CN106232785A - The method prevented or reduce low speed early combustion - Google Patents

Abstract

The invention provides in the electromotor of used-oil lubrication by the method using formulated oil to prevent as lubricating oil or to reduce low speed early combustion.Described formulated oil has and comprises lube oil base stocks as key component and at least one boron-containing compound as the composition of accessory constituent.At least one boron-containing compound described comprises at least one borated dispersants or boron-containing compound and the mixture of non-borated dispersants.Present invention also offers to have and comprise lube oil base stocks as key component and at least one boron-containing compound as the engine lubricating oil of the composition of accessory constituent.The lubricating oil of the disclosure is advantageous particularly as passenger car engine machine oil (PVEO) product.

Description

The method prevented or reduce low speed early combustion

Technical field

It relates to by using formulated oil prevent as lubricating oil or subtract in the electromotor of used-oil lubrication Few low speed early fires the method for (LSPI), and described formulated oil has at least one boracic being present in described formulated oil with specified quantitative Compound, a kind of borated dispersants or boron-containing compound and the mixture of dispersant.The lubricating oil of the disclosure can As passenger car engine machine oil (PVEO) product.

Background technology

Combustion morning propagated in (or " spark ignition ") electromotor at flame described before plug ignition in cylinder 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 overheated spark plug or combustor and be heated to red-hot by engine combustion event before in the application Carbon distribution.

The turbo supercharging gasoline engine that many railway car manufacture business produce at them has been observed that intermittent early combustion, spy Not under low speed and middle high load capacity.Under these loads raised, early combustion often results in serious combustion knock, and it can damage sends out Motivation.Early the reason of combustion is understood the most completely, and may be in fact owing to boiling hot sinking in multiple phenomenon, such as combustor Amass thing, cross turbocharger compressor seal or oil from level rising, the oil seepage of the lubricant vapors of Pcv system entrance And/or fuel droplet lights during compression stroke automatically.

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

Low speed early combustion (LSPI) is that impact is sent out when brake mean-effective pressure (BMEP) is high and engine speed (RPM) is low The abnormal combustion type of motivation operating.This includes using various fuel to include natural gas, gasoline, diesel oil, biomass fuel The explosive motor of material etc..Turbocharged engine miniaturization, slow-revving is most susceptible under these engine conditions The impact of operating, is therefore affected more susceptible to LSPI.Because auto industry is moving towards further miniaturization, the slow-speed of revolution always Change and improve turbocharging to improve auto fuel economy and to reduce CO2 emission, so the hidden danger on LSPI is being held Continuous growth.

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

Although early combustion problem can and by optimizing internal engine parts and by the new component technology of use such as Electronic Control solves, but amendment is desirable for lubricating the lubricant oil composite of such electromotor.Such as, including exploitation In burn engine particularly useful and will prevent or minimize the new oil formula early firing problem when for explosive motor, 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.

Summary of the invention

Disclosure part relates 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 at the electromotor already designing or commercially selling and will The engine technology come prevents or controls the ill-effect of LSPI.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 hindered by LSPI at present can be sent out further Exhibition.Made the product can be in terms of LSPI by what the disclosure provided for preventing or reduce the lubricant formulations solution of LSPI Segmentation.

The disclosure also relates in part in the electromotor that used-oil lubricates by using formulated oil to prevent as lubricating oil 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 Plant the boron-containing compound composition as accessory constituent.At least one boron-containing compound described comprises the dispersion of at least one boration Agent or boron-containing compound and the mixture of dispersant.Put down with the braking of 2000 revs/min (RPM) operating and 18 bars at electromotor All on the basis of effective pressure (BMEP), based on standardization low speed early/25,000 cycle of engine of combustion (LSPI) counting, and make Lubricating oil do not comprise at least one borated dispersants or boron-containing compound and non-borated dispersants mixture send out The low speed reached in motivation early combustion performance compares, and described electromotor shows low speed early combustion to be reduced more than 50%.

The disclosure also relates in part in the electromotor by described oil lubrication by using formulated oil as above The method prevented as lubricating oil or reduce low speed early combustion, wherein said accessory constituent also comprises at least one detersive.Institute State the alkali salt that detersive comprises at least one organic acid, and the alkali salt of at least one organic acid described comprises The magnesium salt of at least one organic acid.

The disclosure also relates in part in the electromotor that used-oil lubricates by using formulated oil conduct as above The method that lubricating oil prevents or reduces low speed early combustion, wherein said accessory constituent also comprises at least one detersive and at least A kind of zinc compound or at least one antiwear additive.Described detersive comprises the alkali salt of at least one organic acid, and The alkali salt of at least one organic acid described comprises the magnesium salt of at least one organic acid.At least one antiwear additive described comprises At least one is derived from secondary alcohol or partly derived from the zinc dialkyl dithiophosphate compound of secondary alcohol.

The disclosure also relates in part to engine lubricating oil, and it has and comprises lube oil base stocks as key component and extremely Few a kind of boron-containing compound is as the composition of accessory constituent.At least one boron-containing compound described comprises at least one boration and divides Powder and/or boron-containing compound and the mixture of non-borated dispersants.Electromotor with 2000 revs/min (RPM) operating and On the basis of the brake mean-effective pressure (BMEP) of 18 bars, count/25,000 based on the early combustion (LSPI) of standardization low speed and send out Motivation circulates, and described electromotor and the lubricating oil of use do not comprise at least one borated dispersants or boron-containing compound and non- The low speed reached in the electromotor of the mixture of borated dispersants early combustion performance compares, and shows low speed early combustion minimizing and is more than 50%.

The disclosure also relates in part to engine lubricating oil as above, and wherein said accessory constituent also comprises at least one Detersive.Described detersive comprises the alkali salt of at least one organic acid, and the alkaline earth of at least one organic acid described Slaine comprises the magnesium salt of at least one organic acid.

The disclosure also relates in part to engine lubricating oil as above, and wherein said accessory constituent also comprises at least one Detersive and at least one zinc compound or at least one antiwear additive.Described detersive comprises the alkali of at least one organic acid Earth metal salt, and the alkali salt of at least one organic acid described comprises the magnesium salt of at least one organic acid.Described at least A kind of antiwear additive comprises at least one zinc dialkyl dithiophosphate compound derived from secondary alcohol.

It has been surprisingly found that according to the disclosure, in the electromotor of used-oil lubrication, comprise at least one by use Kind of boron-containing compound (such as, boration butanimide), preferably at least a kind of borated dispersants or boron-containing compound and non- The formulated oil of the mixture of borated dispersants, as lubricating oil, can realize preventing or reducing LSPI, and described boron-containing compound exists Described lubricating oil exists with specific amount (such as, gross weight based on described lubricating oil from about 0.1 to about 20 weight %).Special Not, for the lubricant formula containing at least one boron-containing compound described, it has been surprisingly found that electromotor with On the basis of the brake mean-effective pressure (BMEP) of 2000 revs/min (RPM) operating and 18 bars, based on the early combustion of standardization low speed (LSPI)/25,000 cycle of engine of counting, the lubricating oil of described electromotor and use does not comprise at least one boration and divides Powder or boron-containing compound compare with the low speed reached in the electromotor of the mixture of non-borated dispersants early combustion performance, Show low speed early combustion and reduce greater than about 50%.It addition, it has been surprisingly found that according to the disclosure, had specific by use The formulated oil of oil base stock (such as, natural gas liquefaction (gas-to-liquids) oil base stock or ester base oil material) as profit Lubricating oil, can realize reducing LSPI in the electromotor by described oil lubrication.

The disclosure further relates in the electromotor by described oil lubrication by using electromotor formulated oil as lubrication The method that oil prevents or reduces low speed early combustion, the composition that described electromotor formulated oil has comprises 70 to 85 weight % at least A kind of lube oil base stocks and at least one dispersion to described electromotor formulated oil contribution 30 to 1500ppm boron of its load capacity Agent；At least one dispersant wherein said comprises at least one borated dispersants or boron-containing compound and the dispersion of non-boration The mixture of agent, the brake mean-effective pressure (BMEP) wherein operated with 18 bars with 2000 revs/min (RPM) at electromotor On the basis of, based on standardization low speed early/25,000 cycle of engine of combustion (LSPI) counting, described electromotor and the lubrication of use The electromotor of the mixture that oil does not comprise at least one borated dispersants or boron-containing compound and non-borated dispersants reaches To low speed early combustion performance 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.

Accompanying drawing explanation

The all concentration pointed out in the drawings are all based on " delivery status " and quote.

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

Fig. 2 figure depicts such as the thermal gravimetric analysis curve of the three kinds of different dispersants described in detail in embodiment A.

Fig. 3 shows various lubricant formula total weight percent based on described formula formula by weight percentage Detail, as described in detail in embodiment B.

Fig. 4 shows the result of the test of the various lubricant formulas illustrated in Fig. 3, as described in detail in embodiment B.

Fig. 5 shows various lubricant formula total weight percent based on described formula formula by weight percentage Detail, as described in detail in embodiment C.

Fig. 6 shows the result of the test of the various lubricant formulas illustrated in Fig. 5, as described in detail in embodiment C.

Fig. 7 shows the Formulation Implementation mode total weight percent based on described formula of the disclosure by weight percentage Formula detailed, as embodiment D describes in detail.

Fig. 8 shows the expection result of the test of the various lubricant formulas of Fig. 7, as described in detail in embodiment D.

Fig. 9 shows the Formulation Implementation mode total weight percent based on described formula of the disclosure by weight percentage Formula detailed, as embodiment E describes in detail.

Figure 10 shows the expection result of the test of the various lubricant formulas of Fig. 9, as described in detail in embodiment E.

Figure 11 shows the Formulation Implementation mode total weight percent based on described formula of the disclosure by weight percentage The formula of meter is detailed, as described in detail in embodiment F.

Figure 12 shows the expection result of the test of the various lubricant formulas of Figure 11, as described in detail in embodiment F.

Figure 13 shows the engine performance mapping result as described in detail in embodiment A.

Detailed description of the invention

All numerical value in detailed description and claims herein are modified described indicated value by " about " or " about ", 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, comprise at least one boron-containing compound by use (such as, boration butanimide), preferably at least a kind of borated dispersants or boron-containing compound and non-borated dispersants The formulated oil of mixture as lubricating oil, can realize preventing or reducing LSPI, described boron-containing compound is in described lubricating oil Exist with specific amount (such as, gross weight based on described lubricating oil from about 0.1 to about 20 weight %).Further, it has been found that In the electromotor of used-oil lubrication, there is the formulated oil of specific oil base stock as lubricating oil by use, can realize Reduce LSPI.Described formulated oil preferably has and comprises lube oil base stocks as key component and at least one boracic chemical combination Thing is as the composition of accessory constituent.At least one boron-containing compound described comprises at least one borated dispersants or containing boronation Compound and the mixture of non-borated dispersants.The lubricating oil of the disclosure includes natural gas, gasoline, bavin at the various fuel of use Various in the explosive motor of oil, bio-fuel etc. with for including bus engine oil and gas engine oil Apply advantageous particularly.

The lubricating oil of the disclosure is particularly useful in explosive motor, and will prevent when for explosive motor or Littleization early combustion 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 may be used for already designing or commercially selling Electromotor and engine technology in the future prevent or control the ill-effect of LSPI.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 hindered by LSPI at present Can develop further.Product energy is made for preventing or reduce the lubricant formulations solution of LSPI by what the disclosure provided Enough segmentations in terms of LSPI.

Lube oil base stocks

Far-ranging lubricating base oil 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 unpurified, refined or that re-refine (the latter also known as regeneration or reprocessed oils) can be used Unconventional oil (or its mixture).Unrefined oil is to directly obtain from naturally occurring or synthetic source and do not purified just to use Those oil.These include the shale oil directly obtained from retorting operation, the oil directly obtained from primary distillation and from esterification The ester oil that process directly obtains.Refined oil is similar to the oil being discussed unrefined oil, and simply refined oil experienced by one or many 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, acid extraction, alkaline extraction, filtration and diafiltration.Rerefined oils is obtained by the method being similar to refined oil Arrive, but as the used oil of raw material before using.

I, II, III, IV and V class is by American Petroleum Institute (API) (American Petroleum Institute) (API Publication 1509；www.API.org) the big class of oil base stock that develops and specify, to set up 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 be less than about 90% saturated hydrocarbons.II class oil base stock has the viscosity index (VI) between about 80 to 120 and containing less than or equal to about 0.03% sulfur With greater than or 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 being not included in I-IV class Interior oil base stock.Following table summarizes this respective character of five classes.

Natural oil includes animal oil, vegetable oil (such as Oleum Ricini and Adeps Sus domestica) and mineral oil.Can use have favourable 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, such as, by they be paraffin, cycloalkanes or blended wax-cycloalkanes.Derived from coal or the oil of shale Also it is available.Natural oil is also by different for their production and the method for purification, and such as their boiling range is straight with them That evaporate 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, be also known oil base stock oil.

Artificial oil includes hydrocarbon ils.Hydrocarbon ils include such as being polymerized oil such with mutual polyolefin (such as, 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 utilize derived from C₆、C₈、C₁₀、C₁₂、C₁₄Alkene or the PAO of its mixture.See 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 is 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 Often comprising the relatively low hydropolymer of the molecular weight ratio of alhpa olefin or oligomer, described alhpa olefin includes but not limited to, 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 and mixture thereof, and mixed olefins Derivative polyolefin.But, at C₁₄To C₁₈In the range of the dimer of higher olefins can be used to provide volatility low can The low viscosity oil base stock accepted.Depending on viscosity grade and starting oligomer, described PAO can be mainly described starting olefin Trimer and the tetramer, with a small amount of higher oligomer, there is the range of viscosities of 1.5 to 12cSt.Concrete application PAO fluid can include 3.0cSt, 3.4cSt and/or 3.6cSt and combinations thereof.It is possible if desired to use have 1.5 to The bimodal compound of the PAO fluid of 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 manufacture easily, described Friedel-Crafts catalyst includes, such as, aluminum chloride, boron trifluoride or boron trifluoride With water, alcohol such as ethanol, propanol or the complex of butanol, carboxylic acid or ester such as ethyl acetate or ethyl propionate.Such as by the U.S. Disclosed in patent No.4,149,178 or 3,382,291, method can be conveniently used at this.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.), hydroisomerization Fischer-Tropsch (Fischer-Tropsch) wax, natural gas liquefaction (GTL) oil base stock and base oil and other wax isomerization oil add The oil base stock of hydrogen isomerization and base oil or its mixture.Fischer-tropsch wax, the high boiling point residual oil of Fiscber-Tropscb synthesis, is sulfur content Low-down higher paraffins hydrocarbon.Amorphous can be used to be hydrocracked/be hydrogenated with for producing the hydrotreating of such oil base stock Isomerization catalyst, such as special lube are hydrocracked (LHDC) catalyst or crystalline hydrocracking/hydroisomerization catalytic One of agent, preferred zeolite catalyst.Such as, 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 integrally joined to herein with it by quoting.Manufacture is hydrocracked/hydro-isomerised fraction oil and Be hydrocracked/method of hydroisomerized wax such as, 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 specially Each being integrally joined to herein with them of profit.Particularly advantageous method at 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, Describing the method utilizing fischer-tropsch wax to feed in 672, the disclosure of which is by quoting being integrally joined to herein with them.

Base oil that natural gas liquefaction (GTL) base oil, fischer-tropsch wax are derivative and the derivative hydroisomerization (wax of other wax Isomerized oil) base oil the most advantageously uses, and can have during 100 DEG C of about 3cSt to about 50cSt effective Kinematic viscosity, preferably from about 3cSt are to about 30cSt, more preferably from about 3.5cSt to about 25cSt, with kinematic viscosity when 100 DEG C about As a example by the GTL4 of 4.0cSt and viscosity index (VI) about 141.The basis that these natural gas liquefaction (GTL) base oils, fischer-tropsch wax are derivative The hydroisomerizing base oil that oil and other wax derive can have effective pour point of about-20 DEG C or lower, and at some The favourable pour point of about-25 DEG C or lower, and effectively pour point about-30 DEG C to about-40 DEG C or lower can be had under part.Can use Base oil that natural gas liquefaction (GTL) base oil, fischer-tropsch wax are derivative and the derivative hydroisomerizing base oil compositions of wax are in example Such as United States Patent (USP) No.6,080,301；6,090,989 and 6, to enumerate in 165,949, described patent is whole by quote with them Body is incorporated herein.

Described alkyl aromatic hydrocarbons can serve as base oil or base oil component and can be containing its weight at least about 5% to spread out It is conigenous aromatic fractions such as benzene-type part or any hydrocarbyl molecular of cycloalkanes type part, or their derivant.These alkyl virtues Hydrocarbon includes that alkylbenzene, alkylnaphthalene, alkyl diphenyl ether, alkyl naphthol, alkyl diphenyl sulfur, alkylated bisphenols A, alkyl sulfur are 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 relevant hydrocarbyl groups is constituted.Described hydrocarbyl group can be with scope from about C₆Until about C₆₀, the most about C₈To about C₂₀Scope often preferably.The mixture of hydrocarbyl group the most preferably, and can exist most about three so Substituent group.Described hydrocarbyl group can optionally contain the substituent group of sulfur-bearing, oxygen and/or nitrogen.Described aromatic group can also spread out Being conigenous natural (oil) source, condition is that at least about the 5% of described molecule is made up of the aromatic fractions of the above-mentioned type.For described For alkyl aromatic component, viscosity about 3cSt when preferably 100 DEG C to about 50cSt, the most more preferably viscosity about 3.4cSt To about 20cSt.In one embodiment, the alkylnaphthalene that wherein alkyl group is mainly made up of is used 1-hexadecylene.Aromatic hydrocarbons Other alkylates can also advantageously use.Such as, naphthalene or methyl naphthalene can by alkene such as octene, decene, laurylene, ten Tetraene or higher level alkene, the alkylation such as mixture of similar alkene.In lubricant oil composite, the valid density 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 produces.See " Friedel-Crafts and relevant 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. See " Friedel-Crafts and relevant reaction ", volume 2, part 1, the 14th, 17 and 18 chapters, see Olah, G.A. and (compile Write), Inter-science Publishers, New York, 1964.Many homogeneous or heterogeneous solid catalysts are this areas Known to the skilled person.Reactivity and the product quality requirement of parent material is depended in the selection of catalyst.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 the polynary of ester, such as binary acid and the list ester of alkanol and monocarboxylic acid Alcohol ester, it can be ensured that additive dissolving power and sealing compatible properties.The ester of former type includes, such as, dicarboxylic acids is the most 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 most own ester of fumaric acid two, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, neighbour Double eicosyl ester of phthalic acid didecyl, decanedioic acid etc..

Useful especially synthetic ester is that (such as neopentyl is polynary by one or more polyhydric alcohol, preferred hindered polyhydric alcohols Alcohol such as neopentyl glycol, trimethylolethane, 2-methyl-2-propyl-1,3-propylene glycol, trimethylolpropane, tetramethylolmethane and Dipentaerythritol) those esters of obtaining with reacting containing the alkanoic acid of 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 branched chain fatty acid or unsaturated fatty acid such as oleic acid accordingly, or the mixture of these materials any.

Suitably synthetic ester component includes trimethylolpropane, tri hydroxy methyl butane, trimethylolethane, tetramethylolmethane And/or dipentaerythritol contains the ester of the monocarboxylic acid of carbon atom from about 5 to about 10 or more with one or more.These esters are Widely commercially available, such as, 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 is to about 30cSt, more preferably from about 3.5cSt to about 25cSt, and the most 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 radicis, Petiolus Trachycarpi, Semen Brassicae campestris, 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, such as, The Mobil P-51 ester of ExxonMobil Chemical Company.

Within motor oil formulations containing renewable ester is included in the disclosure.For such formula, described ester can Regeneration content is generally greater than about 70 weight %, preferably greater than about 80 weight % most preferably greater than about 90 weight %.

Other available fluids of lubricant viscosity include unconventional or unconventional oil base stock, and it is the most 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 skies So mixture of the oil base stock of gas liquefaction (GTL) material, and derived from native paraffin or the isomerized oil/isomery of 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 the waxy material that oil or even non-petroleum derive such as obtains from coal liquefaction or shale oil, and such base oil The mixture of material.

GTL material be via one or more synthesize, combine, convert, reset and/or degrade/deconstruction is from as former Material gaseous carbon, hydrogen-containing compound and/or element such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, The material that ethylene, acetylene, propane, propylene, propine, butane, butylene and butine are derivative.GTL oil base stock and/or base oil are logical Often derived from hydrocarbon, the GTL material of the lubricant viscosity of such as content of wax synthesis hydrocarbon, simpler derived from as raw material of described hydrocarbon itself Gaseous carbon, hydrogen-containing compound and/or element.GTL oil base stock and/or base oil include that boiling point boils at lubricating oil Oil in journey, described oil (1) such as divides 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 synthesized, comprises, such as, Hydrodewaxing or hydroisomerisation catalysts and/ Solvent dewaxing synthesis wax or waxy hydrocarbon；(3) Hydrodewaxing or the catalyst/of hydroisomerization or the Fischer-Tropsch of solvent dewaxing (Fischer-Tropsch, F-T) material (that is, hydrocarbon, waxy hydrocarbon, wax and possible similar oxygenate)；Preferably Hydrodewaxing or add Hydrogen isomerization/be followed by catalyst and/or solvent dewaxing and the F-T waxy hydrocarbon that dewaxes or Hydrodewaxing or hydroisomerization/continue The F-T wax that dewaxes or its mixture with catalyst (or solvent) dewaxing.

The wax of catalyst and/or solvent dewaxing it is followed by derived from GTL material, especially Hydrodewaxing or hydroisomerization Or the GTL oil base stock of wax feed and/or the material derived oil base stock of base oil, preferably F-T and/or base oil, generally To have about 2mm²/ s to about 50mm²During 100 DEG C of/s, kinematic viscosity (ASTM D445) is characterized.They are the most generally with tool The pour point (ASTM D97) having-5 DEG C to about-40 DEG C or lower is characterized.They are the most 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 the such material in the wide range of viscosities reclaimed in process of production each fraction, two or more such evaporate Point mixture and one or both or more kinds of low viscosity fraction with a kind of, two or more viscosity higher fractions Mixture is to produce admixture, and wherein said admixture shows target kinematic viscosity.

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

It addition, described GTL oil base stock and/or base oil are typically (> 90% saturated hydrocarbons of high paraffin hydrocarbon), and permissible The mixture combined with non-annularity isoparaffin containing monocycle paraffin hydrocarbon and multi-ring paraffin hydrocarbon.Cycloalkanes (i.e. ring in such combination Paraffin hydrocarbon) ratio of content changes with the catalyst used and temperature.It addition, GTL oil base stock and/or base oil and add Hydrogen dewaxing or hydroisomerization/oil base stock that dewaxes of catalyst (and/or solvent) and/or base oil be generally of the lowest Sulfur and nitrogen content, each is less than about 10ppm and more typically less than about 5ppm to typically contain these elements.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.It addition, there is not phosphorus and virtue Hydrocarbon makes this material be particularly suitable for allocating low-sulfur, sulfated ash and the product of 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 With any one and mixture thereof of the various oil of V class oil, preferably API II class, Group III, IV class and V class oil and mixture thereof, more Preferably Group III is to V class base oil, because the volatility of they excellences, stability, viscosimetric analysis and spatter property feature.Above-mentioned base Plinth oil plant, when combining in the disclosure disclosed additive component and using, can be used for allocating the LSPI performance with excellence SAE 0W-8、SAE 0W-12、SAE 0W-16、SAE 0W-20、SAE 0W-30、SAE 0W-40、SAE 5W-12、SAE 5W- 16, SAE 5W-20, SAE 5W-30 and SAE 10W-40 product.These oil base stock are when in conjunction with interpolation disclosed in the disclosure When agent component uses, in allotment, there is the SAE 0W-8 of LSPI performance of excellence, SAE 0W-12, SAE 0W-16, SAE 0W- 20, the most effective in 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 based on described combination The gross weight of thing, generally with weight % from about 50 to about 99, preferably from about 70 to about 95 weight % more preferably from about 85 to about The amount of 95 weight % exists.Described base oil can be selected from the crankcase profit being typically used as spark ignition and compression ignition engine Any synthesis of lubricating 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 about 2.5cSt to about 9cSt (or the mm when 100 DEG C²/ s), and more preferably 100 DEG C time about 3.5cSt to about 7cSt (or mm²/ s) and the most more preferably when 100 DEG C about 3.5cSt to about 5cSt (or mm²/s).It is possible if desired to use synthesis and the mixture of natural foundation oil.It is possible if desired to be preferably used The mixture of III, IV and V class.

Dispersant

During electromotor operates, produce the oxidized byproduct insoluble in oil.Dispersant helps to keep these by-products In the solution, thus reduce they depositions on the metal surface.The dispersant used in described lubricant formula can this It it is ashless in matter or one-tenth ash.The most described dispersant is ashless.So-called ashless dispersant is the most substantially It is formed without ash or the little organic material of ash.Such as, the dispersant without metal or without boration metal is considered as nothing Ash.On the contrary, discussed above ash is formed after combustion containing metal detergent.

At least one boron-containing compound can be used in the disclosure.Described boron-containing compound comprises the dispersion of at least one boration Agent, or boron-containing compound and non-boration or the mixture of borated dispersants.Described formula divides from described boration The effective range of the boron of powder or other boron-containing additives from 30ppm to 1500ppm, or more preferably scope from 60ppm to 1000ppm, or most preferred range is from 120ppm to 600ppm.

Preferably, described boron-containing compound includes, such as, and boration butanimide, boration succinate, boration Succinate ester amides, boration Mannich (Mannich) alkali and mixture thereof.

Described non-borated dispersants includes, such as, with the butanimide that the hydrocarbyl succinic anhydride of coupling agent is derivative Or succinate, wherein said coupling agent comprises boron-containing compound.

Preferably, boron is by organic or inorganic boron-containing compound and the mixture of boration butanimide and/or containing boronation Compound and hydrocarbyl succinimide and/or boration butanimide, boration succinate, boration succinate ester amides, Mannich base ester or its mixture are supplied to described lubricating oil.The most single butanimide of described boration butanimide, Double amber imide or its mixture.Effective boron-containing compound includes boration hydrocarbyl succinimide, including several equal molecules Amount (M_n) derivative those in alkyl source between 50 and 5000 dalton, boration hydrocarbyl succinic acid esters, boration alkyl takes The Mannich base in generation, boration alcohol, borated alkoxylated alcohol, boration hydrocarbon based diol, boration alkylamine, boration alkyl Diamidogen, boration alkyl triamine, borated alkoxylated alkylamine, borated alkoxylated hydrocarbyl amide, boracic acidifying alkyl Hydroxy ester, the substituted oxazoline of boration alkyl, boration alkyl substituted imidazolone, etc., and organic boric acid ester Mixture.The borate of N-H and/or OH derivative moiety can also be used.These borates can be inorganic or organic moiety Derivative borate.Borate can utilize boric acid, boration alcohol etc. to prepare.These borates can be as required to start Machine oil formula provides 30 to 1500ppm boron, 60-1200ppm boron, 60-240ppm boron, 240-1200ppm boron, 240-500ppm The concentration of boron or 60-120ppm boron uses, to produce the surprising improvement of beyond thought LSPI performance.

In described lubricating oil, from total plus from described detersive of 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.

Suitably dispersant usually contains the polar group being connected on the hydrocarbon chain that molecular weight is of a relatively high.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, generally by the substituted succinic acid compound of long chain hydrocarbon groups, the typically substituted succinic anhydrides of alkyl 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 and known in document.Describe 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, such as, and european patent application No.471 071, for such purpose it is carried out reference.

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

Butanimide is to be formed by the condensation reaction between the substituted succinic anhydrides of alkyl and amine.Mol ratio is permissible Depend on that polyamines changes.Such as, the substituted succinic anhydrides of alkyl and ethylene amines (such as, diethylenetriamines, triethylene Tetramine, tetren, six ethylidene seven amine, seven ethylidene eight amine etc.) mol ratio.Containing tetren (TEPA) Polyethylene amine often preferably.The high molecular comprising six ethylidene seven amine and seven ethylidene eight amine can also be used many Ethylene amines bottoms.The substituted succinic anhydrides of alkyl can become from about 1:1 to about 5:1 with the ratio of polyethylene amine 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 in Canadian Patent No.1,094,044.

Succinate is formed by the condensation reaction between the substituted succinic anhydrides of alkyl and alcohol or polyhydric alcohol.Mol ratio can To depend on that used alcohol or polyhydric alcohol change.Such as, the substituted succinic anhydrides of alkyl and the condensation product of tetramethylolmethane It it is useful dispersant.

Succinate ester amides is formed by the condensation reaction between the substituted succinic anhydrides of alkyl and alkanolamine.Such as, close Suitable alkanolamine includes that the many alkyl polyamines of ethoxylation, the many alkyl polyamines of propoxylation and the most ethylene of polyene-based polyamines are many Amine.One example is propoxylation diamidogen.Representational example shows in United States Patent (USP) No.4,426,305.

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

Mannich base dispersants is made up of the reaction of alkyl phenol, formaldehyde and amine.See United States Patent (USP) No.4,767,551, its It is incorporated herein.Processing aid and catalyst, such as oleic acid and sulfonic acid, it is also possible to be described reactant mixture Part.The molecular weight ranges of described alkyl phenol is 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；Show in 3,803,039.

The Mannich condensation product that can be used for the typical high molecular weight aliphatic acid in the disclosure modified can be from macromolecule Measure the substituted hydroxy arene of alkyl or containPrepared by the reactant of group.

It is to well known to a person skilled in the art that alkyl replaces amine ashless dispersants agent addition agent；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 1000 to about 2000 daltonian polyisobutylene, or the mixing of such hydrocarbon alkenyl group, described hydrocarbon alkenyl group often with Senior terminal ethylene group.Can be used for the preferred dispersant in the disclosure and be characterized as the M of low-molecular-weight_nIt is about 800 to 1700 Dalton, and the M of high molecular_nIt 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 Amount %.The hydrocarbon part of described dispersant atom can be with scope from C₆₀To C₄₀₀, or from C₇₀To C₃₀₀, or from C₇₀To C₂₀₀.These points Powder can contain neutral and both basic nitrogens, and the mixing of the two.The ratio of described dispersant neutral and alkali and non basic nitrogen can With scope from 1 to 5 to 5 to 1 or more preferably from 1 to 2 to 2 to 1.Dispersant can by borate and/or cyclic carbonate and or Any carboxylic acid such as hydrocarbon carboxylic acids or hydrocarbon carboxylic acids acid anhydride end-blocking.

According to the disclosure, at electromotor with 2000 revs/min (RPM) operating and the brake mean-effective pressure of 18 bars (BMEP) on the basis of, based on standardization low speed early/25,000 cycle of engine of combustion (LSPI) counting, electromotor and use Lubricating oil contains accessory constituent and its amount difference in described lubricating oil being different from least one boron-containing compound described The low speed reached in the electromotor of the amount of at least one boron-containing compound described early combustion performance compares, and shows low speed early combustion Reduce by greater than about 50%, preferably greater than about 70%, and more preferably greater than about 80%.As described herein, similar or the highest Low speed early combustion minimizing can utilize at least one boron-containing compound described and at least one detersive, the preferably detersive in magnesium And/or obtain with the mixture of at least one zinc compound or at least one antiwear additive.

With time in this article, described dispersant concentration is given based on " delivery status ".Generally, described active dispersing agents with add Work oil is paid together.Described " delivery status " dispersant generally contains from about 20 weights 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, such as, 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 described molecule long-chain hydrophobic part 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 at least one organic acid described to comprise at least one organic The magnesium salt of acid.

Can be used for the preferred detersive in the lubricating oil of the disclosure selected from alkaline earth metal sulfonate, alkaline earth metal carboxylation (such as salicylate), alkaline earth phenate, alkali earth metal phosphate and mixture thereof.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 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 reached in the electromotor of hydrochlorate and mixture thereof the amount in lubricating oil early combustion performance compares, described alkaline-earth metal sulphur Hydrochlorate, alkaline earth metal carboxylation, alkaline earth phenate, alkali earth metal phosphate and mixture thereof, and described alkaline-earth metal sulphur Hydrochlorate, alkaline earth metal carboxylation, alkaline earth phenate, alkali earth metal phosphate and mixture thereof the amount foot in described lubricating oil Reduce so that described electromotor shows low speed early combustion.

Can be used for the alkaline-earth metal detersive in the disclosure to be prepared 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 remove subsequently acid sludge and purify and prepare those.The alkaryl of synthesis Sulfonic acid is generally prepared from the Friedel-Crafts product of alkylated benzenes such as benzene and polymer such as tetrapropylene.Below It it is the instantiation of sulfonic acid available in the alkaline earth metal sulfonate detersive that preparation can be used in the disclosure.Should be understood that this The example of sample also functions to illustrate the effect of the alkali salt of such sulfonic acid.In other words, to every kind of cited 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, list and the substituted LOMAR PWA EINECS 246-676-2 of many wax, 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, saturated paraffin sulfonic acid, unsaturated paraffin sulfonic acid, hydroxyl take The paraffin sulfonic acid in generation, four pib sulfonic acids, four pentenesulfonic acid, chlorine substituted paraffin sulfonic acid, nitroso-group substituted paraffin sulfonic acid, stone Oil ring alkyl sulfonic acid, cetyl cyclopenta sulfonic acid, lauryl cyclamic acid, list and the substituted cyclamic acid of many wax, 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, 2,3 or more side chain C₁₂The acid that the benzene of substituent group is derived.Detergent alkylate bottoms, the most single-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 mixture thereof.

Alkaline earth phenates is available detersive classification.These detersives can pass through alkaline earth metal hydroxide or oxide (such as, CaO, Ca (OH)₂, BaO, Ba (OH)₂, MgO, Mg (OH)₂) react with alkyl phenol or sulfenyl phenolate and make.Available Alkyl group include straight or branched C₁-C₃₀Alkyl group, it is preferable that C₄-C₂₀Or its mixing.The suitably example of phenol includes Isobutyl group phenol, 2-ethylhexyl phenol, nonyl phenol, dodecylphenol etc..It should be noted that initial alkyl phenol can be containing 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.), the most described phenol red and alkaline-earth metal alkali reaction.

Preferably phenates compound includes, such as, and phenol magnesium, phenol calcium, high alkalinity phenates compound, the phenol of sulfuration/carbonating Calcium compounds and mixture thereof.

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 and at least one carboxylic acid reaction also remove free water from product and prepare.These compounds can be overbasic, The TBN level wanted with generation.

The detersive made by salicylic acid is the detersive classification of a kind of preferred derived from carboxylic acid.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 the integer of 1 to 4, and M is alkaline-earth metal.Preferably R group be at least C₁₁, preferred C₁₃Or bigger alkyl chain.The replacement of the function that R optionally can not disturbed described detersive Base replaces.M is preferably calcium, magnesium or barium.More preferably M is calcium or magnesium.

The substituted salicylic acid of alkyl can be by Kolbe reaction (seeing United States Patent (USP) No.3,595,791) from phenols system Standby.It is multiple in polar solvent such as water or alcohol that the substituted salicylic alkali salt of described alkyl can pass through alkali salt Decompose and prepare.

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

Salt containing the substantially alkaline-earth metal of stoichiometric amount is referred to as neutral salt and has the total base number of 0 to 100 (TBN is measured by ASTM D2896).Many constituents are overbasic, containing a large amount of alkaline-earth metal chemical combination by excess The metal base that thing reacts with sour gas (such as carbon dioxide) and obtains.Available detersive can be neutral, the most high-alkali Property or the most overbasic.These detersives can neutrality, high alkalinity, the most 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, The high TBN variation of the middle TBN and about 200 up to 600 of about 100 to 200.The mixture of basic, normal, high TBN can be with calcium and magnesium The mixture of Metal Substrate detersive is used together, and includes sulfonate, phenates, salicylate and carboxylate.Mixing TBN detersive Other examples be found in United States Patent (USP) No.7, described in 704,930, described patent is incorporated herein.Metal Can make together with the detersive that metal ratio is 2 and the metal detersive than up to 5 or 10 or 15 than the detersive mixture being 1 With.The detersive of boration can also use.

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 character of detersive, without blending separate material.See United States Patent (USP) No.6,034,039.

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

Other the illustrative detersives can being applied in combination with described alkaline-earth metal detersive include, such as, and 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, magnesium metal and the detersive of calcium metal Ratio ranges is from about 1:0 to about 1:10, preferably from about 1:0 to about 1:4.

Magnesium and the alkaline-earth metal contributed by described detersive 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, 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 measure, scope from about 2mg KOH/g to about 17mg KOH/g, preferably from about 4mg KOH/g to about 14mg KOH/g.By the TBN scope of described magnesium detersive contribution from about 2mg KOH/g to about 17mg KOH/g, preferably from about 3mg KOH/g to about 14mg KOH/g, more preferably from about 5mg KOH/g is to about 10mg 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 more preferably from about 0.6 to about 1.0 weight %.By the sulfated ash scope of described magnesium detersive contribution from about 0.3 to about 1.8 weight %, preferably from about 0.4 to about 1.6 weight %, and 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 The magnesium of 4000ppm.When equaling or exceeding higher engine oil sulfated ash (and using magnesium detersive) of 1.2% ash, Reach the LSPI counting more than 95% to reduce.Sulfated ash level < 1.2% and when using magnesium detersive, can be complete Eliminate LSPI.

For the lubricant formula containing at least one boron-containing compound and at least one detersive of the disclosure, On the basis of the electromotor brake mean-effective pressure (BMEP) with 2000 revs/min (RPM) operating and 18 bars, based on standardization Low speed early/25,000 cycle of engine of combustion (LSPI) counting, the lubricating oil of electromotor and use contain be different from described at least A kind of boron-containing compound and the accessory constituent of at least one detersive described and its amount in described lubricating oil are different from institute The low speed stating at least one boron-containing compound and reach in the electromotor of the amount of at least one detersive described early combustion performance is compared Relatively, show low speed early combustion and reduce by greater than about 50%, preferably greater than about 75%, and more preferably greater than about 95%.

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

With time in this article, described detergent concentration is given based on " delivery status ".Generally, described active cleaning agent with add Work oil is paid together.Described " delivery status " detersive generally contains from about 20 weights 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 %.

Antiwear additive

Metal alkylthiophosphates the most 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 uncle and/or secondary C independently₁To C₈Alkyl group.Can use the derivative ZDDP of primary alconol (1 °) and The mixture of the ZDDP that secondary alcohol (2 °) is derivative.Described R¹And R²Substituent group can be C independently₁-C₁₈Alkyl group, preferably C₂-C₁₂ Alkyl group.Preferably, R¹And R²It is primary or secondary C independently₁To C₈Alkyl group, condition is R¹And R²At least one be secondary C₁ To C₈Alkyl group.The mixture of the ZDDP of the derivative ZDDP of primary alconol and derived from secondary alcohols, 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.

Preferred commercially available zinc dithiophosphate includes secondary zinc dithiophosphate, such as, is available from such as The Lubrizol Corporation is with trade name " LZ 677A ", " LZ 1095 ", " LZ 1389 " and " LZ 1371 ", such as " OLOA 262, such as Afton Chemical are with trade name " HITEC 7169 " and such as with trade name for Chevron Oronite Infineum is with those of trade name Infineum C9417 and Infineum C9414.

Preferably, primary or secondary C of described zinc dialkyl dithiophosphate compound₁To C₈Alkyl group part derives free Alcohol from following: 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 (i-C5), 3-amylalcohol (C5), 3-methyl-2-butanol (primary C-5), 1-hexanol (primary C6), 4-methyl-1-pentene alcohol (primary C6), 4-methyl-2-amylalcohol (i-C6), and 2-ethyl-1-hexanol (primary C8), and mixing Thing.In some cases, be 5 derived from average carbon number and the ZDDP of less alcohol is desirable.In some cases, derived from The ZDDP of the average carbon number alcohol more than 5 is desirable.Table 1 below shows and can be advantageously used in the present invention for manufacturing The alcohol mixture of ZDDP.

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 the amount that the zinc dialkyl dithiophosphate compound of secondary alkyl group is in described lubricating oil, it is sufficient to make electromotor and use Lubricating oil contains and is different from the accessory constituent of described specific zinc dialkyl dithiophosphate compound and it is at described lubricating oil In amount be different from the electromotor of the amount of described specific zinc dialkyl dithiophosphate compound the low speed that reaches early combustion performance Compare, show low speed early combustion and reduce.

It is said that in general, 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 more preferably from about 0.6 weight % is to about 0.8 weight %, Although more or less of amount the most often can advantageously use.Preferably, described ZDDP is the derivative ZDDP of primary alconol and secondary alcohol The mixture of derivative ZDDP, or the ZDDP of the mixture derived from primary and secondary alcohol, and with the pact of described lubricating oil gross weight The amount of 0.6 to 1.0 weight % exists.

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

Preferably, there is described in R¹And R²The zinc dialkyl dithiophosphate compound of primary or secondary alkyl group, wherein R¹With R²Primary or secondary alkyl group is derived from 4-methyl-2-amylalcohol (C6), with gross weight based on described lubricating oil from about 0.1 weight % Amount to about 5.0 weight %, preferably from about 0.1 to about 1.2 weight % more preferably from about 0.2 to about 0.8 weight % exists.

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.

By the Zn content scope of the described zinc compound in described lubricating oil or antiwear additive contribution from about 500ppm to about 2000ppm, preferably from about 600ppm are to about 900ppm.

By the phosphorus content scope of the described zinc compound in described lubricating oil or antiwear additive contribution from about 400ppm to about 2000ppm, preferably from about 500ppm are to about 900ppm.Derived from described secondary ZDDP phosphorus 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 1.05 to about 1.9.

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

The illustrative zinc compound that can be used in the disclosure includes, such as, and sulfonic acid zinc, zinc polycarboxylate, zinc acetate, cycloalkanes Acid zinc, alkenyl succinic acid zinc, acid phosphate zinc salt, phenol zinc, zinc salicylate etc..

For the disclosure the lubricant formula containing at least one boron-containing compound and at least one zinc compound and Speech, on the basis of electromotor is with the brake mean-effective pressure (BMEP) of 2000 revs/min (RPM) operating and 18 bars, based on Standardization low speed early/25,000 cycle of engine of combustion (LSPI) counting, the lubricating oil of electromotor and use contains and is different from institute State at least one boron-containing compound and the accessory constituent of at least one zinc compound described and it is in described lubricating oil Reach in the electromotor of the amount that amount is different from least one boron-containing compound described and at least one zinc compound described is low Speed is early fired performance and is compared, and shows low speed early combustion and reduces greater than about 20%, preferably greater than about 25%, and is more preferably greater than about 30%.

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

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 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 %, And more preferably from about 0.2 to about 0.8 weight % amount exist.

Described zinc compound in the lubricating oil of the disclosure or antiwear additive concentration, gross weight based on described lubricating oil, Can with scope from about 0.1 to about 5.0 weight %, preferably from about 0.2 to 2.0 weight %, and more preferably from about 0.2 weight % is to about 1.0 weight %.In the presence of magnesium detersive and boron-containing additive, it is only necessary to a small amount of ZDDP just produces abnormal low LSPI meter Number.In the presence of such containing magnesium and boron compound, few to 0.1% to the 1.0%ZDDP (phosphorus in electromotor formulated oil 100ppm P to 1000ppm P) beyond thought LSPI performance improvement will be provided.At higher ash level and higher Under TBN level, the ZDDP level of 1.1 to 4.0% just can provide beyond thought LSPI performance improvement.For SAE xW-40 For xW-50 oil (x=0,5,10,15), the ZDDP level of 1.1 to 4.0% changes for providing beyond thought LSPI performance Kind especially useful.

Other additives

Can be used for the formulated oil in the disclosure and can additionally contain one or more other conventional lubricants performances Additive, includes but 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, see Klamann, " lubricant and phase Close product " (Lubricants and Related Products), Verlag Chemie, Deerfield Beach, FL； ISBN0-89573-177-0.Referring also to " " lubricant additive " (the Lubricant Additives) " of M.W.Ranney, 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 integrally joined to herein with it.These additives are generally paid with different amounts of flux oil, and described amount can With scope from 5 weight % to 50 weight %.

In lubricant oil composite, combine the type of the performance additive that the disclosure uses and quantitatively made the most in this article The restriction of the example shown for explanation.

Viscosity index improver

The lubricant oil composite of the disclosure can include viscosity index improver (also referred to as VI modifier, viscosity adjustment Agent and viscosity improver).

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

Suitably 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 is 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.

Suitably the example of 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 suitably viscosity index (VI) Modifier is polymethacrylates (such as, 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 ethylene and the copolymer of propylene, styrene and isoamyl The hydrogenated block copolymer of diene and polyacrylate (such as, the copolymer of the acrylate of various chain lengths).Instantiation bag Include styrene-based-isoprene or the polymer of styrene-butadiene of 50,000 to 200,000 molecular weight.

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

In a kind of embodiment of the disclosure, based on described formulated oil or the gross weight of 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 more preferably less than about 0.5 Weight %.Viscosity improver adds usually used as the concentrate in Macrodilution oil.

In the another embodiment of the disclosure, based on described formulated oil or the gross weight of 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 cause on the metal surface Deposit, the existence of greasy filth or lubricant viscosity increase.Those skilled in the art will know that and varied can be used for lubricating oil Oxidation retarder in compositions.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 (without metal) phenols chemical combination Thing or the neutrality of some phenolic compound or alkaline metal salt.Typical phenolic antioxidant compound is hindered phenol, and it is Containing the phenol of sterically hindered oh group, these include that wherein oh group is in the dihydroxy arylation of neighbour each other or para-position Those derivants of compound.Typical phenol antioxidant includes by C₆The substituted hindered phenol of+alkyl group and these hindered phenols The derivant of alkylidene coupling.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.What other were available be obstructed, and single phenols resists Oxidant can include the 2,6-dialkyl group phenols propanoate ester derivatives being such as obstructed.Bis-phenolic antioxidants can also be advantageously Use in conjunction with the disclosure.The example of the phenol of ortho position coupling 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 of para-position coupling includes such as 4,4 '-bis- (2,6-di-tert-butylphenol) and 4,4 '-methylene-bis-(2,6-di-tert-butylphenols).

One or more catalytic antioxidants of effective dose can also be used.Described catalytic antioxidant comprises effectively A) one or more oil-soluble many metallo-organic compounds 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 by quote with its entirety herein in conjunction with.

The non-phenol type oxidation inhibitors that can use includes 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: the aromatics list of alkylation and non-alkylating aromatic amine, 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 relatively higher alkyl group, Or thiazolinyl, aryl or alkylaryl group, and x is 0,1 or 2.Described aliphatic group R⁸Can be containing 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 R⁹Both of which is Aromatics or replace 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 alkali metal or alkali salt thereof are also available antioxidants.

Preferably antioxidant includes hindered phenol, arylamine.These antioxidants can the most individually or each other group Close and use.The usage amount of such additive can be 0.01 to 5 weight %, preferably 0.01 to about 2 weight %, 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 compositions of the disclosure, (also known as lubricating oil flow improves Agent).These pour-point depressants can add in the lubricating composition of the disclosure and can flow and maybe can topple over reducing described fluid Minimum temperature.The suitably example of pour-point depressant includes polymethacrylates, polyacrylate, polyarylamide, halogen For paraffin and the condensation product of aromatic compounds, carboxylic acid vinyl ester polymer and dialkyl fumarate, the ethylene of 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 prepare.The usage amount of such additive can be about 0.01 to 5 weight %, preferably from about 0.01 to 1.5 weight Amount %.

Seal compatilizer

Sealing compatilizer, by causing fluid or physically changed chemical reaction in elastomer, contributes to expanded elastomers close Sealing.Lubricating oil suitably seals compatilizer and includes organic phosphate, alkoxyl sulfolane, aromatic ester, aromatic hydrocarbons, ester (such as, adjacent benzene Dioctyl phthalate 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 hinders and forms stable foam.Organosilicon It is typical defoamer with organic polymer.Such as, polysiloxanes, such as silicone oil or polydimethylsiloxane, it is provided that froth breaking character. Defoamer is commercially available, it is possible to conventional a small amount of use together with other additives such as demulsifier；Generally these add Add the merging amount of agent less than 1 weight % 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 corroded.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 absorbs water by combining water in water-in-oil emulsion so that only oil contacting metal surface.Again A type of rust-inhibiting additive chemical adhesion, in metal, produces non-reacted surface.The suitably example of additive includes two D2EHDTPA zinc, metal phenates, 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 to change to be by the friction of any lubricant or the surface of the fluid lubrication containing this kind of material Any material of number.Friction improver, also known as anti-friction agent, or lubricity agent or oiliness improver, and change base oil, allotment lubricant Other such agents of the coefficient of friction on the surface that the performance of compositions or functional fluid is lubricated with improvement, the need to If, base oil or the lubricant compositions that can be effectively combined the disclosure 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, such as, and 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, such as, and molybdenum amine, molybdenum two Amine, organotungstate, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum amine complex, carboxylic acid molybdenum etc., and mixture.Class As tungstenio compound can be preferred.

Friction improver in other illustrative engine lubrication oil formulas that can be used for the disclosure includes, such as, and alkane Epoxide fatty acid ester, alkanolamide, polyol fatty acid ester, boration fatty acid glyceride, fatty alcohol ether and mixing thereof Thing.

Illustrative alkoxy fatty acid ester includes, such as, and 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, such as, and 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, such as, and glycerin mono-fatty acid ester, saturated mono-, di-and triglyceride, glycerol Monostearate etc..These can include polyol ester, hydroxyl polyol ester etc..

Illustrative boration fatty acid glyceride includes, such as, boration glycerin mono-fatty acid ester, boration saturated single, 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, polyhydric alcohol dicarboxylic ester 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 make especially with glycerol with the ethoxylation of preferred polyol, propoxylation, butoxylated fatty acid ester Based on polyhydric alcohol.

Illustrative fatty alcohol ether includes, such as, and 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 moiety May be preferred that stearyl, myristyl, C₁₁–C₁₃Hydrocarbon, oleyl, iso stearyl etc..

The usable concentration of friction improver can with scope from 0.01 weight % to 5 weight %, or about 0.1 weight % is to about 2.5 weight %, or about 0.1 weight % is to about 1.5 weight %, or about 0.1 weight % is to about 1 weight %.Concentration containing Mo Often describe according to Mo metal concentration.Favourable Mo concentration can be with scope from 25ppm to 700ppm or more, and preferably scope Often 50-200ppm.All types of friction improvers can individually or use with the mixture with the material of the disclosure.Warp Often, the mixture of two or more friction improvers, or the mixture of friction modifiers and other surface active material, be also Desirable.

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

It should be noted that many additives are as existing containing one or more additives 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 (weight 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 The packaging that oil additive supplier obtains combines in advance.The additive packing with various composition, ratio and characteristic is existing Have, select suitable packaging to 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, based on the early combustion of standardization low speed (LSPI)/25,000 cycle of engine of counting, low speed early combustion minimizing greater than about 95%, or greater than about 97%, or greater than about 99%.

Have that the electromotor formulated oil of 1.2 to 1.6% or higher higher ash level combines disclosed in the disclosure its LSPI event number can be significantly reduced 96% or higher at component by him.There is the electromotor of the relatively low ash level of 0.2 to 1.2% Formulated oil combines other components disclosed in the disclosure can cut LSPI event number completely.

The electromotor that highly easily early combustion (LSPI) affects by low speed is high brake mean-effective pressure (BMEP) and low Those electromotors of operating under motivation rotating speed (RPM).This includes using various fuel to include natural gas, gasoline, diesel oil, biological combustion The explosive motor of material etc..Miniaturization, the slow-speed of revolution, be forced sense (such as turbocharging) electromotor be at these electromotors Operate under state the most susceptible, and be therefore more susceptible to LSPI impact.Have the limiting examples bag of the electromotor of these characteristics Include GM Ecotec and Ford EcoBoost power team and discharge capacity from other high BMEP of about 1L to about 6L (can > 10 Bar) electromotor and to include array, horizontally-opposed (Boxer) and " V " (such as " V8 ", " in upright arrangement 3 ", " in upright arrangement 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 so that the disclosure to be described.

Embodiment

Embodiment A

Formula preparation as shown in Figure 1.All the components as used herein is all commercially available.In described formula use III, IV and V class oil base stock.The dispersant used in described formula is that (it comprises boration polyisobutylene to boration butanimide Butanimide, B/N ratio be equal to about 0.5), (high MW succinimide dispersants 1, it comprises high molecular butanimide The double focusing isobutene. succinimide dispersants of ethylene carbonate end-blocking, total nitrogen about 1%) and high molecular butanimide (height MW succinimide dispersants 2, it comprises double polyisobutenyl succinimide, total nitrogen about 1.2%).

Remaining composition used in described formula 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 in agent.

Formula described in Fig. 1 is tested.Result illustrates in FIG.Sulfated ash experimental evidence ASTM D874 Measure.Boron contents measures according to ASTM D6443.Nitrogen content measures according to ASTM D3228.

Different electromotor parts and control program can significantly affect the generation of LSPI.See, e.g., U.S. Patent application Announce No.2012/1866225 and 2003/0908070, also SAE 2012-02-1148, SAE 2011-01-0340 and SAE 2011-01-0343, all of which is incorporated herein.Additionally, Figure 13 shows that test obtains from taxi scene Driving pattern data.From two kinds of different 2.0L L4TGDI engine types of different original equipment manufacturers with allusion quotation The taxi city driving pattern of type travels 2 weeks.The OBD-II data port utilizing vehicle is collected engine performance data and incites somebody to action Described engine performance data is mapped on the engine torque map delivered of corresponding electromotor.Such as SAE 2011-01-0339 Middle announcement, electromotor is the easiest when they operatings in more than 10 bar BMEP and the region less than 3000rpm engine speed In LSPI.Therefore, any region defined by these operating conditions in the torque diagram of these electromotors is potentially susceptible to LSPI.Root According to the measurement data of OBD-II data monitor, can show how the electromotor with different demarcation tunes permissible based on them Show different LSPI behaviors.Figure 13 shows about 1.2 million data points, summarizes when 2 weeks interim, two kinds of differences Engine type with the operating of typical taxi city driving pattern.Observe by this way and use every kind of engine type Several taxis.In the driving pattern of typical taxi city, electromotor manufactures 1 and averagely exhausts it at LSPI " hazardous area " The 1.67% of the duration of runs, and electromotor manufacture 2 averagely exhausts 0.17%, although both electromotors are all 2.0L array 4- Cylinder TGDI electromotor.Additionally, electromotor manufacture 2 shows the field failure that zero LSPI is relevant, and electromotor manufacture 1 shows Repeatedly relevant for LSPI fault.This further illustrates the different engine flats different responses to LSPI.

For purposes of this disclosure, 2.0L, 4-cylinder TGDI GM Ecotec electromotor is tested for LSPI.Utilize six sections Test procedure measures the LSPI event number occurred under the engine load and velocity conditions of two kinds of different regulations.Every section of examination The program of testing includes 25,000 cycle of engine, and one of them circulation rotates 720 degree corresponding to bent axle.First set condition is 2000RPM and 18 bar BMEP, hereinafter referred to as " high load capacity ".Second set 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.At 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, utilizes and is placed on 4 cylinders pressure transducer in each and supervises Survey peak cylinder pressure.Surge pressure in cylinder exceedes average peak cylinder pressure more than 4.7 standard deviations or 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 Fig. 1 illustrates.

The impact on LSPI of the described test evaluation dispersant chemistry.As it is shown in figure 1, the LSPI of the amount of boron and this oil in formula Count totals has strong correlation.Specifically, along with boron ppm is from 0 increasing to 241, to 507, described LSPI counting is astonishing Ground reduces to 27, to 24 from about 43.This is to reduce 40% with only about 241ppm boron and reduce 48% with about 507ppm boron.Though So the change relatively of the LSPI counting from 0ppm to 241ppm is more than the relative change counted from the LSPI of 241ppm to 507ppm boron Change, but still maintain the beyond thought benefit of the directivity of boron.Even boron improve about 240ppm reduce LSPI counting express one's ideas Unimaginable 40%.Therefore it provides the boron source of 0 to about 1000ppm boron, more preferably 0 to about 500ppm is useful to reducing LSPI 's.It addition, comparative example 5 compares with embodiment 2 and embodiment 11 and also demonstrates borated dispersants and alleviate other Dispersant types The effectiveness of negative effect.Comparative example 5 and embodiment 2 show roughly equal LSPI event count, respectively 22 and 24 Event, although embodiment 2 comprises only boration succinimide dispersants and comparative example 5 does not contains dispersant.Additionally, embodiment 1 Compare with comparative example 1 and 2 with 11, demonstrate that borated dispersants significantly reduces at the lubricant containing only non-borated dispersants In the LSPI event count observed, even if under the highest dispersant source property nitrogen level.

The dispersant used in described test is evaluated further with Thermogravimetric analysis (TGA).Use with platinum reference The TA instrument Q5000TGA of dish.Nitrogen passes through on sample with 60.0 ml/min.The described sample dispersion agent of about 15mg is used In described analysis, and experience temperature below slope program: balance at 50 DEG C, be then passed through about 1 minute temperature ramp to 650 DEG C, 650 DEG C of balances, then isothermal absorption about 15 seconds at 650 DEG C.Described gas is then converted into 60.0 ml/min The oxygen of clock flowing, and 650 DEG C of isothermal absorption 45 seconds the most again.Finally, described temperature through about 30 seconds from 650 DEG C of climbings To 750 DEG C, and 750 DEG C of isothermal absorption 30 seconds again.

Result shows in fig. 2, and shows that the temperature along with reaching 20% and/or 50% weightlessness at TGA in measuring increases, LSPI counts reduction.Three traces on TGA figure represent three kinds of Dispersant types for this analysis.Specifically, dispersion Agent 1 represents high MW succinimide dispersants 1, and dispersant 2 represents high MW succinimide dispersants 2, and dispersant 3 represents boron Acidifying succinimide dispersants.These dispersants reach the temperature the most about 355 DEG C of 20% weightlessness, 344 DEG C and 328 DEG C.This A little dispersants reach the temperature the most about 406 DEG C of 50% weightlessness, 400 DEG C and 377 DEG C.Surprisingly, show relatively low LSPI The described boration succinimide dispersants of counting, the TGA temperature under obtain 20% and 50% weightlessness is higher than demonstrating relatively The described non-boration succinimide dispersants of high LSPI counting.

Embodiment B

Formula preparation as shown in Figure 3.All the components as used herein is all commercially available.In described formula use III, IV and V class oil base stock.

The detersive used in described formula is that (calcium salicylate 1, it contains 7.3%Ca and has middle TBN alkyl sodium salicylate Have the TBN of about 200), low TBN alkyl sodium salicylate (calcium salicylate 2, it contains 2.3%Ca and about 65TBN), high TBN alkyl sulphur Acid calcium (sulfoacid calcium 1, it contains 11.6%Ca and about 300TBN), (sulfoacid calcium 2, it contains 2.0%Ca to low TBN alkyl sulfonic acid calcium About 8TBN) and high TBN alkyl sulfonic acid magnesium (sulfonic acid magnesium 1, it contains 9.1%Mg and about 400TBN).Described TBN scope specifies For: low TBN about 0 to 100, middle TBN about 100 to 200 and high TBN about 200 up to 600.

The dispersant used in described formula is boration butanimide, high molecular butanimide (high MW succinum Acid imide dispersant 1) and high molecular butanimide (high MW succinimide dispersants 2).

Remaining composition used in described formula 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 in agent.

Formula described in Fig. 4 is tested.Result illustrates in the diagram.Sulfated ash experimental evidence ASTM D874 Measure.Boron, calcium and content of magnesium measure according to ASTM D6443.Nitrogen content measures according to ASTM D3228.Utilize 2.0L, 4-cylinder TGDI GM Ecotec electromotor, according to the program described in embodiment 1, carries out LSPI test to formula.

Described test evaluation magnesium detersive and the borated dispersants impact on LSPI.As shown in Figure 4, find that boration divides Powder is used together for LSPI performance the most useful with sulfonic acid magnesium detersive.Comparative example 1 and 2 and embodiment 2 exist Utilize boron source significantly to alleviate or reduce the benefit aspect of LSPI and be repeated in embodiment A the new discovery result identified.Embodiment 4 With 5, both utilize sulfonic acid magnesium detersive and boron source allotment, it was demonstrated that LSPI outstanding under different sulfate ash levels Performance.Since it is known sulfate ash is multiplied to 1.6 weight % meanings to LSPI detrimental, sulfate ash from 0.8 weight % Cause unexpectedly LSPI counting from 0 to 2 increase the least the fact that, be repeated the new discovery knot of these admixtures performance Really, even if under high ash level.Embodiment 4 and 5 respectively show LSPI and reduces 100% and 95%.

Embodiment C

Formula preparation as shown in Figure 5.All the components as used herein is all commercially available.In described formula use III, IV and V class oil base stock.

The detersive used in described formula is that (calcium salicylate 1, it contains 7.3%Ca and has middle TBN alkyl sodium salicylate Have the TBN of about 200), low TBN alkyl sodium salicylate (calcium salicylate 2, it contains 2.3%Ca and about 65TBN), high TBN alkyl sulphur Acid calcium (sulfoacid calcium 1, it contains 11.6%Ca and about 300TBN), (sulfoacid calcium 2, it contains 2.0%Ca to low TBN alkyl sulfonic acid calcium About 8TBN), middle TBN alkyl phenol calcium (phenol calcium 1, it contains 5.5%Ca and about 150TBN) 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, With high TBN about 200 up to 600.

The dispersant used in described formula is boration butanimide and high molecular butanimide.Described formula The antiwear additive of middle use is derived from the ZDDP (it contains 10 weight % phosphorus and prepares from mixing C3 and C6 secondary alcohol) of secondary alcohol and spreads out It is conigenous the ZDDP (it contains 7 weight % phosphorus and prepares from C8 primary alconol) of primary alconol.

Remaining composition used in described formula 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 in agent.

Formula described in Fig. 5 is tested.Result illustrates in figure 6.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.Utilize 2.0L, 4-cylinder TGDI GM Ecotec electromotor, according to the program described in embodiment 1, carries out LSPI test to formula.Described examination Test the impact evaluating three kinds of additive systems (i.e. detersive, dispersant and antiwear additive) to LSPI.As shown in Figure 6, to containing The formula of non-borated dispersants and the formula measurement to the mixture containing non-borated dispersants and borated dispersants In the case of LSPI, boration succinimide dispersants is used to have the uniqueness exceeding high molecular succinimide dispersants LSPI benefit.Comparative example 3, embodiment 6 and embodiment 10 display increase the Boron contents impact on LSPI performance.Along with Boron contents Increase to 240 from 0 and be down to 27 and to 24 to 507ppm, LSPI counting from 46.Boron benefit generation in reducing LSPI frequency Significant and the beyond thought discovery result that presents in figs. 5 and 6 of table.It is clear that embodiment 8 and embodiment 9 present sulfonic acid magnesium Net agent and double dispersant systems and the unique combination of the ZDDP of derived from secondary alcohols.Described pair of dispersant system contains boron source.By with Comparative example 3 compares, it is shown that the uniqueness of this combination, and comparative example 3 employs different salicylic acid calcio detergent system also There is the highest LSPI counting.Even if demonstrating use sulfonic acid magnesium detersive and the ZDDP of derived from secondary alcohols and borated dispersants not It is to eliminate also to substantially reduce LSPI.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.Embodiment 6 compares to also demonstrate with embodiment 12 includes borated dispersants and derived from secondary alcohols in ZDDP and the effectiveness combining this approach of sulfonic acid magnesium detersive and calcium salicylate detersive.Embodiment 12 show with than Relatively example 3 is compared LSPI and is reduced 98%.

Embodiment D

Engine lubrication oil formula in Fig. 7 and 8 is additive and the combination of oil base stock and expection has 7.5- High temperature high shear (10 during 150 DEG C of kinematic viscosity and about 2.5 to 2.9cP during 100 DEG C of about 8.5cSt^-6s^-1) viscosity.Real Execute example P1, the engine lubrication oil formula of P2, P3 estimates 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, embodiment P1, P2 and P3 ([Mg]+[Ca]+[Zn]+[P])/ ([B]+[N]_Dispersant) ratio, it is contemplated that between 1.99 and 4.53.The engine lubrication oil formula of embodiment P4 and P5 is anticipated to be had The content of magnesium of 300ppm to 600ppm.Similarly, embodiment P6, the engine lubrication oil formula of P7 and P8 estimate have about The magnesium calcium ratio of the 1.21 of the content of magnesium of 300ppm to 900ppm and about 0.12 to the embodiment P8 of embodiment P6.Meanwhile, this The TBN of a little embodiments changes from the P9 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 to 1.2 weight % ash from 0.3 weight %.Other ratios identified in Fig. 7 and 8 are also such as indication the most wherein Change as going out.The engine lubrication oil formula of embodiment P9 and P10 is estimated to be respectively provided with about 0.06 He under constant TBN The magnesium calcium ratio of 3.Embodiment P11, the engine lubrication oil formula of P12 and P13 estimate have the scope pact from embodiment P13 The Zn content of 96ppm to the about 635ppm of embodiment P11.Embodiment P11, the anticipated tool of engine lubrication oil formula of P12 and P13 There is the scope phosphorus content from the about 570ppm of the about 87ppm of embodiment P13 to embodiment P11.([Mg]+[Ca])/([Zn]+ [P]) ratio ranges is 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 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. 9 and 10 is additive and the combination of oil base stock and expection has 5.5- High temperature high shear (10 during 150 DEG C of kinematic viscosity and about 2 to 2.5cP during 100 DEG C of about 7.5cSt^-6s^-1) viscosity.Implement Example P14, the engine lubrication oil formula of P15 and P16 estimate 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) ratio estimates model Enclose 2.91 of 1.28 to embodiment P14 from embodiment P16.Similarly, ([Zn]+[P])/([B]+[N]_Dispersant) ratio estimates model Enclose the 1.62 of 0.71 from embodiment P16 and embodiment P14.Finally, ([Mg]+[Ca]+[Zn] of embodiment P14, P15 and P16 +[P])/([B]+[N]_Dispersant) ratio, it is contemplated that between 1.99 and 4.53.The engine lubrication oil formula of embodiment P17 and P18 The anticipated content of magnesium with 300ppm to 600ppm.Similarly, embodiment P19, P20 and P21 engine lubrication oil formula pre- Meter has the magnesium calcium ratio of the 1.21 of about 0.12 to the embodiment P21 of the content of magnesium of about 300ppm to 900ppm and 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 to 1.2 weight % ash from 0.3 weight %.In Fig. 9 and 10 identify other Ratio changes as also as pointed by wherein.The engine lubrication oil formula of embodiment P22 and P23 is estimated constant The magnesium calcium ratio of about 0.06 and 3 it is respectively provided with under TBN.Embodiment P24, the engine lubrication oil formula of P25 and P26 estimate have Scope is from the Zn content of the about 635ppm of the about 96ppm of embodiment P26 to embodiment P24.Embodiment P24, P25 and P26 send out Motivation lubricant formula estimates the phosphorus content having scope from the about 570ppm of the about 87ppm of embodiment P26 to embodiment P24. ([Mg]+[Ca])/([Zn]+[P]) ratio ranges is from the 16.5 of about 2.5 to the embodiment P26 of embodiment P24.([Zn]+[P])/ ([B]+[N]_Dispersant) ratio ranges is from the 0.15 of about 1 to the embodiment P26 of embodiment P24.([Mg]+[Ca]+[Zn]+[P])/ ([B]+[N]_Dispersant) ratio ranges is from the 2.6 of about 3.4 to the embodiment P26 of embodiment P24.

Embodiment F

Engine lubrication oil formula in Figure 11 and 12 is additive and the combination of oil base stock and expection has 9-11cSt High temperature high shear (10 when kinematic viscosity and 150 DEG C of about 2.9 to 3.4cP during 100 DEG C of left and right^-6s^-1) viscosity.Embodiment The engine lubrication oil formula of P27, P28 and P29 estimates 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, 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, embodiment P32, the engine lubrication oil formula of P33 and P34 are estimated Have the content of magnesium of about 300ppm to 900ppm and about 0.12 to the embodiment P34 of embodiment P32 1.21 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 to 1.2 weight % ash from 0.3 weight %.Other ratios identified in Figure 11 and 12 Also change as pointed by wherein.The engine lubrication oil formula of embodiment P35 and P36 is estimated under constant TBN It is respectively provided with the magnesium calcium ratio of about 0.06 and 3.Embodiment P37, the engine lubrication oil formula of P38 and P39 estimate have scope Zn content from the about 635ppm of the about 96ppm of embodiment P39 to embodiment P37.Embodiment P37, the electromotor of P38 and P39 Lubricant formula estimates the phosphorus content having scope from the about 570ppm of the about 87ppm of embodiment P39 to embodiment P37.([Mg] + [Ca])/([Zn]+[P]) ratio ranges is from the 16.5 of about 2.5 to the embodiment P39 of embodiment P37.([Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges is from the 0.15 of about 1 to the embodiment P39 of embodiment P37.([Mg]+[Ca]+[Zn]+[P])/([B]+ [N]_Dispersant) ratio ranges is from the 2.6 of about 3.4 to the embodiment P39 of embodiment P37.The metal concentration used in previous embodiment In finished lubricants in terms of the unit of gross weight %.[N]_DispersantRefer to only be contributed to the nitrogen of finished lubricants by described dispersant Concentration.

All patents and patent applicationss of quoting in this article, test procedure (such as ASTM method, UL method etc.) and its He fully combines by quoting by 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 listing numerical lower limits and numerical upper limits in this article, 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 other amendments various will be this area skill Art personnel are obvious and can make easily under the spirit and scope without departing substantially from the disclosure.Therefore, be not intended to by The scope of the claim appended at this is limited to embodiment and the description illustrated in this article, but described claim should be explained It is the feature of all patentable novelty including 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 embodiment and specific embodiment describes the disclosure.Opened by described above in detail Sending 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. by using formulated oil to prevent as lubricating oil or reducing the side of low speed early combustion in the electromotor of used-oil lubrication Method, described formulated oil has and comprises lube oil base stocks as key component and at least one boron-containing compound as secondary The composition of component；At least one boron-containing compound wherein said comprise at least one borated dispersants or boron-containing compound and The mixture of non-borated dispersants；And it is wherein average with the braking of 2000 revs/min (RPM) operating and 18 bars at electromotor On the basis of effective pressure (BMEP), based on standardization low speed early/25,000 cycle of engine of combustion (LSPI) counting, described The lubricating oil of motivation and use does not comprise the mixed of at least one borated dispersants or boron-containing compound and non-borated dispersants The low speed reached in the electromotor of compound early combustion performance is compared, and shows low speed early combustion and reduces more than 50%.

2. the process of claim 1 wherein that described accessory constituent also comprises at least one detersive, wherein said detersive comprises The alkali salt of at least one organic acid, and the alkali salt of at least one organic acid described to comprise at least one organic The magnesium salt of acid.

3. the process of claim 1 wherein that described accessory constituent also comprises at least one detersive and at least one closes containing zinc impregnation Thing or at least one antiwear additive, wherein said detersive comprises the alkali salt of at least one organic acid, and described at least The alkali salt of a kind of organic acid comprises the magnesium salt of at least one organic acid, and at least one antiwear additive wherein said comprises At least one is derived from the zinc dialkyl dithiophosphate compound of secondary alcohol.

4. the method for claim 1-3, wherein said lube oil base stocks comprises I class, II class, Group III, IV class or V class base Plinth oil；It is 2% to 20% and kinematic viscosity is the ester of 2cSt to 8cSt when 100 DEG C 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 boron-containing compound or borated dispersants selected from boration butanimide, Boration succinate, boration succinate ester amides, boration Mannich base and mixture thereof；And described non-boration Dispersant comprises the derivative butanimide of the succinic anhydrides with coupling agent or succinate, and wherein said coupling agent comprises and contains Boron compound.

6. the method for claim 1-5, wherein boron is by organic or inorganic boron-containing compound and the mixing of boration butanimide Thing, boration succinate, boration succinate ester amides, Mannich base ester or its mixture are supplied to described lubricating oil；Its Described in boration butanimide be single butanimide, double amber imide or its mixture.

7. the method for claim 3-6, wherein in described lubricating oil, the total zinc from described zinc compound and antiwear additive adds On from total alkaline-earth metal of described detersive divided by the ratio of the total boron from described boron-containing compound and borated dispersants It is 9.2 to 45.

8. the method for claim 2-7, the alkali salt of wherein said organic acid is selected from alkaline earth metal sulfonate, alkaline-earth metal Carboxylate, alkaline earth phenate, alkali earth metal phosphate and mixture thereof.

9. the method for claim 2-8, wherein said detersive comprises in (i) sulfonic acid magnesium, phenol magnesium, magnesium salicylate and mixture thereof At least one, and optionally, at least one in sulfoacid calcium, phenol calcium, calcium salicylate and mixture thereof；(ii) at least one has The magnesium salt of machine acid, it is selected from sulfonic acid magnesium, magnesium carboxylates, phenol magnesium, magnesium phosphate and mixture thereof；Or (iii) sulfonic acid magnesium, sulfonic acid magnesium and The mixture of magnesium salicylate, sulfonic acid magnesium and the mixture of phenol magnesium or sulfonic acid magnesium and the mixture of magnesium carboxylates.

10. the method for claim 2-9, magnesium that wherein (i) is contributed by described detersive and alkaline-earth metal are in described lubricating oil Exist with the amount of 500ppm to 5000ppm；(ii) total base number (TBN) contributed by described detersive, is measured by ASTM D2896, Scope is from 2mg KOH/g to 17mg KOH/g；Or the sulfated ash scope that (iii) is contributed by described detersive is from 0.4 to 1.7 Weight %.

The method of 11. claim 3-10, wherein said zinc compound is selected from zinc polycarboxylate, sulfonic acid zinc, zinc acetate, aphthenic acids Zinc, alkenyl succinic acid zinc, acid phosphate zinc salt, phenol zinc and zinc salicylate.

The method of 12. claim 3-11, wherein said zinc dialkyl dithiophosphate compound is expressed from the next

Zn[SP(S)(OR¹)(OR²)]₂

Wherein R¹And R²It is primary or secondary C independently₁To C₈Alkyl group, condition is R¹And R²At least one be secondary C₁To C₈Alkyl Group.

13. engine lubricating oils, it has and comprises lube oil base stocks as key component and at least one boron-containing compound Composition as accessory constituent；At least one boron-containing compound wherein said comprises at least one borated dispersants or boracic Compound and the mixture of non-borated dispersants；And wherein at electromotor with 2000 revs/min (RPM) operating and 18 bars On the basis of brake mean-effective pressure (BMEP), follow based on standardization low speed early/25,000 electromotor of combustion (LSPI) counting Ring, described electromotor does not comprise at least one borated dispersants or boron-containing compound and non-boration with the lubricating oil of use The low speed reached in the electromotor of the mixture of dispersant early combustion performance is compared, and shows low speed early combustion and reduces more than 50%.

The engine lubricating oil of 14. claim 13, wherein said accessory constituent also comprises at least one detersive, wherein said Detersive comprises the alkali salt of at least one organic acid, and the alkali salt of at least one organic acid described comprise to The magnesium salt of few a kind of organic acid.

The engine lubricating oil of 15. claim 13, wherein said accessory constituent also comprises at least one detersive and at least one Planting zinc compound or at least one antiwear additive, wherein said detersive comprises the alkali salt of at least one organic acid, and And the alkali salt of described at least one organic acid comprises the magnesium salt of at least one organic acid, and wherein said at least one Antiwear additive comprises at least one zinc dialkyl dithiophosphate compound derived from secondary alcohol.

By using electromotor formulated oil prevent as lubricating oil or reduce low speed in the electromotor of 16. used-oil lubrications The early method of combustion, the composition that described electromotor formulated oil has comprises at least one lube oil base stocks of 70 to 85 weight % With its load capacity at least one dispersant to described electromotor formulated oil contribution 30 to 1500ppm boron；Wherein said at least one Plant dispersant and comprise at least one borated dispersants or boron-containing compound and the mixture of non-borated dispersants；Wherein exist On the basis of the electromotor brake mean-effective pressure (BMEP) with 2000 revs/min (RPM) operating and 18 bars, based on standardization Low speed early/25,000 cycle of engine of combustion (LSPI) counting, described electromotor does not comprise at least one with the lubricating oil of use The low speed reached in the electromotor of the mixture of borated dispersants or boron-containing compound and non-borated dispersants early combustion performance Compare, show low speed early combustion and reduce more than 50%.