CN105637074A

CN105637074A - Method of lubricating an end-pivot finger follower valve train lash adjuster

Info

Publication number: CN105637074A
Application number: CN201480055227.4A
Authority: CN
Inventors: J·L·琼斯; M·R·萨顿; M·C·戴维斯; D·T·杰恩; W·H·奥赖恩
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2013-08-08
Filing date: 2014-08-06
Publication date: 2016-06-01
Also published as: ES2567566T3; EP2882834B1; CA2920626A1; CA2920626C; JP2015527480A; BR112016002634A2; US20160264908A1; BR112016002634B1; JP5840334B2; WO2015021119A1; EP2882834A1

Abstract

The invention provides a method of lubricating an end-pivot finger follower valve train lash adjuster of a passenger car compression ignition internal combustion engine having a reference mass not exceeding 2610 kg comprising supplying to the internal combustion engine a lubricating composition comprising an oil of lubricating viscosity 0.01 wt % to 3 wt % of a dispersant viscosity modifier, and 0.01 wt % to 3 wt % of a zinc free sulphur-containing antiwear agent, wherein the lubricating composition has a sulphur-content of less than 5000 ppm, a phosphorus content of 1000 ppm or less, and a sulphated ash content of (typically 3000 to 12,000 ppm).

Description

The method of the lubrication driven device valve mechanism clearance adjuster of end pivot finger-type

Invention field

The present invention provides the method for the end driven device valve mechanism clearance adjuster of pivot finger-type lubricating the passenger vehicle compression-ignition engine with the reference mass less than 2610kg, it includes feeding lubricating composition to internal combustion engine, described lubricating composition comprises the oil with lubricant viscosity, 0.01 weight % to 3 weight % dispersant viscosity modifiers, with 0.01 weight % to 3 weight % without zinc containing S antiwear additive, wherein lubricating composition has the sulfur content less than 5000ppm, 1000ppm or less phosphorus content, with 12, 000ppm or less, or 10, 000ppm or less sulfate ash content.

Background of invention

The valve mechanism of known internal combustion engine changes with design and fuel type. Such as, fuel type can be gasoline or diesel oil; And valve mechanism can have the structure of general type, for instance translation cam and bucket, the driven device of end pivot finger-type, push rod or rocking arm. Valve mechanism type specification in " ValveTrainComponents, TechnologyFailureDiagnosis " disclosed in Schaeffler (referring towww.schaeffler-Aftermarket.com, serial number 94410002202266/0/0/1/2010/PDF-GB). When considering valve mechanism design from tribology viewpoint, because it interacts with lubricant, cunning between the particular type of valve mechanism, contact is rolled and is all likely to affect lubrication mechanism to some extent than with metallurgy, it is intended that electromotor metallurgy, contact pressure, contact velocity, surfacing, the relative Structure deformation of slip (or sliding roll ratio) all affects mode that lubricant additive interacts and contributes to and reduce the abrasion of engine pack, corrosion or fatigue.

Such as, the difference of electromotor design allows that different types of valve mechanism designs. By original equipment manufacturer (OEM), valve mechanism design depends on that the designing requirement of its electromotor selects, it is absent from " the best " design of electromotor simultaneously, OEM considers design factor, designs the fuel type such as different from other factors and size of engine combination including valve mechanism.

Should be understood that large diesel engine is not limited to have and be equipped with compression ignition engine or all motor vehicles of active ignited natural gas (NG) or LPG electromotor more than " technology allows maximum cargo dead-weight " of 3,500kg. On the contrary, European Union points out have " technology allows maximum cargo dead-weight " less than 2610kg by the new light vehicle (passenger vehicle and light commercial vehicle) including in ACEA test portion " C " scope, and (whether my change correct?)

Obvious difference is there is between passenger vehicle and large diesel engine. Mean two kinds of electromotor more than 3,500kg with the size difference of no more than 2610kg and can experience visibly different operating condition, for instance load, oil temperature, cycle of operation and engine speed. Design large diesel engine is so that the torque maximization of haul load under maximum fuel economy, and passenger vehicle Design Technology for Diesels is used for the acceleration of transporting under people and maximum fuel economy. Electromotor haul produces different hardware designs relative to the purpose of design transported, and the imparting design produced is for protecting the stress of the lubricant with lubricating engine. Another significantly designs difference is operate each electromotor with haul relative to operation rotating speed per minute (RPM) transported. Neutral diesel oil such as typical 12-13 rises motortruck engine and is typically not greater than 2200rpm, and bus engine is up to 4500rpm. Between large diesel engine and passenger vehicle with the rpm difference represented it is meant that due to more extreme operating condition, passenger vehicle lubricant can be exposed to higher operation temperature, higher shearing, the oxidation of raising and sedimentation rate.

For many years, large diesel engine and the gasoline engine with valve mechanism are paid close attention in electromotor design, and described valve mechanism comprises translation cam and bucket or rocking arm. The prior art list of references being summarized below highlights the coal smoke process improving engine lubricant design to strengthen heavy duty diesel engine such as MackT-10 or T-11, or make gasoline engine, for instance abrasion or sludge in those or PeugeotTU3M electromotor of GF-3 certification or SequenceIIIF authentication requesting form the effort minimized and carry out. The deposit making great efforts to reduce in cam and bucket valve mechanism TDiVolkswagon electromotor is formed.

US2013/0143781 (Barton et al., on May 20th, 2013 is open) disclose method and the lubricating composition of lubricating internal combustion engines, described lubricating composition comprises the oil with lubricant viscosity, with 0.1 weight % to 70 weight % respectively with alcohol and aromatic amine esterification and amidated copolymer, described copolymer comprises the unit derived from following monomer: (i) alpha-olefin, (ii) ethylenically unsaturated carboxylic acids or derivatives thereof, wherein copolymer is obtained by a kind of method, described method includes: (1) makes monomer (i) alpha-olefin, (ii) ethylenically unsaturated carboxylic acids or derivatives thereof reacts to form copolymer, (2) product and the aromatic amine reaction of step (1) are made, (3) copolymer making step (2) reacts to form the copolymer of amidatioon and esterification with alcohol.

US2013/0143780 (Gieselman et al.; on May 20th, 2013 is open) disclose a kind of lubricating composition; it comprises the oil with lubricant viscosity, and comprises the compound of the product of polyolefin, the unsaturated aromatic acylating agent of olefinic (or carboxylic acid reaction thing) and amine. In one embodiment, amine is alicyclic polyamine, and polyolefin is polybutene, and lubricating composition has the sulfate ash content of 0.3 weight % to 1.2 weight % of lubricating composition. Disclose this lubricating composition for having steel or the internal combustion engine on aluminum surface (usual steel surface).

US2012/0184473 (Boffa et al., within 2012, December discloses on the 20th) disclose a kind of lubricant oil composite, it comprises: i) major amount of base oil, ii) at least one soluble molybdenum compounds, and iii) zinc dialkyl dithiophosphate compound, it is wherein at least 10ppm molybdenum derived from the molybdenum content of molybdenum compound based on the gross weight of lubricant oil composite, and is about 200ppm to 500ppm derived from the phosphorus content of zinc dialkyl dithiophosphate compound based on the gross weight of lubricant oil composite. The method also disclosing lubricating engine, it step including operating electromotor with lubricant oil composite.

US2012/0046206 (Gieselman et al., on February 23rd, 2012 is open) disclose a kind of lubricating composition, it comprises and has the oil of lubricant viscosity, dispersant and amine-functionalized additive, wherein amine-functionalized additive is derived from the amine with at least 3 or 4 aromatic groups, and wherein amine-functionalized additive is be obtained by reacting/available product by making to have the amine of at least 3 aromatic groups and carboxylic acid functionalized polymers. During this lubricant is tested for MackT11, and further illustrate the purposes of the olefine sulfide antioxidant of the amount of not indicating.

US2009/0325831 (Mathur et al., on June 30th, 2008 is open) discloses a kind of lubricating composition, and it comprises: the major amount of oil with lubricant viscosity; The viscosity index (VI) that comprises of minor amount improves the multifunctional additive for lubricating oils of copolymer, and described viscosity index (VI) improves the product that copolymer comprises acidylate ethylene-olefin copolymer and polyamines, and wherein polyamines comprises at least 2 primary or secondary amine functional groups. Disclose this lubricating composition method for lubricating automobile engine.

US2009/0305923 (Visger et al., within 2009, December discloses on the 10th) disclose compositions in the lubricant, described compositions comprises the major amount of oil with lubricant viscosity, the esterification nitrogen functionalized copolymer's compositions derived from following monomer with minor amount: i) at least one monomer selected from (a) vi-ny l aromatic monomers, (ii) at least one ��, beta-unsaturated acyl agent; The unit that acylating agent described in a portion derives is esterified; and the derivative unit of acylating agent described in a portion and at least one aromatic amine condensation; described aromatic amine comprises at least one can with the N-H group of the unit condensation of acylating agent monomer derived, and amine is selected from 4-ADPA, 4-phenylazo aniline, 2-aminobenzimidazole and 3-nitroaniline. Disclose this lubricant improve for the viscosity that the coal smoke reducing in large diesel engine causes and be illustrated in MackT-11 test.

US2008/182768 (Devlin et al., on July 31st, 2008 is open) discloses the improvement lubricant compositions for bio-diesel fuel engine applications. biodiesel is with the fuel handling comprising about 5 to about 100 weight % biodiesel fuel component and lubricates with lubricant oil composite, described lubricant oil composite comprises the major amount of oil with lubricant viscosity, multi-functional olefin copolymer with at least one high graft of minor amount, the multi-functional olefin copolymer of described high graft passes through acylating agent and has more than about 1, the olefin copolymer of the number-average molecular weight of 000 reacts the acylated olefin copolymer that grafting degree (DOG) is at least 0.5 weight % to provide acylating agent on olefin copolymer in the presence of radical initiators, and acidylate olefin copolymer and react to provide the multi-functional olefin copolymer of high graft to prepare with amine, the viscosity that wherein multi-functional olefin copolymer of high graft is effective to be used in the lubricant oil composite of electromotor improves the viscosity raising being decreased to less than or being equal to in the lubricant oil composite of the electromotor of the fuel handling to lack biodiesel fuel component. this lubricant performs in T-11 soot deposits is tested.

US2007/0111904 (VanDam, on May 17th, 2007 is open) discloses low-sulfur and low-phosphorous lubricant oil composite, and it comprises: (a) major amount of oil with lubricant viscosity; (b) one or more dispersants; (c) one or more antioxidants; (d) one or more detersives; Wherein lubricant oil composite is substantially free of zinc dialkyl dithiophosphate and comprises no more than 0.1 weight % sulfur, and provides this lubricant oil composite and do not comprise alkylation and non-alkylating aromatic amine and three core molybdenum compounds. Lubricant is assessed in MackT-10 cylinder jacket of diesel engine wear test.

US2006/0264342 (Shaw et al., on November 23rd, 2006 is open) disclose the method that lubrication has the internal combustion engine of cam and rotation tappet, described method includes using a kind of lubricating composition as the lubricant for electromotor, described lubricating composition comprises the base oil with lubricant viscosity, the phosphorus of the amount of 50-900 mass ppm, the sulfur of the amount of 1500-3000 mass ppm, the boron of the amount of 0.0-100ppm, the friction improver of the sulfate ash of the amount less than 1.0 mass % and the amount of 0.0-0.1 mass %, described amount is based on the quality preparing lubricant oil composite completely. preferred lubricating composition also comprises viscosity index improver dispersant. the example of viscosity index improver dispersant includes the product of amine such as polyamines and alkyl replacement list-or dicarboxylic acids, and wherein hydrocarbyl substituent comprises the chain with sufficient length to give compound viscosity index (VI) improvement performance. it is said that in general, viscosity index improver dispersant can be such as vinyl alcohol or C₃-C₁₀Unsaturated monocarboxylic or C₄-C₁₀The C of dicarboxylic acids₄-C₂₄The polymer of beta-unsaturated esters and the unsaturated nitrogen containing monomer with 4-20 carbon atom; The C neutralized with amine, azanol or alcohol₂-C₂₀Alkene and unsaturated C₃-C₁₀The polymer of list-or dicarboxylic acids; Or by by C₄-C₂₀Unsaturated nitrogen containing monomer grafting thereon or is reacted on polymer backbone further by being grafted on by unsaturated acids, then makes ethylene and C that hydroxy-acid group and amine, azanol or the alcohol of grafting acid reacts₃-C₂₀The polymer of alkene.

US2003/0148895 (Robson et al., November 9 calendar year 2001 is open) discloses the lubricant oil composite being intended for reducing the abrasion in PeugeotTU3M gasoline wear test. This test is intended to the abrasion on the research cam of internal combustion engine and tappet. The disclosure of this document demonstrates the boron (derived from borated dispersants) of high relative contents, and requires the molybdenum (derived from such as three core molybdenum additives) increased with significant quantity so that acceptable level is down in cam and tappet abrasion.

US2006/0205614 (Artman et al., JIUYUE disclosed on the 14th in 2006) discloses the low-phosphorous compositions of low-sulfur being suitable to lubrication compression-ignition engine, and it comprises: (a) has the oil of lubricant viscosity; B () is enough to be supplied to the substantially nitrogen-free olefine sulfide antiwear additive of the amount that compositions improves abrasion resistance; C () about 1 is to the about 10 nitrogenous dispersants of weight %; (d) selected from the overbased detergent of salixarate, salicin, Salicylate, glyoxylate and mixture thereof; Described compositions comprise less than about 0.1 weight % phosphorus, less than approximately 0.4 weight % sulfur and have less than approximately 1.2% sulfate ash. The internal combustion engine of example is APICH-4CumminsM11 heavy duty diesel engine.

US8,420,583 (Boegner et al., on May 22nd, 2003 is open) disclose a kind of lubricant oil composite, and it comprises: the major amount of oil with lubricant viscosity; Multi-functional olefin copolymer with at least one high graft of minor amount; the multi-functional olefin copolymer of described high graft is by acidylating agent and having more than about 10; 000 to about 50; the grafting degree (DOG) that the olefin copolymer of the number-average molecular weight of 000 reacts to provide acylating agent on the olefin copolymer in the presence of radical initiators acylated olefin copolymer higher than about 1.5 to about 3.0 weight %, and acidylate olefin copolymer and react to provide the multi-functional olefin copolymer of high graft to prepare with amine. Disclose this lubricating composition for lubricating compression-ignition engine to reduce soot deposits.

US8,168,574 (Visger et al., December disclosed on the 10th in 2009) disclose and reduce the viscosity raising that in large diesel engine, coal smoke causes. Lubricating composition disclosed herein comprises the oil with lubricant viscosity and the esterification nitrogen functionalized copolymers derived from following monomer: (i) at least one monomer selected from (a) vi-ny l aromatic monomers, (ii) at least one ��, beta-unsaturated acyl agent; The unit that acylating agent described in a portion derives is esterified; and the derivative unit of acylating agent described in a portion and at least one aromatic amine condensation; described aromatic amine comprises at least one can with the N-H group of the unit condensation of described acylating agent monomer derived, and described amine is selected from 4-ADPA, 4-phenylazo aniline, 2-aminobenzimidazole and 3-nitroaniline.

US8, 093, 189 (Devlin et al., on March 13rd, 2008 is open) disclose for large diesel engine, particularly CJ-4, the low SAP lubricant oil composite of CI-4PLUS or CI-4 electromotor, it comprises the amine-functionalized olefin copolymer dispersant viscosity index improver of the major amount of oil with lubricant viscosity and minor amount, described dispersant viscosity index improvers comprises the product of acylated olefin copolymer and polyamine compounds, wherein relative to the olefin copolymer dispersant instead comprising non-amine-functionalized non-acylated form, but other is the lubricant oil composite of identical improved form, when lubricant oil composite is polluted by the engine coolant of the about 50:50 mixture comprising water and pure (gathering) ethylene glycol (total) of about 2%, the amount of the olefin copolymer dispersant viscosity index improver filter blocks effectively to suppress coolant and cause exists, as measured by CumminsISMEGR test.

US2006/025316 (Covitch et al., on February 2nd, 2006 is open) disclose the method that lubrication is equipped with the large diesel engine of waste gas circulation, it includes feeding a kind of compositions wherein, described compositions comprises the product of the oily and following material with lubricant viscosity: (a) comprises the polymer of carboxylic-acid functional or its reactive equivalent, described polymer has the number-average molecular weight more than 5,000; (b) amine component of at least one aromatic amine is comprised, described aromatic amine comprises can with described carboxylic-acid functional condensation with at least one amino providing side base and at least one other group comprising at least one nitrogen, oxygen or sulphur atom, wherein said aromatic amine is selected from (i) nitro substituted aniline (such as 3-nitroaniline), and (ii) comprises by-C (O) NR-group ,-C (O) O-group ,-O-group ,-N-N-group or-SO₂The amine of 2 Aromatic moieties that-group connects, wherein R is hydrogen or alkyl, one described Aromatic moieties with described can condensation amino, (iii) quinolin-2-ylamine, (iv) aminobenzimidazole, (v) N, N-dialkyl phenylene diamine and (vi) ring alpha substituted benzylamine.

US2004/038836 (Devlin et al., on February 26th, 2004 open) discloses the lubricant suitable in diesel engine, and it comprises: have the lubricating oil of viscosity suitable in diesel engine; At least one functionalized olefin polymer; With zinc dialkyl dithiophosphate (ZDDP), wherein ZDDP is prepared by the mixture of primary alconol or the mixture of primary and secondary alcohol, and wherein lubricant has as passed through to use high-frequency reciprocating tester (HFRR) to be measured as the high boundary film friction valve more than or equal to 15.

US2003/134754 (Kelley, on July 17th, 2003 is open) discloses a kind of compositions, and described compositions comprises: (a) major amount of APII group mineral oil basestocks comprising at least 300 weight ppm sulfur; B () is adapted to provide for the molybdenum dithiocarbamate of compositions about 25 to the amount of about 600ppm molybdenum; The succinimide dispersants of c succinic acid structure that () replaces based on polyolefin, wherein polyolefin has the number-average molecular weight of at least about 1300; D () is derived from the zinc dialkyl dithiophosphate of at least one secondary alcohol; (e) at least one oxidation retarder selected from hindered phenol, alkylating aromatic amine and olefine sulfide. Said composition is expressed as lubricating engine oil, and it uses conventional high-sulfur base stock preparation for meeting the new spec of ILSACGF-3 and testing in SequenceIIIF gasoline engine.

Design is had to the passenger vehicle diesel engine of the end driven device valve mechanism of pivot finger-type of clearance adjuster, report the less research attempted by reducing this improvement lubricant properties that weares and teares. Therefore, Peugeot describes the test method that title is the test of DW10 clearance adjuster, and it tests laboratory (Automobil-Pr �� ftechnikLandauGmbH) operation at the APL being used for having this design. Lubricant must obtain the abrasion assessed value of 7 or higher with by the wear requirements of this test. It is an object of the invention to the abrasion reducing in the passenger vehicle diesel engine of the end driven device valve mechanism of pivot finger-type with clearance adjuster, in a particular embodiment, have in testing such as DW10 clearance adjuster and be measured as the abrasion assessed value more than 7.

Summary of the invention

As used herein, unless otherwise noted, about the additive being present in lubricating composition described herein amount mention that namely the amount of active substance is quoted based on oil-free.

As used herein, it is inclusive or opening with the transitional term " comprising " of " including ", " containing " or " being characterized by ... " synonym, and is not excluded for other unstated elements or method step. But, as optional embodiment, in the description every time of " comprising " herein, be intended to this term also include phrase " substantially by ... composition " and " by ... form ", wherein not including, " by ... composition ", any element or the step that do not describe, " substantially by ... composition " allows that other of the basic and new features including not affecting the compositions considered or method substantially does not describe element or step.

The present invention relates to the method holding the driven device valve mechanism clearance adjuster of pivot finger-type that lubrication has the passenger vehicle compression-ignition engine of the reference mass less than 2610kg, it includes infeed lubricating composition in internal combustion engine, described lubricating composition comprises the oil with lubricant viscosity, 0.01 weight % to 3 weight % dispersant viscosity modifiers, with 0.01 weight % to 3 weight % without zinc containing S antiwear additive, wherein lubricating composition has the sulfur content less than 5000ppm, 1000ppm or less phosphorus content, (usual 3000-12, 000ppm), or 10, 000ppm or less sulfate ash content.

Passenger vehicle reference mass less than 2610kg is the technical characteristic defined by European Union as described in the emission request of Euro5 and 6. Identical standard is applied by employer's organization ACEA (EuropeanAutomobileManufacturersAssociation) so that it defines light bus in the part C of theACEAEuropeanOilSequencesfor2010. Thus, the inventive method relates to lubricating the light bus compression-ignition engine (diesel engine) comprising the end driven device valve mechanism clearance adjuster of pivot finger-type.

Lubricating composition can have 500-4000ppm or the phosphorus content of the sulfur content of 1000-3000ppm, 300-900ppm, or 400-750ppm and the sulfate ash content of 3000-7000ppm.

Lubricating composition can comprise without zinc containing S antiwear additive, described comprise 0.1-0.5 weight % olefine sulfide without zinc containing S antiwear additive, with the olefin copolymer functionalized further by dispersant amine groups of 0.1-0.5 weight %, wherein olefin copolymer is ethylene-propylene copolymer.

Lubricating composition can comprise 0.1 weight % to 0.4 weight % molybdenum dithiocarbamate without zinc containing S antiwear additive, and the olefin copolymer that 0.1-0.5 weight % dispersant amine groups is functionalized further, and wherein olefin copolymer is ethylene-propylene copolymer.

Lubricating composition disclosed herein can further include the 0.01-0.5 weight % with lubricating composition or the sulfoacid calcium overbased detergent (generally wherein sulfoacid calcium overbased detergent has the TBN of 300-500mgKOH/g) that 0.05-0.3 weight % exists.

Clearance adjuster generally comprises ball-and-socket joint.

Clearance adjuster is generally hydraulic lash adjuster.

Clearance adjuster is generally the hydraulic lash adjuster comprising ball-and-socket joint. In one embodiment, clearance adjuster does not have chrome coating, tin coating, nitride coatings or boride coating.

The present invention further provides lubricating composition and reduce method and the purposes of the abrasion comprised in the internal combustion engine holding the driven device valve mechanism clearance adjuster of pivot finger-type, described lubricating composition comprises:

There is the oil of lubricant viscosity,

0.01 weight % to 3 weight % dispersant viscosity modifiers, and

0.01 weight % to 3 weight % is without zinc containing S antiwear additive, and wherein lubricating composition has the sulfur content less than 5000ppm, 1000ppm or less phosphorus content and usual 3000-12, a 000ppm, or 10,000ppm or less sulfate ash content.

The reduction of abrasion can be passed through the test of PeugeotDW10 clearance adjuster and measure with the conformity assessment value of 7 or higher.

Detailed Description Of The Invention

The present invention provides method and the purposes as described above of lubricating internal combustion engines.

There is the oil of lubricant viscosity

Lubricating composition comprises the oil with lubricant viscosity. Suitable oil includes natural and artificial oil, derived from hydrogenation cracking, hydrogenation and hydrorefined oil, non-refine, refine and refined oil or its mixture again. More detailed description about non-refine, refine and refined oil again is provided in International Publication WO2008/147704, in [0054th]-[0056] section (similar disclosure is provided in U.S. Patent application 2010/197536, referring to [0072]-[0073]). It is respectively described in [0058th] in WO2008/147704-[0059] section (similar disclosure is provided in U.S. Patent application 2010/197536, referring to [0075]-[0076]) about the natural more detailed description with synthetic lubricant fluid. Artificial oil is prepared also by fischer-tropsch reaction, can be generally F-T synthesis hydrocarbon or the wax of hydroisomerization. In one embodiment, oil can pass through the preparation of Fischer-Tropsch natural gas synthetic oil (gastoliquid) synthesis program and other natural gas synthetic oil.

The oil with lubricant viscosity also can such as in April, 2008 version of " AppendixE-APIBaseOilInterchangeabilityGuidelinesforPasse ngerCarMotorOilsand diesel engine Oils ", 1.3rd part, defines described in subtitle 1.3. " BaseStockCategories ". APIGuidelines is also summarized in US Patent No. 7,285,516 (walking to the 12nd hurdle the 10th row referring to the 11st hurdle the 64th).

In one embodiment, the oil with lubricant viscosity can for APII-IV group mineral oil, ester or artificial oil or its mixture. In one embodiment, the oil with lubricant viscosity can be APIII group, III group, IV group mineral oil, ester or artificial oil or its mixture.

The amount of the oil with lubricant viscosity existed is generally the remainder after deducted the amount sum of additive of the present invention and other performance additive by 100 weight %.

Lubricating composition can be concentrate and/or the form preparing lubricant completely. If lubricating composition of the present invention (comprises additive described herein) for the form (it can close with other line of oils and form all or part of final lubricant) of concentrate, then these additives with there is the oil of lubricant viscosity and/or be 1:99-99:1 weight with the ratio of flux oil, or 80:20-10:90 weighing scale. Generally, lubricating composition of the present invention comprises at least 50 weight % or at least 60 weight % or at least 70 weight % or the oil with lubricant viscosity of at least 80 weight %.

Dispersant viscosity modifiers

Lubricating composition of the present invention comprises dispersant viscosity modifiers. Dispersant viscosity modifiers can with 0.05 weight % to 1.5 weight %, or 0.1 weight % to 1 weight %, or 0.1-0.5 weight % exists.

Dispersant viscosity modifiers can include functionalised polyolefin, for instance with acylating agent such as maleic anhydride and amine-functionalized ethylene-propylene copolymer; With amine-functionalized polymethacrylates, or the styrene-maleic anhydride copolymer reacted with amine. The more detailed description of dispersant viscosity modifiers is disclosed in International Publication WO2006/015130 or United States Patent (USP) 4,863,623; 6,107,257; 6,107,258; 6,117,825; With in US7,790,661. In one embodiment, dispersant viscosity modifiers can include United States Patent (USP) 4,863,623 (walking to the 3rd hurdle the 52nd row referring to the 2nd hurdle the 15th) or International Publication WO2006/015130 (referring to page 2 [0008th] section and [0065th]-[0073] the described preparation embodiment of section) described those.

In one particular embodiment, dispersant viscosity modifiers comprises the olefin copolymer functionalized further by dispersant amine groups. Generally, olefin copolymer is ethylene-propylene copolymer.

Olefin copolymer has 5000-100, and 000, or 7500-60,000, or 8000-45, the number-average molecular weight of 000.

Dispersant amine groups can by olefin copolymer (usual ethylene-propylene copolymer) and acylating agent (usual maleic anhydride) with have the aromatic amine reaction of primary or secondary amino and prepare/derive. Generally, dispersant viscosity modifiers can be with maleic anhydride acidylate and the ethylene-propylene copolymer with aromatic amine reaction.

The formation of dispersant viscosity modifiers is well known in the art. Dispersant viscosity modifiers can include such as US Patent No. 7, and the 790,661, the 2nd hurdle the 48th walks to those described in the 10th hurdle the 38th row.

In one embodiment, dispersant viscosity modifiers can be grafted on 15-80 mole of % ethylene, 20-85 mole of %C by olefin carboxylic acid's acylating agent_3-10Preparing on the polymer of ��-monoolefine and 0-15 mole of % non-conjugated diene or triolefin, described polymer has 5000-500, the mean molecule quantity of 000, and makes described graft polymers and amine (usual aromatic amine) react further.

In another embodiment, dispersant viscosity modifiers can be the product of following material: (a) comprises the polymer of carboxylic-acid functional or its reactive equivalent, and described polymer has the number-average molecular weight more than 5,000; (b) amine component of at least one aromatic amine is comprised, described aromatic amine comprises can with described carboxylic-acid functional condensation to provide at least one amino of side base, with at least one other group comprising at least one nitrogen, oxygen or sulphur atom, wherein said aromatic amine is selected from (i) nitro substituted aniline, and (ii) comprises and pass through-C (O) NR-group ,-C (O) O-group ,-O-group ,-N=N-group or-SO₂The amine of 2 Aromatic moieties that-group connects, wherein R is hydrogen or alkyl, one described Aromatic moieties with described can condensation amino, (iii) quinolin-2-ylamine, (iv) aminobenzimidazole, (v) N, N-dialkyl phenylene diamine, (vi) aminodiphenylamine (also referred to as N, N-phenylenediamine) and (vii) ring obtain benzylamine.

The aromatic amine of dispersant viscosity modifiers may also include by general structure NH₂-Ar or T-NH-Ar represent those, wherein T can be alkyl or aromatics, and Ar is aromatic group, replaces aromatic group including nitrogenous or amino, and Ar group includes any one in following structure:

And multiple non-condensation or connect aromatic ring. In these and dependency structure, R^v��R^viAnd R^viiCan independently be except other group described herein ,-H ,-C_1-18Alkyl, nitro ,-NH-Ar ,-N=N-Ar ,-NH-CO-Ar ,-OOC-Ar ,-OOC-C_1-18Alkyl ,-COO-C_1-18Alkyl ,-OH ,-O-(CH₂CH₂-O)_nC_1-18Alkyl and-O-(CH₂CH₂O)_nAr (wherein n is 0-10).

Aromatic amine includes those amine that the carbon atom of wherein aromatic ring structure is connected directly between on amino nitrogen. amine can be monoamine or polyamines. aromatic ring is generally monokaryon aromatic ring (namely derived from the one of benzene), but can include fused aromatic rings, especially derived from those of naphthalene. the example of aromatic amine includes aniline, N-alkyl benzene amine such as methylphenylamine and N-butylaniline, two-(p-aminomethyl phenyl) amine, 4-ADPA, N, N-dimethyl phenylene diamine, naphthylamines, 4-(4-nitrophenylazo) aniline (disperse orange 3), sulfadimidine, 4-phenoxybenzamine, 3-nitroaniline, 4-amino acetanilide (N-(4-aminophenyl) acetamide)), 4-amino-2-hydroxy-benzoic acid phenylester (phenyl amino salicylate), N-(4-methanesulfonylamino-phenyl)-Benzoylamide, various benzylamines such as 2, 5-dimethoxybenzylamine, 4-phenylazo aniline and these replacement variant. other example include p-phenetidine, p-dodecyl polyaniline, cyclohexyl replace naphthylamines and thienyl replace aniline. the example of other suitable aromatic amine include amino replace aromatic compounds and wherein amine nitrogen be the amine of a part for aromatic ring, for instance 3-quinolin-2-ylamine, 5-quinolin-2-ylamine and 8-quinolin-2-ylamine. also including aromatic amine, for instance 2-aminobenzimidazole, it comprises the secondary amino group being connected directly between on aromatic ring and the primary amino radical being connected on imidazole ring. other amine includes N-(4-aniiinophenyl)-3-amino-butanamide or 3-aminopropylimidazol. amine other again includes 2,5-dimethoxybenzylamine.

Other aromatic amine and related compound are disclosed in United States Patent (USP) 6,107,257 and 6,107,258; Some in these include aminocarbazole, benzimidazole, amino indole, amino-pyrroles, amino-indazole quinoline ketone, aminoPyridine, mercapto-triazole, amino phenothiazine, aminopyridine, Aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, chiral lactones, aminothio thiadiazoles and amino benzotriazole. Other suitable amine includes 3-amino-N-(4-aniiinophenyl)-N-butanamide and N-(4-aniiinophenyl)-3-{ (3-aminopropyl)-(Cocoalkyl) amino } butyramide. Other aromatic amine spendable includes the various aromatic amine dyestuff intermediates comprising the multiple aromatic rings connected by such as amide structure. Example includes the material of following general structure:

And isomery variant, wherein R^viiiAnd R^ixIndependently be alkyl or alkoxyl, for instance methyl, methoxy or ethoxy. In one case, R^viiiAnd R^ixIt is all OCH₃, and this material is called FastBlueRR [CAS#6268-05-9].

In another case, R^ixFor OCH₃And R^viiiFor CH₃, and this material is called FastVioletB [99-21-8]. Work as R^viiiAnd R^ixWhen being all ethyoxyl, material is FastBlueBB [120-00-3]. United States Patent (USP) 5,744,429 discloses other aromatic amine compound, particularly aminoalkyl phenothiazine. N-aromatic substituted acid amide compound, for instance described in U.S. Patent application 2003/0030033A1, those can also be used for the object of the invention. It is the substituent group on aromatic carboxylic acid compounci that suitable aromatic amine includes wherein amine nitrogen, and namely the nitrogen in aromatic ring is not sp²Those of hydridization.

Aromatic amine also can comprise the amine reacted with 4-ADPA and formed by aldehyde. Gained amine can be described as has at least 4 aromatic groups, at least 1-NH₂The alkylidene coupling amine of functional group and at least 2 second or tertiary amino. Aldehyde can be aliphatic, alicyclic or aromatics. Aliphatic aldehydes can be linear or branching. The example of suitable aromatic aldehyde includes benzaldehyde or o-Vanillin. The example of aliphatic aldehydes includes formaldehyde (or its reactive equivalent such as formalin or paraformaldehyde), acetaldehyde or propionic aldehyde. Generally, aldehyde can be formaldehyde or benzaldehyde. As selection, this aromatic amine is also by BerichtederDeutschenChemischenGesellschaft (1910), and described in 43,728-39 prepared by method.

It is described in European patent application EP 2401348A by the aromatic amine that aldehyde and 4-ADPA coupling are formed, and also can be expressed from the next:

Wherein each variable:

R¹Can be hydrogen or C_1-5Alkyl (usual hydrogen);

R²Can be hydrogen or C_1-5Alkyl (usual hydrogen);

U can be aliphatic, alicyclic or aromatic group, and condition is when U is for aliphatic series, and aliphatic group can be comprise the linear of 1-5 or 1-2 carbon atom or sub-branched alkyl; And

W can be 0-9 or 0-3 or 0-1 (usual 0).

In one embodiment, aromatic amine includes 4-ADPA, aldehyde (usual formaldehyde) coupling 4-ADPA, nitroaniline (3-nitroaniline), disperse orange-3 (DO3) or its mixture.

Without zinc containing S antiwear additive

Lubricating composition of the present invention comprises without zinc containing S antiwear additive. Without zinc containing S antiwear additive can with 0.01 weight % to the 1.5 weight % of lubricating composition, 0.05 weight % to 1 weight %, or 0.1-0.5 weight % exist.

It is selected from olefine sulfide, molybdenum compound, the amine salt of (sulfo-) phosphorus-containing compound, thiadiazoles and mixture thereof containing S antiwear additive without zinc.

In one embodiment, can be molybdenum compound without zinc containing S antiwear additive. Molybdenum compound can be antiwear additive or antioxidant. Molybdenum compound is selected from molybdenum dialkyl-dithiophosphate, molybdenum dithiocarbamate, the amine salt of molybdenum compound and mixture thereof. Generally, molybdenum compound can be molybdenum dithiocarbamate or molybdenum dithiophosphate.

Molybdenum compound is provided to lubricating composition 0-1000ppm or 5-1000ppm or 10-750ppm, 5ppm to 400ppm or 20ppm to 350ppm molybdenum. Can be used as the example of the molybdenum dithiocarbamate of antioxidant to include with trade name such as Vanlube822^TMAnd Molyvan^TMA is sold by R.T.VanderbiltCo., Ltd., and AdekaSakura-Lube^TMS-100, S-165, S-600 and 525 sell commercial materials or its mixture.

In another embodiment, can be olefine sulfide without zinc containing S antiwear additive. Olefine sulfide can be polysulfide.

In one embodiment, olefine sulfide includes dialkyl polysulfide; Olefine sulfide; The sulfide aliphatic acid ester that natural and synthesis is originated; Three thioketone; Sulfuration thienyl derivant; Sulfuration terpenes; C₂-C₈The sulfuration oligomer of monoolefine; With sulfuration this Alder adduct of Deere, for instance U.S. Patent No. Re27, described in 331 those. Instantiation especially includes sulfurized polyisobutylene, sulfide isobutene, sulfuration diisobutylene, sulfuration TIB, dicyclohexyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and the mixture of di-t-butyl polysulfide, for instance the mixture of di-t-butyl trisulfide, di-t-butyl tetrasulfide and di-t-butyl pentasulfide. It is used as this kind of combination containing S antiwear additive and/or extreme pressure agent, for instance the combination of sulfide isobutene and di-t-butyl trisulfide, the combination of sulfide isobutene and dinonyl trisulfide, the combination of sulfuration tall oil and dibenzyl polysulfide.

In another embodiment, the mixture that polysulfide molecule is three-or tetrasulfide of at least 50 weight %. In other embodiments, at least 55 weight %, or the mixture that polysulfide molecule is three-or tetrasulfide of at least 60 weight %.

Polysulfide includes from oil, fatty acid or ester (such as containing ester olefine sulfide), alkene or polyolefinic sulfuration organopolysulfides.

The oil that can vulcanize includes naturally occurring or synthetic oil, for instance mineral oil, Adeps Sus domestica, carboxylate (such as oleic acid myristyl ester and oleic acid oil base ester) derived from aliphatic alcohol and fatty acid or aliphatic carboxylic acid, and synthesis beta-unsaturated esters or glyceride.

Fatty acid includes those containing 8-30 or 12-24 carbon atom. The example of fatty acid includes oleic acid, linoleic acid, linolenic acid and tall oil. The sulfide aliphatic acid ester prepared by mixing unsaturated fatty acid ester, such as by Animal fat and vegetable oil, obtains including tall oil, Semen Lini oil, soybean oil, rapeseed oil and fish oil.

Polysulfide includes the alkene derived from multiple olefine. Olefine is generally of one or more double bond. In one embodiment, alkene comprises 3-30 carbon atom. In other embodiments, alkene comprises 3-16 or 3-9 carbon atom. In one embodiment, olefine sulfide includes the alkene of derived from propylene, isobutene., amylene or its mixture.

In another embodiment, polysulfide is comprised and is polymerized by known technology and derived from the polyolefin of alkene described above.

In yet another embodiment, polysulfide includes dibutyl tetrasulphide, sulfuration methyl oleate, sulphurized alkyl phenols, sulfurized dipentene, sulfuration bicyclopentadiene, sulfuration terpenes and sulfuration this Alder adduct of Deere.

In another embodiment, olefine sulfide can be containing ester olefine sulfide. Sulfuration 4-carbon butoxy cyclohexene can be included containing ester olefine sulfide.

In yet another embodiment, can be thiadiazole compound without zinc containing S antiwear additive. The example of thiadiazoles includes 2,5-dimercapto-1,3,4-thiadiazoles or its oligomer, alkyl replaces 2,5-dimercapto-1,3,4-thiadiazoles, sulfenyl replaces 2,5-dimercapto-1,3,4-thiadiazoles or its oligomer. Alkyl replaces the oligomer of 2,5-dimercapto-1,3,4-thiadiazoles and is formed to form the oligomer of two or more described thiadiazole unit usually by formation sulfur-sulfide linkage between 2,5-dimercapto-1,3,4-thiadiazole unit. These thiadiazole compounds can also be used in the post processing of the dispersant as hereafter mentioned in forming the dimercaptothiodiazole derivant of polyisobutenyl succinimide.

The example of suitable thiadiazole compound includes dimercaptothiodiazole, 2,5-dimercaptos-[1,3,4]-thiadiazoles, 3,5-dimercapto-[1,2,4]-thiadiazoles, 3,4-dimercapto-[1,2,5]-thiadiazoles, or 4-5-dimercapto-[1,2,3] at least one in-thiadiazoles. Generally use the material such as the 2,5-dimercapto-1,3,4-thiadiazoles or alkyl that are often easily available to replace 2,5-dimercapto-1,3,4-thiadiazoles or sulfenyl replaces 2,5-dimercapto-1,3,4-thiadiazoles.

In one embodiment, without zinc containing S antiwear additive can be the amine salt of (sulfo-) phosphorus-containing compound. The amine salt of (sulfo-) phosphorus-containing compound can be the amine salt (i.e. the amine salt of the hydrocarbon ester of phosphoric acid) of phosphoric acid hydrocarbon ester. The amine salt of phosphoric acid hydrocarbon ester can derived from the amine salt of phosphate ester. The amine salt of phosphoric acid hydrocarbon ester can be expressed from the next:

Wherein:

R³And R⁴Hydrogen can be independently be or generally comprise 4-40, or 6-30, or 6-18, or the hydrocarbon of 8-18 carbon atom, condition is at least one is alkyl; And

R⁵��R⁶��R⁷And R⁸Can independently be hydrogen or alkyl, condition is at least one is alkyl.

R³And/or R⁴Alkyl can be linear, branching or ring-type.

The amine salt of phosphoric acid hydrocarbon ester can be prepared as described in United States Patent (USP) 6,468,946. 10th hurdle 15-63 line description is reacted by phosphorus compound, reacts thereafter the phosphate ester formed to form the amine salt of phosphoric acid hydrocarbon ester with amine. 10th hurdle the 64th walks to the 12nd hurdle the 23rd line description preparation embodiment: make to react between phosphorus pentoxide and alcohol (having 4-13 carbon atom), thereafter with amine (generally81-R) the reaction amine salt to form phosphoric acid hydrocarbon ester.

The amine salt of (sulfo-) phosphorus-containing compound can also for compound described in European patent application EP 2318493A and 2113023A. / the salt without thiamine of available phosphorus compound is obtained disclosed in two EP application by a kind of method; described method includes: make the hydroxyl replacement diester of amine and (i) phosphoric acid; or (ii) the phosphorylated hydroxyl of phosphoric acid replaces diester or the reaction of three esters, and is represented by formula (1) and (1a) in two publications.

Lubricating composition can comprise 0.01 weight % to 1.5 weight % olefine sulfide, the olefin copolymer that 0.05 weight % to 1.5 weight % dispersant amine groups is functionalized further.

Lubricating composition can further include with 0.01-0.75 weight %, or 0.05 weight % to 0.5 weight %, or the molybdate compound that the amount of 0.1 weight % to 0.4 weight % exists, described molybdate compound selects free molybdenum dithiocarbamate and the group (usual molybdenum dithiocarbamate) of molybdenum dithiophosphate composition.

Lubricating composition can comprise 0.01 weight % to 0.75 weight % molybdenum dithiocarbamate, the olefin copolymer that 0.05 weight % to 1.5 weight % dispersant amine groups is functionalized further, and wherein olefin copolymer is ethylene-propylene copolymer.

Lubricating composition can comprise 0.01 weight % to 1.5 weight % olefine sulfide, 0.01 weight % to 0.75 weight % molybdenum dithiocarbamate, the olefin copolymer that 0.05 weight % to 1.5 weight % dispersant amine groups is functionalized further, wherein olefin copolymer is ethylene-propylene copolymer.

Other performance additive

Lubricating composition can be prepared in the oil with lubricant viscosity by being added under the existence of other performance additive (as mentioned below) by the product of methods described herein.

Lubricating composition of the present invention optionally comprises other performance additive. Other performance additive includes following at least one: metal deactivator, viscosity improver, detersive, friction improver, antiwear additive, corrosion inhibitor, dispersant, dispersant viscosity modifiers, extreme pressure agent, antioxidant, foam inhibitor, demulsifier, pour-point depressant, sealing sweller and mixture thereof. Generally, lubrication pockets is prepared completely containing one or more in these performance additive.

In one embodiment, the present invention provides and comprises the parlkaline lubricating composition containing metal detergent further. Metal containing metal detergent can be zinc, sodium, calcium, barium or magnesium. Generally, the metal containing metal detergent can be sodium, calcium or magnesium.

Parlkaline is selected from without thiophenol salt, sulfur-bearing phenates, sulfonate, salixarate, Salicylate and mixture thereof or its boration equivalent containing metal detergent. Can by overbased detergent boric acid agent such as perborate tetrahydrate.

Parlkaline may also comprise " mixing " detersive formed by mixed surfactant system containing metal detergent, described system comprises phenates and/or sulfonate component, such as phenates/Salicylate, sulfonate/phenates, sulfonate/Salicylate, sulfonate/phenates/Salicylate, such as such as United States Patent (USP) 6,429,178; 6,429,179; 6,153,565; Described in 6,281,179. If such as using and mixing sulfonate/phenate detergents, then it is assumed that this mixes detersive equal to the amount introducing the phenates of similar quantity and the different phenates of sulfonate soap and sulfonate detergent respectively.

Generally, parlkaline can be phenates, sulfur-bearing phenates, sulfonate, salixarate and the zinc of Salicylate, sodium, calcium or magnesium salt containing metal detergent. Parlkaline salixarate, phenates and Salicylate are generally of the total base number of 180-450TBN. Overbased sulfonates is generally of 250-600 or the total base number of 300-500. Overbased detergent is as known in the art. In one embodiment, sulfonate detergent can be the dominant linear alkylbenzenesulfonate detersive of the metal ratio with at least 8, as described in [0026th]-[0037] section of U.S. Patent application 2005065045 (and authorize US7,407,919). Dominant linear alkylbenzenesulfonate detersive can be used in particular for helping to improve fuel economy.

Generally, parlkaline can be calcium or magnesium overbased detergent containing metal detergent.

Overbased detergent is as known in the art. Parlkaline material, also referred to as parlkaline or hyperalkaline salt, is generally single phase homogeneous Newtonian systems, it is characterized in that tenor exceed according to metal and with the stoichiometry of the specific acidic organic compound of metal reaction in and can exist. Parlkaline material passes through acid material (usual mineral acid or lower level carboxylic acid, preferably carbon dioxide) to prepare with comprising acidic organic compound, reaction medium, the metal base of stoichiometric excess and the mixture reaction of accelerator such as calcium chloride, acetic acid, phenol or alcohol, described reaction medium comprises at least one inert organic solvents for described acidic organic material (mineral oil, Petroleum, toluene, dimethylbenzene etc.). Acidic organic material is generally of enough carbon numbers to provide the dissolubility in oil. The amount of " excessive " metal (stoichiometry) represents generally according to metal ratio. Term " metal compares " is the total yield ratio with the equivalent of acidic organic compound of metal. Neutral metal salt has the metal ratio of 1. Have with the salt of 3.5 times of as many metals that exists in normal salt that to have the metal of 3.5 equivalents excessive, or the ratio of 4.5. Term " metal ratio " is also explained in the standard textbook that title is " ChemistryandTechnologyofLubricants ", and the 3rd edition, R.M.Mortier and S.T.Orszulik edits, Copyright1997, the 219th page, in subtitle 7.25.

In another embodiment, lubricating composition comprises a certain amount of sulfoacid calcium overbased detergent further and Calcium carbolate overbased detergent makes sulfate ash content be 1000ppm or less (such as 100ppm to 1000ppm, or 300ppm to 900ppm).

In another embodiment, lubricating composition comprises antioxidant, and wherein antioxidant comprises phenol or amine antioxidants or its mixture. Antioxidant includes diaryl amine, alkylation diaryl amine, hindered phenol or its mixture. When it is present, antioxidant is with 0.1 weight % to the 3 weight % of lubricating composition, or 0.5 weight % to 2.75 weight %, or 1 weight % to 2.5 weight % exists.

Diaryl amine or alkylation diaryl amine can be phenyl-a-naphthylamine (PANA), alkylated diphenylamine or alkylation nonox or its mixture. Alkylated diphenylamine can include two-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, two-octylated diphenylamine, two-decylated diphenylamine, decyl diphenylamine and mixture thereof. In one embodiment, diphenylamines can include nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine or its mixture. In another embodiment, alkylated diphenylamine can include nonyl diphenylamine or dinonyldiphenylamine. Alkylation diaryl amine can include octyl group, dioctyl, nonyl, dinonyl, decyl or didecyl nonox.

Hindered phenol antioxidant usually contains sec-butyl and/or the tert-butyl group as steric group. Phenolic group can further by alkyl (being generally linear or branched-alkyl) and/or be connected to bridge linkage group on second aryl and replace. The example of suitable hindered phenol antioxidant includes 2,6-di-t-butyl phenol, 4-methyl-2,6-di-t-butyl phenol, 4-ethyl-2,6-di-t-butyl phenol, 4-propyl group-2,6-DI-tert-butylphenol compounds or 4-butyl-2,6-di-t-butyl phenol or 4-dodecyl-2,6-di-t-butyl phenol. In one embodiment, hindered phenol antioxidant can be ester, it may include such as from the Irganox of Ciba^TML-135. Suitable finds containing being described in more detail in United States Patent (USP) 6,559,105 of ester hindered phenol antioxidant chemistry.

In another embodiment, lubricating composition can comprise dispersant or its mixture. Dispersant can be succinimide dispersants, Mannich dispersant, succinamide dispersant, polyalkylene succinic acid esters, amide or ester-acid amide, or its mixture. In one embodiment, dispersant exists as single dispersant. In one embodiment, dispersant can exist as the mixture of two kinds or three kinds different dispersants, and at least one of which can be succinimide dispersants.

Succinimide dispersants can derived from aliphatic polyamines or its mixture. Aliphatic polyamines can be aliphatic polyamines such as ethylene, propylidene polyamines, butylidene polyamines or its mixture. In one embodiment, aliphatic polyamines can be ethylene. In one embodiment, aliphatic polyamines is selected from that ethylenediamine, diethylenetriamines, trien, tetren, penten, polyamines still be residual and mixture.

In one embodiment, dispersant can be polyalkylene succinic acid esters, amide or ester-acid amide. Such as, polyalkylene succinic acid esters can be polyisobutylene succinic acid ester or its mixture of tetramethylolmethane. Polyalkylene succinic acid ester-amide can be the polyisobutylene succinic acid reacted with alcohol (such as tetramethylolmethane) and polyamines described above.

Dispersant can for the N-long chain alkenyl succinimides replaced. The example of the long chain alkenyl succinimides that N-replaces is polyisobutenyl succinimide. Generally, the polyisobutylene deriving polyisobutylene succinic anhydride has 350-5000 or the number-average molecular weight of 550-3000 or 750-2500. Succinimide dispersants and their preparation are such as disclosed in United States Patent (USP) 3,172,892,3,219,666,3,316,177,3,340,281,3,351,552,3,381,022,3,433,744,3,444,170,3,467,668,3,501,405,3,542,680,3,576,743,3,632,511,4,234,435, Re26,433 and 6,165,235,7,238,650 and EP patent application 0355895A in.

Also can by dispersant by conventional method by with in plurality of reagents any one reaction and post processing. Wherein, these are succinic anhydrides, maleic anhydride, nitrile, epoxide and the phosphorus compound that boron compound (such as boric acid), urea, thiourea, dimercaptothiodiazole, Carbon bisulfide, aldehyde, ketone, carboxylic acid such as p-phthalic acid, hydrocarbon replace. In one embodiment, by the dispersant boration of post processing. In one embodiment, the dispersant making post processing reacts with dimercaptothiodiazole. In one embodiment, the dispersant making post processing reacts with phosphoric acid or phosphorous acid. In one embodiment, dispersant and p-phthalic acid and the acid reaction (as described in U.S. Patent application US2009/0054278) of post processing are made.

When it is present, dispersant can with 0.01 weight % to the 20 weight % of lubricating composition, or 0.1 weight % to 15 weight %, or 0.1 weight % to 10 weight %, or 1 weight % to 6 weight %, or 1-3 weight % exists.

In one embodiment, friction improver is selected from the derivant of the long-chain fatty acid derivative of amine, long-chain fat ester or long chain fatty epoxide; Fatty imidazolines; The amine salt of alkyl phosphoric acid; Fatty alkyl tartrate; Fatty alkyl tartrimide; Fatty alkyl tartramide; Fat glycolate; With fat hydroxyl acetamide. Friction improver can with 0 weight % to the 6 weight % of lubricating composition, or 0.01 weight % to 4 weight %, or 0.05 weight % to 2 weight %, or 0.1 weight % to 2 weight % exists.

As used herein, the term " fatty alkyl " relevant with friction improver or " fat " mean the carbochain with 10-22 carbon atom, usual normal carbon chain.

Suitable frictional improves the example of agent and includes the long-chain fatty acid derivative of amine, fatty ester or fat epoxide; The condensation product of fatty imidazolines such as carboxylic acid and polyalkylene polyamine; The amine salt of alkyl phosphoric acid; Fatty alkyl tartrate; Fatty alkyl tartrimide; Fatty alkyl tartramide; Fatty phosphine hydrochlorate; Fatty phosphites; Boration phospholipid, borated fatty epoxides; Glyceride; Borated glycerol esters; Fatty amine; Alkoxylated fats amine; Borated alkoxylated fatty amine; Hydroxyl and poly-hydroxy aliphatic amine, including tert-hydroxyl fatty amine; Hydroxyalkylamides; The slaine of fatty acid; The slaine of alkylsalicylate; FatAzoles quinoline; Fat ethoxylated alcohol; The condensation product of carboxylic acid and polyalkylene polyamine; Or aliphatic carboxylic acid and guanidine, aminoguanidine, the product of urea or thiourea and salt thereof.

Friction improver may also include material, for instance the Oleum helianthi of sulfurized fatty compound and alkene, molybdenum dialkyl-dithiophosphate, molybdenum dithiocarbamate, polyhydric alcohol and aliphatic carboxylic acid or soya-bean oil monoester.

In another embodiment, friction improver can be long-chain fatty acid ester. In another embodiment, long-chain fatty acid ester can be monoesters, and in another embodiment, long-chain fatty acid ester can be triglyceride.

Lubricating composition optionally comprises at least one antiwear additive further. The example of suitable antiwear additive includes titanium compound, tartrate, tartrimide, the oil-soluble amine salt of phosphorus compound, olefine sulfide, metal dialkyl dithiophosphate (such as zinc dialkyl dithiophosphate), phosphite (such as dibutyl phosphite), phosphonate, compound containing thiocarbamate, for instance thiocarbamate, thiocarbamic acid amide, thiocarbamic acid ether, the thiocarbamate of alkylidene coupling and double; two (S-alkyl Dithiocarbamyl) disulfide. In one embodiment, antiwear additive can include the tartrate as disclosed in International Publication WO2006/044411 or Canadian Patent CA1183125 or tartrimide. Tartrate or tartrimide can contain alkyl-ester group, and wherein the carbon atom sum on alkyl is at least 8. In one embodiment, antiwear additive can comprise the citrate as disclosed in U.S. Patent application 20050198894.

Another kind of additive includes the oil-soluble titanium as disclosed in US7,727,943 and US2006/0014651. Oil-soluble titanium may act as the more than one in antiwear additive, friction improver, antioxidant, sediment monitoring additive or these functions. In one embodiment, oil-soluble titanium is titanium (IV) alkoxide. Titanium alkoxides is formed by monohydric alcohol, polyhydric alcohol or its mixture. Unitary alkoxide can have 2-16 or 3-10 carbon atom. In one embodiment, Titanium alkoxides is isopropyl titanate (IV). In one embodiment, Titanium alkoxides is 2-Ethylhexyl Alcohol titanium (IV). In one embodiment, titanium compound includes the alkoxide of vincial faces 1,2-glycol or polyhydric alcohol. In one embodiment, 1,2-vincial faces glycol includes the fatty-acid monoester of glycerol, and usual fatty acid is oleic acid.

In one embodiment, oil-soluble titanium is titanium carboxylate. In another embodiment, titanium (IV) carboxylate is neodecanoic acid titanium.

In one embodiment, lubricating composition can further include phosphorous antiwear additive. Generally, phosphorous antiwear additive can be zinc dialkyl dithiophosphate, phosphite, phosphate, phosphonate and ammonium phosphate salt or its mixture. Zinc dialkyl dithiophosphate is as known in the art. Antiwear additive can with 0 weight % to the 3 weight % of lubricating composition, or 0.1 weight % to 1.5 weight %, or 0.5 weight % to 0.9 weight % exists.

Extreme pressure (EP) agent in oil-soluble includes sulfur-bearing and the CS of chloride sulfur EP agent, dimercaptothiodiazole or dispersant (usual succinimide dispersants)₂The derivant of derivant, chlorohydrocarbon EP agent and phosphorus EP agent. The example of this kind of EP agent includes chlorinated wax; Olefine sulfide (such as sulfide isobutene), alkyl replace 2,5-dimercapto-1,3,4-thiadiazoles or its oligomer, organic sulfur compound and polysulfide such as dibenzyldisulfide, double; two-(chlorobenzyl) disulphide, dibutyl tetrasulphide, the methyl oleate of sulfuration, sulfenyl phenolate, sulfurized dipentene, sulfuration terpenes and sulfuration Diels alder adducts; Phosphosulfurized hydrocarbon, for instance the product of phosphoric sulfide and Oleum Terebinthinae or methyl oleate; Phosphide, for instance two hydrocarbon and three hydrocarbon phosphite esters, for instance dibutyl phosphite, phosphorous acid two heptyl ester, phosphorous acid dicyclohexyl maleate, phosphorous acid amyl group phenyl ester; The phosphite that phosphorous acid diamyl phenyl ester, phosphorous acid tridecyl ester, phosphorous acid distearyl ester and polypropylene replace; Metal thiocarbamates, for instance dioctyl zinc dithiocarbamate and heptylphenol diacid barium; The amine salt of alkyl and Acidic phosphates or derivant, including the product of such as dialkyl dithiophosphoric acid Yu propylene oxide, subsequently with P₂O₅The amine salt of reaction further; And mixture (as described in US3,197,405).

Can be used for the foam inhibitor in the present composition and include polysiloxanes, ethyl acrylate and 2-EHA and the copolymer of optional vinyl acetate; Demulsifier, including chlorination polysiloxanes, trialkylphosphate, Polyethylene Glycol, polyethylene glycol oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymer.

Can be used for the pour-point depressant in the present composition and include polyalphaolefin, maleic anhydride-styrene copolymers, poly-(methyl) acrylate, polyacrylate or polyacrylamide.

Demulsifier includes trialkylphosphate, and the various polymer of ethylene glycol, ethylene oxide, propylene oxide or its mixture and copolymer.

Metal deactivator includes the derivant (usual tolyl-triazole) of benzotriazole, 1,2,4-triazole, benzimidazole, 2-alkyl dithio benzimidazole or 2-alkyl dithio benzothiazole. Metal deactivator also can be described as corrosion inhibitor.

Seal sweller and include cyclobufene sultone derivant ExxonNecton-37^TMAnd ExxonMineralSealOil (FN1380)^TM(FN3200)��

Commercial Application

Internal combustion engine can be four-stroke engine. Internal combustion engine can have or not have scheme for exhaust gas circulation system. Internal combustion engine can be provided with emission control systems or turbocharger. The example of emission control systems includes diesel particulate filters (DPF) or uses the system of SCR (SCR).

The sulfur content of lubricating composition can be 1 weight % or less, or 0.8 weight % or less, or 0.5 weight % or less, or 0.3 weight % or less. In one embodiment, sulfur content can be 0.001 weight % to 0.5 weight %, or 0.01 weight % to 0.3 weight %. Phosphorus content can be 0.2 weight % or less, or 0.12 weight % or less, or 0.1 weight % or less, or 0.085 weight % or less, or 0.08 weight % or less, or even 0.06 weight % or less, 0.055 weight % or less, or 0.05 weight % or less. In one embodiment, phosphorus content can be 0.04 weight % to 0.12 weight %. In one embodiment, phosphorus content can be 100ppm to 1000ppm, or 200ppm to 600ppm. Total sulfate ash content can be 0.3 weight % to the 1.2 weight % of lubricating composition, or 0.5 weight % to 1.1 weight %. In one embodiment, sulfate ash content can be 0.5 weight % to the 1.1 weight % of lubricating composition.

In one embodiment, lubricating composition can be characterized as having following at least one: (i) of lubricating composition 0.5 weight % or less sulfur content, (ii) 0.12 weight % or less phosphorus content, and the sulfate ash content of (iii) 0.5 weight % to 1.1 weight %.

Lubricating composition can have the SAE viscosity grade of XW-Y, and wherein X can be 0,5,10 or 15; And Y can be 20,30 or 40.

Following example provide the elaboration to the present invention. These embodiments are not exhaustive and are not intended to limit the scope of the present invention.

Embodiment

Embodiment 1 (EX1):For 0W-30 lubricating composition, it comprises: at least 74 weight %APIIII groups/IV group base oil, with the molybdenum dithiocarbamate providing the amount of about 300ppm molybdenum to exist, 0.33 weight % reacts with maleic anhydride and makes, by ethylene-propylene copolymer, the dispersant viscosity modifiers that it reacts with 3-nitroaniline and dimethylamino propylamine (DMAPA) and prepare. Lubricating composition comprises polyisobutenyl succinimide further, the mixture of 2.1 weight % amines and phenolic antioxidants, 0.65 weight % zinc dialkyl dithiophosphate, 0.1 weight % overbased calcium sulfonate, 1 weight % parlkaline Calcium carbolate and 0.6 weight % viscosity improver. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Embodiment 2 (EX2):For 0W-30 lubricating composition, it comprises: at least 74 weight %APIIII groups/IV group base oil, 0.3 weight % olefine sulfide, the dispersant viscosity modifiers being reacted with maleic anhydride by ethylene-propylene copolymer and making it and 3-nitroaniline react with dimethylamino propylamine (DMAPA) and prepare of 0.33 weight %. Lubricating composition comprises polyisobutenyl succinimide further, 2.1 weight % amines and the mixture of phenolic antioxidants, 0.65 weight % zinc dialkyl dithiophosphate, 0.1 weight % overbased calcium sulfonate, 1 weight % parlkaline Calcium carbolate and 0.6 weight % viscosity improver. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Comparative example 1 (CE1): it is similar to EX1, the difference is that this lubricant does not comprise molybdenum dithiocarbamate, dispersant viscosity modifiers or olefine sulfide. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Comparative example 2 (CE2): it is similar to EX1, the difference is that it comprises to provide the molybdenum dithiocarbamate that the amount of 500ppm molybdenum exists, and does not comprise dispersant viscosity modifiers or olefine sulfide. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Comparative example 3 (CE3): it is similar to EX2, the difference is that it comprises 0.2 weight % olefine sulfide and does not comprise molybdenum dithiocarbamate or dispersant viscosity modifiers. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Comparative example 4 (CE4): it is similar to EX1, does not comprise molybdenum dithiocarbamate the difference is that it. Lubricating composition has the sulfate ash content of the phosphorus content less than the sulfur content of 0.3 weight %, about 600ppm and 0.55 weight %.

Lubricant embodiment EX1, EX2 and CE1-CE4 is assessed by the DW10 engine test agreement run of the APL according to 2011-2013. The result obtained about test is shown in following table. Typically for the sample of the assessed value with 7 or bigger, obtain good result, and this test describes the minimum conformity assessment value of 7.

Lubricant embodiment	Assessed value
		CE1	5.75
CE2	6.43
		CE3	5.89
CE4	6.41
		EX1	8.52
EX2	7.46

Being tested that obtain by DW10 clearance adjuster it is shown that the lubricating composition defined by the present invention is by this test, the lubricating composition outside the invention scope advocated does not pass through this test.

More known above-mentioned materials are likely to interact in final preparaton so that the component of final preparaton be likely to from originally add those are different. The product being consequently formed, is likely to be not easy to describe including the product through being formed with its intended use use lubricant compositions of the present invention. But, all such is improved and product is included in the scope of the present invention; The present invention includes the lubricant compositions by said components mixing being prepared.

At this, above-mentioned each file is incorporated by reference into the present invention. Except in embodiment, or outside additionally clearly stating, all quantity describing the amount of material, reaction condition, molecular weight, carbon number etc. in this manual are to be understood that modified by the term " about. Except as otherwise noted, all percent value and ppm value calculate for weight % value and/or based on weight herein. Except as otherwise noted, each chemicals mentioned above or compositions should be understood to contain isomer, by-product, derivant and generally be to be understood that the commercial grade material of other this kind of material being present in commerical grade. But, except as otherwise noted, the scale of each chemical constituent is shown as and eliminates any solvent or flux oil that generally may be present in commercial materials. It is to be understood that the upper and lower bound of amount described herein, scope and ratio can combine independently. Similarly, the scope of each element of the present invention can use with amount together with the scope of other element any or amount.

As used herein, term " hydrocarbyl substituent " or " alkyl " use with its conventional meaning well known to those skilled in the art. Specifically, it refers to have the carbon atom being connected directly between on molecule remainder and mainly have the group of hydrocarbon character. The example of alkyl includes: hydrocarbon substituent, including aliphatic series, alicyclic and aromatic substituent; The hydrocarbon substituent replaced, namely contains the substituent group of the non-hydrocarbon of the main hydrocarbon character not changing substituent group in the context of the present invention; With assorted substituent group, namely there is main hydrocarbon character similarly, but containing the substituent group being different from carbon in ring or chain. The definition in more detail of term " hydrocarbyl substituent " or " alkyl " is described in [0118th]-[0119] section of International Publication WO2008147704, or openly applies for the similar definition in [0137th]-[0141] section of US2010-0197536.

As used herein, detersive total base number (TBN) can be measured by ASTMD2896.

Although explaining the present invention about preferred embodiment, it should be understood that through reading this specification, its each improvement can be appreciated by for those skilled in the art. It is therefore understood that invention disclosed herein is intended to belong to this kind of improvement of scope.

Claims

1. the method that lubrication has the end driven device valve mechanism clearance adjuster of pivot finger-type of the passenger vehicle compression-ignition engine of the reference mass less than 2610kg, it includes infeed lubricating composition in internal combustion engine, described lubricating composition comprises and has the oil of lubricant viscosity, 0.01 weight % to 3 weight % dispersant viscosity modifiers and 0.01 weight % to 3 weight % without zinc containing S antiwear additive, wherein lubricating composition has the sulfate ash content less than the sulfur content of 5000ppm, 1000ppm or less phosphorus content and 3000-12,000ppm.

2. method according to claim 1, wherein lubricating composition has 500-4000ppm or the phosphorus content of the sulfur content of 1000-3000ppm, 300-900ppm, or 400-750ppm and the sulfate ash content of 3000-7000ppm.

3. the method any one of aforementioned claim 1-2, wherein dispersant viscosity modifiers is the olefin copolymer functionalized further by dispersant amine groups.

4. method according to claim 3, wherein olefin copolymer is ethylene-propylene copolymer.

5. the method any one of aforementioned claim 3-4, wherein olefin copolymer has 5000-100, and 000, or 7500-60,000, or 8000-45, the number-average molecular weight of 000.

6. the method any one of aforementioned claim 3-5, wherein dispersant amine groups is derived from olefin copolymer and acylating agent and the aromatic amine reaction with primary or secondary amino.

7. method according to claim 6, wherein aromatic amine comprises 4-ADPA, aldehyde (usual formaldehyde) coupling 4-ADPA, nitroaniline, disperse orange-3 (DO3) or its mixture.

8. the method any one of aforementioned claim 1-7, wherein dispersant viscosity modifiers is with 0.05 weight % to 1.5 weight %, or 0.1 weight % to 1 weight %, or 0.1-0.5 weight % exists.

9. the method any one of aforementioned claim 1-8, is wherein selected from olefine sulfide, molybdenum dithiocarbamate, molybdenum dithiophosphate, the amine salt of (sulfo-) phosphorus-containing compound, thiadiazoles and mixture thereof without zinc containing S antiwear additive.

10. method according to claim 9, wherein olefine sulfide is containing ester olefine sulfide.

11. method according to claim 10, wherein olefine sulfide is sulfuration 4-carbon butoxy cyclohexene.

12. according to the method any one of aforementioned claim 1-11, wherein without zinc containing S antiwear additive with 0.01 weight % to 1.5 weight %, 0.05 weight % to 1 weight %, or 0.1-0.5 weight % exist.

13. according to the method any one of aforementioned claim 1-12, wherein lubricating composition comprises without zinc containing S antiwear additive, described comprise 0.01 weight % to 1.5 weight % olefine sulfide without zinc containing S antiwear additive, the olefin copolymer functionalized further with 0.05 weight % to 1.5 weight % dispersant amine groups, wherein olefin copolymer is ethylene-propylene copolymer.

14. according to the method any one of aforementioned claim 1-13, wherein lubricating composition comprises without zinc containing S antiwear additive, described comprise 0.1-0.5 weight % olefine sulfide without zinc containing S antiwear additive, the olefin copolymer functionalized further with 0.1-0.5 weight % dispersant amine groups, wherein olefin copolymer is ethylene-propylene copolymer.

15. according to the method any one of aforementioned claim 1-14, wherein lubricating composition comprises with 0.01-0.75 weight % further, or 0.05 weight % to 0.5 weight %, or the molybdate compound that the amount of 0.1 weight % to 0.4 weight % exists, described molybdate compound is selected from the group (usual molybdenum dithiocarbamate) being substantially made up of molybdenum dithiocarbamate and molybdenum dithiophosphate.

16. according to the method any one of aforementioned claim 1-12 or 15, wherein lubricating composition comprises 0.1 weight % to 0.4 weight % molybdenum dithiocarbamate without zinc containing the functionalized further olefin copolymer of S antiwear additive and 0.1-0.5 weight % dispersant amine groups, and wherein olefin copolymer is ethylene-propylene copolymer.

17. according to the method any one of aforementioned claim 1-16, wherein lubricating composition comprises antioxidant further, wherein antioxidant comprises phenol or amine antioxidants or its mixture, and wherein antioxidant with 0.1 weight % to 3 weight %, or 0.5 weight % to 2.75 weight %, or 1 weight % to 2.5 weight % exists.

18. according to the method any one of aforementioned claim 1-17, wherein lubricating composition comprises a certain amount of sulfoacid calcium overbased detergent and Calcium carbolate overbased detergent makes sulfate ash content be 1000ppm or less further.

19. method according to claim 18, wherein sulfoacid calcium overbased detergent is with the 0.01-0.5 weight % of lubricating composition, or 0.05-0.3 weight % exists.

20. according to the method any one of aforementioned claim 1-19, wherein clearance adjuster comprises ball-and-socket joint.

21. according to the method any one of aforementioned claim 1-20, wherein clearance adjuster is hydraulic lash adjuster.

22. according to the method any one of aforementioned claim 1-21, wherein clearance adjuster does not have chrome coating, tin coating, nitride coatings or boride coating.