CN106459815A - Method for preventing or reducing low speed pre-ignition - Google Patents

Abstract

A method for preventing or reducing low speed pre-ignition in an engine lubricated with a lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition including a lubricating oil base stock as a major component, and at least one zinc-containing compound or at least one antiwear agent, as a minor component. The at least one antiwear agent includes at least one zinc dialkyl dithiophosphate compound derived from a secondary alcohol. A lubricating engine oil having a composition including a lubricating oil base stock as a major component, and at least one zinc-containing compound or at least one antiwear agent, as a minor component. The lubricating oils of this disclosure are particularly advantageous as passenger vehicle engine oil products.

Description

The method preventing or reducing low speed early combustion

Technical field

It relates to prevent as lubricating oil by using formulated oil in the electromotor of used-oil lubrication or to subtract The method that few low speed early fires (LSPI), described formulated oil is had at least one being present in described formulated oil with specified quantitative and contains zinc Compound or at least one antiwear additive, preferably at least a kind of at least partly zinc dialkyl dithiophosphate chemical combination derived from secondary alcohol Thing.The lubricating oil of the disclosure can be used as passenger car engine machine oil (PVEO) product.

Background technology

Morning combustion in flame propagation (or " spark ignition ") electromotor describes in cylinder before plug ignition The event that air/fuel mixture is lighted.Early combustion is to be caused by the incendiary source beyond spark, described incendiary source such as combustor In focus, run in the application be heated to by engine combustion event before in overheated spark plug or combustor red-hot Carbon distribution.

Many railway car manufacture business have been observed that intermittent early combustion in the turbo supercharging gasoline engine that they produce, special Not under low speed and middle high load capacity.Under the load that these raise, early combustion often results in serious combustion knock, and it can damage sends out Motivation.The reason early combustion, does not understand completely, and may be in fact owing to multiple phenomenons, indoor boiling hot sinking of for example burning Long-pending thing, the level of the lubricant vapors entering from Pcv system raise, oil seepage crosses turbocharger compressor sealing or oil And/or fuel droplet lights during compression stroke automatically.

Early combustion can rapidly increase chamber temperature and lead to the roughness of engine or performance to be lost.Eliminate the tradition of early combustion Method includes, and for example, appropriate spark plug selects, appropriate fuel/air mixture is adjusted and periodically cleans combustor.Machine It is known that part solution for example cools down waste gas recirculation (EGR), but these may be carried out high cost and there are packaging Problems.

It is that impact is sent out when brake mean-effective pressure (BMEP) is high low with engine speed (RPM) that low speed early fires (LSPI) The abnormal combustion type of motivation operating.Miniaturization, slow-revving turbocharged engine is most susceptible in these electromotors Under state, the impact of operating, is therefore affected be more susceptible to LSPI.Because auto industry moving towards always further miniaturization, The slow-speed of revolution and improve turbocharging to improve auto fuel economy and to reduce CO2 emission, so hidden on LSPI Suffer from sustainable growth.

Developing further of slow-revving turbo supercharging gasoline engine is just hindered by LSPI.Solve this problem or Even if mitigating its generation will be the obstacle of original equipment manufacturer's (OEM) clearance technique and efficiency improvement.Lubricant formulations Solution will enable product and segments in terms of LSPI.

Although early combustion problem and can pass through optimization internal engine parts and by using new component technology for example Electronic Control is solving, but it is desirable for changing for the lubricant oil composite lubricating such electromotor.For example, including exploitation New oil formula that is particularly useful and will preventing or minimize early combustion problem when for explosive motor in burn engine, To be desirable.Wish that described lubricant oil composite can be used for lubricating gasoline-fueled spark ignition engine.

Despite the progress of lubricant formula technology, but for effectively preventing or reduce low speed early combustion, in particular for little Type, the engine lubricant oil of slow-revving turbocharged engine, there are still demand.

Content of the invention

Disclosure part is related to new oil formula, and it is particularly useful in explosive motor, and sends out when being used for internal combustion To prevent or minimize early combustion problem during motivation.The lubricant oil composite of the disclosure can be used for lubricating gasoline-fueled spark Igniter motor.The lubricant formulations chemistry of the disclosure can be used for already designing or the electromotor commercially sold and will Prevent or control the ill-effect of LSPI in the engine technology coming.The lubricant formulations chemical scavenging of disclosure OEM technology With the obstacle in efficiency improvement, and the slow-speed of revolution turbo supercharging gasoline engine being hindered by LSPI at present is sent out further Exhibition.Product is enable in terms of LSPI by the lubricant formulations solution for preventing or reducing LSPI that the disclosure provides Subdivision.

The disclosure also relates in part to prevent as lubricating oil by using formulated oil in the electromotor that used-oil lubricates The method stopping or reducing low speed early combustion.Described formulated oil has and comprises lube oil base stocks as key component and at least one Plant zinc compound or at least one antiwear additive as the composition of accessory constituent.Described at least one antiwear additive comprises at least one At least partly zinc dialkyl dithiophosphate compound derived from secondary alcohol.Electromotor with 2000 revs/min (RPM) operating and On the basis of the brake mean-effective pressure (BMEP) of 18 bars, (LSPI) is early fired based on standardization low speed and counts/25,000 Motivation circulates, and reaches in described electromotor and the electromotor using the lubricating oil not comprising at least one zinc compound or antiwear additive To low speed early fire performance and compare, show low speed early combustion and reduce greater than about 20%.

The disclosure also relates in part in the electromotor that used-oil lubricates by using formulated oil conduct as above The method to prevent or reduce low speed early combustion for the lubricating oil, wherein said accessory constituent also comprises at least one boron-containing compound.Institute State boron-containing compound and comprise at least one borated dispersants, and/or the mixture of boron-containing compound and non-borated dispersants.

The disclosure also relates in part in the electromotor that used-oil lubricates by using formulated oil conduct as above The method to prevent or reduce low speed early combustion for the lubricating oil, wherein said accessory constituent also comprises at least one boron-containing compound and extremely A kind of few detersive.Described boron-containing compound comprises at least one borated dispersants, or boron-containing compound and non-boration divide The mixture of powder.Described detersive comprises the alkali salt of at least one organic acid, and described at least one organic acid Alkali salt comprise the magnesium salt of at least one organic acid.

The disclosure also relates in part to engine lubricating oil, and it has and comprises lube oil base stocks as key component and extremely Lack a kind of zinc compound or at least one antiwear additive as the composition of accessory constituent.Described at least one antiwear additive comprises at least A kind of at least partly zinc dialkyl dithiophosphate compound derived from secondary alcohol.Transported with 2000 revs/min (RPM) in electromotor On the basis of turning the brake mean-effective pressure (BMEP) with 18 bars, (LSPI) is early fired based on standardization low speed and counts/25,000 Individual cycle of engine, described electromotor and the electromotor using the lubricating oil not comprising at least one zinc compound or antiwear additive In the low speed that reaches early fire performance and compare, show low speed early combustion and reduce greater than about 20%.

The disclosure also relates in part to engine lubricating oil as above, and wherein said accessory constituent also comprises at least one Boron-containing compound.Described boron-containing compound comprises at least one borated dispersants, and/or boron-containing compound and non-boration divide The mixture of powder.

The disclosure also relates in part to engine lubricating oil as above, and wherein said accessory constituent also comprises at least one Boron-containing compound and at least one detersive.Described boron-containing compound comprises at least one borated dispersants, or boracic chemical combination Thing and the mixture of non-borated dispersants.Described detersive comprises the alkali salt of at least one organic acid, and described The alkali salt of at least one organic acid comprises the magnesium salt of at least one organic acid.

It has been surprisingly found that according to the disclosure, by using as described below in the electromotor of used-oil lubrication Formulated oil, as lubricating oil, enables to prevent or reduces LSPI, and described formulated oil comprises at least one zinc compound or at least A kind of antiwear additive, preferably at least a kind of at least partly zinc dialkyl dithiophosphate compound derived from secondary alcohol, it is described Existed with specific amount (for example, the gross weight based on described lubricating oil, from about 0.1 weight % to about 5.0 weight %) in lubricating oil. Particularly, for the lubricant formula containing described at least one zinc compound or at least one antiwear additive, carefully Other places finds, in electromotor with the basis of 2000 revs/min (RPM) operating and the brake mean-effective pressure (BMEP) of 18 bars On, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, described electromotor is contained with the lubricating oil using The low speed reaching in the electromotor of the accessory constituent different from described at least one zinc compound or antiwear additive is had early to fire performance Compare, show low speed early combustion and reduce greater than about 20%.In addition, it has been surprisingly found that according to the disclosure, by using tool There is the formulated oil of specific oil base stock (for example, natural gas liquefaction (gas-to-liquids) oil base stock or ester base oil material) As lubricating oil, enable to reduce LSPI in the electromotor with described oil lubrication.

The disclosure further relates in the electromotor that used-oil lubricates by using electromotor formulated oil as lubricating oil, prevents The method stopping or reducing low speed early combustion, the composition that described electromotor formulated oil has comprises the lube base of 70 to 85 weight % Oil plant and its load capacity described electromotor formulated oil is contributed 400ppm to about 2000ppm phosphorus at least one zinc compound or At least one antiwear additive；Wherein said at least one antiwear additive comprises at least one at least partly dialkyl group two derived from secondary alcohol D2EHDTPA zinc compound；Wherein in electromotor with the brake mean-effective pressure of 2000 revs/min (RPM) operating and 18 bars (BMEP), on the basis of, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, described electromotor with make With not comprising the low speed early combustion property reaching in the electromotor of the lubricating oil of at least one zinc compound or at least one antiwear additive Can compare, show low speed early combustion and reduce greater than about 50%.

The other objects and advantages of the disclosure will become apparent in detailed description from behind.

Brief description

The all concentration summarized in figure are all based on " delivery status " and quote.

Fig. 1 shows the total weight percent based on described formula for various lubricant formulas formula by weight percentage Describe in detail in detail, and the result of the test of various lubricant formula, such as embodiment A.

Fig. 2 shows the total weight percent based on described formula for various lubricant formulas formula by weight percentage Describe in detail in detail, such as embodiment B.

Fig. 3 shows the result of the test of the various lubricant formulas illustrating in Fig. 2, such as describes in detail in embodiment B.

Fig. 4 shows the total weight percent based on described formula for various lubricant formulas formula by weight percentage Describe in detail in detail, such as embodiment C.

Fig. 5 shows the result of the test of the various lubricant formulas illustrating in Fig. 4, such as describes in detail in embodiment C.

Fig. 6 shows the Formulation Implementation mode of the disclosure total weight percent based on described formula by weight percentage Formula detailed, such as describe in detail in embodiment D.

Fig. 7 shows the expected result of the test of the various lubricant formulas of Fig. 6, such as describes in detail in embodiment D.

Fig. 8 shows the Formulation Implementation mode of the disclosure total weight percent based on described formula by weight percentage Formula detailed, such as describe in detail in embodiment E.

Fig. 9 shows the expected result of the test of the various lubricant formulas of Fig. 8, such as describes in detail in embodiment E.

Figure 10 shows the Formulation Implementation mode of the disclosure total weight percent based on described formula by weight percentage The formula of meter is detailed, such as describes in detail in embodiment F.

Figure 11 shows the expected result of the test of the various lubricant formulas of Figure 10, such as describes in detail in embodiment F.

Figure 12 shows the engine performance mapping result as described in detail in embodiment A.

Specific embodiment

All numerical value in the detailed description and claims of this paper modify described indicated value by "about" or "approximately", And considering test error and variation, this will be that those of ordinary skill in the art expect to obtain.

It has now been found that in the electromotor of used-oil lubrication, by using formulated oil as lubricating oil, enabling Prevent or reduce LSPI, described formulated oil comprises at least one zinc compound or at least one antiwear additive, preferably at least a kind of At least partly zinc dialkyl dithiophosphate compound derived from secondary alcohol, (for example, it measured with specific in described lubricating oil Based on the gross weight of described lubricating oil, from about 0.1 weight % to about 5.0 weight %) exist.Further, it has been found that used-oil In the electromotor of lubrication, by using there is the formulated oil of specific oil base stock as lubricating oil, enable to reduce LSPI.Institute State formulated oil and preferably have and comprise lube oil base stocks as key component and at least one zinc compound or at least one Antiwear additive is as the composition of accessory constituent.Described at least one antiwear additive comprise at least one at least partly derived from secondary alcohol two Alkyl zinc dithiophosphate compound.The lubricating oil of the disclosure is particularly advantageous as PVEO product.

The lubricating oil of the disclosure is particularly useful in explosive motor, and will prevent when for explosive motor or Littleization early fires problem.The lubricant oil composite of the disclosure can be used for lubricating gasoline-fueled spark ignition engine.

As described herein, the lubricant formulations chemistry of the disclosure can be used for already designing or commercially selling Prevent or control the ill-effect of LSPI in the engine technology in electromotor and future.The lubricant formulations chemistry of the disclosure is clear Except the obstacle in OEM technology and efficiency improvement, and make the slow-speed of revolution turbo supercharging gasoline engine being hindered by LSPI at present Can develop further.Product is enable by the lubricant formulations solution for preventing or reducing LSPI that the disclosure provides Enough subdivisions in terms of LSPI.

Lube oil base stocks

Lubricating base oil in extensive range is as known in the art.It is natural for can be used for the lubricating base oil in the disclosure Oil and both artificial oils, and can be using (the latter is also known as regeneration or reprocessed oils) unpurified, refined or that re-refine Unconventional oil (or its mixture).Unrefined oil is to directly obtain and do not purified from naturally occurring or synthetic source just to use Those oil.Shale oil that these include directly obtaining from retorting operation, the oil directly obtaining from primary distillation and from esterification The ester oil that process directly obtains.Refined oil experienced one or many similar to the oil that unrefined oil is discussed, simply refined oil Individual purification step is to improve at least one lubricating oil property.Many methods of purification familiar to the person skilled in the art.These method bags Include solvent extraction, second distillation, sour extraction, alkaline extraction, filtration and diafiltration.Rerefined oils are obtained by the method similar to refined oil Arrive, but be used in the past as the used oil of raw material.

I, II, III, IV and V class is by American Petroleum Institute (API)（American Petroleum Institute）(API Publication 1509；Www.API.org) the oil base stock big class of development and regulation, to set up to lubricant base oil Guide.I class oil base stock has the viscosity index (VI) between about 80 to 120 and contains greater than about 0.03% sulfur and/or less than about 90% Saturated hydrocarbons.II class oil base stock has the viscosity index (VI) between about 80 to 120 and contains less than or equal to about 0.03% sulfur and be more than Or it is equal to about 90% saturated hydrocarbons.Group III oil plant have greater than about 120 viscosity index (VI) and containing less than or equal to about 0.03% sulfur and Greater than about 90% saturated hydrocarbons.IV class includes polyalphaolefin (PAO).V class oil base stock includes the base oil being not included in I-IV class Material.Following table summarizes this respective property of five classes.

Natural oil includes animal oil, vegetable oil (such as Oleum Ricini and Adeps Sus domestica) and mineral oil.Can be favourable using having The animal and plant oil of thermo oxidative stability.In natural oil, mineral oil is preferred.Mineral oil by their natural origin is Change widely, for example, by they be paraffin, cycloalkanes or blended wax-cycloalkanes.Oil derived from coal or shale It is also available.Natural oil also press different for their production and the method for purification, for example their boiling range and they be straight Evaporating or cracking, hydrorefined or solvent extraction.

II class and/or Group III hydrotreating or the oil base stock being hydrocracked, including artificial oil such as polyalphaolefin, alkyl Aromatic hydrocarbons and synthetic ester, are also known oil base stock oil.

Artificial oil includes hydrocarbon ils.Hydrocarbon ils include for example being polymerized oil such with mutual polyolefin (for example, polybutene, polypropylene, Propylene isobutylene copolymers, ethylene-olefin copolymer and ethylene-alpha-olefin copolymer).Polyalphaolefin (PAO) oil base oil material is Conventional synthetic hydrocarbon oil.For example, it is possible to using derived from C₆、C₈、C₁₀、C₁₂、C₁₄Alkene or the PAO of its mixture.Referring to the U.S. Patent No.4,956,122；4,827,064；With 4,827,073.

PAO is known material and is typically available from supplier such as ExxonMobil on big commercial size Chemical Company, Chevron Phillips Chemical Company, BP and other suppliers, its equal molecule of number Amount generally from about 250 to about 3,000, but PAO can be made into viscosity is up to about 150cSt (100 DEG C).Described PAO leads to Than relatively low hydropolymer or oligomer, described alhpa olefin includes but is not limited to the molecular weight often comprising alhpa olefin, C₂To about C₃₂α Alkene, and C₆To about C₁₆Alhpa olefin such as 1- hexene, 1- octene, 1-decene, 1- laurylene, 1-tetradecylene etc. are preferred.Excellent The polyalphaolefin of choosing is poly- 1- hexene, poly- 1- octene, poly- 1-decene and poly- 1- laurylene, 1- tetra- decene and its mixture, and Polyolefin derived from mixed olefins.However, in C₁₄To C₁₈In the range of higher olefins dimer can be used to provide volatilization Property low acceptable low viscosity oil base stock.Depending on viscosity grade and starting oligomer, described PAO can be mainly described The trimer of starting olefin and the tetramer, with a small amount of higher oligomer, have the range of viscosities of 1.5 to 12cSt.Specifically The PAO fluid of application can include 3.0cSt, 3.4cSt and/or 3.6cSt and combinations thereof.It is possible if desired to use have The bimodal compound of the PAO fluid of 1.5 to 150cSt range of viscosities.

Described PAO fluid can be by polymerized alpha alkene in the presence of polymerization catalyst such as Friedel-Crafts catalyst Hydrocarbon and easily manufacture, described Friedel-Crafts catalyst includes, for example, aluminum chloride, boron trifluoride or boron trifluoride Complex with water, alcohol such as ethanol, propanol or butanol, carboxylic acid or ester such as ethyl acetate or ethyl propionate.For example by the U.S. Disclosed in patent No.4,149,178 or 3,382,291, method here can be conveniently used.Other descriptions of PAO synthesis see Following United States Patent (USP) No.3,742,082；3,769,363；3,876,720；4,239,930；4,367,352；4,413,156； 4,434,408；4,910,355；4,956,122；With 5,068,487.C₁₄To C₁₈The dimer of alkene in United States Patent (USP) No.4, Described in 218,330.

Other available lube oil base stocks include wax isomerization oil base oil material and base oil, including hydroisomerization Content of wax oil plant (such as content of wax oil plant such as gas oil, slack wax, fuels hydrocracker bottoms etc.), hydroisomerizing The Fischer-Tropsch changed（Fischer-Tropsch）Wax, natural gas liquefaction (GTL) oil base stock and base oil and other wax isomerization oil The oil base stock of hydroisomerization and base oil or its mixture.Fischer-tropsch wax, the high boiling point residual oil of Fiscber-Tropscb synthesis, is that sulfur contains Measure low-down higher paraffins hydrocarbon.Hydrotreating for producing such oil base stock can be hydrocracked using amorphous/add Hydrogen isomerization catalyst, such as special lube are hydrocracked (LHDC) catalyst or crystalline hydrocracking/hydroisomerization is urged One of agent, preferred zeolite catalyst.For example, a kind of available catalyst is such as United States Patent (USP) No.5, described in 075,269 ZSM-48, the disclosure of which is passed through to quote to be incorporated herein with it.Manufacture is hydrocracked/hydro-isomerised fraction oil and Be hydrocracked/method of hydroisomerized wax for example, United States Patent (USP) No.2,817,693；4,975,177；4,921,594 Hes 4,897,178 and British patent No.1,429,494；1,350,257；Described in 1,440,230 and 1,390,359.Aforementioned special Each being incorporated herein with them of profit.Particularly advantageous method in european patent application No.464546 and Described in 464547, described patent application is incorporated herein also by quoting.United States Patent (USP) No.4,594,172 and 4,943, The method using fischer-tropsch wax charging is described, the disclosure of which is passed through to quote being incorporated herein with them in 672.

Natural gas liquefaction (GTL) base oil, base oil derived from fischer-tropsch wax and hydroisomerization (wax derived from other waxes Isomerized oil) base oil advantageously uses in the disclosure, and can have effective during 100 DEG C of about 3cSt to about 50cSt Kinematic viscosity, preferably from about 3cSt to about 30cSt, more preferably from about 3.5cSt to about 25cSt, with kinematic viscosity when 100 DEG C about 4.0cSt and as a example the GTL4 of viscosity index (VI) about 141.Basis derived from these natural gas liquefaction (GTL) base oil, fischer-tropsch wax Oily and hydroisomerizing base oil derived from other waxes can have about -20 DEG C or lower of effective pour point, and at some Can have about -25 DEG C or lower of favourable pour point under part, and effective about -30 DEG C to about -40 DEG C or lower of pour point.Available Natural gas liquefaction (GTL) base oil, base oil derived from fischer-tropsch wax and hydroisomerizing base oil compositionss derived from wax are in example As United States Patent (USP) No.6,080,301；6,090,989 and 6, enumerate in 165,949, described patent is whole with them by quoting Body is incorporated herein.

Described alkyl aromatic hydrocarbons can serve as base oil or base oil component and can be at least about 5% spreading out containing its weight It is conigenous any hydrocarbyl molecular of aromatic fractions such as benzene-type part or cycloalkanes type part, or their derivant.These alkyl virtues Hydrocarbon includes alkylbenzene, alkylnaphthalene, alkyl diphenyl ether, alkyl naphthol, alkyl diphenyl sulfur, alkylated bisphenols A, alkyl sulfur for diphenol Deng.Described aromatic hydrocarbons can be monoalkylation, di, polyalkylated, etc..Described aromatic hydrocarbons can be single or multiple official Energyization.Described hydrocarbyl group can also by alkyl group, alkenyl group, alkynyl group, group of naphthene base, cycloalkenyl groups and The mixture of other related hydrocarbyl groups is constituted.Described hydrocarbyl group can be with scope from about C₆Until about C₆₀, wherein about C₈To about C₂₀Scope often preferably.The mixture of hydrocarbyl group often preferably, and there may be most about three so Substituent group.Described hydrocarbyl group can the optional substituent group containing sulfur-bearing, oxygen and/or nitrogen.Described aromatic group can also spread out It is conigenous natural (oil) source, condition is at least about the 5% of described molecule to be made up of the aromatic fractions of the above-mentioned type.For described Viscosity about 3cSt to about 50cSt, often more preferably viscosity about 3.4cSt for alkyl aromatic component, when preferably 100 DEG C To about 20cSt.In one embodiment, the alkylnaphthalene being mainly made up of 1- hexadecylene using wherein alkyl group.Aromatic hydrocarbons Other alkylates can also advantageously use.For example, naphthalene or methyl naphthalene can by alkene for example octene, decene, laurylene, ten The alkylation such as tetraene or higher level alkene, the mixture of similar alkene.In lubricant oil composite, the usable concentration of alkyl aromatic hydrocarbons, depends on In application, can be about 2% to about 25%, preferably from about 4% to about 20%, and more preferably from about 4% to about 15%.

The alkyl aromatic hydrocarbons of the alkylated aromatic hydrocarbons such as disclosure can be by the Friedel- of known aromatic compounds Crafts alkylation is producing.Referring to《Friedel-Crafts and related reaction》（Friedel-Crafts and Related Reactions）, Olah, G.A. (write), Inter-science Publishers, New York, and 1963.Example As aromatic compounds, such as benzene or naphthalene, in the presence of friedel-crafts catalysts by alkene, alkyl halide or alcohol alkylation. Referring to《Friedel-Crafts and related reaction》, volume 2, part 1, the 14th, 17 and 18 chapter, referring to Olah, G.A. (compiles Write), Inter-science Publishers, New York, 1964.Many homogeneous or multiphase solid catalyst is this area Known to the skilled person.The selection of catalyst depends on the reactivity of parent material and product quality requires.It is, for example possible to use Strong acid such as AlCl₃、BF₃Or HF.In some cases, relatively mild catalyst such as FeCl₃Or SnCl₄It is preferred.Up-to-date Alkylation techniques use zeolite or solid super-strong acid.

Ester constitutes available oil base stock.By using ester, the ester of such as binary acid and single alkanol and monocarboxylic acid polynary Alcohol ester it can be ensured that additive dissolving power and sealing compatible properties.The ester of previous type includes, and for example, dicarboxylic acids are for example adjacent Phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, fumaric acid, oneself two Acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic etc. and various alcohol such as butanol, hexanol, lauryl alcohol, 2- The ester of ethyl hexanol etc..The instantiation of the ester of these types include dibutyl adipate, decanedioic acid two (2- ethylhexyl) ester, The just own ester of fumaric acid two, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, neighbour Double eicosane base ester of phthalic acid didecyl, decanedioic acid etc..

Useful especially synthetic ester be by one or more polyhydric alcohol, (for example neopentyl is polynary for preferred hindered polyhydric alcohols Alcohol for example neopentyl glycol, trimethylolethane, 2- methyl-2-propyl -1,3- propylene glycol, trimethylolpropane, tetramethylolmethane and Dipentaerythritol) with those esters obtained from alkane acid reaction containing at least about 4 carbon atoms, the preferred C of described alkanoic acid₅Extremely C₃₀Acid, such as saturated straight chain fatty acid include octanoic acid, capric acid, lauric acid, myristic acid, Palmic acid, stearic acid, arachidic acid and mountain Yu acid, or corresponding branched chain fatty acid or unsaturated fatty acid such as Oleic acid, or the mixture of these materials any.

Suitable synthetic ester component includes trimethylolpropane, tri hydroxy methyl butane, trimethylolethane, tetramethylolmethane And/or dipentaerythritol and one or more contain about 5 to about 10 or the monocarboxylic acid of more carbon atoms ester.These esters are can Extensively commercially available, for example, the Mobil P-41 of ExxonMobil Chemical Company and P-51 ester.

Can be used for kinematic viscosity when the preferred synthetic ester in the disclosure has 100 DEG C of about 3cSt to about 50cSt, preferably About 3cSt to about 30cSt, more preferably from about 3.5cSt are to about 25cSt, and more preferred about 2cSt to about 8cSt.Can be used for the disclosure In V race base oil preferably comprise concentration about 2% to the ester of about 20%, preferably from about 5% to about 15%.

Ester derived from recyclable materials such as Cortex cocois radiciss, Petiolus Trachycarpi, Semen Brassicae campestriss, Semen sojae atricolor, Helianthi etc. is also available.These Ester can be monoesters, diester, polyol ester, multiple ester or its mixture.These esters are widely commercially available, for example, The Mobil P-51 ester of ExxonMobil Chemical Company.

Motor oil formulations containing renewable ester are included within the disclosure.For such formula, described ester can Regeneration content is generally greater than about 70 weight %, and preferably greater than about 80 weight % are simultaneously most preferably greater than about 90 weight %.

Other available fluids of lubricant viscosity include unconventional or unconventional oil base stock, and it is processed, preferably Catalysis processing, or synthesis, to provide high-performance lubrication property.

Unconventional or unconventional oil base stock/base oil includes one or more of：Derived from one or more day So mixture of the oil base stock of gas liquefaction (GTL) material, the and isomerized oil/isomery derived from native paraffin or wax feed Dewaxing carburetion oil base stock, mineral and/or non-mineral oil waxy feeds such as slack wax, native paraffin and content of wax oil plant such as gas Oil, waxy fuel are hydrocracked bottoms, waxy residue liquid, hydrocrackates, hot tearing carburetion or other mineral, mineral The waxy material that oily or even waxy material derived from non-petroleum for example obtains from coal liquefaction or shale oil, and such base oil The mixture of material.

GTL material is from as former via one or more synthesis, combination, conversion, rearrangement and/or degraded/deconstruction The gaseous carbon of material, hydrogen-containing compound and/or element for example hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, Ethylene, acetylene, propane, propylene, propine, butane, butylene and material derived from butine.GTL oil base stock and/or base oil are logical The often GTL material derived from hydrocarbon, the lubricant viscosity of such as content of wax synthesis hydrocarbon, described hydrocarbon itself is derived from simpler as raw material Gaseous carbon, hydrogen-containing compound and/or element.GTL oil base stock and/or base oil include boiling point and boil in lubricating oil Oil in journey, described oil (1) is for example divided by distilling and be then subjected to final wax procedure of processing from the GTL material of synthesis From/fractional distillation, described wax procedure of processing includes one or both of catalytic dewaxing process or solvent dewaxing process, to produce pour point fall The lubricating oil of low/low pour point；(2) the wax isomerization oil synthesizing, comprises, for example, Hydrodewaxing or hydroisomerisation catalysts and/ Solvent dewaxing synthesis wax or waxy hydrocarbon；(3) Fischer-Tropsch of Hydrodewaxing or hydroisomerisation catalysts and/or solvent dewaxing (Fischer-Tropsch, F-T) material (that is, hydrocarbon, waxy hydrocarbon, wax and possible similar oxygenate)；Preferably Hydrodewaxing or plus The F-T waxy hydrocarbon of hydrogen isomerization/be followed by catalyst and/or solvent dewaxing and dewax or Hydrodewaxing or hydroisomerization/continue With catalyst (or solvent) dewaxing and dewax F-T wax or its mixture.

It is followed by the wax of catalyst and/or solvent dewaxing derived from GTL material, especially Hydrodewaxing or hydroisomerization Or the GTL oil base stock of wax feed and/or base oil, the material derived oil base stock of preferably F-T and/or base oil, generally To have about 2mm²/ s to about 50mm²When 100 DEG C of/s, kinematic viscosity (ASTM D445) is characterized.They are in addition generally to have The pour point (ASTM D97) having -5 DEG C to about -40 DEG C or lower is characterized.They are also generally to have about 80 to about 140 or bigger Viscosity index (VI) (ASTM D2270) be characterized.

Term GTL oil base stock and/or base oil and/or wax isomerization oil base oil material and/or base oil are interpreted as Including each fraction of the such material in the wide range of viscosities reclaiming in process of production, two or more such evaporate Point mixture and one or two or more kinds of low viscosity fraction with a kind of, two or more viscosity higher fractions To produce admixture, wherein said admixture shows target kinematic viscosity to mixture.

Derive described GTL oil base stock and/or the described GTL material of base oil is preferably F-T material (that is, hydrocarbon, the content of wax Hydrocarbon, wax).

In addition, described GTL oil base stock and/or base oil typically high paraffin hydrocarbon (>90% saturated hydrocarbons), and permissible The mixture combining with non-annularity isoparaffin containing monocyclic paraffin hydrocarbon and multi-ring paraffin hydrocarbon.Cycloalkanes (i.e. ring in such combination Paraffin hydrocarbon) ratio of content changes with the catalyst being used and temperature.In addition, GTL oil base stock and/or base oil and plus Hydrogen dewaxing or hydroisomerization/oil base stock that dewaxes of catalyst (and/or solvent) and/or base oil generally have very low Sulfur and nitrogen content, typically contain these elements each be less than about 10ppm and be more typically less than about 5ppm.From F-T material, GTL oil base stock that especially F-T wax obtains and/or the sulfur of base oil and nitrogen content are substantially zeroed.In addition, there is not phosphorus and virtue Hydrocarbon makes this material be particularly suitable for allocating the product of low-sulfur, sulfated ash and phosphorus (low SAP).

Can be used for the base oil used by the formulated oil in the disclosure and correspond to API I class, II class, Group III, IV class Various oily any one oily with V class and its mixture, preferably API II class, Group III, IV class and V class oil and its mixture, more Preferably Group III is to V class base oil and its mixture, because their excellent volatility, stability, viscosimetric analysis and spatter property are special Levy.Above-mentioned oil base stock when with reference to disclosed in the disclosure additive component use when, can be used for allocating have excellent The SAE 0W-8 of LSPI performance, SAE 0W-12, SAE 0W-16, SAE0W-20, SAE 0W-30, SAE 0W-40, SAE 5W- 12nd, SAE 5W-16, SAE 5W-20, SAE 5W-30 and SAE 10W-40 product.These oil base stock are when in conjunction with institute in the disclosure When disclosed additive component uses, there is SAE 0W-8, SAE 0W-12, the SAE 0W- of excellent LSPI performance in allotment 16th, especially effective in SAE 0W-20, SAE 0W-30, SAE 0W-40 and SAE 5W-30 oil.

Described base oil constitutes the key component of the engine oil lubricant oil composite of the disclosure, and is based on described combination The gross weight of thing, generally with from about 50 to about 99 weight %, is preferably from about 70 to about 95 weight % and is more preferably from about 85 to about 95 The amount of weight % exists.Described base oil can be selected from the crankcase lubrication being typically used as spark ignition and compression ignition engine Any synthesis of oil or natural oil.Described base oil, according to ASTM standard, suitably has when 100 DEG C about 2.5cSt to about 12cSt (or mm²/ s) kinematic viscosity and preferably when 100 DEG C about 2.5cSt to about 9cSt (or mm²/ s), and more preferably 100 DEG C when about 3.5cSt to about 7cSt (or mm²/ s) and in some applications more preferably when 100 DEG C about 3.5cSt to about 5cSt (or mm²/s).It is possible if desired to the mixture using synthesis and natural foundation oil.It is possible if desired to preferably use The mixture of III, IV and V class.

Antiwear additive

Metal alkylthiophosphates more particularly wherein said metal ingredient are the metal dialkyl dithio phosphorus of zinc Hydrochlorate or zinc dialkyl dithiophosphate (ZDDP) are the useful constituents of the lubricating oil of the disclosure.ZDDP can derived from primary alconol, Secondary alcohol or its mixture.Preferably ZDDP compound is typically expressed from the next

Zn[SP(S)(OR¹)(OR²)]₂

Wherein R¹And R²It is independently uncle and/or secondary C₁To C₈Alkyl group.Can using ZDDP derived from primary alconol (1 °) and The mixture of ZDDP derived from secondary alcohol (2 °).Described R¹And R²Substituent group can be independently C₁-C₁₈Alkyl group, preferably C₂-C₁₂ Alkyl group.Preferably, R¹And R²It is independently primary or secondary C₁To C₈Alkyl group, condition is R¹And R²At least one be secondary C₁ To C₈Alkyl group.The mixture of the ZDDP of ZDDP and derived from secondary alcohols derived from primary alconol, wherein R can be used¹And R²It is C₁To C₈ Alkyl group.These alkyl groups can be straight or branched.Kiki fang alkyl group can also be used.

Preferably commercially available zinc dithiophosphate includes secondary zinc dithiophosphate, such as, is available from such as The Lubrizol Corporation with trade name " LZ 677A ", " LZ 1095 ", " LZ1389 " and " LZ 1371 ", for example " OLOA 262, such as Afton Chemical are with trade name " HITEC 7169 " and for example with trade name for Chevron Oronite Infineum with trade name Infineum C9417 and Infineum C9414 those.

Preferably, primary or secondary C of described zinc dialkyl dithiophosphate compound₁To C₈Alkyl group partly derives free From following alcohol：2- propanol (C3), n-butyl alcohol (n-C4), 1- isobutanol (1-i-C4), 2- butanol (2-C4), 1- amylalcohol (primary C- 5), 3- methyl-1-butanol (primary C-5), 2- amylalcohol (C5), 3- amylalcohol (C5), 3- methyl -2- butanol (C5), 1- hexanol (primary C6), 4- methyl-1-pentene alcohol (primary C6), 4- methyl -2- amylalcohol (C6), and 2- ethyl -1- hexanol (primary C8), and its mixture.At some In the case of, derived from average carbon number be 5 and the ZDDP of less alcohol is desirable.In some cases, derived from average carbon number The ZDDP of the alcohol more than 5 is desirable.Table 1 below shows the alcohol for manufacturing the ZDDP being advantageously used in the disclosure Mixture.

Table 1. can be used for preparing the alcohol mixture (weight %) of ZDDP

I-C3,	2-C4 ,-	1-i-C4,	N-C4 ,-	i-C5	n-C5	i-C6	C6	C8
									Secondary	Secondary	Primary	Primary	Secondary	Primary	Secondary	Primary	Primary
20.2%	4.0%					75.7%
									8.4%	3.2%	11.7%						76.6%
45.2%	6.2%	19.4%	1.4%	8.8%	19.1%
									42.3%	2.4%					55.3%
23.2%	13.3%							63.6%
									5.7%	2.3%					92.1%
4.6%	63.1%					32.3%
									4.1%	2.4%	52.6%						40.9%
7.7%	1.8%							90.6%
									9.1%		0.4%				89.3%	0.4%	0.8%
42.0%		0.5%				56.5%	0.2%	0.9%
									33.9%						66.1%
0.3%		0.2%				99.6%
										85.6%							14.4%

The R of described zinc dialkyl dithiophosphate compound¹And R²Primary or secondary alkyl group, and there is described R¹And R²Primary Or amount in described lubricating oil for the zinc dialkyl dithiophosphate compound of secondary alkyl group is it is sufficient to making electromotor and using Lubricating oil contains different from the accessory constituent of described specific zinc dialkyl dithiophosphate compound and it is in described lubricating oil In amount be different from the low speed that reaches in the electromotor of amount of described specific zinc dialkyl dithiophosphate compound and early fire performance Compare, early combustion reduces to show low speed.

In general, the gross weight based on described lubricating oil, the usage amount of described ZDDP can be from about 0.4 weight % to about 1.2 weight %, preferably from about 0.5 weight % is to about 1.0 weight %, and is more preferably from about 0.6 weight % to about 0.8 weight % although more Many or less amount also often can advantageously use.Preferably, described ZDDP is primary, secondary or mixing ZDDP, and with described profit The amount of about 0.6 to 1.0 weight % of lubricating oil gross weight exists.

Preferably, described have R¹And R²The zinc dialkyl dithiophosphate compound of primary or secondary alkyl group, wherein R¹With R²Primary or secondary alkyl group derived from 2- ethyl -1- hexanol (primary C8), with the gross weight based on described lubricating oil from about 0.1 weight Measure % to about 5.0 weight %, preferably from about 0.1 to about 1.2 weight % and be more preferably from about the amount presence of 0.2 to about 0.8 weight %.

Preferably, described have R¹And R²The zinc dialkyl dithiophosphate compound of primary or secondary alkyl group, wherein R¹With R²Primary or secondary alkyl group derived from 4- methyl -2- amylalcohol (i-C6), with the gross weight based on described lubricating oil from about 0.1 weight Measure % to about 5.0 weight %, preferably from about 0.1 to about 1.2 weight % and be more preferably from about the amount presence of 0.2 to about 0.8 weight %.

Preferably, described zinc dialkyl dithiophosphate compound is derived from C₃To C₈Secondary alcohol or its mixture.Further, excellent Selection of land, described zinc dialkyl dithiophosphate compound is derived from C₁To C₈Primary alconol and C₁To C₈The mixture of secondary alcohol.

The Zn content scope contributed by the described zinc compound in described lubricating oil or antiwear additive is from about 500ppm to about 2000ppm, preferably from about 600ppm are to about 900ppm.

The phosphorus content scope contributed by the described zinc compound in described lubricating oil or antiwear additive is from about 400ppm to about 2000ppm, preferably from about 500ppm are to about 900ppm.Phosphorus derived from described secondary ZDDP is preferably from 0 to 900ppm and more preferably From 400 to 900ppm.

Described Zinc in Lube Oil and phosphorus ratio ranges from about 1.0 to about 2.0, preferably from about 1.1 to about 1.9.

The total metal being provided by described detersive and the ratio by described zinc compound and total metal of antiwear additive offer From about 0.8 to 4.8, preferably from about 1.4 to 4.0, and it is more preferably from about 1.5 to 3.7.

The illustrative zinc compound that can be used in the disclosure includes, for example, zinc polycarboxylate, sulfonic acid zinc, zinc acetate, cycloalkanes Sour zinc, alkenyl succinic acid zinc, acid phosphate zinc salt, phenol zinc, zinc salicylate etc..

According to the disclosure, in electromotor with the brake mean-effective pressure of 2000 revs/min (RPM) operating and 18 bars (BMEP), on the basis of, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, electromotor and use Lubricating oil contains different from the accessory constituent of described at least one zinc compound or at least one antiwear additive and it is described Amount in lubricating oil reaches in the electromotor of amount different from described at least one zinc boron compound or at least one antiwear additive Early combustion performance compares low speed, shows low speed early combustion and reduces greater than about 20%, preferably greater than about 25%, and is more preferably greater than about 30%.Similar or even more high low speed early fires minimizing can be using described at least one zinc compound or at least one wear-resistant Agent is obtained with least one boron-containing compound as described herein and/or the mixture with least one detersive.

Preferably, there is described R¹And R²The zinc dialkyl dithiophosphate compound of primary or secondary alkyl group, wherein R¹With R²Primary or secondary alkyl group derived from 2- propanol (C3), 2- butanol (2-C4), 1- isobutanol (1-i-C4) or n-amyl alcohol (n-C5), With the gross weight based on described lubricating oil from about 0.1 weight % to about 5.0 weight %, preferably from about 0.1 to about 1.2 weight % more The amount of preferably from about 0.2 to about 0.8 weight % exists.

Described zinc compound in the lubricating oil of the disclosure or wear-resistant agent concentration, based on the gross weight of described lubricating oil, With scope from about 0.1 to about 5.0 weight %, preferably from about 0.2 to 2.0 weight %, and 0.2 weight % can be more preferably from about to about 1.0 weights Amount %.It is only necessary to a small amount of ZDDP just produces abnormal low LSPI counting in the presence of magnesium detersive and boron-containing additive.Containing Magnesium and boron compound such in the presence of, as little as 0.1% to 1.0 weight %ZDDP (the phosphorus 100ppm P in electromotor formulated oil To 1000ppm P) unexpected LSPI performance improvement will be provided.Under higher ash level and higher TBN level, The ZDDP level of 1.1 to 4.0 weight % just can provide unexpected LSPI performance improvement.For SAE xW-40 and xW-50 For oily (x=0,5,10,15), the ZDDP level of 1.1 to 4.0 weight % is for the unexpected LSPI performance improvement of offer particularly Useful.

Dispersant

During electromotor operates, produce the oxidized byproduct insoluble in oil.Dispersant helps keep these by-products In the solution, thus reducing their depositions on the metal surface.Dispersant used in described lubricant formula can this It is ashless in matter or one-tenth ash.Preferably described dispersant is ashless.So-called ashless dispersant is after combustion substantially Do not form ash or the little organic material of ash.For example, the dispersant without metal or no boration metal is considered as no Ash.On the contrary, discussed above form ash after combustion containing metal detergent.

At least one boron-containing compound can be used in the disclosure.Described boron-containing compound comprises at least one boration dispersion Agent, or the mixture of boron-containing compound and non-borated dispersants.In described formula be derived from described borated dispersants or its The effective range of the boron of his boron-containing additive is 30ppm to 1500ppm, or preferred scope is 60ppm to 1000ppm, or Most preferably scope is 120ppm to 600ppm.

Preferably, described boron-containing compound includes, for example, boration butanimide, boration succinate, boration Succinate ester amides, boration Mannich (Mannich) alkali and its mixture.

Described non-borated dispersants include, for example, butanimide derived from the hydrocarbyl succinic anhydride with coupling agent Or succinate, wherein said coupling agent comprises boron-containing compound.

Preferably, boron is by the mixture of organic or inorganic boron-containing compound and boration butanimide, boration succinum Acid esters, boration succinate ester amides, Mannich base ester or its mixture are supplied to described lubricating oil.Described boration succinum Acid imide is preferably single butanimide, double amber imide or its mixture.Effectively boron-containing compound includes boration hydrocarbon Base butanimide, including number-average molecular weight (M_n) derived from alkyl source between 50 and 5000 dalton those, boration Hydrocarbyl succinic acid esters, the Mannich base that boration alkyl replaces, boration alcohol, borated alkoxylated alcohol, boration alkyl two Alcohol, boration alkylamine, boration alkyl diamidogen, boration alkyl triamine, borated alkoxylated alkylamine, boration alcoxyl Base hydrocarbyl amide, boracic is acidified the hydroxy ester of alkyl, the oxazoline that boration alkyl replaces, the imidazoles that boration alkyl replaces Quinoline ketone, etc., and the mixture of organic boric acid ester.The borate of N-H and/or OH derivative moiety can also be used.These boron Acid esters can be inorganic or borate derived from organic moiety.Borate can be using the preparation such as boric acid, boration alcohol.These boron Acid esters can be as needed to provide 60 to 1200ppm boron, 60-240ppm boron, 240-1200ppm in motor oil formulations The concentration of boron, 240-500ppm boron or 60-120ppm boron uses, to produce the surprising improvement of unexpected LSPI performance.

In described lubricating oil, add total from described detersive from total zinc of described zinc compound and antiwear additive Alkaline-earth metal is from about 9.2 to 45 divided by the ratio of the total boron from described boron-containing compound and borated dispersants, preferably from About 11 to 15.

Suitable dispersant usually contains the polar group being connected on the of a relatively high hydrocarbon chain of molecular weight.Described polar group Usually contain at least one nitrogen, oxygen or P elements.Typical hydrocarbon chain contains 50 to 400 carbon atoms.In some examples, described Hydrocarbon chain can be with scope from 6 to 50 carbon atoms.

Chemically, many dispersants can be characterized as phenates, sulfonate, sulfuration phenates, salicylate, naphthenate, hard Fat acid salt, carbaminate, thiocarbamate, phosphorus derivant.Useful especially dispersant classification is that alkenyl succinic acid spreads out Biology, the succinic acid compound generally being replaced by long chain hydrocarbon groups, the succinic anhydrides that typically alkyl replaces and polyhydroxy or many Amino-compound reacts and produces.Constitute the long chain hydrocarbon groups of the lipophilic fraction giving the deliquescent described molecule of oil, often Rule are polyisobutylene group.Many examples of such dispersant are commercial known with document.Description is such The exemplary U patent of dispersant is United States Patent (USP) No.3,172,892；3,2145,707；3,219,666；3,316,177； 3,341,542；3,444,170；3,454,607；3,541,012；3,630,904；3,632,511；3,787,374 and 4,234, 435.Other kinds of dispersant is in United States Patent (USP) No.3,036,003；3,200,107；3,254,025；3,275,554；3, 438,757；3,454,555；3,565,804；3,413,347；3,697,574；3,725,277；3,725,480；3,726, 882；4,454,059；3,329,658；3,449,250；3,519,565；3,666,730；3,687,849；3,702,300；4, 100,082；Described in 5,705,458.Further describing of dispersant can see, for example, european patent application No.471 071, for such purpose reference is carried out to it.

The succinic acid that alkyl replaces and the succinic anhydride derivative of alkyl replacement are useful dispersants.Particularly, pass through The hydrocarbon in the succinic acid compound of hydrocarbon replacement, preferably described hydrocarbon substituent with least 50 carbon atoms replaces succinic acid compound The butanimide, succinate or the succinate ester amides that react and prepare with the alkylene amines of at least one equivalent are that especially have , but sometimes, it is probably useful for having the hydrocarbon substituent between 20-50 carbon atom.

Butanimide is that the condensation reaction between the succinic anhydrides and amine being replaced by alkyl is formed.Mol ratio is permissible Change depending on polyamines.For example, alkyl replaces succinic anhydrides and ethylene amines (for example, diethylenetriamines, triethylene Tetramine, tetren, six ethylidene seven amine, seven ethylidene eight amine etc.) mol ratio.Containing tetren (TEPA) Polyethylene amine often preferably.Can also be using comprising six ethylidene seven amine and the high molecular of seven ethylidene eight amine is many Ethylene amines bottoms.The succinic anhydrides that alkyl replaces and the ratio of polyethylene amine can be from about 1:1 to about 5:1 change Change.Representational example is in United States Patent (USP) No.3,087,936；3,172,892；3,219,666；3,272,746；3,322, 670；With 3,652,616,3,948,800；Show with Canadian Patent No.1,094,044.

Condensation reaction between succinic anhydrides that succinate is replaced by alkyl and alcohol or polyhydric alcohol is formed.Mol ratio can To change depending on used alcohol or polyhydric alcohol.For example, alkyl replaces succinic anhydrides and the condensation product of tetramethylolmethane It is useful dispersant.

Condensation reaction between succinic anhydrides that succinate ester amides are replaced by alkyl and alkanolamine is formed.For example, close It is many that suitable alkanolamine includes the many alkyl polyamines of ethoxylation, the many alkyl polyamines of propoxylation and for example many ethylene of polyene-based polyamines Amine.One example is propoxylation diamidogen.Representational example shows in United States Patent (USP) No.4,426,305.

Used in paragraph above, the usual scope of molecular weight of described Hydrocarbyl-substituted succinic anhydride will be 800 and 2,500 Between dalton or higher.Above-mentioned product can be with reaction after various reagents such as sulfur, oxygen, formaldehyde, carboxylic acid such as Oleic acid.Above-mentioned Product can also be with reaction after the boron compound such as dispersant of boric acid, borate or height boration, to form every mole point Powder product typically has the borated dispersants of from about 0.1 to about 5 mole of boron.

Mannich base dispersants are made up of the reaction of alkyl phenol, formaldehyde and amine.Referring to United States Patent (USP) No.4,767,551, its It is incorporated herein.Processing aid and catalyst, such as Oleic acid and sulfonic acid or described reactant mixture Part.The molecular weight ranges of described alkyl phenol are from 800 to 2,500.Representative example is in United States Patent (USP) No.3,697,574；3, 703,536；3,704,308；3,751,365；3,756,953；3,798,165；With 3,803,039 in show.

The Mannich condensation product that can be used for the typical high molecular weight aliphatic acid modification in the disclosure can be from macromolecule Measure the hydroxy arene of alkyl replacement or containThe reactant preparation of group.

Alkyl replace amine ashless dispersants agent addition agent be well known to a person skilled in the art；See, e.g., United States Patent (USP) No.3,275,554；3,438,757；3,565,804；3,755,433,3,822,209, and 5,084,197.

Preferably dispersant includes boration butanimide, including from single butanimide, double amber imide and/ Or those derivants of the mixture of single and double butanimide, wherein said hydrocarbyl succinimide is derived from hydrocarbon thiazolinyl （hydrocarbylene）Group such as M_nFrom about 500 to about 5000 dalton or from about 1000 to about 3000 dalton or about The polyisobutylene of 1000 to about 2000 dalton, or the mixing of such hydrocarbon alkenyl group, described hydrocarbon alkenyl group often carries Senior terminal ethylene group.Can be used for the M that the preferred dispersant in the disclosure is characterized as low-molecular-weight_nIt is about 800 to 1700 Dalton, and the Mn of high molecular is about 1700 to about 5000 dalton or higher.Other preferred dispersants include succinic acid- Ester and amide, the Mannich adduct of alkyl phenol-polyamines-coupling, their capped derivatives and other related components.So The usage amount of additive can be about 0.1 to 20 weight %, preferably from about 0.5 to 8 weight %, or more preferably 0.5 to 4 weight %.Institute The hydrocarbon part stating dispersant atom can be with scope from C₆₀To C₄₀₀, or from C₇₀To C₃₀₀, or from C₇₀To C₂₀₀.These dispersants are permissible Containing neutral and both basic nitrogens, and the mixture of the two.

The ratio of described dispersant neutral and alkali and non basic nitrogen can be with scope from 1 to 5 to 5 to 1 or more preferably from 1 to 2 to 2 Ratio 1.Dispersant can be by borate and/or cyclic carbonate and/or any carboxylic acid such as hydrocarbon carboxylic acids or hydrocarbon carboxylic acids acid anhydride envelope End.

For the lubrication containing at least one boron-containing compound and at least one zinc compound or antiwear additive for the disclosure For oil formula, in electromotor with the basis of 2000 revs/min (RPM) operating and the brake mean-effective pressure (BMEP) of 18 bars On, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, electromotor is contained not with the lubricating oil using Be same as the accessory constituent of described at least one boron-containing compound and at least one zinc compound or antiwear additive and its described Amount in lubricating oil is different from sending out of the amount of described at least one boron-containing compound and at least one zinc compound or antiwear additive The low speed that reaches in motivation early fires performance and compares, and shows low speed early combustion and reduces greater than about 20%, preferably greater than about 25%, and more It is preferably greater than about 30%.

When using herein, described dispersant concentration is given based on " delivery status ".Generally, described active dispersing agents with plus Work oil is paid together.Described " delivery status " dispersant contains from about 20 weights generally in described " delivery status " dispersant product Measure % to about 80 weight % or from about 40 weight % to the active dispersing agents of about 60 weight %.

Detersive

The illustrative detersive that can be used in the disclosure includes, and for example, alkaline-earth metal detersive or alkaline-earth metal are peace and quiet The mixture of agent.Typical alkaline-earth metal detersive is anionic materials, its contain the long-chain hydrophobic part of described molecule and The less anion of described molecule or the hydrophilic parts of oleophobic.The anionicsite of described detersive derived from organic acid, Such as sulfur acid, carboxylic acid, phosphorous acid, phenol or its mixture.Counter ion is alkaline-earth metal.Preferably, described detersive comprises The alkali salt of at least one organic acid, and the alkali salt of described at least one organic acid comprise at least one organic The magnesium salt of acid.

The preferred detersive that can be used in the lubricating oil of the disclosure is selected from alkaline earth metal sulfonate, alkaline earth metal carboxylation (such as salicylate), alkaline earth phenate, alkali earth metal phosphate and its mixture.Contain with the lubricating oil that used Detersive be different from described alkaline earth metal sulfonate, alkaline earth metal carboxylation, alkaline earth phenate, alkali earth metal phosphate and its Mixture and its amount are different from described alkaline earth metal sulfonate, alkaline earth metal carboxylation, alkaline earth phenate, alkaline-earth metal phosphorus The low speed that hydrochlorate and its mixture reach in the electromotor of the amount in lubricating oil early fires performance and compares, described alkaline-earth metal sulphur Hydrochlorate, alkaline earth metal carboxylation, alkaline earth phenate, alkali earth metal phosphate and its mixture, and described alkaline-earth metal sulphur Hydrochlorate, alkaline earth metal carboxylation, alkaline earth phenate, the alkali earth metal phosphate and its mixture amount foot in described lubricating oil So that described electromotor shows low speed, and early combustion reduces.

Can be used for the alkaline-earth metal detersive in the disclosure to prepare by conventional method known in the art.

Alkaline earth metal sulfonate is preferred detersive classification.Can be used for preparing the sulfur acid of described alkaline earth metal sulfonate Including sulfonic acid, thiosulfonic acid, sulfinic acid, sulfenic acids, partial ester sulphuric acid, sulfurous acid and thiosulfuric acid.Sulfonic acid is preferred.

Described sulfonic acid is usually mahogany acid or synthetically prepared alkarylsulphonic acid.Among mahogany acid, most useful Product be by the suitable petroleum distillate of sulfonation and subsequently remove acid sludge and purify and prepare those.The alkaryl of synthesis Sulfonic acid generally to be prepared from the Friedel-Crafts product of alkylated benzenes such as benzene and polymer such as tetrapropylene.Below It is the instantiation that can be used for available sulfonic acid in the alkaline earth metal sulfonate detersive in the disclosure in preparation.It should be understood that this The example of sample also functions to the effect of the alkali salt of such sulfonic acid is described.In other words, to cited every kind of sulfonic acid, meaning It is intended to also be understood as illustrating its corresponding basic alkaline earth metal salt.

Such sulfonic acid includes mahogany acid, bright stock sulfonic acid, vaseline sulfonic acid, the LOMAR PWA EINECS 246-676-2 of single and many wax replacement, whale Cerul chlorobenzenesulfonic acid, cetyl phenol sulfonic acid, cetyl phenol two sulfacid, spermaceti epoxide caprylyl benzenesulfonic acid, two cetyl thianthrenes Sulfonic acid, dilauryl beta-naphtholsulfonic acid, two caprylyl nitro-naphthalene-monosulfonic acids, saturation paraffin sulfonic acid, unsaturated paraffin sulfonic acid, hydroxyl take The paraffin sulfonic acid in generation, four pib sulfonic acids, four pentenesulfonic acid, the paraffin sulfonic acid of chlorine replacement, the paraffin sulfonic acid of nitroso-group replacement, stone Oil ring alkyl sulfonic acid, spermaceti cyclopentyl sulfonic acid, lauryl cyclamic acid, the cyclamic acid of single and many wax replacement, dodecane Base benzenesulfonic acid, " dimer alkylation " sulfonic acid etc..

Wherein alkyl group contains the alkyl substituted benzene sulfonic acid of at least 8 carbon atoms, and including detergent alkylate, " bottom remains Thing " sulfonic acid, can be used for the disclosure.The latter be from by the propylene tetramer or Isobutylene Trimers alkylation on phenyl ring introduce 1, 2nd, 3 or more side chains C₁₂The acid derived from benzene institute of substituent group.Detergent alkylate bottoms, mainly singly-and double-ten two The mixture of alkylbenzene, can obtain as the by-product in house detergent manufacture.

Preferably alkaline earth metal sulfonate includes sulfonic acid magnesium, sulfoacid calcium and its mixture.

Alkaline earth phenates are available detersive classifications.These detersives can pass through alkaline earth metal hydroxide or oxide (for example, CaO, Ca (OH)₂, BaO, Ba (OH)₂, MgO, Mg (OH)₂) react and make with alkyl phenol or sulfenyl phenolate.Available Alkyl group include straight or branched C₁-C₃₀Alkyl group is it is preferable that C₄-C₂₀Or its mixing.The example of suitable phenol includes Isobutyl group phenol, 2- ethylhexyl phenol, nonyl phenol, dodecylphenol etc..It should be noted that initial alkyl phenol can contain more than one Individual be independently of one another straight or branched alkyl substituent and can from 0.5 to 6 weight % use.When using unvulcanised alkyl During phenol, described sulfur product can be obtained by method as known in the art.These methods include heat phenol and sulfuration The mixture of agent (including elementary sulfur, halogenation sulfur such as sulfur dichloride etc.), then described phenol red and alkaline-earth metal alkali reaction.

Preferably phenates compound includes, for example, phenol magnesium, phenol calcium, high alkalinity phenates compound, the phenol of sulfuration/carbonating Calcium compounds and its mixture.

The alkali salt of carboxylic acid also is used as detersive.These carboxylic acid detergents can pass through basic alkaline earth metal chemical combination Thing with least one carboxylic acid reaction and removes free water from product and prepares.These compounds can be overbasic, To produce the TBN level wanted.

It is a kind of detersive classification of preferred derived from carboxylic acid by the detersive that salicylic acid makes.Available salicylate Including long chain alkyl salicylates.A kind of available constituent family is following formula

Wherein R is the alkyl group with 1 to about 30 carbon atom, and n is 1 to 4 integer, and M is alkaline-earth metal.Preferably R group be at least C₁₁, preferred C₁₃Or bigger alkyl chain.R optionally can not disturbed the replacement of the function of described detersive Base replaces.M is preferably calcium, magnesium or barium.More preferably M is calcium or magnesium.

The salicylic acid that alkyl replaces can be by Kolbe reaction (referring to United States Patent (USP) No.3,595,791) from phenols system Standby.The salicylic alkali salt that described alkyl replaces can be multiple in polar solvent such as water or alcohol by alkali salt Decompose and to prepare.

Preferably carboxylate compounds include non-carbonated magnesium salicylate (carboxylate)；Magnesium salicylate (the carboxylic of carbonating Hydrochlorate)；Non-carbonated calcium salicylate (carboxylate)；The calcium salicylate (carboxylate) of carbonating；And its mixture.

Salt containing the substantially alkaline-earth metal of stoichiometric amount is referred to as neutral salt and has 0 to 100 total base number (TBN, by ASTM D2896 measurement).Many constituents are overbasic, pass through excessive alkaline-earth metal chemical combination containing a large amount of The metal base that thing reacts and obtains with sour gas (such as carbon dioxide).Available detersive can be neutral, slightly high-alkali Property or highly overbasic.These detersives can neutrality, high alkalinity, highly overbasic magnesium salicylate, sulfonate, phenol The mixture of salt and/or calcium salicylate, sulfonate and phenates uses.Described TBN scope can from about 0 to 100 low TBN, About 100 to 200 middle TBN and about 200 up to 600 high TBN changes, including as little as 0 to up to 600.Basic, normal, high TBN Mixture can be used together with the mixture of calcium and magnesium metal base detersive, and include sulfonate, phenates, salicylate and Carboxylate.Other examples of mixing TBN detersive are found in United States Patent (USP) No.7, and described in 704,930, described patent is passed through to draw With being incorporated herein.Metal than the peace and quiet agent composition for 1 can with metal than the detersive for 2 and metal than up to 5 or 10 or 15 detersive is used together.The detersive of boration can also be used.

Alkali earth metal phosphate is also used as detersive and is as known in the art.

Detersive can be simple detersive or so-called mix or complicated detersive.The detersive of the latter can provide two Plant the property of detersive, without the separate material of blending.Referring to United States Patent (USP) No.6,034,039.

Suitable detersive includes magnesium sulfonate, calcium sulfonate, calcium phenates, magnesium phenates, calcium salicylate, magnesium salicylate With other related components (including boration detersive) and its mixture.Preferably detersive includes sulfonic acid magnesium, sulfoacid calcium, phenol Magnesium, phenol calcium, magnesium salicylate, calcium salicylate and its mixture.

Other the illustrative detersives being applied in combination with described alkaline-earth metal detersive are included, for example, alkali metal Detersive or the mixture of alkali metal salicylate detergent.

In comprising the detersive of mixture of organic acid magnesium salt and organic acid calcium salt, the detersive of magnesium metal and calcium metal Ratio ranges are from about 1:0 to about 1:10, preferably from about 1:0 to about 1:4.

The magnesium contributed by described detersive and alkaline-earth metal are measured from about 500ppm to about present in described lubricating oil 5000ppm, preferably from about 1000ppm to about 2500ppm.The magnesium contributed by described detersive is measured present in described lubricating oil From about 100ppm to about 3000ppm, it is preferably from about 300ppm to about 2500ppm, more preferably from about 750ppm to about 2000ppm.

The total base number (TBN) contributed by described detersive, by ASTM D2896 measurement, scope is from about 2mg KOH/g to about 17mg KOH/g, preferably from about 4mg KOH/g are to about 14mgKOH/g.The TBN scope contributed by described magnesium detersive is from about 2mg KOH/g to about 17mgKOH/g, preferably from about 3mg KOH/g are to about 14mg KOH/g.

The sulfated ash scope contributed by described detersive from about 0.4 to about 1.7 weight %, preferably from about 0.5 to about 1.6 weight %, and it is more preferably from about 0.6 to about 1.0 weight %.The sulfated ash scope contributed by described magnesium detersive is from about 0.3 to about 1.8 weight %, preferably from about 0.4 to about 1.6 weight %, and it is more preferably from about 0.6 to about 1.0 weight %.The disclosure The sulfated ash of engine lubricating oil preferably contain less than about 1.6 weight %, and/or more preferably less than about 4000ppm Magnesium.When equaling or exceeding higher engine oil sulfated ash (and using magnesium detersive) of 1.2% ash, reach and be more than 95% LSPI counts and reduces.In sulfated ash level<1.2% and using magnesium detersive when, LSPI can be completely eliminated.

The lubricating oil containing at least one zinc compound or antiwear additive and at least one detersive for the disclosure is joined Fang Eryan, on the basis of electromotor is with the brake mean-effective pressure (BMEP) of 2000 revs/min (RPM) operating and 18 bars, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, electromotor and the lubricating oil of use contain different In the accessory constituent of described at least one zinc compound or antiwear additive and at least one detersive and it is in described lubricating oil In amount be different from the electromotor of amount of described at least one zinc compound or antiwear additive and at least one detersive and reach Low speed early fire performance and compare, show low speed early combustion and reduce greater than about 50%, preferably greater than about 75%, and more preferably greater than about 95%.

Further, for the disclosure containing at least one zinc compound or antiwear additive, at least one boron-containing compound and For the lubricant formula of at least one detersive, average with the braking of 2000 revs/min (RPM) operating and 18 bars in electromotor On the basis of effective pressure (BMEP), (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, electromotor Contain different from described at least one zinc compound or antiwear additive, at least one boron-containing compound and extremely with the lubricating oil using A kind of few accessory constituent of detersive and its amount in described lubricating oil be different from described at least one zinc compound or Antiwear additive, at least one boron-containing compound early fire performance with the low speed reaching in the electromotor of the amount of at least one detersive to be compared Relatively, show low speed early combustion and reduce greater than about 50%, preferably greater than about 75%, and be more preferably greater than about 95%.

Detergent concentration in the lubricating oil of the disclosure, based on the gross weight of described lubricating oil, can with scope from about 1.0 to About 6.0 weight %, preferably from about 2.0 to 5.0 weight %, and it is more preferably from about 2.0 weight % to about 4.0 weight %.Profit in the disclosure In lubricating oil, based on the gross weight of described lubricating oil, the amount of described alkaline earth metal sulfonate preferably can be with scope from about 0.5 to about 2.5 weight %, preferably from about 0.5 to about 2.0 weight %, and it is more preferably from about 0.5 to about 1.5 weight %.Lubricating oil in the disclosure In, based on the gross weight of described lubricating oil, the amount of described alkaline earth phenate preferably can be with scope from about 0.5 to about 2.5 weight Amount %, preferably from about 0.5 to about 2.0 weight %, and it is more preferably from about 0.5 to about 1.5 weight %.In the lubricating oil of the disclosure, base In the gross weight of described lubricating oil, the amount of described alkaline earth metal carboxylation can with scope from about 1.0 to about 4.0 weight %, preferably from About 1.0 to about 3.0 weight %, and it is more preferably from about 1.5 to about 2.5 weight %.In the lubricating oil of the disclosure, based on described lubrication The gross weight of oil, the amount of described alkali earth metal phosphate can be with scope from about 1.0 to about 4.0 weight %, and preferably from about 1.0 to about 3.0 weight %, and it is more preferably from about 1.5 to about 2.5 weight %.

When using herein, described detergent concentration is given based on " delivery status ".Generally, described active cleaning agent with plus Work oil is paid together.Described " delivery status " detersive contains from about 20 weights generally in described " delivery status " detersive product Measure % to about 80 weight % or from about 40 weight % to the active cleaning agent of about 60 weight %.

Other additives

The formulated oil that can be used in the disclosure can be in addition containing one or more other conventional lubricants performance Additive, includes but is not limited to other antiwear additives, other dispersants, other detersives, corrosion inhibitor, antirust agent, metallic blunt Agent, EP agent, anti-seizing dose, wax modifiers, viscosity index improver, viscosity modifier, fluid loss reducing agent, sealing Compatilizer, friction modifiers, lubricity agent, anti-staining agent, colour former, defoamer, demulsifier, emulsifying agent, thickening agent, wetting agent, Gellant, adhesive, coloring agent and other.For the summary of many commonly-used additive, referring to Klamann,《Lubricant and phase Close product》（Lubricants and Related Products）, Verlag Chemie, Deerfield Beach, FL； ISBN 0-89573-177-0.Referring also to M.W.Ranney "《Lubricant additive》（Lubricant Additives）", by Noyes Data Corporation of Parkridge, NJ publish (1973)；Referring further to United States Patent (USP) No.7,704,930, The disclosure of which is incorporated herein with it.These additives generally carry different amounts of flux oil and pay, and described amount can With scope from 5 weight % to 50 weight %.

The type of the performance additive using with reference to the disclosure in lubricant oil composite and quantitation are not herein made The restriction of the example showing for illustrating.

Viscosity index improver

Viscosity index improver (also referred to as VI modifier, viscosity adjustment can be included in the lubricant oil composite of the disclosure Agent and viscosity improver).

Viscosity index improver is supplied to lubricant height and low temperature operability.These additives give in the temperature raising Under shear stability and viscosity qualified at low temperature.

Suitable viscosity index improver includes high-molecular-weight hydrocarbons, polyester and has viscosity index improver and dispersant two concurrently Plant the viscosity index improver dispersant of effect.The typical molecular weight of these polymer about 10,000 to 1, between 500,000, More typically from about 20,000 to 1,200,000, and more generally about 50,000 and 1, between 000,000.

The example of suitable viscosity index improver is methacrylate, butadiene, alkene or alkylated styrenes Linear or star polymer and copolymer.Polyisobutylene is conventional viscosity index improver.Another kind of suitable viscosity index (VI) Modifier is polymethacrylates (for example, the copolymer of the alkyl methacrylate of various chain lengths), its some preparations Act also as pour-point depressant.Other suitable viscosity index improvers include copolymer, styrene and the isoamyl of ethylene and propylene The hydrogenated block copolymer of diene and polyacrylate (for example, the copolymer of the acrylate of various chain lengths).Instantiation bag Include the styrene-based-isoprene of 50,000 to 200,000 molecular weight or the polymer of styrene-butadiene.

Olefin copolymer, can be from Chevron Oronite Company LLC with trade name(example As "8921 " and "8941”)；From Afton Chemical Corporation with Trade name "" (for example "5850B”；With from The Lubrizol Corporation with trade name "7067C " is commercially available.Polyisoprene polymer can from Infineum International Limited for example with Trade name " SV 200 " is commercially available；Diene-styrene copolymer can from Infineum International Limited for example with Trade name " SV260 " is commercially available.

In a kind of embodiment of the disclosure, based on the gross weight of described formulated oil or engine lubricating oil, described viscous The usage amount of degree index improver can be less than about 2.0 weight %, preferably less than about 1.0 weight %, and is more preferably less than about 0.5 weight Amount %.Viscosity improver adds usually as the concentrate in Macrodilution oil.

In the another embodiment of the disclosure, based on the gross weight of described formulated oil or engine lubricating oil, described The usage amount of viscosity index improver can from 0.25 to about 2.0 weight %, preferably 0.15 to about 1.0 weight %, and more preferably 0.05 to about 0.5 weight %.

Antioxidant

Antioxidant hinders base oil in the oxidative degradation of viability.Such degraded may lead on the metal surface Deposit, the presence of greasy filth or lubricant viscosity increase.Those skilled in the art will know that varied can be used for lubricating oil Oxidation retarder in compositionss.See, e.g., previously cited Klamann,《Lubricant and Related product》, and the U.S. Patent No.4,798,684 and 5,084,197.

Available antioxidant includes hindered phenol.These phenol antioxidant can be ashless (no metal) phenols chemical combination The neutrality of thing or some phenolic compounds or alkaline metal salt.Typical phenolic antioxidant compound is hindered phenol, and it is Phenol containing sterically hindered oh group, these include wherein oh group in the dihydroxy arylation of neighbour each other or para-position Those derivants of compound.Typical phenol antioxidant is included by C₆Hindered phenol and these hindered phenols that+alkyl group replaces Alkylidene be coupled derivant.The example 2- tert-butyl group -4- heptyl phenol of such phenolic material；The 2- tert-butyl group -4- is pungent Base phenol；The 2- tert-butyl group -4- dodecylphenol；2,6- di-t-butyl -4- heptyl phenol；2,6- di-t-butyl -4- dodecylphenol；2- Methyl-6-tert butyl -4- heptyl phenol；With 2- methyl-6-tert butyl -4- dodecylphenol.Other available single phenols that are obstructed resist Oxidant can include the 2,6- dialkyl group phenols propanoate ester derivatives being for example obstructed.Bis-phenolic antioxidants can also be advantageously Use in conjunction with the disclosure.The example of the phenol that ortho position is coupled includes：2,2 '-bis- (4- heptyl -6- tert-butyl phenols)；2,2 '-it is bis- that (4- is pungent Base -6- tert-butyl phenol)；With 2,2 '-bis- (4- dodecyl -6- tert-butyl phenols).The bis-phenol that para-position is coupled includes such as 4,4 '-and bis- (2,6- di-tert-butylphenol) and 4,4 '-methylene-bis- (2,6- di-tert-butylphenols).

One or more catalytic antioxidant of effective dose can also be used.Described catalytic antioxidant comprises effectively A) one or more oil-soluble many metallo-organic compound of amount；With the b of effective dose) one or more substituted N, N'- bis- Aryl phenylenediamine compound or c) one or more hindered phenol compound；Or b) and c) combination.Catalytic antioxidation Agent, in United States Patent (USP) No.8, is described more fully in 048,833, described patent pass through to quote with its overall herein in conjunction with.

The non-phenol type oxidation inhibitors that can use include aromatic amine antioxidant, and these can be with regard to this or and phenols It is applied in combination.The representative instance of non-phenol antioxidant includes：Alkylation and non-alkylating aromatic amine, the aromatics list of such as following formula Amine：R⁸R⁹R¹⁰N, wherein R⁸It is aliphatic series, aromatics or replacement aromatic group, R⁹It is aromatics or replacement aromatic group, and R¹⁰It is H, alkane Base, aryl；Or R¹¹S(O)_XR¹², wherein R¹¹It is alkylidene, alkenylene or sub- aromatic alkyl group, R¹²Be compared with higher alkyl group, Or thiazolinyl, aryl or alkylaryl group, and x is 0,1 or 2.Described aliphatic group R⁸Can contain former from 1 to 20 carbon Son, and preferably comprise from 6 to 12 carbon atoms.Described aliphatic group is radical of saturated aliphatic group.Preferably, R⁸And R⁹The two is all Aromatics or replacement aromatic group, and described aromatic group can be fused ring aromatic group, such as naphthyl.Aromatic group R⁸And R⁹ Can connect together with other groups such as S.

Typical aromatic amine antioxidant has the alkyl substituents groups of at least 6 carbon atoms.The example of aliphatic group Including hexyl, heptyl, octyl group, nonyl and decyl.Usually, described aliphatic group will be free from more than 14 carbon atoms.Available The general type of the amine antioxidant in this compositions includes diphenylamines, nonox, phenothiazine, iminodibenzyl and hexichol Base phenylenediamine.The mixture of two or more aromatic amines is also available.Polymeric amine antioxidants can also be used.Can be used for The instantiation of the aromatic amine antioxidant in the disclosure includes：P, p'- dioctyl diphenylamine；T-octyl phenyl-alpha-naphthylamine；Benzene Base-αnaphthylamine；With to octyl phenyl-αnaphthylamine.

Sulfenyl phenolate and its alkali metal or alkali salt are also available antioxidant.

Preferably antioxidant includes hindered phenol, arylamine.These antioxidants can individually or each other group by type Close and use.The usage amount of such additive can be 0.01 to 5 weight %, preferably 0.01 to about 2 weight %, and more preferably zero to about 1.5 weight %, more preferably zero to less than 1 weight %.

Pour-point depressant (PPD)

It is possible if desired to add conventional pour-point depressant to the compositionss of the disclosure, (also known as lubricating oil flow improves Agent).These pour-point depressants can be added in the lubricating composition of the disclosure and can flow or can topple over to reduce described fluid Minimum temperature.The example of suitable pour-point depressant includes polymethacrylates, polyacrylate, polyarylamide, halogen Ethylene for the condensation product of paraffin and aromatic compounds, carboxylic acid vinyl ester polymer and dialkyl fumarate, fatty acid Base ester and the terpolymer of allyl vinyl ether.United States Patent (USP) No.1,815,022；2,015,748；2,191,498；2, 387,501；2,655,479；2,666,746；2,721,877；2,721,878；Describe under available pour point with 3,250,715 Depressant prescription and/or its preparation.The usage amount of such additive can be about 0.01 to 5 weight %, preferably from about 0.01 to 1.5 weight Amount %.

Sealing compatilizer

Sealing compatilizer passes through to cause fluid or physically changed chemical reaction in the elastomer, contributes to expanded elastomers Sealing member.Lubricating oil suitably seals compatilizer and includes organophosphorus ester, alkoxyl sulfolane, aromatic ester, aromatic hydrocarbons, ester (for example, neighbour Phthalic acid butyl benzyl ester) and polybutenyl succinic anhydride.The usage amount of such additive can be about 0.01 to 3 weight %, Preferably from about 0.01 to 2 weight %

Defoamer

Defoamer can advantageously be added to lubricant compositions.These reagent hinder and form stable foam.Organosilicon It is typical defoamer with organic polymer.For example, polysiloxanes, such as silicone oil or polydimethylsiloxane, froth breaking property is provided. Defoamer is commercially available it is possible to conventional a small amount of use together with other additives such as demulsifier；Generally these add Plus the merging amount of agent is less than 1 weight % and is frequently less than 0.1 weight %.

Inhibitor and rust-inhibiting additive

Rust-inhibiting additive (or corrosion inhibitor) is the change that water or other pollutant are resisted in the metal surface that protection is lubricated Learn the additive corroding.These additives diversified are commercially available.

A type of rust-inhibiting additive is preferential wetting metal surface, protects its polar compound with oil film.Another The rust-inhibiting additive of type is by absorbing water with reference to water so that only having oily contacting metal surface in water-in-oil emulsion.Again A type of rust-inhibiting additive chemical adhesion, in metal, produces non-reacted surface.The example of suitable additive includes two D2EHDTPA zinc, metal phenatess, basic metal sulfonates, fatty acid and amine.The usage amount of such additive can be about 0.01 to 5 weight %, preferably from about 0.01 to 1.5 weight %.

Friction improver

Friction improver is that the friction that can change the surface by any lubricant or the fluid lubrication containing this kind of material is Any material of number.Friction improver, also known as anti-friction agent, or lubricity agent or oiliness improver, and change base oil, allotment lubricant The performance of compositionss or functional fluid to improve other such agents of the coefficient of friction on the surface being lubricated, if necessary If, the base oil of the disclosure can be effectively combined or lubricant compositions use.Reduce the friction improver of coefficient of friction It is particularly advantageous for combining with the base oil of the disclosure and lubricant oil composite.

Illustrative friction improver can include, for example, organo-metallic compound or material, or its mixture.Explanation Organic metal friction improver in the engine lubrication oil formula that can be used for the disclosure of property includes, for example, molybdenum amine, molybdenum two Amine, organotungstate, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complex, carboxylic acid molybdenum etc., and its mixture.Class As tungstenio compound can be preferred.

The friction improver that other are illustrative to can be used in the engine lubrication oil formula of the disclosure includes, for example, alkane Epoxide fatty acid ester, alkanolamide, polyol fatty acid ester, boration fatty acid glyceride, fatty alcohol ether and its mixing Thing.

Illustrative alkoxy fatty acid ester includes, for example, Myrj 45, fatty acid polyethylene glycol ester Deng.These can include polyoxypropylene stearate, polybutylene stearate, polyoxyethylene isostearate, polyoxypropylene Isostearate, polyoxyethylene palmitate etc..

Illustrative alkanolamide includes, for example, lauric acid diethyl alkanolamide, Palmic acid diethyl alkanolamide Deng.These can include Oleic acid diethyl alkanolamide, stearic acid diethyl alkanolamide, Oleic acid diethyl alkanolamide, gather Ethoxylation alkyl amide, poly- propoxylation hydrocarbyl amide etc..

Illustrative polyol fatty acid ester includes, for example, glycerin mono-fatty acid ester, saturation mono-, di- and triglyceride, glycerol Monostearate etc..These can include polyol ester, hydroxyl polyol ester etc..

Illustrative boration fatty acid glyceride includes, for example, boration glycerin mono-fatty acid ester, boration saturation list, Two and triglyceride, boration glyceryl monostearate etc..In addition to glycerine polyol, these can also include trihydroxy methyl third Alkane, tetramethylolmethane, sorbitan etc..These esters can be polyhydric alcohol monocarboxylate, polynary alcohol esters of dicarboxylic acids and polyhydric alcohol sometimes Tricarboxylic ester.Can be with preferably glycerine monoleate, diolein, triolein, glyceryl monostearate, glycerol two Stearate and glycerol tristearate and corresponding glycerol monopalmitate, dipalmitin and glycerol three Palmic acid Ester, and respective isostearate, linoleate etc..Sometimes it may be preferred to described glyceride and containing any these Mixture.Can be made especially with glycerol with the ethoxylation of preferred polyol, propoxylation, butoxylated fatty acid ester Based on polyhydric alcohol.

Illustrative fatty alcohol ether includes, for example, stearyl ether, myristyl ether etc..Alcohol, including carbon number from C₃To C₅₀'s Those, can be ethoxylated, propoxylation or butoxylated, to form corresponding fatty alkyl ether.Described basis alcohol part May be preferred that stearyl, myristyl, C₁₁–C₁₃Hydrocarbon, oleyl, iso stearyl etc..

The usable concentration of friction improver can be with scope from 0.01 weight % to 5 weight %, or about 0.1 weight % is to about 2.5 weights Amount %, or about 0.1 weight % is to about 1.5 weight %, or about 0.1 weight % is to about 1 weight %.Concentration containing Mo is often according to Mo Metal concentration describes.Favourable Mo concentration can be from 25ppm to 700ppm or more with scope, and preferred scope is often 50- 200ppm.All types of friction improvers can individually or with the mixture with the material of the disclosure use.Often, two kinds or The mixture of more kinds of friction improvers, or the mixture of friction modifiers and other surface active material, are also desirable.

When lubricant oil composite contains one or more above-mentioned additive, described additive is with enough to make it execute its The amount of predetermined function is admixed in described compositionss.Can be used for the typical amount table below 1 of the such additive in the disclosure Middle display.

It should be noted that many additives are as existing containing one or more additive with a certain amount of base oil diluent Concentrate together ships from additive manufacturer there.Therefore, the weight metering in table below, and mention wherein Other amounts, refer to the amount (that is, non-diluted agent part of described composition) of active component.Percentage by weight (the weight being indicated below Amount %) it is gross weight based on lubricant oil composite.

The typical amount of other lubricating oil components of table 2.

Aforementioned additive is entirely commercially available material.These additives can independently add, but generally can be from profit Combine in advance in the packaging that oil additive supplier obtains.The additive packing with various composition, ratio and characteristic is existing Have, select suitable packaging will consider the final composition that must use.

The electromotor formulated oil of the disclosure shows LSPI and substantially eliminates.LSPI substantially eliminate it is meant that electromotor with On the basis of the brake mean-effective pressure (BMEP) of 2000 revs/min (RPM) operating and 18 bars, early fired based on standardization low speed (LSPI) count/25,000 cycle of engine, low speed early combustion reduces by greater than about 95%, or greater than about 97%, or greater than about 99%.

Have 1.2 to 1.6% or higher higher ash level electromotor formulated oil combine the disclosure disclosed in other LSPI event number can be significantly reduced 96% or higher by component.There is the electromotor allotment of 0.2 to 1.2% relatively low ash level Oil can cut LSPI event number completely with reference to the other components disclosed in the disclosure.

Highly easily it is subject to the electromotor that low speed early fires (LSPI) and affects to be in high brake mean-effective pressure (BMEP) and low Those electromotors of operating under motivation rotating speed (RPM).This includes including natural gas, gasoline, diesel oil, biological combustion using various fuel The explosive motor of material etc..Miniaturization, the slow-speed of revolution, be forced sense (such as turbocharging) electromotor be in these electromotors Operate under state the most susceptible, and be therefore more susceptible to LSPI impact.Have the non-limiting examples bag of the electromotor of these characteristics Including GM Ecotec and Ford EcoBoost power team and discharge capacity other high BMEP from about 1L to about 6L (can>10 Bar) electromotor and to include in upright arrangement, horizontally-opposed (Boxer) and " V " (such as " V8 ", " in upright arrangement 3 ", " array 4 ", " level pair Put 4 " etc.) geometric configuration have the electromotor of the combustion cylinder between 2-10.Additionally, the demarcation of described electromotor and operating Set point can significantly affect both frequency and the seriousness of LSPI event.

There is provided following non-limiting example that the disclosure to be described.

Embodiment

Embodiment A

Formula preparation as shown in Figure 1.All the components as used herein are all commercially available.In described formula using III, IV and V class oil base stock.

Used in described formula antiwear additive be ZDDP derived from secondary alcohol (its contain 10 weight % phosphorus and from mixing C3 and Prepared by C6 secondary alcohol) and the ZDDP (it contains 7 weight % phosphorus and prepares from C8 primary alconol) derived from primary alconol.In addition, making in described formula With only having the antiwear additive of zinc and only phosphorus.

Used in described formula, remaining composition is viscosity index improver, antioxidant, dispersant, antiwear additive, pour point Depressant, corrosion inhibitor, matal deactivator, sealing compatible additive, defoamer, inhibitor, rust-inhibiting additive and friction change Enter one or more of agent.

Formula described in Fig. 1 is tested.Result illustrates in FIG.Sulfated ash experimental evidence ASTM D874 Measure.Zinc and phosphorus content measure according to ASTM D6443.

Existing file record, different electromotor parts and control program can significantly affect the generation of LSPI.Referring to example As, U.S. Patent Application Publication No.2012/1866225 and 2003/0908070, also SAE 2012-02-1148, SAE 2011-01-0340 and SAE2011-01-0343, all of which is incorporated herein.Additionally, Figure 12 show from The driving pattern data that taxi field test obtains.Two kinds of different 2.0L from different original equipment manufacturers L4TGDI engine type is travelled 2 weeks with typical taxi city driving pattern.OBD-II data port using vehicle is received Collect engine performance data and described engine performance data is mapped in the engine torque map delivered of corresponding electromotor On.As announced in SAE 2011-01-0339, electromotor works as them more than 10 bar BMEP with less than 3000rpm engine speed Region in operate when be especially susceptible to LSPI.Therefore, in the torque diagram of these electromotors by these operating conditions define any Region is potentially susceptible to LSPI.According to the measurement data of OBD-II data monitor, can show that there is starting of different demarcation How machine is tuned based on them can show different LSPI behaviors.Figure 12 shows about 1.2 million data points, collects Interim when 2 weeks, two kinds of different engine types are with the operating of typical taxi city driving pattern.By this way Observe several taxis using every kind of engine type.In the driving pattern of typical taxi city, electromotor manufacture 1 exists LSPI " hazardous area " averagely exhausts the 1.67% of its duration of runs, and electromotor manufacture 2 averagely exhausts 0.17% although both Electromotor is all 2.0L array 4- cylinder TGDI electromotor.Additionally, electromotor manufacture 2 shows the related scene event of zero LSPI Barrier, and electromotor manufacture 1 shows the related fault of multiple LSPI.This further illustrates different engine flats to LSPI Different responses.

For purposes of this disclosure, 2.0L, 4- cylinder TGDI GM Ecotec electromotor is used for LSPI to be tested.Using six sections Test procedure is measuring the LSPI event number occurring under the engine loads of two kinds of different regulations and velocity conditions.Every section of examination The program of testing includes 25,000 cycle of engine, and one of circulation rotates 720 degree corresponding to bent axle.First group of condition be 2000RPM and 18 bar BMEP, hereinafter referred to as " high load capacity ".Second group of condition is 1500RPM and 12.5 bar BMEP, hereinafter referred to as " underload ".Test procedure includes two sections of high load capacities, is followed by two sections of low-load, is followed by two sections of high load capacities.In test procedure Before beginning, also carry out the preheatings in 30 minutes under 2000RPM and 4 bar BMEP.Every kind of tested lubricant repeats this test journey Sequence four times.LSPI event only counts during high load capacity section, is supervised using being placed on pressure transducer in each for 4 cylinders Survey peak cylinder pressure.Surge pressure in cylinder exceedes average peak cylinder pressure and is more than 4.7 standard deviations or is less than institute State average peak cylinder pressure and be more than 4.7 standard deviations, be just counted as LSPI event.The result of such LSPI test exists Illustrate in Fig. 1.

The impact to LSPI for the described test evaluation ZDDP.As shown in figure 1, on reducing LSPI counting, using derived from secondary alcohols ZDDP than using ZDDP derived from primary alconol more preferably.Embodiment 1 shows, every 25,000 cycle of engine, using secondary ZDDP About 27 LSPI events can be obtained, and comparative example 1, under equal zinc and phosphorus content, show that primary ZDDP has and expect not The higher counting arriving, 34 countings.Therefore, the formula having the ZDDP of derived from secondary alcohols shows unexpected LSPI minimizing 20%.By using secondary ZDDP or mainly use secondary ZDDP to reduce this new discovery that LSPI counts as a result, it is possible to lubricant Formula is highly profitable.Embodiment 2 presents the situation of the ZDDP handling rate wherein taking high level, and shows, by increasing The amount of ZDDP in described formula, it is possible to reduce, almost eliminate LSPI count.Finally, comparative example 2 and 3 by check respectively for zinc and The impact of phosphorus, probes into the benefit of ZDDP further.Comparative example 2 using the antiwear additive of only zinc, with embodiment 1 and comparative example 1 Under equal handling rate, produce 36 LSPI and count.On the other hand, comparative example 3 is using the antiwear additive of only phosphorus, with embodiment 1 and the equal handling rate of comparative example 1 under, produce 55 LSPI events.Comparative example 2, compared with comparative example 3, is apparent from described zinc Unique benefit in controlling LSPI to count for the compound.It is also possible to find out the ill-effect using the only antiwear additive of phosphorus.

Embodiment B

Formula preparation as shown in Figure 2.All the components as used herein are all commercially available.In described formula using III, IV and V class oil base stock.

Used in described formula, antiwear additive is the ZDDP derived from the secondary alcohol and ZDDP derived from primary alconol.

Used in described formula, dispersant is that (it is sub- that it comprises boration polyisobutene succinic acyl to boration butanimide Amine, B/N ratio be equal to about 0.5), (high MW succinimide dispersants 1, it comprises ethylene carbonate to high molecular butanimide The double focusing isobutene. succinimide dispersants of ester end-blocking, total nitrogen about 1%) and high molecular butanimide (high MW succinyl Asia Amine dispersant 2, it comprises double polyisobutenyl succinimide, total nitrogen about 1.2%).

Used in described formula, remaining composition is viscosity index improver, antioxidant, dispersant, antiwear additive, pour point Depressant, corrosion inhibitor, matal deactivator, sealing compatible additive, defoamer, inhibitor, rust-inhibiting additive and friction change Enter one or more of agent.

Formula described in Fig. 2 is tested.Result illustrates in figure 3.Sulfated ash experimental evidence ASTM D874 Measure.Boron, zinc and phosphorus content measure according to ASTM D6443.Nitrogen content measures according to ASTM D3228.Using 2.0L, 4- cylinder TGDI GM Ecotec electromotor, the program according to described in embodiment 1, LSPI test is carried out to formula.

The impact to LSPI of described test evaluation borated dispersants and the ZDDP derived from secondary alcohol.As shown in figure 3, using Borated dispersants and secondary ZDDP are unexpectedly beneficial to LSPI performance.Embodiment 1, comparative example 4, comparative example 5 and embodiment 3 All using the secondary ZDDP antiwear additive of same treatment rate, and described dispersant is in change.As the Boron contents in these admixtures refer to Show, increase with Boron contents, LSPI counts and unexpectedly reduces.Specifically, the embodiment 3 with about 507ppm boron only has 24 LSPI events, the comparative example 4 and 5 existing without boron is respectively provided with 46 and 43 LSPI events.Never boron, arrive 240ppm boron, arrive 507ppm boron, LSPI counts and be reduced to 27 from 46 respectively, to 24.That is, 40%LSPI is decreased with 240ppm boron Decrease 48%LSPI with about 507ppm boron.Described LSPI reduces estimated increasing with boron level and continues.It has been apparent from making With benefit together with secondary ZDDP for the borated dispersants.Comparative example 1 also by display borated dispersants and primary ZDDP inferior position, Demonstrate the uniqueness of borated dispersants and secondary ZDDP and unexpected benefit.When there is identical boron water with comparative example 1 When flat embodiment 1 compares, comparative example 1 shows, when described secondary ZDDP is converted to primary ZDDP, LSPI counts to be increased to from 27 34.

Comparative example 8 shows the example wherein not using dispersant, and LSPI is counted as 22.Although this with contain boric acid The admixture changing dispersant is essentially identical, but this further demonstrates borated dispersants and reduce in the oil for business application Effectiveness in LSPI.Typically require issuable greasy filth and other particulate matters during dispersant is used for being dispersed in normal operation Matter.Comparative example 4 compared with comparative example 4 it is shown that non-borated dispersants can cause LSPI to increase almost 100%, and boration Dispersant is applied in combination decreases LSPI frequency individually or with other non-borated dispersants.

Embodiment C

Formula preparation as shown in Figure 4.All the components as used herein are all commercially available.In described formula using III, IV and V class oil base stock.

Used in described formula, detersive is that (calcium salicylate 1, it contains 7.3%Ca and has middle TBN alkyl sodium salicylate Have about 200 TBN), low TBN alkyl sodium salicylate (calcium salicylate 2, it contains 2.3%Ca and about 65TBN), high TBN alkyl sulphur Sour calcium (sulfoacid calcium 1, it contains 11.6%Ca and about 300TBN), low TBN alkyl sulfonic acid calcium (sulfoacid calcium 2, its contain 2.0%Ca and About 8TBN) and high TBN alkyl sulfonic acid magnesium (sulfonic acid magnesium 1, it contains 9.1%Mg and about 400TBN).Described TBN scope is defined as： Low TBN about 0 to 100, middle TBN about 100 to 200 and high TBN about 200 up to 600.

Used in described formula, dispersant is boration butanimide and high molecular butanimide.

Used in described formula, antiwear additive is the ZDDP derived from the secondary alcohol and ZDDP derived from primary alconol.

Used in described formula, remaining composition is viscosity index improver, antioxidant, dispersant, antiwear additive, pour point Depressant, corrosion inhibitor, matal deactivator, sealing compatible additive, defoamer, inhibitor, rust-inhibiting additive and friction change Enter one or more of agent.

Formula described in Fig. 4 is tested.Result illustrates in Figure 5.Sulfated ash experimental evidence ASTM D874 Measure.Calcium, magnesium, boron, zinc and phosphorus content measure according to ASTM D6443.Nitrogen content measures according to ASTM D3228.Using 2.0L, 4- cylinder TGDI GMEcotec electromotor, the program according to described in embodiment 1, LSPI test is carried out to formula.

The impact to LSPI for the described three kinds of additive systems of test evaluation (i.e. detersive, dispersant and antiwear additive).As Fig. 5 Shown, to the formula containing non-borated dispersants with to the mixture containing non-borated dispersants and borated dispersants Formula measurement LSPI in the case of, had using boration succinimide dispersants and exceed high molecular butanimide and divide The LSPI benefit of the uniqueness of powder.Comparative example 6, embodiment 4 and embodiment 8 display increase the impact to LSPI performance for the Boron contents. Increase to 240 with Boron contents from 0, to 507ppm, LSPI counts and is down to 27 from 46, to 24.Boron is in reducing LSPI frequency Benefit represents the significant and unexpected discovery result presenting in figures 4 and 5.Embodiment 6 and embodiment 7 present sulphur The unique combination of the ZDDP of sour magnesium detersive and double dispersant systems and derived from secondary alcohols.Described pair of dispersant system contains boron source. By comparing it is shown that this uniqueness combining with comparative example 6, comparative example 6 employs different salicylic acid calcio detersives System simultaneously has the worst LSPI counting.Show the ZDDP using sulfonic acid magnesium detersive and derived from secondary alcohols and borated dispersants Even if not being to eliminate unexpected to substantially reduce LSPI yet.Desirable ([Mg]+[Ca]+[Zn]+[P])/([B]+[N]_Dispersant) Total concentration ratio be about 2.5 to 7, more preferably from about 3.3 to 5.Comparative example 4 compares to also demonstrate with embodiment 10 includes boration The effectiveness combining this approach of the ZDDP of dispersant and derived from secondary alcohols and sulfonic acid magnesium detersive and calcium salicylate detersive.Real Apply example 10 and show that LSPI reduces 98% compared with comparative example 6.

Embodiment D

Engine lubrication oil formula in Fig. 6 and 7 is that the group of additive and oil base stock merges expection and has 7.5- 8.5cSt about 100 DEG C when kinematic viscosity and high temperature high shear (10 when 150 DEG C of about 2.5 to 2.9cP^-6s^-1) viscosity.Real The engine lubrication oil formula applying P1, P2, P3 is expected that boron and dispersant nitrogen ratio are respectively 0.05,0.15 and 0.51.These Total Boron contents expected range in formula is from 50ppm to 800ppm.([Mg]+[Ca])/([B]+[N]_Dispersant) ratio expected range From 1.28 to the embodiment P1 of embodiment P3 2.91.Similarly, ([Zn]+[P])/([B]+[N]_Dispersant) ratio expected range from The 0.71 of embodiment P3 and the 1.62 of embodiment P1.Finally, ([Mg]+[Ca]+[Zn]+[P]) of embodiment P1, P2 and P3/ ([B]+[N]_Dispersant) ratio is it is contemplated that between 1.99 and 4.53.The engine lubrication oil formula of embodiment P4 and P5 is expected have The content of magnesium of 300ppm to 600ppm.Similarly, the engine lubrication oil formula of embodiment P6, P7 and P8 is expected have about The magnesium calcium ratio of the 1.21 of about 0.12 to the embodiment P8 of the content of magnesium of 300ppm to 900ppm and embodiment P6.Meanwhile, this The TBN of a little embodiments is from the P9 change of 6.8 to the embodiment P6 of embodiment P8.Similarly, the sulphuric acid in embodiment P4, P5 and P6 Salt content of ashes changes from 0.3 weight % to 1.2 weight % ash.In Fig. 6 and 7, other ratios of identification are also such as pointed wherein As change.The engine lubrication oil formula of embodiment P9 and P10 is expected to be respectively provided with about 0.06 and 3 under constant TBN Magnesium calcium ratio.The engine lubrication oil formula of embodiment P11, P12 and P13 is expected there is the pact from embodiment P13 for the scope The Zn content of 96ppm to the about 635ppm of embodiment P11.The engine lubrication oil formula of embodiment P11, P12 and P13 is expected tool There is the phosphorus content from the about 87ppm to the about 570ppm of embodiment P11 of embodiment P13 for the scope.([Mg]+[Ca])/([Zn]+ [P]) ratio ranges are from the 16.5 of about 2.5 to the embodiment P13 of embodiment P11.([Zn]+[P])/([B]+[N]_Dispersant) ratio model Enclose 0.15 of about 1 to the embodiment P13 from embodiment P11.([Mg]+[Ca]+[Zn]+[P])/([B]+[N]_Dispersant) ratio ranges From about 3.4 to c embodiment P13 of c embodiment P11 2.6.

Embodiment E

Engine lubrication oil formula in Fig. 8 and 9 is that the group of additive and oil base stock merges expection and has 5.5- 7.5cSt about 100 DEG C when kinematic viscosity and high temperature high shear (10 when 150 DEG C of about 2 to 2.5cP^-6s^-1) viscosity.Implement The engine lubrication oil formula of example P14, P15 and P16 is expected that boron and dispersant nitrogen ratio are respectively 0.05,0.15 and 0.51.This Total Boron contents expected range in a little formula is from 50ppm to 800ppm.([Mg]+[Ca])/([B]+[N]_Dispersant) the estimated model of ratio Enclose 2.91 of 1.28 to the embodiment P14 from embodiment P16.Similarly, ([Zn]+[P])/([B]+[N]_Dispersant) the estimated model of ratio Enclose 1.62 of 0.71 and embodiment P14 from embodiment P16.Finally, ([Mg]+[Ca]+[Zn] of embodiment P14, P15 and P16 +[P])/([B]+[N]_Dispersant) ratio is it is contemplated that between 1.99 and 4.53.The engine lubrication oil formula of embodiment P17 and P18 The estimated content of magnesium with 300ppm to 600ppm.Similarly, the engine lubrication oil formula of embodiment P19, P20 and P21 is pre- Meter has the magnesium calcium ratio of the 1.21 of the content of magnesium of about 300ppm to 900ppm and about 0.12 to the embodiment P21 of embodiment P19 Rate.Meanwhile, the TBN of these embodiments is from 9 changes of 6.8 to the embodiment P19 of embodiment P21.Similarly, embodiment P17, Sulfate ash content in P18 and P19 changes from 0.3 weight % to 1.2 weight % ash.Other ratios of identification in Fig. 8 and 9 Also change as pointed wherein.The engine lubrication oil formula of embodiment P22 and P23 is expected under constant TBN It is respectively provided with about 0.06 and 3 magnesium calcium ratio.The engine lubrication oil formula of embodiment P24, P25 and P26 is expected there is scope Zn content from the about 96ppm to the about 635ppm of embodiment P24 of embodiment P26.Embodiment P24, P25 and the electromotor of P26 Lubricant formula is expected there is the phosphorus content from the about 87ppm to the about 570ppm of embodiment P24 of embodiment P26 for the scope.([Mg] + [Ca])/([Zn]+[P]) ratio ranges are from the 16.5 of about 2.5 to the embodiment P26 of embodiment P24.([Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges are from the 0.15 of about 1 to the embodiment P26 of embodiment P24.([Mg]+[Ca]+[Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges are from the 2.6 of about 3.4 to the embodiment P26 of embodiment P24.

Embodiment F

Engine lubrication oil formula in Figure 10 and 11 is that the group of additive and oil base stock merges expection and has 9-11cSt Kinematic viscosity and high temperature high shear (10 when 150 DEG C of about 2.9 to 3.4cP when 100 DEG C of left and right^-6s^-1) viscosity.Embodiment The engine lubrication oil formula of P27, P28 and P29 is expected that boron and dispersant nitrogen ratio are respectively 0.05,0.15 and 0.51.These Total Boron contents expected range in formula is from 50ppm to 800ppm.([Mg]+[Ca])/([B]+[N]_Dispersant) ratio expected range From 1.28 to the embodiment P27 of embodiment P29 2.91.Similarly, ([Zn]+[P])/([B]+[N]_Dispersant) ratio expected range From 0.71 and embodiment P27 of embodiment P29 1.62.Finally, embodiment P27, P28 and P29 ([Mg]+[Ca]+[Zn]+ [P])/([B]+[N]_Dispersant) ratio is it is contemplated that between 1.99 and 4.53.The engine lubrication oil formula of embodiment P30 and P31 is pre- Meter has the content of magnesium of 300ppm to 600ppm.Similarly, the engine lubrication oil formula of embodiment P32, P33 and P34 is expected There is the 1.21 of the content of magnesium of about 300ppm to 900ppm and about 0.12 to the embodiment P34 of embodiment P32 magnesium calcium ratio. Meanwhile, the TBN of these embodiments is from 9 changes of 6.8 to the embodiment P32 of embodiment P34.Similarly, embodiment P30, P31, Sulfate ash content in P32 changes from 0.3 weight % to 1.2 weight % ash.Other ratios of identification in Figure 10 and 11 Change as pointed wherein.The engine lubrication oil formula of embodiment P35 and P36 is expected to divide under constant TBN Not there is about 0.06 and 3 magnesium calcium ratio.The engine lubrication oil formula of embodiment P37, P38 and P39 be expected to have scope from The Zn content of the about 96ppm of embodiment P39 to the about 635ppm of embodiment P37.The electromotor profit of embodiment P37, P38 and P39 Lubricating oil formula is expected there is the phosphorus content from the about 87ppm to the about 570ppm of embodiment P37 of embodiment P39 for the scope.([Mg]+ [Ca])/([Zn]+[P]) ratio ranges are from the 16.5 of about 2.5 to the embodiment P39 of embodiment P37.([Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges are from the 0.15 of about 1 to the embodiment P39 of embodiment P37.([Mg]+[Ca]+[Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges are from the 2.6 of about 3.4 to the embodiment P39 of embodiment P37.

All patents and patent applicationss of herein quoting, test procedure (such as ASTM method, UL method etc.) and its He is fully combined by quoting document, and reaching not inconsistent with the disclosure and this kind of combination of this kind of disclosure is all judiciaries The degree of license.

When herein listing numerical lower limits and numerical upper limits, the scope from any lower limit to any upper limit is desired 's.Although having specifically described the illustrated embodiment of the disclosure it should be appreciated that various other modification will be this area skill Art personnel are obvious and can make easily under without departing substantially from spirit and scope of the present disclosure.Therefore, be not intended to by The scope of the claim appended by here is limited to the embodiment herein illustrating and description, but described claim should be explained It is the feature including all patentable novelty being present in the disclosure, including will be by disclosure art All features that technical staff treats as its equivalent features.

More than have been made with reference to numerous embodiments and specific embodiment describes the disclosure.Opened by described above in detail Send out, many versions will emerge in those skilled in the art's brain.All so obviously change in claim Within complete preset range.

Claims (16)

1. in the electromotor of used-oil lubrication, prevent or reduce the side of low speed early combustion as lubricating oil by using formulated oil Method, described formulated oil has and comprises lube oil base stocks as key component and at least one zinc compound or at least Plant antiwear additive as the composition of accessory constituent；Wherein said at least one antiwear additive comprises at least one dioxane derived from secondary alcohol Base phosphordithiic acid zinc compound；And wherein averagely had with the braking of 2000 revs/min (RPM) operating and 18 bars in electromotor On the basis of effect pressure (BMEP), (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, described start The low speed that machine and the lubricating oil using do not comprise to reach at least one zinc compound or the electromotor of antiwear additive early fires performance Compare, early combustion reduces more than 20% to show low speed.

2. the method for claim 1 wherein that described accessory constituent also comprises at least one boron-containing compound, wherein said containing boronation Compound comprises at least one borated dispersants or boron-containing compound and the mixture of non-borated dispersants.

3. the method for claim 1 wherein that described accessory constituent also comprises at least one boron-containing compound and at least one is peace and quiet Agent, wherein said boron-containing compound comprises at least one borated dispersants or boron-containing compound and non-borated dispersants Mixture, and wherein said detersive comprises the alkali salt of at least one organic acid, and described at least one is organic The alkali salt of acid comprises the magnesium salt of at least one organic acid.

4. the method for claim 1-3, wherein said lube oil base stocks comprise I class, II class, Group III, IV class or V class base Plinth oil；It is that when 2% to 20% and 100 DEG C, kinematic viscosity is the ester of 2cSt to 8cSt that wherein said V class base oil comprises concentration Base oil, and described Group III base oil comprises GTL base oil.

5. the method for claim 1-4, wherein said zinc compound is selected from sulfonic acid zinc, zinc acetate, zinc naphthenate, alkenyl succinate Sour zinc, acid phosphate zinc salt, phenol zinc and zinc salicylate.

6. the method for claim 1-5, wherein said zinc dialkyl dithiophosphate compound is expressed from the next

Zn[SP(S)(OR¹)(OR²)]₂

Wherein R¹And R²It is independently primary or secondary C₁To C₈Alkyl group, condition is R¹And R²At least one be secondary C₁To C₈Alkyl Group.

7. the method for claim 1-6, wherein said zinc dialkyl dithiophosphate compound is derived from (i) C₃To C₈Secondary alcohol, or Its mixture；Or (ii) C₁To C₈Primary alconol and C₁To C₈The mixture of secondary alcohol.

8. the method for claim 2-7, wherein said boron-containing compound or borated dispersants be selected from boration butanimide, Boration succinate, boration succinate ester amides, boration Mannich base and its mixture；And described non-boration Dispersant comprises butanimide or the succinate derived from succinic anhydrides with coupling agent, and wherein said coupling agent comprises to contain Boron compound.

9. the method for claim 3-8, wherein in described lubricating oil, the total zinc from described zinc compound and antiwear additive adds The upper ratio divided by the total boron from described boron-containing compound and borated dispersants for total alkaline-earth metal being derived from described detersive It is 9.2 to 45.

10. the method for claim 3-9, the alkali salt of wherein said organic acid is selected from alkaline earth metal sulfonate, alkaline earth gold Belong to carboxylate, alkaline earth phenate, alkali earth metal phosphate and its mixture.

The method of 11. claim 3-10, wherein said detersive comprises (i) sulfonic acid magnesium, phenol magnesium, magnesium salicylate and its mixture In at least one, and optionally, at least one in sulfoacid calcium, phenol calcium, calcium salicylate and its mixture；(ii) at least one The magnesium salt of organic acid, it is selected from sulfonic acid magnesium, magnesium carboxylates, phenol magnesium, magnesium phosphate and its mixture；Or (iii) sulfonic acid magnesium, sulfonic acid magnesium With the mixture of the mixture, sulfonic acid magnesium and phenol magnesium of magnesium salicylate or the mixture of sulfonic acid magnesium and magnesium carboxylates.

Magnesium that the method for 12. claim 3-11, wherein (i) are contributed by described detersive and alkaline-earth metal are in described lubricating oil Existed with the amount of 500ppm to 5000ppm；(ii) total base number (TBN) contributed by described detersive, by ASTM D2896 measurement, Scope is from 2mg KOH/g to 17mg KOH/g；Or (iii) sulfated ash scope of being contributed by described detersive is from 0.4 to 1.7 Weight %.

13. engine lubricating oils, it has and comprises lube oil base stocks as key component and at least one zinc compound Or at least one antiwear additive is as the composition of accessory constituent；Wherein said at least one antiwear additive comprises at least one derived from secondary The zinc dialkyl dithiophosphate compound of alcohol；And wherein in electromotor with the system of 2000 revs/min (RPM) operating and 18 bars On the basis of dynamic mean effective pressure (BMEP), (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, Described electromotor and the lubricating oil using do not comprise the low speed reaching at least one zinc compound or the electromotor of antiwear additive Early combustion performance is compared, and shows low speed early combustion minimizing and is more than 20%.

The engine lubricating oil of 14. claim 13, wherein said accessory constituent also comprises at least one boron-containing compound, wherein Described boron-containing compound comprises at least one borated dispersants or boron-containing compound and the mixture of non-borated dispersants.

The engine lubricating oil of 15. claim 13, wherein said accessory constituent also comprises at least one boron-containing compound and extremely A kind of few detersive, wherein said boron-containing compound comprises at least one borated dispersants or boron-containing compound and non-boric acid Change the mixture of dispersant, and wherein said detersive comprises the alkali salt of at least one organic acid, and described extremely A kind of few alkali salt of organic acid comprises the magnesium salt of at least one organic acid.

To prevent as lubricating oil by using electromotor formulated oil in the electromotor of 16. used-oil lubrications or to reduce low speed The method of early combustion, the composition that described electromotor formulated oil has comprises lube oil base stocks and its load of 70 to 85 weight % Amount contributes at least one zinc compound of 400ppm to about 2000ppm phosphorus or at least one wear-resistant to described electromotor formulated oil Agent；Wherein said at least one antiwear additive comprises at least one at least partly zinc dialkyl dithiophosphate derived from secondary alcohol Compound；Wherein in electromotor with the basis of 2000 revs/min (RPM) operating and the brake mean-effective pressure (BMEP) of 18 bars On, (LSPI) is early fired based on standardization low speed and counts/25,000 cycle of engine, described electromotor is with the lubricating oil using not The low speed comprising to reach at least one zinc compound or the electromotor of at least one antiwear additive early fires performance to be compared, and shows Early combustion reduces more than 50% low speed.