comprises alkyl phenol sulfonic according to the present invention.Above-mentioned sulfonic acid can be sulfurized.

Carboxylic acid comprises monocarboxylic acid and di-carboxylic acid.Preferred monocarboxylic acid is to contain 8-30, those of 8-24 carbon atom particularly.(when this specification sheets was pointed out carbonatoms in the carboxylic acid, the carbon atom in the carboxyl was included among this number).Monocarboxylic example is isocaprylic acid, stearic acid, oleic acid, palmitinic acid He docosoic.Need, can use isocaprylic acid with the form of the C8 acid isomer body mixture of trade(brand)name " Cekanoic " sale with Exxon Chemical.Other suitable acid are those and dicarboxylic acid with carbon atom of 2 or the described carboxyl of more a plurality of separations that have on alpha-carbon atom that uncle replaces.In addition, the dicarboxylic acid that has more than 35 carbon atoms, a for example 36-100 carbon atom also is suitable.Unsaturated carboxylic acid can be a sulfurized.

The preferred carboxylic acid of one class is the aromatic carboxylic acid.Described aromatic carboxylic acid's aromatic structure can contain heteroatoms, as nitrogen and oxygen.Preferably, this structure only comprises carbon atom; More preferably this structure contains six or more a plurality of carbon atom; For example benzene is a kind of preferred construction.Described aromatic carboxylic acid can be contained one or more aromatic structures, and as one or more phenyl ring, it can be condensed or connect by alkylidene bridge.

Described carboxylic acid structure can be connected on the described aromatic structure directly or indirectly.Optimization acid's group directly with aromatic structure on carbon atom, link to each other as the carbon atom on the phenyl ring.Described aromatic structure also can contain other functional group, and as hydroxyl or sulfonate group, it can be directly or indirectly links to each other with carbon atom on the aromatic structure.Aromatic carboxylic acid's preferred embodiment is Whitfield's ointment and sulphurated derivatives thereof, as the Whitfield's ointment and the derivative thereof of alkyl replacement.The salicylic method that is used to vulcanize for example alkyl replacement is that one of ordinary skill in the art are known.

Usually carboxylation (for example by the Kolbe-Schmitt method) the preparation Whitfield's ointment by phenates, in this case, Whitfield's ointment is generally to obtain with carboxylation phenol blended form (usually in thinner) not.

The salicylic preferred substituents of oil soluble is an alkyl substituent.In the Whitfield's ointment that alkyl replaces, this alkyl advantageously contains individual, preferred 9-30 of 5-100, particularly 14-20 carbon atom.Exist under the situation of a plurality of alkyl, the mean number of carbon atom preferably is 9 to guarantee enough oil solubles at least in all alkyl.

Described metal detergent can be a neutral or peralkaline, and these terms are as known in the art.The detergent additive composition can comprise one or more detergent additives, and it can be neutral purification agent, overbased detergent or both mixtures.The total basicnumber of purification agent (TBN) is 15-600 aptly.

The purification agent that generally is used to prepare lubricating oil composition also comprises " mixing " purification agent that forms with the blended surfactant system, as phenates/salicylate (being called " phenalates " sometimes), sulfonate/phenates, sulfonate/salicylate, sulfonate/phenates/salicylate, for example in U.S. patent 6,153,565; 6,281,179; 6,429,178; With 6,429, described in 179.

The detergent additive composition can comprise two or more purification agents, for example alkali metal salicylate detergent such as sodium purification agent and alkaline-earth metal purification agent such as calcium purification agent and/or magnesium purification agent.Described detergent additive composition also can comprise ashless detergent, promptly metal-free purification agent, and it is organic acid organic salt form usually.The preferably metallic purification agent of described purification agent, and the 1st family and group II metal be preferably as the metal in the described purification agent, more preferably calcium and magnesium, particularly calcium.

Usually, one or more purification agents are used for heavy-duty diesel oil (HDD) engine oil composition, its consumption provides about 4.0-about 11.5, about 9.5, the preferred TBN of about 7.0-about 8.25 of 6.0-according to appointment for this lubricating oil composition.In passenger car diesel engine lubricant composition (PCDO), usually the addition of purification agent provides about 5.0-about 12.0, about 11.0, the preferred TBN of about 7.0-about 10.5 of 6.0-according to appointment for this lubricating oil composition.Spark ignition engine with passenger car machine oil (PCMO) in, the addition of purification agent provides about 2.5-about 9.9, about 8.0, the preferred TBN of about 4.5-about 7.25 of 4.0-according to appointment for this lubricating oil composition usually.In power transmission fluids (PTF), usually the addition of purification agent provides about 0.0-about 10.0, about 5.0, the preferred TBN of about 1.0-about 2.5 of 0.5-according to appointment for this lubricating oil composition.Be under the situation of mixing purification agent of sulfonate detergent, sulfurized phenates purification agent or Containing Sulfur phenates and/or sulfonate composition at described purification agent, use the above-mentioned purification agent of convention amount can in described lubricating oil composition, introduce nearly 0.04 quality % even reach 0.15 quality %, the sulphur of the about 0.12 quality % of 0.06-according to appointment.

In one embodiment, The present invention be more particularly directed to contain its amount introduce in every kilogram of finished lube at least about 9mmol (the about 50mmol of 12-according to appointment), for example at least about 18mmol (the about 33mmol of 18-according to appointment), especially at least about the salicylate purification agent of 24mmol Whitfield's ointment soap and the lubricating oil composition of the above-mentioned not hydropolymer of the about 2.5 quality % of about 1.0 quality %-.

In another embodiment, the invention particularly relates to low ash content composition, it has less than 1.1 quality %, as less than 1.05 quality %, preferably less than ash content (in sulfated ash or the SASH) content of 0.8 quality %; And the about 0.40 quality % of about 0.10 quality %-, the sulphur content of the about 0.35 quality % of 0.15 quality %-, the preferred about 0.30 quality % sulphur of about 0.20 quality %-according to appointment, said composition contain its amount introduce in every kilogram of finished lube at least about 9mmol, for example at least about 18mmol, preferably at least about the salicylate purification agent and the above-mentioned not hydropolymer of the about 2.5 quality % of about 1.0 quality %-of 24mmol Whitfield's ointment soap.

Anti-wear agent can be reduced friction and overwear vt., and usually based on containing sulphur or phosphorus or the two compound.Dialkyl phosphorodithioic acid metal-salt is often as anti-wear agent and antioxidant.Described metal can be basic metal or alkaline-earth metal or aluminium, lead, tin, molybdenum, manganese, nickel or copper.Modal is that described zinc salt (ZDDP) is used for lubricating oil in the gross weight 0.1-10 of lubricating oil composition, the amount of preferred 0.2-2 quality %.They can prepare according to known technology: at first form dialkyl phosphorodithioic acid (DDPA), usually by one or more alcohol or phenol and P ₂S ₅Reaction, use then in the zn cpds and formed DDPA.For example, can have 1-18 by making, the primary alconol of preferred 2-12 carbon atom and the mixture reaction of secondary alcohol make phosphorodithioic acid.As selection, can prepare multiple phosphorodithioic acid, the alkyl on wherein a kind of phosphorodithioic acid meets sechy-drocarbyl fully and alkyl on other phosphorodithioic acid meets uncle's alkyl fully.For making zinc salt, can use any alkalescence or neutral zn cpds, but the described oxide compound of the most normal use, oxyhydroxide and carbonate.Because use excessive basic zinc compound in neutralization reaction, commercially available additive often contains excessive zinc.

ZDDP provides outstanding abrasion protection with low relatively cost, and can be used as antioxidant.Preferably, the zinc dialkyl dithiophosphate composition that comprises one or more zinc dialkyl dithiophosphates can be used among the present invention, said composition contains the mixture of primary alkyl and secondary alkyl especially, the main molar ratio of wherein secondary alkane fiduciary point is in the amount of alkyl for example 60mol%, advantageously 75mol%, 85mol% at least more particularly at least at least.Preferably, the phosphorodithioic acid Zn composition has secondary alkyl of 90mol% and 10mol% primary alkyl.

When using, contain S antiwear additive and can in described lubricating oil composition, introduce nearly 0.15 quality % even nearly 0.30 quality %, the sulphur of the about 0.25 quality % of 0.16-according to appointment with convention amount.

Antioxidant can improve the oxidation resistance of described composition, and can play a role by combine and make peroxide modified with superoxide, thereby by decompose hydroperoxide or make oxide catalyst be inertia to make them harmless.Antioxidant can be divided into free-radical scavengers (as space hindered phenol, secondary aromatic amine and organic copper salt); Hydrogen peroxide decomposition agent (as organosulfur and organophosphorus additive); And multi-functional material.Described antioxidant (or oxidation retarder) comprises hindered phenol, aromatic amine compound, preferably has a C ₅-C ₁₂The alkylphenol thioester of the alkaline-earth metal of alkyl group side chain and non-metal, ashless alkylidene group bridging phenol, phosphorus sulfuration and sulfurized hydrocarbon, phosphorous acid esters, metal and do not have the thiocarbamate (ester) of metal and derivative, as U.S. patent 4, oil-soluble copper compounds described in 867,890 and molybdate compound.In practice of the present invention, use or do not use some antioxidant may bring some benefit.For example, in one embodiment, the preferred anti-oxidant compositions that comprises hindered phenol that uses with ester group.In another embodiment, the preferred anti-oxidant compositions that comprises secondary aromatic amine and described hindered phenol that uses.Preferably, contain aromatic amine such as diphenylamine and/or hindered phenol compound, the anti-oxidant compositions of 5-two (the alkyl)-4-hydroxy phenyl carboxylicesters (IRGANOX that sells by Ciba Speciality Chemicals for example as 3 ^L135) be useful.

Friction improver comprises the interface additive that reduces frictional coefficient, therefore can improve fuel economy.Example is the ester of polyvalent alcohol such as the monoglyceride of higher fatty acid, for example XU 61518.10; The butanediol ester of the ester of long-chain polycarboxylic acid and dibasic alcohol such as dimerization unsaturated fatty acids; The oxazoline compound; And alkoxylated alkyl group replacement monoamine, and alkyl ether amine, for example the butter aliphatic ether amine of the tallow amine of ethoxylation and ethoxylation.Molybdate compound and ashless dithiocar-bamate (ester) also are the examples of known friction improver.Usually, the consumption of one or more organic friction improvers with the quality of described oil compositions count 0.1-0.5, as 0.2-0.4 quality %.

Can be used for the molybdate compound among the present invention, preferred molybdenum-sulphur compound can be monokaryon or multinuclear.If this compound is a multinuclear, it contains the molybdenum nuclear of being made up of non-metallic atom such as sulphur, oxygen and selenium so, preferably is made up of sulphur basically.

For make that described molybdenum-sulphur compound is oil soluble or oily dispersibility, makes one or more parts combine with molybdenum atom in this compound.The combination of described part comprise as in the situation of gegenion by electrostatic interaction in conjunction with and between covalent attachment and static in conjunction with between in conjunction with intermediate forms.The combination by different way of part in the same compound.For example, a kind of part can covalent attachment and other part can the static combination.

Preferably, described part or every kind of part are the single anion types, and the example of this type of part is phosphorodithioic acid root class, dithiocarbamic acid root class, xanthan acid group class, carboxylate radical class, sulfo-xanthan acid group class, phosphate radical class and alkyl (preferred alkyl) and derivative thereof.Preferably, be under the situation of polynuclear compounds for example at molybdenum-sulphur compound, the ratio of the molybdenum atom number in the described nuclear and the single anion ligand number that can give this compound oil soluble or oily dispersibility is greater than 1: 1, as at least 3: 2.

The oil soluble of described molybdenum-sulphur compound or oily dispersibility can be subjected to being present in the influence of the total number of carbon atoms between all compound parts.The total number of carbon atoms that is present in all alkyl of described compound part is 21 usually at least, as 21-800, and for example at least 25, at least 30 or at least 35.For example, the carbonatoms in each alkyl is 1-100 normally, preferably 1-40 and more preferably 3-20.The example of molybdenum-sulphur compound comprises double-core molybdenum-sulphur compound and three nuclear molybdenum-sulphur compounds.An example of double-core molybdenum-sulphur compound is expressed from the next:

R wherein ₁-R ₄Expression has straight chain, side chain or the aromatic hydrocarbyl of 1-24 carbon atom independently; X ₁-X ₄Represent Sauerstoffatom or sulphur atom independently.These four alkyl R ₁-R ₄Can be same to each other or different to each other.

In a preferred implementation, molybdenum-sulphur compound is three nuclear molybdenum-sulphur compounds of oil soluble or oily dispersibility.In U.S. patent 5,888,945; 5,906,968; 6,010,987; 6,110,878; 6,153,564; 6,232,276; 6,358,894; 6,541,429; 6,569,820; With the example that discloses three nuclear molybdenum-sulphur compounds in the european patent application 02078011, by reference described document is incorporated in this specification sheets into particularly wherein disclosed content respectively about molybdenum compound or additive characteristic.

Preferably, described three nuclear molybdenum-sulphur compounds are by formula Mo ₃S _kE _xL _nA _pQ _zExpression, wherein k is at least 1 integer; E represents to be selected from the non-metallic atom of oxygen and selenium; X can be 0 or integer, and preferred k+x is 4 at least, is more preferably 4-10, as 4-7, and most preferably 4 or 7; L represents to give the part of this molybdenum-sulphur compound oil soluble or oily dispersibility, and preferred L is a single anion ligand; N is the integer of 1-4; A represents to be different from the negatively charged ion of L, if L is an anion ligand; P can be 0 or integer; Q represents the sub-compound of neutral power supply; And z is 0-5 and comprises non-stoichiometric value.

One of ordinary skill in the art can be appreciated that forming described three nuclear molybdenum-sulphur compounds need select suitable part (L) and other negatively charged ion (A), this for example depends on the E atom that exists in the nuclear and the number of sulphur atom, if if total anionic charge of the i.e. E atom that is existed by sulphur atom, L and the A contribution that exists must be-12.If described anionic charge surpasses-12, so described three nuclear molybdenum-sulphur compounds also can have the positively charged ion that is different from molybdenum, for example (alkyl) ammonium, amine or sodium.

The example of Q comprises water, alcohol, amine, ether and phosphine.It is believed that and exist the sub-compound Q of power supply only to exist in order to fill any empty hapto on described three nuclear molybdenum-sulphur compounds.The example of A can have any valency, for example monovalence and divalence, and comprise disulphide negatively charged ion, hydroxide radical, alkoxide anion, acyl ammonia negatively charged ion and thiocyanate ion or derivatives thereof; Preferred A represents the disulphide negatively charged ion.Preferably, L is a single anion ligand, as phosphorodithioic acid root class, dithiocarbamic acid root class, xanthan acid group class, carboxylate radical class, sulfo-xanthan acid group class, phosphate radical class and alkyl (preferred alkyl) and derivative thereof.When n is 2 or when bigger, described part can be identical or different.In one embodiment, be independent of other embodiments, k is 4 or 7, and n is 1 or 2, and L is a single anion ligand, and p is an integer of giving this compound neutral charge according to the anionic charge on the A, and x and z are respectively 0.In another embodiment, be independent of other embodiments, k is 4 or 7, and L is a single anion ligand, n be 4 and p, x and z be respectively 0.Other examples of molybdate compound comprise carboxylic acid molybdenum and molybdenum nitrogen complex compound, and it can be a sulfurized.

With the molybdenum compound of sulfur-bearing as friction improver and/or antioxidant and for example provide with conventional amount used under the situation of the about 250ppm of about 20ppm-, the amount use of the about 125ppm Mo of 50ppm-according to appointment, described compound can be introduced about 0.004 quality % or more or about 0.008 quality % or more, the about 0.090 quality % of 0.004 quality %-, the sulphur of the about 0.025 quality % of 0.008-according to appointment according to appointment in lubricating oil composition.

Boron also may reside in the lubricating oil composition of the present invention.Boron-containing additive can prepare by making the reaction of boron compound and oil soluble or oily dispersibility additive or compound.Boron compound comprises boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boronic acid containing such as substituted boracic acid (boronic acid), boric acid, tetraboric acid and metaboric acid, hydroborate (boronhydrides), boron amide (boron amides) and borated multiple ester.The example of boron-containing additive comprises the boronation dispersion agent; The boronation dispersant; The borate of basic metal or mixed alkali metal or alkaline-earth metal; Boronation overbased metal purification agent; The boronation epoxide; Boric acid ester; The sulfuration boric acid ester; And boric acid acid amides (borate amide).A kind of preferred boron-containing additive is the boronation dispersion agent.

The example of other additives comprises rust-preventive agent, sanitas, pour point depressant, defoamer and viscosity modifier.

Can use the rust-preventive agent that is selected from non-ionic type polyoxyalkylene polyol and ester, polyoxyalkylene phenol and anionic alkylsulphonic acid.

Can use to have copper and plumbous sanitas, desired but it is not that the present invention fills a prescription usually.Described compound is generally thiadiazoles polysulfide, its derivative and the polymkeric substance thereof that contains 5-50 carbon atom.Be typically 1,3, the derivative of 4-thiadiazoles, for example the U.S. patent 2,719, and 125; 2,719,126; With 3,087, those that describe in 932.In U.S. patent 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; With 4,193, other similar substances have been described in 882.Other additives are sulfo-and polythio sulfinyl amines of thiadiazoles, and for example the U.K. patent specification 1,560, those that describe in 830.Benzotriazole derivatives also belongs to examples of such additives.When containing these compounds in the described lubricating oil composition, they preferably exist with the amount that is no more than 0.2 quality % (A.I.).

Can use a spot of breakdown of emulsion component.A kind of preferred breakdown of emulsion component obtains describing in EP 330,522.It obtains by making oxirane and the adducts reaction that is obtained by the reaction of di-epoxide and polyvalent alcohol.The consumption of described emulsion splitter should be no more than 0.1 quality %A.I..0.001-0.05 the processing ratio of quality % (A.I.) suits.

The pour point depressant that is called the lubricating oil improving agent in addition can reduce the minimum temperature that liquid can flow and maybe can topple over.Described additive is known.Typical those additives that improve described fluid low-temperature fluidity are C ₈And C ₁₈Dialkyl group fumarate/vinyl acetate copolymer, polyalkyl methacrylate etc.

The defoamer that can be by comprising the polysiloxane type such as the chemical compound lot of silicone oil or polydimethylsiloxane provide foam control.

Viscosity index improver (or viscosity modifier) can be given lubricating oil high-temp and low temperature operability, and makes it keep shear stable and also show acceptable viscosity or flowability at low temperatures at elevated temperatures.The compound that is suitable for use as viscosity modifier is high molecular weight hydrocarbon polymer normally, as the multipolymer of polyisobutene, ethene and propylene and high alpha-olefin; Polyester is as polymethacrylate; Hydrogenant poly-(vinylbenzene-altogether-divinyl or-isoprene) polymkeric substance with and mapping mode (as star polymer); And poly-(vinylbenzene-be total to-maleic anhydride) polymkeric substance of esterification.The number-average molecular weight of oil soluble viscosity modified polymkeric substance normally at least 15,000-1,000,000, preferred 20,000-600,000, it is by gel permeation chromatography or light scattering method measuring.Edit first version, 1992, Blackie Academic ﹠amp by R.M.Mortier and S.T.Orzulik; Professional, " Chemistry ﹠amp; Technology of Lubricants " content of the 5th chapter incorporates this paper into.Used VM can have single function, maybe can be multi-functional, improves performance and dispersing property as showing viscosity index.Decentralized olefin copolymer and decentralized polymethacrylate are the examples of decentralized viscosity index improving additives.By being connected to, multiple functional structure such as amine, pure and mild acid amides chemistry prepare the decentralized viscosity index improving additives on the polymkeric substance, the number-average molecular weight of wherein said polymkeric substance preferably at least 15,000, as 20,000-600,000, this is by gel permeation chromatography or light scattering method measuring.Used polymkeric substance can be hereinafter with regard to viscosity modifier described those.Thereby, amine molecule can be introduced giving dispersiveness and/or anti-oxidation characteristics, and the phenol molecule can be introduced to improve antioxidant property.Therefore, specific examples is with grafting behind reactive monomer such as the maleic anhydride and uses for example alcohol or amine deutero-ethylene-propylene interpretation then.If the decentralized viscosity modifier is used for the present invention, the nitrogen content of described lubricating oil composition also comprises and comes from that part of of this decentralized viscosity modifier.The example of decentralized viscosity modifier is the Hitec that Afton Corp. makes and sells ^5777.U.S. patent 4,867, and 890 and 5,958,848 have described the example of decentralized viscosity index improver, therefore incorporate it into this paper.Generally speaking, viscosity modifier, whether no matter be multi-functional, its consumption depends on the required viscosity grade of described lubricating oil composition (as SAE 10W-40), for example in the quality consumption of described oil compositions be 0.001-2, preferred 0.01-1.5, as the polymkeric substance of 0.1-1 quality %.

When being used for lubricating oil composition, the typical significant quantity of above-mentioned additive is as follows:

Additive	Quality %a.i. *(wide region)	Quality %a.i. *(preferable range)
			The multi-functional viscosity improver detersive of viscosity improver anticorrisive agent oxidation retarder anti-friction composition dispersant antiwear additive pour-point depressant antirust agent defoamer demulsifier	0.01-6 0.0-5 0.01-5 0.01-5 0.1-20 0.0-5 0.01-6 0.01-6 0.01-5 0.0-0.5 0.001-0.3 0.0-0.5	0.01-4 0.01-1.5 0.01-3 0.01-1.5 0.1-8 0.05-5 0.01-4 0.01-4 0.01-1.5 0.001-0.2 0.001-0.15 0.001-0.2

^*Quality % activeconstituents based on final lubricating oil composition

Multifunctional additive for lubricating oils is formed in it and uses two or more additives of pre-treatment and promote dissolving or the dispersive facilitated method of additive in lubricating oil composition.When preparation contained the lubricating oil composition of broad variety additive (being sometimes referred to as " binder component "), each additive can be introduced separately into.Yet, in many cases, advantageously described additive is introduced as multifunctional additive for lubricating oils (the so-called additive " bag " (being also referred to as " adpack ") that contains two or more additives).

In the preparation of described lubricating oil composition, the additive of introducing with the multifunctional additive for lubricating oils form that contains described additive is common way.When adopting multiple additives, although this is dispensable, but may be that ideal prepares one or more multifunctional additive for lubricating oils (being also referred to as additive-package) that contain described additive, thus, the some additives except that viscosity modifier, multi-functional viscosity modifier and pour point depressant can be added to simultaneously in the described lubrication viscosity oil to form lubricating oil composition.Can promote described multifunctional additive for lubricating oils to be dissolved in the lubricating oil by thinner or solvent and by the mixing of following mild heat, but this be dispensable.Usually the described multifunctional additive for lubricating oils of preparation to be comprising the described additive of appropriate amount, thereby is provided at concentration required in the end formulation when the lubrication viscosity oil merging of this multifunctional additive for lubricating oils and predetermined amount.Need, add viscosity modifier or multi-functional viscosity modifier and pour point depressant then respectively to form lubricating oil composition.

Multifunctional additive for lubricating oils can comprise in activeconstituents 1-90, as 10-80, preferred 20-80, more preferably 40-70 quality % as described in additive, all the other are oily carrier or diluted fluid (for example lubrication viscosity oil).Described final lubricating oil composition can contain the described multifunctional additive for lubricating oils of 5-40 quality % usually.

The amount of additive in described final lubricating oil composition depends on the type of described oil compositions usually, for example, the heavy duty diesel engine lubricating oil composition in the quality of described oil compositions preferably have 7-25, more preferably 8-23, as the additive (comprising any diluted fluid) of 8-20 quality %.The passenger car engine oil composition is gasoline or the diesel motor oil compositions additive that tends to have low amount for example, for example in the quality 2-16 of described oil compositions, as 3 or 4 to 14, preferred 5-12, the additive of 6-10 quality % especially.Above-mentioned consumption does not comprise not hydrogenated olefins polymkeric substance, viscosity modifier and pour point depressant.

Generally speaking, the viscosity of described multifunctional additive for lubricating oils is higher than the viscosity of described lubricating oil composition.The kinematic viscosity of common described multifunctional additive for lubricating oils under 100 ℃ is at least 50, as 100-200, preferred 120-180mm ²s ^-1(or cSt).

Therefore, the method for preparing lubricating oil composition of the present invention can comprise and lubrication viscosity oil and one or more additives or the multifunctional additive for lubricating oils that contains two or more additives mixed and sneaks into other binder components such as viscosity modifier and non-essential multi-functional viscosity modifier and pour point depressant then.

Also can by with lubrication viscosity oil, contain the multifunctional additive for lubricating oils of two or more binder components, hydrogenated olefins polymkeric substance and viscosity modifier and non-essential multi-functional viscosity modifier and pour point depressant do not mix, thereby prepare lubricating oil composition of the present invention.

Preferred lubricating oil composition of the present invention is the multi-grade oil composition with viscosity grade SAE 10W-X, SAE 5W-X and SAE 0W-X, and wherein X represents 20,30 and 40; The characteristic of different grades can find in SAE J300 categorizing system.

The lubricating oil composition of preparing fully of the present invention preferably has the about 1.0 quality % of about 0.15 quality %-, the sulphur content of the about 0.35 quality % of 0.20 quality %-according to appointment.Preferably, the described Noack volatility of preparing lubricating oil composition (lubrication viscosity oil adds all additives) fully be not more than 13, as being not more than 12, preferably being not more than 10.Of the present invention prepare fully lubricating oil composition in the total mass of described lubricating oil composition preferably have less than about 1500ppm, for example about 500-1500ppm, preferably less than 1250ppm, for example the about 1250ppm of about 500-, be more preferably less than about 1200ppm, the about 1200ppm of about 500ppm-even be more preferably less than about 850ppm, the phosphorus content of about 500-850ppm for example for example.

The lubricating oil composition of preparing fully of the present invention preferably has about 1.9 quality % or littler, preferred about 1.1 quality % or littler, for example about 1.05 quality % or littler sulfated ash (SASH) content.

Measure the content of p and s according to ASTM D5185 method; " TBN " is the total basicnumber of measuring by ASTMD2896; Measure nitrogen content according to method ASTM D4629; And according to method ASTM D874 mensuration sulfated ash.

Be used at lubricating oil composition of the present invention under the situation of HDD, this lubricating oil composition preferably satisfy at least ACEA E2-96#5, more preferably at least ACEA E7-04 and/or API CI-4, as ACEA E4-99#3 at least, the performance requriements of ACEA E6-04 and/or API CJ-4 regulation at least especially.Be used at lubricating oil composition of the present invention under the situation of PCDO, described lubricating oil composition preferably satisfy at least ACEA B2-98#2, more preferably at least ACEA B3-04, as ACEAB4-04/ACEA C3-04 at least, the performance requriements of ACEA B5-04/ACEA C3-04/ACEA C2-04 regulation at least especially.Be used at lubricating oil composition of the present invention under the situation of PCMO, described lubricating oil composition preferably satisfies at least ACEA A2-96#3/API SJ, more preferably ACEAA3-04/ACEA C3-04, for example API SL/ILSAC GF-3, the performance requriements of ACEAA5-04/ACEA C2-04/ACEA C3-04/API SM/ILSAC GF-4 regulation at least especially at least at least.

After will be appreciated that at two or more additives, comprising that arbitrarily two or more purification agents are blended in the described oil compositions, between them, may interact.Described interaction may take place in mixing process or take place under any condition subsequent that said composition stands, and is included in the use under the Working environment of said composition.When joining other supplementary additive in the present composition or adding fashionablely with oil ingredient, also may interact.Described interaction can comprise the interaction of the chemical structure that changes described additive.Thereby composition of the present invention comprises wherein and for example between any described additive interactional composition has taken place, and wherein interactional composition for example do not take place between the component in being blended into described oil.

Described lubricating oil composition can be used for lubricated mechanical engine parts, especially oil engine, as compression ignition type (diesel oil) engine or spark-ignited (gasoline) engine or manual or automatic transmission box unit, this realizes by described lubricating oil being joined the described engine/gearbox of its neutralization operation.

Used term " alkyl " refers to that the group of being paid close attention to mainly is made up of hydrogen atom and carbon atom and is bonded to the rest part of described molecule by carbon atom in this specification sheets, but the ratio of not getting rid of with the main hydrocarbon character that is not enough to damage this group exists other atoms or group.Terminology used here " comprises " existence that is used to illustrate described feature, integer, step, component or group, but does not get rid of the existence of one or more other features, integer, step, component or group or additional.When this paper uses term " to comprise ", term " basically by ... form " ex hoc genus anne saying be preferred embodiment a kind of, and term " by ... form " ex hoc genus anne saying be term " basically by ... form " a kind of preferred implementation.Terminology used here " oil soluble " or " oily dispersibility " be not meant additive can be solvable with all proportions in described oil, dissolving, misciblely maybe can be suspended in the described oil.Yet, its mean really described additive in oil for example solvable or stable dispersion to the degree that is enough to its predictive role of performance in the environment for use of described oil compositions.In addition, additional as previously discussed those of other additives of introducing may influence the solvability or the dispersiveness of described additive." main amount " refers to the 50 quality % that surpass described composition, as greater than 70 quality %, and preferred 75-97 quality %, particularly 80 to 95 or 90 quality %." minor amount " refers to 50 quality % less than described composition, as less than 30 quality %, and 3-25 quality % for example, preferred 5 or 10 to 20 quality %.Unless otherwise mentioned, all per-cents of listing are to be Based Quality % with the activeconstituents, promptly do not consider carrier or thinning oil.Abbreviation SAE represents Society of AutomotiveEngineers, and one by the tissue of viscosity grade to grading of lubricating oils.

Embodiment

Now only to specifically describe the present invention as follows for demonstration:

Embodiment 1

By mixed lubrication viscosity base oil; Purification agent/inhibitor (DI) bag that comprises salicylate purification agent, dispersion agent, ZDDP and defoamer; Viscosity modifier (VM) and the lubricating oil improving agent (LOFI) that flows, the lubricating oil composition of the representative heavy duty diesel engine of ACEA E4-99#3 specified requirement with conventional 10W40 crankcase oil satisfied in preparation.Resultant composition has the nitrogen content of every kilogram of finished lube 0.1 quality %; 0.3 the phosphorus of the sulfated ash of the sulphur content of quality %, 1.9 quality % (SASH) content, 1250ppm and 43mmol Whitfield's ointment soap.

Based on 4 kinds of lubricating oil compositions of above-mentioned formulation.Sample 1 as a comparative example, does not contain the 450M of interpolation _nPolybutene (PIB).Represent sample 2,3 of the present invention and 4 to contain the 450M of 0.5,1 and 2 quality % respectively _nPIB.Test the consistency of these 4 kinds of samples and paracril then, adopt Mercedes Benz (MB) or the used test bed testing of Daimler Chrysler (DC), testing method VDA6753014 especially; Maschinenfabrik Augsburg ﹠amp; The used test bed testing of N ü rnberg (MAN), testing method DIN 53521 (nitrile sealing material) especially; And the used test bed testing of Motoren und Turbinen Union (MTU), testing method DIN 53521 (nitrile sealing material) especially.The results are shown in down in the Table II.Under repeated test situation repeatedly, be averaged the result.

Table II

Test bed testing	Performance	Ultimate value	Sample 1 (0)	Sample 2 (0.5)	Sample 3 (1)	Sample 4 (2)
							MBSEAL NBR	EAB *	-35％max	-45	-44	-37
	TS **	-20％max	-20	-19	-11
								V ***	0-10％	0	0	0
	H ****	-8 to+2pts.	0	0	0
								Test #	---	＞5	2	3	0
MANSEAL NBR	EAB	-30％max	-43	---	-36	-32
								TS	-20％max	-23	---	-12	-12
	V	0 to+10%	2	--	2	2
								H	-10pts.max	-1	---	-1	-1
	Test #	---	＞5	0	3	2
							MTUSEAL NBR	EAB	-35％max	-40	-34	-36	-33
	TS	-20％max	-23	-11	-16	-17
								V	0 to 10%	2	2	2	2
	H	0 to-10pts.	-1	-1	-1	-2
								Test #	---	＞5	2	2	2

^*Elongation at break; ^*Tensile strength; ^{* *}Volume; ^{* * *}Hardness

As directed, in each test bed testing, the improvement performance be enough to provide by test is provided in the interpolation of PIB, and particularly with regard to EAB and TS, and basic components is defective.

Embodiment 2

By mixed lubrication viscosity base oil; Purification agent/inhibitor (DI) bag that comprises salicylate purification agent, dispersion agent, ZDDP and defoamer; Viscosity modifier and LOFI (lubricating oil flow improving agent), the lubricating oil composition of the heavy duty diesel engine of ACEA E6-04 specified requirement with low SAPS (sulfated ash, phosphorus, sulphur) the 10W40 crankcase oil of representative satisfied in preparation.Resulting composition has the nitrogen content in every kilogram of finished lube 0.16 quality %; 0.25 the phosphorus of the sulfated ash of the sulphur content of quality %, 0.25 quality % (SASH) content, 800ppm and 24mmol Whitfield's ointment soap.

Based on 4 kinds of lubricating oil compositions of above-mentioned formulation.Sample 5 as a comparative example, does not contain additional 450M _nPolybutene (PIB).Represent sample 2,3 of the present invention and 4 to contain the 950M of 2.1,2.5 and 3.0 quality % respectively _nPIB.With the test bed testing described in the embodiment 1 consistency of these 4 kinds of samples and paracril is tested then.The results are shown in down in the Table III.

Table III

Test bed testing	Performance	Ultimate value	Sample 5 (0)	Sample 6 (2.1)	Sample 7 (2.5)	Sample 8 (3.0)
							MBSEAL NBR	EAB *	-35％max	-57	-31	-33	-27
	TS **	-20％max	-35	-11	-12	-11
								V ***	0 to+10%	2	2	2	2
	H ****	-8 to+2pts.	1	-2	1	-1
							MANSEAL NBR	EAB	-30％max	-55	-28	---	-27
	TS	-20％max	-48	-10	---	-10
								V	0 to+10%	5	5	---	5
	H	-10pts.max	-2	-3	---	-4

As directed, effect of the present invention is particularly evident in the low SAPS HDD lubricating oil with the preparation of salicylate purification agent.Again, in each test bed testing, the improvement performance be enough to provide by test is provided in the interpolation of PIB, and particularly with regard to EAB and TS, and basic components is defective.

Embodiment 3

By mixed lubrication viscosity base oil; Purification agent/inhibitor (DI) bag that comprises sulfonate and sulfuration phenates purification agent, dispersion agent, ZDDP, molybdenum-sulphur compound and defoamer; Dispersion agent/viscosity modifier and LOFI (lubricating oil flow improving agent), the heavy duty diesel engine that the PC-10 specified requirement is satisfied in preparation is with the lubricating oil composition of representing the 15W40 crankcase oil.Resulting composition has the phosphorus of SASH content, 50ppm molybdenum and 1000ppm of nitrogen content, the 0.94 quality % of sulphur content, the 0.14 quality % of 0.31 quality %.

Based on 4 kinds of lubricating oil compositions of above-mentioned formulation.Sample 9 as a comparative example, does not contain the 950M of interpolation _nPolybutene (PIB).Represent sample 10,11 of the present invention and 12 to contain the 950M of 0.5,1.0 and 2.0 quality % respectively _nPIB.With the test bed testing described in the embodiment 1 consistency of these 4 kinds of samples and paracril is tested then.The results are shown in down in the Table IV.

Table IV

Test bed testing	Performance	Ultimate value	Sample 9 (0)	Sample 10 (0.5)	Sample 11 (1.0)	Sample 12 (2.0)
							MBSEAL NBR	EAB *	-35％max	-37	-29	-23	-21
	TS **	-20％max	-18	-13	-9	-7
								V ***	0 to+10%	2.1	2	2	2
	H ****	-8 to+2pts.	-2	-2	-2	-2

As directed, effect of the present invention also is tangible in the lubricating oil with phenates and sulfonate detergent preparation.The improvement performance that is enough to provide by test is provided for the interpolation of PIB, and particularly with regard to EAB, and basic components is defective.

Embodiment 4

Based on 5 kinds of lubricating oil compositions of the formulation that provides among the embodiment 3.Sample 13 as a comparative example, does not contain the 950M of interpolation _nPolybutene (PIB).Represent sample 14,15,16 of the present invention and 17 to contain the 950M of 2,3,4 and 5 quality % respectively _nPIB.With the high temperature corrosion test bed testing described in the ASTM D6594 corrodibility of these 5 kinds of samples, particularly copper corrosion performance are tested then.The results are shown in down in the Table V.

Table V

Performance	Ultimate value	Sample 13	Sample 14 (2)	Sample 15 (3)	Sample 16 (4)	Sample 17 (5)
							Cu	20max	111	24	13	12	9
Pb	120max	44	36	37	38	42
							Sn	50max	0	2	2	2	2
The Cu bar	3	4B	1A	1A	1A	1A

As directed, in the lubricating oil composition that contains remarkable sulphur content, add PIB and further improved copper corrosion performance, and make, and the prescription that does not contain PIB is not by this test by HTCBT.

The disclosure of all patents as herein described, paper and other data is all incorporated in this specification sheets by reference.Herein and the narration of " composition comprises multiple described component, formed or be made up of it basically by multiple described component " that exist in the claims, should be understood to also comprise by described various ingredients being mixed the composition of making.Principle of the present invention, preferred implementation and operator scheme have been described in above specification sheets.Yet, can not think that the invention that the applicant submits to is only limited to disclosed embodiment, illustrative rather than restrictive because disclosed embodiment should be considered as.One of ordinary skill in the art can change in the case of without departing from the spirit of the present invention.

Claims (13)

1. an improvement contains the method for the consistency of copper corrosion performance in the lubricating oil composition of one or more additives of the lubrication viscosity oil of main amount and minor amount and/or itself and nitrile sealing material, described composition has the total mass at least 0.1 quality % in lubricating oil composition, 0.15-0.40 quality % especially, the sulphur content of 0.20-0.35 quality % more particularly, this method comprise significant quantity, for example in the total mass 0.2-10.0 quality % of described lubricating oil composition, preferred 0.5-5 quality %, the more preferably at least a not hydropolymer of 1.0-2.5 quality %, preferred olefin polymers or multipolymer, as polybutene and/or polyisobutene add and/or introduce as described in the lubricating oil composition.

2. the process of claim 1 wherein that described lubrication viscosity oil has the sulphur content of the total mass 0.001-0.10 quality % in lubrication viscosity oil, preferred 0.005-0.05 quality % sulphur and comprises the non-essential at least a described additive that the sulfocompound of at least 0.005 quality % sulphur is provided in the quality of described composition.

3. claim 1 or 2 method, at least a additive that wherein comprises sulfocompound is selected from dialkyl phosphorodithioic acid metal-salt, sulfonate detergent, sulfuration phenates purification agent, the molybdenum compound of sulfur-bearing, ashless dithiocar-bamate (ester) and combination thereof.

4. each method among the claim 1-3, wherein said lubricating oil composition has following feature one of at least, preferably have both: in total mass (a) the 0.5-1.9 quality % of described composition, as 0.8-1.1 quality %, preferred 0.90-1.05 quality %, for example be not more than 1.1 quality %, preferably be not more than sulfated ash (SASH) content of 1.05 quality %, and/or (b) less than 1500ppm, preferably less than 1250ppm, as 500-1250ppm, be more preferably less than 1200ppm, as 500-1200ppm, even be more preferably less than 850ppm, phosphorus content as 500-850ppm.

5. each method among the claim 1-4, wherein said lubricating oil composition comprises the salicylate purification agent, its amount for said composition provide in every kilogram of described composition at least 9mmol, as 18mmol at least, preferred 24mmol at least, as the Whitfield's ointment soap of 12-50mmol, preferred 18-33mmol.

6. each method among the claim 1-5, wherein said lubricating oil composition comprises nitrogenous dispersion agent and/or decentralized viscosity modifier, its amount for described composition 0.08-0.35 quality % is provided, as the nitrogen of 0.09-0.25 quality %, preferred 0.10-0.20 quality %.

7. each method among the claim 1-6, wherein said lubricating oil composition have in the total mass of described composition less than 1500ppm, as 500-1500ppm, preferably less than 1250ppm, as 500-1250ppm, be more preferably less than 1200ppm, as 500-1200ppm in addition be more preferably less than 850ppm, as the phosphorus content of 500-850ppm.

8. each method among the claim 1-7, wherein said lubrication viscosity oil comprise total mass at least 50 quality % in described composition, as at least 60 quality %, the mineral oil of at least 70 quality % especially.

9. each method among the claim 1-8, wherein said composition is the crankcase lubricating oil composition that power transmission fluids or oil engine such as heavy-duty diesel oil (HDD) engine are used, and randomly, described composition satisfy ACEA E2-96#5, as among ACEA E7-04 and the API CI-4 one of at least, preferred ACEA E4-99#3, more preferably one of at least performance requriements among ACEA E6-04 and the API CJ-4.

10. each method among the claim 1-9, wherein said not hydropolymer (multipolymer) have 450-2300, as the number-average molecular weight of 450-1300, for example 450-950.

11. one kind contains at least 0.15 quality %, as 0.15-0.49 quality %, the lubricating oil composition of preferred 0.20-0.35 quality % sulphur content, it comprises the lubrication viscosity oil of main amount, minor amount comprise at least a additive with additive of sulphur content, with minor amount, as at least 0.2 quality %, as 0.5-5.0 quality %, not hydrogenated olefins polymkeric substance such as polybutene or the polyisobutene of preferred 1.0-2.5 quality %, and in randomly following one or more: (i) be selected from dialkyl phosphorodithioic acid metal-salt, sulfonate detergent, sulfuration phenates purification agent, the molybdenum compound of sulfur-bearing, the sulfur-containing additive of ashless dithiocar-bamate (ester) is (ii) in sulfated ash (SASH) content of the quality 0.5-1.9 quality % of described composition; (iii) in the quality of described composition less than 1500ppm, as the phosphorus content of 500-1250ppm, the nitrogenous dispersion agent and/or the decentralized viscosity modifier of 0.08-0.35 quality % nitrogen (iv) is provided for described composition; (v) provide in every kilogram of composition at least 9mmol, as the salicylate purification agent of 12-50mmol Whitfield's ointment soap.

12. comprise the multifunctional additive for lubricating oils of the lubricating oil additive of main amount, it obtains the lubricating oil composition of claim 11 when mixing with lubrication viscosity oil.

13. the purposes of hydrogenated olefins polymkeric substance, preferred polybutene or polyisobutene not, it is used to improve the copper corrosion performance of sulfur-bearing lubricating oil composition and/or improves sulfur-bearing and/or the lubricating oil composition of Whitfield's ointment soap and the consistency between paracril, particularly paracril engine and the wheel box sealing material.