CN103074143B - Lubricant oil composite - Google Patents
Lubricant oil composite Download PDFInfo
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- CN103074143B CN103074143B CN201210369519.8A CN201210369519A CN103074143B CN 103074143 B CN103074143 B CN 103074143B CN 201210369519 A CN201210369519 A CN 201210369519A CN 103074143 B CN103074143 B CN 103074143B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
Abstract
Lubricant oil composite, it comprises the compound of one or more formula (I) of the oil of major amount of lubricant viscosity and minor amount：Wherein R1, R2, R3, R4And R5Independently represent alkyl or the replacement alkyl without aryl substituent.
Description
Technical field
The present invention relates to including the lubricant oil composite of a class aniline compound.Described aniline compound can be used as lubricating oil
Compositionss, especially have the low-level sulfated ash of fall（SASH）Crankcase lubricating oil composition ashless tbn（Total alkali
Value）Promoting agent.
Background of invention
Concern for environment has led to ongoing effort to reduce compression ignition（With diesel oil as fuel）And spark ignition（With vapour
Oil is fuel）The CO of light-duty explosive motor, hydrocarbon and nitrogen oxides（NOx）Discharge.In addition, ongoing effort reduces compression point
The particle emission of fiery explosive motor.In order to meet the discharge standard for heavy-duty diesel oil locomotive that will appear from, original set
Standby manufacturer（OEM）To depend on using extra exhaust aftertreatment device.This exhaust aftertreatment device may include catalysis and turns
Change device and/or grain catcher, this catalytic converter can comprise one or more oxidation catalyst, NOX storage catalyst and/or
NH3Reducing catalyst.
Oxidation catalyst, by exposure in elements/compounds some present in engine exhaust, is especially exposed to
It is incorporated in the phosphorus and phosphorus compound in waste gas by the degraded of phosphorous lube oil additive, poisoning can be become and less have
Effect.Reducing catalyst in engine exhaust due to both base oil and the sulfur-bearing lube oil additive for lubricant is blended
Degraded and the sulfur that introduces and sulphur compound are sensitive.Grain catcher can become to be blocked by calx, and this calx is degraded
Product containing metal lubrication oil additive.
In order to ensure long service life it is necessary to find the lubricating oil that this after-treatment device is brought with minimum negative effect
Additive, and the heavy-duty diesel oil for " new maintenance is filled " and " filling first "（HDD）The OEM specification requirement 0.4 of lubricant
The maximum sulfur of quality %, the maximum phosphorus content of 0.12 mass % and the sulfate ash content less than 1.1 mass %, this lubrication
Agent is referred to as " middle SAPS " lubricant（Wherein " SAPS " is the acronym of " sulfated ash, phosphorus, sulfur "）.In the future, OEM can
Further these maximum level are restricted to the sulfated ash of the phosphorus, the sulfur of 0.02 mass % and 0.8 mass % of 0.08 mass %,
And this lubricant is referred to as " low SAPS " lubricant oil composite.
Amount with the lubricant additive reducing phosphorous, sulfur and ash is compatible with exhaust aftertreatment device to provide
Neutralization low SAPS lubricant, lubricant oil composite must continue to provide high-caliber greasy property, including enough purifications,
And this is by " new maintenance " and " filling first " specification domination of OEM, such as ACEA E6 and MB of heavy-duty engine lubricant
p228.51（Europe）With API CI-4+ and API CJ-4（The U.S.）Specification.Classify as the lubrication line of oils meeting above-listed industrial standard
The criterion of compound is well known by persons skilled in the art.
The ability with combustion acid by-product in lubricant can be improved, described by-product is equipped with waste gas recirculation
（EGR）System, increases in the electromotor of condensation egr system that especially wherein waste gas is cooled before being recycled, and leads to
Cross the total base number improving compositionss（TBN）The displacement time limit of lubricant can be extended.In history, TBN passes through sulfated ash
The high alkaline detergent introducing compositionss provides.Promote component offer using the TBN not contributing sulfated ash and there is high TBN water
Flat lubricant oil composite will be favourable.Because causing corrosion known to high alkalinity component and, in some cases, reduction being moistened
The compatibility between fluoroelastomer encapsulant used in sliding oil composition and electromotor, corrodes and excellent so providing and not causing
This kind of component that choosing can not adversely affect the sealing member compatibility will be preferred.Due to the need to improved fuel economy
Want, the less lubricant of viscosity, such as 0W and 5W 20 and 30 rank lubricants have become increasingly prevalent.In order to allow this
That plants lubricant is easier preparation, and the amount of the polymer being introduced by additive is preferably minimized.Therefore it provides non-polymer
Type ashless tbn sources will be further preferred.
United States Patent (USP) No.5,525,247；5,672,570 and 6,569,818 are related to " low ash " lubricant oil composite, its
Middle sulfate ash content passes through to substitute high alkaline detergent reduction with neutral detergents.This series lubricant agent is described by these patents
For providing enough purifications, but do not require this series lubricant agent enough TBN will to be provided to start for use in such as HDD
Machine.U.S. Patent application 2007/0203031 describes high TBN nitrogenous dispersant to be used as ashless tbn sources.
United States Patent (USP) No.4,100,082；4,200,545；4,320,021,4,663,063；4,708.809 and Russia is special
Profit application SU1825780 describes as lube oil additive（For example, dispersant/detersive）Aminophenol compound.The U.S.
Patent No.2,511,750；3,634,248；4,269,720；4,335,006；4,411,805 and 6,242,394 describe conduct
The stabilizer of lubricant oil composite（Antioxidant）Some aniline compounds.United States Patent (USP) No.4,778,654 describes can use
Make the alkyl benzene amine/formaldehyde co-oligomer of corrosion inhibiter.
CO-PENDING EP 2 206 764A1 of the applicant describes aniline compound as the ashless tbn of lubricating oil
Source.Two alkyl being connected with nitrogen-atoms preferably wherein are the aniline compounds of the di-alkyl replacement of straight chained alkyl.Provide
The example of two-branched (two -2- ethylhexyls) compounds, but for it, the TBN performance in lubricating oil does not provide data.
Content of the invention
It has been found that the di-alkyl aniline material that some alkoxyls replace can carry when the additive as lubricating oil
For improved TBN performance.This kind of oil also has enhanced fluoroelastomer seal compatibility, for example, tested by VW-6/AK6 and survey
As amount.
Therefore, in the first aspect, the present invention provide lubricant oil composite, its comprise the oil of major amount of lubricant viscosity and
The compound of one or more formula (I) of minor amount：
Wherein R1, R2, R3, R4And R5Independently represent alkyl or the replacement alkyl without aryl substituent.
The compound of formula (I) is characterised by that they have two different branched-alkyls being connected with nitrogen-atoms.Described
One of branched-alkyl with nitrogen-atoms be in alpha-position carbon atom at branched and another branched-alkyl with nitrogen-atoms be in β-position
Carbon atom at branched.It has been found that this particular configuration provides enhanced TBN performance.
Preferably, described lubricating oil meet the ACEA E6 of heavy-duty engine lubricant, MB p228.51, API CI-4+ and
One or more of performance criteria in API CJ-4 specification.
According to second aspect, the present invention is provided to preparation is according to the lubricant oil composite of any of the above-described claim
Concentrate, described concentrate comprises the compound of one or more formula of about 2.5 to about 30 mass % (I)；About 10 to about
The nitrogenous dispersant of 40 mass %；About 2 to about 20 mass % amine antioxidants, phenolic antioxidant, molybdenum compound or they
Mixture；About 5-40 mass % detersive；About 2 to about 20 mass % metal dialkyl dithiophosphates.
According to third aspect of the present invention, there is provided the compound of formula (I)：
Wherein R1, R2, R3, R4And R5Independently represent alkyl or the replacement alkyl without aryl substituent.
According to the 4th aspect of the present invention, there is provided improve lubricating oil composition improve SASH content in difference in the case of
The method of the TBN of thing, the method includes adding one or more change according to the 3rd aspect in described lubricant oil composite
Compound.
According to the 5th aspect, the present invention provides compound according to the 3rd aspect as ashless lubricating oil compositionss
The purposes in TBN source.
Specific embodiment
The compound that can be used as the ashless tbn sources of lubricant oil composite has formula (I)：
Preferably, R1, R2, R3, R4And R5Independently represent alkyl.
Preferably, R1Represent methyl or ethyl, methyl is preferred.
Preferably, R3Represent methyl or ethyl, ethyl is preferred.
Wherein R1And/or R3Represent longer alkyl, the embodiment of alkyl for example containing 3-12 carbon atom is also at this
In bright scope.
Preferably, R2Represent the alkyl containing 3-12 carbon atom, this group can be straight chain or branched.
Preferably, R4Represent the alkyl containing 3-12 carbon atom, this group can be straight chain or branched.
Preferably, R5Represent methyl or ethyl so that phenyl ring is methoxy or ethoxy replacement.It is further preferred that R5Represent
Ethyl.Wherein R5Represent longer alkyl, for example, contain the embodiment of alkyl of 3-12 carbon atom also within the scope of the present invention.
In a preferred embodiment, the compound of formula (I) has following structure：
In another preferred embodiment, the compound of formula (I) has following structure：
Preferably, the compound of the present invention has at least about 50, preferably at least about 100, more preferably at least about
140, the most preferably at least TBN of about 180mg KOH/g（According to ASTM D-2896 and/or ASTM D-4793 measurement）.
Preferably, the compound of the present invention is at least about 200 DEG C, preferably at least about 250 DEG C, more preferably at least about
Have at a temperature of 300 DEG C>99% weight loss, by thermogravimetric analysiss（In atmosphere, with the temperature ramp of 10 DEG C/min）
Measure.
The forming method of the compound of formula (I) should it will be apparent to those skilled in the art that.Describe below one
The method being suitable for a bit.
Aniline and the aniline such as phenetidine replacing are commercially available.N, N- dialkyl aniline and the derivant replacing
Such as N, N- dialkyl group phenetidine can prepare as follows：Make suitable aniline or substituted derivant such as phenetidine
Press 1 with aldehyde/ketone:2 or excess molar ratio in the presence of reducing agent such as sodium triacetoxyborohydride in dichloromethane solvent
Reaction.These methods are well-known and are described in the literature, see, for example, Jn.Org.Chem（1996）, 61,
pp.3489-3862.
Another kind of method includes making suitable aniline or substituted aniline and halogenated alkyl（For example, bromination alkyl) press 2:1
Mol ratio, reacts in the presence of triethylamine in acetonitrile solvent.
Another method makes aniline or substituted derivant such as phenetidine and aldehyde/ketone by 1:2 or excess molar ratio
React in methanol solvate in the presence of hydrogen and 10%Pd/C catalyst.These methods be known to and many such sides
Method is described in such as United States Patent (USP) No.2,045,574.
Asymmetric compound of the present invention can be passed through using progressively using said method and other method in a similar fashion
Prepared by approach, wherein an alkyl is connected on nitrogen-atoms, then connects second different alkyl.
The oil of the lubricant viscosity that can use within the scope of the present invention can selected from Natural lubricating oils, synthetic lubricant fluid and they
Mixture.Lubricating oil can have such as gasoline engine machine oil, mineral lubricating oil from light fraction mineral oil to heavy grease
Range of viscosities with heavy-duty diesel oil.In general, the viscosity that described oil records at 100 DEG C is of about 2 centistokes(cst)s
（centistoke）To about 40 centistokes(cst)s, especially from about 4 centistokes(cst)s are to about 20 centistokes(cst)s.
Natural oil includes animal oil and vegetable oil（Such as Oleum Ricini, Adeps Sus domestica）；Liquid petroleum and alkane, cycloalkanes and combination chain
The mineral oil of the hydrofinishing of alkane-naphthene types, solvent process or acid treatment.Oil from coal or the lubricant viscosity of shale
Also serve as useful base oil.
Synthetic lubricant fluid includes the hydrocarbon ils that hydrocarbon ils and halogen replace, the such as alkene of polymerization and mutual polymerization（For example, polybutene,
Polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1- hexene), poly- (1- octene), poly- (1-decene)）；Alkylbenzene
（For example, detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2- ethylhexyl) benzene）；Polyphenyl（For example, biphenyl, terphenyl,
Alkylating polyphenol）；With alkylating diphenyl ether and alkylating diphenyl sulfide and its derivant, analog and homologue.Source
From the gas of Fiscber-Tropscb synthesis hydrocarbon to the artificial oil of liquid technique or useful, they are commonly referred to gas to liquid, or " GTL " base oil.
Wherein terminal hydroxyl passed through to be esterified, the modified oxyalkylene polymer such as etherificate and interpretation and theirs is derivative
Thing constitutes another kind of known synthetic lubricant fluid.Their example includes by the polymerization of ethylene oxide or propylene oxide preparing
Polyoxyalkylene polymers, and the alkyl of polyoxyalkylene polymers and aryl ether（For example, molecular weight is 1000 methyl-polyisopropylene
The diphenyl ether of the glycol ethers or molecular weight Polyethylene Glycol for 1000-1500）；With their list and multi-carboxylate, such as second
Acid esters, the C of mixing3-C8Fatty acid ester and the C of TEG13Oxygen-containing acid diesters.
Another kind of suitable synthetic lubricant fluid includes dicarboxylic acids（For example phthalic acid, succinic acid, alkyl succinic acid and
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.）With various alcohol（Such as butanol, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, diethylene glycol
Monoether, propylene glycol etc.）Ester.The instantiation of this kind of ester includes dibutyl adipate, decanedioic acid two (2- ethylhexyl) ester, richness
The just own ester of horse acid two, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, adjacent benzene
Dioctyl phthalate didecyl, decanedioic acid two (eicosyl) ester, the 2- ethylhexyl diester of linoleic acid dimer, and by 1 mole of last of the ten Heavenly stems
The complex ester that diacid reacts and formed with 2 moles of TEG and 2 moles of 2 ethyl hexanoic acid.
The ester that can be used as artificial oil is also included by C5-C12Monocarboxylic acid and polyhydric alcohol and polyol ester such as neopentyl glycol,
Trimethylolpropane, tetramethylolmethane, dipentaerythritol, tripentaerythritol make those.
The for example poly- alkyl of oil based on silicon, poly- aryl, poly-alkoxyl or poly- aryloxy group silicone oil and silicic acid ester oil composition are another
The useful syntholube of class；This oil includes tetraethyl orthosilicate, silicic acid four isopropyl ester, silicic acid four (2- ethylhexyl) ester, silicon
Sour four (4- methyl -2- ethylhexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4- methyl -2- ethylhexyl) two silica
Alkane, poly- (methyl) siloxanes and poly- (aminomethyl phenyl) siloxanes.Other synthetic lubricant fluids include the liquid ester of phosphorous acid（For example
Tricresyl phosphate, trioctyl phosphate, the diethyl ester of decylphosphonic acid）And PolyTHF.
The oil of lubricant viscosity may include Group I, the base oil of Group II, Group III oil base stock or above-mentioned oil base stock
Blend.Preferably, the oil of lubricant viscosity is Group II, Group III oil base stock or their mixture, or Group I basis
Oil plant and the mixture of one or more ii and Group III oil base stock.Preferably, the oil of major amount of lubricant viscosity is
II group, Group III, Group IV or Group V oil base stock, or their mixture.Oil base stock or base stock blend are excellent
Choosing has at least 65%, more preferably at least 75%, for example, at least 85% saturate content.Most preferably, oil base stock or base oil
Material blend has the saturate content more than 90%.Preferably, oily or oily blend will have less than 1wt%, preferably smaller than
The sulfur content of 0.6wt%, more preferably less than 0.4wt%.
Preferably, by Noack volatility test（ASTM D5880）The volatility of the oil of measurement or oily blend is less than
Or it is equal to 30%, preferably lower than or equal to 25%, more preferably less than or equal to 20%, most preferably equal to 16%.Preferably, oil
Or the viscosity index (VI) of oil blend（VI）It is at least 85, preferably at least 100, most preferably from about 105-140.
Definition and American Petroleum Institute to oil base stock and base oil in the present invention（API）Publication " Engine Oil
Licensing and Certification System ", Industry Services Department, the 14th edition,
In December, 1996, annex 1, those definition in 1998 12 months are identical.Oil base stock is classified as follows by described publication：
a）Group i base oils material comprises the saturate less than 90% and/or the sulfur more than 0.03%, and viscosity index (VI) is more than
Or be equal to 80 and be less than 120, using test method specified in table 1.
b）Group II oil base stock comprises the saturate more than or equal to 90% and the sulfur less than or equal to 0.03%, and glues
Degree index is more than or equal to 80 and is less than 120, using test method specified in table 1.
c）Group III oil base stock comprises the saturate more than or equal to 90% and the sulfur less than or equal to 0.03%, and
Viscosity index (VI) is more than or equal to 120, using test method specified in table 1.
d）Group iv base oils material is poly alpha olefin（PAO）.
e）Group V oil base stock includes all other oil base stock being not included in I, II, III or IV group.
The analysis method of Table I-oil base stock
| Performance | Test method |
| Saturate | ASTM D 2007 |
| Viscosity index (VI) | ASTM D 2270 |
| Sulfur | ASTM D 2622 |
| ASTM D 4294 | |
| ASTM D 4927 | |
| ASTM D 3120 |
The lubricant oil composite of the present invention can contain one or more further and be formed clearly containing metal detergent or ash
Net agent.Form detersive containing metal detergent or ash and be not only used as detersive to reduce or to remove deposit but also be used as acid neutralizing agent
Or antirust agent, thus reduce abrasion and corrode and extend engine life.Detersive usually contains has long hydrophobic tail
Polar head, and polar head includes the slaine of acidic organic compound.This salt can comprise substantially stoichiometry
Metal, in this case, their commonly known as normal salt or neutral salt, and generally there is the total base number of 0-80 or TBN leads to
Often（Can be measured by ASTM D-2896 and/or ASTM D-4793）.By making excessive metallic compound（As oxide or hydrogen
Oxide）With sour gas（As carbon dioxide）Reaction can introduce a large amount of metal base.Gained high alkaline detergent includes neutralization
Detersive is as metal base（Such as carbonate）The outer layer of micelle.This high alkaline detergent can have 150 or bigger
TBN, and generally will have 250 to 450 or higher TBN.In the presence of the compound of formula (I), it is possible to reduce high alkalinity is peace and quiet
The amount of agent, or can be using the detersive of the high alkalinity level with reduction（For example, TBN is the detersive of 100-200）, or in
Property detersive, this leads to the corresponding reduction of the SASH content of lubricant oil composite, and their performance does not reduce.
The detersive that can use includes metal especially alkali metal or alkaline-earth metal, such as sodium, potassium, lithium, calcium and magnesium
Oil-soluble neutrality and overbased sulfonate, phenates, sulfuration phenates, thio-phosphonates, salicylate and naphthenate and other
Oil-soluble carboxylate.The most frequently used metal is calcium and magnesium（They can be simultaneously provided in in the detersive of lubricant）And calcium
And/or the mixture of magnesium and sodium.Especially suitable metal detergent is neutrality and the high alkalinity sulfonic acid of the TBN with 20-450
Calcium, and there is neutrality and high alkalinity calcium phenates and the sulfuration phenates of the TBN of 50-450.The combination of detersive can be used, whether
High alkalinity, neutral or the two.
Sulfonate can be prepared by sulfonic acid, the sulfonation of the aromatic hydrocarbon that sulfonic acid is generally replaced by alkyl and obtain, such as by stone
The fractional distillation of oil or obtained by the alkylation of aromatic hydrocarbon those.Example include by make benzene,toluene,xylene, naphthalene, biphenyl or
Their halogen derivativess are as chlorobenzene, chlorotoluene and chloronaphthalene alkylation obtain.Alkylation can be entered in the presence of a catalyst
OK, wherein alkylating agent has about 3 to more than 70 carbon atoms.The aromatics that alkylaryl sulfonate replaces generally for each alkyl
Structure division contains about 9 to about 80 or more carbon atoms, preferably approximately 16 to about 60 carbon atoms.
Oil-soluble sulfonic acid salt or alkarylsulphonic acid can use the oxide of metal, hydroxide, alkoxide, carbonate, carboxylate,
Sulfide, sulfhydrate, nitrate, borate and ether neutralization.The amount of metallic compound is selected according to the desired TBN of final product
Select, but usually stoichiometry the desired amount of about 100-220 mass %（Preferably at least 125 mass %）.
The slaine of phenol and phenol red is made by the reaction with suitable metallic compound such as oxide or hydroxide
Standby and neutral or overbased product can be obtained by method well-known in the art.Phenol red can by make phenol and sulfur or
Sulfur-containing compound such as hydrogen sulfide, a halogenation sulfur or dihalide reaction of Salmon-Saxl, to prepare, are usually the mixture of compound with formation
Product, wherein 2 or more phenol abutment bridge joint by sulfur-bearing.
The lubricant oil composite of the present invention can contain one or more ashless dispersant further, when being added to lubricating oil
The deposit that when middle, they efficiently reduce when for gasoline and Diesel engine is formed.Can be used for the nothing of the present composition
Ash powder packets contain have can with the oil-soluble polymerization of the functional group treating scattered particle association long chain backbone.Generally, such
Dispersant comprises amine, alcohol, amide or the ester polar moieties being generally connected with polymer backbone via bridging group.Described ashless
Dispersant is permissible, for example, the monocarboxylic acid replacing selected from long chain hydrocarbons and the oil-soluble salt of polybasic carboxylic acid or their anhydride, ester,
Amino ester, amide, acid imide and oxazoline；The thio carboxy acid ester derivative of long chain hydrocarbons；There is the polyamines being directly connected to thereon
The long chain aliphatic hydrocarbon of structure division；And the Mannich that the phenol being replaced by long-chain is formed with formaldehyde and polyalkylenepolyaminess condensation
（Mannich）Condensation product.In use dispersant most commonly be known to succinimide dispersants, it be alkyl replace
Succinic anhydrides and poly- (alkylene amines）Condensation product.Single butanimide and double amber imide dispersant（With mixing of they
Compound）Known to being all.
Preferably, ashless dispersant is number-average molecular weightMore than or equal to 4,000, such as 4,000-20,000
" high molecular " dispersant.Accurate molecular weight ranges will depend upon and form the polymer type of dispersant, the functional group existing
Quantity and polar functional group used type.For example, for dispersant derived from polyisobutylene, high molecular weight dispersant is
The dispersant being formed by the polymer backbone that number-average molecular weight is of about 1680 to about 5600.Typically commercially available polyisobutenyl
It is of about 900 to about 2300 that dispersant contains number-average molecular weight, by maleic anhydride（MW=98）Functionalization be big with molecular weight
Polyisobutylene polymer derived from the polyamines of about 100 to about 350.The polymer of low-molecular-weight may also be used for forming macromolecule
Amount dispersant, this passes through to carry out multiple polymer chain combination in dispersant, it is possible to use method as known in the art is real
Existing.
Preferably dispersant group includes poly alpha olefin dispersant derived from polyamines, especially ethylene/butylene alpha-olefin and poly-
Isobutenyl dispersant.Ashless dispersant especially preferably derived from polyisobutylene, described polyisobutylene is succinic anhydrides
Base replace, and with poly- ethylene amines, such as polyethyene diamine, tetren；Or polyoxy alkylidene polyamines, such as polyoxy Asia
Propyl diamine, trishydroxymethylaminomethane；Hydroxy compounds, such as tetramethylolmethane；With combinations thereof reaction.One kind is especially
The combination that preferably dispersant package is discussed further below：(A) succinic acid anhydride group replace and with (B) hydroxy compounds, such as season
Penta tetrol；(C) polyoxy alkylidene polyamines, such as polyoxypropylene diamine, or (D) polyalkylene diamidogen, such as polyethyene diamine and
The polyisobutylene of tetren reaction, wherein for every mole (A) using about 0.3 to about 2 mole (B), (C) and/
Or (D).It is sub- with (B) polyalkylene polyamine such as four that another kind of preferably dispersant package comprises (A) polyisobutenyl succinic anhydride
The combination of aliphatic primary amine such as tetramethylolmethane or trishydroxymethylaminomethane that ethyl five amine and (C) polyhydric alcohol or polyhydroxy replace,
As described in United States Patent (USP) No.3,632,511.
Another kind of ashless dispersant includes mannich base condensation products.Generally, these products are by will about 1 mole of alkane
Monohydroxy or polyhydroxy benzenes and about 1 to 2.5 mole carbonyl compound that base replaces（Such as formaldehyde and paraformaldehyde）About
0.5 to 2 mole of polyalkylenepolyamines condensations and prepare, such as United States Patent (USP) No.3, disclosed in 442,808 like that.This kind of graceful
The uncommon alkali condensation product of Buddhist nun can include the polymer product of the polyreaction of metallocene catalyst as the substituent group in phenyl group, or
Person can be substituted with containing this according to similar mode described in United States Patent (USP) No.3,442,808 on succinic anhydrides
Polymer compound reaction.Above-mentioned publication describes using metallocene catalyst system synthesis functionalization and/
Or the example of derivative olefin polymer.
Dispersant can carry out further work-up by various routine post processing such as borations, such as United States Patent (USP)
General teaching in No.3,087,936 and 3,254,025.The boration of dispersant can be easily by using boron compound, example
The dispersant that ester as boron oxide, halogenation boron, boric acid and boric acid processes acyl nitrogen-containing is realized, and the consumption of described boron compound be enough to
Nitrogen compositionss for every mole of acylation provide the boron of about 0.1 to about 20 atomic ratio.Useful dispersant contains about
0.05 to about 2.0 mass %, such as about 0.05 to about 0.7 mass % boron.Described boron（As dehydration boric acid polymer（Main
If (HBO2)3）Occur in the product）It is considered to be connected as amine salt, such as imidodicarbonic diamide with dispersant acid imide and imidodicarbonic diamide
Metaborate.Boration can be carried out as follows：By about 0.5-4 mass %, such as about 1 to about 3 mass %（Based on acyl group
The quality of nitrogen compound）Boron compound, preferred boric acid（Usually as slurry）Add to acyl group nitrogen compound and about 135
DEG C to about 190 DEG C, such as heat about 1 to about 5 hour at 140 DEG C -170 DEG C under agitation, then nitrogen stripping.Or
Person, boron processes and can be carried out by boric acid is added in dicarboxylic acids material and the thermal reaction mixture of amine eliminating water simultaneously.Also
Reaction method after other generally known in the art can be applied.
Dispersant can also be by reacting to carry out further work-up with so-called " end-capping reagent ".Traditionally, nitrogenous point
Powder " has been blocked " adverse effect to reduce these dispersants to fluoroelastomer engine sealing.Many end-capping reagents and
Method is known.In known " end-capping reagent ", alkaline dispersing agent amino is changed into non-alkaline structure division（Such as acyl ammonia
Base or imino group) those end-capping reagents be most suitable.For example in United States Patent (USP) No.4,839,071；4,839,072 and 4,
Nitrogenous dispersant and Acetacetic acid alkyl ester is described in 579,675（Such as ethyl acetoacetate（EAA））Reaction.For example exist
The reaction of nitrogenous dispersant and formic acid is described in United States Patent (USP) No.3,185,704.Nitrogenous dispersant and other suitable end-blocking
The product of agent is described in United States Patent (USP) No.4,663,064（Hydroxyacetic acid）；4,612,132；5,334,321；5,356,
552；5,716,912；5,849,676；5,861,363（Alkyl and alkylene carbonate, for example, ethylene carbonate）；5,328,
622（Monoepoxide）；5,026,495；5,085,788；5,259,906；5,407,591（Many-epoxide（For example double-ring
Oxide））With 4,686,054（Maleic anhydride or succinic anhydrides）In.Aforementioned list is not limit, nitrogenous dispersant end-blocking
Other methods are well known by persons skilled in the art.
In order to enough piston deposits control, about 0.03 mass % can be provided to about by for lubricant oil composite
0.15 mass %, the amount of preferably approximately 0.07 to about 0.12 mass % nitrogen adds nitrogenous dispersant.
Ashless dispersant is alkalescence in nature and therefore has the TBN that can be about 5 to about 200mgKOH/g, this
Whether whether the property depending on polar group and dispersant processed by boration or with end-capping reagent.However, high-caliber alkalescence
Dispersant nitrogen is known to have adverse effect to the fluoroelastomer material being used to form engine sealing, it is therefore preferable that making
With offer piston deposit is controlled with the dispersant of necessary minimum flow, and substantially do not use dispersant, or preferably do not use
The dispersant that TBN is more than 5.Preferably, the amount of the dispersant of employing will contribute at most 4 for lubricant oil composite, preferably up to 3mg
The TBN of KOH/g.Further preferably dispersant provides at most 30% for lubricant oil composite, preferably up to 25% TBN.
Other additives can be attached in the present composition and enable them to meet specific requirement.Can wrap
The example including the additive in lubricant oil composite is metal antirusting agent, viscosity index improver, corrosion inhibiter, oxidizing and depressing
Agent, friction improver, other dispersant, defoamer, antiwear additive and pour-point depressant.Hereafter will be discussed in some interpolations
Agent.
Aluminum, lead, tin, molybdenum, manganese, nickel, copper is commonly used for antiwear additive and antioxidant.Described metal can be alkali metal or alkali
Earth metal, or aluminum, lead, stannum, molybdenum, manganese, nickel or copper.The most often with 0.1-10wt%, the preferably amount of 0.2-2wt% is used for lubricating oil to zinc salt
In, gross weight based on lubricant oil composite.They can be prepared as follows according to known technology：It is initially formed dialkyldisulfide
For phosphoric acid（DDPA）, generally formed with the reaction of P2S5 by one or more alcohol or phenol, then use in zinc compound and institute's shape
The DDPA becoming.For example, it is possible to phosphordithiic acid is manufactured by the reaction of primary and secondary alcohol mixture.Or, can prepare many
Plant phosphordithiic acid, the alkyl on one of which phosphordithiic acid is entirely sechy-drocarbyl in nature, on other phosphordithiic acid
Alkyl be entirely primary alkyl in nature.In order to manufacture zinc salt, it is possible to use any alkaline or neutral zinc compound, but
Often use oxide, hydroxide and carbonate.Commercially available additive generally comprises excessive zinc, and this is owing in neutralization reaction
Using excessive basic zinc compound.
Preferably dihydrocarbyl dithiophosphate zinc phosphate be dihydrocarbyl dithiophosphate phosphoric acid oil-soluble salt and can be by below general formula table
Show：
Wherein R and R' can be the identical or different alkyl containing 1 to 18, preferably 2 to 12 carbon atoms, and includes
The group of such as alkyl, thiazolinyl, aryl, aralkyl, alkaryl and alicyclic group etc.It is especially preferred as R and R ' base
It is the alkyl containing 2-8 carbon atom.Therefore, these groups can be such as ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl
Base, sec-butyl, amyl group, n-hexyl, isohesyl, n-octyl, decyl, dodecyl, octadecyl, 2- ethylhexyl, phenyl, fourth
Base phenyl, cyclohexyl, methylcyclopentyl, acrylic, cyclobutenyl.In order to obtain oil-soluble, in phosphordithiic acid, carbon atom is total
Number（Namely R and R'）It is typically about 5 or higher.Dihydrocarbyl dithiophosphate zinc phosphate therefore can include dialkyl dithio phosphorus
Sour zinc.When using containing about 0.02 to about 0.12 mass %, such as about 0.03 to about 0.10 mass % or about 0.05 to
The phosphorus level of about 0.08 mass %（Gross mass based on compositionss）Lubricant compositions when, the present invention possibly especially has
?.In a preferred embodiment, the lubricant oil composite of the present invention contains major part（For example, more than 50mol%, for example
More than 60mol%）Zinc dialkyl dithiophosphate derived from secondary alcohol.
Oxidation retarder or antioxidant reduce the tendency that mineral oil goes bad in use.Oxidation deterioration can be by lubrication
Sludge in agent, the clear lacquer deposit of metal surface and confirmed by viscosity increase.These oxidation retarder include
Hindered phenol, preferably comprise C5-C12The alkali salt of alkyl phenol thioesters of alkyl side chain, nonyl phenol calcium sulfide, oil-soluble phenates
With the hydrocarbon of sulfuration phenates, phosphorus sulfuration or sulfuration, phosphide, metal thiocarbamates, such as in United States Patent (USP) No.4,867,890
Described oil-soluble copper compounds and molybdate compound.
The typical oil-soluble aromatic amine with least two aromatic groups being directly connected to an amine nitrogen contains 6-16
Carbon atom.This amine can contain more than two aromatic group.Containing at least three aromatic groups, two of which aromatic group altogether
By covalent bond or by atom or group（Such as oxygen or sulphur atom or-CO- ,-SO2- or alkylidene) connect and two straight
The compound being connected in succession on an amine nitrogen is also regarded as thering is at least two arylamine being directly connected to the aromatic group on nitrogen.Virtue
Ring is generally by one or more taking selected from alkyl, cycloalkyl, alkoxyl, aryloxy group, acyl group, acyl amino, hydroxyl and nitro
Replace for base.
It is commonly employed in combination multiple antioxidants.In a preferred embodiment, the lubricant oil composite of the present invention
Containing about 0.1 to about 1.2 mass % amine antioxidants and about 0.1 to about 3 mass % phenolic antioxidant.At another
In preferred embodiment, the lubricant oil composite of the present invention contains about 0.1 to about 1.2 mass % amine antioxidants, greatly
About 0.1 to about 3 mass % phenolic antioxidant and by the amount providing about 10 to about 1000ppm molybdenums for lubricant oil composite
Molybdenum compound.
The representative example of suitable viscosity improver is the copolymer of polyisobutylene, ethylene and propylene, polymethyl
The copolymer of acid esters, methacrylate copolymer, unsaturated dicarboxylic acid and vinyl compound, styrene and acrylic acid seriess
The partially hydrogenated copolymer of the interpretation of ester and styrene/isoprene, phenylethylene/butadiene partially hydrogenated common
Polymers and the partially hydrogenated copolymer of isoprene/butadiene, and the partially hydrogenated homopolymerization of butadiene and isoprene
Thing.
May also include the friction modifiers compatible with other compositions of product oil and fuel economy reagent.Such material
Example includes the monoglyceride of higher fatty acids, such as glycerin mono-fatty acid ester；Long-chain polybasic carboxylic acid and the ester of glycol, such as dimerization
The butanediol ester of unsaturated fatty acid；Isoxazoline compound；Monoamine, diamidogen and the alkyl ether replacing with the alkyl of alkoxylate
The tallow amine of amine, such as ethoxylation and the tallow ether amine of ethoxylation.
Other known friction improver includes oil-soluble organo-molybdenum compound.Such organic-molybdenum friction improver is also profit
Sliding oil composition provides the effect of antioxidant and antiwear additive.The example of such oil-soluble organo-molybdenum compound includes dithio ammonia
Base formates, dithiophosphatess, dithiophosphinic acid salt, xanthates, Thioxanthate salt, sulfide etc., and they
Mixture.The especially preferably dithiocar-bamate of molybdenum, dialkyl dithiophosphate, alkyl xanthate and alkane
Base Thioxanthate salt.
Additionally, described molybdenum compound can be acidic molybdenum compound.These compounds will be as by ASTM test D-664 or D-
2896 titration procedure are reacted with basic nitrogen compound as being measured and are typically sexavalence.Including be molybdic acid, molybdic acid
Ammonium, sodium molybdate, potassium molybdate and other alkali metal molybdate and other molybdenum salt, such as molybdic acid hydrogen sodium, MoOCl4、MoO2Br2、
Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compound.
The molybdenum compound that can be used for the present composition includes the organic molybdenum with following formula：
Mo(ROCS2)4With Mo (RSCS2)4
Wherein R is the organic group being selected from the group：Alkyl, aryl, aralkyl and alkoxyalkyl, usually contain 1-30
Carbon atom, preferably comprises 2-12 carbon atom, the alkyl of most preferably 2-12 carbon atom.It is particularly preferably the dioxane of molybdenum
Base dithiocar-bamate.
The another kind of organic molybdenum that can be used for lubricating composition of the present invention is tri-nuclear molybdenum compound, especially formula
Mo3SkLnQzThose molybdenum compounds and its mixture, wherein L is the independently selected part containing organic group, wherein organic
Group has enough to make compound solvable or dispersible carbon number in oil, n be 1 to 4, k between 4 to 7, during Q is selected from
Property supplied for electronic compound, such as water, amine, alcohol, phosphine and ether, z is 0-5, and includes non-stoichiometric value.In all part organic groups
Should there are at least 21 entire carbon atom in group, for example, at least 25, at least 30, or at least 35 carbon atoms.
Dispersant viscosity index modifier had both played the effect of viscosity index improver, also functioned to the effect of dispersant.Point
The example of powder-viscosity index improver includes amine（Such as polyamines）The list replacing with alkyl or the product of dicarboxylic acids,
Wherein hydrocarbyl substituent comprises the chain that length be enough to make compound have the viscosity index (VI) property improved.In general, viscosity index (VI) changes
Entering agent dispersant can be, for example, the C of vinyl alcohol4To C24Beta-unsaturated esters or C3To C10Unsaturated monocarboxylic or C4To C10Binary
Carboxylic acid and the polymer of the unsaturated nitrogen containing monomer containing 4 to 20 carbon atoms；C2To C20Alkene neutralizes with amine, azanol or alcohol
Unsaturated C3-C10List or the polymer of dicarboxylic acids；Or ethylene and C3To C20The polymer of alkene, it passes through C4To C20No
Saturation nitrogen containing monomer is grafted to thereon or by being grafted on polymer backbone by unsaturated acids and then making the carboxylic acid group of grafting acid
Group reacts and reacts further with amine, azanol or alcohol.
Pour-point depressant, also referred to as lube oil flow improvers（LOFI）, when reducing flow of fluid or can be dumped
Minimum temperature.Such additives are well-known.Those typical additives improving fluid low temperature flow are fumaric acid C8-
C18Dialkyl/vinyl acetate copolymer, and polymethacrylates.Polysiloxane type defoamer, such as silicon can be passed through
Ketone oil or polydimethylsiloxane are providing foam control.
Some above-mentioned additives can provide multiple effect；Thus, for example, single additive can serve as dispersant-oxygen
Change inhibitor.This mode is known, does not need herein to be further elaborated on.
In the present invention, may preferably further comprise the additive keeping blend viscosity stability.Therefore, although containing polar group
The additive of group achieves suitably low viscosity in the pre- blending stage, it has been observed that some composition viscosities when long term storage
Increase.The additive that this viscosity of effective control increases is included by single with used in the preparation of ashless dispersant as elucidated before
Or dicarboxylic acids or anhydride reaction and the long chain hydrocarbons of functionalization.
When lubricating composition contains one or more above-mentioned additive, generally by every kind of additive so that this additive
The amount that its required function can be provided is mixed in base oil.
When lubricating composition contains one or more above-mentioned additive, generally by every kind of additive so that this additive
The amount that its required function can be provided is mixed in base oil.When crankcase lubricant uses, the representativeness of these additives
Effective dose as follows.All values listed all are given with mass percent active component.
Table II
The lubricant oil composite of the preparation completely of the present invention preferably have at least 8.5, preferably at least 9, such as about 8.5 to
About 13, preferably approximately 9 to about 13, more preferably from about 9 to about 11mgKOH/g TBN（ASTM D-2896 and/or ASTM
D-4739）.
The lubricant oil composite of the preparation completely of the present invention preferably has about 1.1 mass % or lower, and preferably approximately 1.0
Quality % or lower, more preferably from about 0.8 mass % or lower sulfated ash（SASH）Content（ASTM D-874）.
Preferably, the lubricant oil composite of the preparation completely of the present invention is by the nothing of the compound including at least one formula (I)
At least the 5% of grey TBN source acquisition compositionss TBN, preferably at least 10%, more preferably at least 20%.It is further preferred that the present invention's joins completely
System lubricant oil composite by least one formula (I) compound obtain compositionss TBN at least 5%, preferably at least 10%, more excellent
Choosing at least 20%, and by the ashless tbn sources beyond the compound of formula (I), obtain being less than of compositionss TBN including alkaline dispersing agent
25%, preferably smaller than 20%, more preferably less than 15%.
The lubricant oil composite of the preparation completely of the present invention further preferably has less than about 0.4 mass %, more preferably little
In about 0.35 mass %, more preferably less than about 0.03 mass %, the sulfur content of e.g., less than about 0.15 mass %.Preferably,
The lubricant oil composite of preparation completely（The oil of lubricant viscosity adds all additives and additive diluent）Noack volatility
（ASTM D5880）To be at most 13, such as at most 12, preferably up to 10.The lubricant oil composite of the preparation completely of the present invention is excellent
Choosing has at most 1200ppm phosphorus, for example at most 1000ppm phosphorus, or at most 800ppm phosphorus.
May cater to the need but be not required is, prepares one or more multifunctional additive for lubricating oils containing additive（Dense
Contracting thing is sometimes referred to as additive bag）, thus several additives can be simultaneously introduced in oil to form lubricant oil composite.For
The concentrate preparing lubricant oil composite of the present invention is permissible, for example, one or more formula containing about 5 to about 30 mass %
(I) compound；The nitrogenous dispersant of about 10 to about 40 mass %；The amine antioxidants of about 2 to about 20 mass %,
Phenol antioxidant, molybdenum compound or its mixture；The detersive of about 5-40 mass %；About 2 to about 20 mass %
Metal dialkyl dithiophosphate.
Final composition can use 5-25 mass %, preferably 5-18 mass %, the concentrate of usual 10-15 mass %, residue
The oil for lubricant viscosity and viscosity improver.
The all wt representing herein（And quality）Percentage rate（Unless otherwise stated）It is all based on additive and/or additive
The active component of bag（A.I.）, do not include any diluent accompanying.However, detersive is formed generally in flux oil, should
Flux oil does not remove from product, and the TBN of detersive is generally carried by the active cleaning agent in the flux oil accompanying
For.Therefore, when being related to detersive, weight（And quality）Percentage rate（Unless otherwise stated）It is all active component and accompanying
The gross weight of flux oil（Or quality）Percentage rate.
The present invention will be further understood by reference to following examples.
Embodiment
(I) synthesis of 4- ethyoxyl-N- (4- methyl amyl- 2- yl) aniline
4- ethoxybenzene is added in 1 liter of three neck round bottom be equipped with thermometer, charging hopper and mechanical agitator
Amine（20.00g, 143mmol）, in advance in mortar pulverize sodium triacetoxyborohydride（38.30g, 171mmol）With
475ml dichloromethane.4-methyl-2 pentanone is added in charging hopper（15.98g, 157mmol）With 25ml dichloromethane.Warp
By funnel, ketone is added slowly in this flask and allows reaction to carry out overnight.After reacting, add saturation via funnel
NaHCO3Solution.Then use saturation NaHCO again3Solution washs organic faciess, washes with water again, then using MgSO4It is dried.
After filtering under vacuo and evaporating, obtain the faint yellow oil of 31g.This product is used for following steps（ii）.
（ii）The synthesis of 4- ethyoxyl-N- (2- ethylhexyl)-N- (4- methyl amyl- 2- yl) aniline
Previous step (i) is added in 1 liter of three neck round bottom be equipped with thermometer, charging hopper and mechanical agitator
4- ethyoxyl-N- (the 4- methyl amyl- 2- yl) aniline of middle preparation（31.00g, 140mmol）, in advance in mortar pulverize three second
Acyloxy borohydride sodium（37.50g, 168mmol）With 475ml dichloromethane.2- ethyl hexanal is added in charging hopper
（20.58g, 154mmol）With 25ml dichloromethane.Via funnel, aldehyde is added slowly in this flask and allows reaction to carry out
Night.After reacting, add saturation NaHCO via funnel3Solution.Then use saturation NaHCO again3Solution washs organic faciess, then
Secondary wash with water, then using MgSO4It is dried.After filtering under vacuo and evaporating, obtain 71.3g peony oil.Test below
This product, it is labeled as synthetic example 1 there.
Synthetic example 2
（iii）The synthesis of 4- ethyoxyl-N- (butyl- 2- yl) aniline
4- ethoxybenzene is added in 2 liters of three neck round bottoms be equipped with thermometer, charging hopper and mechanical agitator
Amine（50.00g, 357mmol）, in advance in mortar pulverize sodium triacetoxyborohydride（104g, 464mmol）And 700ml
Dichloromethane.2-butanone is added in charging hopper（31.2g, 429mmol）With 50ml dichloromethane.Via funnel, ketone is slow
Ground is added in this flask and allows reaction carry out two days.Then pass through to add saturation NaHCO via funnel3Solution will react sudden
Go out.Then use saturation NaHCO3Solution washs organic faciess, washes with water again, then using MgSO4It is dried.Filter under vacuo
After evaporation, obtain 70.4g peony oil.This product is used for following steps（iii）.
（iv）The synthesis of 4- ethyoxyl-N- (2- ethylhexyl)-N- (butyl- 2- yl) aniline
It is equipped with addition previous step in 2 liters of three neck round bottoms of thermometer, charging hopper and mechanical agitator（iii）
4- ethyoxyl-N- (the butyl- 2- yl) aniline of middle preparation（70.00g, 140mmol）, in advance in mortar pulverize triacetoxyl group
Borohydride sodium（105g, 471mmol）With 750ml dichloromethane.2- ethyl hexanal is added in charging hopper（58.0g,
435mmol）With 50ml dichloromethane.Via funnel, aldehyde is added slowly in this flask and allows reaction carry out two days.Then
By adding saturation NaHCO via funnel3Solution will react quenching.Then use saturation NaHCO3Solution washs organic faciess, uses again
Water washing, then using MgSO4It is dried.After filtering under vacuo and evaporating, obtain 108.2g peony oil.Test this below
Product, it is labeled as synthetic example 2 there.
Comparative example（Synthetic example 3）
By 450g phenetidine（3.28 mole）, 1682g 2- ethyl hexanal（13.1 moles）, 45g 10%Pd/C and 2L
Dry methanol adds Parr reactor.With hydrogen, reactor is pressurized to 10 bars and is heated to 100 DEG C under agitation.Supervised by HPLC
Measured reaction is to completing.Then reactor cooled to room temperature and is filtered to remove catalyst.The distillation of reactant mixture produces
800g product, passes through1H- and13C-NMR confirms the structure of this product.
The reaction process of above-mentioned synthesis shows as follows：
TBN performance
The basicity of lubricant oil composite can be measured by acidometric titration.The neutralization number of gained is expressed as total base number, or TBN,
And can be using various method measurements.In this using method ASTM D-4739（Current potential HCI）.ASTM 4739 method
It is favourable to measure TBN dilution/reservation in Engine Block Test and for used oil.
TBN tests
Preparation in base oil contain dispersant, peace and quiet agent composition, antioxidant, ZDDP antiwear additive, pour-point depressant and
The lubricant oil composite of the preparation completely of viscosity improver.This lubricant oil composite（Represent business crankcase lubricant）It is used as
With reference to lubricant.The compound containing 1.68 mass % synthetic examples 1 for the preparation（Oily A）Compound with synthetic example 2（Oily B）
Preparation completely lubricant oil composite.It is also tested for containing 1.00 mass %（Oily C）With 2.00 mass %（Oily D）Synthetic example 3
The preparation completely of control compounds lubricant oil composite.The base oil of additional quantity is added in every kind of sample to provide phase
When gross mass.Measure the TBN of every kind of gained sample according to each of ASTM D4739（Unit is mg KOH/g）.Result
It is shown in lower Table III.
Table III
| Embodiment | Reference | Oily A | Oily B | Oily C | Oily D |
| Reference sample（g） | 95.0 | 47.5 | 47.5 | 47.5 | 47.5 |
| The base oil adding（g） | 5.0 | 1.66 | 1.66 | 2 | 1.5 |
| Aniline compound（g） | - | 0.84 | 0.84 | 0.5 | 1.0 |
| Gross weight（g） | 100 | 50 | 50 | 50 | 50 |
| TBN, according to D-4739 | 8.75 | 10.49 | 11.60 | 8.87 | 8.97 |
| Δ TBN, with respect to reference, according to D-4739 | - | 1.74 | 2.85 | 0.12 | 0.22 |
As indicated, the compound of the present invention as in oily A and oily B using effectively improve lubricant oil composite
TBN, is measured by ASTM D-4739, but SASH content is no contributed.Synthetic example 3 have di-alkyl branched arrangement but
The control compounds of not according to the invention are not given in terms of TBN and are markedly improved.This is even wherein using greater amount
Compound（2.00 mass %vs.1.64 mass %）Oily D in the case of also such.
Fluoroelastomer seal compatibility is tested
VW-6/AK6 test in test oil A and contain N, N- bis--n-hexyl -4- phenetidine replace the compounds of this invention
Similar oil.This program test lubricating oil and the compatibility of Viton fluoroelastomer encapsulant.Reference without compound
The elongation at break of oil and novel sealing are in a ratio of average -34.5%.For oily A, be averagely -51%, for containing N, N- bis--just oneself
The oil of base -4- phenetidine, is -64%.These tests show, the compound of the present invention with two linear alkyl chain
Similar compound is compared, and has much lower impact to encapsulant.
Claims (21)
1. lubricant oil composite, comprises the oil of major amount of lubricant viscosity and the compound of one or more formula (I) of minor amount：
Wherein R1, R2, R3, R4And R5Independently represent alkyl or the replacement alkyl without aryl substituent.
2. lubricant oil composite according to claim 1, wherein R1Represent methyl or ethyl.
3. lubricant oil composite according to claim 2, wherein R1Represent methyl.
4. lubricant oil composite according to claim 1, wherein R3Represent methyl or ethyl.
5. lubricant oil composite according to claim 2, wherein R3Represent methyl or ethyl.
6. the lubricant oil composite according to claim 4 or 5, wherein R3Ethyl.
7. lubricant oil composite as claimed in one of claims 1-5, wherein R5Represent methyl or ethyl.
8. lubricant oil composite according to claim 7, wherein R5Represent ethyl.
9. lubricant oil composite according to claim 1, has the TBN of at least 6mg KOH/g, is measured according to ASTM D-4739.
10. lubricant oil composite according to claim 9, has the TBN of 6-15mg KOH/g, is measured according to ASTM D-4739.
11. lubricant oil composites according to claim 1, have the SASH content of at most 1.1 mass %.
12. lubricant oil composites according to claim 11, have the SASH content of at most 1.0 mass %.
13. lubricant oil composites according to claim 11, have the SASH content of at most 0.8 mass %.
At least the 10% of 14. lubricant oil composites according to claim 1, wherein compositionss TBN stems from including at least one
The ashless tbn sources of the compound of formula (I), measure according to ASTM D-4739.
At least the 15% of 15. lubricant oil composites according to claim 14, wherein compositionss TBN stems from including at least one
The ashless tbn sources of the compound of formula (I), measure according to ASTM D-4739.
At least the 20% of 16. lubricant oil composites according to claim 14, wherein compositionss TBN stems from including at least one
The ashless tbn sources of the compound of formula (I), measure according to ASTM D-4739.
17. lubricant oil composites according to claim 1, have a sulfur content less than 0.4 mass %, and at most 1200ppm
Phosphorus.
18. are used for the concentrate according to the lubricant oil composite of any one of claim 1-17 for the preparation, and described concentrate comprises
The compound of the formula (I) described in 2.5 to 30 one or more of quality % claim 1；The nitrogenous dispersant of 10 to 40 quality %；
2 to 20 quality % amine antioxidants, phenolic antioxidant, molybdenum compound or their mixture；5 to 40 quality % detersives；
With 2 to 20 quality % metal dialkyl dithiophosphates.
The compound of 19. formulas (I)：
Wherein R1, R2, R3, R4And R5Independently represent alkyl or the replacement alkyl without aryl substituent.
The TBN of 20. raising lubricant oil composites and the method for different raising SASH content, the method includes to described lubricating oil
Add one or more compound according to claim 19 in compositionss.
21. compounds according to claim 19 are as the purposes in ashless lubricating oil compositionss TBN source.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11183113.7 | 2011-09-28 | ||
| EP11183113.7A EP2574656B1 (en) | 2011-09-28 | 2011-09-28 | Lubricating oil compositions comprising p-alkoxy-N,N-dialkyl-aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103074143A CN103074143A (en) | 2013-05-01 |
| CN103074143B true CN103074143B (en) | 2017-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210369519.8A Active CN103074143B (en) | 2011-09-28 | 2012-09-27 | Lubricant oil composite |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130252865A1 (en) |
| EP (1) | EP2574656B1 (en) |
| JP (1) | JP5973301B2 (en) |
| CN (1) | CN103074143B (en) |
| CA (1) | CA2791282C (en) |
| SG (1) | SG188776A1 (en) |
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|---|---|---|---|---|
| US9969950B2 (en) * | 2012-07-17 | 2018-05-15 | Infineum International Limited | Lubricating oil compositions containing sterically hindered amines as ashless TBN sourcces |
| EP3066178B1 (en) * | 2013-11-04 | 2019-01-09 | Basf Se | Lubricant composition |
| WO2015148301A1 (en) | 2014-03-28 | 2015-10-01 | Cummins Filtration Ip, Inc. | Ashless oil additives and their use as tbn boosters |
| US9574158B2 (en) | 2014-05-30 | 2017-02-21 | Afton Chemical Corporation | Lubricating oil composition and additive therefor having improved wear properties |
| US20160032213A1 (en) | 2014-07-31 | 2016-02-04 | Chevron U.S.A. Inc. | Sae 15w-30 lubricating oil composition having improved oxidative stability |
| SG11201803725SA (en) | 2016-01-22 | 2018-06-28 | Chevron Oronite Co | Synergistic lubricating oil composition containing a mixture of olefin copolymer dispersant-type viscosity improver and amine compound |
| US10662391B2 (en) * | 2017-02-21 | 2020-05-26 | Chevron Oronite Company Llc | Lubricating oil compositions containing borated dispersants and amine compounds and methods of making and using same |
| US10435643B2 (en) | 2017-03-06 | 2019-10-08 | Chevron Oronite Company Llc | Lubricating oil compositions containing amine compounds having improved seal performance |
| CN115261104B (en) * | 2019-08-14 | 2023-08-25 | 胜牌全球产品知识产权有限公司 | Lubricant composition containing ashless TBN molecules |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5973301B2 (en) | 2016-08-23 |
| CA2791282A1 (en) | 2013-03-28 |
| JP2013072088A (en) | 2013-04-22 |
| SG188776A1 (en) | 2013-04-30 |
| US20130252865A1 (en) | 2013-09-26 |
| EP2574656A1 (en) | 2013-04-03 |
| CA2791282C (en) | 2019-05-14 |
| CN103074143A (en) | 2013-05-01 |
| EP2574656B1 (en) | 2014-04-02 |
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