CN105950262A

CN105950262A - Lubricating oil compositions with enhanced piston cleanliness

Info

Publication number: CN105950262A
Application number: CN201610255066.4A
Authority: CN
Inventors: R·霍根杜恩; B·B·霍根杜恩
Original assignee: Chevron Oronite Technology BV
Current assignee: Chevron Oronite Technology BV
Priority date: 2015-02-13
Filing date: 2016-02-06
Publication date: 2016-09-21
Anticipated expiration: 2036-02-06
Also published as: EP3056556A1; CN105950262B; EP3056556B1; SG10201601063QA; CA2919739A1

Abstract

Disclosed herein are low and medium sulfur, phosphorus, and sulfated ash (low and medium SAPS) lubricating oil compositions for providing enhanced piston cleanliness in an internal combustion engine. The lubricating oil compositions comprise at least one Mannich reaction product prepared by the condensation of a poly isobutylsubstituted hydroxyaromatic compound, wherein the polyisobutyl group is derived from polyisobutene containing at least 70 wt. % methylvinylidene isomer and has a number average molecular weight of from 400 to 2,500, an aldehyde, an amino acid or ester derivative thereof, and an alkali metal base.

Description

There is the lubricant oil composite of the piston cleanliness of enhancing

Background of invention

1. technical field

The present invention relates generally to low and middle sulfur, the profit of p and s acidifying ash (sulfated ash) (low and in " SAPS ") Sliding oil composition, in order to strengthen the piston cleanliness of internal combustion engine.

2. prior art

When selecting lubricating oil, the viscosity grade of engine oil is key feature.Lubricating oil is typically according to electromotor institute Temperature and shearing condition when the climate temperature exposed and electromotor run select.Thus, described oil is in ambient temperature Under must be the most low viscous, thus provide enough lubrications when engine cold-start, and entirely can bear at electromotor Lotus maintains enough viscosity to lubricate electromotor when running.

SAE categorizing system SAE J300 defines engine oil classifications viscosity specification.Single-stage is designated as SAE20,30,40,50 and 60 grade, and by low shear rate kinematic viscosity range (ASTM D445) at 100 DEG C with And the minimum high-rate of shear viscosity (such as ASTM D4683, CEC L-36-A-90 or ASTM D5481) at 150 DEG C Definition.Be appointed as the engine oil low temperature cranking viscosity (ASTM D5293) according to them of SAE 0W to 25W, temperature pumping is glued Degree (ASTM4684) and 100 DEG C at minimum movement viscosity classify.

Multigrade lubricating oil runs in wide temperature range.Typically, they are identified by two numerals, such as 5W-30 Or 10W-30.First digit in multistage label refers to measure at high shear rates according to cold cranking simulator (CCS) Clean boot temperature (such as-20 DEG C) viscosity requirement (ASTM D5293) required for multi-grade oil.Generally speaking, there is low CCS The lubricant of viscosity allows electromotor to start the most more easily, and thus improves under those ambient temperatures Engine stabilization.

Second digit in multistage label refers to lubricant viscosity at the normal operating temperature, and with at 100 DEG C Kinematic viscosity (Kv) measure (ASTM D445).High temperature viscosity needs the minimum and maximum motion including at 100 DEG C viscous Degree.If the viscosity under high temperature needs to prevent at the thinnest the caused engine scuffing of electromotor run duration lubricating oil. But, lubricating oil was not intended to be viscous, because excessive viscosity may result in pump the viscosity resistance that lubricant is unnecessary Power and acting, it correspondingly can increase fuel consumption.Generally speaking, at 100 DEG C, the Kv of lubricant is the lowest, and lubricant is at fuel Mark obtained in economic testing is the highest.

Thus, for given multi-grade oil label up to standard, specific multi-grade oil have to meet strict low temperature simultaneously With high temperature viscosity requirement, it is set by SAE specification such as SAE J300.

Only be blended the oil base stock of different viscosities characteristic may not make formula meet some multi-grade oil low temperature and High temperature viscosity requirement.Described formula is additive for realizing the main tool of this target, and it is commonly referred to viscosity modifier Or viscosity index (VI) (V.I.) modifier.Generally, in order to reach target minimum high temperature viscosity, need to add a large amount of viscosity adjustment Agent.But, the increase of viscosity modifier usage amount causes the low-temperature lubrication viscosity improved.For being formulated in fuel economy test In show the ever-increasing demand of the crankcase lubricant improving performance and ordering about industry development low viscosity grade and start Machine lubricant, such as SAE0W-20,0W-30,5W-20 and 5W-30.

Requirement with low viscosity, high fuel economy lubricant is consistent because environmental factors and guarantee with and show For the compatibility of the pollution control equipment (such as three-way catalytic converter and particulate trap) that electromotor is used in combination, continue It is continuing effort to reduce sulfate ash, the content of p and s in crankcase lubricant.Be applicable to lubricant formulations has especially The slaine that antioxidation-antiwear additive is dialkyl dithiophosphoric acid root of effect, particularly its zinc salt, commonly referred to ZDDP.While such additive provides splendid performance, for lubricant, ZDDP contributes to sulfate ash, phosphorus With each in sulfur.

Catalytic converter typically comprises one or more oxidation catalysts, NO_XStore catalyst and/or NH₃Reduction catalysts Agent.The catalyst comprised in this article generally comprises the combination of catalytic metal such as platinum and metal-oxide.Catalytic converter It is assembled in gas extraction system, such as in the discharge duct of motor vehicles, thus toxic gas is converted into non-toxic gas.Catalysis turns Change device use be considered for slowing global warming trend and antagonism other environmental hazard it is critical that.But, make For exposing to element-specific or the result of compound, particularly phosphorus-containing compound such as ZDDP, catalyst may be poisoned and lead Cause to lose efficacy, if useless.

Particulate trap would generally be assembled in gas extraction system, particularly in Diesel engine, thus prevents white carbon black Grain or the most tiny condensation granule or its condensation product (i.e. " diesel soot ") discharge to environment.Except contaminated air, water With other element of environment, diesel soot is considered as carcinogen.But, these catchers may due to calx quilt Blocking, described calx is the degraded of the lube oil additive (including that common ash generates detergent additives) comprising metal Product.

In order to ensure the service life that after-treatment device is long-term, it is thus necessary to determine that such device is produced by lube oil additive Minimum negative effect.For this, OEM often to the maximum sulfur of " newly servicing filling " and " filling first " lubricant, phosphorus and/ Or the limit value that sulfate ash level set is different.Such as, when being applied to light-duty passenger car internal combustion engine, sulfur content is typically Needing less than equal to 0.30wt%, phosphorus content is less than or equal to 0.08wt%, and sulfated ash content is less than or equal to 0.8wt%.But, when lubricating composition is applied to heavy duty internal combustion engine, maximum sulfur, phosphorus and/or sulfated ash content can Being different.Such as, in those heavy-duty engine, maximum sulfated ash content can be as high as 1.6wt%.Such profit Sliding oil composition also known as " middle SAPS " (sulfate ash of content, p and s in i.e.).When maximum sulfate ash up to During 1.0wt%, lubricant oil composite will be referred to as " low SAPS " lubricant oil composite, such as petrol engine, and " LEDL " (i.e. low emission diesel fuel lubricity agent) fluid composition, for Diesel engine.

Different tests has been established and standardization is to measure the SAPS content in any specific lubricant oil composite.Example As, in Europe, the lubricant meeting ACEA gasoline and Diesel engine low SAPS specification especially have to pass through " CEC L-78- T-99 " test, after making Volkswagen's Turbo-DI automotive diesel electromotor run the time cycle extended, Alternate cycles between idling and full load, measures spatter property and the level of adhesion of piston ring.The similar specification of different tightnesses With testing standard it has also been found that in other countries and regions, such as Japan, Canada and the U.S..

But, meet low SAPS environmental standard and can't eliminate the needs for providing enough greasy properties.Motor vehicles fire Spark ignition and diesel engine have valvetrain system, including valve, cam and rocking bar, all need lubrication and avoid abrasion. Additionally, engine oil must provide for sufficient detergency, so that it is guaranteed that the cleanliness factor of electromotor suppress the generation of deposit, institute State unburned and imperfect combustion and the product of engine oil degeneration that deposit is hydrocarbon fuel.

As above, the needs of catalytic converter integrity are kept to have to cause to use less phosphate and phosphorous Additive.But, due to for neutralizing the acid of oxidization deriving and the lasting need of polar oxygenated residue suspended in the lubricant Asking, the use of detersive, typically metal sulphonate detergent is typically inevitably.But, these detersives can be led Cause the formation of sulfate ash.Under the environmental standard that the overwhelming majority is current enough peace and quiet far away from order to realize by using Metal sulfate detersive necessary to performance, can exceed allowed content of ashes.Reducing the peralkaline level of detersive can Reduce the level of produced ash, but it also reduces the acid neutralization capacity of lubricant compositions, can cause potentially sending out Motivation piston and the acid corrosion of other parts.

Oil-soluble Mannich condensation product is applicable to IC engine lubricating oil.These products generally act as dispersant, in order to Dispersion greasy filth, varnish and coating, and prevent the formation of deposit.Generally speaking, traditional oil-soluble Mannich condensation product leads to The reaction crossing the substituted phenol of polyisobutyl group and formaldehyde and amine or polyamines is formed.Such as, numbered 7,964,543；8,394, 747；8,455,681；The United States Patent (USP) of 8,722,927 and 8,729,297 disclose by 0.01wt% to 10.0wt% (wherein polyisobutyl group group is derived from comprising at least to combine the substituted hydroxy aromatic compound of polyisobutyl group under reaction condition The polyisobutylene of the methylvinylidene isomer of 50wt% also has the number-average molecular weight of about 400 to about 5000), aldehyde, amino The Mannich condensation product that acid or its ester and alkali metal base are formed can be used for engine oil composition.In these patents Each piece disclose the most in an embodiment the Mannich condensation product of 1wt% added to complete synthesis (fully Formulated) SAE class 5 W-30 base oil, SAE class 5 W-40 base oil and SAE grade 10W-40 base oil.

Thus, it is desirable to provide the low and middle SAPS lubricant oil composite improved, it is to overcome bad fuel economy SAE 0W multigrade lubricant.

Summary of the invention

According to one embodiment of the present invention, it is provided that a kind of lubricant oil composite, comprise:

(a) gross weight based on lubricant oil composite meter, more than the base oil component of 65wt%, its fortune at 100 DEG C Kinetic viscosity (Kv) is about 3.5 to about 4.5 centistokes (cSt)；

(b) gross weight based on lubricant oil composite meter, at least one Mannich reaction of about 3.0wt% to about 10wt% Product, it is by the substituted hydroxy aromatic compound of polyisobutyl group, aldehyde, aminoacid or its ester derivant and the condensation of alkali metal base Preparing, wherein, polyisobutyl group group is derived from the polyisobutylene of the methylvinylidene isomer comprising at least about 70wt% And there is the number-average molecular weight of about 400 to about 2,500；

C () is different from least one ashless dispersant of component (b)；

Wherein, the sulfur content that lubricant oil composite has less than or equal to about 0.30wt%, phosphorus content less than or equal to about 0.09wt%, and sulfated ash content is less than or equal to about 1.60wt%, measures according to ASTM D 874, based on lubricating oil The gross weight meter of compositions；And further, wherein lubricant oil composite is SAE J300 couple meeting in November, 2007 revision In the multigrade lubricating oil compositions of the specification that 0W-X multi-stage engine oil requires, wherein X is 20,30,40,50 or 60.

Second embodiment of the invention, it is provided that a kind of method for improving internal combustion engine spatter property, institute The method of stating comprise use lubricant oil composite to run described internal combustion engine, described lubricant oil composite comprises:

(a) gross weight based on lubricant oil composite meter, more than the base oil component of 65wt%, its Kv at 100 DEG C It is about 3.5 to about 4.5cSt；

C () is different from least one ashless dispersant of component (b)；

According to third embodiment of the present invention, it is provided that the purposes of a kind of lubricant oil composite, described lubricating oil composition Thing comprises:

C () is different from least one ashless dispersant of component (b)；

Wherein, the sulfur content that lubricant oil composite has less than or equal to about 0.30wt%, phosphorus content less than or equal to about 0.09wt%, and sulfated ash content is less than or equal to about 1.60wt%, measures according to ASTM D 874, based on lubricating oil The gross weight meter of compositions；And further, wherein lubricant oil composite is SAE J300 couple meeting in November, 2007 revision In the multigrade lubricating oil compositions of the specification that 0W-X multi-stage engine oil requires, wherein X is 20,30,40,50 or 60, is used for changing The piston cleanliness of kind internal combustion engine.

Except other factors, the present invention is based on it has surprisingly been found that the combination of the i.e. dispersant of the present invention can provide The required piston cleaning strengthened in modern low and middle SAPS lubricant (i.e. for the SAE 0W multigrade lubricant of internal combustion engine) Performance.The combination of the dispersant of the application of the invention, can prepare to adhere to test by piston cleanliness and piston ring and thus obtain Low and the middle SAPS lubricant (i.e. SAE 0W multigrade lubricant) of the fuel economy that must improve.It is also believed that the present invention's divides The combination of powder can further provide in low and middle SAPS lubricant (i.e. for the SAE 0W multigrade lubricant of internal combustion engine) Seal compatibility.

The detailed description of preferred implementation

Before being discussed in greater detail the present invention, the term that will be defined as follows:

Definition

As used in this article, term hereafter has following implication, the most on the contrary:

The term " total alkali number " used in this article or " TBN " refer to that in 1g sample the milligram number with KOH is suitable Alkali number.Thus, higher TBN number has reacted more alkaline product, and has therefore reacted bigger basicity deposit.Sample ASTM test No. D2896-11 or arbitrarily other equivalent steps that TBN can be published by May 15th, 2011 are surveyed Fixed.

Term " metal " refers to alkali metal, alkaline-earth metal or its mixture.

Term " alkaline-earth metal " refers to calcium, barium, magnesium and strontium.

Term " alkali metal " refers to lithium, sodium, potassium, rubidium and caesium.

Term " sulfate ash " refers to that containing metallic additive (such as calcium, magnesium, molybdenum, zinc etc.) is in lubricant oil composite Content, and typically measure according to ASTM D874, it is expressly incorporated herein by reference.

Terminology used in this article " Mannich condensation product " refers to by polyisobutyl group the most described herein The mixture of the product that substituted hydroxy aromatic compound is obtained with aldehyde and amino acid whose condensation reaction, is formed and has following formula Condensation product.Following formula is only used as being considered some examples of some Mannich condensation product of the present invention and being provided, and unexpectedly Figure gets rid of other possible Mannich condensation product that method described herein can be used to be formed.

Wherein R, R₁, X and W be as defined herein.

The present invention relates to a kind of lubricant oil composite, comprise:

C () is different from least one ashless dispersant of component (b)；

Wherein, the sulfur content that lubricant oil composite has less than or equal to about 0.30wt%, phosphorus content less than or equal to about 0.09wt%, and sulfated ash content is less than or equal to about 1.60wt%, gross weight meter based on lubricant oil composite；And And further, wherein lubricant oil composite is that the SAE J300 meeting in November, 2007 revision wants for 0W-X multi-stage engine oil The multigrade lubricating oil compositions of the specification asked, wherein X is 20,30,40,50 or 60.

Compared with the general internal combustion engine lubricating oil comprising more high phosphorus, sulfur and sulfated ash content, the lubricating oil of the present invention Compositions from the angle of environment for more suitably.The lubricant oil composite of the present invention also promotes catalytic converter and microgranule to receive In the service life that storage is longer, provide required piston cleanliness simultaneously.

Generally speaking, in the lubricant oil composite of the present invention, the content of sulfur is less than or equal to about 0.30wt%, based on lubrication The gross weight meter of fluid composition, the sulfur content of e.g., from about 0.01wt% to about 0.30wt%.In one embodiment, the present invention Lubricant oil composite in the content of sulfur less than or equal to about 0.20wt%, gross weight meter based on lubricant oil composite, such as The sulfur content of about 0.01wt% to about 0.20wt%.In one embodiment, the containing of sulfur in the lubricant oil composite of the present invention Amount is less than or equal to about 0.10wt%, gross weight meter based on lubricant oil composite, e.g., from about 0.01wt% to about 0.10wt% Sulfur content.

In one embodiment, in the lubricant oil composite of the present invention, the content of phosphorus is less than or equal to about 0.09wt%, Gross weight meter based on lubricant oil composite, the phosphorus content of e.g., from about 0.01wt% to about 0.09wt%.At a kind of embodiment In, in the lubricant oil composite of the present invention, the content of phosphorus is less than or equal to about 0.08wt%, gross weight based on lubricant oil composite Gauge, e.g., from about 0.01wt% are to the phosphorus content of about 0.08wt%.In one embodiment, the lubricant oil composite of the present invention The content of middle phosphorus is less than or equal to about 0.07wt%, and gross weight meter based on lubricant oil composite, e.g., from about 0.01wt% is to about The phosphorus content of 0.07wt%.In one embodiment, in the lubricant oil composite of the present invention content of phosphorus less than or equal to about 0.05wt%, gross weight meter based on lubricant oil composite, the phosphorus content of e.g., from about 0.01wt% to about 0.05wt%.

In one embodiment, by the content of sulfate ash produced by the lubricant oil composite of the present invention according to ASTM D 874 is determined as less than or equal to about 1.60wt%, such as, measure according to ASTM D 874 and be about 0.10 to about The sulfated ash content of 1.60wt%.In one embodiment, by sulphuric acid produced by the lubricant oil composite of the present invention The content that ashing divides is determined as less than or equal to about 1.00wt% according to ASTM D 874, such as, be determined as according to ASTM D 874 The sulfated ash content of about 0.10 to about 1.00wt%.In one embodiment, by the lubricant oil composite institute of the present invention The content of the sulfate ash produced is determined as less than or equal to about 0.80wt% according to ASTM D 874, such as according to ASTM D 874 measure the sulfated ash content being about 0.10 to about 0.80wt%.In one embodiment, by the lubricating oil of the present invention The content of sulfate ash produced by compositions is determined as less than or equal to about 0.60wt% according to ASTM D 874, such as root The sulfated ash content being about 0.10 to about 0.60wt% is measured according to ASTM D 874.

The lubricant oil composite of the present invention is complete synthesis, low or middle SAPS multigrade lubricating oil compositions, meets 2007 The specification that the SAE J300 of revision in November requires for 0W-X multi-stage engine oil, wherein X is 20,30,40,50 or 60.One Planting in embodiment, the lubricant oil composite of the present invention is complete synthesis, low or middle SAPS SAE 0W-20 multigrade lubricating oil group Compound.In one embodiment, the lubricant oil composite of the present invention is complete synthesis, low or middle SAPS SAE 0W-30 is multistage Lubricant oil composite.In one embodiment, the lubricant oil composite of the present invention is complete synthesis, low or middle SAPS SAE 0W-40 multigrade lubricating oil compositions.In one embodiment, the lubricant oil composite of the present invention is complete synthesis, in low one-tenth SAPS SAE 0W-50 multigrade lubricating oil compositions.In one embodiment, the lubricant oil composite of the present invention is complete synthesis , low or middle SAPS SAE 0W-60 multigrade lubricating oil compositions.

Base oil component

Gross weight meter based on lubricant oil composite, the lubricant oil composite of the present invention comprise more than 65wt% 100 At DEG C, Kv is about the base oil component of 3.5 to about 4.5cSt.It practice, this means that base oil component is selected from one or more symbols Close and state natural oil, artificial oil or its mixture that 100 DEG C of Kv require.In one embodiment, based on lubricant oil composite Gross weight meter, 100 DEG C of Kv that the lubricant oil composite of the present invention comprises at least about 70wt% are about the base of 3.5 to about 4.5cSt Plinth oil ingredient.In one embodiment, gross weight meter based on lubricant oil composite, the lubricant oil composite of the present invention comprises 100 DEG C of Kv of at least about 75wt% are about the base oil component of 3.5 to about 4.5cSt.

In one embodiment, gross weight meter based on compositions, the lubricant oil composite of the present invention comprises and is more than 65wt% is until 100 DEG C of Kv of about 85wt% are about the base oil component of 3.5 to about 4.5cSt.In one embodiment, base In the gross weight meter of lubricant oil composite, the lubricant oil composite of the present invention comprises 100 DEG C of Kv of about 70wt% to about 85wt% It is about the base oil component of 3.5 to about 4.5cSt.In one embodiment, gross weight meter based on lubricant oil composite, this 100 DEG C of Kv that the lubricant oil composite of invention comprises about 75wt% to about 85wt% are about the basic line of oils of 3.5 to about 4.5cSt Point.

Generally speaking, the base oil component of 100 DEG C of Kv about 3.5 to about 4.5cSt includes at least one mineral oil base oil Material.Generally speaking, at least one mineral oil base stocks used in base oil composition is selected from spark ignition and compression API group I, any crude mineral oils of II, III, IV, V or its mixing used in the crankcase lubricating oil of igniter motor Thing.Oil base stock is defined as the lubricant composition that multiple different method can be used to prepare by API principle.

Group I base oil is usually directed to the lubricating base oil derived from oil, has the saturate content (root less than 90wt% Measure according to ASTM D 2007) and/or it is more than the total sulfur content of 300ppm (according to ASTM D 2622, ASTM D 4294, ASTM D 4297 or ASTM D 3120 measures), and viscosity index (VI) (VI) more than or equal to 80 and is less than 120 (according to ASTM D 2270 measure).

Group II base oil is usually directed to the lubricating base oil derived from oil, and total sulfur content is every equal to or less than 300 parts Million parts (ppm) (measures according to ASTM D 2622, ASTM D 4294, ASTM D 4927 or ASTM D 3120), equal to or Saturate content (measuring according to ASTM D 2007) more than 90wt%, and viscosity index (VI) (VI) be 80 to 120 (according to ASTM D 2270 measures).

Group III base oil is usually directed to the lubricating base oil derived from oil, and sulfur is less than 300ppm, and saturate content is more than 90wt%, and VI is 120 or bigger.In one embodiment, group III oil base stock comprises the saturated of at least about 95wt% Hydrocarbon.In another embodiment, group III oil base stock comprises the saturated hydrocarbons of at least about 99wt%.Art used herein Language " primary amount " refers to gross weight meter based on compositions, more than 50wt% or greater than about 70wt% or about 80 to about The amount of 95wt% or about 85 to about 95wt%.

Group IV base oil is poly alpha olefin (PAOs).

Group V base oil include organizing I, II, III or IV other base oils all not to be covered.

In a preferred embodiment, 100 DEG C of Kv be about the base oil component of 3.5 to about 4.5cSt for group II or III oil base stock.In another preferred embodiment, the base oil component of 100 DEG C of Kv about 3.5 to about 4.5cSt is group III oil base stock.

Lubricant oil composite can comprise other base oil component of minor amount.Such as, lubricant oil composite can include The base oil derived from Natural lubricating oils, synthetic lubricant fluid or its mixture of minor amount.Suitably base oil includes by closing The oil base stock becoming wax and the isomerization of slack wax and obtain, and by being hydrocracked (rather than solvent extraction) crude oil Aromatics and polar compound and the hydrocracking base oil material that generates.

Suitably natural oil includes mineral lubricating oil, such as liquid petroleum, that solvent processes or the paraffin of acid treatment, ring Alkane or the mineral lubricating oil of paraffinic-naphthenic mixed type, derived from coal or the oil of shale, animal oil, vegetable oil (example Such as rapeseed oil, Oleum Ricini and Adeps Sus domestica) etc..

Suitably synthetic lubricant fluid includes but not limited to hydrocarbon ils and halo hydrocarbon ils, such as polymerization and interpolymerized hydrocarbon, the most poly-fourth Alkene, polypropylene, propylene-isobutylene copolymers, chloro polybutene, poly-(1-hexene), poly-(1-octene), poly-(1-decene) etc. and Mixture；Alkylbenzene, such as detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2-ethylhexyl) benzene etc.；Polyphenyl, such as Biphenyl, terphenyl, alkylated polyphenyls etc.；Alkylated diphenyl ethers and alkylation diphenyl sulfide, and derivant, similar Thing and homolog etc..

Other synthetic lubricant fluid includes but not limited to by polymerization less than the alkene of 5 carbon atoms, such as ethylene, third Alkene, butylene, isobutene., amylene and mixture thereof and the oil prepared.The method preparing such polymeric oil is art technology Known to personnel.

Other synthetic hydrocarbon oil includes the liquid polymers with the alpha-olefin of appropriate viscosity.Particularly suitable synthetic hydrocarbon oil For C₆To C₁₂The hydrogenated liquid oligomers of alpha-olefin, such as 1-decene trimer.

The synthetic lubricant fluid of another kind includes but not limited to alkylene oxide polymers, i.e. terminal hydroxy group such as by esterification or Person is etherified and the homopolymer of modification, interpretation and derivant thereof.These oil are for example, by oxirane or Polymerization of Propylene Oxide The oil of preparation, the alkyl of these polyoxyalkylene polymers and phenyl ether (such as mean molecule quantity be 1,000 methyl polypropylene glycol Ether, molecular weight is the Polyethylene Glycol diphenyl ether of 500-1000, and molecular weight is the polypropylene glycol Anaesthetie Ether of 1,000 to 1,500 Deng), or its list and polycarboxylate, such as acetas, the C of mixing₃-C₈Fatty acid ester, or the C of TEG₁₃Oxyacid Diester.

The synthetic lubricant fluid of another kind includes but not limited to dicarboxylic acids such as phthalic acid, succinic acid, alkyl Acid, alkenyl succinic acid, maleic acid, Azelaic Acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, Alkyl malonic acid, alkenyl malonic etc. and different alcohol such as butanol, hexanol, dodecanol, 2-ethylhexyl alcohol, ethylene glycol, The ester of diethylene glycol monoether, propylene glycol etc..The special example of these esters includes dibutyl adipate, decanedioic acid two (2-ethyl Hexyl) ester, fumaric acid di-n-hexyl ester, decanedioic acid dioctyl ester, Azelaic Acid diisooctyl ester, Azelaic Acid diiso decyl ester, benzene Dioctyl phthalate dioctyl ester, phthalic acid didecyl ester, decanedioic acid two eicosyl ester, the 2-ethylhexyl two of linoleic acid dimer Ester, by making the 2 ethyl hexanoic acid of the decanedioic acid of mole TEG with two moles and two moles react the complex ester formed Deng.

It is suitable for the ester for artificial oil also to include but not limited to by carboxylic acid and the alcohol such as first with about 5 to about 12 carbon atoms Alcohol, ethanol etc., polyhydric alcohol and polyol ethers such as neopentyl glycol, trimethylolpropane, tetramethylolmethane, dipentaerythritol, three seasons Penta tetrol etc. prepare those.

The most poly-alkyl of silicon-based oil, poly-aryl, poly-alkoxyl or poly-aryloxy group silicone oil and silicic acid ester oil, comprise another Plant the synthetic lubricant fluid of useful kind.Particularly example include but not limited to silicon tetraethyl acid esters, tetra isopropyl esters of silicon acis, four- (2-ethylhexyl) esters of silicon acis, four-(4-methylhexyl) esters of silicon acis, four (to tert-butyl-phenyl) esters of silicon acis, hexyl-(4-methyl- 2-amoxy) disiloxane, poly-(methyl) siloxanes, poly-(aminomethyl phenyl) siloxanes etc..Other synthetic lubricant fluid bag being suitable for Include but to be not limited to comprise the liquid ester such as tri-o-cresyl phcsphate (tricresyl phosphate) of acid of phosphorus, tricresyl phosphate pungent Ester, the diethylester etc. of decane phosphonic acids, PolyTHF etc..

Lubricating oil can derived from unrefined, refine and refined oil, can be natural, synthesis or such as Two or more mixture any of upper described type.Non-refined oil is by naturally occurring or synthetic source (such as coal, shale or drip Blue or green sand) directly obtain, without further refine or process.The example of non-refined oil includes but not limited to by retorting operation direct The shale oil obtained, distillation the oil directly obtained or the ester oil directly obtained by esterification process, each of which kind exists Use on the premise of the most after further treatment.Refined oil is similar with non-refined oil, except they are in one or more purifications Step is further processed improve one or more characteristic.These purification techniques are known to a person skilled in the art , and such as include solvent extraction, secondary distillation, acid or alkali extraction, filtration, diafiltration, hydrogenation treatment, dewaxing etc..Refine again Oil is for process what the oil through using obtained with those the similar processes being used for obtaining refined oil.Such refine again Oil that is that oil also known as regenerates or that reprocess, and generally entered one by the technology relating to removing useless additive and oil decomposition product Step processes.

Lube oil base stocks derived from the hydroisomerization of wax can be used as, and is either used alone still It is used in combination with aforementioned natural and/or synthesis oil base stock.Such wax isomerization oil by naturally occurring or synthetic wax or its Mixture is carried out hydroisomerization by hydroisomerisation catalysts and produces.

The slack wax that native paraffin is typically reclaimed by the solvent dewaxing of mineral oil；Synthetic wax is typically by taking The wax that torr is synthetically formed.

Mannich reaction products

Gross weight meter based on lubricant oil composite, the lubricant oil composite of the present invention will further comprise about 3.0wt% To at least one Mannich reaction products of about 10wt%, it passes through the substituted hydroxy aromatic compound of polyisobutyl group, aldehyde, aminoacid Or prepared by the condensation of its ester derivant and alkali metal base, wherein polyisobutyl group group is derived from comprising at least about 70wt% first The polyisobutylene of base ethenylidene isomer and number-average molecular weight are about 400 to about 2,500.Generally speaking, main Manny Uncommon condensation product can be represented by the structure of Formulas I:

Wherein, each R independently be-CHR '-, R ' is the branched or linear alkyl with 1 to about 10 carbon atom, has The cycloalkyl of about 3 to about 10 carbon atoms, has the aryl of about 6 to about 10 carbon atoms, has about 7 to about 20 carbon atoms Alkaryl, or there is the aralkyl of about 7 to about 20 carbon atoms, R₁For polyisobutyl group group, derived from comprising at least about The polyisobutylene of 70wt% methylvinylidene isomer and number-average molecular weight are about 400 to about 2,500.

X is hydrogen, alkali metal ion or the alkyl with 1 to about 6 carbon atom；

W is-[CHR "]-_m, wherein each R " independently be H, there is the alkyl of 1 to about 15 carbon atom or have 1 To the replacement alkyl of about 10 carbon atoms, and one or more substituent group selected from amino, acylamino-, benzyl, carboxyl, hydroxyl, Hydroxy phenyl, imidazole radicals, imino group, phenyl, sulfide base or sulfydryl；And m is the integer of 1 to 4.

Y is hydrogen, has 1 to about 10 alkyl of carbon atom ,-CHR ' OH, and wherein R ' is as defined above, or

Wherein Y ' is-CHR ' OH, and wherein R ' is as defined above；And R, X and W are as defined above；

Z is the hydroxyl phenylic group of hydroxyl, following formula:

Or

Wherein, R, R₁, Y ', X and W as defined above,

And n is the integer of 0 to 20, condition is as n=0, and Z is necessary for:

Wherein R, R₁, Y ', X and W as defined above.

In one embodiment, R₁The number-average molecular weight of polyisobutyl group group is about 500 to about 2,500.Real in one Execute in mode, R₁The number-average molecular weight of polyisobutyl group group is about 700 to about 1,500.In one embodiment, R₁Poly-isobutyl The number-average molecular weight of base group is about 700 to about 1,100.In one embodiment, R₁Polyisobutyl group group is derived from comprising The polyisobutylene of at least about 70wt% methylvinylidene isomer.In one embodiment, R₁Polyisobutyl group group derives The polyisobutylene of self-contained at least about 90wt% methylvinylidene isomer.

In compound of formula I as above, X is alkali metal ion, and most preferably sodium or potassium ion.Implement at another kind In mode, in compound of formula I as above, X is the alkyl selected from methyl or ethyl.

In one embodiment, R is CH₂, R₁Derived from comprising the poly-of at least about 70wt% methylvinylidene isomer It is CH that isobutene. and number-average molecular weight are about 700 to about 1,100, W₂, X is sodium ion and n is 0 to 20.

The Mannich condensation product used in the lubricant oil composite of the present invention can be by combining at reaction conditions Prepared by the substituted hydroxy aromatic compound of polyisobutyl group, aldehyde, aminoacid or its ester derivant and alkali metal base, Qi Zhongju The number-average molecular weight of isobutyl groups is about 400 to about 2,500.In one embodiment, Mannich condensation product is by such as Prepared by the Mannich condensation of lower material:

A the substituted hydroxy aromatic compound of () polyisobutyl group, has a following formula:

Wherein R₁For polyisobutyl group group, derived from the poly-isobutyl comprising at least about 70wt% methylvinylidene isomer Alkene and number-average molecular weight are about 400 to about 2,500, R₂For hydrogen or the low alkyl group with 1 to about 10 carbon atom, and R₃ For hydrogen or-OH；

(b) formaldehyde or there is the aldehyde of following formula:

Wherein R ' is the branched or linear alkyl with 1 to about 10 carbon atom, has the ring of about 3 to about 10 carbon atoms Alkyl, has the aryl of about 6 to about 10 carbon atoms, has the alkaryl of about 7 to about 20 carbon atoms, has about 7 to about 20 The aralkyl of individual carbon atom；

C () aminoacid or its ester derivant, have a following formula:

Wherein W be-[CHR "]-_m, wherein each R " and independently be H, the alkyl with 1 to about 15 carbon atom or tool There is the replacement alkyl of 1 to about 10 carbon atom, and one or more substituent group is selected from amino, acylamino-, benzyl, carboxyl, hydroxyl Base, hydroxy phenyl, imidazole radicals, imino group, phenyl, sulfide base or sulfydryl；And m is the integer of 1 to 4, and A is hydrogen or tool There is the alkyl of 1 to about 6 carbon atom；With

(d) alkali metal base.

The substituted hydroxy aromatic compound of polyisobutyl group

The multiple substituted hydroxy aromatic compound of different polyisobutyl groups can be used for preparing the Mannich condensation of the present invention Product.Key feature is that polyisobutyl group substituent group is sufficiently large thus oil-soluble gives final Mannich condensation product.Always For, needs for allowing the carbon number in Mannich condensation product oil-soluble polyisobutyl group substituent group are and about C₂₀Phase Closely or bigger.This is corresponding to the molecular weight of about 400 to about 2,500.It is expected that the C on phenol ring₂₀Or bigger alkyl Substituent group is positioned at the para-position of OH group on phenol.

The substituted hydroxy aromatic compound of polyisobutyl group is typically the substituted phenol of polyisobutyl group, wherein polyisobutyl group part Derived from comprising the polyisobutylene of at least about 70wt% methylvinylidene isomer, and it is further preferred that polyisobutyl group portion Divide derived from the polyisobutylene comprising at least about 90wt% methylvinylidene isomer.Terminology used in this article is " poly-different Butyl or polyisobutyl group substituent group " relate to the polyisobutyl group substituent group on hydroxyl aromatic ring.The number of polyisobutyl group substituent group is divided equally Son amount is about 400 to about 2,500.In one embodiment, the number-average molecular weight of polyisobutyl group part is about 450 to about 2, 500.In one embodiment, the number-average molecular weight of polyisobutyl group part is about 700 to about 1,500.At a kind of embodiment In, the number-average molecular weight of polyisobutyl group part is about 700 to about 1,100.

In a preferred embodiment, polyisobutyl group substituent group is connected to hydroxyl virtue relative to hydroxylic moiety with para-position Ring is at least about the 60% of whole polyisobutyl group substituted phenol molecule.In one embodiment, polyisobutyl group substituent group is relative Be connected to that hydroxyl aromatic ring is whole polyisobutyl group substituted phenol molecule with para-position in hydroxylic moiety at least about 80%.Excellent in one In the embodiment of choosing, it is whole that polyisobutyl group substituent group is connected to hydroxyl aromatic ring relative to the hydroxylic moiety on phenol ring with para-position At least about the 90% of polyisobutyl group substituted phenol molecule.

Dibasic phenol is similarly the original material of the Mannich condensation product being applicable to the present invention.Dibasic phenol is for closing Fit, as long as they are replaced as follows, on phenol ring, i.e. there is unsubstituted ortho position.The suitably example of phenesic acid Son is with C₂₀Or bigger polyisobutyl group substituent group etc. is in the orthoresol derivant of para-orientation.

In one embodiment, the substituted phenol of polyisobutyl group has a following formula:

Wherein R₁For polyisobutyl group group, derived from the poly-isobutyl comprising at least about 70wt% methylvinylidene isomer Alkene and number-average molecular weight are about 400 to about 2,500, and Y is hydrogen.

What suitably polyisobutylene can use as described in United States Patent (USP) 4,152,499 and 4,605,808 is borontrifluoride Boron (BF₃) prepared by alkylation catalyst, the content of these lists of references is expressly incorporated herein by reference.There is high alkyl Asia ethylene The commercially available polyisobutylene of base content includes being purchased from BASF's1000,1300 and 2300.

Being monosubstituted phenol for preparing the preferred polyisobutyl group substituted phenol of Mannich condensation product, wherein polyisobutyl group takes Dai Ji is connected to phenol ring in para-position.However, it is possible to other polyisobutyl group substituted phenol carrying out mannich condensation reaction can also be used for Prepare the Mannich condensation product according to the present invention.

Solvent

Solvent can be used for helping process and the reaction of polyisobutyl group substituted phenol when preparing Mannich condensation product. and suitable The example of solvent be hydrocarbon compound, such as heptane, benzene, toluene, chlorobenzene, arsol, the neutral oil of lubricant viscosity, paraffin And cycloalkanes. the example of other commercially available suitable aromatic mixtures solvent includesAromatic 100N neutral oil,150N neutral oil.

In one embodiment, Mannich condensation product can be initially dissolved in the arsol that alkyl replaces. and logical Chang Di, the alkyl substituent on arsol has about 3 to about 15 carbon atoms. in one embodiment, on arsol Alkyl substituent there are about 6 to about 12 carbon atoms.

Aldehyde

Include formaldehyde for forming the suitable aldehyde of Mannich condensation product or there is the aldehyde of following formula

Wherein R ' is the branched or linear alkyl with 1 to about 10 carbon atom, has the ring of about 3 to about 10 carbon atoms Alkyl, has the aryl of about 6 to about 10 carbon atoms, has an alkaryl of about 7 to about 20 carbon atoms, or have about 7 to The aralkyl of about 20 carbon atoms.

Representational aldehyde includes but not limited to aliphatic aldehyde, such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal and heptan Aldehyde. aromatic aldehyde can also be used for preparing Mannich condensation product, such as benzaldehyde and alkylbenzaldehyde, such as p-tolualdehyde. also Be suitable for is to produce formaldehydogenic reagent, such as paraformaldehyde and formalin such as formalin. preferably implement in one In mode, it is adaptable to the aldehyde of preparation Mannich condensation product is formaldehyde or formalin. formaldehyde refers to its whole forms, including gas Body, liquid and solid. the example of gas formaldehyde is monomer CH₂O and the trimer with following formula, (CH₂O)₃(metaformaldehyde).

The example of liquid formaldehyde is as follows:

Monomer CH in ether₂O.

Monomer CH in water₂O, has formula CH₂(H₂O)₂(methylene ethylene glycol) and HO (-CH₂O)_n-H.

Monomer CH in methanol₂O, has formula OHCH₂OCH₃And CH₃O(-CH₂O)_n-H.

Formalin is commercially available aqueous solution and different alcoholic solutions. suitably aqueous solution is the solution of 37%-50%. and good fortune You Malin is the aqueous solution of 37%. commercially available formaldehyde can also is that linear or ring-type (metaformaldehyde) polymer. and linear polymer Can be low-molecular-weight or heavy polymer.

Aminoacid

It is applicable to be formed the suitable aminoacid of Mannich condensation product or its ester derivant includes the amino with following formula Acid

Wherein W be-[CHR "]-_m, wherein each R " and independently be H, the alkyl with 1 to about 15 carbon atom or tool There is the replacement alkyl of 1 to about 10 carbon atom, and one or more substituent group is selected from amino, acylamino-, benzyl, carboxyl, hydroxyl Base, hydroxy phenyl, imidazole radicals, imino group, phenyl, sulfide base or sulfydryl；And m is the integer of 1 to 4, and A is hydrogen or tool There is the alkyl of 1 to about 6 carbon atom. alkyl is preferably methyl or ethyl.

In one embodiment, aminoacid is glycine.

Terminology used in this article " amino acid salts " relates to the amino acid whose salt with following formula

Wherein W is as defined above, and M is alkali metal ion. and preferably, M is sodium ion or potassium ion. it is highly preferred that X For sodium ion.

Be given be applicable to some examples Table I below of the a-amino acid of preparation Mannich condensation product.

Table I

* 0.1 ionic strength

* * 20 DEG C and 0.1 ionic strength

Alkali metal base

Alkali metal hydroxide, alkali metal alkoxylate is included for forming the suitable alkali metal base of Mannich condensation product Thing etc..In one embodiment, alkali metal base is the alkali metal hydroxide selected from sodium hydroxide, Lithium hydrate or potassium hydroxide Thing.

In one embodiment, aminoacid can add with the form of alkali metal ion salt.In one embodiment, Alkali metal ion is sodium ion or potassium ion.In a preferred embodiment, alkali metal ion is sodium ion.

For preparing the general step of Mannich condensation product

For formed Mannich condensation product reaction can with batch or hold in a continuous or semi-continuous manner OK.The pressure of this reaction is typically atmospheric pressure, but reaction can be as required at sub-atmospheric pressures or mistake atmospheric pressure Carry out under power.

The temperature of this reaction can very broadly change.The temperature range of this reaction can be about 10 DEG C to about 200 DEG C, or about 50 DEG C to about 150 DEG C, or about 70 DEG C to about 130 DEG C.

Reaction can be carried out in the presence of diluent or diluent mixture.Guarantee that reactant the most closely connects Touch so that they carry out reacting is important.This is important considering, because being used for the initial of mannich condensation reaction Material includes the substituted hydroxy aromatic compound of polyisobutyl group of relative non-polarity, and the aminoacid of relative polarity or its ester derive Thing.Therefore have to look for one group of suitable reaction condition or the diluent of all original materials will be dissolved.

Diluent for this reaction allows for dissolving the original material of this reaction and allowing reaction material mutual Contact.The mixture of diluent can be used for this reaction.Be applicable to the diluent of this reaction include water, alcohol (include methanol, Ethanol, isopropanol, 1-propanol, n-butyl alcohol, isobutanol, sec-butyl alcohol, butanediol, 2-Ethylhexyl Alcohol, 1-amylalcohol, 1-hexanol, second two Alcohol etc.), DMSO, NMP, HMPA, cellulose solvent, diethylene glycol dimethyl ether, different ether (include diethyl ether, THF, diphenyl ether, two Alkane etc.), aromatic diluent (including toluene, benzene, o-Dimethylbenzene, meta-xylene, xylol, mesitylene etc.), ester, alkane Hydrocarbon (including pentane, hexane, heptane, octane etc.) and different natural and synthesis flux oils (include 100 neutral oils, 150 neutrality Oil, poly alpha olefin, F-T synthesis base oil etc.), and the mixture of these diluent.Form biphase diluent mixture example If methanol and heptane are the diluent being applicable to this reaction.

First described reaction can be by making hydroxy aromatic compound and alkali metal base react, subsequently by adding aminoacid Or its ester derivant and aldehyde are carried out, or aminoacid or its ester derivant can with aldehyde reaction, subsequently by adding hydroxyaromatic Compound and alkali metal base are carried out, etc..

It is believed that aminoacid such as glycine or its ester derivant can generate medium spacing with the reaction of aldehyde such as formaldehyde

It ultimately forms cyclic formula

It is believed that these intermediate products can be with hydroxy aromatic compound and alkali reaction to form the Mannich condensation of the present invention Product.

Alternatively, it is believed that hydroxy aromatic compound can produce medium spacing with the reaction of aldehyde

It is additionally considered that this intermediate product can be with aminoacid or its ester derivant and alkali reaction to form the Manny of the present invention Uncommon condensation product.

Response time may rely on temperature and is extensively varied.Response time can be about 0.1 hour to about 20 hours, Or about 2 hours to about 10 hours, or about 3 hours to about 7 hours.

The feed molar ratio (CMR) of reactant can also change in a wide range.Lower Table I is given at using different feeds The list of the different formulas that may occur in which during mol ratio.When minima, oil-soluble Mannich condensation product should be preferably containing at least One polyisobutyl group substituted phenol ring and an amino acid group, it connects an aldehyde radical and an alkali metal.Gathering of this molecule The feed molar ratio of the substituted phenol/aldehyde/amino acid/base of isobutyl group is also shown in lower Table II, and it is 1.0: 1.0: 1.0: 1.0. Other feed molar ratio is possible, and uses other feed molar ratio to may result in the different molecular forming different formulas.

Table II

Ashless dispersant

Except Mannich reaction products as above, the lubricant oil composite of the present invention will further comprise at least one Ashless dispersant.Generally speaking, suitable ashless dispersant can be polyalkylene succinic anhydride ashless dispersant, unazotized Ashless dispersant and the nitrogenous ashless dispersant of alkalescence.It is applicable to another the such group of bag used herein as dispersant Including the copolymer containing carboxylate, described carboxylate has other polar functional base one or more, including amine, amide, Asia Amine, acid imide, hydroxyl, carboxyl etc..These products can be by long chain alkyl acrylate or methacrylate and such as Shangguan The incompatible preparation of monomer copolymerization of energy base.Such group includes alkyl methacrylate-vinylpyrrolidone copolymer, methyl Alkyl acrylate-di-alkyaminoethyl group methacrylate copolymer etc., and high molecular amide and polyamide or ester With the polyester such as poly-stearate of tetren, polyvinyl and other poly-stearmide.

Polyalkylene succinic anhydride ashless dispersant includes polyisobutenyl succinic anhydride (PIBSA).Used herein Polyalkylene succinic anhydride in the number-average molecular weight of polyalkylene afterbody would is that at least about 350 or about 750 to about 3000 or about 900 to about 1100.

In one embodiment, the mixture of polyalkylene succinic anhydride is used.In this embodiment, described mixed Compound can comprise low-molecular-weight polyalkylene succinic anhydride component such as number-average molecular weight and be about the poly-alkylene of 350 to about 1000 Base succinic anhydrides, and high molecular polyalkylene succinic anhydride component such as number-average molecular weight is about the poly-Asia of 1000 to about 3000 Alkyl succinic anhydride.In one embodiment, low and high molecular weight component is polyisobutenyl succinic anhydride.Replaceable Ground, the polyalkylene succinic anhydride component of different molecular weight can be combined into dispersant, and other is joined above as above The mixture of the dispersant examined.

Generally speaking, polyalkylene succinic anhydride is obtained by the product of polyalkylene such as polyisobutylene with maleic anhydride ?.When preparing such polyalkylene succinic anhydride, it is possible to use conventional polyisobutylene, or high methyl ethenylidene gathers Isobutene..Polyalkylene succinic anhydride can use routine techniques to prepare, such as those skilled in the art in preparation process Known heating, chlorination, free radical, acid catalysis or any other method.Suitable polyalkylene used herein The example of succinic anhydrides is the hot PIBSA (polyisobutenyl succinic anhydride) disclosed in United States Patent (USP) 3,361,673；In the U.S. Chlorination PIBSA disclosed in patent 3,172,892；Heat disclosed in United States Patent (USP) 3,912,764 and the mixing of chlorination PIBSA Thing；High succinic acid disclosed in United States Patent (USP) 4,234,435 compares PIBSA；In United States Patent (USP) 5,112,507 and 5,175,225 Disclosed in poly-PIBSA；High succinic acid disclosed in United States Patent (USP) 5,565,528 and 5,616,668 is than poly-PIBSA；In U.S. Free radical PIBSA disclosed in state's patent 5,286,799,5,319,030 and 5,625,004；By in United States Patent (USP) 4,152, 499, the PIBSA that the high methyl ethenylidene polybutene disclosed in 5,137,978 and 5,137,980 prepares；By at European patent The high succinic acid that high methyl ethenylidene polybutene disclosed in the open EP 355 895 of application prepares compares PIBSA；Special in the U.S. Profit 5,792, the trimer PIBSA disclosed in 729, in United States Patent (USP) 5,777,025 and European Patent Application Publication EP 542 Sulfonic acid PIBSA disclosed in 380；With the warp disclosed in United States Patent (USP) 5,523,417 and european patent application EP 602 863 The PIBSA purified, is expressly incorporated herein by reference the content of these lists of references.

Unazotized ashless dispersant includes the derivant of polyalkylene succinic anhydride, such as succinic acid, the of succinic acid Family and/or second family list or two slaines, by polyalkylene succinic anhydride, acid chloride or other derivant and alcohol (such as HOR¹, wherein R¹Be the alkyl group of 1 to 10 carbon atom) etc. the succinate that formed of reaction, and mixture.

As required, aforesaid polyalkylene succinic anhydride ashless dispersant and/or unazotized ashless dispersant are permissible Multiple different post-treatment reagents is used to carry out post processing.Such as, aforementioned polyalkylene succinic anhydride and/or unazotized ashless Dispersant can cause cyclic carbonate to react under conditions of reacting with oh group with cyclic carbonate being enough to.Described Reaction is generally implemented within the temperature range of about 0 DEG C to about 250 DEG C, or about 100 DEG C to about 200 DEG C, or about 50 DEG C to about 180℃。

Described reaction can undope (neat) carry out, wherein polyalkylene succinic anhydride or unazotized ashless dispersants Agent and cyclic carbonate combine at the correct ratio, its for individually or exist catalyst (such as acid, alkalescence or Lewis acid catalyst).The suitably example of catalyst includes but not limited to phosphoric acid, boron trifluoride, alkyl or aryl sulfonic acid, alkali Metal or alkaline-earth metal (alkali or alkaline) carbonate.Be used for as above preparing polyalkylene succinic anhydride Identical solvent or diluent may be alternatively used for cyclic carbonate post processing.In a preferred embodiment, herein The cyclic carbonate of middle use is DOX (dioxolan)-2-ketone (ethylene carbonate).

Nitrogen-containing basic is that the lubricant oil composite adding it contributes alkali number or BN (permissible without ash (without metal) dispersant Measure according to ASTM D 2896), without introducing extra sulfate ash.For preparing the soliquid of the present invention Basic nitrogen compound must comprise basic nitrogen, measures according to ASTM D664 test or D2896.It is the most oil-soluble.Alkali Property nitrogen compound selected from butanimide, polysuccinimide, carboxylic acid amide, hydrocarbyl monoamine, hydrocarbyl polyamine, non-the most graceful Buddhist nun wishes the Mannich condensation product of the substituted phenol of alkyl, formaldehyde and the polyamines of product, phosphamide, thio-phosphamide, phosphono Amine, dispersant viscosity index improvers, and mixture.These basic nitrogen compounds are described below (the most each necessary Retain at least one basic nitrogen).Arbitrary nitrogenous compositions can use such as boron to locate after being come by step known in the art Reason, as long as making described compositions continue to comprise basic nitrogen.

Butanimide and the polysuccinimide ashless dispersant that can use in the lubricant oil composite of the present invention exist Disclosed in substantial amounts of document and be known in the art.The butanimide of specific fundamental type and by term " succinyl Imines " associated materials summarized is e.g., as disclosed in United States Patent (USP) 3,219,666；3,172,892；3,272,746；4,234, 435 and 6,165,235, its content is expressly incorporated herein by reference.Succinic based dispersants has multiple different chemical constitution. A kind of Succinic based dispersants can be represented by following formula:

Wherein each R¹Independently be hydrocarbyl group, such as derived from polyolefinic group.Generally, hydrocarbyl group is alkane Base, such as polyisobutyl group.Alternatively, R¹Group can comprise about 40 to about 500 carbon atoms, and these atoms can be with table It is shown as aliphatic form.R²For alkylen group, common for ethylidene (C₂H₄) group.

Substituent group is typically 2 to about 16 carbon atoms and usually 2 to 6 carbon atoms by its derivative polyolefin The homopolymer of polymerizable alkylene hydrocarbon monomer and interpretation.It is reacted to form carboxylic dispersant composition's with succinic acid acylating reagent Amine can be monoamine or polyamines.

Term " butanimide " is understood to include multiple amide, acid imide in the art and can also be formed Amidine.But, primary product is butanimide, and this form is generally accepted as referring to succinic acid or the acid of alkenyl substituted Acid anhydride and the product of nitrogen-containing compound.In a preferred embodiment, due to its value of purchase, butanimide is served as reasons Those butanimides prepared by hydrocarbyl succinic anhydride and ethylene amines or polyamines, wherein, hydrocarbyl group comprises about 24 to about 350 Individual carbon atom, the feature of ethylene amines is ethylene diamine, diethylenetriamines, trien, four sub-second especially Base five amine and the poly-ethylene amines of higher molecular weight.Particularly preferred is by the polyisobutcnyl succinic of 70 to 128 carbon atoms The mean molecule quantity of anhydride and tetren or the poly-ethylene amines of higher molecular weight or such as mixture is about 205 Those butanimides prepared by daltonian poly-ethyleneamine mixtures.In one embodiment of the invention, in profit The ashless dispersant used in sliding oil composition is the polyisobutentyl group being about 700 to about 2300 derived from number-average molecular weight Two butanimides.

Term " butanimide " also includes hydrocarbyl succinic acid or anhydride and the co-oligomer of many secondary amine, and described many secondary amine remove Two or more secondary amine groups, comprise at least one tertiary amine nitrogen.Normally, this compositions has 1,500 to 50,000 Mean molecule quantity.Typical compound will be prepared by making polyisobutenyl succinic anhydride and the reaction of ethylene piperazine.

As required, as above, aforementioned butanimide and polysuccinimide ashless dispersant can use many Plant different post-treatment reagents and carry out post processing, such as, use cyclic carbonate.The polyamine moieties of the after-treatment products obtained One or more nitrogen by hydroxy alkylene oxygen carbonyl, hydroxyl poly-(oxyalkylene) oxygen carbonyl, hydroxy alkylidene, hydroxy alkylidene gather (oxyalkylene) or its mixture replace.

Aforesaid butanimide and polysuccinimide, including post-treatment composition as above, it is also possible to reaction Form borated dispersants.Except boric acid, the example of suitable boron compound includes boron oxide compound, boron halogenide and boric acid Ester.Normally, in the present compositions relative to basic nitrogen or the hydroxyl of every equivalent, about 0.1 equivalent can be used to about 1 The boron compound of equivalent.

Carboxylic acid amide ashless dispersant also uses as nitrogenous ashless dispersant.Such compound is typically disclosed in the U.S. Patent 3,405,064, its content is expressly incorporated herein by reference.These compounds are generally by making on main aliphatic chain There are at least 12 to about 350 aliphatic carbon atom and there is enough pendent fatty race groups as required to tend to making point Son is in oil-soluble carboxylic acid or anhydride or its ester react to provide single or multiple carboxylic acyloxy with amine or hydrocarbyl polyamine such as ethylene amines Prepared by amine.In one embodiment, carboxylic acid amide can be by (1) formula R²The carboxylic acid of COOH, wherein R²For C_12-20Alkyl or This acid of person and the mixture of polyisobutylene yl carboxylic acid, wherein polyisobutentyl group comprises 72 to 128 carbon atoms and (2) are sub- Polyethylene polyamine, particularly trien or tetren or its mixture, prepare.

The nitrogenous ashless dispersant being suitable for of another kind is hydrocarbyl monoamine and hydrocarbyl polyamine, preferably in United States Patent (USP) 3, Type disclosed in 574,576, is expressly incorporated herein by reference its content.Hydrocarbyl group, preferably alkyl or there is Or two unsaturated sites generally comprise 9 to about 350, or the thiazolinyl (olefinic) of about 20 to about 200 carbon atoms.? In a kind of embodiment, suitable hydrocarbyl polyamine is for such as by making polyisobutenyl chloride and polyalkylene polyamine the most sub- Ethylamine such as ethylene diamine, diethylenetriamines, tetren, 2-aminoethylpiperazine, trimethylene diamidogen, The reaction such as propylene diamidogen and derivative those.

The nitrogenous ashless dispersant being suitable for of another kind is except the Mannich of Mannich reaction products described above Compound.These compounds are by phenol or C_9-200Alkyl phenol, aldehyde such as formaldehyde or formaldehyde predecessor such as paraformaldehyde (paraformaldehyde) prepare with amines.Amine can be single or multiple amine, and typical compound is by alkylamine Prepared by such as methyl amine or ethylene amines such as diethylenetriamines or tetren etc..Phenol material can cure, and And preferably dodecylphenol or C_80-100Alkyl phenol.The typical Mannich base that can be used for the present invention is disclosed in United States Patent (USP) 3,539,663,3,649,229,3,368,972 and 4,157,309, its content is expressly incorporated herein by reference.Its content is led to Cross with reference to the United States Patent (USP) 3,539,663 that is expressly incorporated herein disclose by make to have at least 50 carbon atoms, preferably 50 to 200 The alkyl phenol of carbon atom and formaldehyde and alkylene polyamine HN (ANH)_nH reacts the Mannich base prepared, and wherein A is 2 to 6 The saturated divalent alkyl hydrocarbon of carbon atom and n are 1-10, and the condensation product of described alkylene polyamine can further with urea Or thiourea reaction.These Mannich bases generally can be by making as the utilization of the original material for preparing lube oil additive Mannich base is processed to significantly improve in boron is introduced to compound with routine techniques.

The nitrogenous ashless dispersant being suitable for of another kind is phosphamide and phosphonic amide, e.g., as disclosed in United States Patent (USP) 3, 909,430 and 3,968,157, its content is expressly incorporated herein by reference.These compounds can have at least one by formation Prepared by the phosphorus compound of individual P-N key.They such as can be by making phosphoryl chloride phosphorus oxychloride and hydrocarbon based diol in the case of there is monoamine Prepared by reaction, or by making phosphoryl chloride phosphorus oxychloride react prepare with difunctional secondary amine and single function amine.Thio-phosphamide can lead to Cross unsaturated hydrocarbon compound such as polyethylene, polyisobutylene, polypropylene, the second making to comprise 2 to 450 or more carbon atom Alkene, 1-hexene, 1,3-hexadiene, isobutene., 4-methyl-1-pentene etc. and Phosphoric sulfide and as defined above nitrogen-containing compound are special It not alkylamine, alkyl diamine, alkyl polyamine or alkylene amines such as ethylene diamine, diethylenetriamines, triethylene Prepared by the reaction such as tetramine, tetren.

Suitably ashless dispersant can also include amine dispersant, and it is aliphatic halogenide and the amine of relatively high molecular weight The preferably product of polyalkylene polyamine.The example of such amine dispersant includes such as in United States Patent (USP) 3,275,554,3, 438,757,3,454,555 and 3, those disclosed in 565,804, its content is expressly incorporated herein by reference.

Suitably ashless dispersant can also is that polymerization, and it is oil-soluble monomer such as decyl-octyl methacrylate, ethylene The interpretation of base decyl ethers and high molecular weight olefin and the monomer comprising polar substituent.Polymeric dispersant includes such as in the U.S. Patent 3,329,658,3,449,250 and 3, those described in 666,730, its content is expressly incorporated herein by reference.

Generally speaking, present in the lubricant oil composite of the present invention content range of ashless dispersant based on lubricating oil The gross weight of compositions is calculated as about 0.1 to about 10wt%.In one embodiment, deposit in the lubricant oil composite of the present invention The content range gross weight based on lubricant oil composite of ashless dispersant be calculated as about 1 to about 8wt%.

The lubricant oil composite of the present invention can also comprise other conventional additives, and it can give or improve and wherein disperse Or dissolve any target property of the lubricant oil composite of these additives.Any additive well known by persons skilled in the art is all Can be used for lubricant oil composite disclosed herein.Some suitable additive has been disclosed in Mortier et al. " Chemistry and Technology of Lubricants ", the second edition, London, Springer, (1996)；And Leslie R.Rudnick, " Lubricant Additives:Chemistry and Applications ", New York, Marcel Dekker (2003), both is expressly incorporated herein by reference.Such as, lubricant oil composite can be with antioxidant, antiwear additive, and detersive is such as Metal detergent, antirust agent, fog remover, demulsifier, metal inactivator, friction modifiers, pour-point depressant, defoamer, helps Solvent, the compatible agent of encapsulation, corrosion inhibitor, ashless dispersant, dyestuff, extreme pressure agent etc., and mixture are blended.Multiple additives is Known and commercially available.These additives or their similar compounds are utilized for the blending step of routine to be prepared The lubricant oil composite of the present invention.

Generally speaking, when using when, the concentration range of every kind of additive in lubricant oil composite is based on lubricating oil The gross weight meter of compositions can be about 0.001wt% to about 20wt%, about 0.01wt% to about 15wt%, or about 0.1wt% to about 10wt%.

The lubricant oil composite of the present invention can comprise one or more antioxidants, and it can reduce or prevent base oil Oxidation. any antioxidant well known by persons skilled in the art all can be used in lubricant oil composite. suitably antioxidation The non-limitative example of agent include amine-based antioxidant (such as alkyl diphenylamine such as dinonylated diphenylamines, dioctylated two Aniline and octylated/butylated diphenylamines, phenyl-α-naphthylamine, the substituted phenyl-α-naphthylamine of alkyl or aryl alkyl, alkane The P-pHENYLENE dI AMINE of base, tetramethyl diamino-diphenyl amine etc.), phenolic antioxidant (such as 2-tert-butyl phenol, 4-methyl- 2,6-di-tert-butylphenols, 2,4,6-tri-tert-butyl phenols, 2,6 ditertiary butyl p cresol, 2,6-di-tert-butylphenols, 4,4 '-methylene Double-(2,6-di-tert-butylphenol), 4,4 '-thiobis (6-di-t-butyl orthoresol) etc.), thio-based antioxidants (such as two Laurels Base-3,3 '-thiodipropionate, sulfurized phenolic antioxidant etc.), phosphorio antioxidant (such as phosphite ester/salt etc.), dithio Zinc phosphate, oil-soluble copper compounds and combinations thereof. content gross weight based on the lubricant oil composite meter of antioxidant can be About 0.01wt% is to about 10wt%, about 0.05wt% to about 5wt%, or about 0.1wt% to about 3wt%.

The lubricant oil composite of the present invention can comprise detersive. detersive effect that is that comprise metal or that form ash For in order to reduce or to remove the detersive of deposit and acid neutralizing agent or antirust agent, thus reducing abrasion and corrode and extend Engine life. detersive generally comprises the polar head with long hydrophobic tail. and described polar head comprises acidic organic compound Slaine. described salt can comprise the most stoichiometric metal, in this case they be described generally as normal salt or Neutral salt. substantial amounts of metal base can be by making metallic compound (such as oxide or hydroxide) and the sour gas of excess (such as carbon dioxide) reaction introduces.

The detersive that can use includes oil-soluble neutrality and overbased sulfonates, phenates, sulfuration phenates, phosphonothiolic acid Salt, salicylate and naphthenate, and other oil-soluble metal carboxylate, described metal particularly alkali metal or alkaline earth gold Belonging to, such as barium, sodium, potassium, lithium, calcium and magnesium. the most frequently used metal is calcium and magnesium, and the mixture of calcium and/or magnesium and sodium, and it can It is concurrently present in the detersive used in the lubricant.

Commercial products usually neutrality or peralkaline. overbased metal detersive is generally by making hydrocarbon, and detersive is sour Such as sulfonic acid, carboxylate/ester etc., metal-oxide or hydroxide (such as calcium oxide or calcium hydroxide) and accelerator such as two Toluene, the mixture carbonating of first alcohol and water are formed. such as, in carbonating, in order to prepare overbased calcium sulfonate, and calcium oxide Or calcium hydroxide reacts with atmospheric carbon dioxide and forms calcium carbonate. sulfonic acid uses CaO or Ca (OH) of excess₂Neutralize and formed Sulfonate.

Overbased detergent can be low peralkaline, such as, have the overbased salt less than 100BN. a kind of embodiment party In formula, the BN of low overbased salt can be about 5 to about 50. in another embodiment, and the BN of low overbased salt can be about 10 to about 30. in another embodiment, and the BN of low overbased salt can be about 15 to about 20.

Overbased detergent is peralkaline in can being, such as, have BN and be about the overbased salt of 100 to about 250. one In kind of embodiment, the BN of middle overbased salt is about 100 to about 200. in another embodiment, and the BN of middle overbased salt is About 125 to about 175.

Overbased detergent can be high peralkaline, such as, have the BN overbased salt more than 250. a kind of embodiment party In formula, the BN of high overbased salt can be about 250 to about 550.

In one embodiment, detersive can be one or more alkali metal of the substituted hydroxyaromatic carboxylic acid of alkyl Or alkali salt. suitably hydroxy aromatic compound includes monokaryon monohydroxy and polyhydroxy aromatic hydrocarbons, has 1 to 4 and excellent Selecting 1 to 3 oh group. suitably hydroxy aromatic compound includes phenol, catechol, resorcinol, hydroquinone, pyrogaelol, cresol Deng. preferably hydroxy aromatic compound is phenol.

The alkali metal salt of the substituted hydroxyaromatic carboxylic acid of alkyl or the alkyl replacement part of alkali salt are derived from having The alpha-olefin of about 10 to about 80 carbon atoms. the alkene used can be linear, isomerization is linear, branched or part Branched linear. described alkene can be the mixture of linear alpha-olefin, the mixture of isomerization linear alpha-olefin, mixing of branched olefin Compound, the mixture of part branched linear or any aforesaid mixture.

In one embodiment, it is possible to use the mixture that mixture is positive alpha-olefin of linear alpha-olefin, described Positive alpha-olefin has the alkene of about 12 to about 30 carbon atoms selected from per molecule. and in one embodiment, positive alpha-olefin uses At least one solid or liquid catalyst isomerization.

In another embodiment, described alkene is the branched olefinic oligomeric acrylamide with about 20 to about 80 carbon atoms Thing or its mixture, the i.e. branched alkene footpath of derived from propylene polymerization. described alkene can also use other functional group to take Generation, such as oh group, hydroxy-acid group, hetero atom etc. in one embodiment, branched olefinic propylene oligomer or its mixing Thing has about 20 to about 60 carbon atoms. and in one embodiment, branched olefinic propylene oligomer or its mixture have about 20 to about 40 carbon atoms.

In one embodiment, comprise in the alkali metal or alkali salt of the substituted hydroxyaromatic carboxylic acid of alkyl At least about 75mol% (the most about 80mol%, at least about 85mol%, at least about 90mol%, at least about 95mol%, or Person at least about 99mol%) alkyl group, the alkyl base of the alkali salt detersive of the substituted hydroxy benzoic acid of such as alkyl Group is C₂₀Or higher level. in another embodiment, the alkali metal of the substituted hydroxyaromatic carboxylic acid of alkyl or alkaline-earth metal Salt is alkali metal or the alkali salt of the substituted hydroxy benzoic acid of alkyl, and it is derived from the substituted hydroxy benzoic acid of alkyl, its Middle alkyl group is the residue of positive alpha-olefin, and described positive alpha-olefin comprises at least 75mol%C₂₀Or the positive alpha-olefin of higher level.

In another embodiment, comprise in the alkali metal or alkali salt of the substituted hydroxyaromatic carboxylic acid of alkyl At least about 50mol% (the most about 60mol%, at least about 70mol%, at least about 80mol%, at least about 85mol%, Or at least about 90mol%, at least about 95mol%, or at least about 99mol%) alkyl group, the substituted hydroxyl of such as alkyl The alkali metal of yl benzoic acid or the alkyl group of alkali salt are about C₁₄To about C₁₈.

Alkali metal or the alkali salt of the substituted hydroxyaromatic carboxylic acid of alkyl obtained would is that ortho position and para-position are different The mixture of structure body. in one embodiment, this product will contain from about 1 to 99% ortho isomer and 99 to 1% para-positions are different Structure body. in another embodiment, this product will contain from about 5 to 70% ortho positions and 95 to 30% para-isomers.

The alkali metal of the substituted hydroxyaromatic carboxylic acid of alkyl or alkali salt can be neutral or peralkaline. generally Ground, the alkali metal of the substituted hydroxyaromatic carboxylic acid of peralkaline alkyl or alkali salt are such, and wherein alkyl is substituted The alkali metal of hydroxyaromatic carboxylic acid or the BN of alkali salt have passed through such as to add alkali source (such as Calx) and acidity crosses alkali The method of value compound (such as carbon dioxide) and improve.

Sulfonate can be prepared by sulfonic acid, and it obtains typically via the substituted aromatic hydrocarbons of sulfonated alkyl, described The substituted aromatic hydrocarbons of alkyl is such as obtained by the fractional distillation of oil or is obtained by the alkylation of aromatic hydrocarbons. and example includes passing through alkylation Benzene,toluene,xylene, naphthalene, diphenyl or their halo derivatives and obtain those. catalyst can be there is in alkylation And have about 3 and carry out to the alkylating reagent more than 70 carbon atoms. alkylaryl sulfonate generally comprises about 9 To about 80 or more carbon atom, preferably from about 16 to about 60 carbon atom substituted aromatic fractions of every alkyl.

Oil-soluble alkali hydrochlorate or alkarylsulphonic acid can use oxide, hydroxide, alkoxide, carbonate/ester, carboxylic The ether of hydrochlorate/ester, sulfide, sulfhydrate, nitrate, borate and metal neutralizes. and the amount of metallic compound is based on finally Target TBN of product selects, but typical case in the range of target chemical measure about 100 to about 220wt% (preferably at least about 125wt%).

By making appropriate metallic compound such as oxide or hydroxide carry out with neutrality or peralkaline product The slaine of phenol and phenol red is prepared in reaction, can be obtained by methods known in the art. and phenol red can be by making Phenol carries out reacting preparing with sulfur or sulfur-containing compound such as hydrogen sulfide, single halogenation sulfur or dihalide sulfur, thus is formed logical It is often that the product of compound mixture, wherein 2 or more phenol are bridged by sulfur-bearing bridged bond.

Normally, the content of other detersive gross weight based on lubricant oil composite meter can be about 0.001wt% extremely About 25wt%, about 0.05wt% are to about 20wt%, or about 0.1wt% to about 15wt%.

The lubricant oil composite of the present invention can comprise one or more friction modifiers, its can reduce mobile parts it Between friction. any friction modifiers well known by persons skilled in the art all can be used for lubricant oil composite. suitably rub The non-limitative example of modifying agent includes aliphatic carboxylic acid；Derivant (such as alcohol, ester, borate, amide, the metal of aliphatic carboxylic acid Salt etc.)；Mono-, di-or the substituted Phosphoric acid or phosphonic acid of trialkyl；Biological (the example of the rank of mono-, di-or the substituted Phosphoric acid or phosphonic acid of trialkyl Such as ester, amide, slaine etc.)；Mono-, di-or the substituted amine of trialkyl；List or the substituted amide of dialkyl group, and combinations thereof. at certain In a little embodiments, the example of friction modifiers includes but not limited to the fatty amine of alkoxylate；Boric acid flower fat epoxide； Fatty phosphites/ester, fat epoxide, fatty amine, borated alkoxylated fatty amine, the slaine of fatty acid, fat Fat acid amide, glyceride, borated glycerol esters；With such as in United States Patent (USP) 6, the fatty imidazolines disclosed in 372,696, by it Appearance is expressly incorporated herein by reference；By C₄To C₇₅, or C₆To C₂₄, or C₆To C₂₀Fatty acid ester and selected from ammonia and alkanolamine etc. The friction modifiers that the product of nitrogen-containing compound etc. obtain, and mixture. the amount of friction modifiers is based on lubrication line of oils The gross weight meter of compound can be about 0.01wt% to about 10wt%, about 0.05wt% to about 5wt%, or about 0.1wt% is extremely About 3wt%.

The lubricant oil composite of the present invention can comprise one or more wear resistences, and it can reduce friction and excessively grind Damaging. any antiwear additive well known by persons skilled in the art all can be used for lubricant oil composite. and suitably antiwear additive is unrestricted Property example includes zinc dithiophosphate, metal (such as Pb, Sb, Mo etc.) salt of phosphordithiic acid root, aminodithioformic acid root Metal (such as Zn, Pb, Sb, Mo etc.) salt, metal (such as Zn, Pb, Sb etc.) salt of fatty acid, boron compound, phosphate ester, Asia Phosphate ester, the amine salt of phosphate ester or the product of the amine salt of thiophosphate, bicyclopentadiene and D2EHDTPA, and group Closing. amount gross weight based on the lubricant oil composite meter of antiwear additive can be about 0.01wt% to about 5wt%, about 0.05wt% extremely About 3wt%, or about 0.1wt% to about 1wt%.

In specific embodiment, antiwear additive is aluminum, lead, tin, molybdenum, manganese, nickel, copper such as dialkyl dithiophosphoric acid Zinc compound. the metal of aluminum, lead, tin, molybdenum, manganese, nickel, copper can be alkali metal or alkaline-earth metal, or aluminum, lead, stannum, molybdenum, Manganese, nickel or copper. in some embodiments, described metal is zinc. in other embodiments, dihydrocarbyl dithiophosphate phosphate metal The alkyl group of salt has about 3 to about 22 carbon atoms, about 3 to about 18 carbon atoms, about 3 to about 12 carbon atoms, or about 3 To about 8 carbon atoms. in another embodiment, alkyl group is linear or branched.

The amount of aluminum, lead, tin, molybdenum, manganese, nickel, copper, the dialkyl group two being included herein in disclosed lubricant oil composite The amount of D2EHDTPA zinc salt, according to the assay of phosphorus. in some embodiments, and lubricant oil composite disclosed herein Phosphorus content gross weight based on lubricant oil composite be calculated as about 0.01wt% to about 0.14wt%.

The lubricant oil composite of the present invention can comprise one or more foams in hibitors or defoamer, and it can crush Foam in oil.Any foam in hibitors well known by persons skilled in the art or defoamer all can be used for lubricating oil composition Thing.Suitably the nonrestrictive example of foam in hibitors or defoamer include silicone oil or polydimethylsiloxane, fluorosilicone, Alkoxylated fatty acid, polyethers (such as Polyethylene Glycol), branched polyethylene base ether, acrylate polymers, metering system Acid alkyl ester polymer, poly-alkoxyamine and combinations thereof.In some embodiments, foam in hibitors or defoamer comprise list Tristerin, Polyethylene Glycol cetylate, trialkyl-single sulfur phosphate ester, the ester of sulforicinoleic acid, benzoyl acetone, water Poplar acid methyl ester, glyceryl monooleate or glyceryl dioleate.The amount of foam in hibitors or defoamer is based on lubricating oil composition The gross weight meter of thing can be about 0.001wt% to about 5wt%, about 0.05wt% to about 3wt%, or about 0.1wt% is to about 1wt%.

The lubricant oil composite of the present invention can comprise one or more pour-point depressants, and it can reduce lubricating oil composition The pour point of thing.Any pour-point depressant well known by persons skilled in the art all can be used for lubricant oil composite.Suitably pour point The nonrestrictive example of depressant includes polymethacrylates/salt, acrylate polymers, methacrylate Ester polymer, two (four alkane phenol) phthalic acid ester (di (tetra-paraffin phenol) phthalate), four chains The condensation substance of the condensation substance of alkane phenol, chloroalkane hydrocarbon and naphthalene, and combinations thereof.In some embodiments, pour-point depressant bag Containing ethylene-vinyl acetate copolymer, chloroalkane hydrocarbon and the condensation substance of phenol, alkyl styrenes etc..The amount of pour-point depressant Gross weight meter based on lubricant oil composite can be about 0.01wt% to about 10wt%, about 0.05wt% to about 5wt%, or About 0.1wt% to about 3wt%.

In one embodiment, the lubricant oil composite of the present invention does not comprise one or more demulsifiers.Separately In a kind of embodiment, the lubricant oil composite of the present invention can comprise one or more demulsifiers, and it can promote to expose To water or the Oil-water separation of the lubricant oil composite of steam.Any demulsifier well known by persons skilled in the art all can by with In lubricant oil composite.The suitably nonrestrictive example of demulsifier includes anion surfactant (such as alkyl-naphthalene Sulfonate, alkylbenzenesulfonate etc.), Nonionic alkoxylated alkyl phenol resin, alkylene oxide polymer (the most poly- Oxirane, poly(propylene oxide), oxirane, the block copolymer etc. of expoxy propane), the ester of oil-soluble acid, polyoxyethylene mountain Pears polysaccharide ester, and combinations thereof.Amount gross weight based on the lubricant oil composite meter of demulsifier can be about 0.01wt% to about 10wt%, about 0.05wt% are to about 5wt%, or about 0.1wt% to about 3wt%.

The lubricant oil composite of the present invention can comprise one or more corrosion inhibitors, and it can reduce corrosion.This area Any corrosion inhibitor known to the skilled person all can be used for lubricant oil composite.The suitably non-limitative example of corrosion inhibitor Including half ester or the amide of dodecyl succinate, phosphate ester, thiophosphate, alkyl imidazoline, sarcosine, and combinations thereof. Amount gross weight based on the lubricant oil composite meter of corrosion inhibitor can be about 0.01wt% to about 5wt%, about 0.05wt% extremely About 3wt%, or about 0.1wt% to about 1wt%.

The lubricant oil composite of the present invention can comprise one or more extreme pressures (EP) agent, and it is possible to prevent sliding metal table Face is blocked under the conditions of extreme pressure.Any extreme pressure agent well known by persons skilled in the art all can be used for lubricant oil composite.Generally Ground, extreme pressure agent be can be combined with metallochemistry with formation skin covering of the surface compound, described skin covering of the surface prevent under high load with The coarse welding of opposed metallic surfaces.Suitably the nonrestrictive example of extreme pressure agent include vulcanizing animal or plant fat or Oil, vulcanizes animal or plant fatty acid ester, the trivalent of phosphorus or the ester of all or part of esterification of pentahydric acid, olefine sulfide, two hydrocarbon Polysulfide, vulcanizes diels-Alder adduct, vulcanizes bicyclopentadiene, fatty acid ester and the sulfur of single unsaturated olefin Change or co-vulcanization mixture, the co-vulcanization mixture of fatty acid, fatty acid ester and alpha-olefin, the many sulfur of the substituted dialkyl of sense Compound, sulfur for aldehyde, sulfur for ketone, episulfide compounds, sulfur-bearing acetal derivatives, the co-vulcanization blend of terpenes and non-ring olefin, And polysulfide olefin product, the amine salt of phosphate ester or the amine salt of thiophosphate, and combinations thereof.The amount of extreme pressure agent based on The gross weight meter of lubricant oil composite can be about 0.01wt% to about 5wt%, about 0.05wt% to about 3wt%, or about 0.1wt% to about 1wt%.

The lubricant oil composite of the present invention can comprise one or more antirust agent, and it can suppress ferrous metal surface Corrosion.Any antirust agent well known by persons skilled in the art all can be used for lubricant oil composite.The suitably non-limit of antirust agent Property example processed includes nonionic polyoxyalkylene agents, such as polyoxyethylene laurel ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl Base phenyl ether, NONIN HS 240, polyoxyethylene octyl stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene Sugar alcohol monostearate, polyoxyethylene 80 sorbitan monooleate and polyethylene glycol monooleate；Stearic acid and other fat Acid；Dicarboxylic acids；Metallic soap；Fatty acid amine salt；The slaine of weight sulfonic acid；The inclined carboxylate of polyhydroxy-alcohol；Phosphide；(short chain) alkene Base succinic acid；Its partial ester and nitrogen containing derivative thereof；Synthesis alkyl aryl sulfonate/salt, such as metal dinonylnaphthalene sulfonic acid ester/salt； Etc., and mixture.Amount gross weight based on the lubricant oil composite meter of antirust agent can be about 0.01wt% to about 10wt%, about 0.05wt% are to about 5wt%, or about 0.1wt% to about 3wt%.

The lubricant oil composite of the present invention can comprise one or more multifunction additives.Suitably multifunction additive Non-limitative example include sulfurated dithioaminoformyloxyoxy molybdenum, sulfuration organic disulfide is for phosphoric acid oxygen molybdenum (sulfurized Oxymolybdenum organophosphorodithioate), single glycerol oxygen molybdenum, diethylization amide oxygen molybdenum (oxymolybdenum diethylate amide), amine-molybdenum complex chemical compound, and sulfur-bearing molybdenum complex chemical compound.

The lubricant oil composite of the present invention can comprise one or more viscosity index improvers.Suitably viscosity index (VI) changes The nonrestrictive example entering agent includes but not limited to olefin copolymer, such as ethylene-propylene copolymer, styrene-isoamyl two Alkene copolymer, is hydrated styrene-isoprene copolymer, polybutene, polyisobutylene, polymethacrylates/salt, vinylpyridine Pyrrolidone and methacrylate/salt copolymer, and the viscosity index improver of Dispersant types.These viscosity improvers are permissible Optionally use graft materials such as maleic anhydride to be grafted, and graft materials such as can be with amine, amide, nitrogen heterocyclic ring Compound or alcohol are reacted to form multi-functional viscosity improver (dispersant viscosity modifier).Other example of viscosity modifier Including star polymer (such as comprising the star polymer of isoprene/styrene/isoprene three block).Viscosity modifier Another example include poly-(methyl) alkyl acrylate/salt of low brookfield viscosity and high shear stability, there is high Bu Shi Functionalized poly (methyl) alkyl acrylate/salt of the dispersant characteristics of viscosity and high shear stability, weight average molecular weight is 700 To 2,500 daltonian polyisobutylene, and mixture.The amount gross weight based on lubricant oil composite of viscosity index improver Meter can be about 0.01wt% to about 25wt%, about 0.05wt% to about 20wt%, or about 0.3wt% to about 15wt%.

The lubricant oil composite of the present invention can comprise one or more metal inactivator.Suitably metal inactivator is non- Limitative examples includes double salicylidene propane diamine, triazole derivative, thiadiazoles derivative, and mercaptobenzimidazole.

As required, at least one Mannich reaction products (b) and/or at least one ashless dispersant (c) can be independent Ground provides or provides together as additive bag or concentrate, at least one of which Mannich reaction products (b) and/or at least A kind of ashless dispersant (c) and optionally mix together with aforementioned lubricants additive to that be substantially inert, be typically The organic diluent of liquid such as mineral oil, Petroleum, benzene, toluene or dimethylbenzene are to form multifunctional additive for lubricating oils.These concentrate Thing generally comprises the diluent of about 20wt% to about 80wt%.Typically, 100 DEG C of viscosity is about 4 to about 8.5cSt and preferably The neutral oil being about 4 to about 6cSt will be used as diluent, although artificial oil and compatible with additive and final lubricating oil Other organic liquid can be used as.Additive bag typically will comprise one or more with reference to as above with aim parameter and ratio Different additive, thus help the combination of lubrication viscosity oil guiding with must measuring.

Lubricant oil composite disclosed herein is used for lubricating internal combustion engines such as spark ignition engine or compression Ignited diesel engine, such as heavy duty diesel engine or be equipped with the compression of at least one exhaust gas recirculatioon (EGR) system Ignited diesel engine；Catalytic converter；And particulate trap.It is arbitrary that such engine oil composition can be used for lubrication All main moving components in the steam engine of reciprocating internal combustion engine, reciprocating compressor and crankcase designs.Should at motor vehicles In with, engine oil composition may be additionally used for cools hot engine parts, keeps electromotor to avoid getting rusty and depositing, and seals Ring and valve are to avoid leaking combustion gas.

For heavy duty diesel engine, main type service is light as disclosed in US 40 CFR 86.090-2 Type, medium-sized and heavy heavy duty diesel engine.The factor that this classification is based on for example, gross vehicle weight (GVW), vehicle use and grasp Make mode, other Car design feature, engine horsepower and the design of other electromotor and operating characteristic.Hereinafter HD diesel The universal description of the main services kind of electromotor:

(1) light heavy-duty Diesel engine is usually non-axle sleeve, and will not design reconstruction；Their rated horsepower leads to It is often 70 to 170.Car body type in this group can include that the heavy-duty vehicle for underloading truck chassis is assembled, van-type goods Car, many halts van, recreation vehicle, and some single shaft straight line truck.Typical case's application of such electromotor includes individual People transports, the traction of underloading business and conveying, passenger services, agricultural and building industry.Electromotor in this group is generally used for GVW and leads to In the vehicle of often less than 19,500 pounds.

(2) medium-sized heavy duty diesel engine can be axle sleeve or non-axle sleeve, and can design reconstruction；They Rated horsepower is usually 170 to 250.Car body type in this group can include school bus, Biaxial linear truck, and city is drawn Car, and multiple different purpose-built vehicle, the most small-sized dump truck and the dumper of the compressor with compressed garbage. Typical case's application of such electromotor includes the traction of business short distance and intra-urban transportation and picks up.Electromotor in this group is usual In the vehicle that GVW is 19,500 to 33,000 pounds.

(3) heavy heavy duty diesel engine be axle sleeve and be designed for repeatedly rebuilding；Their rated horsepower is usual More than 250.Car body type in this group can be included in the tractor of distance traction application of intercity use, truck and Bus.Electromotor in this group is generally used in the GVW vehicle more than 33,000 pounds.

Nonrestrictive example hereafter is the explanation present invention.

Preparation oil A, and contrast oil 1 and 2, and test piston cleanliness and piston ring adhesive tendencies, according to popular turbine Supercharging DI tests, Europe passenger cars diesel engines test (CEC-L-78-T-99), its be by European motor vehicle manufacturers association in The ACEA A/B issued for 2004 and a part for C specification.This test is used for simulating the repetitive cycling of high-speed cruising, subsequently Idle running.Four cylinders turbo-charged direct injection automotive diesel electromotor (VW TDi) of popular 1.9 liters of provided in-line are installed in be sent out On motivation energy meter station.Between 30 minutes, 40 DEG C of oil pump idle running and 150 minutes, 145 DEG C of oil pump full speed runnings (4150rpm) Circulation 54 hours, 2 hierarchical process be performed, middle oil will not be full of.After described program, carbon and the paint of evaluating piston are heavy Long-pending and groove carbon is filled.Piston ring carries out ring adhere to evaluate.Shown in result Table III below.Oil A and contrast oil The SAE J300 being formulated to meet in November, 2007 revision each of in 1 and 2 wants for 0W-20 multi-stage engine oil The specification asked.

Oil A:

The preparation complete synthesis lubricant oil composite of 0W-20 viscosity grade, it comprises 79.23wt% group III base oil (4.1cSt, 100 DEG C), two succinimide dispersants, the Mannich of 3.0wt% that the ethylene carbonate of about 8wt% processes are anti- Answer product (polyisobutyl group substituted phenol (and use has and prepares more than the polyisobutylene of 70wt% methylvinylidene isomer, 1, 000 number-average molecular weight), Sodium Glycinate and the product of formaldehyde), and the detersive of typical amount, phosphorous antiwear additive, antioxygen Agent, friction modifiers, foam in hibitors, viscosity index improver, pour-point depressant and flux oil.The sulfate ash of oil A Content is about 0.79wt%, and sulfur content is about 0.18wt%, and phosphorus content is about 0.074wt%.

Contrast oil 1: the basic formula replicating oil A, except contrast oil 1 have 79.7wt% group III base oil (4.1cSt, 100 DEG C) and the Mannich reaction products of 1.50wt%.The sulfated ash content of contrast oil 1 is about 0.82wt%, and sulfur content is About 0.18wt%, and phosphorus content is about 0.07wt%.Contrast oil 1 is 0W-20 viscosity grade lubricant oil composite.

Contrast oil 2: the basic formula replicating oil A, except contrast oil 2 have 79.7wt% group III base oil (4.1cSt, 100 DEG C) and the Mannich reaction products of 2.25wt%.The sulfated ash content of contrast oil 2 is about 0.79wt%, and sulfur content is About 0.18wt%, and phosphorus content is about 0.074wt%.Contrast oil 2 is 0W-20 viscosity grade lubricant oil composite.

Table III

Test-types: VWTDI2:SAE:0W-20

List in lower Table IV according to ACEA standard B4, the passing through of B5, C3 and VW limit value/failure mark.If VW 504/ 507 limit values are pass through, then remaining specification also by.

Table IV

Will be understood that and embodiment disclosed herein can be made multiple different improvement.Therefore, above Explanation should not be built as limiting, and be only used as the exemplary illustration of preferred implementation.Such as, as above and make For the function that performs for the best mode embodiment of the present invention for illustrative purposes only.Other arrangements and methods are permissible Made in the case of without departing substantially from scope and spirit of the present invention by those skilled in the art.Additionally, those skilled in the art Will be able to contemplate other deformation in scope and spirit.

Claims

1. lubricant oil composite, comprises:

A () gross weight based on lubricant oil composite meter, more than the base oil component of 65wt%, its motion at 100 DEG C is glued Degree (Kv) is 3.5 to 4.5 centistokes (cSt)；

(b) gross weight based on lubricant oil composite meter, at least one Mannich reaction products of 3.0wt% to 10wt%, its Prepared by the condensation of the substituted hydroxy aromatic compound of polyisobutyl group, aldehyde, aminoacid or its ester derivant and alkali metal base, Wherein, polyisobutyl group group derived from the polyisobutylene of the methylvinylidene isomer comprising at least 70wt% and has 400 To the number-average molecular weight of 2,500；With

C () is different from least one ashless dispersant of component (b)；

Wherein, the sulfur content that lubricant oil composite has is less than or equal to 0.30wt%, and phosphorus content is less than or equal to 0.09wt%, And sulfated ash content is less than or equal to 1.60wt%, measures according to ASTM D 874, based on lubricant oil composite total Weight meter；And further, wherein lubricant oil composite is that to meet the SAE J300 of in November, 2007 revision multistage for 0W-X The multigrade lubricating oil compositions of the specification of engine oils demand, wherein X is 20,30,40,50 or 60.

2. lubricant oil composite, comprises:

(a) gross weight based on lubricant oil composite meter, the first foundation oil ingredient of 50 to 65wt%, its fortune at 100 DEG C Kinetic viscosity (Kv) is 3.5 to 4.5 centistokes (cSt)；

(b) gross weight based on lubricant oil composite meter, second base oil component of 10 to 30wt%, its Kv at 100 DEG C Be 5.5 to 6.5cSt；

(c) gross weight based on lubricant oil composite meter, at least one Mannich reaction products of 1.5wt% to 10wt%, its Prepared by the condensation of the substituted hydroxy aromatic compound of polyisobutyl group, aldehyde, aminoacid or its ester derivant and alkali metal base, Wherein, polyisobutyl group group derived from the polyisobutylene of the methylvinylidene isomer comprising at least 70wt% and has 400 To the number-average molecular weight of 2,500；With

D () is different from least one ashless dispersant of component (c)；

Wherein, the sulfur content that lubricant oil composite has is less than or equal to 0.30wt%, and phosphorus content is less than or equal to 0.09wt%, And sulfated ash content is less than or equal to 1.60wt%, measures according to ASTM D 874, based on lubricant oil composite total Weight meter；And further, wherein lubricant oil composite is that to meet the SAE J300 of in November, 2007 revision multistage for 0W-X The multigrade lubricating oil compositions of the specification of engine oils demand, wherein X is 20,30,40,50 or 60；

Condition is, sulfated ash content gross weight based on the lubricant oil composite meter having when lubricant oil composite less than or During equal to 0.60wt%, there is at least 3.0wt% in Mannich reaction products gross weight based on lubricant oil composite meter.

3. the lubricant oil composite of claim 1 or 2, it is SAE 0W-20 multigrade lubricating oil compositions or the multistage profit of 0W-30 Sliding oil composition.

4. the lubricant oil composite of claim 1 or 2, sulfur content is 0.01wt% to 0.30wt%, and phosphorus content is 0.01wt% To 0.07wt%, and sulfated ash content is 0.10wt% to 0.8wt%, measures according to ASIM D 874, based on lubrication The gross weight meter of fluid composition.

5. the lubricant oil composite of claim 1, wherein base oil component is Group III base oil.

6. the lubricant oil composite of claim 1, gross weight meter based on lubricant oil composite, comprise 70wt%'s to 85wt% Base oil component, its Kv at 100 DEG C is 3.5 to 4.5cSt.

7. the lubricant oil composite of claim 1 or 2, wherein the polyisobutyl group base of the substituted hydroxy aromatic compound of polyisobutyl group Group is derived from the polyisobutylene comprising at least 90wt% methylvinylidene isomer.

8. the lubricant oil composite of claim 1 or 2, wherein the polyisobutyl group base of the substituted hydroxy aromatic compound of polyisobutyl group The number-average molecular weight of group is 500 to 2,500.

9. the lubricant oil composite of claim 1 or 2, wherein aldehyde is formaldehyde or paraformaldehyde, and alkali is alkali metal hydroxide, and And aminoacid is glycine.

10. the lubricant oil composite of claim 1 or 2, at least one of which Mannich reaction products has following formula

Wherein, each R independently be-CHR '-, wherein R ' is for have the branched of 1 to 10 carbon atom or linear alkyl, has 3 To the cycloalkyl of 10 carbon atoms, there is the aryl of 6 to 10 carbon atoms, there is the alkaryl of 7 to 20 carbon atoms, or tool There are the aralkyl of 7 to 20 atoms, R₁For polyisobutyl group group, derived from comprising at least 70wt% methylvinylidene isomer Polyisobutylene and number-average molecular weight be 400 to 2,500；

X is hydrogen, alkali metal ion or the alkyl with 1 to about 6 carbon atom；

W is-[CHR "]-_m, wherein each R " independently be H, there is the alkyl of 1 to 15 carbon atom or there is 1 to 10 carbon The replacement alkyl of atom, and one or more substituent group is selected from amino, acylamino-, benzyl, carboxyl, hydroxyl, hydroxy phenyl, miaow Oxazolyl, imino group, phenyl, sulfide base or sulfydryl；And m is the integer of 1 to 4；

Y is hydrogen, have the alkyl of 1 to 10 carbon atom ,-CHR ' OH, and wherein R ' is as defined above, or

Z is the hydroxyl phenylic group of hydroxyl, following formula:

Or

Wherein, R, R₁, Y ', X and W as defined above,

And n is the integer of 0 to 20, condition is as n=0, and Z is necessary for:

Wherein R, R₁, Y ', X and W as defined above.

The lubricant oil composite of 11. claim 1 or 2, at least one of which ashless dispersant is selected from polyalkylene succinic anhydride Ashless dispersant, unazotized ashless dispersant and the nitrogenous ashless dispersant of alkalescence.

The lubricant oil composite of 12. claim 1 or 2, the amount of at least one of which ashless dispersant be 0.1wt% extremely 10wt%, gross weight meter based on lubricant oil composite.

The lubricant oil composite of 13. claim 1 or 2, comprises one or more lube oil additives further, and it is selected from antioxygen Agent, detersive, antirust agent, fog remover, demulsifier, metal inactivator, friction modifiers, antiwear additive, pour-point depressant, disappear Infusion, cosolvent, the compatible agent of encapsulation, corrosion inhibitor, dyestuff, extreme pressure agent and mixture thereof.

The lubricant oil composite of 14. claim 1 or 2, it is heavy duty diesel engine lubricating oil composite.