CN110114447A

CN110114447A - Lubricating composition comprising N- alkylated diphenylamine

Info

Publication number: CN110114447A
Application number: CN201780080961.XA
Authority: CN
Inventors: J·J·汉索恩; 张琰湜
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2016-12-27
Filing date: 2017-12-13
Publication date: 2019-08-09
Also published as: DK3562921T3; WO2018125569A1; CA3046788A1; EP3562921A1; EP3562921B1; ES2914785T3; US20190367833A1

Abstract

Lubricating composition includes the oil with lubricant viscosity, N- alkylated diphenylamine compound and a) ashless antioxidant and b) at least one of high alkalinity calcium detersive.Ashless antioxidant can be selected from diarylamine antioxidant, phenol antioxidant and combinations thereof.Lubricating composition may include less than the phosphorus of 0.15 weight %.

Description

Lubricating composition comprising N- alkylated diphenylamine

Background

The exemplary implementation scheme is related to the additive for lubricating composition, and it was found that makees with N- alkylated diphenylamine It is the deposition kicker in internal combustion engine for improving the related specific application of sediment monitoring.

United States Patent (USP) No.3,779,923 describes alkylated methylene dianiline (MDA) tar as in lubricant compositions Antioxidant.The compound is formed with phosphorus base catalyst.

United States Patent (USP) No.8,242,066 describe the aniline compound that can be used as the ashless tbn sources of lubricant oil composite, The lubricant oil composite is compatible with fluoroelastomer engine sealing material.

United States Patent (USP) No.4,100,082；4200545；4,320,021 and 4,663,063；4,708.809 usually by amino Phenolic compounds is described as lube oil additive (such as dispersing agent/detersive).

A test for assessing deposit formation is " Standard Test Method for Determination of Moderately High Temperature Piston Deposits by Thermo-Oxidation Engine Oil Simulation Test-TEOST MHT, " ASTM D7097-09.MHT TEOST, it will be described herein by reference, and be a kind of Bench test, it is intended to the deposit of engine oil forms trend in ring belt and upper piston top area during prediction operation, It and is one of test method needed for defining API category identification engine oil in specification D 4485.

It has been found that some methylene-bisaniline compounds (MDA) improve the thermal oxidation in engine oil and improve thin Film inoxidizability.However, preparing high-performance enginer oil on MHT TEOST will affect the performance of other key areas.For example, A large amount of addition dispersing agents and detersive can viscosity performance to lubricating composition or sealing performance have a negative impact.

Preferably lubricating composition can be tested in the bench test with such as MHT TEOST in igniter motor and be provided Good sediment monitoring, while other performance characteristic being also provided.

It briefly describes

According to the one aspect of exemplary implementation scheme, lubricating composition includes the oil with lubricant viscosity, N- alkylation At least one of bisaniline compounds and oil and ashless antioxidant with lubricant viscosity and high alkalinity calcium detersive. Ashless antioxidant can be selected from diarylamine antioxidant, phenol antioxidant and combinations thereof.Lubricating composition includes to be less than The phosphorus of 0.15 weight %.

According to the another aspect of exemplary implementation scheme, a method of for reducing deposit formation in internal combustion engine, Including with the lubricating composition lubricating internal combustion engines.

According to the other side of exemplary implementation scheme, the method for forming lubricating composition includes forming N- alkylation two Aniline compound and by N- alkylated diphenylamine compound and oil and ashless antioxidant and high alkalinity with lubricant viscosity The combination of at least one of calcium detersive.Ashless antioxidant can be selected from diarylamine antioxidant, phenol antioxidant and its Combination.Lubricating composition includes the phosphorus less than 0.15 weight %.

In the various aspects of exemplary implementation scheme:

N- alkylated diphenylamine compound is alkylene coupling.

It is measured according to ASTM D-2896, lubricating composition has at least TBN of 4mg KOH/g.

N- alkylated diphenylamine includes that at least one is selected from cyclic alkyl, the N- alkyl of acyclic alkyl groups and combinations thereof.

N- alkyl is cyclohexyl.

N- alkylated diphenylamine is N, N'- alkylated diphenylamine compound.

N- alkylated diphenylamine compound be lubricating composition at least 0.10 weight % or lubricating composition at least 0.15 weight %, or at least 0.2 weight %, or at least 0.4 weight %.

N- alkylated diphenylamine compound is the at most 4.0 weight % of lubricating composition or at most 3 weights of lubricating composition Measure %, or at most 1.5 weight %, or at most 1.2 weight %.

N- alkylated diphenylamine compound indicates by structure I described below to IV and the formula of A1 to any of A8, And their mixture.

Alkylene is C₁-C₃Alkylidene.

N- alkylated diphenylamine compound is selected from 4,4'-2- ethylhexyl methylene dianiline (MDA), 4,4'- cyclohexylmethylenes Diphenylamines and its mixture.

Oil with lubricant viscosity is at least 40 weight % of lubricating composition.

Ashless antioxidant is at least 0.1 weight % of lubricating composition, or at least 0.2 weight %, or at least 0.4 weight Measure %, or the at most 4 weight % of at least 0.6 weight % or lubricating composition, or at most 1.2 weight %, or at most 1 weight %.

The ratio of ashless antioxidant and N- alkyl diphenyl amine compounds is 20:1 to 1:20.

Ashless antioxidant includes phenolic ester and diaryl amine.

Ashless antioxidant further includes olefine sulfide.

High alkalinity calcium detersive is selected from sulfonate, not the phenates of sulfur-bearing, the phenates of sulfur-bearing, salixarate, salicylate, Its mixture and its boration equivalent.

High alkalinity calcium detersive is to measure at least 2mg KOH/g total base number according to ASTM D-2896 to composition delivering (TBN) amount exists.

High alkalinity calcium detersive is at least 0.01 weight % or at least 0.1 weight % of lubricating composition, or at least 0.5 weight Measure %, or at most 3 weight %, or at most 2 weight %.

By weight, the ratio of calcium and magnesium is at least 9:10 in lubricating composition.

Lubricating composition also includes polyalkylene succinic acid imide dispersing agent, wherein the imido polyolefin tool of polyalkylene succinic There is at least 300 number-average molecular weight.

Lubricating composition also includes zinc dialkyl dithiophosphate.

Lubricating composition includes at least phosphorus of 0.02 weight %.

N- alkylated diphenylamine compound is the reaction product of at least one of diphenylamines and aldehyde and ketone.

It is described in detail

It is related to the method for lubricating composition and lubricating internal combustion engines in terms of exemplary implementation scheme.Lubricating composition includes N- Alkylated diphenylamine compound has in the oil and ashless antioxidant and calcium high alkaline detergent of lubricant viscosity at least It is a kind of.Ashless antioxidant can be selected from diarylamine antioxidant, phenol antioxidant and its mixture.Exemplary lubricating combination Object includes the phosphorus less than 0.15 weight %.

N- alkylated diphenylamine

In lubricating composition, exemplary N- alkylated diphenylamine compound improves deposition properties, such as passes through MHT TEOST Measurement, while good TBN being provided, without being formulated for heavy duty diesel engine (HD) and passenger vehicle engine application When have a negative impact to antioxygenic property and (in some cases, improve).For example, in testing, N, N'- dicyclohexyl methylene Base diphenylamines (Cy MDA) can provide the improvement of MHT TEOST in HD and passenger car preparation, while additionally aid anti-oxidant Performance, especially in the Daimler oxidation test in HD preparation.

In illustrative N- alkylated diphenylamine compound, two aromatic rings are alkylene couplings, for example, having C₁-C₃ Alkylene, especially alkylidene, such as methylene, ethylidene, methylmethylene, methyl ethylidene or dimethylmethylene.It can Easily to prepare N- alkylation methylene-bisaniline compounds.However, it is to be understood that it is also contemplated that other alkylene are coupled N- alkylated diphenylamine compound.

" N- alkylation " refers to that one or two amido and diphenylamines on aromatic ring of the alkyl by being connected to diphenylamines connect It connects.Each of these N- alkyl can be C₁-C₂₄Alkyl, such as C₃Or more advanced alkyl, and can be selected from acyclic Shape alkyl, cyclic alkyl and combinations thereof.In an exemplary embodiment, each amido of diphenylamines, which has, is no more than an alkane Base.Illustrative N- alkylation methylene dianiline (MDA) is N, and N- is alkylated methylene dianiline (MDA), and two of them amido is all by alkyl Change.

Illustrative N, N- alkylation methylene dianiline (MDA) contain the aromatic ring connected no more than two by alkylene.Although The method for generating N- alkylated diphenylamine compound may cause the structure with more than two aromatic rings by alkylene connection, but In an exemplary embodiment, these N- are alkylated the molar ratio of more aromatics aniline compounds Yu N- alkylated diphenylamine compound 1:10 can be not more than in lubricating composition.

N- be alkylated alkylene coupling bisaniline compounds can the formula as shown in structure I indicate:

Wherein R¹And R²Independently selected from, or at least 3, or at least 4, or at least 5 or at least six carbon atom, or at most 20, Or at most 12, or at most 10, or at most 8 carbon atoms,

R³And R⁴Alkyl independently selected from 1-6 carbon atom,

Each n is 0 to 3 or 0 to 2 or 0 to 1 or 0, and

X indicates alkylene, as described above, for example

-CH₂-。

In one embodiment, R¹And R²It independently is general formula form,

Wherein R⁵And R⁶Alkane independently selected from H and 1 to 20 carbon atom or 1 to 12 carbon atom or 1 to 8 carbon atom Base, and wherein R⁵And R⁶At least one of be not H or in which R⁵And R⁶It is formed together ring.In one embodiment, R⁵It is H or C₁-C₃Alkyl, R⁶It is C₂-C₈Alkyl or C₄-C₆Alkyl.In another embodiment, R⁵And R⁶It is formed together C₄-C₈Ring.

In one embodiment, N- alkylated diphenylamine compound is expressed from the next:

N- alkylated diphenylamine compound can be the 4,4'-N- alkylated diphenylamine compound being expressed from the next:

Suitable for R¹And R²General formula C_nH_2n+1Representative acyclic alkyl groups include straight chain and branched alkyl, such as methyl, Ethyl, n-propyl, normal-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Myristyl, cetyl, stearyl, eicosyl, docosyl, tetracosyl, 1- methyl-propyl, 2,2- dimethyl Propyl, isobutyl group, isopentyl, isohesyl, 2- ethylhexyl, different heptyl, 2- ethylheptyl, 2- propylheptyl, iso-octyl, 2- second Base octyl, 2- butyl octyl, 2- hexyl octyl, isodecyl, 2- butyl decyl, 2- hexyl decyl, 2- octyldodecyl, 2- oneself Base dodecyl, isotridecyl, 2- dodecyl cetyl, 2- decyl alkyl, 4- methyl -2- amyl, 2- 14 Alkyl octyl-decyl, monomethyl branch iso stearyl and its isomers and combination.In specific embodiments, acyclic alkyl groups The branching on second or more high-carbon, such as 2- ethylhexyl, 2- ethylheptyl, 2- ethyloctanyl etc..

Suitable for R¹And R²General formula C_nH_2n-1Representative naphthenic base include cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl And combinations thereof.

Suitable for R³And R⁴Representative alkyl include acyclic alkyl groups, such as methyl, ethyl, propyl, butyl, amyl, oneself Base and its mixture and isomers.In one embodiment, 0 n does not have R on aromatic ring³And R⁴Substituent group.

Exemplary N- alkylated diphenylamine compound includes the compound of formula A-1 to A-8:

In a particular embodiment, N- alkylated diphenylamine compound is selected from 4,4'-2- cyclohexylmethylene diphenylamines (CY-MDI) (formula A1) and 4,4'-2- ethylhexyl methylene dianiline (MDA) (EHL-MDI) (formula A2).

N- alkylated diphenylamine compound can be present in lubricating composition with the concentration of at least 0.1 weight %, can be down to More 5 weight %.For example, the concentration of compound can be at least 0.15 weight %, or at least 0.4 weight % of lubricating composition, Or at least 1.5 weight %, or at most 5.0 weight %, or at most 2.5 weight %.The compound can also with individualism or and its Its additive is present in concentrate together, and contains less amount of oil.In concentrate, the amount of the compound can be profit At least 2 times of concentration in sliding composition, or at least 3 times.

As used herein, TBN is according to ASTM D2896-15, Standard Test Method for Base Number of Petroleum Products by Potentiometric Perchloric Acid Titration,ASTM International, West Conshohocken, PA, 2011, DOI:10.1520/D2896-15 measurement.

In all fields, it being measured according to ASTM D2896, N- alkylated diphenylamine compound has at least 50mg KOH/g, Or the TBN of at least 100mg KOH/g.

In all fields, which has at least TBN.

Lubricating composition according to claim 1, wherein the composition has at least TBN of 4mgKOH/g, root It is measured according to ASTM D-2896.

N- alkylated diphenylamine compound especially has in terms of improving the deposition properties in the low lubricating composition of phosphorus content Effect.In exemplary lubricating composition, the phosphorus content of lubricating composition at most 0.15 weight %, such as at most 0.12 weight %, Or at most 0.11 weight %, or at most 0.08 weight %, or at most 0.05 weight %, or at most 0.04 weight %, or at most 0.02 weight %.The phosphorus content of lubricating composition can be at least 0.01 weight %, or at least 0.02 weight %, or at least 0.03 Weight %.Suitable additive for providing such low content phosphorus for lubricating composition includes zinc dialkyl dithiophosphate (ZDDP), as described below.

The method for preparing N- alkylated diphenylamine compound

Exemplary compounds can be prepared for example by diphenylamines, such as 4,4'- methylene dianiline (MDA), 2,4'- methylene two Aniline, 2,2'- methylene dianiline (MDA)s and their mixture.

In one embodiment, by making diphenylamines and one or more aldehydes or ketones with 1:2 or excess molar ratio in alcohol Reaction is in solvent (such as methanol or toluene) to prepare N- alkylated diphenylamine compound.

Aldehydes or ketones can have general formula:

Corresponding to R above¹And R², R⁵And R⁶At least one of be not H.

In one embodiment, aldehydes or ketones can be C₂-C₁₂Aldehydes or ketones, such as C₂-C₉Aldehyde or C₂-C₆Aldehyde or C₃-C₁₀ Ketone or C₃-C₇Ketone.

The ketone example that can be used to form the compound includes the methyl alkyl ketones and ethyl alkyl ketone of 3-12 carbon atom, Wherein alkyl can be alicyclic or cricoid.The example of this kind of ketone is methyl, ethyl, propyl, fourth including wherein moieties Base, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl and theirs is various different Those of configuration formula.The example of ketone includes acetone, 2- butanone, 2 pentanone, propione, 4- methyl -2- butanone, methyl-n-butyl ketone, 4- first Base-methyl-n-butyl ketone, 4- heptanone, 5 methy 12 hexanone, 5,6- dimethyl-methyl-n-butyl ketone, 5,5- dimethyl-methyl-n-butyl ketone, 4,5- diformazans Base-methyl-n-butyl ketone, 4- ethyl-methyl-n-butyl ketone, 5- ethyl-methyl-n-butyl ketone, 4,5,5- trimethyls-methyl-n-butyl ketone, 2-HEPTANONE, 3- heptanone, 5,5- Dimethyl -2-HEPTANONE, 4,5- dimethyl -2-HEPTANONE, 5- ethyl -2-HEPTANONE, 4- ethyl -2-HEPTANONE, methyln-hexyl ketone, 3- octanone, 4- Octanone, 6- methyl-methyln-hexyl ketone, 7,7- dimethyl-methyln-hexyl ketone, 6- methyl -3- octanone, 6- ethyl octanone, methyl n-heptyl ketone, 3- nonanone, 4- nonanone, butyl ketone, 2- decanone, 3- decanone, 4- decanone, 5- decanone, cyclobutanone, cyclopentanone, cyclohexanone, methyl-cyclohexyl ketone, second Base-cyclohexanone, cycloheptanone, cyclooctanone etc..

As example, 4,4'- methylene dianiline (MDA)s and aldehyde/ketone with 1:2 or excessive molar ratio suitable solvent (such as Toluene) in more than 100 DEG C at a temperature of react.Except the water formed in dereaction.Once reaction is completed, solvent is removed.It can be with By the way that product is re-dissolved in suitable solvent (such as methanol) and sodium borohydride is added come purified product.It pours the mixture into In water, product is extracted with ethyl acetate.Remove solvent, the product purified.Illustrative reaction scheme is shown in scheme 1:

Scheme 1:

Wherein R⁵And R⁶As described above.

N- alkylated diphenylamine compound can also by making methylene dianiline (MDA) and one or more aldehydes or ketones with 1:2 or Excess molar ratio is in hydrogen and hydrogenation catalyst such as platinum in methanol solvate, and palladium, (itself or carrying are suitably carrying for cobalt or nickel On body such as carbon) in the presence of reaction to prepare, such as such as United States Patent (USP) No.2,045,574 and 3, described in 779,923.

In general, reaction leads to each-NH₂Group it is monosubstituted, although there may be two a small amount of substituted compounds.

Lubricating composition can have lubrication viscous by the way that N- alkylated diphenylamine compound and ashless antioxidant to be added to In the oil of degree, optionally in the presence of other performance additive (as described below), or by the way that N- alkylation two will be used to form The reagent of aniline is added in the oil with lubricant viscosity to prepare.Lubricating composition can further comprise other performance addition Agent, such as antioxidant, dispersing agent in addition, antiwear additive and friction modifiers.The method for forming lubricating composition includes being formed N- alkylated diphenylamine compound is simultaneously ashless by N- alkylated diphenylamine compound and the oily and at least one with lubricant viscosity Antioxidant and/or the combination of high alkalinity calcium detersive, to provide comprising the lubricating composition less than 0.15 weight % phosphorus.

Ashless antioxidant

Lubricating composition may include one or more selected from diarylamine antioxidant, phenol antioxidant and its mixture Ashless antioxidant (AAO).AAO can be at least 0.2 weight %, for example, at least 0.3 weight %, or at most 5 weight %, or At most 2.5 weight %, or at most 2 weight %, or the concentration of at most 1 weight % are present in lubricating composition.AAO and N- alkyl The weight ratio of diphenylamines compound can be at least 1:20 or at most 20:1.

Exemplary phenol antioxidant for use in the present invention includes alkylated diphenylamine antioxidant, such as C₁-C₂₄It is single Alkylation, dialkylation and more alkylated diphenylamines, such as such as United States Patent (USP) No.2,943,112；4824601；5672752； 6204412；6315925；Described in 6,355,839 and U.S. Publication No.2015/0307803 and 2016/0017252.Especially have It is monoalkylation and dialkylated diphenylamine, wherein alkyl includes at least six carbon atom, and for example, at least 8, or at least 9 A carbon atom.

The exemplary phenol antioxidant that can be used includes bis- (1,1- the dimethyl-ethyI) -4- hydroxy-benzenepropanoic acids of 3,5- C₇-C₉Branched alkyl ester, 2-TBP, 2- tert-butyl-4-methyl-Phenol, 2- tert-butyl -5- methylphenol, 2,4- bis- Tert-butyl phenol, 2,4- dimethyl -6- tert-butyl phenols, 2- tert-butyl -4- metoxyphenol, 3- tert-butyl -4- methoxybenzene Phenol, 2,5- di-tert-butyl hydroquinones, 2,6- di-t-butyl -4- alkyl phenols, such as 2,6- DI-tert-butylphenol compounds, 2,6- di-t-butyls-fourth Base -4- methylphenol and 2,6- di-t-butyl -4- ethyl -phenol, 2,6- di-t-butyl -4- alkoxy phenols, such as tertiary fourth of 2,6- bis- Base -4- metoxyphenol and 2,6- di-t-butyl -4- thanatol, 3,5- di-tert-butyl-4-hydroxyl benzyl sulfydryl octyl second Acid esters, alkyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester such as n-octadecane base -3- (3,5- di-t-butyl -4- Hydroxy phenyl) propionic ester, normal-butyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester and 2'- ethylhexyl -3- (3,5- Di-tert-butyl-hydroxy phenyl) propionic ester, 2,6- di-t-butyls-alpha, alpha-dimethyl amino paracresol, 2,2'- di-2-ethylhexylphosphine oxides (4- alkane Base -6- tert-butyl phenol), such as 2,2'- di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenol, 2,2- di-2-ethylhexylphosphine oxides (4- ethyl -6- uncle Butylphenol), bisphenols, such as 4,4'- butylidenebis (3 methy 6 tert butyl phenol, 4,4'- di-2-ethylhexylphosphine oxides (2,6- bis- tertiary fourths Base phenol), 4,4'- bis- (2,6- DI-tert-butylphenol compounds), 2,2- (two p-hydroxybenzenes) propane, 2,2- bis- (3,5- di-t-butyls- 4- hydroxy phenyl) propane, 4,4'- cyclohexylidenes are bis- (2,6- tert-butyl phenol), bis- [3- (3, the 5- bis- tertiary fourths of hexamethylene glycol- Base -4- hydroxy phenyl) propionic ester], triethylene glycol is bis- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic ester], and 2,2'- Thio-[diethyl -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], 3,9- bis- { 1,1- dimethyl -2- [3- (uncles 3- Butyl -4- hydroxy-5-methyl base-phenyl) propionyloxy] ethyl } 2,4,8,10- tetra- oxaspiro [5,5] hendecanes, 4,4'- is thio Bis- (3 methy 6 tert butyl phenols) and 2,2'- thiobis (4,6- di-tert-butyl resorcin), such as four [methylene -3- of polyphenol (3,5- di-tert-butyl-hydroxy phenyl) propionic ester] methane, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) fourth Alkane, 1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, double-[3,3'- bis- (4'- hydroxyl -3'- uncles Butyl phenyl) butyric acid] glycol ester, 2- (3', 5'- di-tert-butyl-hydroxy phenyl) methyl -4- (2 ", 4 "-di-t-butyls - 3 "-hydroxy phenyls) methyl-6-tert-butylphenol and bis- (2'- hydroxyl -3'- tert-butyl -5'- the methylbenzyl) -4- methylbenzenes of 2,6- Phenol, p-tert-butylphenol-formaldehyde condensation products and p-tert-butylphenol-acetaldehyde condensation object.

Antioxidant based on phenol usually contains sec-butyl and/or tert-butyl as steric restriction group.Phenolic group group can be into One step is by alkyl (for example, linear or branched alkyl group) and/or is connected to the bridged group of the second aromatic group and replaces.

The example of specially suitable hindered phenol antioxidant include 2,6- DI-tert-butylphenol compounds, 4,4'- di-2-ethylhexylphosphine oxides-(2, 6- DI-tert-butylphenol compounds), 4- methyl -2,6- di-t-butyl phenol, 4- ethyl -2,6- DI-tert-butylphenol compounds, 4- propyl -2,6- DI-tert-butylphenol compounds, 4- butyl -2,6- DI-tert-butylphenol compounds, 4- dodecyl -2,6- DI-tert-butylphenol compounds, 2,2'- methylene Bis- (4- methyl-6-tert-butylphenols), 2,2'- methylene-bis(4-ethyl-6-t-butyl phenol)s, such as example in U.S. Publication No.2009/0111720；Described in 2010/0269774 and 2012/0103290.In one embodiment, hindered phenol antioxygen Agent can be ester, such as United States Patent (USP) No.No.6, those of described in 559,105, such as 3- (the tertiary fourth of 4- hydroxyl -3,5- bis- Base-phenyl) propionic acid alkyl alcohol ester.Hindered phenolic ester as a kind of is with Irganox^TML-135 is sold, and can be obtained from Ciba.

The phenol antioxidant being present in lubricating composition can be at least 0.1 weight % of lubricating composition, or extremely Few 0.5 weight %, or at least 1.5 weight %, or at least 2.5 weight %, and can with the at most 5 weight % of lubricating composition, Such as at most 4 weight %, or at most 3 weight %.

The example that can be used for the alkylated diphenylamine of this paper includes those of following general formula:

Wherein R⁷, R⁸, R⁹And R¹⁰It each is selected from H and C₈-C₂₄Or C₈-C₁₂Alkyl, and wherein R⁷, R⁸, R⁹And R¹⁰In extremely Few one is not H.In one embodiment, R⁸And R¹⁰(and optionally there are also R⁹) it is not H.The contraposition substitution of alkyl is common 's.

The example of alkylated diphenylamine includes dinonyldiphenylamine, nonyl diphenylamine, octyl diphenylamine, dioctyl hexichol Amine, dodecyl diphenylamine, decyl diphenylamine and their mixture.

The method for being used to prepare mono-alkylated diphenylamine is described in United States Patent (USP) No.5,672,752.Selectivity production p, The method of p '-dialkylated diphenylamine is described in U.S. Patent Publication No.2016/0017252.

Other exemplary diarylamine antioxidants include the alkylation nonox of general type:

Wherein R⁷, R⁸Respectively as defined above and R⁷And R⁸At least one of be not H.

The example for being alkylated nonox includes octyl, dioctyl, nonyl, dinonyl, decyl and dodecylphenyl naphthalene Amine, such as N- (dodecylphenyl) naphthalene -1- amine:

In one embodiment, the ratio of diaryl amine and N- alkyl diphenyl amine compounds is 20:1 to 1:20.

The alkylation diaryl amine being present in lubricating composition can be at least 0.1 weight % of lubricating composition, or At least 0.2 weight %, or at least 0.4 weight %, or at least 0.5 weight %, or at least 1.0 weight %, or at least 2.5 weights % is measured, and can be the at most 5 weight % of lubricating composition, such as at most 2.5 weight %, or at most 1.5 weight %.

Phenol can be used and/or be alkylated the mixture of diarylamine antioxidant.When using alkylation diaryl amine and When phenol antioxidant, the total amount of ashless antioxidant can be at least 0.1 weight % of lubricating composition, or at least 0.8 weight %, or at least 1.5 weight %, or at least 3 weight % are measured, and can be the at most 5 weight % of lubricating composition, such as at most 4 weight %, or at most 3.5 weight %.

High alkalinity calcium detersive

In one embodiment, lubricating composition includes one or more high alkalinity calcium detersives.In an embodiment party In case, lubricating composition includes alkaline-earth metal high alkaline detergent, and presenting in an amount at least sufficient to will measure extremely according to ASTM D-2896-15 Few 2mg KOH/g total base number (TBN) is delivered to lubricant.Composition.

High alkalinity calcium detersive can be selected from sulfonate, not the phenates of sulfur-bearing, the phenates of sulfur-bearing, salixarate, salicylic acid Salt and its mixture or its boration equivalent.High alkaline detergent can be acidified with boric acid agent such as Boric acid boron.

High alkalinity calcic detersive may also include " mixing " detersive formed with mixed surfactant system, described mixed Closing surfactant system includes phenates and/or sulfonate component, such as phenates/salicylate, sulfonate/phenates, and sulfonate/ Salicylate, sulfonate/phenates/salicylate, such as example, in United States Patent (USP) No.6,429,178；6429179；6153565； With 6,281,179 in describe.When using mixed sulfonate/phenate detergents, it is believed that mixing detersive is equal to difference Introduce the different phenates of same amount of phenates and sulfonate soap and the amount of sulfonate detergent.

The example of high alkalinity calcic detersive includes sulfonate, phenates (including sulfur-bearing and not the phenates of sulfur-bearing), The calcium salt of salixarate and salicylate.The total base number of this overbased sulfonate, salixarate, phenates and salicylate It can be 120 to 700 or 250 to 600 or 300 to 500 (based on oil-free).

High alkalinity calcium sulfonate, salixarate, phenates and salicylate usually have 120 to 700TBN total base number. The total base number of overbased sulfonate is usually 120 to 700 or 250 to 600 or 300 to 500 (based on oil-free).

" high alkalinity " refers to that calcium phase is more than the amount of stoichiometry for soap counter ion counterionsl gegenions (such as sulfonate radical).High alkalinity calcium is clear Net agent can have at least 3:1, or at least 4:1, or the metal of at least 6:1: counter ion counterionsl gegenions ratio.

The example of sulfonate detergent includes straight chain and branch-alkylbenzene sulfonate detersive and their mixture, It can have at least 8 metal ratio, as example the U.S. announces described in No.2005065045.Linear alkylbenzene (LAB) can have company The phenyl ring of any position on straight chain is connect, usually in 2,3 or 4 or their mixture.Linear alkylbenzene sulfonate (LAS) is clear Net agent can be used in particular for helping improve fuel economy.

In one embodiment, alkylbenzene sulfonate detersive can be branch-alkylbenzene sulfonate, linear alkylbenzene (LAB) Or mixtures thereof sulfonate,.

In one embodiment, lubricating composition can be free of linear alkylbenzene sulfonate (LAS) detersive.Sulfonate is peace and quiet Agent can be the calcium salt of one or more oil-soluble alkyl toluene sulfonate compounds, such as U.S. Patent Publication It is disclosed described in No.20080119378.

Lubricating composition may include at least 0.01 weight % or at least 0.1 weight %, or the high alkalinity of at least 0.5 weight % Calcium detersive, in some embodiments, at most 3 weight %, or the high alkalinity calcium detersive of at most 2 weight %.

Oil with lubricant viscosity

Lubricating composition may include having the oil of lubricant viscosity as its accessory constituent or main component, such as lubricating combination At least 5 weight % of object, or at least 10 weight %, or at least 20 weight %, or at least 30 weight %, or at least 40 weight %, Or at least 60 weight %, or at least 80 weight %, or at most 98 weight %, or at most 95 weight %.

It is existing with lubricant viscosity oil amount usually can be from 100 weight % subtract compound as described above and Remaining surplus after the amount of antioxidant and the summation of any other performance additive.

Suitable oil includes natural and synthetic oil, and derived from being hydrocracked, the oil of hydrogenation and hydrofinishing is not refined, essence System, or mixtures thereof rerefined oils.It does not refine, the oil for refining and re-refining, and natural and synthetic oil is described in such as WO 2008/147704 and the U.S. announce No. 2010/197536.Synthetic oil can also be prepared by Fischer-Tropsch reaction, and usually may be used To be the fischer-tropsch hydrocarbon or wax of hydroisomerization.Oil can pass through Fischer-Tropsch gas-liquid systhesis program and other gas- The preparation of liquid program.

Oil with lubricant viscosity can also be defined as in April, 2008 version " Appendix E-API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils ", specified in 1.3 knot titles 1.3 " Base Stock Categories ".API Guide also in United States Patent (USP) No.7, It is summarized in 285,516.Five kinds of base oil groups are as follows: group I (sulfur content>0.03 weight %, and/or<90 weight % saturation Object, viscosity index (VI) 80-120)；Group II (sulfur content<0.03 weight %, and>90 weight % saturates, viscosity index (VI) 80-120)； Group III (sulfur content<0.03 weight %, and>90 weight % saturates, viscosity index (VI)>120)；Group IV (all poly alpha olefins (PAOs))；With a group V (every other to be not included in I, II, III or IV group in).The exemplary oil packet with lubricant viscosity API group I is included, II is organized, organizes III, organizes or mixtures thereof IV, group V oil.In some embodiments, the oil with lubricant viscosity is Or mixtures thereof API group I organizes II, organizes III, or group IV oil,.In some embodiments, the oil with lubricant viscosity is API Or mixtures thereof group I organizes II, or group III oil,.In one embodiment, the oil with lubricant viscosity can be API group II, Or mixtures thereof group III mineral oil, organizes IV synthetic oil,.In some embodiments, at least 5 weight % of lubricating composition, or At least 10 weight %, or at least 20 weight %, or at least 40 weight % are poly alpha olefin (Group IV).

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

Kinematic viscosity of the oil at 100 DEG C with lubricant viscosity can at most 12mm²/ s or at most 8mm²/ s (cSt), and It can be at least 12mm at 100 DEG C²/ s, and at least 3.5mm in other embodiments²/s.As used herein, kinematic viscosity exists Pass through ASTM D445-14, Standard Test Method for Kinematic Viscosity of at 100 DEG C Transparent and Opaque Liquids(and Calculation of Dynamic Viscosity),”ASTM International, West Conshohocken, PA, 2003, DOI:10.1520/D0445-14 is determined, is properly termed as KV_ 100。

The viscosity grade of oil depends on final use.For passenger car and diesel engine, viscosity grade can be SAE- 5W-30, SAE 10W-30 or SAE 15W-40.Base oil can be two or more fractions with different oligomer distributions Mixture.Fraction rich in lower oligomers is usually mixed with the fraction rich in higher oligomers, with oligomeric needed for acquisition Object distribution.However, generating, there is any group of subassembly of the compound of required oligomer distribution to be all acceptable.For this The fraction of blending can be the different distillation fractions from same procedure, or can obtain from entirely different oligomerization process. Single fraction can be used for producing different multi-grade oils, for example, SAE 10W-30 and SAE15W-40 oil.What is obtained after blending is compound Object can hydrogenate or various fractions can hydrogenate before mixing.

For two-stroke marine diesel engine, viscosity grade can be SAE-40 to SAE-60, correspond to 12.5 to 26mm²The KV_100 of/s.For example, the KV_100 of SAE-50 grades of oil is 16.3-21.9mm²/s.Start for two-stroke marine diesel oil The cylinder oil of machine can be configured to realize 19 to 21.5mm²The KV_100 of/s.The viscosity can pass through additive and base oil Mixture obtains, such as contains a group I mineral base oil, such as neutral flux (such as 500NS or 600NS) and BrightStock Base oil.Any other combination of the base oil of mineral or synthetic base oil or plant origin can be used, it is mixed with additive It closes, there is the viscosity compatible with 50 grade of SAE.

As an example, the oil formulation for being suitable as the lubricant cylinder of low speed two-stroke marine diesel engine contains Group I base oil (bottoms, the KV_100 28-32mm of the BSS type of 18 to 25 weight %²/ s, the density at 15 DEG C are 895-915kg/m³) and the group I base oil of 600 type of SN of 50-60 weight % (distillate, density at 15 DEG C are 880- 900kg/m³, KV_100 is about 12mm²/s)。

In certain embodiments, lubricating composition can contain synthetic ester base fluid.Synthetic ester can have to be measured at 100 DEG C 2.5mm²/ s to 30mm²The kinematic viscosity of/s.In one embodiment, lubricating composition includes the KV_ less than 50 weight % 100 be at least 5.5mm²/ s, or at least 6mm²/ s, or at least 8mm²The synthetic ester base fluid of/s.

Exemplary synthetic oil includes poly-alpha olefins, polyester, polyacrylate and polymethacrylates and its copolymer. The example of synthetic ester includes dicarboxylic acids (for example, being selected from phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic, horse Come sour, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid and alkene Propylmalonic acid) and alcohol (for example, selected from butanol, hexanol, dodecanol, 2-Ethylhexyl Alcohol, ethylene glycol, diethylene glycol monoether and third Glycol) ester.The specific example of these esters includes dibutyl adipate, and decanedioic acid two (2- ethylhexyl) ester, fumaric acid two is just Own ester, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, phthalic acid two Last of the ten Heavenly stems ester, decanedioic acid docosane base ester, linoleic acid 2- ethyl hexyl diester dimer, and by making 1 mole of decanedioic acid and 2 mole four Glycol and 2 moles of 2 ethyl hexanoic acids react the complex ester to be formed.

The ester that can be used as synthetic oil further includes by C₅To C₁₂Monocarboxylic acid and polyalcohol and polyol ethers such as neopentyl glycol, three Ester made of hydroxymethyl-propane, pentaerythrite, dipentaerythritol and tripentaerythritol.Ester is also possible to monoesters, such as with commodity Name Priolube 1976^TM(C₁₈Alkyl-COO-C₂₀Alkyl) it obtains.

Synthetic ester base oil can be less than 50 weight % of composition, or less than 40 weight %, or less than 35 weight %, Or less than 28 weight %, or less than 21 weight %, or less than 17 weight %, or less than 10 weight %, or less than 5 weights of composition The amount of amount % is present in lubricating composition.In one embodiment, lubricating composition is free or substantially free of KV_100 It is at least 5.5mm²The synthetic ester base fluid of/s.

The example of natural oil includes animal and plant oil, such as long-chain fatty acid ester.Example includes linseed oil, sunflower Oil, sesame seed oil, tallow oil, lard, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil (soybean Oil), olive oil, whale oil, herring oil, pilchard oil, coconut oil, palm-kernel oil, babassu oil, rapeseed oil and soybean oil (soya oil)。

The amount of the existing oil with lubricant viscosity is usually that exemplary N- alkylation methylene two is subtracted from 100 weight % Remaining surplus after the total amount of aniline compound and other performance additive.

Other performance additives

Other than exemplary N- alkylated diphenylamine compound disclosed herein, lubricating composition also may include it is a kind of or A variety of performance additives additionally below: antioxidant (is different from above-mentioned), dispersing agent, viscosity modifier, wear-resistant/anti scuffing Reagent, matal deactivator, friction modifiers, extreme pressure agent, foam in hibitors, demulsifier, pour-point depressant, corrosion inhibitor are close Seal sweller, TBN kicker etc..Other performance additive is suitably adapted for providing the performance for the lubricating composition prepared completely Characteristic, such as passenger car or HD engine lubricant.

A. detersive

Other than high alkalinity calcium detersive discussed above, lubricating composition is also optionally comprising at least one peace and quiet Agent.Exemplary detersive for use in the present invention includes overbased metal-containing detergents, and wherein metal is not calcium.

Metal containing metal detergent can be zinc, sodium, barium or magnesium.In one embodiment, lubricating composition includes Alkaline-earth metal high alkaline detergent presents in an amount at least sufficient at least 2mg KOH/g total base number that will be measured according to ASTM D-2896-15 (TBN) it is delivered to lubricating composition.

Overbased metal-containing detergents can be selected from sulfonate, not the phenates of sulfur-bearing, the phenates of sulfur-bearing, salixarate, water Poplar hydrochlorate and its mixture or its boration equivalent.High alkaline detergent can be acidified with boric acid agent such as Boric acid boron.

Overbased metal-containing detergents may also include " mixing " detersive formed by mixed surfactant system, described Mixed surfactant system includes phenates and/or sulfonate component, such as phenates/salicylate, sulfonate/phenates, sulfonic acid Salt/salicylate, sulfonate/phenates/salicylate, such as example, in United States Patent (USP) No.6,429,178；6,429,179；6, Described in 153,565 and 6,281,179.When using mixed sulfonate/phenate detergents, it is believed that mixing detersive etc. It is same as introducing the different phenates of same amount of phenates and sulfonate soap and the amount of sulfonate detergent respectively.

The example of overbased metal-containing detergents includes sulfonate, phenates (including sulfur-bearing and not the phenates of sulfur-bearing), The zinc salt of salixarate and salicylate, sodium salt and magnesium salts.This overbased sulfonate, salixarate, phenates and bigcatkin willow The total base number of hydrochlorate can be 120 to 700 or 250 to 600 or 300 to 500 (based on oil-free).

In general, overbased metal-containing detergents can be sulfonate, phenates, sulfur-bearing phenates, salixarate or salicylic acid The zinc salt of salt, sodium salt or magnesium salts.The total base number of overbased sulfonate, salixarate, phenates and salicylate be usually 120 to 700TBN.The total base number of overbased sulfonate is usually 120 to 700 or 250 to 600 or 300 to 500 (based on oil-free).

Overbased metal-containing detergents can be alkali or alkaline earth metal salt.In one embodiment, high alkalinity is clear Net agent can be phenates, sulfur-bearing phenates, sulfonate, the sodium salt of salixarate and salicylate, calcium salt, magnesium salts or its mixing Object.In one embodiment, high alkaline detergent is or mixtures thereof calcium detersive, magnesium detersive.In an embodiment In, high alkalinity calcium detersive can with to lubricating composition deliver at least 500 weight ppm calcium and be no more than 3000 weight ppm calcium, Or at least 1000 weight ppm calcium, or at least 2000 weight ppm calcium, or exist no more than the amount of 2500 weight ppm calcium.One In a embodiment, high alkaline detergent can be to be no more than the magnesium of 500 weight ppm to lubricating composition delivering, or is no more than 330 weight ppm, or it is no more than 125 weight ppm, or the amount presence no more than 45 weight ppm.In one embodiment, it lubricates Composition is substantially free of (i.e. containing the magnesium generated less than 10ppm) by high alkaline detergent.In one embodiment, high-alkali Property detersive can be to deliver at least 200 weight ppm magnesium, or at least 450 weight ppm magnesium, or at least 700 weights to lubricating composition The amount for measuring ppm magnesium exists.In one embodiment, the detersive of calcic and magnesium may be present in lubricating composition.It can be with There are calcium and magnesium detersive, so that the weight ratio of calcium and magnesium is 10:1 to 1:10 or 8:3 to 4:5 or 1:1 to 1:3.At one In embodiment, high alkaline detergent is free of or is substantially free of sodium.

Overbased sulfonate detergents can have 12 to less than 20 or 12 to 18 or 20 to 30 or 22 to 25 metal Than.

In one embodiment, lubricating composition can be free of linear alkylbenzene sulfonate (LAS) detersive.Sulfonate is peace and quiet Agent can be the metal salt of one or more oil-soluble alkyl toluene sulfonate compounds, such as U.S. Patent Publication Described in No. 20080119378.

Lubricating composition may include at least 0.01 weight %, or the detersive of at least 0.1 weight %.In some embodiments In, the at most detersive of 2 weight %, or the detersive of at most 1 weight %.

B. antioxidant

Other than AAO listed above, lubricating composition is optionally also comprising at least one antioxidant.It can be used for this hair Bright exemplary antioxidants include olefine sulfide.It includes propylene, fourth that the example to form the suitable alkene of olefine sulfide, which can be vulcanized, Alkene, isobutene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene, endecatylene, tridecylene, Tetradecene, pentadecane alkene, hexadecene, heptadecene, octadecene, 19 carbenes, eicosylene and its mixture.One In a embodiment, hexadecene, heptadecene, octadecene, 19 carbenes, or mixtures thereof eicosylene and its dimerization Object, trimer and tetramer are particularly useful alkene.

Alternatively, alkene can be the Diels-Alder adduct and beta-unsaturated esters of diene such as 1,3-butadiene, such as acrylic acid Butyl ester.Another kind of olefine sulfide includes fitter acids and its ester.Fatty acid is usually obtained from vegetable oil or animal oil；It usually contains 4 to 22 carbon atoms.The example of suitable fitter acids and its ester includes triglycerides, oleic acid, linoleic acid, palmitoleic acid and its mixed Close object.Fatty acid can be from lard, tall oil, peanut oil, soybean oil, cottonseed oil, obtains in or mixtures thereof sunflower oil.? In one embodiment, fatty acid and/or ester and olefin.When it is present, lubricating composition may include at least 0.1 weight % Or at least 0.5 weight %, or at least 1 weight % antioxidant, in some embodiments, at most 3 weight %, or at most 2.75 Weight %, or at most 2.5 weight %, or at most 1.2 weight % these additional antioxidants.

C. dispersing agent

Lubricating composition optionally also includes at least one dispersing agent in addition to exemplary compounds.Exemplary dispersing agent packet Succinimide dispersants, Mannich dispersant, succinamide dispersing agent and polyalkylene succinic acid esters, amide and ester-acid amide are included, And their mixture.

Succinimide dispersants can be derived from or mixtures thereof aliphatic polyamines.It is more that aliphatic polyamines can be ethylidene Or mixtures thereof amine, propylidene polyamines, butylidene polyamines,.In one embodiment, it is more to can be ethylidene for aliphatic polyamines Amine.In one embodiment, aliphatic polyamines can be selected from ethylenediamine, diethylenetriamines, trien, four ethylidene five Amine, penten, polyamines stillage bottom and its mixture.

In one embodiment, dispersing agent can be polyalkylene succinic acid esters, amide or ester-acid amide.Polyalkylene succinic Acid ester-amide can be the polyisobutylene succinic acid reacted with alcohol as described above (such as pentaerythrite) and polyamines.Polyolefin amber The example of amber acid esters includes the polyisobutylene succinic acid ester and its mixture of pentaerythrite.

Dispersing agent can be the long chain alkenyl succinimides of N- substitution.The reality of N- substitution long chain alkene base succinimide Example is polyisobutenyl succinimide.In general, the number-average molecular weight of the polyisobutene of derivative polyisobutylene succinic anhydride is at least 300, or at least 350, or at least 500, or at least 550, or at least 750, and can at most 5000, or at most 3000, or at most 2500.This succinimide can be formed by such as high vinylidene polyisobutylenes and maleic anhydride.Succinimide dispersion Agent and its preparation are disclosed in, for example, United States Patent (USP) No.3,172,892；3,219,666；3,316,177；3,340,281；3, 351,552；3,381,022；3,433,744；3,444,170；3,467,668；3,501,405；3,542,680；3,576, 743；3,632,511；4,234,435；Re 26,433 and 6,165,235 and 7,238,650 and EP patent application 0 355 895 A。

Exemplary dispersing agent can also be post-processed by being reacted with any various reagents by conventional method.Its Middle organic boron compound (such as boric acid), urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid such as terephthalic acid (TPA), hydrocarbon Substituted succinic anhydride, maleic anhydride, nitrile, epoxides and phosphorus compound.In one embodiment, post-treated dispersion Agent is boration.In one embodiment, post-treated dispersing agent is reacted with dimercaptothiodiazole.In an embodiment party In case, post-treated dispersing agent is reacted with phosphoric acid or phosphorous acid.In one embodiment, post-treated dispersing agent with it is right Phthalic acid and acid reaction (as described in US publication 2009/0054278).

Dispersant viscosity modifiers (DVM) are to provide the dispersing agent of dispersibility and viscosity modifier.Example DVM is by polymer system At the polymer such as olefin polymer (for example, ethylene propylene copolymer) and/or vinylaromatic polymer are (for example, poly- Styrene), used ethylenic unsaturated carboxylic acid material (such as with one or more amine and/or have sulfonate functional groups The functionalized maleic anhydride of side functional group) carried out free radical grafting.For example, in United States Patent (USP) No.4,863,623；5, 264,140；5,409,623；6,107,257；6,107,258；6117825；U.S. Publication No.2012/0178656；2012/ 0178659；This DVM is disclosed in 2009/0305923 and WO 2016044262.

When it is present, lubricating composition may include at least 0.01 weight %, or at least 0.1 weight %, or at least 0.5 weight %, or the dispersing agent of at least 1 weight % are measured, in some embodiments, at most 20 weight %, or at most 15 weight %, or extremely More 10 weight %, or the dispersing agent of at most 6 weight % or at most 3 weight %.

D. antiwear additive

Lubricating composition is optionally also comprising at least one antiwear additive.The example for being suitable for the invention suitable antiwear additive includes Titanium compound, tartrate, tartrimide, the oil-soluble amine salt of phosphorus compound, olefine sulfide, metal dihydrocarbyl dithiophosphate phosphorus Hydrochlorate (such as zinc dialkyl dithiophosphate (ZDDP)), phosphite ester (such as dibutyl phosphite), phosphonate ester, first containing sulfo-amino The compound of acid esters, such as thiocarbamate, thiocarbamate amide, thiocarbamate, alkylidene coupling Thiocarbamate and bis- (S- alkyl Dithiocarbamyl) disulphide.In one embodiment, antiwear additive can To include tartrate or tartrimide, such as U.S. Patent Publication No.2006/0079413；2006/0183647；With 2010/ Described in 0081592.Tartrate or tartrimide can contain alkyl group, and wherein the total number of carbon atoms on alkyl is At least 8.In one embodiment, antiwear additive may include citrate, in U.S. Patent Publication No.20050198894 It is disclosed.

When it is present, lubricating composition may include at least 0.01 weight %, or at least 0.1 weight %, or at least 0.5 weight The antiwear additive of % is measured, and in some embodiments, at most 3 weight %, or at most 1.5 weight %, or at most 0.9 weight % Antiwear additive.

In one embodiment, lubricating composition is free or substantially free of phosphorous antiwear additive.For example, phosphorous wear-resistant Agent, if any, its amount makes lubricating composition have the phosphorus no more than 0.15 weight %, or at most 1.1 weight % Phosphorus, or the phosphorus of at most 0.8 weight %.For example, the secondary ZDDP of C3/6 mixing can exist at most 1.2 weight %, or at most 1 weight Measure %, or at most 0.5 weight %.

E. oil-soluble titanium

Lubricating composition may include one or more oil-soluble titaniums, can be used as antiwear additive, and friction modifiers resist Oxidant, one or more of sediment monitoring additive or these functions.The example of oil-soluble titanium is disclosed in the U.S. The patent No. 7,727,943 and US publication the 2006/0014651st.The example of oil-soluble titanium includes titanium (IV) alcohol Salt, such as isopropyl titanate (IV) and 2-Ethylhexyl Alcohol titanium (IV).These alkoxide can be by monohydric alcohol, ortho position 1,2- glycol, polyalcohol Or mixtures thereof formed.Unitary alkoxide can have 2 to 16 or 3 to 10 carbon atoms.In one embodiment, titanium compound packet The alkoxide of the glycol of 1,2- containing ortho position or polyalcohol.1,2- vicinal diols include the fatty-acid monoester of glycerol, and wherein fatty acid can be with It is such as oleic acid.Other exemplary oil-soluble titaniums include titanium carboxylate, such as neodecanoic acid titanium.

When being present in lubricating composition, a part of the amount comprising oil-soluble titanium as antiwear additive.

F. extreme pressure (EP) agent

Lubricating composition may include extreme pressure agent.The example of oil-soluble extreme pressure agent includes the EP agent of sulfur-bearing and the sulphur containing chlorine, The CS of dimercaptothiodiazole or dispersing agent₂Derivative (usually succinimide dispersants), the derivative of chlorinated hydrocabon EP reagent With phosphorus EP reagent.The example of this EP agent includes chlorinated wax；Olefine sulfide (such as sulfide isobutene), 2,5-, bis- mercapto that alkyl replaces Base -1,3,4- thiadiazoles and its oligomer, organic sulfur compound and polysulfide, such as dibenzyldisulfide, double-(chlorobenzyl) two Sulfide, dibutyl tetrasulphide vulcanize methyl oleate, sulfenyl phenolate, sulfurized dipentene, vulcanization terpenes and vulcanization Diels- Alder adduct；Phosphosulfurized hydrocarbon, such as the reaction product of phosphoric sulfide and turpentine oil or methyl oleate；Phosphate, such as two hydrocarbon and three hydrocarbon Phosphite ester, such as dibutyl phosphite, two heptyl ester of phosphorous acid, phosphorous acid dicyclohexyl maleate, phosphorous acid amyl phenyl ester；Phosphorous acid diamyl The phosphite that base phenyl ester, phosphorous acid tridecane base ester, phosphorous acid distearyl base ester and propylidene replace；Metal thiophosphate ammonia Base formates, such as dioctyl zinc dithiocarbamate and heptylphenol diacid barium；The amine salt of alkyl and Acidic phosphates spreads out Biology, the amine salt of the reaction product including such as dialkyl dithiophosphoric acid and propylene oxide, then further with P₂O₅Reaction； And its mixture.Some useful extreme pressure agents are described in United States Patent (USP) No.3,197,405.

When it is present, lubricating composition may include at least 0.01 weight %, or at least 0.1 weight %, or at least 0.5 weight The extreme pressure agent of % is measured, in some embodiments, at most 3 weight %, or at most 1.5 weight %, or the pole of at most 0.9 weight % Press agent.

G. foam in hibitors

Lubricating composition may include foam in hibitors.The foam in hibitors that can be used for lubricant compositions includes poly- silicon oxygen Alkane；The copolymer of ethyl acrylate and 2-EHA and optional vinyl acetate；Demulsifier, including the poly- silicon of fluorination Oxygen alkane, trialkylphosphate, polyethylene glycol, polyethylene oxide, polypropylene oxide and (epoxy ethane-epoxy propane) polymer.

H. viscosity modifier

Lubricating composition may include viscosity modifier.It can be used for the viscosity modifier of lubricant compositions (otherwise referred to as Viscosity index improver or viscosity improver) it is usually polymer, including polyisobutene, polymethacrylates (PMA) and poly- Methacrylate, diene polymer, alkyl styrenes are esterified styrene-maleic anhydride copolymer, hydrogenation alkenyl virtue Hydrocarbon-conjugated diene copolymer and polyolefin (also referred to as olefin copolymer or OCP).PMA is by the metering system with different alkyl It is prepared by the mixture of acid ester monomer.Alkyl can be the linear chain or branched chain group containing 1-18 carbon atom.Most of PMA are viscous Spend regulator and pour-point depressant.In one embodiment, viscosity modifier is comprising ethylene and one or more advanced The polyolefin of alkene such as propylene.

When it is present, lubricating composition may include at least 0.01 weight %, or at least 0.1 weight %, or at least 0.3 weight %, or the polymeric viscosity modifiers of at least 0.5 weight % are measured, and in some embodiments, at most 10 weight %, or extremely More 5 weight %, or the polymeric viscosity modifiers of at most 2.5 weight %.

I. corrosion inhibitor and matal deactivator

Lubricating composition may include corrosion inhibitor.It can be used for corrosion inhibitor/metallic blunt of exemplary lubricating composition Agent includes fatty amine, octylame caprylate, the condensation product of dodecenyl-succinic acid or acid anhydrides and fatty acid such as oleic acid and polyamines, The derivative (for example, tolyl-triazole) of benzotriazole, 1,2,4- triazole, benzimidazole, two Thiobenzimidazole of 2- alkyl and The thio benzothiazole of 2- alkyl two.

J. pour-point depressant

Lubricating composition may include pour-point depressant.The pour-point depressant that can be used for exemplary lubricating composition includes poly- α- Alkene, the ester of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylate and polyacrylamide.

K. friction modifiers

Lubricating composition may include friction modifiers.The friction modifiers that can be used for exemplary lubricating composition include fat The condensation product and alkyl phosphorus of acid derivative, such as amine, ester, epoxides, fatty imidazolines, carboxylic acid and polyalkylene-polyamine The amine salt of acid.Friction modifiers can be Ashless friction modifying agent.This friction modifiers are that those are being subjected to ASTM D 874 Those of any sulfate ash is not generated when condition usually (referring to ASTM D874-13a, " Standard Test Method For Sulfated Ash from Lubricating Oils and Additives ", ASTM International, West Conshohocken, PA, 2013).If additive does not provide tenor to lubricant compositions, it is called " without gold Belong to ".As used herein, term " fatty alkyl " related with friction modifiers or " fat " refer to 8 to 30 carbon atoms Carbochain, usually linear carbon chain.

The amount of ashless point of friction modifiers can be 0.1 to 3 weight % (or 0.12 to 1.2 or 0.15 to 0.8 in lubricant Weight %).The material can also separately exist in concentrate, or exist together with other additives, and contain small amount Oil.In concentrate, the amount of material can be 2 to 10 times of above-mentioned concentration amount.

In one embodiment, Ashless friction modifying agent can be expressed from the next:

Wherein D and D' is independently selected from-O-, > NH, > NR²³, by the way that D and D' group is formed together and in two > C=O R is formed between group²¹The imide group that-N < group is formed；E is selected from-R²⁴-O-R²⁵, > CH₂, > CHR²⁶, > CR²⁶R²⁷, > C (OH)(CO₂R²²), > C (CO₂R²²)₂With > CHOR²⁸；Wherein R²⁴And R²⁵Independently selected from > CH₂, > CHR²⁶, > CR²⁶R²⁷, > C (OH) (CO₂R²²) and > CHOR²⁸；Q is 0 to 10, and condition is as q=1, and E is not > CH₂, and as n=2, two E are not all > CH₂； P is 0 or 1；R²¹It independently is hydrogen or alkyl, usually contains 1 to 150 carbon atom, condition is to work as R²¹When for hydrogen, p 0, q is big In or equal to 1；R²²It is alkyl, usually contains 1-150 carbon atom；R²³, R²⁴, R²⁵, R²⁶And R²⁷It independently is alkyl；R²⁸For hydrogen Or alkyl, contain 1 to 150 carbon atom or 4 to 32 carbon atoms or 8 to 24 carbon atoms.In certain embodiments, hydrocarbon Base R²³, R²⁴And R²⁵It can be the alkyl of straight chain or mainly straight chain.

In certain embodiments, Ashless friction modifying agent is the fatty ester of various hydroxycarboxylic acids, amide or acid imide, example Such as tartaric acid, malolactic acid, glycolic and mandelic acid.The example of suitable material includes tartaric acid two (2- ethylhexyl) ester (i.e. tartaric acid two (2- ethylhexyl) ester), two (C₈-C₁₀) tartrate, two (C_12-15) tartrate, two oil base tartrates, Oil base tartrimide and oil base maleimide.

In certain embodiments, Ashless friction modifying agent can be selected from amine, the long-chain rouge of fatty ester or fat epoxide Pipecolic acid derivative；Fatty imidazolines, such as the condensation product of carboxylic acid and polyalkylene polyamine；The amine salt of alkyl phosphoric acid；Tartaric acid rouge Fat Arrcostab；Fatty alkyl tartrimide；Fatty alkyl tartramide；Fatty phosphonate ester；Fatty phosphites；Boration phosphorus Rouge, borated fatty epoxides；Glyceride；Borated glycerol esters；Fatty amine；Alkoxylated fats amine；Boration alkoxy Change fatty amine；Hydroxyl and polyhydroxy fatty amine, including tert-hydroxyl fatty amine；Hydroxyalkyl amide；Fatty acid metal salts；Alkylated salicylamide The metal salt of hydrochlorate；Fatty oxazoline；Fatty ethoxylated alcohol；The condensation product of carboxylic acid and polyalkylenepolyamines；Or come from rouge The reaction product of fat carboxylic acid and guanidine, aminoguanidine, urea or thiocarbamide and its salt.

Friction modifiers may also include such as sulfurized fatty compound and alkene, the sunflower oil of polyalcohol and aliphatic carboxylic acid Or the material of soya-bean oil monoester.

In another embodiment, friction modifiers can be long-chain fatty acid ester.In another embodiment, long Chain fatty acid ester can be monoesters, and in another embodiment, long-chain fatty acid ester can be triglycerides.

Molybdenum compound is also referred to as friction modifiers.Illustrative molybdenum compound is without dithiocarbamate part or matches Body.

Nitrogenous molybdenum material includes molybdenum-amine compounds, fatty described in 329,327, and by molybdenum source such as United States Patent (USP) No.6 The organic molybdenum of oil and diamine reactant preparation, such as United States Patent (USP) No.6, described in 914,037.Other molybdenum compounds disclose In US publication No.20080280795.By making the compound containing sexavalence molybdenum atom and formula NR²⁹R³⁰R³¹The primary of expression, Secondary or reactive tertiary amine, available molybdenum amine compounds, wherein R²⁹, R³⁰And R³¹It is each independently hydrogen or 1-32 carbon atom Alkyl, and wherein R²⁹, R³⁰And R³¹At least one of be alkyl with 4 or more carbon atoms or be expressed from the next:

Wherein R³²The chain alkylene with 10 or more carbon atoms is represented, s is 0 or 1, R³³And/or R³⁴Represent hydrogen original Son, alkyl, chain triacontanol base or the alkyl amino with 2-4 carbon atom, and as s=0, R³³And R³⁴Not all be hydrogen atom or Alkyl.

The specific example of suitable amine includes monoalkyl (or alkenyl) amine, such as tetradecylamine, stearic amine, oil Amine, tallow alkyl amine harden tallow alkyl amine and soybean oil alkylamine；Dialkyl group (or alkenyl) amine, such as N- myristyl first Amine, N- pentadecyl methyl amine, N- cetyl methyl amine, N- stearyl methylamine, N- oil base methylamine, N- cocoyl methylamine, N- tallow alkyl methylamine, N- harden tallow alkyl methylamine, N- soybean oil alkyl methylamine, two-tetradecylamines, two-pentadecyls Amine, two-hexadecylamines, distearyl amine, two oleyl amines, bis- (2- hexyl decyl) amine, bis- (2- octyldodecyl) amine, bis- (2- Decyl alkyl) amine, tallow dialkylamine, hardening tallow dialkylamine and soybean oil dialkylamine；With trialkyl (alkene Base) amine such as tetradecyldimethylamine, hexadecyldimethyl benzyl ammonium amine, octadecyldimethylamine, tallow alkyl dimethyl amine, Harden tallow alkyl dimethyl amine, soybean oil Alkyl Dimethylamine, two oleyl methyl amine, three-tetradecylamines, three stearic amines With three oil base amine.There are two the alkyl (or alkenyl) with 14-18 carbon atom for suitable secondary amine tool.

The example of compound containing sexavalence molybdenum atom includes molybdenum trioxide or its hydrate (MoO₃.nH₂O), molybdic acid (H₂MoO₄), alkali metal molybdate (Q₂MoO₄), wherein Q indicates alkali metal, such as sodium or potassium, ammonium molybdate ((NH₄)₂MoO₄Or Seven molybdate (NH₄)₆[Mo₇O₂₄]·4H₂O), MoOCl₄, MoO₂Cl₂, MoO₂BR₂, Mo₂O₃Cl₆Deng.Due to their availability, Molybdenum trioxide or its hydrate, molybdic acid, alkali metal molybdate and ammonium molybdate are usually suitable.In one embodiment, Lubricating composition includes molybdenum amine compounds.

Other suitable organic molybdenums can be fat oil, and the reaction of monoalkylation Alkylenediamine and molybdenum source produces Object.This kind of material is usually prepared in two steps, and the first step includes preparing amino amides/glyceride mixture, second step at high temperature Including mixing molybdenum.

The example for the fat oil that can be used includes cottonseed oil, peanut oil, coconut oil, Linseed oil, palm-kernel oil, olive Oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acid), soybean oil, sunflower oil, herring oil, pilchard oil and Butter.These fat oils are commonly known as the glyceride of fatty acid, triacylglycerol or triglycerides.

The example for some monoalkylation Alkylenediamines that can be used includes dimethylaminopropyl amine, methylaminoethyl Amine, butylamino propyl amine, Butylaminoethyl amine, octyl amino propyl amine, octyl amino ethylamine, dodecylamino third Base amine, dodecylamino ethylamine, hexadecylamino propyl amine, hexadecylamino ethylamine, octadecylamino third Base amine, octadecylamino ethylamine, isopropoxide propyl -1,3- diaminopropanes and octyloxy propyl -1,3- diamino third Alkane.Also the monoalkylation Alkylenediamine derived from fatty acid can be used.Example include N- Cocoalkyl -1,3- propane diamine (C), N- tall oil alkyl -1,3- propane diamine (T) and N- oil base -1,3- propane diamine (O), all commodity are all from Akzo Nobel.

The molybdenum source mixed in fat oil/diamine complexes is usually oxygen-containing molybdenum compound, similar to the above, including molybdic acid Ammonium, sodium molybdate, molybdenum oxide and its mixture.A kind of suitable molybdenum source includes molybdenum trioxide (MoO₃)。

It is commercially available to include containing nitrogen-molybdenum compound, for example, derived from Adeka710, it is molybdenum amination Object and Molyvan 855 are closed, can be obtained from R.T.Vanderbilt.

Can be present in lubricant compositions with 0.005 to 2 weight % of composition containing nitrogen-molybdenum compound or 0.01 to 0.02 to the 1.0 weight % of 1.3 weight % or composition.Molybdenum compound can provide 0 to 1000ppm for lubricant compositions, Or 5 to 1000ppm or 10 to 750ppm, the molybdenum of 5ppm to 300ppm or 20ppm to 250ppm.

L. demulsifier

Demulsifier for use in the present invention includes trialkylphosphate and ethylene glycol, ethylene oxide, propylene oxide and its The various polymer and copolymer of mixture.

M. sweller is sealed

The sealing sweller that can be used for this paper includes Cycloene derivate, such as Exxon Necton-37^TM(FN 1380) With Exxon Mineral Seal Oil^TM(FN 3200)。

N.TBN kicker

Useful TBN kicker is Anthranilate (ester of ortho-aminobenzoic acid), is such as example described in the U.S. It announces in No.20140187458, such as ortho-aminobenzoic acid last of the ten Heavenly stems ester.

Example lubricating composition

Engine lubricant in different embodiments can have composition shown in table 1.All additives are based on nothing Oil meter reaches.

Illustrative N- alkylated diphenylamine compound is often more effective in low magnesium lubricating composition.In lubricating composition In, the weight ratio of calcium and magnesium can be at least 90:10, in one embodiment, at most 10:90.As described above, calcium can be by High alkaline detergent such as sulfoacid calcium provides.In one embodiment, lubricating composition includes the magnesium less than 500ppm, or is less than The magnesium of 200ppm, or the magnesium less than 100ppm.

Table 1:Exemplary lubricating composition

The purposes of lubricating composition

Lubricating composition as described herein can be used for reducing in the method that deposit is formed in internal combustion engine.Internal combustion engine lubrication Composition lubrication.

The final use of lubricating composition as described herein includes the lubricant cylinder as internal combustion engine, for example, passenger car or Heavy type, medium-sized or light diesel vehicle, but also be used as two-stroke marine diesel engine, put-put such as motorcycle and The engine oil of two-stroke gasoline engine oil engine is used as transmission base lubricant, including gear and automatic transmission fluid, and is used for other Industry oil, such as hydraulic lubricant.

The illustrative methods of lubricating machinery device (such as bus engine cylinder) include supplying exemplary lubricating composition Described device should be arrived.

In general, lubricating composition is added in the lubricating system of internal combustion engine, then during its operation by lubricating combination Object is transported to the cylinder of engine.

Internal combustion engine can be gasoline engines, diesel-fueled engine, such as two-stroke marine diesel engine, or Natural gas fueled engines, blend gasoline/alcohol engine or bio-diesel fuel engine applications.Internal combustion engine can be 2 strokes Or 4 Stroke Engine.

In one embodiment, disclosed technology provides the method for lubrication two-stroke or quartastroke engine, including Lubricating composition as disclosed herein is provided to internal combustion engine.

Internal combustion engine can be passenger car internal combustion engine.Passenger car internal combustion engine can have the reference matter no more than 2610kg Amount.Unleaded gas can be used in passenger vehicle engine.Unleaded gas is well known in the art, and by British Standard BS EN 228:2008 (entitled " Automotive Fuels-Unleaded Petrol-Requirements and Test Methods ") definition.Internal combustion engine is also possible to heavy-duty diesel oil internal combustion engine.Heavy-duty diesel oil internal combustion engine can have more than 3,500kg's " the maximum load quality technically allowed ".Engine can be compression ignition engine or positive ignited natural gas (NG) or LPG (liquefied petroleum gas) engine.

No matter the sulphur of fuel, grey (ASTM D-874) content of phosphorus or sulfate is how, and lubricating composition can be all suitable as Lubricant cylinder.The sulfur content of lubricating composition be especially suitable for engine oil lubricants can be 1 weight % or less, Or 0.8 weight % or less or 0.5 weight % or less or 0.3 weight % or less.In one embodiment, sulfur content It can be in the range of 0.001 weight % to 0.5 weight % or 0.01 weight % to 0.3 weight %.Phosphorus content can be 0.2 Weight % or less or 0.12 weight % or less or 0.1 weight % or less or 0.085 weight % or less or 0.08 Weight % or less, or even 0.06 weight % or less, 0.055 weight % or less or 0.05 weight % or less.One In a embodiment, phosphorus content can be 100ppm to 1000ppm or 200ppm to 600ppm.Total sulfate ash content can be with It is 2 weight % or less or 1.5 weight % or less or 1.1 weight % or less or 1 weight % or less or 0.8 weight Measure % or less or 0.5 weight % or less or 0.4 weight % or less.In one embodiment, sulfate ash content It can be for 0.05 weight % to 0.9 weight % or 0.1 weight % to 0.2 weight % or to 0.45 weight %.

It is not intended to limit the range of exemplary implementation scheme, following example illustrate the preparation of embodiment compound and is commented Valence.

Embodiment

All reactants and additive are expressed on oil-free basis.

The synthesis of embodiment 1:4,4'- cyclohexylmethylene diphenylamines (CY-MDI)

By 4,4'- methylene dianiline (MDA) (MDA) (1 equivalent), cyclohexanone (2.1 equivalent) and acetic acid (0.05 equivalent) and toluene It is added in flask together and is heated to reflux and removes water.It is completed once imines is formed, by the way that toluene and remaining second is removed in vacuum Acid.In methyl alcohol by the dissolution of obtained imines, it and is cooled to using ice bath lower than 10 DEG C.Sodium borohydride is added portionwise, and (2.2 work as Amount), keep reaction temperature to be lower than 15 DEG C.Then solution is warmed to room temperature and is stirred for 2 hours.Once reduction is completed, will mix It closes object to be quenched with water, product is extracted with ethyl acetate.Without being further purified.The reaction results in chemical combination shown in table 2 Object A-1.

The synthesis of embodiment 2:4,4'-2- ethylhexyl methylene dianiline (MDA) (EHL-MDI)

The method for repeating embodiment 1 uses 2- ethyl hexanal (2.1 equivalent) to replace the cyclohexanone as ketone.The reaction causes Form compound A-2 shown in table 2:

Using the method for Examples 1 and 2, by filtering or by the way that collection product is extracted with ethyl acetate, following amine is used Product shown in table 2 is formed with ketone/aldehyde:

Table 2: diamine compound

Embodiment 3: lubricating composition

According to N prepared by Examples 1 and 2, N'- dialkyl methylene radical bisaniline compounds are commented in various preparations Valence.

A. higher internal combustion engine lubricant

The lubricating composition of 5W-30 engine lubricant is suitable as using benchmark preparation preparation as shown in table 3.Institute There is concentration to be based on oil-free (that is, activity basis).

Table 3: benchmark lubricating composition B1

1. dinonylated diphenylamine

2.3- (3,5- di-tert-butyl-hydroxy phenyl) alkyl propionates

3. the combination of polyisobutenyl succinimide dispersing agent, Mn 1600-2300

The alkylated diphenylamine of Examples 1 and 2 is added in benchmark composition, as shown in table 4, is respectively formed lubrication group Close object L1 and L2.

Table 4: lubricant oil composite preparation

Composition	B1	L1	L2
				B1	100	99.5	99.5
A-1		0.5
				A-2			0.5
% phosphorus	0.075	0.075	0.075
				D2896TBN(mg KOH/kg)	7.5	9.1	8.7

Lubricating composition B1, L1 and L2 are evaluated in following oxidation bench test:

1. on the antioxidative influence of film: the oxidation of pressure differential scanning calorimetry (DSC) (PDSC) test measurement composition lures Lead the time (OIT).This is the standard test procedure of the lubricating oil industry based on CECL-85T-99.In the test, group will be lubricated It closes object and is heated to high temperature, usually about 25 DEG C lower than the average decomposition temperature of sample to be tested (it is in this case 215 DEG C, 690kPa), and the time that composition starts decomposition is measured.It is longer with the testing time that minute reports, it composition and wherein deposits Additive oxidation stability it is better.

2. deposit (MHT TEOST): being measured according to ASTM D7097-09.MHT TEOST method is assessed in reciprocating hair It is formed in motivation with deposit of the ring zone at a temperature of closely related.The organic metal that predetermined concentration is approximately equal to 8.5g is urged Agent mixture recycles 24 hours on the deposition rod of coiling at 285 DEG C, while the air of 10ml/min is added.In test Weighing deposition rod after preceding and test.Deposit and stick deposit are equal to total deposition after any test collected after cleaning rod Object.In MHT TEOST, lower deposition shows preferable sediment monitoring performance.

Obtain as the result is shown in table 5.

Table 5: the oxidation results of lubricant oil composite preparation

Embodiment	PDSCOIT min	L-85-99OIT min	MHT TEOST mg
				B1	67	80	42
L1	109	97	13
				L2	84	82	18

Shown in table 5 the result shows that, compared with benchmark preparation (B1), the alkylated diphenylamine containing Examples 1 and 2 Lubricating composition (L1 and L2) (for example, internal combustion engine lubricant) provides excellent antioxygenic property and unexpected deposit Control performance.

B. low-phosphorous internal combustion engine lubricant

The lubricating combination of 5W-30 engine lubricant is suitable as using benchmark preparation (B2) preparation as shown in table 6 Object.All concentration are based on oil-free (i.e. active).

Table 6: benchmark lubricating composition B2

1. the combination of diaryl amine and hindered phenol

2. the combination of polyisobutenyl succinimide dispersing agent, Mn 1600-2300

Diamines A-1, A-3 and A-4 are added in benchmark composition B1 with amount shown in table 7, to form lubricating composition L3, L4 and L5.Other lubricating composition (C1) is prepared with amine antioxidants.

Table 7: lubricant oil composite preparation

Composition	B2	L3	L4	L5	C1
						B2	100	99.5	99.5	99.5	99.5
A-1		0.5
						A-4			0.5
A-3				0.5
						Aminic AO					0.5
% phosphorus	0.038	0.038	0.038	0.038	0.038
						TBN,mg KOH/g(D2896)	8.7	9.6	9.5		9

As described above, assessing lubricating composition B2, L3, L4, L5 and C1 in oxidation bench test.It obtains as the result is shown In table 8.

Table 8: the oxidation results of lubricant oil composite preparation

Embodiment	PDSCOIT min	L-85-99OIT min	MHT TEOST mg
				B2	65	104	39
L3	94	125	16
				L4	102	160	15
L5	87	108	16
				C1	70	105	40

Shown in table 8 the result shows that containing alkylated diphenylamine A-1, A-3 and A-4 exemplary lubricating composition (L3, L4 and L5) (for example, internal combustion engine lubricant) provide the excellent antioxygenic property and unexpected compared with benchmark preparation (B2) Sediment monitoring performance, show that exemplary alkyl diphenylamines are highly effective in low-phosphorous preparation.In addition, these of 0.5% Alkylated diphenylamine is in PDSC and MHT TEOST test than adding other by 0.5% amine antioxidants (C1) to reference system The performance of agent improves significant much higher.

C. internal combustion engine lubricant

The lubricating combination of 15W-40 engine lubricant is suitable as using benchmark preparation (B3) preparation as shown in table 9 Object.All concentration are based on oil-free (that is, activity basis).

Table 9:Benchmark lubricating composition B3

By diamines A-1 and A-2 with shown in table 10 amount be added benchmark composition B3 in, with formed lubricating composition L6 and L7。

Table 10:Lubricant oil composite preparation

Composition	B3	L6	L7
				B3	100	99.5	99.5
A-2		0.5
				A-1			0.5
% phosphorus	0.11	0.11	0.11
				TBN mg KOH/g(D2896)	11.8	12.7	13.2

As described above, evaluating lubricating composition B3, L6 and L7 in oxidation bench test.Obtain as the result is shown in table 11 In.

Table 11: the oxidation results of lubricant oil composite preparation

Embodiment	PDSCOIT min	MHT TEOST mg
			B3	84	20
L6	87	5.5
			L7	89	4.6

Shown in table 11 the result shows that containing alkylated diphenylamine A-1 and A-2 exemplary lubricating composition (L6 and L7) (for example, internal combustion engine lubricant) provides excellent antioxygenic property and unexpected sediment monitoring performance, when with base When quasi- preparation (B3) is compared, show that exemplary alkyl diphenylamines are highly effective in these formulations.

As used herein, with the use of its ordinary meaning, this is those skilled in the art for term " hydrocarbyl substituent " or " alkyl " Well known to member.Specifically, it refers to the carbon atom with molecule rest part is directly connected to and with main hydrocarbon feature Group.Mainly hydrocarbon feature refers to that in substituent group at least 70% or at least 80% atom is hydrogen or carbon.

The example of alkyl includes:

(i) hydrocarbon substituent, i.e., aliphatic (for example, alkyl or alkenyl), alicyclic (for example, naphthenic base, cycloalkenyl) replaces Base and aromatics-, the aromatic substituent and its middle ring of aliphatic series-and alicyclic-substitution complete (example by another part of molecule Such as, two substituent groups are formed together ring) cyclic substituents；

(ii) the hydrocarbon substituent replaced contains the substituent group of non-alkyl, in the context of the present invention, they will not change Becoming the main hydrocarbon property of substituent group, (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxy, sulfydryl, alkyl thiol, nitro are sub- Nitro and sulphur oxygroup)；

(iii) miscellaneous substituent group while having main hydrocarbon feature, can contain the miscellaneous original in addition to carbon in ring or chain Son, the substituent group being otherwise made of carbon atom.

Representative alkyl includes normal-butyl, isobutyl group, sec-butyl, n-pentyl, amyl, neopentyl, n-hexyl, positive heptan Base, Zhong Gengji, n-octyl, secondary octyl, 2- ethylhexyl, n-nonyl, Zhong Renji, undecyl, secondary undecyl, dodecane Base, secondary dodecyl, tridecyl, secondary tridecyl, myristyl, secondary myristyl, cetyl, secondary cetyl, firmly Aliphatic radical, eicosyl, docosyl, tetracosyl, 2- butyl octyl, 2- butyl decyl, 2- hexyl octyl, the 2- hexyl last of the ten Heavenly stems Base, 2- octyl-decyl, 2- hexyl dodecyl, 2- octyldodecyl, 2- decyl alkyl, 2- dodecyl hexadecane Base, 2- hexyl decyl octyl-decyl, 2- myristyl octyl-decyl, monomethyl branch iso stearyl etc..

Representative aryl includes phenyl, tolyl, xylyl, cumenyl, mesitylene base, benzyl, phenethyl, benzene Vinyl, cinnamyl, benzhydryl, trityl, ethylphenyl, propyl phenyl, butyl phenyl, amyl phenyl, hexyl phenyl, Heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, undecyl phenyl, dodecylphenyl, benzyl phenyl, styrene Change phenyl, to cumyl phenyl, Alpha-Naphthyl, betanaphthyl and its mixture.

Hetero atom includes sulphur, oxygen, nitrogen, and including substituent group, such as pyridyl group, furyl, thienyl and imidazole radicals.It is logical Often, it for every ten carbon atoms in alkyl, will be present no more than two, and in one embodiment, be no more than one Substituents.In some embodiments, substituents are not present in alkyl.

Representative aliphatic group can contain 4 to 14 carbon atoms, 6 to 12 carbon atoms or 8 to 10 carbon atoms.Properly The example of alkyl include butyl, isobutyl group, amyl, isopentyl, neopentyl, hexyl, amyl, heptyl, octyl, iso-octyl, 2- Ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, 2- propylheptyl, tridecyl, isotridecyl, ten Tetraalkyl, 4- methyl -2- amyl, propylheptyl and combinations thereof.

Alkylene is the divalent equivalent of alkyl, such as alkylidene.

Every document above-mentioned is all incorporated herein by reference.In addition to explicitly pointing out it in embodiment or in addition Outside, specified quantity of material, reaction condition, molecular weight, all numerical value of carbon atom number etc. are interpreted as by " about " repairing in this specification Decorations.Unless otherwise stated, the every kind of chemicals or composition that are mentioned above should be interpreted that commercial grade material, can contain different Structure body, by-product and are generally understood as being present in other such materials in business level at derivative.However, unless otherwise indicated, Otherwise the amount of every kind of chemical constituent does not include any solvent or flux oil, can be typically found in commercial materials.It should be understood that Upper and lower bound as described herein, range and ratio limitation can be combined independently.Similarly, the model of of the invention every kind element Enclosing and measuring can be used together with the range of any other element or amount.

It should be appreciated that variant disclosed above and other feature and function or its alternative solution can be combined to it is many other In different systems or application.Those skilled in the art can then carry out various fail to predict or unexpected replacing at present Generation, modification, variation or improvement, these are also intended to be covered by following following claims.

Claims

1. a kind of lubricating composition, it includes:

A) with the oil of lubricant viscosity；

B) N- alkylated diphenylamine compound；With

C) at least one of following:

I) be selected from diarylamine antioxidant, the ashless antioxidant of phenol antioxidant and combinations thereof, and

Ii) high alkalinity calcium detersive；

Wherein lubricating composition includes the phosphorus less than 0.15 weight %.

2. lubricating composition according to claim 1, wherein N- alkylated diphenylamine compound is alkylene coupling.

3. lubricating composition according to claim 1 or 2 measures wherein the lubricating composition has according to ASTM D-2896 At least 4mg KOH/g TBN.

4. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine includes that at least one is selected from Cyclic alkyl, the N- alkyl of acyclic alkyl groups and combinations thereof.

5. lubricating composition according to claim 4, wherein N- alkyl is cyclohexyl.

6. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine is N, N'- alkylation two Aniline compound.

7. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is lubricating combination At least 0.10 weight % of the object or at least 0.15 weight % of lubricating composition, or at least 0.2 weight %, or at least 0.4 weight Measure %.

8. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is lubricating combination The at most 4.0 weight % of the object or at most 3 weight % of lubricating composition, or at most 1.5 weight %, or at most 1.2 weight %.

9. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is by following formula table Show:

Wherein R¹And R²Alkyl independently selected from 1-24 carbon atom；

R³And R⁴Alkyl independently selected from 1 to 6 carbon atom；

Each n is 0 to 3, and

X indicates alkylene.

10. lubricating composition according to any one of the preceding claims, wherein alkylene is C₁-C₃Alkylidene.

11. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is by following formula table Show:

Wherein R¹And R²Alkyl independently selected from 1-24 carbon atom.

12. lubricating composition according to claim 11, wherein N- alkylated diphenylamine compound is expressed from the next:

13. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is selected from:

And its mixture.

14. lubricating composition according to claim 13, wherein N- alkylated diphenylamine compound is selected from 4,4'-2- ethylhexyl Methylene dianiline (MDA), 4,4'- cyclohexylmethylene diphenylamines and its mixture.

15. lubricating composition according to any one of the preceding claims, wherein the oil with lubricant viscosity is lubricating composition At least 40 weight %.

16. lubricating composition according to any one of the preceding claims, wherein ashless antioxidant be lubricating composition extremely Few 0.1 weight %, or at least 0.2 weight %, or at least 0.4 weight %, or at least 0.6 weight % or lubricating composition be extremely More 4 weight %, or at most 1.2 weight %, or at most 1 weight %.

17. lubricating composition according to any one of the preceding claims, wherein ashless antioxidant and the amination of N- alkyl diphenyl The ratio for closing object is 20:1-1:20.

18. lubricating composition according to any one of the preceding claims, wherein ashless antioxidant includes phenolic ester and diaryl Amine.

19. lubricating composition according to any one of the preceding claims, wherein ashless antioxidant further includes olefine sulfide.

20. lubricating composition according to any one of the preceding claims, wherein high alkalinity calcium detersive is selected from sulfonate, be free of The phenates of sulphur, the phenates of sulfur-bearing, salixarate, salicylate, mixture and its boration equivalent.

21. lubricating composition according to any one of the preceding claims, wherein high alkalinity calcium detersive to composition to deliver Existed according to the amount of ASTM D-2896 measurement at least 2mg KOH/g total base number (TBN).

22. lubricating composition according to any one of the preceding claims, wherein high alkalinity calcium detersive is lubricating composition At least 0.01 weight % or at least 0.1 weight %, or at least 0.5 weight %, or at most 3 weight %, or at most 2 weight %.

23. lubricating composition according to any one of the preceding claims, wherein the weight ratio of calcium and magnesium is in lubricating composition At least 9:10.

24. lubricating composition according to any one of the preceding claims also includes polyalkylene succinic acid imide dispersing agent, wherein The number-average molecular weight of the polyolefin group is at least 300.

25. lubricating composition according to any one of the preceding claims also includes zinc dialkyl dithiophosphate.

26. lubricating composition according to any one of the preceding claims, wherein lubricating composition includes at least 0.02 weight % Phosphorus.

27. lubricating composition according to any one of the preceding claims, wherein N- alkylated diphenylamine compound is diphenylamines With the reaction product of at least one of aldehyde and ketone.

28. a kind of reduce the method that deposit is formed in internal combustion engine, including the lubricating combination with any one of preceding claims Object lubricating internal combustion engines.

29. the purposes that the lubricating composition of any one of claim 1-27 is used for lubricating internal combustion engines.

30. a kind of method for forming lubricating composition, comprising:

Form N- alkylated diphenylamine compound；With

By N- alkylated diphenylamine compound and there is the oily of lubricant viscosity and at least one of following combination:

Selected from diarylamine antioxidant, the ashless antioxidant of phenol antioxidant and combinations thereof, and

High alkalinity calcium detersive；