CN106459812A

CN106459812A - Method of lubricating an internal combustion engine

Info

Publication number: CN106459812A
Application number: CN201580024035.1A
Authority: CN
Inventors: M·加里克拉古兹; J·G·卢普; M·H·T·特鲁昂; W·奥赖恩
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2014-03-12
Filing date: 2015-02-23
Publication date: 2017-02-22
Anticipated expiration: 2035-02-23
Also published as: ES2945598T3; CA2941721A1; US20170073606A1; EP3116980A1; CN106459812B; WO2015138108A1; SG11201607423WA; EP3116980B1; SG10201807892XA

Abstract

The invention provides a method of lubricating an internal combustion engine equipped with a centrifugal oil mist separator, wherein the lubricant contains 0.1 wt % to 8 wt % soot resulting from operation of the engine, and wherein the lubricant composition comprises an oil of lubricating viscosity, and 0.2 wt % to 3 wt % of a soot dispersing additive, wherein the soot dispersing additive comprises a polymer chain having a number average molecular weight of 500 to 20,000, and wherein the soot dispersing additive has a shear stability index of 0 to 20.

Description

The method of lubricating internal combustion engines

Invention field

The present invention provides the method that lubrication is equipped with the internal combustion engine of centrifugal type oil mist separator, and wherein lubricant comprises 0.1 The cigarette ash that weight % is produced to 8 weight % by power operation, and wherein lubricant compositions comprise the oil with lubricant viscosity With 0.2 weight % to 3 weight % cigarette ash dispersing additives, wherein cigarette ash dispersing additive comprises with 500-20, and 000 number is equal The polymer chain of molecular weight and the shear stability index of 0-20.

Background of invention

Equipment manufacturers design internal combustion engine in recent years in the way of helping reduce various greenhouse gases or particulate matter, And/or they use in processing meanss such as diesel particulate filters or SCR (SCR) later.Engine designs Recent development be that centrifugal type oil mist separator is attached to engine, usual diesel engine (generally has open or closed Crankcase) in.Centrifugal type oil mist separator generally becomes deposited thing (denseness is from sticky/mud shape to hard viscosity change) and blocks up Plug, if collecting enough deposits, it reduces efficiency and/or so that device is lost ability and make oil from engine completely Ooze.Think that this problem is particularly evident in large diesel engine.

Summary of the invention

The present invention allow internal combustion engine (usual compression ignition engine) have following at least one：The oil mist separator reducing Plugged filter and the deposit reducing for example sticky/mud shape is to hard adherent deposit.

Unless otherwise noted, as used herein, with regard to being present in the amount of additive in lubricating composition described herein Refer to based on oil-free, that is, the amount of active material is quoted.

As used herein, with " inclusion ", " containing " or " feature be ... " synonymous transitional term "comprising" be inclusive or Open, and it is not excluded for other unstated elements or method and step.However, as optional embodiment, in " bag herein Contain " each description in it is intended to this term also includes phrase " substantially by ... form " and " Consists of ", wherein " Consists of " Do not include any element or the step not described, " substantially by ... form " allows including substantially not affecting considered combination Basic and new features other of thing or method does not describe element or step.

As used herein, statement " compression-ignition engine " is intended to including the internal combustion engine with least part of compression ignition. Therefore, this invention is intended to include lubrication compression-ignition engine and spark auxiliary compression igniting internal combustion engine method.

The present invention relates to the method that lubrication is equipped with the internal combustion engine of centrifugal type oil mist separator, wherein lubricant comprises 0.1 Weight % is to 8 weight %, or 0.3 weight % to 6 weight % (or usual 0.5 weight % is to 4 weight %) is grasped by engine Make the cigarette ash that produces, and wherein lubricant compositions comprise the oil with lubricant viscosity and 0.2 weight % and divide to 3 weight % cigarette ashes Scattered additive, wherein cigarette ash dispersing additive comprise with 500-20, and the polymer chain of 000 number-average molecular weight and 0-20 cut Cut stability index.Generally, cigarette ash dispersing additive can comprise derived from having 500-20, the polyene of 000 number-average molecular weight The dispersant viscosity modifiers of hydrocarbon and/or the dispersant comprising aromatic amine structure division.

In one embodiment, the present invention relates to lubrication be equipped with centrifugal type oil mist separator internal combustion engine method, Wherein lubricant comprises the cigarette ash that 0.1 weight % is produced by power operation to 8 weight %, and wherein lubricant compositions comprise There is oil and 0.2 weight % to 3 weight % cigarette ash dispersing additives of lubricant viscosity, wherein cigarette ash dispersing additive comprises to have 500-20, the polymer chain of 000 number-average molecular weight and the shear stability index of 0-20, and cigarette ash dispersing additive is to pass through Carboxylic acid functionalized polymers (usual polyisobutylene succinic anhydride) with there is at least amine of 4 aromatic groups and aldehyde (such as formaldehyde) React and obtain the/available dispersant comprising aromatic amine structure division.Aromatic amine can be expressed from the next：

Wherein each variable：

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

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

U can be aliphatic, alicyclic or aromatic group, and condition is when U is aliphatic series, and aliphatic group can be for comprising 1-5 Or the linear or sub-branched alkyl of 1-2 carbon atom；And w can be 0-9 or 0-3 or 0-1 (usual 0).

In one embodiment, the present invention relates to lubrication be equipped with centrifugal type oil mist separator internal combustion engine method, Wherein lubricant comprises the cigarette ash that 0.1 weight % is produced by power operation to 8 weight %, and wherein lubricant compositions comprise There is oil and 0.2 weight % to 3 weight % cigarette ash dispersing additives of lubricant viscosity, wherein cigarette ash dispersing additive comprises to have 500-20, the polymer chain of 000 number-average molecular weight and the shear stability index of 0-20, and wherein cigarette ash dispersing additive is Comprise the dispersant viscosity modifiers of aromatic amine structure division, wherein dispersant viscosity modifiers are to use Aromatic moieties sense The olefin copolymer changed, usual olefin copolymer is ethylene-propylene copolymer.

In one embodiment, the present invention relates to lubrication be equipped with centrifugal type oil mist separator internal combustion engine method, Wherein lubricant comprises 0.1 weight % to 8 weight %, or 0.3 weight % to 6 weight % (or usual 0.5 weight % is to 4 weights Amount %) cigarette ash that produced by power operation, and wherein lubricant compositions comprise：

There is the oil of lubricant viscosity,

Cigarette ash dispersing additive, wherein cigarette ash dispersing additive comprise derived from having 500-20,000 number-average molecular weight Polyolefinic dispersant viscosity modifiers, and there is the shear stability index of 0-20, and comprise aromatic amine structure division Dispersant,

Wherein comprise the dispersant of aromatic amine structure division and dispersant viscosity modifiers all with 0.2 weight of lubricating composition Amount % to 3.0 weight %, or 0.3 weight % to 2.0 weight %, or the handling rate of 0.4 weight % to 1.5 weight % are deposited ?.

There is the oil of lubricant viscosity,

To 3 weight % cigarette ash dispersing additives, wherein cigarette ash dispersing additive comprises with 500-20 0.2 weight %, and 000 The polymer chain of number-average molecular weight and 0-20 shear stability index, and different from cigarette ash dispersing additive ashless amber , with 1 weight % to 8 weight %, or 2 weight % exist to 6 weight % for acid imide dispersant, wherein succinimide dispersants. Generally, succinimide dispersants comprise polyisobutenyl succinimide, and wherein dispersant has the TBN of at least 40mg KOH/g And existed with the amount of 1.2 weight % of lubricating composition to 5 weight %.

There is the oil of lubricant viscosity, 0.2 weight % is to 3 weight % cigarette ash dispersing additives, wherein cigarette ash dispersing additive Comprise with 500-20, the polymer chain of 000 number-average molecular weight and the shear stability index of 0-20, with 0.01 weight % extremely 0.9 weight %, or 0.05 weight % is to 0.8 weight %, or 0.1 weight % is to 0.7 weight %, or 0.2 weight % is extremely The overbased sulfonates detersive that 0.6 weight % exists.

There is the oil of lubricant viscosity, 0.2 weight % is to 3 weight % cigarette ash dispersing additives, wherein cigarette ash dispersing additive Comprise with 500-20, the polymer chain of 000 number-average molecular weight and the shear stability index of 0-20, different from cigarette ash dispersion The ashless succinimide dispersants of additive, wherein succinimide dispersants with 1 weight % to 8 weight %, or 2 weights Amount % to 6 weight % exists, with 0.01 weight % to 0.9 weight %, or 0.05 weight % is to 0.8 weight %, or 0.1 Weight % is to 0.7 weight %, or the overbased sulfonates detersive that 0.2 weight % to 0.6 weight % exists.

Internal combustion engine can have open or closed crankcase, generally open crankcase.Open and closed bent axle Case ventilation is as known in the art.For example, open crankcase ventilation is passed through to include hydrocarbon, carbon monoxide, NOx and particulate matter Discharge outside cylinder exhaust combusted products in interior altering and prevent pressure from being formed in the crankcase.In sealed crankcase ventilation (CCV), in system, crank case gases are generally filtered except oil mist removal and other particle, to be then returned in gas handling system.

Generally, inventive combustion engine can have sealed crankcase ventilation.

The heavy vehicle (HDV) comprising inventive combustion engine can have more than 2700kg (or 6000 U.S.'s pounds), or More than 2900kg, or more than 3000kg, or more than 3300kg, or more than 3500kg, or more than 3700kg or super Cross the loading mass (sometimes referred to as gross vehicle weight rating (GVWR)) of 3900kg (or 8500 U.S.'s pounds).Generally, load matter The upper limit of amount or GVWR is set by national government, and can be 10000kg, or 9000kg, or 8000kg, or 7500kg.The upper range of loading mass can be at most 400,000kg, or at most 200,000kg, or at most 60, 000kg, or at most 44,000kg, or at most 40,000kg.Generally, 120, more than 000 loading mass is used for highway Use car.

The vehicle comprising inventive combustion engine with the loading mass more than 2700kg (or 3,500kg) can be dress It is furnished with compression ignition engine or the large diesel engine of passive ignited natural gas (NG) or LPG engine.On the contrary, European Union Show, for the novel light vehicle (passenger vehicle and light commercial vehicles) including in the range of ACEA test portion " C ", have not " technology allows maximum laden mass " more than 2610kg.

Generally, internal combustion engine can be for being suitable to be provided with the diesel oil of power to the vehicle of the loading mass having more than 2,700kg Machine.

Centrifugal type oil mist separator is generally with 2500-10000, or 4000-8000, or 5000-7000rpm rotation.

In one embodiment, internal combustion engine is heavy diesel compression ignition (or the igniting of spark auxiliary compression) internal combustion Machine.

There is obvious difference between passenger vehicle and large diesel engine.They are different in terms of size, are not more than respectively With more than 3,500kg GVWR, this means that two kinds of engine can experience visibly different operating condition, for example to 2610kg Load, oil temperature, working cycles and engine speed.Design large diesel engine is so that the moment of torsion of traction payload is in maximum fuel Maximize under economy, and passenger vehicle Design Technology for Diesels is used for transporting personnel and acceleration under maximum fuel economy.Engine Traction produces different hardware design with respect to the purpose of design transported and gives the profit being designed for protecting and lubricate engine The gained stress of lubrication prescription.Another obvious design difference is to operate each engine per minute with respect to the operation of transport to haul Rotating speed (RPM).The for example typical 12-13 of large diesel engine rises motortruck engine and is typically not greater than 2200rpm, and bus engine can Reach 4500rpm.

In another embodiment, the method that the present invention provides operation centrifugal type oil mist separator, wherein to centrifugal oil Mist separator provides and comprises 0.1 weight % to 8 weight %, or 0.3 weight % to 6 weight % (or usual 0.5 weight % is to 4 Weight %) cigarette ash separation with lubricator with lubricating composition disclosed herein.

Detailed Description Of The Invention

The method that the present invention provides lubricating internal combustion engines as disclosed.

There is the oil of lubricant viscosity

Lubricating composition comprises the oil with lubricant viscosity.This kind of oil includes natural and artificial oil, derived from being hydrocracked, Hydrogenation and hydrorefined oil, do not refine, refine, refined oil or its mixture again.Do not refine, refine and refined oil again more detailed Carefully it is described in International Publication WO2008/147704, in [0054th]-[0056] section, (similar disclosure is special in the U.S. for offer There is provided, referring to [0072]-[0073] in profit application 2010/197536).Natural and synthetic lubricant fluid more detailed description is retouched respectively It is set forth in that in [0058th]-[0059] section of WO2008/147704, (similar disclosure is provided in U.S. Patent application 2010/ In 197536, referring to [0075]-[0076]).Artificial oil also can be prepared by fischer-tropsch reaction, and typically hydroisomerization Fischer-Tropsch hydrocarbon or wax.In one embodiment, oil can be by Fischer-Tropsch gas to liquid synthesis program preparation and other gas to liquid oil.

The oil with lubricant viscosity also can be as " Appendix E-API Base Oil Interchangeability In April, 2008 version of Guidelines for Passenger Car Motor Oils and Diesel Engine Oils " This, the 1.3rd part, subtitle 1.3. " Base Stock Categories " described definition.API Guidelines is also summarized in In United States Patent (USP) US 7,285,516 (referring to the 11st hurdle the 64th row to the 12nd hurdle the 10th row).

In one embodiment, the oil with lubricant viscosity can be combined into oil for API I to III group mineral oil, IV, Or V group cycloalkane or Lipase absobed oil, or its mixture.In one embodiment, the oil with lubricant viscosity can be API II group, III group mineral oil or IV are combined into oil or its mixture.

The amount of the oil with lubricant viscosity existing is usually and deducts additive of the present invention and other from 100 weight % Surplus after the amount sum of energy additive.

Lubricating composition can be concentrate and/or the form preparing lubricant completely.If lubricating composition of the present invention (comprising additives disclosed herein) is that (it can be combined with other oil completely or partially to be formed for the form of concentrate Whole lubricant), then these additives include 1 with the oil with lubricant viscosity and/or with the ratio of flux oil:99-99:1 weight meter, Or 80:20-10:The scope of 90 weight meters.Generally, lubricating composition of the present invention comprises at least 50 weight %, or at least 60 weights Amount %, or at least 70 weight %, or at least 80 weight % have the oil of lubricant viscosity.

Cigarette ash dispersing additive

Cigarette ash dispersing additive can have by appropriate additive is dissolved in 6.0-6.1mm²/ s or cSt is (according to ASTM D445 measures at 100 DEG C) in I group or II group mineral oil to prepare 9-13mm²/ s or cSt solution in Orbahn shearing test Test solution in (ASTM D6278) and be measured as 0-20, or 0-15, or 0-10, or the shear stability index of 0-5.

Cigarette ash dispersing additive can be with 0.2 weight % of lubricating composition to 3 weight %, or 0.2 weight % is to 2.5 Weight %, or 0.3 weight % exists to 1.4 weight %.

Cigarette ash dispersing additive can have the shear stability index of 0-10 and with 0.2 weight % to 2.5 weight %, or 0.3 weight % exists to 1.4 weight %.

Cigarette ash dispersing additive can have the shear stability index of 0-5 and with 0.2 weight % to 2.5 weight %, or 0.3 weight % exists to 1.4 weight %.

Cigarette ash dispersing additive of the present invention can be the polyolefin of 000 number-average molecular weight derived from having a 500-20, bag Dispersant viscosity modifiers containing aromatic amine structure division, or comprise the dispersant of aromatic amine structure division.

In one embodiment, lubricating composition comprises the dispersant viscosity modifiers of aromatic amine structure division, With the dispersant comprising aromatic amine structure division.

The dispersant viscosity modifiers that comprise aromatic amine structure division as the present invention and comprise aromatic amine structure division point Powder all in the presence of, respective handling rate can be 0.2 weight % of lubricating composition to 3.0 weight %, or 0.3 weight % To 2.0 weight %, or 0.4 weight % is to 1.5 weight %.

Dispersant viscosity modifiers

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

Dispersant viscosity modifiers may include functionalised polyolefin, such as with acylating agent such as maleic anhydride and amine-functionalized Ethylene-propylene copolymer.

In one particular embodiment, dispersant viscosity modifiers comprise to use further dispersant amine groups functionalization Olefin copolymer.Generally, olefin copolymer is ethylene-propylene copolymer.

Olefin copolymer has 5000-20, and 000, or 6000-18,000, or 7000-15, the 000 equal molecule of number Amount.

Olefin copolymer can have and is measured as 0-20 by Orbahn shearing test as described above (ASTM D6278), or 0-10, or the shear stability index of 0-5.

Dispersant viscosity modifiers can be by olefin copolymer (usual ethylene-propylene copolymer) and acylating agent (usual Malaysia Acid anhydrides) and there is the aromatic amine reaction of at least one primary or secondary amino and prepare/obtain.Reaction with acylating agent can be in peroxidating Carry out in the presence of thing initiator, subsequently acidylate olefin copolymer and aromatic amine reaction.Dispersant viscosity modifiers can have In the presence of machine solvent, usual API I group or II group or III group mineral oil or be substantially not present lower preparation.Also can use API IV and V group oil.

The formation of dispersant viscosity modifiers is well known in the art.Dispersant viscosity modifiers may include the such as U.S. Patent US 7,790,661, the 2nd hurdle the 48th row to described in the 10th hurdle the 38th row those.

In one embodiment, dispersant viscosity modifiers can be grafted on 15-80 by olefin carboxylic acid's acylating agent and rub You are % ethene, 20-85 mole of %C_3-10Prepare on the polymer of α-monoolefine and 0-15 mole of % non-conjugated diene or triolefin, Described polymer has 5000-20,000 mean molecule quantity, and makes described graft polymers and amine (usual aromatic amine) enter one Step reaction.

In another embodiment, dispersant viscosity modifiers can be the product of following material：A () comprises carboxylic acid Sense or the polymer of its reactive equivalent, described polymer has the number-average molecular weight more than 5,000-20,000；(b) Comprise the amine component of at least one aromatic amine (Aromatic moieties are derived by it), described aromatic amine comprises at least one can It is condensed to provide the amino of side base with described carboxylic-acid functional, and at least one comprises other of at least one nitrogen, oxygen or sulphur atom Group, wherein said aromatic amine is selected from (i) nitro substituted aniline, (ii) comprise to pass through-C (O) NR- group ,-C (O) O- group ,- O- group ,-N=N- group or-SO₂The amine of 2 Aromatic moieties that-group connects, wherein R is hydrogen or alkyl, described virtue One of race's structure division is condensed amino with described, (iii) aminoquinoline, (iv) aminobenzimidazole, (v) N, N- bis- Alkylphenylenediaminin, (vi) aminodiphenylamine (also referred to as N, N- phenylenediamine) and (vii) cyclosubstituted benzylamine.

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

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

The carbon atom that aromatic amine includes wherein aromatic ring structure is connected directly between those amine on ammonia nitrogen.Amine can be monoamine Or polyamines.Aromatic ring is usually monokaryon aromatic ring (i.e. one kind derived from benzene), but may include fused aromatic rings, especially derived from naphthalene Those.The example of aromatic amine includes aniline, N- alkyl benzene amine such as methylphenylamine and N- butylaniline, two-(p- aminomethyl phenyl) Amine, 4-ADPA, N, N- dimethyl phenylene diamine, naphthylamines, 4- (4- nitrophenylazo) aniline (disperse orange 3), sulfanilamide (SN) two First pyrimidine, 4- phenoxybenzamine, 3- nitroaniline, 4- amino acetanilide (N- (4- aminophenyl) acetamide)), 4- amino- 2- hydroxy-benzoic acid phenylester (phenyl amino salicylate), N- (4- methanesulfonylamino-phenyl)-benzamide, various benzylamine such as 2,5- Dimethoxybenzylamine, 4- phenylazo aniline and these replacement variant.Other examples include p-phenetidine, p- 12 Naphthylamines and the aniline of thienyl replacement that alkyl benzene amine, cyclohexyl replace.The example of other suitable aromatic amines includes amino and takes The aromatic compounds in generation and wherein amine nitrogen are the amine of a part for aromatic ring, such as 3- aminoquinoline, 5- aminoquinoline and 8- amino Quinoline.Also include aromatic amine, such as 2- aminobenzimidazole, it comprises a secondary amino group being connected directly between on aromatic ring and connection Primary amino radical on imidazole ring.Other amine include N- (4- aniiinophenyl) -3- amino-butanamide or 3- aminopropylimidazol.Again Other amine includes 2,5- dimethoxybenzylamine.

Other aromatic amines and related compound are disclosed in United States Patent (USP) 6,107,257 and 6,107,258；In these one A little inclusion aminocarbazoles, benzimidazole, amino indole, amino-pyrroles, amino-indazole quinoline ketone, aminoPyridine, mercapto-triazole, ammonia Base phenthazine, aminopyridine, Aminopyrazine, aminopyrimidine, pyridine, pyrazine, pyrimidine, chiral lactones, aminothio thiadiazoles With amino BTA.Other suitable amine include 3- amino-N- (4- aniiinophenyl)-N- butanamide and N- (4- Aniiinophenyl) -3- { (3- aminopropyl)-(Cocoalkyl) amino } butyramide.Spendable other aromatic amine includes comprising The various aromatic amine dyestuff intermediates of the multiple aromatic rings being connected by such as amide structure.Example includes the material of following general structure Material：

And its isomery variant, wherein R^viiiAnd R^ixIt independently is alkyl or alkoxyl, such as methyl, methoxyl group or ethoxy Base.In one case, R^viiiAnd R^ixIt is all OCH₃, and this material is referred to as Fast Blue RR [CAS#6268-05-9].

In another case, R^ixFor OCH₃And R^viiiFor CH₃, and this material is referred to as Fast Violet B [99-21-8]. Work as R^viiiAnd R^ixWhen being all ethyoxyl, material is Fast Blue BB [120-00-3].United States Patent (USP) 5,744,429 discloses it Its aromatic amine compound, particularly aminoalkyl phenthazine.N- aromatic substituted acid amide compound, such as U.S. Patent application Described in 2003/0030033A1, those can also be used for the object of the invention.It is aromatic carboxylic acid that suitable aromatic amine includes wherein amine nitrogen Substituent on compound, that is, the nitrogen in aromatic ring is not sp²Those of hydridization.

Aromatic amine also can comprise the amine being reacted with 4-ADPA and being formed by aldehyde.Gained amine can be described as having to Few 4 aromatic groups, at least one-NH₂Functional group and at least 2 secondary or tertiary amino alkylidenes are coupled amine.Aldehyde can be fat Race, alicyclic or aromatics.Aliphatic aldehydes can be linear or branched.The example of suitable aromatic aldehyde includes benzaldehyde or o- Vanillic aldehyde.The example of aliphatic aldehydes includes formaldehyde (or its reactive equivalent such as formalin or paraformaldehyde), acetaldehyde or propionic aldehyde. Generally, aldehyde can be formaldehyde or benzaldehyde.Alternatively, this aromatic amine also can pass through Berichte der Deutschen Chemischen Gesellschaft (1910), prepared by method described in 43,728-39.

European patent application EP 2 401 is described in by the aromatic amine that aldehyde and 4-ADPA are coupled and are formed In 348 A, and also can be represented by formula (1)：

Wherein each variable：

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

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

In one embodiment, aromatic amine includes 4-ADPA, aldehyde (usual formaldehyde) is coupled 4-ADPA, 3- nitroaniline, disperse orange -3 (4-4- nitrobenzophenone-azoaniline, 4- nitrophenylazo aniline or DO3) or its mixing Thing.

Cigarette ash dispersing additive can be by carboxylic acid functionalized polymers as known in the art (usual polyisobutene amber Amber acid anhydrides) react with the amine (usual aldehyde (such as formaldehyde coupling 4-ADPA)) with least 4 aromatic groups and obtain/ The available dispersant comprising aromatic amine structure division.This kind of cigarette ash dispersing additive is described in such as US 8,557,753 In.This kind of cigarette ash dispersing additive can have and is measured as 0-10 by Orbahn shearing test (ASTM D6278), or 0-5 Shear stability index.

Carboxylic acid functionalized polymers (usual polyisobutylene succinic anhydride) and the amine with least 4 aromatic groups react Products therefrom can be expressed from the next：

Wherein each variable is independently：R¹Can be hydrogen or C_1-5Alkyl (usual hydrogen)；R²Can be hydrogen or C_1-5Alkyl is (generally Hydrogen)；U can be aliphatic, alicyclic or aromatic group, condition be when U be aliphatic series when, aliphatic group can for comprise 1-5 or The linear or sub-branched alkyl of 1-2 carbon atom；BB is polymer backbone and can be polyisobutene or polyolefinic copolymer (particularly ethylene-alpha-olefin such as ethylene-propylene copolymer).BB can be replaced by a succinimide group as shown in the above formula, Or it can be replaced by multiple succinimide groups.

In addition to above formula, also can form other structures, including trimer, tetramer, relatively high polymer or its mixture.

When BB is for polyisobutene, gained carboxylic acid functionalized polymers typically polyisobutylene succinic anhydride.Generally, W as defined in formula (1) can be 1-5, or 1-3.

When BB is different from polyisobutene and has grafting maleic anhydride thereon (or other carboxylic-acid functional), one or Multiple grafted maleic anhydride groups are the succinimide of amine of the present invention.The number of succinimide group can be 1-40, or Person 2-40, or 3-20.

When cigarette ash dispersing additive is derived from polyisobutene, its number-average molecular weight is (by gel permeation chromatography, polyphenyl Ethene standard) can be 350-5000, or 550-3000 or 750-2500.(therefore, polyisobutylene succinic anhydride can have, I.e. derived from the polyisobutene with any of above molecular weight).Commercially available polyisobutylene polymer have 550,750,950 to 1000th, 1550,2000 or 2250 number-average molecular weight.Some commercially available polyisobutylene polymer can be by having Different Weight One or more polyisobutylene polymer is obtained by mixing number-average molecular weight illustrated above.

When cigarette ash dispersing additive is derived from polyisobutylene succinic anhydride, polyisobutylene succinic anhydride can pass through this area In known reaction, for example pass through " alkene " reaction or " Diels Alder " reaction form and (generally passes through Diels Alder Reaction obtains/can get).

In one embodiment, aromatic amine can be the isatoic anhydride and 4- ammonia that can react with carboxylic acid functionalized polymers The product of base diphenylamines.Carboxylic acid functionalized polymers may include polyisobutylene succinic anhydride, maleic anhydride-styrene copolymerization Thing, the ester of maleic anhydride-styrene copolymers, (alpha-olefin maleic anhydride) copolymer；Styrene-the second of maleic anhydride grafting Alkene-alpha-olefine polymers；Polymethacrylates；Polyacrylate；Polyhydroxycarboxyliacid acid (includes poly- hydroxy stearic acid)；(i) hydrogen Change the alkenyl aryl conjugated diene copolymer hydrogenated copolymer of styrene-butadiene (particularly), (ii) is grafted with maleic anhydride Polyolefin (particularly ethylene-propylene copolymer) maleic anhydride graft copolymer, or its mixture.Generally, aromatic amine can Think the product of isatoic anhydride and 4-ADPA, it can be with polyisobutylene succinic anhydride or (special with maleic anhydride It is ethylene-propylene copolymer) polyolefin that is grafted or the reaction of its mixture.The more detailed description of this aromatic amine is provided in US 8, In 637,437.

Overbased sulfonates detersive

In one embodiment, lubricating composition comprises overbased sulfonates detersive.Overbased sulfonates detersive Can be with 0.01 weight % to 0.9 weight %, or 0.05 weight % is to 0.8 weight %, or 0.1 weight % is to 0.7 weight Measure %, or 0.2 weight % exists to 0.6 weight %.

Sulfonate can be by list-or dialkyl substituted benzene (or naphthalene, indenyl, indanyl or dicyclopentadienyl) sulfonic acid system Standby, wherein alkyl can comprise 6-40, or 8-35 or 9-30 carbon atom.

Alkyl derived from polypropylene or can comprise the linear of at least 10 carbon atoms or branched-alkyl.Suitable alkyl Example includes branched and/or linear decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, hexadecane Base, heptadecyl, octadecyl, vaccenic acid base, nonadecyl, eicosyl, heneicosyl, docosyl, 20 Trialkyl, tetracosyl, pentacosyl, cerul or its mixture.

In one embodiment, hydrocarbyl-substituted sulfonic may include polypropylene benzene sulfonic acid and C₁₆-C₂₄Alkyl benzene sulphonate or its Mixture.

Overbased sulfonates generally have 250-600, or the total base number of 300-500.Overbased detergent is this area In known.In one embodiment, sulfonate detergent can be the dominant linear alkylbenzene of the metal ratio with least 8 Sulfonate detergent, such as [0026th]-[0037] of U.S. Patent application 2005065045 (and being authorized with US 7,407,919) Duan Suoshu.Dominant linear alkylbenzenesulfonate detersive can be used in particular for helping improve fuel economy.

Overbased detergent is as known in the art.The parlkaline material of further referred to as parlkaline or hyperalkaline salt is usual For single-phase homogeneous Newtonian systems, it is characterized in that tenor is exceeded for according to metal and had with the specific acidity of metal reaction In the stoichiometry of machine compound and can exist.Parlkaline material pass through acid material (usual inorganic acid or low-grade carboxylic acid, excellent Select carbon dioxide) with comprise acidic organic compound, reaction medium, the metal base of stoichiometric excess and accelerator such as chlorination The mixture of calcium, acetic acid, phenol or alcohol reacts and prepares, and described reaction medium comprises at least one and is used for described acid organic material The inert organic solvents (mineral oil, naphtha, toluene, dimethylbenzene etc.) of material.It is former that acidic organic material generally has enough carbon Subnumber is to provide the solubility in oil.The amount of " excessive " metal (stoichiometry) is generally according to metal than expression.Term " metal Than " for metal total yield and the equivalent of acidic organic compound ratio.Neutral metal salt has 1 metal ratio.There is normal salt Present in 3.5 times of metals salt have 3.5 equivalents metal excessive, or 4.5 ratio.Term " metal ratio " is also explained in title Standard for " Chemistry and Technology of Lubricants " is taught book, the 3rd edition, R.M.Mortier and S.T.Orszulik edits, version in 2010, page 219, in subtitle 7.25.Generally, overbased sulfonates of the present invention can have 3.5:1-40:1, or 5:1-30:1, or 12:1-25:1 metal ratio.Generally, overbased sulfonates of the present invention have 300- 500 TBN and 12:1-25:1 metal ratio.In different embodiments, overbased sulfonates detersive has 12 to being less than 20, or 12-18, or 20-30, or the metal ratio of 22-25.

In one embodiment, overbased sulfonates detersive comprise overbased calcium sulfonate, sodium sulfonate, sulfonic acid magnesium or its Mixture.Generally, overbased sulfonates be/comprise sulfoacid calcium.

In one embodiment, overbased sulfonates detersive comprises the metal ratio with 18-40 and has 300- 500, or the calcium sulfonate detergents of the TBN of 325-425.

Other performance additive

Lubricating composition can pass through the product of methods described herein optionally in other performance additive (as mentioned below) In the presence of add to have in the oil of lubricant viscosity and prepare.

Lubricating composition of the present invention optionally comprises other performance additive.Other performance additive includes following at least one Kind：Metal deactivator, viscosity improver (different from cigarette ash dispersing additive of the present invention), detersive, friction improver, wear-resistant Agent, corrosion inhibitor, dispersant (those different from the present invention), extreme pressure agent, antioxidant, foam inhibitor, demulsifying agent, pour point Depressant, sealing sweller and its mixture.Generally, prepare lubricating oil completely and comprise one of these performance additive or many Kind.

In one embodiment, the present invention provides the overbased sulfonates removing the essential characteristic being defined as the present invention peace and quiet The lubricating composition that parlkaline contains metal detergent is comprised further outside agent.Metal containing metal detergent can for zinc, sodium, Calcium, barium or magnesium.Generally, the metal containing metal detergent can be sodium, calcium or magnesium.

Parlkaline is selected from without thiophenol salt, sulfur-bearing phenates, salixarate, salicylate containing metal detergent and its mixes Compound, or its boration equivalent.Can be by the such as Boric acid boron acidifying of overbased detergent boric acid agent.

Parlkaline may also include, containing metal detergent, " mixing " detersive being formed with mixed surfactant system, described System comprises phenates and/or sulfonate component, for example phenates/salicylate, sulfonate/phenates, sulfonate/salicylate, sulphur Hydrochlorate/phenates/salicylate, such as United States Patent (USP) 6,429,178；6,429,179；6,153,565；With 6,281,179 institutes State.If for example using " mixing " sulfonate/phenate detergents then it is assumed that " mixing " detersive is equal to introduces similar quantity respectively Phenates and the independent phenates of sulfonate soap and the amount of sulfonate detergent.

Generally, parlkaline contains metal detergent can be phenates, sulfur-bearing phenates, salixarate or salicylate Zinc, sodium, calcium or magnesium salts.Parlkaline salixarate, phenates and salicylate generally have the total base number of 180-450TBN.

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

In another embodiment, lubricating composition comprise further to have the TBN of 200-275 calcium phenoxide parlkaline clear Net agent.

In one embodiment, lubricating composition comprises 0.01 weight % further to 2 weight %, or 0.1-1 weight The detersive different from overbased sulfonates detersive of amount %, wherein other detersives be selected from without thiophenol salt, sulfur-bearing phenates, Sulfonate, salixarate, salicylate and its mixture, or its boration equivalent.

In one embodiment, lubricating composition comprises " the mixing " being formed with mixed surfactant system further Detersive, described system comprises phenates and/or sulfonate component, for example phenates/salicylate, sulfonate/phenates, sulfonate/ Salicylate or sulfonate/phenates/salicylate.

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

Diaryl amine or alkylation diaryl amine can be PA (PANA), alkylated diphenylamine or alkylation Nonox, or its mixture.Alkylated diphenylamine may include two-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, Two-octylated diphenylamine, two-decylated diphenylamine, decyl diphenylamine and its mixture.In one embodiment, diphenylamines May include nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl diphenylamine or its mixture.In another embodiment party In case, alkylated diphenylamine may include nonyl diphenylamine or dinonyldiphenylamine.Alkylation diaryl amine may include octyl group, two- Octyl group, nonyl, two-nonyl, decyl or two-decyl phenyl naphthylamines.

Hindered phenol antioxidant usually contains sec-butyl and/or the tert-butyl group as steric group.Phenolic groups can be further By alkyl (generally linear or branched-alkyl) and/or the bridge linkage group that is connected on the second aromatic group replaces.Suitable hindered phenol The example of antioxidant includes 2,6- di-t-butyl phenol, 4- methyl -2,6- di-t-butyl phenol, 4- ethyl -2,6- two-uncle Butylphenol, 4- propyl group -2,6- di-t-butyl phenol or 4- butyl -2,6- di-t-butyl phenol or 4- dodecyl -2, 6- di-t-butyl phenol.In one embodiment, hindered phenol antioxidant can be ester, and may include for example from Ciba Irganox^TML-135.What suitable hindered phenol antioxidant containing ester was chemical is described in more detail in United States Patent (USP) 6,559,105 In find.

In another embodiment, lubricating composition can comprise dispersant (different from cigarette ash dispersing additive) or its mixing Thing.Dispersant can be succinimide dispersants, Mannich dispersant, succinamide dispersant, polyalkylene succinic acid esters, acyl Amine or ester-acid amide, or its mixture.In one embodiment, dispersant can exist as single dispersant.Implement at one In scheme, dispersant can exist as the mixture of two or three different dispersant, and wherein at least one can be amber Acid imide dispersant.

Succinimide dispersants can be derived from aliphatic polyamines or its mixture.Aliphatic polyamines can be aliphatic polyamines such as Asia Polyethylene polyamine, propylidene polyamines, butylidene polyamines or its mixture.In one embodiment, aliphatic polyamines can be sub- second Quito amine.In one embodiment, aliphatic polyamines are selected from ethylenediamine, diethylenetriamines, trien, four sub- second Base five amine, penten, polyamines kettle be residual and its mixture.

In one embodiment, dispersant can be polyalkylene succinic acid esters, acid amides or ester-acid amide.For example, polyolefin Succinate can be polyisobutylene succinic acid ester or its mixture of pentaerythrite.Polyalkylene succinic acid ester-amide can be The polyisobutylene succinic acid reacted with alcohol (such as pentaerythrite) and polyamines as described above.

The long chain alkenyl succinimides that dispersant can replace for N-.The reality of the long chain alkenyl succinimides that N- replaces Example is polyisobutenyl succinimide.The polyisobutene generally deriving polyisobutylene succinic anhydride has 350-5000, or The number-average molecular weight of 550-3000 or 750-2500.Succinimide dispersants and their preparation are e.g., as disclosed in United States Patent (USP) 3,172,892、3,219,666、3,316,177、3,340,281、3,351,552、3,381,022、3,433,744、3,444, 170th, 3,467,668,3,501,405,3,542,680,3,576,743,3,632,511,4,234,435, Re 26,433 and 6, 165,235th, in 7,238,650 and EP patent application 0 355 895A.

Also can by dispersant by conventional method by with plurality of reagents in any one reaction and post-process.Wherein, this Be a bit boron compound (such as boric acid), urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid such as terephthalic acid (TPA), Succinyl oxide, maleic anhydride, nitrile, epoxides and phosphorus compound that hydrocarbon replaces.In one embodiment, dividing post processing Powder boration.In one embodiment, the dispersant of post processing and dimercaptothiodiazole is made to react.In an embodiment In, make dispersant and phosphoric acid or the phosphorous acid reaction of post processing.In one embodiment, make the dispersant of post processing and to benzene Dioctyl phthalate and acid reaction (as described in U.S. Patent application US2009/0054278).

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

In one embodiment, lubricating composition disclosed herein comprises to divide containing different from cigarette ash of the present invention further The ashless dispersant of the succinimide dispersants of scattered additive, wherein succinimide dispersants have at least 40mg KOH/g TBN, and described dispersant with 1.2 weight % of lubricating composition to 5 weight %, or 1.8 weight % are deposited to 4.5 weight % ?.

Succinimide dispersants can comprise polyisobutenyl succinimide, wherein derives polyisobutenyl succinimide Polyisobutene there is 350-5000, or the number-average molecular weight of 750-2500.

In one embodiment, friction improver is selected from the long-chain fatty acid derivative of amine, long-chain fat ester or length The derivative of chain fatty epoxides；Fatty imidazolines；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fatty alkyl wine Stone acid imide；Fatty alkyl tartramide；Fatty glycolate；With fatty hydroxyl acetamide.Friction improver can be with lubrication group 0 weight % of compound is to 6 weight %, or 0.01 weight % is to 4 weight %, or 0.05 weight % is to 2 weight %, or 0.1 weight % exists to 2 weight %.

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

The example of suitable frictional modifier includes long-chain fatty acid derivative, fatty ester or the fat epoxide of amine；Fat The condensation product of fat imidazoline such as carboxylic acid and polyalkylene polyamine；The amine salt of alkyl phosphoric acid；Fatty alkyl tartrate；Fatty alkane Base tartrimide；Fatty alkyl tartramide；Fatty phosphonate；Fatty phosphites；Boration phosphatide, borated fatty ring Oxide；Glyceride；Borated glycerol esters；Fatty amine；Alkoxylated fats amine；Borated alkoxylated fatty amine；Hydroxyl and Poly- hydroxy aliphatic amine, including tert-hydroxyl fatty amine；Hydroxyalkylamides；The slaine of aliphatic acid；The metal of alkylsalicylate Salt；FatOxazoline；Fatty ethoxylated alcohol；Carboxylic acid and the condensation product of polyalkylene polyamine；Or aliphatic carboxylic acid and guanidine, The product of aminoguanidine, urea or thiocarbamide and its salt.

Friction improver may also include material such as sulfurized fatty compound and alkene, molybdenum dialkyl-dithiophosphate, two sulphur Sunflower oil for carbamic acid molybdenum, polyalcohol and aliphatic carboxylic acid or soya-bean oil monoester.

In another embodiment, friction improver can be long-chain fatty acid ester.In another embodiment, long-chain fat Fat acid esters can be monoesters, and in another embodiment, long-chain fatty acid ester can be triglycerides.

Lubricating composition optionally comprises at least one antiwear additive further.The example of suitable antiwear additive include titanium compound, Tartrate, tartrimide, the oil-soluble amine salt of phosphorus compound, olefine sulfide, metal dialkyl dithiophosphate are (for example Zinc dialkyl dithiophosphate), phosphite (such as dibutyl phosphite), phosphonate, containing thiocarbamate change The thio ammonia that compound, such as thiocarbamate, thiocarbamate acid amides, thiocarbamic acid ether, alkylidene are coupled Carbamate and double (S- alkyl Dithiocarbamyl) disulfide.In one embodiment, antiwear additive may include as state Tartrate disclosed in the open WO 2006/044411 or Canadian Patent CA 1 183 125 in border or tartrimide.Winestone Hydrochlorate or tartrimide can contain alkyl-ester group, and the carbon atom sum wherein on alkyl is at least 8.In an embodiment party In case, antiwear additive can comprise the citrate as disclosed in U.S. Patent application 20050198894.

Another kind of additive includes the oil-soluble titanium as disclosed in US 7,727,943 and US2006/0014651. Oil-soluble titanium may act as in antiwear additive, friction improver, antioxidant, sediment monitoring additive or these functions More than one.In one embodiment, oil-soluble titanium is titanium (IV) alkoxide.Titanium alkoxides by monohydric alcohol, polyalcohol or Its mixture is formed.Unitary alkoxide can have 2-16 or 3-10 carbon atom.In one embodiment, Titanium alkoxides are isopropanol Titanium (IV).In one embodiment, Titanium alkoxides are 2-Ethylhexyl Alcohol titanium (IV).In one embodiment, titanium compound bag Include the alkoxide of vincial faces 1,2- glycol or polyalcohol.In one embodiment, 1,2- vincial faces glycol includes the aliphatic acid list of glycerine Ester, usual aliphatic acid is oleic acid.

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

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

Dissolve in the extreme pressure in oil (EP) agent and include sulfur-bearing and chloride sulphur EP agent, dimercaptothiodiazole or dispersant (generally Succinimide dispersants) CS₂The derivative of derivative, chlorinated hydrocabon EP agent and phosphorus EP agent.The example of this kind of EP agent includes chlorine Change wax；2,5- dimercapto-1,3,4-thiadiazole or its oligomer that olefine sulfide (such as sulfide isobutene), alkyl replace, have Machine sulfide and polysulfide, such as benzyl disulfide, double (chlorobenzyl) two sulphur, dibutyl four sulphur, sulfuration methyl oleate, sulfuration Alkylphenol, sulfurized dipentene, sulfuration terpenes and sulfuration Diels Alder adduct；Phosphosulfurized hydrocarbon such as phosphoric sulfide and turpentine oil Or the product of methyl oleate；Phosphide such as two hydrocarbon and three hydrocarbon phosphite esters such as dibutyl phosphite, phosphorous acid two heptyl ester, phosphorous Sour dicyclohexyl ester, phosphorous acid amyl group phenyl ester；Phosphorous acid diamyl phenyl ester, phosphorous acid tridecane base ester, phosphorous acid distearyl Ester and the phosphite of polypropylene replacement；Metal thiocarbamates, such as dioctyl zinc dithiocarbamate and Heptylphenol diacid barium；The amine salt of alkyl and Acidic phosphates or derivative, including such as dialkyl dithiophosphoric acid and oxidation Propylene, subsequently further with P₂O₅The amine salt of the product of reaction；And its mixture (as described in US 3,197,405).

Can be used for the foam inhibitor in the present composition and include polysiloxanes, ethyl acrylate and 2-EHA Copolymer with optional vinyl acetate；Demulsifying agent, including fluorinated silicones, trialkylphosphate, polyethylene glycol, polyoxy Change ethene, PPOX and (ethylene oxide-propylene oxide) polymer.

Other viscosity improvers may include embedding containing (i) vi-ny l aromatic monomers block and (ii) conjugated diene olefinic monomer The block copolymer (such as hydrogenated styrene-butadiene copolymer or hydrogenated styrene isoprene copolymer) of section, poly- methyl Acrylate, ethylene-alpha-olefin copolymer, comprise the hydrogenation star polymer of conjugate diene monomer such as butadiene or isoprene, Or its mixture.

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

Demulsifying agent includes trialkylphosphate, and ethylene glycol, ethylene oxide, propylene oxide or its mixture is various Polymer and copolymer.

Metal deactivator includes the derivative (usual tolyl-triazole) of BTA, 1,2,4- triazole, benzimidazole, 2- Alkyl two Thiobenzimidazole or the thio benzothiazole of 2- alkyl two.Metal deactivator also can be described as corrosion inhibitor.

Sealing sweller includes cyclobufene sultone derivative Exxon Necton-37^TM(FN 1380) and Exxon Mineral Seal Oil^TM(FN 3200).

Commercial Application

In one embodiment, oil mist separator can be driven by oil impeller machine.This is commonly available by diesel engine again Pressurized lubrication oil drive.This turbine being arranged in the bottom enclosure of device makes centrifugal rotor rotate.Exist and oil is supplied back Separator delivery pipe in oil sump.Centrifugal rotor can carry and be stacked on a large amount of conical disc going up each other, and carries out herein Mist of oil is separated with blow-by gas, and cigarette ash can be assembled there during power operation.When Pan Dui rotates, dirty bent axle Case gas stands to add up to 25 000m/s²(82 000ft/s²) centrifugal acceleration.

Without being bound by theory it is believed that these centrifugal force be equivalent to terrestrial gravitation effect 2500 times so that oil droplet is from gas In separate.Got rid of from the edge of disk after spontaneously and be thrown to the inwall of oil mist separator shell, it therefrom by Comb outlet returns in oil sump.On the other hand, clean gas enter the outlet of device, subsequently into the air inlet discrimination of engine Pipe.In addition to being separator, Pan Dui acts also as fan, blow-by gas are extracted from crankcase and avoiding device on Pressure drop.Internal pressure control valve guarantees that crankcase pressure always remains in suitable working range, although in inlet manifold Any pressure change.This kind of oil mist separator is as known in the art, and withTrade mark is commercially available.

Internal combustion engine can be 4 Stroke Engine.Internal combustion engine can be with or without scheme for exhaust gas circulation system.Internal combustion engine can be installed There are emission control systems or turbocharger.The example of emission control systems includes diesel particulate filters (DPF), or makes System with SCR (SCR).

Lubricating composition can have 1.2 weight % or less total sulfate ash content.

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

In one embodiment, the feature of lubricating composition can be for having (i) 0.5 weight % or less sulphur contains Amount, (ii) 0.15 weight % or less phosphorus content, and (iii) 0.5 weight % contain to 1.5 weight % or less sulfate ash Amount.

The feature of lubricating composition can for have following at least one：I () 0.2 weight % is to 0.4 weight % or less Sulfur content, the phosphorus content of (ii) 0.08 weight % to 0.15 weight %, and (iii) 0.5 weight % is to 1.5 weight % or less Sulfate ash content.

The feature of lubricating composition can be the sulfate ash content with 0.5 weight % to 1.2 weight %.

As used herein, TBN is (total base number) by the measurement of D4739 (buffer) methods described.

The feature of lubricating composition can be total base number (TBN) content with least 5mg KOH/g.

The feature of lubricating composition can be for having 6-13mg KOH/g, or the total base number (TBN) of 7-12mg KOH/g Content.

Lubricating composition can have the SAE viscosity grade of XW-Y, and wherein X can be 0,5,10 or 15；And Y can for 16, 20th, 30 or 40.

Internal combustion engine disclosed herein can have the steel surface on cylinder block, cylinder boring or piston ring.

Internal combustion engine can have steel, or aluminium alloy, or aluminium composite surface.

Generally, be there is the maximum load matter more than 3,500kg by the vehicle that compression-ignition engine of the present invention is provided with power Amount.

Following examples provide the elaboration to the present invention.These embodiments are non-exhaustive, and are not intended to limit the present invention Scope.

Embodiment

Cigarette ash dispersing molecule A polyisobutenyl ash disperser (EXA)

The 2M hydrochloric acid of 500mL is added and is equipped with overhead, thermocouple, there is the interpolation funnel of nitrogen pipeline and cold In 1 liter of four-neck flask of condenser.Add 184.2g 4-ADPA (being also described as N- phenyl-pphenylenediamine), and by flask It is heated to 75 DEG C.Then load 37% formalin of 40.5g in adding funnel and through 30 minutes, solution is dropwise added Enter in flask.Keep the flask at 4 hours at 100 DEG C.Then flask is cooled to environment temperature.Added 80g's through 30 minutes 50/50wt/wt sodium hydrate aqueous solution.At the end of reaction, by being filtrated to get solid product.This material can be described as alkyl It is coupled poly- aromatic amine.

It is being equipped with overhead, thermocouple, the liquid level lower inlet with nitrogen pipeline and the Dean with condenser (wherein polyisobutene has 2000 to load polyisobutylene succinic anhydride (1270.0g) in 3 liters of four-neck flask of Stark trap Number-average molecular weight) and flux oil (1400.1g).Flask is heated to 90 DEG C.It is slowly added to above-mentioned alkyl and be coupled poly- aromatic amine (442.0g).Then temperature is improved to 110 DEG C, and hold up to any residual water of removing.Then temperature is improved to 160 DEG C And keep 10 hours.Add a part of super-cell in flask, then flask contents are passed through Part II diatom Native filter aid.Products therefrom is the dark oil of the nitrogen content with 0.65 weight %.

A series of 15W-40 diesel fuel lubricity compositions are prepared according to table 1 below.Composition comprises the section of cigarette ash dispersing molecule To assess the tendency of blocking centrifugal type oil mist separator.

Table 1 diesel fuel lubricity agent composition¹

1. unless otherwise noted, all amounts illustrated above are weight %, and are based on oil-free, and include other of low content Additive, including corrosion inhibitor, pour-point depressant, ashless tbn accelerator and foam inhibitor.

2. use aromatic amine amination OCP (8000Mn) base DVM accelerator (as6586H obtains)

3. use OCP (64000Mn) the base DVM of 4- amino-diphenylamines amination (as Afton5777 obtain)

4. as cigarette ash dispersing molecule A above

5. boracic and/or no boron succinimide dispersants

6. the combination of alkylated diphenylamine, hindered phenol and olefine sulfide

7. the business CJ-4 lubricant obtaining as Chevron DELO 400LE

8. there are the PIB succinimide dispersants of the mixture of aromatic amine and polyetheramine head base

9. estimated value

The oil mist separator incrustation of assessment lubricating composition and cigarette ash are processed.Oil mist separator compatibility be equipped with by Assess in the diesel-powered truck of 2010EC DD15 engine that Detroit Diesel Corporation (DDC) manufactures.Engine It is equipped withCentrifugal type oil mist separator.250,000 miles to almost 600,000 miles of field test is commented Estimate oil.Test checks all oil mist separators (OMS) device and evaluates mud deposit formation and discharge after completing at the scene Blockage.OMS mud deposit assessed value is specified as follows：

Soot-treating capacity can be in igniter motor test (such as Mack T 11 engine test) and bench test Measurement.Assess the Mack T-11 performance of lubricant by ASTM standard program D7156 methods described.Generally, improve in viscosity 12mm²During/s (cSt), with regard to having the sample of higher dust content, obtain preferable result.For API CJ-4 lubricant, 4mm is improved in kinematic viscosity by limit requirements lubricant²Contain at least 3.5 weight % cigarette ashes during/s, improve 12mm in viscosity²/ Contain at least 6.0 weight % cigarette ashes during s, and improve 15mm in viscosity²At least 6.7 weight % cigarette ashes are contained, each test during/s Method is all at 100 DEG C.The result of these tests is summarized in table 2 below.

Table 2 oil mist separator compatibility and T-11 cigarette ash are processed

Acquired results show, lubricating composition disclosed herein prevents plugged filter in oil mist separator and provides excellent Elegant soot-treating capacity.

Some above-mentioned materials known may interact in final preparaton so that the component of final preparaton may be with Originally those adding are different.The product being consequently formed, including through with its intended use use lubricant compositions of the present invention and The product being formed may be not easy to describe.However, all such improves and product is included within the scope of the present invention；This Invention includes the lubricant compositions by preparing said components mixing.

Above-mentioned each file is incorporated by reference into the present invention.In addition to the embodiment, or otherwise expressly noted, at this Described in specification, all quantity of the amount of material, reaction condition, molecular weight, carbon number etc. should be understood to be repaiied by wording " about " Decorations.Unless otherwise noted, each chemicals being mentioned above or composition should be understood to contain isomers, accessory substance, spread out The commercial grade material of the biological and usual this kind of material of other that should be understood to be present in commerical grade.However, unless otherwise noted, The amount of each chemical constituent is expressed as eliminating any solvent or the flux oil that generally may be present in commercial materials.It should be understood that The upper and lower bound of amount described herein, scope and ratio can independently combine.Similarly, the scope of each element of the present invention and amount can To be used together with the scope of any other element or amount.

As used herein, term " hydrocarbyl substituent " or " alkyl " are made with its conventional meaning well known to those skilled in the art With.Specifically, it refers to the group having the carbon atom being connected directly between on molecule remainder and mainly having hydrocarbon property.Hydrocarbon The example of base includes：Hydrocarbon substituent, including aliphatic, alicyclic and aromatic substituent；The hydrocarbon substituent replacing, that is, contain at this Do not change the substituent of the non-hydrocarbon of main hydrocarbon property of substituent in bright context；With miscellaneous substituent, similarly have Main hydrocarbon property, but contain the substituent different from carbon in ring or chain.Term " hydrocarbyl substituent " or " alkyl " more detailed Definition is described in [0118th]-[0119] section of International Publication WO2008147704, or disclosed application US 2010- Similar definition in [0137th] of 0197536-[0141].

Although explained the present invention with regard to preferred embodiment it should be understood that through read this specification, its various improvement Can be understood by those skilled in the art.It is therefore understood that invention disclosed herein is intended to belong to claims This kind of improvement of book scope.

Claims

1. the method that lubrication is equipped with the internal combustion engine of centrifugal type oil mist separator, wherein lubricant comprises 0.1 weight % to 8 weights The cigarette ash that amount % is produced by power operation, and wherein lubricant compositions comprise the oil with lubricant viscosity, and 0.2 weight % To 3 weight % cigarette ash dispersing additives, wherein cigarette ash dispersing additive comprises with 500-20,000 number-average molecular weight poly- Compound chain and the shear stability index of 0-20.

2. method according to claim 1, the feature of wherein lubricating composition is that have (i) 0.5 weight % or less sulphur contains Amount, (ii) 0.15 weight % or less phosphorus content, and (iii) 0.5 weight % contain to 1.5 weight % or less sulfate ash Amount.

3. the method according to any one of aforementioned claim, the feature of wherein lubricating composition be have following at least one： (i) 0.2 weight % to 0.4 weight % or less sulfur content, the phosphorus content of (ii) 0.08 weight % to 0.15 weight %, and (iii) 0.5 weight % to 1.5 weight % or less sulfate ash content.

4. the method according to any one of aforementioned claim, the feature of wherein lubricating composition is that have 0.5 weight % to 1.2 The sulfate ash content of weight %.

5. the method according to any one of aforementioned claim, the feature of wherein lubricating composition is that have at least 5mg KOH/g Total base number (TBN) content.

6. the method according to any one of aforementioned claim, the feature of wherein lubricating composition is with 6-13mg KOH/g, Or total base number (TBN) content of 7-12mg KOH/g.

7. the method according to any one of aforementioned claim, is wherein had super by the vehicle that compression-ignition engine is provided with power Cross the maximum laden mass of 3,500kg.

8. the method according to any one of aforementioned claim, wherein cigarette ash dispersing additive have by Orbahn shearing test (ASTM D6278) is measured as 0-20, or 0-15, or 0-10, or the shear stability index of 0-5.

9. the method according to any one of aforementioned claim, wherein cigarette ash dispersing additive are with 0.2 weight of lubricating composition Amount % to 3 weight %, or 0.2 weight % is to 2.5 weight %, or 0.3 weight % exists to 1.4 weight %.

10. the method according to any one of aforementioned claim, wherein cigarette ash dispersing additive have the shear stability of 0-10 Index and with 0.2 weight % to 2.5 weight %, or 0.3 weight % exists to 1.4 weight %.

11. according to the method for any one of aforementioned claim, and wherein cigarette ash dispersing additive has the shear stability of 0-5 and refers to Count and with 0.2 weight % to 2.5 weight %, or 0.3 weight % exists to 1.4 weight %.

12. is to comprise aromatic amine structure division according to the method for any one of aforementioned claim, wherein cigarette ash dispersing additive Dispersant viscosity modifiers, or the dispersant comprising aromatic amine structure division.

13. is to comprise aromatics amine structure according to the method for any one of aforementioned claim 1-12, wherein cigarette ash dispersing additive Partial dispersant viscosity modifiers, wherein dispersant viscosity modifiers are the olefin-copolymerization with Aromatic moieties functionalization Thing, usual olefin copolymer is ethylene-propylene copolymer.

14. methods according to claim 13, wherein olefin copolymer have 0-10, or the shear stability index of 0-5.

15. according to the method for any one of aforementioned claim 13-14, wherein dispersant amine groups derived from olefin copolymer with Acylating agent and the aromatic amine reaction with primary or secondary amino.

16. methods according to claim 15, wherein aromatic amine comprise 4-ADPA, aldehyde (usual formaldehyde) is coupled 4- amino Diphenylamines, nitroaniline, 4- nitrophenylazo aniline (disperse orange -3) or its mixture.

17. according to the method for any one of aforementioned claim 1-12, and wherein cigarette ash dispersing additive is by carboxylic acid functionalized Polymer (usual polyisobutylene succinic anhydride) reacts and obtains with having at least amine of 4 aromatic groups and aldehyde (such as formaldehyde) To/available the dispersant comprising aromatic amine structure division.

18. according to the method for any one of aforementioned claim, and wherein lubricating composition comprises phenol further or amine resists Oxidant or its mixture, and wherein antioxidant with 0.1 weight % to 3 weight %, or 0.5 weight % is to 2.75 weights Measure %, or 1 weight % exists to 2.5 weight %.

19. comprise with 0.01 weight % to 0.9 weight according to the method for any one of aforementioned claim, wherein lubricating composition Amount %, or 0.05 weight % is to 0.8 weight %, or 0.1 weight % is to 0.7 weight %, or 0.2 weight % is to 0.6 weight The overbased sulfonates detersive that amount % exists.

20. according to the method for any one of aforementioned claim, and wherein overbased sulfonates detersive has 12 to less than 20, or Person 12-18, or 20-30, or the metal ratio of 22-25.

21. according to the method for any one of aforementioned claim, the calcium sulfonate detergents wherein with the metal ratio of 18-40 have 300-500, or the TBN of 325-425.

22. comprise overbased calcium sulfonate according to the method for any one of aforementioned claim, wherein overbased sulfonates detersive.

23. comprise 0.01 weight % to 2 weights further according to the method for any one of aforementioned claim, wherein lubricating composition Amount %, or the detersive different from overbased sulfonates detersive of 0.1-1 weight %, wherein other detersives are selected from and do not contain Thiophenol salt, sulfur-bearing phenates, sulfonate, salixarate, salicylate and its mixture or its boration equivalent.

24. comprise with blending surface activity further according to the method for any one of aforementioned claim, wherein lubricating composition " mixing " detersive of agent System forming, described system comprises phenates and/or sulfonate component, such as phenates/salicylate, sulphur Hydrochlorate/phenates, sulfonate/salicylate or sulfonate/phenates/salicylate.

25. according to the method for any one of aforementioned claim, and it further includes phosphorous antiwear additive, usual dialkyl dithio Trbasic zinc phosphate.

26. comprise to disperse different from cigarette ash according to the method for any one of aforementioned claim, wherein lubricating composition further The ashless succinimide dispersants of additive, wherein succinimide dispersants with 1 weight % to 8 weight %, or 2 weights Amount % to 6 weight % exists.

27. methods according to claim 26, wherein succinimide dispersants comprise polyisobutenyl succinimide, wherein spread out The polyisobutene bearing polyisobutenyl succinimide has 350-5000, or the number-average molecular weight of 750-2500.

28. methods according to claim 26, wherein succinimide dispersants comprise polyisobutenyl succinimide, wherein divide Powder is had at least TBN of 40mg KOH/g and is existed with the amount of 1.2 weight % of lubricating composition to 5 weight %.

29. have on cylinder block, cylinder boring or piston ring according to the method for any one of aforementioned claim, wherein internal combustion engine Steel surface.

30. have steel or aluminium alloy or aluminium compound table according to the method for any one of aforementioned claim, wherein internal combustion engine Face.

31. have 1.2 weight % or less total sulfur according to the method for any one of aforementioned claim, wherein lubricating composition Hydrochlorate ash content.

32. is centrifugal type oil mist separator according to the method for any one of aforementioned claim, wherein oil mist separator.

33. according to the method for claim 32, and wherein centrifugal type oil mist separator is with 2500-10000, or 4000-8000, or Person 5000-7000rpm rotates.

34. have sealed crankcase ventilation according to the method for any one of aforementioned claim, wherein internal combustion engine.

35. have the SAE viscosity grade of XW-Y according to the method for any one of aforementioned claim, wherein lubricating composition, its Middle X is 0,5,10 or 15；And Y is 16,20,30 or 40.