CN107922873A

CN107922873A - Lubricant with calcic detergent is used to improve the purposes that low speed early fires with it

Info

Publication number: CN107922873A
Application number: CN201680039372.2A
Authority: CN
Inventors: 克里斯汀·弗莱彻; 威廉·Y·拉姆; 杨孔盛; 杰瑞米·斯泰尔
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2015-07-16
Filing date: 2016-07-14
Publication date: 2018-04-17
Anticipated expiration: 2036-07-14
Also published as: CN107922873B; RU2018104014A3; CA2991769C; KR102103653B1; JP2018520240A; EP3322781A1; RU2720202C2; BR112018000353B1; RU2018104014A; CA2991769A1; MX371195B; JP6708831B2; KR20180048596A; EP3322781B1; BR112018000353A2; MX2018000152A

Abstract

A kind of method of lubricant oil composite and the enhanced internal combustion engine of operation.The lubricant oil composite includes the high alkali cleaning agent of base oil, TBN more than 225mg KOH/g and the TBN at most low alkalinity/neutral detergents of 175mg KOH/g more than 50wt.%.The total amount of calcium from the high alkali cleaning agent and the low alkalinity/neutral detergent is by the gross weight meter of the lubricant oil composite, is extremely less than 2400ppm more than 1100ppm by weight.Relative to commercially available lubricant oil composite, the lubricant oil composite and the method effectively can reduce low speed morning combustion event in the enhanced internal combustion engine lubricated using the lubricant oil composite.

Description

Lubricant with calcic detergent is used to improve the purposes that low speed early fires with it

Technical field

This disclosure relates to the lubricant compositions containing one or more oil soluble additives and this kind of lubricant combination Thing is used to improve the purposes that low speed early fires.

Background technology

Turbocharged engine or supercharged engine (i.e. enhanced internal combustion engine) are likely to occur referred to as random early combustion or low The abnormal combustion phenomenon of fast early combustion (or " LSPI ").LSPI be a kind of early combustion event may include very high pressure spike, Burning and pinking ahead of time during improper crank shaft angle.It is all these, individually and in combination, it may cause engine Degenerate and/or be badly damaged.However, because LSPI events only contingently occur in a manner of uncontrolled, it is difficult to differentiate this The cause of phenomenon and provide contain its solution.

Early combustion is a kind of combustion type, is that the indoor air fuel mixture of burning lights sky desired by igniter The result burnt before gas fuel mixture.The problem of early combustion is typically during high engine speeds are run, because starting A part of combustion chamber can be heated to being enough lighting the temperature of air fuel mixture in contact by the heat that machine operation produces.It is this The early combustion of type is sometimes referred to as hot spot and early fires.

Recently, low speed and in observe intermittent abnormal combustion in enhanced internal combustion engine to high load capacity.Citing comes Say, in engine with 3,000rpm or smaller, underload, at least 10 bars of brake mean-effective pressure (brake mean Effective pressure, BMEP) operation during, low speed early combustion (low-speed pre-ignition, LSPI) may Occur with a kind of random and random manner.During low engine speed is run, the compression stroke time is most long.

The use of several open studies have shown that turbocharger, engine design, engine coatings, piston-shaped, fuel Selection, and/or oil additives may cause the increase of LSPI events.A kind of theory thinks, from piston gap (Piston volume tube with Space between Cylinder head gasket) enter engine chamber machine oil drop spontaneous combustion be probably LSPI events a cause. Accordingly, it would be desirable to be able to effectively reduce or eliminate oil additives component and/or the combination of the LSPI in enhanced internal combustion engine.

The content of the invention

This disclosure relates to a kind of lubricant oil composite and the method for running enhanced internal combustion engine.Lubricant oil composite includes big It is more than in the lubricant viscosity base oil of 50wt.%, at least total base number of 0.3wt.% (total base number, TBN) The low alkalinity of the high alkali cleaning agent of 225mg KOH/g and at least TBN of 0.2wt.% less than or equal to 175mg KOH/g/in Property detergent, the calcium total amount of wherein high alkali cleaning agent and low alkalinity/neutral detergent exists, by lubricant oil composite gross weight Meter, more than 1100ppm (by weight) to less than in the range of 2400ppm (by weight).Lubricant oil composite can use Low speed early combustion event is effectively reduced in the enhanced internal combustion engine of lubricant oil composite lubrication.

In another embodiment, the disclosure provides the method that the low speed being used to reduce in enhanced internal combustion engine early fires event. Method includes the use of the step of lubricant oil composite lubricates enhanced internal combustion engine, and the lubricant oil composite includes being more than High alkali cleaning agent and at least of the TBN of the lubricant viscosity base oil of 50wt.%, at least 0.3wt.% more than 225mg KOH/g The TBN of 0.2wt.% at most low alkalinity/neutral detergents of 175mg KOH/g.High alkali cleaning agent and low alkalinity/neutrality de-sludging The total amount of the calcium of agent (presses weight more than 1100ppm (by weight) by lubricant oil composite gross weight meter to 2400ppm is less than Gauge) in the range of.Enhanced internal combustion engine is run and is lubricated using lubricant oil composite, so as to moisten using lubricant oil composite Low speed morning combustion event is likely to reduced in sliding engine.

In any one previous embodiment, high alkali cleaning agent can include high alkalinity calcic detergent.High alkalinity contains Calcium detergent may be selected from high alkaline calcium sulfonate detergent and overbased calcium phenate's detergent.In each example, it is high-alkali Property detergent can be the mixture of calcic detergent or two or more high alkalinity calcic detergents.In each foregoing reality Apply in example, one or more high alkalinity calcic detergents can provide for lubricant oil composite, by lubricant oil composite gross weight Meter, about 900 to about 2000ppm (by weight) calcium.

In any one previous embodiment, low alkalinity/neutral detergent can be calcic detergent, and low alkalinity/ Neutral calcic detergent can be the detergent selected from sulfoacid calcium detergent and calcium phenoxide detergent.In the aforementioned embodiment, moisten At least 4wt.% of total detergent can come from low alkalinity/neutral detergent in sliding oil composition.In each previous embodiment In, the ratio of the total metal mM number (M) of lubricant oil composite and total base number (TBN) can more than 4.5 to about 10.0 or big In the range of 8 to about 10.

In each previous embodiment, the reduction that low speed early fires (LSPI) event is represented by test oil LSPI event phases For the ratio (hereinafter " LSPI ratios ") of reference oil LSPI events, wherein it is lubricating oil composition to include with reference to oil R-1 Thing provides the high alkalinity calcic detergent of the amount of about 2400ppm calcium as unique detergent in lubricant oil composite.Foregoing In embodiment, the LSPI that LSPI events are represented by during 25,000 cycle of engine is counted, and wherein engine is with 2000 Brake mean-effective pressure (BMEP) operation of rpm (RPM), 18,000kPA.

In each previous embodiment, base oil can be selected from Group I, Group II, Group III, Group IV or Group V Base oil, and it is foregoing in two or more combination.In other embodiments, the base oil more than 50wt.% is selected from The group consisted of：Group II, Group III, Group IV or Group V base oil, and it is foregoing in two or more Combination, wherein the base oil more than 50wt.% is not by providing additive component or viscosity index improver in the composition And the flux oil produced.

In each previous embodiment, lubricant oil composite can include selected from friction modifiers, antiwear additive, disperse One or more components of agent, antioxidant and viscosity index improver.

In the previous embodiment of approach described herein, engine can be less than 3000 rpms in operation (rpm) brake mean-effective pressure (BMEP) that engine speed is produced more than 1,500kPa is horizontal, or the hair with 2000rpm Motivation rotating speed produces the BMEP of 1,800kPa.

In each previous embodiment, lubricant oil composite can effectively be aoxidized by 33 experimental benches of TEOST and tested.

In each previous embodiment, low alkalinity/neutral detergent can include low alkalinity/neutrality calcic detergent, And by low alkalinity/neutrality calcic detergent for the calcium ppm (by weight) of lubricant oil composite offer and by high alkalinity calcic The ratio for the calcium ppm (by weight) that detergent provides for lubricant oil composite can be 0.05 to 1.0.

It is that total calcium that lubricant oil composite provides can be by profit by high alkali cleaning agent in each previous embodiment Sliding oil composition gross weight meter 1100ppm to 1800ppm (by weight).

It is total calcium that lubricant oil composite provides by low alkalinity/neutrality calcic detergent in each previous embodiment Can be by lubricant oil composite gross weight meter 50ppm to 1000ppm (by weight).

In each previous embodiment, lubricant oil composite can include no more than 10wt.% group iv base oils, Group V base oil, or its combination.In each previous embodiment, lubricant oil composite includes the Group V base less than 5wt.% Plinth oil.

In each previous embodiment, high alkalinity calcic detergent can be high alkaline calcium sulfonate detergent.

In each previous embodiment, high alkalinity calcic detergent can not gone optionally including overbased calcium salicylate Dirty agent.

In each previous embodiment, lubricant oil composite can not optionally include any detergent containing magnesium, or Lubricant oil composite can be free of magnesium.

In each previous embodiment, lubricant oil composite can not contain any group iv base oils.

In each previous embodiment, lubricant oil composite can not contain any Group V base oil.

The definition of following term is provided to illustrate the implication of some terms used herein.

Term " fluid composition " " lubricating composition ", " lubricant oil composite ", " lubricating oil ", " lubricant compositions ", " profit Sliding composition ", " lubricant compositions fully allocated ", " lubricant ", " crankcase oils ", " crankcase lubricant ", " machine oil ", " engine lubricant ", " electric motor oil " and " motor lubricant " are considered to be the synonymous term that can be exchanged completely, refer to Finished product lubrication product comprising the base oil more than 50wt.% and a small amount of additive composition.

As used herein, term " additive bag ", " multifunctional additive for lubricating oils ", " compositions of additives ", " oil additives Bag ", " oil additives concentrate ", " crankcase additive bag ", " crankcase multifunctional additive for lubricating oils ", " electric motor oil additive Bag ", " electric motor oil concentrate " are considered to be the synonymous term that can be exchanged completely, refer to the base oil for being more than 50wt.% The part of lubricant oil composite outside raw mixture.Additive bag can include or not include viscosity index improver or drop Solidifying agent.

Term " high alkalinity " is related to metal salt, such as the metal salt of sulfonic acid, formic acid, salicylic acid, and/or phenol, wherein existing The amount of metal exceed stoichiometry.This kind of salt can (that is, they can include and be more than with the level of conversion more than 100% The theoretical amount of metal needed for 100% be converted into acid its " just ", " neutrality " salt).Expression " metal ratio " is commonly abbreviated as MR, for referring to, according to known chemical reactivity and stoichiometry, in high alkalinity salt in total chemical equivalent of metal and neutral salt Stoichiometric ratio of metal.Just or in neutral salt metal ratio is one, and MR is more than one in high alkalinity salt.They Commonly known as high alkalinity, hyperalkaline or superbased salt, and can be organic sulfuric acid, formic acid, salicylic acid and/or phenol Salt.In the disclosure, the TBN of high alkali cleaning agent is more than 225mg KOH/g.High alkali cleaning agent can be that respective TBN is big In the combination of two or more high alkali cleaning agent of 225mg KOH/g.

In the disclosure, the TBN of low alkalinity/neutral detergent at most 175mg KOH/g.Low alkalinity/neutral detergent can To be respective TBN at most two or more low alkalinities of 175mg KOH/g and/or the combination of neutral detergent.At some In the case of, " high alkalinity " can be abbreviated as " OB ", and in some cases, " low alkalinity/neutrality " can be abbreviated as " LB/N ".

Term " total metal " refers to total metal, metalloid or transition metal in lubricant oil composite, including by lubricating The metal that the detergent component of fluid composition provides.

As used herein, term " hydrocarbyl substituent " or " alkyl " with known to those skilled in the art it General sense uses.Exactly, it refer to the carbon atom with the remainder for being directly connected in molecule and mainly with The group of hydrocarbon feature.The example of alkyl includes：

(a) hydrocarbon substituent, i.e. aliphatic substitution (such as alkyl or alkenyl), cycloaliphatic substituents (such as cycloalkyl, ring Alkenyl) and through aromatic series, aliphatic and alicyclic substituted aromatic substituents, and its middle ring is another part by molecule The ring substituents (such as two substituents form alicyclic moiety together) of completion；

(b) hydrocarbon substituent being substituted, i.e., under the background of the disclosure, contain the non-alkyl for not changing main hydrocarbon substituent Substituent (such as halogen (especially chloro and fluorine-based), hydroxyl, alkoxy, sulfydryl, alkyl thiol, nitro, nitroso, amido, Alkylamino and sulphur epoxide)；With

(c) miscellaneous substituent, i.e., under the background of the disclosure, otherwise by carbon atom while there is main hydrocarbon feature Substituent containing the atom in addition to carbon in the ring or chain of composition.Hetero atom can include sulphur, oxygen and nitrogen, and cover substitution Base, such as pyridine radicals, furyl, thienyl and imidazole radicals.In general, in alkyl in every ten carbon atoms there will be no more than Two kinds, such as no more than a kind of substituents；In general, it will be not present substituents in alkyl.

As used herein, unless otherwise expressly specified, otherwise term " wt.% " means that the component represents opposite In the percentage of the weight of all compositions.

Term as used herein " solubility ", " oil-soluble " or " dispersibility " can with but may not represent the compound Or additive is solvable, soluble, miscible or can be suspended in all proportions in oil.However, preceding terms Them are represented, for example, the degree of its predictive role is solvable, can suspend, can be enough to play in using the oily environment Dissolving or can Investigation of stabilized dispersion of nano in it is described oil in.Moreover, other additives it is extra be incorporated to can also allow to be incorporated to if necessary compared with The special additive of high-content.

Term " TBN " as used in this article be used to represent as measured by the method as ASTM D2896 with milligram KOH/ grams of composition is the total base number of unit.

Term " alkyl " as used in this article refers to the straight chain of about 1 to about 100 carbon atom, branched chain, ring and/or takes For saturation chain part.

Term " alkenyl " as used in this article refers to the straight chains of about 3 to about 10 carbon atoms, branched chain, ring and/or takes For unsaturated chain part.

Term " aryl " as used in this article refer to may include alkyl, alkenyl, alkaryl, amido, hydroxyl, alkoxy, The list and polycyclc aromatic compound of halo atom substituents and/or hetero atom (including but not limited to nitrogen, oxygen and sulphur).

The lubricant of this specification, the combination of component or independent component are likely to be suitable for various types of internal combustion engines.It is suitable Engine type is closed to can include but is not limited to：Heavy-duty diesel engine, car, light load diesel engine, medium seed diesel engine, hair peculiar to vessel Motivation or motorcycle engine.Internal combustion engine can be diesel engine, petrol engine, natural gas engine, bio-fuel hair Motivation, diesel oil/bio-fuel hybrid engine, gasoline/bio fuel hybrid engine, ethanol engine, gasoline/ethanol mixing Engine, compressed natural gas (compressed natural gas, CNG) engine, or its mixture.Diesel engine can be with It is compression ignition engine.Diesel engine can be the compression ignition engine that there is spark ignition to aid in.Petrol engine It can be spark ignition engine.Internal combustion engine can also be used with mains power or battery source power combination.So configured starts Machine is commonly referred to as hybrid engine.Internal combustion engine can be 2- strokes, 4- strokes or rotating engine.Suitable internal combustion engine includes Marine diesel engine (such as inland is peculiar to vessel), aviation piston engine, underload diesel engine and motorcycle, motor vehicle, machine Car and truck engine.

Internal combustion engine can contain and belong to one or more of following component：Aluminium alloy, lead, tin, copper, cast iron, magnesium, pottery Porcelain, stainless steel, composite material, and/or its mixture.Component can be coated, such as use diamond-like carbon coating, profit Sliding coating, phosphorous coating, coating containing molybdenum, graphite paint, coating containing nano-particle, and/or its mixture.Aluminium alloy can include Alumina silicate, aluminium oxide or other ceramic materials.In one embodiment, aluminium alloy is silicic acid aluminium surface.As used herein, art Language " aluminium alloy " be intended to " aluminium composite material " it is synonymous come describe a component comprising aluminium or surface and another component microcosmic or Mutually mixed or reaction on nearly microscopic scale, regardless of its concrete structure.This will include any with metal and tool in addition to aluminum There are the Conventional alloys of nonmetalloid or the compound or class alloy structure of compound (as having class ceramic material).

Lubricant oil composite for internal combustion engine can be adapted for any engine, no matter sulphur, phosphorus or sulfate ash How is (ASTM D-874) content.The sulfur content of oil lubricating agent can be about 1wt% or smaller or about 0.8wt% or smaller or About 0.5wt% or smaller or about 0.3wt% or smaller or about 0.2wt% or smaller.Sulfur content can be with one embodiment In about 0.001wt% to about 0.5wt% or about 0.01wt% to about in the range of 0.3wt%.Phosphorus content can be about 0.2wt% or Smaller or about 0.1wt% or smaller or about 0.085wt% or smaller or about 0.08wt% or smaller or even about 0.06wt% or smaller, about 0.055wt% or smaller or about 0.05wt% or smaller.Phosphorus content can be in one embodiment About 50ppm to about 1000ppm or about 325ppm to about 850ppm.Overall sulfate content of ashes can be about 2wt% or smaller or About 1.5wt% or smaller or about 1.1wt% or smaller or about 1wt% or smaller or about 0.8wt% or smaller or about 0.5wt% or smaller.Sulfated ash content can be about 0.05wt% to about 0.9wt% or about in one embodiment 0.1wt% or about 0.2wt% are to about 0.45wt%.In another embodiment, sulfur content can be about 0.4wt% or smaller, and phosphorus contains Amount can be about 0.08wt% or smaller, and sulfate ash is about 1wt% or smaller.In another embodiment, sulfur content can It is about 0.3wt% or smaller, phosphorus content is about 0.05wt% or smaller, and sulfate ash can be about 0.8wt% or smaller.

In one embodiment, lubricant oil composite is machine oil, and wherein lubricant oil composite can have (i) about 0.5wt% Or the sulfur content of smaller, the phosphorus content of (ii) about 0.1wt% or smaller and (iii) about 1.5wt% or the sulfate ash of smaller Content.

In certain embodiments, lubricant oil composite is adapted to (such as containing the combustion of about 1% to about 5% sulphur by low-sulphur fuel Material) provide power engine be used together.Vehicle on highway fuel contains about 15ppm sulphur (or about 0.0015% sulphur).Profit Sliding oil composition is adapted to be used together with enhanced internal combustion engine, including turbocharging internal-combustion engines or supercharged engine.

In addition, the lubricant of this specification may adapt to meet one or more industry specification requirements, such as ILSAC GF- 3、GF-4、GF-5、GF-6、PC-11、CI-4、CJ-4、ACEA A1/B1、A2/B2、A3/B3、A3/B4、A5/B5、C1、C2、C3、 C4, C5, E4/E6/E7/E9, Euro 5/6, Jaso DL-1, low SAPS, medium SAPS, or original equipment manufacturer's specification, such as Dexos^TM 1、Dexos^TM2nd, MB- ratify 229.51/229.31, VW 502.00,503.00/503.01,504.00, 505.00、506.00/506.01、507.00、508.00、509.00、BMW Longlife-04、Porsche C30、PeugeotAutomobile B71 2290, B71 2296, B71 2297, B71 2300, B71 2302, B71 2312, B71 2007, B71 2008、Ford WSS-M2C153-H、WSS-M2C930-A、WSS-M2C945-A、WSS-M2C913A、WSS-M2C913-B、 WSS-M2C913-C, GM 6094-M, Chrysler MS-6395, or herein the PCMO in unmentioned any past or future or HDD specifications.In certain embodiments, applied for passenger car electric machine oil (passenger car motor oil, PCMO), into The amount of phosphorus is 1000ppm or smaller or 900ppm or smaller or 800ppm or smaller in product fluid.

Other ironwares may be not suitable for being used together with disclosed lubricant." functional fluid " be forgive it is various The term of fluid, the fluid include but not limited to, dragger hydraulic fluid；Power transmission fluid, including：Automatic transmission stream Body, buncher fluid and manual transmission fluid；Hydraulic fluid, including dragger hydraulic fluid；Some gear oils；Power Diverter fluid；For wind turbine, the fluid of compressor；Some industrial fluids；With with the relevant fluid of power train part.Should Note that in each in these fluids, such as in automatic transmission fluids, there are various types of fluid, because For various speed changers the fluid with dramatically different functional characteristic is resulted in the need for different designs.This and term " lubrication flow Body " is different, it is not used in generation or transmission power.

On dragger hydraulic fluid, for example, these fluids are for all in addition to engine is lubricated in dragger The universal product of lubrication applications.These lubrication applications can include：Gear-box, power output device and clutch, rear axle, deceleration Gear, wet brake and hydraulic services lubrication.

When functional fluid is automatic transmission fluids, automatic transmission fluids must have be enough to be used in clutch plate Transmit the friction of power.However, the friction coefficient of fluid has the tendency declined, because temperature caused by fluid heats during operation Degree influences.Dragger hydraulic fluid or automatic transmission fluids keep its great friction coefficient particularly significant at high temperature, otherwise make Dynamic system or automatic transmission may break down.This is not the function of machine oil.

Tractor fluids, and for example super dragger oil universal (Super Tractor Universal Oils, STUO) or the transmission of general dragger is oily (Universal Tractor Transmission Oils, UTTO), can be by machine oil Efficiency and speed changer, differential mechanism, finally drive planetary gear, wet brake and hydraulic pressure efficiency to combine.Although many is used for Allocate UTTO or STUO fluids additive it is functionally similar, if but merge it is improper they may have illeffects.Citing For, some wear-resistant and extreme pressure additives for being used for machine oil may be extremely corrosive to the copper part in hydraulic pump. It may be unfavorable for wet braking efficiency for the detergent and dispersant of gasoline or diesel engine efficiency.It is exclusively used in eliminating wet type The friction modifiers of brake noise may lack heat endurance necessary to machine oil efficiency.Each in these fluids, no matter work( Can be property, dragger or lubrication, it is to be designed to meet what specific and stringent manufacturer required.

The disclosure provides the formulated novel lubricating oil admixture as vehicle crankcase lubricant.Embodiment of the disclosure Can provide has improved lubricating oil suitable for crankcase application and in terms of following characteristics：Air incorporation, alcohol fuel Compatibility, inoxidizability, wear-resistant efficiency, bio-fuel compatibility, defoaming characteristics, antifriction, fuel economy, early combustion prevention, Antirust, greasy filth and/or flue dust dispersibility, piston cleanliness, deposition is formed and water tolerance.

The machine oil of the disclosure can be by, is such as described in detail below, added into suitable formulation of base oil thing it is a kind of or Multiple additives are allocated.Additive can be combined or, alternatively in the form of additive bag (or concentrate) with base oil, can Individually to be combined with base oil (or the mixture of the two).According to the additive of addition and its corresponding proportion, complete dispensing machine Oil can show improved performance characteristics.

The other details and advantage of the disclosure will illustrate partly in the following description, and/or can be by putting into practice the disclosure Learn.The details and advantage of the disclosure can by means of the key element that is particularly pointed out in the appended claims and combination realizing and Obtain.It is to be understood that foregoing general description and described in detail below being only exemplary and explanatory and not limiting and advocated Disclosure.

Embodiment

The various embodiments of the disclosure provided lubricant oil composite and available for the low speed morning reduced in enhanced internal combustion engine The method of combustion event (LSPI).In particular, the enhanced internal combustion engine of the disclosure is included in turbocharging internal-combustion engines and booster-type Combustion engine.Enhanced internal combustion engine includes spark-ignited direct injection and/or fuel nozzle injection-type engine.Spark-ignition internal combustion engine can To be petrol engine.

The composition of the present invention includes the lubricant oil composite containing lubricant viscosity base oil and special additive composition. Disclosed method uses the lubricant oil composite containing compositions of additives.It is as described in greater detail below, lubricating oil composition Thing may unexpectedly be had for reducing low speed morning combustion event in the enhanced internal combustion engine lubricated using lubricant oil composite Effect.

In certain embodiments, spark-ignited direct injection or the fuel nozzle injection of turbocharger or booster are configured with The combustion chamber of formula internal combustion engine or cylinder wall are run and are lubricated using lubricant oil composite, so as to moisten using lubricant oil composite Low speed morning combustion event can be reduced in sliding engine.

Optionally, method of the invention can include measuring early fires event using the low speed of the internal combustion engine of oil lubrication Step.In this kind of method, internal combustion engine LSPI events are reduced up to 50% or more or, it is highly preferred that up to 75% or more, and LSPI events are that LSPI during 25,000 cycle of engine is counted, wherein engine with 2000 revs/min and 18, 000kPa brake mean-effective pressures are run.

As described in greater detail below, embodiment of the disclosure can be provided significantly and gone out in terms of LSPI events are reduced The improvement that people expects, while maintain calcium de-sludging agent concentration relatively high in lubricant oil composite.Embodiment of the disclosure can also Unexpected improvement is provided in the tests of TEOST 33, while also reduces LSPI events.

In embodiment of the disclosure, lubricant oil composite can also be tested by TEOST 33.

Detergent

Lubricant oil composite includes one or more high alkali cleaning agent and one or more low alkalinity/neutral detergents. It is adapted to detergent matrix to include:Phenolate, sulfur-bearing phenolate, sulfonate, cup aromatic acid salt (calixarates), Liu Fang hydrochlorates (salixarates), salicylate, carboxylic acid, phosphoric acid, single thiophosphate and/or phosphordithiic acid, alkyl phenol, sulphur coupling methyl groups Phenolic compounds or methylene-bridged phenol.It is adapted to detergent and its preparation method to be more fully described in many patents disclose, wraps Include US 7,732,390 and the bibliography wherein enumerated.Detergent matrix can use such as, but not limited to following alkali metal Or alkaline-earth metal salinization：Calcium, magnesium, potassium, sodium, lithium, barium, or its mixture.In certain embodiments, detergent not baric.It is adapted to Detergent can include mahogany acid and aryl long-chain list or dioxane aromatic sulfonic acid for benzyl, tolyl and xylyl Alkali or alkaline earth metal salt.It is adapted to the example of other detergents to include but not limited to：Calcium phenoxide, sulfur-bearing calcium phenoxide, sulfoacid calcium, Cup aromatic acid calcium (calcium calixarates), willow aromatic acid calcium (calcium salixarates), calcium salicylate, calcium carboxylates, Calcium phosphate, single thiophosphate calcium and/or phosphordithiic acid calcium, alkyl phenol calcium, sulphur coupling methyl groups phenol calcium compound, methylene-bridged Phenol calcium, phenol magnesium, magnesium containing phenylmercaptan, sulfonic acid magnesium, cup aromatic acid magnesium (magnesium calixarates), willow aromatic acid magnesium (magnesium salixarates), magnesium salicylate, magnesium carboxylates, magnesium phosphate, single thiophosphate magnesium and/or phosphordithiic acid magnesium, Alkyl phenol magnesium, sulphur coupling methyl groups phenol magnesium compound, methylene-bridged phenol magnesium, sodium phenate, sulfur-bearing sodium phenate, sodium sulfonate, cup aromatic acid Sodium (sodium calixarates), willow aromatic acid sodium (soudium salixarates), sodium salicylate, carboxylic acid sodium, sodium phosphate, Single thiophosphate sodium and/or phosphordithiic acid sodium, alkyl phenol sodium, sulphur coupling methyl groups phenol sodium compound or methylene-bridged phenol sodium.

High alkali cleaning agent is in the art it is well known that and can be alkali or alkaline earth metal high alkali cleaning Agent.This kind of detergent can be by making metal oxide or metal hydroxides be made with matrix and carbon dioxide gas precursor reactant It is standby.Matrix is typically acid, for example, the acid of the formic acid of the sulfonic acid, aliphatic substitution such as aliphatic substitution or the phenol of aliphatic substitution.

Term " high alkalinity " is related to metal salt, and such as the metal salt of sulfonic acid, formic acid and phenol, the amount of metal present in it surpasses Over-stoichiometric.This kind of salt can (that is, they can include converting acid more than 100% with the level of conversion more than 100% For the theoretical amount of the metal needed for its " just ", " neutrality " salt).Expression " metal ratio " is commonly abbreviated as MR, for referring to, according to Known chemical reactivity and stoichiometry, in high alkalinity salt total chemical equivalent of metal with neutral salt metal it is stoichiometric Ratio.Just or in neutral salt metal ratio is one, and MR is more than one in high alkalinity salt.They are commonly known as high-alkali Property, hyperalkaline or superbased salt, and can be the salt of organic sulfuric acid, formic acid or phenol.

High alkali cleaning agent has more than 225 milligrams KOH/ grams of TBN, or such as another example, about 250 milligrams KOH/ grams or The TBN of bigger or about 300 milligram KOH/ grams or TBN or about 350 milligram KOH/ grams or the TBN of bigger of bigger or about 375 millis TBN or about 400 milligram KOH/ grams of gram KOH/ grams or bigger or the TBN of bigger.

It is adapted to the example of high alkali cleaning agent to include but not limited to：It is overbased calcium phenate, high alkalinity sulfur-bearing calcium phenoxide, high-alkali Property sulfoacid calcium, high alkalinity cup aromatic acid calcium (overbased calcium calixarates), high alkalinity willow aromatic acid calcium It is (overbased calcium salixarates), overbased calcium salicylate, high alkalinity calcium formate, high alkalinity calcium phosphate, high-alkali Property list and/or phosphordithiic acid calcium, high alkalinity alkyl phenol calcium, high alkalinity sulphur coupling methyl groups phenol calcium compound, high alkalinity methylene Bridging phenol calcium, high alkalinity phenol magnesium, high alkalinity magnesium containing phenylmercaptan, overbased magnesium sulphonates, high alkalinity cup aromatic acid magnesium (overbased Magnesium calixarates), high alkalinity willow aromatic acid magnesium (overbased magnesium salixarates), high alkalinity Magnesium salicylate, high alkalinity magnesium formate, high alkalinity magnesium phosphate, high alkalinity list and/or phosphordithiic acid magnesium, high alkalinity alkyl phenol magnesium, High alkalinity sulphur coupling methyl groups phenol magnesium compound or high alkalinity methylene-bridged phenol magnesium.

The metal of high alkali cleaning agent and the ratio of matrix can be 1.1:1 or 2:1 or 4:1 or 5:1 or 7:1 or 10: 1。

In certain embodiments, detergent effectively can reduce or prevent within the engine to get rusty.

By the gross weight meter of lubricant oil composite, detergent can with most 10wt% or about at most 8wt% or at most About 4wt% or greater than about 4wt% to about 8wt% exist.

Detergent can so as to for finished fluid provide about 1100 to about 3500ppm metals amount exist.In other implementations In example, detergent can provide about 1100 to about 3000ppm metal or about 1150 to about 2500ppm gold for finished fluid Category or about 1200 to about 2400ppm metal.

The lubricant oil composite of the disclosure include at least one TBN more than 225 milligrams KOH/ grams high alkali cleaning agent and At least one TBN at most 175 milligrams KOH/ grams of neutrality/low alkalinity detergents.The disclosure is additionally included in method using this kind of Lubricant oil composite or the method for lubricating engine, lubricate engine by using the lubricant oil composite and operation are started Machine.

The high alkalinity of the lubricant oil composite of the disclosure and the calcium total amount of low alkalinity/neutral detergent exist, by lubricating oil group Compound gross weight meter, more than 1100ppm (by weight) to less than in the range of 2400ppm (by weight).

High alkali cleaning agent can be high alkalinity calcic detergent.High alkalinity calcic detergent can be selected from high alkalinity sulfonic acid Calcium detergent, overbased calcium phenate's detergent and overbased calcium salicylate detergent.In certain embodiments, high alkalinity calcic is gone Dirty agent includes high alkaline calcium sulfonate detergent.In certain embodiments, high alkali cleaning agent is one or more calcic detergents, Preferably, high alkali cleaning agent is sulfoacid calcium detergent.

In certain embodiments, one or more high alkalinity calcic detergents provide about 900 to about for finished fluid 2400ppm calcium.Such as another example, one or more high alkalinity calcic detergents can so as to for finished fluid provide about 900 to About 2000ppm calcium or about 900 is to about 1800ppm calcium or about 1100 to 1600ppm calcium or about 1200 to the amount of 1500ppm calcium In the presence of.

The TBN of low alkalinity/neutral detergent at most 175mg KOH/g or at most 150mg KOH/g.Low alkalinity/neutrality is gone Dirty agent can include calcic detergent.Low alkalinity neutrality calcic detergent can be selected from sulfoacid calcium detergent, calcium phenoxide detergent With calcium salicylate detergent.In certain embodiments, low alkalinity/neutral detergent is the mixed of calcic detergent or calcic detergent Compound.In certain embodiments, low alkalinity/neutral detergent is sulfoacid calcium detergent or calcium phenoxide detergent.

Low alkalinity/neutral detergent forms at least 2.5wt.% of total detergent in lubricant oil composite.In some realities Apply in example, at least 4wt.% or at least 6wt.% of total detergent or at least 8wt.% or at least in lubricant oil composite 10wt.% or at least 12wt.% or at least 20wt.% are low alkalinity/neutral detergents, its optionally can be low alkalinity/ Neutral calcic detergent.

In certain embodiments, one or more low alkalinities/neutrality calcic detergent provides for lubricant oil composite, by profit Sliding oil composition gross weight meter, about 50 to about 1000ppm calcium (by weight).In certain embodiments, one or more low alkali Property/neutrality calcic detergent provides for lubricant oil composite, by lubricant oil composite gross weight meter, 75 to less than 800ppm or 100 to 600ppm or 125 to 500ppm (by weight) calcium.

In certain embodiments, total metal mM number (M) of lubricant oil composite and the ratio of the TBN of lubricant oil composite Rate is in the range of more than 4.5 to about 10.0.In certain embodiments, total metal mM number (M) and the TBN of lubricant oil composite Ratio more than 8 in the range of less than 10.0 or 8 to 9.5 or 8.1 to 9.0.

In certain embodiments, the ppm of the calcium provided by low alkalinity/neutral detergent for lubricant oil composite is (by weight Meter) with the ratio of the ppm (by weight) of the calcium provided by high alkalinity calcium detergent for lubricant oil composite it is about 0.01 to about 1 or about 0.03 to about 0.7 or about 0.05 to about 0.5 or about 0.08 to about 0.4.

High alkalinity calcic detergent can be high alkaline calcium sulfonate detergent.High alkalinity calcic detergent can optionally not Including overbased calcium salicylate detergent.Lubricating oil optionally can not include any detergent containing magnesium or without magnesium.At this In any one disclosed embodiment, the amount of sodium can be limited in lubricating composition, by lubricant oil composite gross weight meter, no Sodium more than 150ppm.

Base oil

The base oil for lubricant oil composite can be selected from such as American Petroleum Institute (API) (American herein Petroleum Institute, API) base oil interchangeability guide (Base Oil Interchangeability Guidelines the Group I specified in) is to any one of Group V base oil.Five kinds of base oil groups are as follows：

Table 1

Group I, Group II and Group III are that mineral oil processes raw material.Group iv base oils contain pure synthetic molecules material, Produced by the polymerization of ethylenically unsaturated hydrocarbons class.Many Group V base oils are also pure synthetic product, and can include diester, Polyol ester, polyalkylene glycol, alkylated aromatic hydrocarbon, polyphosphate, polyvinylether and/or polyphenyl ether etc., but can also It is naturally-produced oil, such as vegetable oil.It should be noted that although Group III base oil derives from mineral oil, what these fluids were undergone Stringent processing causes its physical characteristic to be very similar to some pure synthetics, such as PAO.Therefore, in the industry, can claim to derive from The oil of Group III base oil is complex fluids.

Can be mineral oil, animal oil, vegetable oil, artificial oil for the base oil in disclosed lubricant oil composite, Or its mixture.Suitable oil can derive from hydrocracking, hydrogenation, hydrofinishing, unrefined, refining and refine again Oil, and its mixture.

Unrefined oil be those from natural, mineral or synthesis source without or almost locate without further purification The oil of reason.Refined oil is similar to unrefined oil, but they have already passed through one or more purification step processing, it is possible to create The improvement of one or more characteristics.The example of suitable purification technique be solvent extraction, second distillation, acid or alkali extraction, filtering, Infiltration etc..Being refined to the oil of edible grade may or may not be applicable in.Edible oil is also referred to as white oil.In some embodiments In, lubricant oil composite is without edible oil or white oil.

Refined oil is also referred to as reclaimed oil or reprocessed oils again.These oils are similar to refined oil and are obtained using same or like method .Usually these oil are processed further by being directed to the technology of the useless additive of removal and oil decomposition product.

Mineral oil can be included by probing or the oil obtained from plant and animal or its any mixture.Such as this kind of oil It may include but be not limited to：Castor oil, lard, olive oil, peanut oil, corn oil, soybean oil and linseed oil, and mineral lubricant Oil, such as liquid petroleum and alkane cycloalkane or mixing paraffinic-naphthenic through solvent handle or through acid treatment Mineral lubricating oil.This kind of oil if necessary can partly or completely perhydrogenating.Oil from coal or shale can also be applicable.

Applicable synthetic lubricant fluid can include：Hydrocarbon ils, such as polymerization, oligomerization or mutual polyolefin (such as polybutene, poly- third Alkene, propylene/isobutylene copolymers)；Poly- (1- hexenes), poly- (1- octenes), the trimer or oligomer of 1- decene, for example, poly- (1- Decene), this kind of material is commonly referred to as alpha-olefin, and its mixture；Alkylbenzene (such as dodecyl benzene, tetradecyl benzene, two nonyls Base benzene, two (2- ethylhexyls)-benzene)；Polyphenyl (such as biphenyl, terphenyl, alkylated polyphenyls)；Diphenyl alkane, alkylation two Phenyl alkanes, alkylated diphenyl ethers and alkylation diphenyl sulfide, and its derivative, analog and homologue, or Its mixture.Poly alpha olefin is typically hydrogenation material.

Other synthetic lubricant fluids include polyol ester, diester, liquid ester (such as tricresyl phosphate, the phosphoric acid of phosphoric acid The diethylester of three monooctyl esters and decane phosphonic acids), or PolyTHF.Artificial oil can pass through Fischer-Tropsch reaction (Fischer- Tropsch reactions) produce and usually can be hydroisomerization fischer-tropsch hydrocarbon or wax.In one embodiment, oil can To be prepared by Fischer-Tropsch gas-liquid systhesis step, and other natural gas synthetic oils.

The base oil more than 50wt.% that lubricating composition includes can be selected from the group consisted of：Group I, Group II, Group III, Group IV, Group V and it is foregoing in two or more combination, and wherein more than 50wt.% Base oil is not the base oil produced because providing additive component or viscosity index improver in the composition.In another embodiment In, the base oil more than 50wt.% that lubricating composition includes can be selected from the group consisted of：Group II, Section III Group, Group IV, Group V and it is foregoing in two or more combination, and wherein more than 50wt.% base oil be not by The flux oil for providing additive component or viscosity index improver in the composition and producing.

The amount of existing lubrication viscosity oil can be deduct 100wt% efficiency additive capacities summation after residue, institute Stating efficiency additive includes viscosity index improver and/or pour-point depressant and/or other pre-treatment additives.For example, can deposit Can be substantial amounts of in the lubrication viscosity oil in finished fluid, such as larger than about 50wt%, greater than about 60wt%, be greater than about 70wt%, greater than about 80wt%, greater than about 85wt%, or greater than about 90wt%.

Lubricant oil composite can include group iv base oils, Group V base oil or its combination no more than 10wt.%. In each previous embodiment, lubricant oil composite includes the Group V base oil less than 5wt.%.Lubricant oil composite is free of There are any group iv base oils.Lubricant oil composite does not contain any Group V base oil.

Lubricant oil composite may also include one or more optional components for being selected from various additives as described below.

Antioxidant

Lubricant oil composite herein can also be optionally containing one or more antioxidants.Anti-oxidant compounds are It is known and including for example, phenolate, phenol sulfide, olefine sulfide, sulphur phosphatization terpene, sulfurised ester, aromatic amine, alkyl Diphenylamines (such as nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine), phenyl-α-naphthylamine, alkane Base phenyl-α-naphthylamine, steric hindrance non-aromatic amine, phenol, hindered phenol, soluble molybdenum compounds, macromolecular antioxidant, or its mixing Thing.Anti-oxidant compounds can be used alone or in combination.

Sterically hindered phenolic antioxidant can contain sec-butyl and/or the tert-butyl group as space steric hindrance group.Phenolic group can be through alkyl And/or it is connected to the bridging group of another aromatic radical and is further substituted.It is adapted to the example of sterically hindered phenolic antioxidant to include：2,6- Di-t-butyl phenol, 4- methyl -2,6- di-t-butyls phenol, 4- ethyls -2,6 di t butyl phenol, 4- propyl group -2,6- two - Tert-butyl phenol or 4- butyl -2,6- di-t-butyls phenol or 4- dodecyl -2,6- di-t-butyl phenol.In an implementation In example, sterically hindered phenolic antioxidant can be ester, and can include, for example, the IRGANOX available from BASF^TML-135 or source In 2,6- di-t-butyls phenol and the addition compound product of alkyl acrylate, wherein alkyl can contain about 1 to about 18 or about 2 to About 12 or about 2 to about 8 or about 2 to about 6 or about 4 carbon atoms.Another commercially available sterically hindered phenolic antioxidant can be ester, And the ETHANOX available from Albemarle Corporation can be included^TM4716。

Applicable antioxidant can include diaryl amine and high molecular weight phenol.In one embodiment, lubricating oil composition Thing can be containing diaryl amine Yu high molecular weight phenol mixture so that each antioxidant can be enough to provide, by lubricating oil group The final weight meter of compound, the amount of at most about 5wt.% exist.In one embodiment, antioxidant can be, by lubricating oil group The final weight meter of compound, about 0.3 to about 1.5wt.% diaryl amines and about 0.4 to about 2.5wt.% high molecular weight phenol mixing Thing.

It can include through vulcanizing the example for the suitable alkene for forming olefine sulfide：Propylene, butylene, isobutene, polyisobutene, Amylene, hexene, heptene, octene, nonene, decene, hendecene, laurylene, tridecylene, tetradecene, ten pentaenes, hexadecylene, 17 Alkene, octadecylene, 19 alkene, icosa alkene or its mixture.In one embodiment, hexadecylene, 17 alkene, octadecylene, 19 alkene, Icosa alkene or its mixture, and its dimer, trimer and four polymer are especially suitable alkene.Alternatively, alkene It can be diels-Alder adduct of diene (such as 1,3- butadiene) and beta-unsaturated esters (such as butyl propyleneglycol acid esters) (Diels-Alder adduct)。

Another kind of olefine sulfide includes sulfide aliphatic acid and its ester.Aliphatic acid be usually obtained from vegetable oil or animal oil and Usually contain about 4 to about 22 carbon atoms.It is adapted to the example of aliphatic acid and its ester to include triglycerides, oleic acid, linoleic acid, palm fibre Palmitic acid oleic acid or its mixture.In general, aliphatic acid is obtained from lard, pine tar, peanut oil, soybean oil, cottonseed oil, sunflower oil or it is mixed Compound.Aliphatic acid and/or ester can be mixed with alkene, such as alpha-olefin.

One or more antioxidants can be in the about 0wt% to about 20wt% of lubricant oil composite or about 0.1wt% extremely About 10wt% or about 1wt% are to existing in the range of about 5wt%.

Antiwear additive

Lubricant oil composite herein can also be optionally containing one or more antiwear additives.It is adapted to the example bag of antiwear additive Include but be not limited to：D2EHDTPA metal salt；Dialkyl dithiophosphoric acid metal salt；Phosphate or its salt；Phosphate；Phosphorous acid Ester；Phosphorus-containing carboxylic acid ester or acid amides；Olefine sulfide；Compound containing thiocarbamate, including thiocarbamate, alkylene Base is coupled thiocarbamate and double (S- alkyl Dithiocarbamyl) disulphide；And its mixture.It is adapted to Antiwear additive can be molybdenum dithiocarbamate.Phosphorous antiwear additive is more fully described in European patent 612839.Dialkyl group Metal in disulfide group phosphate can be alkali metal, alkaline-earth metal, aluminium, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc.Applicable Antiwear additive can be with zine dialkyldithiophosphates.

It is adapted to other examples of antiwear additive to include：Titanium compound, tartrate, tartrimide, phosphorus compound it is oily molten Property amine salt, olefine sulfide, phosphite ester (such as dibutyl phosphite), phosphonate ester, compound (such as sulphur containing thiocarbamate For carbamate, thiocarbamate acid amides, thiocarbamic acid ether, alkylidene coupling thiocarbamate and double (S- alkyl Dithiocarbamyl) disulphide).Tartrate or tartrimide can contain alkyl group, wherein The summation of carbon atom can be at least 8 on alkyl.In one embodiment, antiwear additive can include citrate.

Antiwear additive can include about 0wt% to about 15wt% or about 0.01wt% to about in lubricant oil composite 10wt% or about 0.05wt% to about 5wt% or about 0.1wt% to about 3wt% in the range of exist.

Wear-resistant immunomodulator compounds can be dihydrocarbyl dithiophosphate trbasic zinc phosphate (ZDDP), its P:Zn ratios are about 1:0.8 to about 1: 1.7。

Boron-containing compound

Lubricant oil composite herein can be optionally containing one or more boron-containing compounds.

The example of boron-containing compound include borate, borated fatty amine, boration epoxides, boration detergent with And borated dispersants, such as boration succinimide dispersant, as disclosed in U.S. Patent No. 5,883,057.

If it does, boron-containing compound can be enough to provide the at most about 8wt% of lubricant oil composite, about 0.01wt% extremely The amount of about 7wt%, about 0.05wt% to about 5wt% or about 0.1wt% to about 3wt% uses.

Dispersant

Lubricant oil composite can optionally additionally comprise one or more dispersing agents or its mixture.Dispersant is commonly referred to as For ashless type dispersants, because they do not contain the metal to form ash content and when being added to profit before in lubricant oil composite They are generally not provided any ash content when in lubrication prescription.Ashless type dispersants, which are characterized by, is connected to relatively high molecular weight hydrocarbon chain Polar group.Typical ashless dispersant includes N- substitution long-chain alkenyl succimides.N- substitutes long-chain alkenyl succimide Example including polyisobutene substituent number-average molecular weight about 350 to about 50,000 or to about 5,000 or to about 3,000 models Enclose interior polyisobutene succinimide.Succinimide dispersant and its preparation are disclosed in, such as U.S. Patent No. 7, In No. 897,696 or U.S. Patent No. 4,234,435.Polyolefin can be by containing about 2 to about 16 or about 2 to about 8 or about 2 It is prepared by the polymerisable monomer to about 6 carbon atoms.Succinimide dispersant is typically by polyamine, typically poly- (ethylidene Amine), the acid imide of formation.

The disclosure comprises additionally at least one polyisobutene succinimide dispersant in one embodiment, it is from number Average molecular weight is about 350 to about 50,000 or to about 5000 or to the polyisobutene in the range of about 3000.Polyisobutene succinyl Imines can be used alone or be used with other dispersant packages.

In certain embodiments, if including polyisobutene, it can have more than 50mol%, more than 60mol%, be more than 70mol%, the terminal double bond content more than 80mol% or more than 90mol%.This kind of PIB is also referred to as highly reactive property PIB (“HR-PIB”).Number-average molecular weight is that the HR-PIB in the range of about 800 to about 5000 is suitable in embodiment of the disclosure.Often Rule PIB is typically below 50mol%, the end less than 40mol%, less than 30mol%, less than 20mol% or less than 10mol% Terminal double bond content.

HR-PIB of the number-average molecular weight in the range of about 900 to about 3000 can be what is be adapted to.This kind of HR-PIB it is commercially available or It can be synthesized by the polymerization of the isobutene in the presence of non-chlorinated catalyst (such as boron trifluoride), such as U.S. in Boerzel et al. Described in the U.S. Patent No. 5,739,355 of state's patent the 4,152,499th and Gateau et al..When for foregoing heat During alkene reaction, due to increased reactivity, HR-PIB can bring higher reaction conversion ratio and relatively low deposit to be formed Amount.Appropriate methodology is described in U.S. Patent No. 7,897,696.

In one embodiment, the disclosure comprises additionally at least one and derives from polyisobutylene butanedioic anhydride (" PIBSA ") Dispersant.The average succinic acid parts that can have per polymer between about 1.0 and about 2.0 of PIBSA.

Chromatographic technique can be used to measure for the active % of alkenyl or dialkyl succinylsuccinate acid anhydride.This method is described in U.S. Patent No. In 5th column of No. 5,334,321 and the 6th column.

The conversion percentages of polyolefin be using U.S. Patent No. 5,334,321 the 5th column and the 6th column in equation by What active % was calculated.

Unless otherwise stated, otherwise all percentages are that number is divided equally with weight percents and all molecular weight Son amount.

In one embodiment, dispersant can derive from poly alpha olefin (PAO) succinic anhydride.

In one embodiment, dispersant can derive from olefin maleic anhydride copolymer.For example, can incite somebody to action Dispersant is described as poly- PIBSA.

In one embodiment, dispersant can derive from the acid anhydrides for grafting on ethylene-propylene copolymer.

The suitable dispersant of one kind can be Mannich base (Mannich bases).Mannich base is by higher molecular weight The material that the condensation of alkyl-substituted phenols, polyalkylene polyamine and aldehyde (such as formaldehyde) is formed.Mannich base is described in greater detail in In U.S. Patent No. 3,634,515.

The suitable dispersant of one kind can be high-molecular weight ester or half esteramides.

Suitable dispersant can also be by conventional method by being post-processed with any one reaction in various reagents.This Wherein there are boron, urea, thiocarbamide, two coloured glaze base thiadiazoles, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon replaced succinate acid anhydride, maleic acid Acid anhydride, nitrile, epoxides, carbonic ester, cyclic carbonate ester, steric hindrance phenolic ester and phosphorus compound.US 7,645,726、US 7,214,649 It is incorporated herein in entirety by reference with US 8,048,831.

In addition to carbonic ester and boric acid post-process, two kinds of compounds can be used through being designed to improve or assigning not Various post processings with characteristic are post-processed or further work-up.This kind of post processing is included in U.S. Patent No. 5,241, Those summarized in 27th to 29 column of No. 003, are herein incorporated by reference hereby.This kind of processing includes, and uses following processing：

Inorganic phosphorous acid or dehydrate (such as U.S. Patent No. No. 3,403,102 and No. 4,648,980)；

Organophosphor compound (such as U.S. Patent No. 3,502,677)；

Phosphorus pentasulfide；

The boron compound (such as U.S. Patent No. No. 3,178,663 and No. 4,652,387) having already mentioned above；

Carboxylic acid, polybasic carboxylic acid, acid anhydrides and/or carboxylic acid halides (such as U.S. Patent No. 3,708,522 and the 4,948,386th Number)；

Epoxides, polyepoxide or thioepoxide (such as U.S. Patent No. 3,859,318 and the 5,026th, No. 495)；

Aldehydes or ketones (such as U.S. Patent No. 3,458,530)；

Carbon disulfide (such as U.S. Patent No. 3,256,185)；

Glycidol (such as U.S. Patent No. 4,617,137)；

Urea, thiocarbamide or guanidine (such as U.S. Patent No. 3,312,619, No. 3,865,813 and British patent GB 1, 065,595)；

Organic sulfonic acid (such as U.S. Patent No. 3,189,544 and British patent GB 2,140,811)；

Alkenyl cyanide (such as U.S. Patent No. No. 3,278,550 and No. 3,366,569)；

Dicthenone (such as U.S. Patent No. 3,546,243)；

Diisocyanate (such as U.S. Patent No. 3,573,205)；

Alkane sultone (such as U.S. Patent No. 3,749,695)；

1,3- dicarbonyl compounds (such as U.S. Patent No. 4,579,675)；

The sulfuric ester of alcohol alcoxylates or phenol (such as U.S. Patent No. 3,954,639)；

Cyclic lactone (such as U.S. Patent No. 4,617,138, No. 4,645,515, No. 4,668,246, the 4,963rd, No. 275 and No. 4,971,711)；

Cyclic carbonate ester or the linear monocarbonate of sulfocarbonate or makrolon or chloro-formate (such as U.S. Patent No. 4, No. 612,132, No. 4,647,390, No. 4,648,886, No. 4,670,170)；

Containing nitronic acid (such as United States Patent (USP) 4,971,598 and British patent GB 2,140,811)；

The shielded chlorination dicarbapentaborane oxygen compound of hydroxyl (such as U.S. Patent No. 4,614,522)；

Lactams, sulphur lactams, thiolactone or two thiolactones (such as U.S. Patent No. 4,614,603 and the 4,666th, No. 460)；

Cyclic carbonate ester or the linear monocarbonate of sulfocarbonate or makrolon or chloro-formate (such as U.S. Patent No. 4, No. 612,132, No. 4,647,390, No. 4,646,886, No. 4,670,170)；

Containing nitronic acid (such as U.S. Patent No. 4,971,598 and British patent GB 2,440,811)；

Cyclic carbramates, Cyclothiocarbamate or epidithio for carbamate (such as U.S. Patent No. 4, No. 663,062 and No. 4,666,459)；

Hydroxyaliphatic carboxylic acids (such as U.S. Patent No. 4,482,464, No. 4,521,318, the 4,713,189th Number)；

Oxidant (such as U.S. Patent No. 4,379,064)；

Phosphorus pentasulfide and polyalkylene polyamine (such as U.S. Patent No. 3,185,647)；

Combination (such as U.S. Patent No. 3,390,086, the 3,470,098th of carboxylic acid or aldehydes or ketones and sulphur or sulfur chloride Number)；

The combination (such as U.S. Patent No. 3,519,564) of hydrazine and carbon disulfide；

The combination (such as U.S. Patent No. 3,649,229, No. 5,030,249, No. 5,039,307) of aldehyde and phenol；

The combination (such as U.S. Patent No. 3,865,740) of the O- diester of aldehyde and phosphordithiic acid；

The combination (such as U.S. Patent No. 4,554,086) of hydroxyaliphatic carboxylic acids and boric acid；

The combination (such as U.S. Patent No. 4,636,322) of hydroxyaliphatic carboxylic acids and formaldehyde and phenol；

The combination (such as U.S. Patent No. 4,663,064) of hydroxyaliphatic carboxylic acids and aliphatic dicarboxylic acid；

The combination (such as U.S. Patent No. 4,699,724) of formaldehyde and phenol and hydroxyacetic acid；

The combination (such as U.S. Patent No. 4,713,191) of hydroxyaliphatic carboxylic acids or oxalic acid and diisocyanate；

Combination (such as the U.S. Patent No. of the inorganic acid or acid anhydrides of phosphorus or its inclined sulphur or whole sulfur analogs and boron compound No. 4,857,214)；

Organic diacid and unrighted acid and nitroso arylamine, are optionally followed by boron compound and ethyl glycolate Change the combination (such as U.S. Patent No. 4,973,412) of reagent；

The combination (such as U.S. Patent No. 4,963,278) of aldehyde and triazole；

The combination (such as U.S. Patent No. 4,981,492) of aldehyde and triazole and boron compound；

Cyclic lactone and boron compound and combine (such as U.S. Patent No. No. 4,963,275 and No. 4,971,711).It is above-mentioned Patent is incorporated by herein with it.

The TBN for being adapted to dispersant can be about 10 to about 65 on oil-free basis, equivalent to containing about 50% flux oil Dispersant sample on measure when about 5 to about 30 TBN.

If it does, dispersant can be enough to provide, based on the final weight of lubricant oil composite, at most about 20wt%'s Amount uses.Another amount that dispersant can be used can be that based on the final weight of lubricant oil composite, about 0.1wt% is to about 15wt% or about 0.1wt% are to about 10wt% or about 3wt% to about 10wt% or about 1wt% to about 6wt% or about 7wt% To about 12wt%.In certain embodiments, lubricant oil composite uses mixed dispersant system.It can be used and press any desired ratio Unitary class dispersant or two classes or more class dispersant mixture.

Friction modifiers

Lubricant oil composite herein can also be optionally containing one or more friction modifiers.It is adapted to friction modifiers The friction modifiers containing metal and without metal can be included, and may include but be not limited to：Imidazoline, acid amides, amine, fourth two Acid imide, alkoxylated amines, alkoxylate ether amines, amine oxide, amidoamines, nitrile, glycine betaine, quaternary ammonium, imines, amine salt, ammonia Base guanidine, alkanolamide, phosphonate ester, metal-containing compound, glyceride, sulfurized fatty compound and alkene, sunflower oil are other natural Produce plant or animal oil, dicarboxylic ester, the ester of polyalcohol or partial ester and one or more aliphatic or aromatic carboxylic acid etc..

Suitable friction modifiers can contain selected from straight chain, branched chain or aromatic hydrocarbyl or its mixture and can be with It is saturated or unsaturated alkyl.Alkyl can be made of carbon and hydrogen or hetero atom (such as sulphur or oxygen).Alkyl can be about 12 To about 25 carbon atom ranges.In certain embodiments, friction modifiers can be long-chain fatty acid ester.In another embodiment In, long-chain fatty acid ester can be monoesters or diester or (three) glyceride.Friction modifiers can be higher fatty acid amide, long-chain Fatty ester, long chain fatty epoxide derivative or long-chain imidazoline.

Other suitable friction modifiers can include organic ashless (no metal) nitrogen-free organic friction modifiers.This kind of friction Modifying agent can include the ester by making carboxylic acid and acid anhydrides be formed with reaction of alkanol, and generally include to be covalently bonded in oleophylic The terminal polar group (such as carboxyl or hydroxyl) of property hydrocarbon chain.One example of organic ashless nitrogen-free friction modifiers is commonly known as glycerine Monoleate (GMO), it can the mono-, di- containing oleic acid and three esters.Other suitable friction modifiers descriptions are in United States Patent (USP) In 6th, 723, No. 685, it is incorporated in entirety by reference herein.

Amine friction modifiers can include amine or polyamine.This kind of compound can have linear saturation or undersaturated alkyl Or its mixture, and about 12 to about 25 carbon atoms can be contained.It is adapted to other examples of friction modifiers to include alkoxy Change amine and alkoxylate ether amines.This kind of compound can have linear saturation or undersaturated alkyl or its mixture.They can be with Contain about 12 to about 25 carbon atoms.Example includes ethoxylated amine and ethoxylation ether amines.

Amine and acid amides can so use or with boron compound (such as boron oxide, halogenation boron, metaboric acid ester, boric acid or boron Sour mono-, di- or trialkyl ester) adduct or reaction product form.Other suitable friction modifiers descriptions are in U.S. Patent No. In 6,300, No. 291, it is incorporated in entirety by reference herein.

Friction modifiers can optionally in such as from about 0wt% to about 10wt% or about 0.01wt% to about 8wt% or about The scope of 0.1wt% to about 4wt% exists.

Containing molybdenum component

Lubricant oil composite herein can also be optionally containing one or more molybdate compounds.Soluble molybdenum compounds There can be the feature efficiency of antiwear additive, antioxidant, friction modifiers or its mixture.Soluble molybdenum compounds can include Molybdenum dithiocarbamate, molybdenum dialkyl-dithiophosphate, phosphonodithious acid molybdenum, the amine salt of molybdenum compound, xanthic acid molybdenum, sulphur For xanthic acid molybdenum, molybdenum sulfide, carboxylic acid molybdenum, molybdenum alkoxide, three core organic molybdenums, and/or its mixture.Molybdenum sulfide includes two sulphur Change molybdenum.Molybdenum disulfide can be in the form of stable dispersions.In one embodiment soluble molybdenum compounds can be selected from by with The group of lower composition：Molybdenum dithiocarbamate, molybdenum dialkyl-dithiophosphate, the amine salt of molybdenum compound, and its mixture. Soluble molybdenum compounds can be molybdenum dithiocarbamate in one embodiment.

The suitable example of workable molybdenum compound is included in the commercial material sold under for example following trade name：Come from The Molyvan 822 of R.T.Vanderbilt Co., Ltd.^TM、Molyvan^TMA、Molyvan 2000^TMWith Molyvan 855^TM And the Sakura-Lube from Adeka Corporation^TMS-165、S-200、S-300、S-310G、S-525、S-600、 S-700 and S-710, and its mixture.Suitable molybdenum component is described in US 5,650,381, US RE 37,363 E1, US In 38,929 E1 and US RE of RE, 40,595 E1, it is incorporated in entirety by reference herein.

In addition, molybdenum compound can be acidic molybdenum compound.Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other molybdenums Acid alkali metal salt and other molybdenum salt, such as molybdic acid hydrogen sodium, MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆, molybdenum trioxide or similar acid Molybdenum compound.Alternatively, composition can provide molybdenum by the molybdenum/sulfide complex of basic nitrogen compound, such as in such as U.S. Patent No. 4, No. 263,152, No. 4,285,822, No. 4,283,295, No. 4,272,387, No. 4,265,773, the 4,261,843rd Number, described in the 4th, 259, No. 195 and the 4th, 259, No. 194 and U.S. Patent Publication case the 2002/0038525th, This is incorporated in entirety by reference.

Another kind of suitable organic molybdenum is tri-nuclear molybdenum compound, such as formula Mo₃S_kL_nQ_zTri-nuclear molybdenum compound with And its mixture, wherein S represent sulphur, L represents the ligand with organic group independently selected, and the organic group, which has, to be enough The carbon number of compound solubility in the oil or dispersibility is assigned, n is that 1 to 4, k is that 4 to 7, Q is selected from neutral supplied for electronic The group of compound, such as water, amine, alcohol, phosphine and ether, and z is in the range of 0 to 5 and including non-stoichiometry value.All There may be at least 21 entire carbon atoms in the organic group of ligand, such as at least 25, at least 30 or at least 35 carbon atoms.Its Its suitable molybdenum compound is described in U.S. Patent No. 6,723,685, is incorporated in entirety by reference herein.

Soluble molybdenum compounds can be enough to provide about 0.5ppm to about 2000ppm, about 1ppm to about 700ppm, about The amount of 1ppm to about 550ppm, about 5ppm to about 300ppm or about 20ppm to the molybdenum of about 250ppm exists.

Titanium-containing compound

Another kind of additive includes oil-soluble titanium.Oil-soluble titanium can serve as antiwear additive, friction modified More than one in agent, antioxidant, deposit-control additives, or these functions.In one embodiment, oil-soluble titanium can To be titanium (IV) alkoxide.Titanium alkoxides can be formed by monohydric alcohol, polyalcohol or its mixture.Unitary alkoxide can have 2 to 16 or 3 to 10 carbon atoms.In one embodiment, Titanium alkoxides can be titanium (IV) isopropoxide.In one embodiment, Titanium alkoxides can be with It is 2-Ethylhexyl Alcohol titanium (IV).In one embodiment, titanium compound can be the alkoxide of 1,2- glycol or polyalcohol.Implement one In example, 1,2- glycol includes fatty mono glyceride, such as oleic acid.In one embodiment, oil-soluble titanium can be carboxylic acid Titanium.In one embodiment, carboxylic acid titanium (IV) can be neodecanoic acid titanium.

In one embodiment, oil-soluble titanium can be in lubricant oil composite so as to providing by weight zero to about The amount of the titanium of 1500ppm or by weight about 10ppm to 500ppm or about 25ppm to the titanium of about 150ppm exists.

Compound containing transition metal

In another embodiment, oil-soluble compounds can be compound or metalloid containing transition metal.Transition metal It may include but be not limited to：Titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten etc..Suitable metalloid includes but not limited to：Boron, silicon, antimony, tellurium Deng.

In one embodiment, can be by the weight ratio of Ca/M about 0.8:1 to about 70:The oil-soluble used in the range of 1 Compound is titanium-containing compound, and wherein M is total metal in lubricant compositions as described above.Titanium-containing compound can fill When antiwear additive, friction modifiers, antioxidant, deposit-control additives, or more than one in these functions.It can be used in or can For being various Ti (IV) compound in the titanium-containing compound in the preparation of the oil soluble material of disclosed technology, such as titanium (IV) oxygen Compound；Titanium (IV) sulfide；Titanium (IV) nitrate；Titanium (IV) alkoxide, such as methanol titanium, titanium ethanolate, titanium propanolate, isopropyl titanate, fourth Alcohol titanium, 2-Ethylhexyl Alcohol titanium；And other titanium compounds or complex compound, include but not limited to：Phenol titanium；Carboxylic acid titanium, such as 2- second Base -1-3- adipic acids titanium (IV) or Titanium Citrate or oleic acid titanium；And (triethanolamine acid group) isopropyl titanate (IV).Disclosed The other forms of the titanium of technical connotation lid include titanium phosphate, such as phosphordithiic acid titanium (such as dialkyl dithiophosphate) and sulphur Sour titanium (such as alkylbenzenesulfonate), or usually titanium compound and the reaction of various acidic materials forming salts (such as oil-soluble salt) Product.Apart from the others, thus titanium compound can derive from organic acid, alcohol and glycol.Ti compounds can also with dimerization or Oligomerization form exists, and contains Ti--O--Ti structures.This kind of titanium material is commercially available or can easily pass through the technology to fields For personnel prepared by suitable synthetic technology apparent easy to know.They are at room temperature solid or liquid presence, are depended on Specific compound.The form of solution in the atent solvent that they can also be adapted to provides.

In one embodiment, titanium can with Ti modify dispersant, such as succinimide dispersant, form provide.It is this kind of Material can be mixed by forming titanium between Titanium alkoxides and alkyl replaced succinate acid anhydride (such as alkenyl (or alkyl) succinic anhydride) It is prepared by acid anhydrides.Gained titanate-succinate intermediate can be used directly or it can be with any one in following many kinds of substance A reaction：(a) have freely, can be condensed -- polyamine class succimide/acid amides dispersant of NH functional groups；(b) polyamine class The component of succimide/acid amides dispersant, i.e. alkenyl (or alkyl) succinic anhydride and polyamine；(c) replaced succinate acid anhydride is passed through Hydroxyl polyester dispersants prepared by the reaction with polyalcohol, amino alcohol, polyamine or its mixture.Alternatively, titanate-succinic acid Salt intermediate can with other reagents, such as alcohol, amino alcohol, ether alcohol, Aethoxy Sklerol or polyalcohol or fatty acid response, and directly Ti is given to lubricant using its product, or is further reacted as described above with succinic acid dispersant.For example, 1 part of (by mol) tetraisopropyl titanate can be with about 2 parts of (by mol) polyisobutene replaced succinate acid anhydrides at 140-150 DEG C Lower reaction 5 to 6 obtains titanium modification dispersant or intermediate when small.Obtained material (30g) can further with from polyisobutene The succinimide dispersant of replaced succinate acid anhydride is reacted with polyethylenepolyamine mixture (127 grams+flux oil) at 150 DEG C 1.5 it is small when, produce titanium modification succinimide dispersant.

Another titanium-containing compound can be Titanium alkoxides and C₆To C₂₅The reaction product of carboxylic acid.Reaction product can be by following formula table Show：

Wherein n is that n is the integer selected from 2,3 and 4, and R is the alkyl containing about 5 to about 24 carbon atoms, Huo Zheyou Following formula represents：

Wherein each R¹、R²、R³And R⁴It is identical or different, and be to be selected from the hydrocarbon containing about 5 to about 25 carbon atoms Base.Suitable carboxylic acid can include but is not limited to：Caproic acid, octanoic acid, laurate, myristic acid, palmitic acid, stearic acid, arachidic acid, Oleic acid, erucic acid, linoleic acid, leukotrienes, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid etc..

In one embodiment, oil-soluble titanium can in lubricant oil composite so as to provide by weight 0 to 3000ppm titaniums or by weight 25 are to about 1500ppm titaniums or by weight about 35ppm to 500ppm titaniums or about 50ppm to about The presence of the amount of 300ppm.

Viscosity index improver

Lubricant oil composite herein can also be optionally containing one or more viscosity index improvers.Suitable viscosity Index improver can include polyolefin, olefin copolymer, ethylene/propene copolymer, polyisobutene, hydrogenated styrene-isoamyl Diene polymer, styrene/maleate copolymer, hydrogenated styrene/butadiene copolymer, hydrogenated isoprene polymer, Alpha-olefin maleic anhydride multipolymer, polymethacrylates, polyacrylate, alkyl styrenes, hydrogenated alkenyl aryl Conjugated diene copolymer, or its mixture.Viscosity index improver can include star polymer, and be adapted to example description to exist U.S. Patent No. 8,999,905 B2.

Lubricant oil composite herein is in addition to viscosity index improver or replaces viscosity index improver can also Optionally contain one or more dispersing agents viscosity index improver.Suitable viscosity index improver can include functionalization polyene Hydrocarbon, for example, the functionalized ethylene-propylene copolymer of reaction product through acylating agent (such as maleic anhydride) Yu amine；Through Amine or functionalized polymethacrylates, or esterification maleic anhydride-styrol copolymer with amine reaction.

The total amount of viscosity index improver and/or dispersant viscosity index improvers can be the pact of lubricant oil composite 0wt% to about 20wt%, about 0.1wt% are to about 15wt%, about 0.1wt% to about 12wt% or about 0.5wt% to about 10wt%.

Other optional additives

Other additives can be selected to perform one or more functions necessary to lubricating fluid.In addition, mentioned adds Add the one or more in agent can be it is multi-functional and provide in addition to function specified herein or different from herein In specify function function.

Other efficiency additives can optionally be included according to the lubricant oil composite of the disclosure.Other efficiency additives can With in addition to the specified additive of the disclosure, and/or can include one or more of following：Metal deactivators, It is viscosity index improver, ashless tbn synergist, friction modifiers, antiwear additive, corrosion inhibitor, antirust agent, dispersant, scattered Agent viscosity index improver, extreme pressure agent, antioxidant, foam in hibitors, demulsifying agent, emulsifying agent, pour-point depressant, sealed expander And its mixture.In general, the lubricating oil fully allocated will contain one or more of these efficiency additives.

Suitable metal deactivators can include, derivative, the dimercapto thiophene of benzotriazole (usual tolyl-triazole) Oxadiazole derivative, 1,2,4- triazoles, benzimidazole, 2- alkyl-dithios benzimidazole or 2- alkyl-dithio benzothiazoles；Bubble Foam inhibitor, including the copolymer of ethyl acrylate and 2- ethylhexyl acrylates and optionally vinyl acetate；Breaking Agent, including trialkylphosphate, polyethylene glycol, polyethylene glycol oxide, polypropylene oxide and (ethylene oxide-propylene oxide) polymerization Thing；Pour-point depressant, including the ester of maleic anhydride-styrene, polymethacrylates, polyacrylate or polyacrylamide.

Suitable foam in hibitors includes silicon class compound, such as siloxanes.

Suitable pour-point depressant can include polymethyl methacrylate or its mixture.Pour-point depressant can be enough to provide, Based on the final weight of lubricant oil composite, about 0wt% to about 1wt%, about 0.01wt% to about 0.5wt% or about The amount of 0.02wt% to about 0.04wt% exists.

Suitable antirust agent can be single compound or the compound with the characteristic for suppressing ferrous metal surface corrosion Mixture.The non-limiting examples of antirust agent useful herein include：Oil-soluble high molecular weight organic acid, such as 2- ethyl hexyls Acid, laurate, myristic acid, palmitic acid, oleic acid, linoleic acid, leukotrienes, behenic acid and cerinic acid；And including dimerization The oil-soluble polybasic carboxylic acid of acid and trimer acid, as those are as producing pine tar aliphatic acid, oleic acid and linoleic acid.It is other suitable The corrosion inhibitor of conjunction includes long-chain alpha, omega-dicarboxylic acid and alkenyl succinic acid of the molecular weight ranges in about 600 to about 3000, its Middle alkenyl contains about 10 or more carbon atoms, such as tetrapropylene base succinic acid, tetradecene base succinic acid and hexadecylene base succinic acid. Another kind of applicable sour corrosion inhibitor be have in alkenyl the alkenyl succinic acids of about 8 to about 24 carbon atoms with alcohol (such as Polyethylene glycol) half ester.The correspondence half amide of this kind of alkenyl succinic acid is also suitable.Applicable antirust agent is that high molecular weight is organic Acid.In certain embodiments, machine oil is free of antirust agent.

If it does, antirust agent can be enough to provide, based on the final weight of lubricant oil composite, about 0wt% is to about The amount of 5wt%, about 0.01wt% to about 3wt%, about 0.1wt% to about 2wt% use.

In a general sense, suitable crankcase lubricant can include the additive group in the scope listed in the following table Point.

Table 2

The percentage of each component represents the weight hundred of each component based on the weight of final lubricant oil composite above Divide ratio.The remainder of lubricant oil composite is made of one or more base oils.

Additive for allocating compositions described herein can be blended into basis individually or with various sub-portfolios In oil.However, it is possible to it is adapted to using multifunctional additive for lubricating oils (i.e. additive and diluent, such as hydrocarbon solvent) while blends all groups Point.Additive for allocating compositions described herein can be blended into base oil individually or with various sub-portfolios. However, it is possible to it is adapted to using multifunctional additive for lubricating oils (i.e. additive and diluent, such as hydrocarbon solvent) while blends all components.

The disclosure provides and is deployed into the novel lubricating oil admixture as automotive engine lubrication agent.The implementation of the disclosure Example can provide the lubricating oil for being suitable for engine application, there is provided the improvement of following one or more features：Low speed morning combustion event, Antioxidant, wear-resistant efficiency, antirust, fuel economy, water tolerance, air incorporation, sealing protection, reduction deposition, i.e., it is logical TEOST 33 is crossed to test, and defoaming characteristics.

The lubricant fully allocated routinely contains additive bag, herein referred to as dispersant/inhibitor bag or DI bags, It will provide characteristic necessary to composite.Suitable DI bags description in such as U.S. Patent No. 5,204,012 and the 6th, In No. 034,040.Can there are dispersant, sealed expander, antioxidant, foam in the additive types that additive bag includes Inhibitor, lubricant, antirust agent, corrosion inhibitor, demulsifying agent, viscosity index improver etc..The several of these component are Known to those skilled in the art, and usually made with convention amount together with additive described herein and composition With.

Following instance is to the illustrative and not limiting of disclosed method and composition.It is usually being run into field and The other suitable modifications and adjustment of those skilled in the art's various conditions apparent easy to know and parameter belong to the disclosure In spirit and scope.All patents and publication enumerated herein are incorporated herein in entirety by reference completely.

Example

Prepare the lubricant oil composite fully allocated containing conventional additives and measure the low speed morning of lubricant oil composite Combustion event.Each lubricant oil composite contains a large amount of base oils, basic conventional disperse agent inhibitor (dispersant Inhibitor, DI) bag and viscosity index improver, wherein basis DI bags (being less than viscosity index improver) account for lubricating oil composition About the 8 to 12wt.% of thing.Basic DI includes dispersant, antiwear additive, antifoaming agent and the antioxidant of convention amount, such as Illustrated in table 3 below.Exactly, basic DI includes succinimide dispersant, boration succinimide dispersant, is in There is provided the molybdate compounds of amount of lubricant oil composite about 80ppm molybdenums, organic friction modifiers, one or more antioxidants and One or more antiwear additives (unless specified otherwise herein).One or more viscosity that basic DI bags also blend about 5 to about 10wt% refer to Number modifier.Group i base oils are used as diluent.Substantial amounts of base oil (about 78 to about 87wt%) is Group III base oil.Become The component of change describes in detail in following table and in the discussion of example.Unless specified otherwise herein, all values otherwise listed all are to make The percentage by weight for being component in lubricant oil composite (i.e. active ingredient adds flux oil (if present)) statement.

Table 3- bases DI bags composition

Component	Wt.%
		Antioxidant	0.5 to 2.5
Antiwear additive, including any aluminum, lead, tin, molybdenum, manganese, nickel, copper	0.7 to 5.0
		Antifoaming agent	0.001 to 0.01
Detergent *	0.0
		Dispersant	2.0 to 6.0
Modifying agent containing metal friction	0.05 to 1.25
		Without metal friction modifying agent	0.01 to 0.5
Pour-point depressant	0.05 to 0.5
		Processing oil	0.25 to 1.0

* detergent is different in following experiment, therefore is arranged to de-sludging dosage for the purpose of basic composite Zero.

Low speed is measured in 2.0 liters of GM, 4 cylinder Ecotec turbocharging gasoline-type direct injection (GDI) engines early to fire (LSPI) event.One complete LSPI igniter motors test is made of 4 test loops.In single test loop, repeat Two operational phases or link are to produce LSPI events.In stage A, when LSPI occurs in most probable, engine is with about 2000rpm and about 18,000kPa brake mean-effective pressures (BMEP) operation.In stage B, there is LSPI when unlikely When, engine is with about 1500rpm and about 17,000kPa BMEP operations.For each stage, collect and start through 25,000 times The data of machine circulation.The structure of test loop is as follows：B- stage, B- stage in A- stage, A- stage A- stage, A stage.Each stage Separated by idle period.Because LSPI statistically significants during stage A, the LSPI event datas considered in this example are only Including the LSPI produced during stage A is run.Therefore, tested for a complete LSPI igniter motor, data usually pass through 16 stages produce and for assessing more oily and oily efficiency of the invention altogether.

By monitor peak cylinder pressure (peak cylinder pressure, Ρ Ρ) and in the combustion chamber 2% can LSPI events are judged during combustible material burning (MFB02).The threshold value of peak cylinder pressure is calculated for each cylinder and each stage, and And typically 65,000 to 85,000kPa.The threshold value of MFB02 is calculated for each cylinder and each stage, and is usually stopped upper Point after (After Top Dead Center, ATDC) about 3.0 to about 7.5 degree in crank angle (Crank Angle Degree, CAD in the range of).In single cycle of engine, LSPI is recorded when beyond the threshold value of PP and MFB02.LSPI events can be permitted Multimode is reported.The ambiguity being related to is counted per cycle of engine in order to remove report, wherein different igniting Engine Block Tests Different cycle of engine numbers can be used to carry out, more oily and oily opposite LSPI events report in the form of " LSPI ratios " of the invention Accuse.By this way, become clear showing relative to the improvement of some normal responses.

All reference oils are commercially available engine oils, meet all ILSAC GF-5 duty requirements, including by hereafter The TEOST 33 of discussion is tested.

In the following example, using basic composite test high alkalinity calcium detergent and neutrality/low alkalinity calcium detergent Combination.LSPI ratios are reported in the form of the LSPI events of test oil are relative to the ratio of the LSPI events of reference oil " R-1 ".R- 1 is to use basis DI bags and allocated with that can provide the high alkalinity calcium detergent of the amount of about 2400ppm Ca for lubricant oil composite Lubricant oil composite.The more detailed deployment information of reference oil R-1 described below.When LSPI events subtract for R-1 Approve the considerable improvement in terms of LSPI when the reduction of LSPI events is more than when being more than 50% (LSPI ratios are less than 0.5) less When 70% (LSPI ratios are less than 0.3), the further improvement in terms of LSPI is approved, when the reduction of LSPI events is more than 75% When (LSPI ratios are less than 0.25), the further improvement in terms of LSPI is approved, and when the LSPI events for R-1 Reduction when being more than 80% (LSPI ratios be less than 0.20), approve the further improvement in terms of LSPI, and when relative to When the reduction of LSPI events is more than 90% (LSPI ratios are less than 0.10) for R-1, further changing in terms of LSPI is approved It is kind.Therefore the LSPI ratios of R-1 reference oils are regarded as 1.00.

TEOST-33 tests are the experimental bench tests of the oxidative degradation and/or the hot coking that can be used for assessment machine oil.According to survey Examination, about 100mL test oils be used for 12 circulation/2 it is small when test in.Test causes on hollow heating rod (TEOST deposition rods) Oil (about 100 grams) bulk oxidation, the heating rod will during test calculus deposits.Test oil is every with about 0.5 gram Minute flows through the rod, while test part circulates 12 times through 200-480 DEG C of temperature range.Total deposition is the performance ginseng of measurement Number.Total deposition is deposition on rod and the summation of deposition in the oil that is removed by filtration.The deposition that measures to be shown to add The efficiency of agent composition is poorer.Exactly, weight increase is tested for 30 milligrams or less of test oil by TEOST 33.

The TBN measured values being given in the table below are based on ASTM D2896.TBN measured values are used to report in table 4 below The total metal mM number for the example fluids fully allocated:TBN.

Table 4

* the measured value of icp analysis is used

Tank oil R-1 and R-2 is included as the reference oil for showing current state-of-the-art technology.Reference oil R-1 is by about 80.7wt.% Group III base oil, 12.1wt.% are obtained from Afton Chemical Corporation's 11150PCMO additives bag and the allotment of 7.2wt.%35SSI ethylene/propene copolymers viscosity index improver. 11150 by bus electric motor oil additive bag be API SN, the DI bags of ILSAC-GF-5 and ACEA A5/B5 qualities.R-1 is also shown Show following characteristic and Partial Elements analysis：

Reference oil R-1

R-2 only contains the calcic detergent that than the present invention oil of test there is more high calcium to load.R-1 and R-2 meet ILSAC All duty requirements of GF-5, and therefore displaying will pass through performance in TEOST-33 experimental benches aoxidize test.Comparative example C-1, C-2, C-3 and C-4 are not commercially available fluids, but through being designed to displaying those skilled in the art in modification de-sludging Agent system is come the technical problem that is undergone when meeting LSPI performance requirements.

As shown in table 4, when the amount of the calcium from high alkalinity (" OB ") detergent is reduced to about from about 2400ppm During 1600ppm calcium, exist in terms of LSPI efficiency and significantly improve.Contrast R-1 and C-1, LSPI ratio reduction about 78%, but due to The reduction of calcium, the performance in TEOST-33 tests is from by being changed into failure.If the amount of the calcium from OB detergents is further 1100ppm (C-2) is reduced to, LSPI ratios even more significantly improve；However, under this calcium content, surveyed in TEOST-33 Performance in examination is still poor.In C-3, detergent system is completely eliminated, is shown：Without detergent, LSPI improves 100%. Equally, however, the tests of TEOST 33 performance failure.Example I-5 uses low alkalinity sodium sulfonate rather than present example I-1, I- 2nd, the low alkalinity sulfoacid calcium used in I-3 and I-4, and show：The low alkali of calcic is replaced using low alkalinity containing sodium/neutral detergent Property/neutral detergent can obtain significantly reducing for LSPI ratios.

By combining low alkalinity or neutrality (" LB/N ") calcium detergent (I-1 to I-4) and OB calcium detergents, can obtain Unexpected improvement in terms of LSPI, without sacrificing the performance in the oxidation test of TEOST-33 experimental benches.It is of the invention real Example I-1 is tested by TEOST-33 and is provided more significantly improving for LSPI events at the same time, and relative to R-1, LSPI ratios reduce almost 81%.The LSPI ratios that present example I-2 and I-3 provide even bigger reduce, without losing in TEOST-33 tests Performance.Example I-4 displayings replace LB/N sulfoacid calciums using LB/N calcium phenoxides.I-4 displays that significantly improving for LSPI ratios, and Tested by TEOST 33.Example shown in table 4 is clearly shown：, can by adding the extra calcium from LB/N calcium detergents To keep the amount of the calcium from OB calcium detergents to be tested under high level yet by TEOST 33 and ensure LSPI ratios Significantly reduce.In addition, unexpectedly, even if without the presence of a large amount of OB calcium detergents, the result obtained in the tests of TEOST 33 It can also be improved.In fact, compensating OB calcium detergents with LB/N calcium detergent, change unexpectedly and surprisedly The kind tests of TEOST 33 also reduce LSPI ratios at the same time.

Notebook data is shown, with LB/N Ca sulfonate with the benefit of the amount more than the 8%LB/N Ca sulfonate in total detergent OB Ca sulfonate is repaid the improvement of LSPI is provided while keeps the performance in the tests of TEOST 33.

Many places refer to multiple United States Patent (USP)s and other files in whole this specification.The file of all such references is bright Really it is incorporated by the disclosure, it is the same just as illustrating completely herein.

After the practice of specification and embodiment disclosed herein is considered, the other embodiments of the disclosure are to affiliated The technical staff in field is apparent from aobvious.As used in entire disclosure and claims, " one (a) " and/or " one (an) " it can refer to one or more than one.Unless specified otherwise herein, all expression otherwise used in the specification and in the claims Component, characteristic amount numeral, such as molecular weight, percentage, ratio, reaction condition are interpreted as in all examples by art Language " about " is modified, and no matter term " about " whether there is.Therefore, unless providing on the contrary, otherwise present specification and claims Middle illustrated numerical parameter is approximation that can be depending on the desirable properties for attempting to obtain by the disclosure to change.It is minimum Limit, and be not intended to limit the scope that equivalent principle is applied to claims, each numerical parameter should at least roots According to the effective digital reported number and round up technology by the way that application is general and explain.Although illustrate the extensive of the disclosure The number range and parameter of scope are approximations, but the numerical value illustrated in particular instance is report reported as precisely as possible.However, Any numerical value, itself contains the certain error for necessarily leading to the standard deviation present in its corresponding test measured value.Only will it wish Specification and example be considered as it is exemplary, wherein the true scope of the disclosure and spirit specified by claims below.

In practice, previous embodiment is to significantly changing sensitivity.Therefore, embodiment is not intended to be limited to the spy being described above Determine example.On the contrary, previous embodiment is in spirit and scope of the appended claims, including its can be used as legal issue etc. Jljl.

Applicant is not intended to any disclosed embodiment contributing to the public, and any disclosed modification to a certain extent Or it may be the scope for belonging to claims on literal to change, it is one of this paper that them are thought under equivalent principle Point.

It is to be understood that each component, compound, substituent or parameter disclosed herein should be understood to be disclosed to Individually or one or more of component other with each disclosed herein, compound, substituent or parameter combine Use.

It should also be clear that for each component disclosed herein, compound, substituent or parameter each amounts/values or The scope of amounts/values be interpreted as also by with it is public for any other component disclosed herein, compound, substituent or parameter The range combinations of each amounts/values or amounts/values opened disclose, and purpose disclosed herein two kinds for this description or more Thus various ingredients, compound, any combinations of the scope of the amounts/values of substituent or parameter or amounts/values are also combined with each other open.

It is also to be understood that each scope disclosed herein is interpreted as having identical significant figure within the scope of the disclosed The disclosure of each particular value of number of words purpose.Therefore, scope 1 to 4 is interpreted as the expression of value 1,2,3 and 4 and discloses.

It is also to be understood that each lower limit of each scope disclosed herein is interpreted as with being directed to identical group herein Point, each certain combinations of values in each upper limit and each scope of compound, substituent or each scope disclosed in parameter It is open.Therefore, will appreciate in view of this disclosure that for by by each upper limit of each lower limit of each scope and each scope or with it is each In the range of each certain combinations of values, or by the way that each upper limit of each scope and each certain combinations of values in each scope are spread out The disclosure of raw all scopes.

In addition, specification or component disclosed in example, compound, the specific amounts/values of substituent or parameter should be understood that For the lower limit of scope or the disclosure of the upper limit, and it is possible thereby to other places in the application disclosed in be used for same composition, change Any other lower limit or the upper limit combination of compound, the scope of substituent or parameter or specific amounts/values, form the component, chemical combination The scope of thing, substituent or parameter.

Claims

1. a kind of lubricant oil composite, comprising：

Lubricant viscosity base oil more than 50wt.%；

The high alkali cleaning agent of at least 0.3wt.%, the high alkali cleaning agent measure total alkali by the method for ASTM D-2896 Value is more than 225mg KOH/g, and

Low alkalinity/neutral detergent of at least 0.2wt.%, the side that the low alkalinity/neutral detergent passes through ASTM D-2896 Method measures total base number at most 175mg KOH/g, wherein from the high alkali cleaning agent and the low alkalinity/neutral detergent The total amount of calcium presses the gross weight meter of the lubricant oil composite, is being more than 1100ppm by weight to being less than by weight In the range of 2400ppm.

2. lubricant oil composite according to claim 1, wherein the high alkali cleaning agent includes high alkalinity calcic de-sludging Agent.

3. lubricant oil composite according to claim 2, wherein the high alkalinity calcic detergent, which includes, is selected from high alkalinity The compound of sulfoacid calcium detergent and overbased calcium phenate's detergent.

4. lubricant oil composite according to claim 1, wherein LSPI events are reduced up to 75% or more, and described LSPI events are that LSPI during 25,000 cycle of engine is counted, wherein the engine be with 2000 revs/min and 18,000kPa brake mean-effective pressures are run.

5. lubricant oil composite according to claim 1, wherein the low alkalinity/neutral detergent include low alkalinity/in Property calcic detergent.

6. lubricant oil composite according to claim 1, is selected from by sulfonic acid wherein the low alkalinity/neutral detergent includes The detergent of the group of calcium detergent and calcium phenoxide detergent composition.

7. lubricant oil composite according to claim 1, wherein the one or more high alkalinity calcic detergent is institute State lubricant oil composite and gross weight meter by the lubricant oil composite is provided, by weight about 900ppm is to being less than about The calcium of 2000ppm.

8. lubricant oil composite according to claim 1, wherein the lubricant oil composite have more than 4.5 to about The ratio of total metal mM number and the total base number of the lubricant oil composite in the lubricant oil composite in the range of 10.0 Rate.

9. lubricant oil composite according to claim 1, wherein the lubricant oil composite is effectively tested by TEOST33 Platform oxidation test.

10. lubricant oil composite according to claim 1, additionally comprises one or more selected from the group consisted of Component：Friction modifiers, antiwear additive, dispersant, antioxidant and viscosity index improver.

11. lubricant oil composite according to claim 1, wherein the base oil more than 50wt.% is selected from by following The group of composition：In Group II, Group III, Group IV, Group V base oil, and aforementioned base oil two or more Combination, and wherein the base oil more than 50wt.% is not by providing additive component or viscosity in the composition Index improver and the flux oil produced.

12. lubricant oil composite according to claim 1, wherein total metal mM number in the lubricant oil composite 8 are greater than to less than 10 with the ratio of the TBN of lubricant, and the lubricant oil composite includes the institute of at least 0.25wt.% State low alkalinity/neutral detergent.

13. lubricant oil composite according to claim 2, wherein the low alkalinity/neutral detergent include low alkalinity/in Property calcic detergent, and by the low alkalinity/neutrality calcic detergent for the lubricant oil composite provide by weight Calcium ppm with being by ratio of the high alkalinity calcic detergent for the ppm of calcium by weight of lubricant oil composite offer 0.05 to 1.0.

14. lubricant oil composite according to claim 2, wherein being described by one or more high alkali cleaning agent Lubricant oil composite provide total calcium be by the gross weight meter of the lubricant oil composite, by weight 1100ppm extremely 1800ppm。

15. lubricant oil composite according to claim 6, wherein being gone by one or more low alkalinity/neutrality calcics Dirty agent is by the gross weight meter of the lubricant oil composite, by weight 50ppm for total calcium that the lubricant oil composite provides To 1000ppm.

16. lubricant oil composite according to claim 1, wherein the lubricant oil composite is using the lubricating oil group In the enhanced internal combustion engine of compound lubrication, relative to multiple low in using the same engine with reference to lubricating oil R-1 lubrications Fast early combustion event, effectively reduces low speed early combustion event.

17. a kind of method that low speed for being used to reduce in enhanced internal combustion engine early fires event, comprising：

Enhanced internal combustion engine is lubricated using lubricant oil composite, the lubricant oil composite includes

Lubricant viscosity base oil more than 50wt.%；

Low alkalinity/neutral detergent of at least 0.2wt.%, the side that the low alkalinity/neutral detergent passes through ASTM D-2896 Method measures total base number at most 175mg KOH/g；Wherein from the high alkali cleaning agent and the low alkalinity/neutral detergent The total amount of calcium presses the gross weight meter of the lubricant oil composite, is being more than 1100ppm by weight to being less than by weight In the range of 2400ppm, and

Run the engine lubricated using the lubricant oil composite.

18. according to the method for claim 17, wherein the lubricant compositions aoxidize survey by 33 experimental benches of TEOST Examination.

19. according to the method for claim 18, wherein LSPI events are based on during 25,000 cycle of engine LSPI is counted, wherein the engine is with 2000 revs/min (revolutions per minute, RPM) and 18,000kPa Brake mean-effective pressure (brake mean effective pressure, BMEP) is run, and is using the lubricating oil The low speed in the enhanced internal combustion engine of composition lubrication early fires event, relative to using with reference to lubricating oil R-1 profits Early combustion event is reduced multiple low speed in sliding same engine.

20. according to the method for claim 19, wherein the low alkalinity neutral detergent includes calcic detergent, the height Alkali detergent includes calcic detergent, and the high alkali cleaning agent provides for the lubricant oil composite, by the profit The gross weight meter of sliding oil composition, by weight about 900ppm are extremely less than about the calcium of 2000ppm.

21. according to the method for claim 19, wherein lubricating step lubrication is configured with turbocharger or booster Spark-ignition direct-injection engine or fuel nozzle jet type internal combustion engine combustion chamber or cylinder wall.

22. according to the method for claim 19, additionally comprising measurement uses the internal combustion engine of the oil lubrication Low speed early fires the step of event.