CN103074143A - Lubricating oil compositions - Google Patents

Lubricating oil compositions Download PDF

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Publication number
CN103074143A
CN103074143A CN2012103695198A CN201210369519A CN103074143A CN 103074143 A CN103074143 A CN 103074143A CN 2012103695198 A CN2012103695198 A CN 2012103695198A CN 201210369519 A CN201210369519 A CN 201210369519A CN 103074143 A CN103074143 A CN 103074143A
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lubricating oil
quality
oil composition
compound
oil
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CN103074143B (en
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G·坎迪多
J·P·哈特利
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Infineum International Ltd
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Infineum International Ltd
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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

A lubricating oil composition comprising a major amount of oil of lubricating viscosity and a minor amount of one or more compounds of formula (I): wherein R 1 , R 2 , R 3 , R 4 and R 5 independently represent alkyl or substituted alkyl having no aryl substituent.

Description

Lubricating oil composition
Technical field
The present invention relates to comprise the lubricating oil composition of a class aniline compound.Described aniline compound can be used as lubricating oil composition, especially has ashless tbn (total basicnumber) promotor of the crankcase lubricating oil composition that falls low-level sulfated ash (SASH).
Background of invention
Concern for environment has caused ongoing effort to reduce CO, hydrocarbon and oxynitride (NOx) discharging of the light-duty explosive motor of ignition (take diesel oil as fuel) and spark ignition (take gasoline as fuel).In addition, ongoing effort reduces the particle emission of compression-ignition, internal combustion engine.In order to satisfy the emission standard for the heavy-duty diesel oil locomotive that is about to appearance, original equipment manufacturer (OEM) will depend on and use extra exhaust aftertreatment device.This exhaust aftertreatment device can comprise catalytic converter and/or grain catcher, and this catalytic converter can comprise one or more oxide catalysts, NOx storage catalyst and/or NH 3Reducing catalyst.
Oxide catalyst is owing to be exposed in some elements/compounds that exists in the engine exhaust, especially is exposed to degraded by phosphorous lubricating oil additive and is incorporated in the phosphorus and phosphorus compound in the waste gas, can become to poison and not too effective.Responsive owing to being used for sulphur and sulphur compound that the two the degraded of the base oil of blend lubricant and sulfur-bearing lubricating oil additive introduces in the engine exhaust of reducing catalyst.Grain catcher can become and be stopped up by calx, and this calx is the product of the containing metal lubricating oil additive of degraded.
In order to ensure long work-ing life, must find the lubricating oil additive that this after-treatment device is brought minimum negative impact, and for the maximum phosphorus content of the maximum sulfur of the OEM specification requirement 0.4 quality % of heavy-duty diesel oil (HDD) lubricant of " new safeguard fill " and " first filling ", 0.12 quality % be lower than the sulfate ash content of 1.1 quality %, this lubricant is called as " middle SAPS " lubricant (wherein " SAPS " is the acronym of " sulfated ash, phosphorus, sulphur ").In the future, OEM can further be restricted to these maximum level the phosphorus of 0.08 quality %, the sulphur of 0.02 quality % and the sulfated ash of 0.8 quality %, and this lubricant is called as " low SAPS " lubricating oil composition.
The amount of the lubricant additive of, sulphur phosphorous along with reducing and ash content is to provide the neutralization low SAPS lubricant compatible with exhaust aftertreatment device, lubricating oil composition must continue to provide high-caliber lubricity, comprise enough purifications, and this is by " the new maintenance " and the domination of " filling first " specification of OEM, such as ACEA E6 and the MB p228.51(Europe for the heavy duty engine lubricant) and API CI-4+ and the API CJ-4(U.S.) specification.The criterion that classifies as the lubricating oil composition that satisfies above-listed industrial standards is well known by persons skilled in the art.
Can improve in the lubricant and the ability of combustion acid by product, described by product is being equipped with exhaust gas recirculation (EGR) system, especially wherein increase in the engine of the condensation egr system that before recirculation, is cooled of waste gas, and can prolong the displacement time limit of lubricant by the total basicnumber (TBN) that improves composition.In history, TBN provides by the high alkaline detergent of sulfated ash being introduced composition.It will be favourable using the TBN enhancement component of not contributing sulfated ash that the lubricating oil composition with high TBN level is provided.Because the high alkalinity component is known cause corrosion and, in some cases, reducing the consistency between the fluoroelastomer sealing material that uses in lubricating oil composition and the engine, will be preferred so this kind component that does not cause the corrosion and preferably can not adversely affect the sealing member consistency is provided.Because to the needs of improved fuel economy, the lubricant of viscosity not too, for example 0W and 5W 20 and 30 rank lubricants have become more and more general.In order to allow the easier preparation of this kind lubricant, the amount of the polymkeric substance of introducing by additive preferably reduces to minimum.Therefore, it will be further preferred providing the non-polymeric ashless tbn sources.
U.S. Patent No. 5,525,247; 5,672,570 and 6,569,818 relate to " low ash content " lubricating oil composition, and wherein sulfate ash content reduces by substituting high alkaline detergent with neutral purification agent.These patents are described as the purification that provides enough with this series lubricant agent, but do not require this series lubricant agent will provide enough TBN for use in for example HDD engine.U.S. Patent application 2007/0203031 has been described and has been used the nitrogenous dispersion agent of high TBN as ashless tbn sources.
U.S. Patent No. 4,100,082; 4,200,545; 4,320,021,4,663,063; 4,708.809 and russian patent application SU1825780 aminophenol compound as lubricating oil additive (for example, dispersion agent/purification agent) has been described.U.S. Patent No. 2,511,750; 3,634,248; 4,269,720; 4,335,006; 4,411,805 and 6,242,394 have described some aniline compound of the stablizer (antioxidant) as lubricating oil composition.U.S. Patent No. 4,778,654 have described the alkyl benzene amine that can be used as inhibiter/formaldehyde co-oligomer.
The applicant's common unsettled EP 2 206 764A1 have described the ashless tbn sources of aniline compound as lubricating oil.The aniline compound that two-alkyl that preferred two alkyl that wherein are connected with nitrogen-atoms are straight chained alkyls replaces.The example of two-branching (two-2-ethylhexyl) compound is provided, but has not provided data for its TBN performance in lubricating oil.
Summary of the invention
Have now found that two-alkyl benzene amine material that some alkoxyl group replaces can provide improved TBN performance when as lubricated oil additives.This kind oil also has the fluoroelastomer seal compatibility of enhancing, for example passes through the such of VW-6/AK6 experimental measurement.
Therefore, in first aspect, the invention provides lubricating oil composition, it comprises the compound of one or more formulas (I) of the oil of lubricant viscosity of main amount and minor amount:
Figure BDA00002212455500031
R wherein 1, R 2, R 3, R 4And R 5Represent independently alkyl or do not contain the substituted alkyl of aryl substituent.
The compound of formula (I) is characterised in that they have two different branched-alkyls that are connected with nitrogen-atoms.One of described branched-alkyl is being the carbon atom place branching of β-position with nitrogen-atoms being the carbon atom place branching of alpha-position and another branched-alkyl with nitrogen-atoms.Have been found that this particular configuration provides the TBN performance of enhancing.
Preferably, described lubricating oil satisfies in ACEA E6, MB p228.51, API CI-4+ and the API CJ-4 specification of heavy duty engine lubricant one or more performance criteria.
According to second aspect, the invention provides for the preparation of the enriched material according to the lubricating oil composition of above-mentioned arbitrary claim, described enriched material comprises about 2.5 compounds to about 30 one or more formulas of quality % (I); About 10 to about 40 quality % nitrogenous dispersion agents; About 2 to about 20 quality % amine antioxidantss, phenolic antioxidant, molybdenum compound or their mixture; About 5-40 quality % purification agent; With about 2 to about 20 quality % metal dialkyl dithiophosphates.
According to third aspect of the present invention, provide the compound of formula (I):
Figure BDA00002212455500041
R wherein 1, R 2, R 3, R 4And R 5Represent independently alkyl or do not contain the substituted alkyl of aryl substituent.
The 4th aspect according to the present invention provides the method that improves the TBN of lubricating oil composition in the situation that does not improve simultaneously SASH content, and the method comprises in described lubricating oil composition adds one or more compounds according to the 3rd aspect.
According to the 5th aspect, the invention provides according to the compound of the 3rd the aspect purposes as ashless lubricating oil composition TBN source.
Embodiment
The compound that can be used as the ashless tbn sources of lubricating oil composition has formula (I):
Figure BDA00002212455500051
Preferably, R 1, R 2, R 3, R 4And R 5Represent independently alkyl.
Preferably, R 1Represent methylidene or ethyl, methyl are preferred.
Preferably, R 3Represent methylidene or ethyl, ethyl are preferred.
R wherein 1And/or R 3Represent longer alkyl, for example contain 3-12 carbon atom alkyl embodiment also within the scope of the present invention.
Preferably, R 2Representative contains the alkyl of 3-12 carbon atom, and this group can be straight chain or branching.
Preferably, R 4Representative contains the alkyl of 3-12 carbon atom, and this group can be straight chain or branching.
Preferably, R 5It is that methoxy or ethoxy replaces that thereby represent methylidene or ethyl make phenyl ring.More preferably, R 5Represent ethyl.R wherein 5Represent longer alkyl, for example contain 3-12 carbon atom alkyl embodiment also within the scope of the present invention.
In a preferred embodiment, the compound of formula (I) has following structure:
Figure BDA00002212455500052
In another preferred embodiment, the compound of formula (I) has following structure:
Figure BDA00002212455500061
Preferably, it is about at least 50 that compound of the present invention has, preferably about at least 100, and more preferably about at least 140, most preferably at least approximately the TBN(of 180mg KOH/g measures according to ASTM D-2896 and/or ASTM D-4793).
Preferably, compound of the present invention preferably about at least 250 ℃, more preferably has under about at least 300 ℃ temperature at about at least 200 ℃〉99% weight loss, measure by thermogravimetric analysis (in air, with the temperature ramp of 10 ℃/min).
The formation method of the compound of formula (I) should it will be apparent to those skilled in the art that.The method that some are fit to is described below.
The aniline of aniline and replacement for example phenetidine is commercially available.N, the derivative of N-dialkyl aniline and replacement is N for example, and N-dialkyl group phenetidine can followingly be prepared: the derivative that makes suitable aniline or replacement for example phenetidine and aldehyde/ketone for example reacts in dichloromethane solvent in the presence of the triacetoxyl group sodium borohydride at reductive agent by 1:2 or excess molar ratio.These methods are well-known and are described in the literature, referring to for example Jn.Org.Chem(1996), 61, pp.3489-3862.
Another kind method comprises that the aniline and the halogenated alkyl (for example, the bromination alkyl) that make suitable aniline or replacement press the 2:1 mol ratio, reacts in acetonitrile solvent in the presence of triethylamine.
The derivative that another method makes aniline or replacement for example phenetidine and aldehyde/ketone reacts in methanol solvate in the presence of hydrogen and 10%Pd/C catalyzer by 1:2 or excess molar ratio.These methods are that such methods that know and many for example are described in the U.S. Patent No. 2,045,574.
Asymmetric compound of the present invention can use aforesaid method and other method by adopting progressively approach preparation by similar mode, wherein an alkyl is connected on the nitrogen-atoms, then connects second different alkyl.
The oil of the lubricant viscosity that can use within the scope of the present invention can be selected from natural lubricating oil, ucon oil and their mixture.Lubricating oil can have from lighting end mineral oil to heavy grease for example range of viscosities of petrol engine oil, mineral lubricating oils and heavy-duty diesel oil.Generally speaking, the viscosity that described oil records under 100 ℃ is that about 2 centistokes(cst)s (centistoke) are to about 40 centistokes(cst)s, particularly about 4 centistokes(cst)s to about 20 centistokes(cst)s.
Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard); Hydrofining, solvent treatment or the acid-treated mineral oil of liquid petroleum and alkane, cycloalkanes and mixing alkane-naphthenic hydrocarbon type.The oil that is derived from the lubricant viscosity of coal or shale also is used as useful base oil.
Ucon oil comprises the hydrocarbon ils that hydrocarbon ils and halogen replace, the alkene of polymerization and mutually polymerization (for example, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly-(1-hexene), poly-(1-octene), poly-(1-decene)) for example; Alkylbenzene (for example, dodecylbenzene, Tetradecylbenzene, dinonyl benzene, two (2-ethylhexyl) benzene); Polyphenyl (for example, biphenyl, terphenyl, alkylating polyphenol); With alkylating phenyl ether and alkylating diphenyl sulfide and derivative, analogue and homologue.The gas that is derived from the synthetic hydrocarbon of fischer-tropsch is to the synthetic oil of liquid technique or useful, and they are commonly referred to gas to liquid, or " GTL " base oil.
Wherein the oxyalkylene polymer by modifications such as esterification, etherificates and interpretation and their derivative consist of another kind of known ucon oil to terminal hydroxyl.Their example comprises the polyoxyalkylene polymers that is prepared by the polymerization of ethylene oxide or propylene oxide, with the alkyl of polyoxyalkylene polymers and aryl ethers (for example, molecular weight is that 1000 methyl-poly-Isopropanediol ether or molecular weight are the diphenyl ether of the polyoxyethylene glycol of 1000-1500); With their list and multi-carboxylate, for example C of acetic ester, mixing 3-C 8The C of fatty acid ester and TEG 13The oxygen acid diester.
Another kind of suitable ucon oil comprises the ester of di-carboxylic acid (such as phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc.) and various alcohol (such as butanols, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, Diethylene Glycol monoether, propylene glycol etc.).The specific examples of this class ester comprises the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two (eicosyl) ester, linoleic acid dimer, and the complex ester that is formed by the 2 ethyl hexanoic acid reaction of the TEG of 1 mole sebacic acid and 2 moles and 2 moles.
The ester that can be used as synthetic oil also comprises by C 5-C 12Those that monocarboxylic acid and polyvalent alcohol and polyol ester such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol are made.
Oil based on silicon consists of another kind of useful synthetic lubricant such as poly-alkyl, poly-aryl, poly-alkoxyl group or poly-aryloxy silicone oil and silicic acid ester oil; This oil comprises tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four (2-ethylhexyl) ester, silicic acid four (4-methyl-2-ethylhexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, six (4-methyl-2-ethylhexyl) sily oxide, poly-(methyl) siloxanes and poly-(aminomethyl phenyl) siloxanes.Other ucon oil comprises liquid ester (for example diethyl ester of Tritolyl Phosphate, trioctyl phosphate, decylphosphonic acid) and the polytetrahydrofuran of phosphorous acid.
The oil of lubricant viscosity can comprise the base oil blend of I group, II group, III group oil base stock or above-mentioned oil base stock.Preferably, the oil of lubricant viscosity is II group, III group oil base stock or their mixture, or the mixture of I group oil base stock and one or more II and III group oil base stock.Preferably, the oil of the lubricant viscosity of main amount is II group, III group, IV group or V group oil base stock, or their mixture.Oil base stock or oil base stock blend preferably have at least 65%, and more preferably at least 75%, at least 85% saturates content for example.Most preferably, oil base stock or oil base stock blend have the saturates content greater than 90%.Preferably, oily or oily blend will have less than 1wt%, preferably less than 0.6wt%, most preferably less than the sulphur content of 0.4wt%.
Preferably, the oil of measuring by Noack volatility test (ASTM D5880) or the volatility of oily blend are less than or equal to 30%, preferably are less than or equal to 25%, are more preferably less than or equal 20%, most preferably are less than or equal to 16%.Preferably, viscosity index (VI) oily or oily blend is at least 85, preferably at least 100, and about 105-140 most preferably.
Among the present invention to definition and API (API) publication " Engine Oil Licensing and Certification System " of oil base stock and base oil, Industry Services Department, the 14 edition, in December, 1996, those definition in the appendix 1,1998 year 12 months are identical.Described publication is classified as follows oil base stock:
A) I group oil base stock comprises less than 90% saturates and/or greater than 0.03% sulphur, and viscosity index is used the test method of regulation in the table 1 more than or equal to 80 and less than 120.
B) II group oil base stock comprises more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and viscosity index is used the test method of regulation in the table 1 more than or equal to 80 and less than 120.
C) III group oil base stock comprises more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and viscosity index is used the test method of regulation in the table 1 more than or equal to 120.
D) IV group oil base stock is poly-alpha olefins (PAO).
E) V group oil base stock comprise all other be not included in oil base stock in I, II, III or the IV group.
The analytical procedure of Table I-oil base stock
Performance Test method
Saturates ASTM D 2007
Viscosity index ASTM D 2270
Sulphur ASTM D 2622
ASTM D 4294
ASTM D 4927
ASTM D 3120
Lubricating oil composition of the present invention can further contain one or more containing metal purification agents or ash content forms purification agent.Containing metal purification agent or ash content form purification agent not only as purification agent reducing or to remove settling but also as acid neutralizing agent or rust-preventive agent, thereby reduce wear and corrode and prolong engine life.Purification agent contains the polar head with long hydrophobicity afterbody usually, and polar head comprises the metal-salt of acidic organic compound.This salt can comprise the basically metal of stoichiometry, and in this case, they are commonly called normal salt or neutral salt, and usually has total basicnumber or the TBN common (can measure by ASTM D-2896 and/or ASTM D-4793) of 0-80.Can introduce a large amount of metal base by making excessive metallic compound (such as oxide compound or oxyhydroxide) and sour gas (such as carbonic acid gas) reaction.The gained high alkaline detergent comprises that the purification agent of neutralization is as the skin of metal base (for example carbonate) micella.This high alkaline detergent can have 150 or larger TBN, and usually will have 250 to 450 or higher TBN.In the presence of the compound of formula (I), can reduce the amount of high alkaline detergent, (for example maybe can use the purification agent of the high alkalinity level with reduction, TBN is the purification agent of 100-200), or neutral purification agent, this causes the corresponding reduction of the SASH content of lubricating oil composition, and their performance does not reduce.
Operable purification agent comprises metal especially basic metal or alkaline-earth metal, for example the oil soluble neutrality of sodium, potassium, lithium, calcium and magnesium and overbased sulfonate, phenates, sulfuration phenates, thio-phosphonates, salicylate and naphthenate and other oil soluble carboxylate salt.The most frequently used metal is the mixture of calcium and magnesium (they can be provided at the purification agent for lubricant simultaneously) and calcium and/or magnesium and sodium.Especially the metal detergent that is fit to is neutrality and the high alkaline calcium sulfonate with TBN of 20-450, and has neutrality and high alkalinity calcium phenates and the sulfuration phenates of the TBN of 50-450.Can use the combination of purification agent, no matter be high alkalinity, neutrality or the two.
Sulfonate can be prepared by sulfonic acid, and the sulfonation of the aromatic hydrocarbon that sulfonic acid replaces by alkyl usually obtains, those that are for example obtained by the fractionation of oil or the alkylation by aromatic hydrocarbon.Example comprises by making those that benzene,toluene,xylene, naphthalene, biphenyl or their halogen derivative such as chlorobenzene, toluene(mono)chloride and chloronaphthalene alkylation obtain.Alkylation can be carried out in the presence of catalyzer, and wherein alkylating agent has about 3 to greater than 70 carbon atoms.The aromatic structure that alkylaryl sulfonate replaces for each alkyl usually partly contains about 9 to about 80 or more carbon atom, and preferably approximately 16 is to about 60 carbon atoms.
The oxide compound of oil-soluble sulfonic acid salt or an alkarylsulphonic acid available metal, oxyhydroxide, alkoxide, carbonate, carboxylate salt, sulfide, sulfhydrate, nitrate, borate and ether neutralization.The amount of metallic compound is selected according to the TBN of final product expectation, but the about 100-220 quality %(that is generally the stoichiometry aequum is preferred at least 125 quality %).
The metal-salt of phenol and phenol red is by preparing with suitable metallic compound such as the reaction of oxide compound or oxyhydroxide, and neutrality or high alkalinity product can be obtained by method well-known in the art.Phenol red can prepare by making phenol and sulphur or sulfocompound such as hydrogen sulfide, a halogenation sulphur or dihalide reaction of Salmon-Saxl, is generally the product of the mixture of compound with formation, and wherein 2 or more phenol are by the abutment bridge joint of sulfur-bearing.
Lubricating oil composition of the present invention can further contain one or more ashless dispersants, and the settling that they reduce effectively when being used for gasoline and diesel motor in the time of in adding lubricating oil to forms.The ashless dispersant that can be used for the present composition comprise have can with the oil soluble polymerization long-chain skeleton of the functional group of particle association to be disperseed.Usually, this type of dispersion agent comprises amine, alcohol, acid amides or the ester polar structure part that usually is connected with polymer backbone via bridging group.Described ashless dispersant is passable, for example, is selected from the monocarboxylic acid of long chain hydrocarbon replacement and oil soluble salt, ester, amino ester, acid amides, imide He the oxazoline of polycarboxylic acid or their acid anhydrides; The thio carboxy acid ester derivative of long chain hydrocarbon; Long chain aliphatic hydrocarbon with the polyamines structure division that is directly connected on it; And by the phenol of long-chain replacement and Mannich (Mannich) condensation product of formaldehyde and polyalkylenepolyamines condensation formation.The most common dispersion agent is the succinimide dispersants of knowing in the use, and it is the alkyl succinyl oxide that replaces and the condensation product that gathers (alkylene amines).Single succinimide and double amber imide dispersion agent (with their mixture) are all known.
Preferably, ashless dispersant is number-average molecular weight
Figure BDA00002212455500111
More than or equal to 4,000, for example 4,000-20, " high molecular " dispersion agent of 000.Accurate molecular weight ranges will depend on the quantity of functional group of the polymer type that forms dispersion agent, existence and the type of used polar functional group.For example, for the dispersion agent that polyisobutene is derived, high molecular weight dispersant is to be the dispersion agent that about 1680 to about 5600 polymer backbone forms by number-average molecular weight.It is about 900 to about 2300 that typical commercially available polyisobutenyl dispersion agent contains number-average molecular weight, functionalized and be the about 100 polyisobutene polymkeric substance of deriving to about 350 polyamines with molecular weight by maleic anhydride (MW=98).Low-molecular-weight polymkeric substance also can be used for forming high molecular weight dispersant, and this is undertaken by the multiple polymer link is incorporated in the dispersion agent, can use method as known in the art to realize.
Preferred dispersion agent group comprises the poly-alpha olefins dispersion agent that polyamines is derived, especially ethylene/butylene alpha-olefin and polyisobutenyl dispersion agent.Especially preferred is ashless dispersant derived from polyisobutene, and described polyisobutene is that the succinyl oxide base replaces, and with poly-ethyleneamines, for example polyethyene diamine, tetren; Or polyoxy alkylidene polyamines, for example polyoxy trimethylene diamine, Tutofusin tris; Oxy-compound, for example tetramethylolmethane; With their composite reaction.A kind of especially preferred dispersion agent combination is combination as described below: (A) the succinyl oxide base replace and with (B) oxy-compound, for example tetramethylolmethane; (C) polyoxy alkylidene polyamines, polyoxy trimethylene diamine for example, or (D) polyalkylene diamines, the polyisobutene of polyethyene diamine and tetren reaction for example wherein uses about 0.3 to about 2 moles (B), (C) for every mole (A) and/or (D).The preferred dispersion agent combination of another kind comprises (A) polyisobutenyl succinic anhydride and (B) polyalkylene polyamine such as tetren and (C) polyvalent alcohol or the aliphatic primary amine of poly-hydroxy replacement such as the combination of tetramethylolmethane or Tutofusin tris, such as U.S. Patent No. 3, described in 632,511.
Another kind of ashless dispersant comprises mannich base condensation products.Usually, these products are to prepare with about 1 to 2.5 mole of carbonyl compound (for example formaldehyde and paraformaldehyde) and about 0.5 to 2 mole of polyalkylenepolyamines condensation by monohydroxy or the polyhydroxy-benzene that about 1 mole of alkyl is replaced, such as U.S. Patent No. 3, disclosed such in 442,808.This class mannich base condensation products can comprise that the polymer product of polyreaction of metallocene catalyst is as the substituting group on the phenyl group, perhaps can according to U.S. Patent No. 3, described in 442,808 similarly mode with contain this compound reaction of substituted polymkeric substance on succinyl oxide.The example of the olefin polymer that uses synthetic functionalized of metallocene catalyst system and/or derive has been described in above-mentioned publication.
Dispersion agent can by various conventional aftertreatments for example boration carry out further aftertreatment, such as U.S. Patent No. 3,087, general instruction in 936 and 3,254,025.The boration of dispersion agent can be easily by using boron compound; for example the ester of boron oxide, halogenation boron, boric acid and boric acid is processed the dispersion agent that contains acyl group nitrogen and is realized that the consumption of described boron compound is enough to provide about 0.1 boron to about 20 atomic ratios for the nitrogen composition of every mole of acidylate.Useful dispersion agent contains about 0.05 to about 2.0 quality %, and for example about 0.05 to about 0.7 quality % boron.(the boric acid polymkeric substance (mainly is (HBO to described boron as dewatering 2) 3) appear in the product) be considered to be connected to amine salt with dispersion agent imide and imide the metaborate of imide for example.Boration can followingly carry out: with about 0.5-4 quality %; about 1 to the about 3 quality %(quality based on the acyl group nitrogen compound for example) boron compound; preferred boric acid (usually as slurry) is added in the acyl group nitrogen compound and at about 135 ℃ to about 190 ℃; for example under agitation heated about 1 to about 5 hours under 140 ℃-170 ℃, then nitrogen stripping.Perhaps, boron is processed and can be undertaken by dewatering simultaneously in the thermal reaction mixture that boric acid is added to di-carboxylic acid material and amine.Can also use other afterreaction method generally known in the art.
Dispersion agent can also be by carrying out further aftertreatment with so-called " end-capping reagent " reaction.Traditionally, nitrogenous dispersion agent by " end-blocking " to reduce these dispersion agents to the disadvantageous effect of fluoroelastomer engine sealing.Many end-capping reagents and method are known.In known " end-capping reagent ", those end-capping reagents that alkaline dispersing agent amino changed into non-alkaline structure part (for example amido or imino-) are only.For example in U.S. Patent No. 4,839,071; The reaction of nitrogenous dispersion agent and Acetacetic acid alkyl ester (for example methyl aceto acetate (EAA)) has been described in 4,839,072 and 4,579,675.For example in U.S. Patent No. 3,185, the reaction of nitrogenous dispersion agent and formic acid has been described in 704.The reaction product of nitrogenous dispersion agent and other suitable end-capping reagent is described in U.S. Patent No. 4,663, the 064(oxyacetic 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(is many-epoxide (for example two-epoxide)) and 4,686,054(maleic anhydride or succinyl oxide) in.Aforementioned list is not limit, and other method of nitrogenous dispersion agent end-blocking is well known by persons skilled in the art.
For enough piston deposit control, can be by provide about 0.03 quality % to about 0.15 quality % for lubricating oil composition, preferably approximately 0.07 to the amount of about 0.12 quality % nitrogen is added nitrogenous dispersion agent.
Ashless dispersant be in nature alkalescence and therefore have and can be about TBN of 5 to about 200mgKOH/g, this depends on that the character of polar group and dispersion agent are whether by boration or noly process with end-capping reagent.Yet, high-caliber alkaline dispersing agent nitrogen is known to have harmful effect to the fluoroelastomer material that is used to form engine sealing, therefore, the preferred use the dispersion agent of the necessary minimum quantity of piston deposit control is provided, basically do not use dispersion agent, or preferably do not use TBN greater than 5 dispersion agent.Preferably, the amount of the dispersion agent of employing will be lubricating oil composition contribution at the most 4, the preferred at the most TBN of 3mg KOH/g.Further preferred dispersants provides at the most 30%, preferred at the most 25% TBN for lubricating oil composition.
They other additive can be attached in the present composition so that can meet specific requirement.The example that can be included in the additive in the lubricating oil composition is metal antirusting agent, viscosity index improver, inhibiter, oxidation retarder, friction improver, other dispersion agent, defoamer, anti-wear agent and pour point reducer.Hereinafter will discuss some additives in more detail.
Dialkyldisulfide is commonly used for anti-wear agent and antioxidant for phosphate metal salt.Described metal can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.Zinc salt is the most normal with 0.1-10wt%, and the amount of preferred 0.2-2wt% is used for lubricating oil, based on the gross weight of lubricating oil composition.They can be prepared as follows according to known technology: at first form dialkyldisulfide for phosphoric acid (DDPA), the reaction by one or more alcohol or phenol and P2S5 forms usually, then uses in the zn cpds and formed DDPA.For example, can make phosphorodithioic acid by the reaction of primary alconol and secondary alcohol mixture.Perhaps, can prepare multiple phosphorodithioic acid, wherein the alkyl on a kind of phosphorodithioic acid is sechy-drocarbyl in nature fully, and the alkyl on other phosphorodithioic acid is uncle's alkyl in nature fully.In order to make zinc salt, can use any alkalescence or neutral zn cpds, but the most normal use oxide compound, oxyhydroxide and carbonate.Commercially available additive comprises excessive zinc usually, and this is owing to use excessive basic zinc compound in neutralization reaction.
Preferred dialkyldisulfide is that dialkyldisulfide also can be expressed by the following formula for the oil soluble salt of phosphoric acid for zinc phosphate:
Figure BDA00002212455500141
Wherein R and R' contain 1 to 18, the identical or different alkyl of preferred 2 to 12 carbon atoms, and comprise the group such as alkyl, thiazolinyl, aryl, aralkyl, alkaryl and alicyclic group.Especially preferably be the alkyl that contains 2-8 carbon atom as R and R ' base.Therefore, these groups can be for example ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.In order to obtain oil soluble, the sum of carbon atom in the phosphorodithioic acid (namely R and R') is typically about 5 or higher.Therefore dialkyldisulfide can comprise zinc dialkyl dithiophosphate for zinc phosphate.When use contains about 0.02 to about 0.12 quality %, for example about 0.03 to about 0.10 quality % or during the lubricant compositions of the about 0.05 phosphorus level to about 0.08 quality % (based on the total mass of composition), the present invention may be particularly useful.In a preferred embodiment, lubricating oil composition of the present invention contains major part (for example, surpass 50mol%, for example surpass 60mol%) derived from the zinc dialkyl dithiophosphate of secondary alcohol.
Oxidation retarder or antioxidant reduce the tendency that mineral oil in use goes bad.Deterioration by oxidation can be confirmed by the varnish shape settling of the sludge in the lubricant, metallic surface and by the viscosity increase.These oxidation retarder comprise hindered phenol, preferably contain C 5-C 12The hydrocarbon of the alkaline earth salt of the alkylphenol thioesters of alkyl group side chain, nonyl phenol sulfurated lime, oil soluble phenates and sulfuration phenates, phosphorus sulfuration or sulfuration, phosphide, metal thiocarbamate, such as U.S. Patent No. 4, oil-soluble copper compounds described in 867,890 and molybdate compound.
Have at least two typical oil-soluble aromatic amine that are directly connected to the aromatic group of an amine nitrogen and contain 6-16 carbon atom.This amine can contain more than two aromatic groups.Contain altogether at least three aromatic groups, wherein two aromatic groups by covalent linkage or by atom or group (for example oxygen or sulphur atom or-CO-,-SO 2-or alkylidene group) connect and two be directly connected to a compound on the amine nitrogen and also be regarded as having at least two arylamine that are directly connected to the aromatic group on the nitrogen.Aromatic ring is replaced by one or more substituting groups that are selected from alkyl, cycloalkyl, alkoxyl group, aryloxy, acyl group, acyl amino, hydroxyl and nitro usually.
Usually use in combination multiple antioxidants.In a preferred embodiment, lubricating oil composition of the present invention contain about 0.1 to about 1.2 quality % amine antioxidantss and about 0.1 to about 3 quality % phenolic antioxidants.In another preferred embodiment, lubricating oil composition of the present invention contains about 0.1 to about 1.2 quality % amine antioxidantss, and about 0.1 to about 3 quality % phenolic antioxidants with by about 10 molybdenum compounds to the amount of about 1000ppm molybdenum are provided for lubricating oil composition.
The representative example of the viscosity modifier that is fit to is interpretation and the partially hydrogenated multipolymer of styrene/isoprene, the partially hydrogenated multipolymer of phenylethylene/butadiene and the partially hydrogenated multipolymer of isoprene/butadiene of multipolymer, vinylbenzene and the acrylic acid series ester of multipolymer, polymethacrylate, alkylmethacrylate polymer, unsaturated dicarboxylic acid and the vinyl compound of polyisobutene, ethene and propylene, and the partially hydrogenated homopolymer of divinyl and isoprene.
Also can comprise the friction modifiers compatible with other composition of processed oil and fuel economy reagent.The example of materials comprises the monoglyceride of higher fatty acid, for example glyceryl monooleate; The ester of long-chain polycarboxylic acid and glycol, for example butanediol ester of dimerization unsaturated fatty acids; Oxazoline compound; With monoamine, diamines and the alkyl ether amine of oxyalkylated alkyl replacement, for example the tallow ether amine of the tallow amine of ethoxylation and ethoxylation.
Other known friction improver comprises oil-soluble organo-molybdenum compound.Such organic-molybdenum friction improver also provides the effect of antioxidant and anti-wear agent for lubricating oil composition.The example of this type of oil-soluble organo-molybdenum compound comprises dithiocar-bamate, dithiophosphates, dithiophosphinic acids salt, xanthogenate, Thioxanthate salt, sulfide etc., and their mixture.Especially preferred is dithiocar-bamate, dialkyl dithiophosphate, alkyl xanthate and the alkylthio xanthogenate of molybdenum.
In addition, described molybdenum compound can be acid molybdenum compound.These compounds will like that react with basic nitrogen compound and sexavalence normally as being measured by ASTM test D-664 or D-2896 titration program.What comprise is molybdic acid, ammonium molybdate, Sodium orthomolybdate, potassium molybdate and other alkali metal molybdate and other molybdenum salt, for example molybdic acid hydrogen sodium, MoOCl 4, MoO 2Br 2, Mo 2O 3Cl 6, molybdic oxide or similar acid molybdenum compound.
The molybdenum compound that can be used for the present composition comprises the organic molybdenum with following formula:
Mo (ROCS 2) 4And Mo (RSCS 2) 4
Wherein R is selected from lower group organic group: alkyl, aryl, aralkyl and alkoxyalkyl, usually contain 1-30 carbon atom, and preferably contain 2-12 carbon atom, most preferably contain the alkyl of 2-12 carbon atom.Particularly preferably be the dialkyl dithiocarbamate of molybdenum.
The another kind of organic molybdenum that can be used for lubricating composition of the present invention is three nuclear molybdenum compound, especially formula Mo 3S kL nQ zThose molybdenum compounds and composition thereof, wherein L is the independent part that contains organic group of selecting, wherein organic group has is enough to make compound solvable or dispersible carbonatoms in oil, n is 1 to 4, k is between 4 to 7, and Q is selected from neutral supplied for electronic compound, such as water, amine, alcohol, phosphine and ether, z is 0-5, and comprises non-stoichiometric value.In all part organic groups, should there be at least 21 total carbon atoms, for example at least 25, at least 30, or at least 35 carbon atoms.
Dispersion agent-viscosity index improver had both played the effect of viscosity index improver, also played the effect of dispersion agent.The example of dispersion agent-viscosity index improver comprises amine (for example polyamines) and the list of alkyl replacement or the reaction product of di-carboxylic acid, and wherein hydrocarbyl substituent comprises length is enough to make compound to have the chain that viscosity index is improved property.Generally speaking, the viscosity index improver dispersion agent can be, for example, and the C of vinyl alcohol 4To C 24Unsaturated ester or C 3To C 10Unsaturated monocarboxylic or C 4To C 10Di-carboxylic acid and the polymkeric substance that contains the unsaturated nitrogen containing monomer of 4 to 20 carbon atoms; C 2To C 20Alkene and the unsaturated C that neutralizes with amine, azanol or alcohol 3-C 10The polymkeric substance of list or di-carboxylic acid; Or ethene and C 3To C 20The polymkeric substance of alkene, it passes through C 4To C 20Unsaturated nitrogen containing monomer is grafted on it or by unsaturated acid being grafted to the hydroxy-acid group and amine, azanol or the alcohol that then make grafting acid on the polymer backbone and reacts and further reaction.
Pour point reducer is also referred to as lubricating oil flow improving agent (LOFI), the minimum temperature when the reduction fluid flow maybe can be dumped.Examples of such additives is well-known.Those typical additives that improve the fluid low-temperature fluidity are fumaric acid C 8-C 18Dialkyl/vinyl acetate copolymer, and polymethacrylate.Can pass through the polysiloxane type defoamer, for example silicone oil or polydimethylsiloxane provide foam control.
Some above-mentioned additives can provide multiple effect; Therefore, for example, single additive can serve as dispersion agent-oxidation retarder.This mode is known, does not need herein further to elaborate.
In the present invention, also can preferably include the additive that keeps the blend viscosity stability.Therefore, although the additive of polar functionalities has been realized suitable low viscosity in the pre-blend stage, observe some composition viscosity increase when standing storage.Effectively the additive that increases of this viscosity of control comprise by with as previously described ashless dispersant preparation in the list that uses or di-carboxylic acid or anhydride reaction and functionalized long chain hydrocarbon.
When lubricating composition contains one or more above-mentioned additives, usually with every kind of additive so that this additive can provide the amount of its required function mixed in base oil.
When lubricating composition contains one or more above-mentioned additives, usually with every kind of additive so that this additive can provide the amount of its required function mixed in base oil.When using in crankcase lubricant, the representational significant quantity of these additives is as follows.All values of listing all provide with the mass percent activeconstituents.
Table II
Figure BDA00002212455500171
Figure BDA00002212455500181
The fully lubricating oil composition of preparation of the present invention preferably has at least 8.5, and preferably at least 9, for example about 8.5 to about 13, preferably approximately 9 is to about 13, more preferably about 9 to about 11mgKOH/g TBN(ASTM D-2896 and/or ASTM D-4739).
The fully lubricating oil composition of preparation of the present invention preferably has about 1.1 quality % or lower, preferably approximately 1.0 quality % or lower, more preferably about 0.8 quality % or lower sulfated ash (SASH) content (ASTM D-874).
Preferably, the lubricating oil composition of fully preparation of the present invention obtains at least 5% of composition TBN by the ashless tbn sources of the compound that comprises at least a formula (I), and preferably at least 10%, more preferably at least 20%.More preferably, the lubricating oil composition of fully preparation of the present invention obtains at least 5% of composition TBN by the compound of at least a formula (I), preferably at least 10%, more preferably at least 20%, with the compound ashless tbn sources in addition by formula (I), comprise alkaline dispersing agent obtain composition TBN less than 25%, preferably less than 20%, be more preferably less than 15%.
The fully lubricating oil composition of preparation of the present invention further preferably has less than about 0.4 quality %, is more preferably less than about 0.35 quality %, is more preferably less than about 0.03 quality %, for example less than the sulphur content of about 0.15 quality %.Preferably, the Noack volatility (ASTM D5880) of lubricating oil composition (oil of lubricant viscosity adds all additives and additive thinner) of preparation will be at the most 13 fully, for example at the most 12, preferably at the most 10.The fully lubricating oil composition of preparation of the present invention preferably has at the most 1200ppm phosphorus, 1000ppm phosphorus at the most for example, or 800ppm phosphorus at the most.
May cater to the need but not necessarily be, prepare one or more multifunctional additive for lubricating oils that contain additive (enriched material is called additive-package sometimes), several additives can be added simultaneously thus in the oil to form lubricating oil composition.Enriched material for the preparation of lubricating oil composition of the present invention is passable, for example, contains the compound of one or more formulas (I) of about 5 to about 30 quality %; The about 10 nitrogenous dispersion agents to about 40 quality %; About 2 amine antioxidantss to about 20 quality %, phenol antioxidant, molybdenum compound or its mixture; The purification agent of about 5-40 quality %; With the about 2 metal dialkyl dithiophosphates to about 20 quality %.
Final composition can use 5-25 quality %, preferred 5-18 quality %, and the enriched material of common 10-15 quality %, remaining is oil and the viscosity modifier of lubricant viscosity.
The all wt that this paper represents (and quality) percentage (except as otherwise noted) all based on the activeconstituents (A.I.) of additive and/or additive-package, does not comprise any thinner that accompanies.Yet purification agent forms in thinning oil usually, and this thinning oil is not removed from product, and the TBN of purification agent is provided by the active purification agent in the thinning oil that accompanies usually.Therefore, when relating to purification agent, weight (and quality) percentage (except as otherwise noted) all is gross weight (or quality) percentage of activeconstituents and the thinning oil that accompanies.
Will be by further understanding the present invention with reference to following examples.
Embodiment
(I) 4-oxyethyl group-N-(4-methylpent-2-yl) aniline is synthetic
In the 1 liter of three neck round-bottomed flask that is equipped with thermometer, feed hopper and mechanical stirrer, add 4-phenetidine (20.00g, the triacetoxyl group sodium borohydride (38.30g, 171mmol) of 143mmol), in mortar, pulverizing in advance and 475ml methylene dichloride.In feed hopper, add 4-methyl-2 pentanone (15.98g, 157mmol) and 25ml methylene dichloride.Via funnel add to lentamente ketone in this flask and allow the reaction spend the night.After reaction, add saturated NaHCO via funnel 3Solution.And then use saturated NaHCO 3The solution washing organic phase washes with water again, then uses MgSO 4Dry.Under vacuum, after filtration and the evaporation, obtain the 31g light yellow oil.This product is used for following steps (ii).
(ii) 4-oxyethyl group-N-(2-ethylhexyl)-N-(4-methylpent-2-yl) aniline is synthetic
4-oxyethyl group-N-(4-methylpent-2-yl) aniline (31.00g of preparation in the step (i) above in the 1 liter of three neck round-bottomed flask that is equipped with thermometer, feed hopper and mechanical stirrer, adding, 140mmol), the triacetoxyl group sodium borohydride (37.50g, 168mmol) of in mortar, pulverizing in advance and 475ml methylene dichloride.In feed hopper, add 2-ethyl hexanal (20.58g, 154mmol) and 25ml methylene dichloride.Via funnel add to lentamente aldehyde in this flask and allow the reaction spend the night.After reaction, add saturated NaHCO via funnel 3Solution.And then use saturated NaHCO 3The solution washing organic phase washes with water again, then uses MgSO 4Dry.Under vacuum, after filtration and the evaporation, obtain 71.3g scarlet oil.The below tests this product, and it is labeled as synthetic example 1 there.
Synthetic example 2
(iii) 4-oxyethyl group-N-(fourth-2-yl) aniline is synthetic
In the 2 liter of three neck round-bottomed flask that is equipped with thermometer, feed hopper and mechanical stirrer, add 4-phenetidine (50.00g, the triacetoxyl group sodium borohydride (104g, 464mmol) of 357mmol), in mortar, pulverizing in advance and 700ml methylene dichloride.In feed hopper, add 2-butanone (31.2g, 429mmol) and 50ml methylene dichloride.Via funnel add to lentamente ketone in this flask and allow the reaction carried out two days.Then by add saturated NaHCO via funnel 3Solution will react quencher.Then use saturated NaHCO 3The solution washing organic phase washes with water again, then uses MgSO 4Dry.Under vacuum, after filtration and the evaporation, obtain 70.4g scarlet oil.This product is used for following steps (iii).
(iv) 4-oxyethyl group-N-(2-ethylhexyl)-N-(fourth-2-yl) aniline is synthetic
Be equipped with step above adding in 2 liter of three neck round-bottomed flask of thermometer, feed hopper and mechanical stirrer (iii) in 4-oxyethyl group-N-(fourth-2-yl) aniline (70.00g of preparation, 140mmol), the triacetoxyl group sodium borohydride (105g, 471mmol) of in mortar, pulverizing in advance and 750ml methylene dichloride.In feed hopper, add 2-ethyl hexanal (58.0g, 435mmol) and 50ml methylene dichloride.Via funnel add to lentamente aldehyde in this flask and allow the reaction carried out two days.Then by add saturated NaHCO via funnel 3Solution will react quencher.Then use saturated NaHCO 3The solution washing organic phase washes with water again, then uses MgSO 4Dry.Under vacuum, after filtration and the evaporation, obtain 108.2g scarlet oil.The below tests this product, and it is labeled as synthetic example 2 there.
Comparative example-(synthetic example 3)
The dried methyl alcohol of 450g phenetidine (3.28 moles), 1682g 2-ethyl hexanal (13.1 moles), 45g 10%Pd/C and 2L is added the Parr reactor.With hydrogen reactor is pressurized to 10 bar and under agitation is heated to 100 ℃.By the HPLC monitoring reaction to finishing.Then with reactor cooling to room temperature and by removing by filter catalyzer.The distillation of reaction mixture produces the 800g product, by 1H-and 13C-NMR confirms the structure of this product.
Above-mentioned synthetic reaction process shows below:
The TBN performance
Can measure by acidometric titration the basicity of lubricating oil composition.The neutralization value of gained is expressed as total basicnumber, or TBN, and can make the measurement that ins all sorts of ways.At this using method ASTM D-4739(current potential salt acidometric titration).Dilution/reservation is favourable to ASTM 4739 methods to measure TBN in Engine Block Test and for used oil.
The TBN test
Preparation contains the fully lubricating oil composition of preparation of dispersion agent, purification agent mixture, antioxidant, ZDDP anti-wear agent, pour point reducer and viscosity modifier in base oil.This lubricating oil composition (representing commercial crankcase lubricant) is used as with reference to lubricant.Preparation contains the lubricating oil composition of preparing fully of the compound (oily B) of the compound (oily A) of 1.68 quality % synthetic examples 1 and synthetic example 2.Also tested and contained 1.00 quality %(oil C) and 2.00 quality %(oil D) lubricating oil composition of preparing fully of control compounds of synthetic example 3.The base oil of additional quantity is added in every kind of sample so that suitable total mass to be provided.TBN(unit according to the every kind of gained sample of each mensuration among the ASTM D4739 is mg KOH/g).The results are shown in the lower Table III.
Table III
Embodiment Reference Oil A Oil B Oil C Oil D
With reference to sample (g) 95.0 47.5 47.5 47.5 47.5
The base oil (g) that adds 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 is according to D-4739 8.75 10.49 11.60 8.87 8.97
Δ TBN is with respect to reference, according to D-4739 - 1.74 2.85 0.12 0.22
As shown, compound of the present invention is as using the TBN that effectively improves like that lubricating oil composition among oily A and the oily B, by ASTM D-4739 measurement, but to SASH content without contribution.Synthetic example 3 have two-alkyl-branched arrange but non-control compounds according to the present invention does not provide significant improvement aspect TBN.This in addition use therein in the oily D situation of greater amount compound (2.00 quality %vs.1.64 quality %) also like this.
The test of fluoroelastomer seal compatibility
Test oil A and contain N in VW-6/AK6 test, N-two-n-hexyl-4-phenetidine replaces the similar oil of the compounds of this invention.The consistency of this program test lubricating oil and Viton fluoroelastomer sealing material.The elongation at break and the novel sealing that do not contain the reference oil of compound are in a ratio of on average-34.5%.For oily A, on average be-51%, for containing N, the oil of N-two-n-hexyl-4-phenetidine is-64%.These tests show, compound of the present invention with compare with the similar compound of two linear alkyl chain, sealing material is had much lower impact.

Claims (12)

1. lubricating oil composition comprises the compound of one or more formulas (I) of the oil of lubricant viscosity of main amount and minor amount:
Figure FDA00002212455400011
R wherein 1, R 2, R 3, R 4And R 5Represent independently alkyl or do not contain the substituted alkyl of aryl substituent.
2. according to claim 1 lubricating oil composition, wherein R 1Represent methylidene or ethyl, preferable methyl.
3. according to claim 1 or the lubricating oil composition of claim 2, wherein R 3Represent methylidene or ethyl, preferred ethyl.
4. according to the lubricating oil composition of above-mentioned arbitrary claim, R wherein 5Represent methylidene or ethyl, preferred ethyl.
5. according to the lubricating oil composition of above-mentioned arbitrary claim, have at least 6mg KOH/g, the TBN of preferred 6-15mg KOH/g measures according to ASTM D-4739.
6. according to the lubricating oil composition of above-mentioned arbitrary claim, have at the most 1.1 quality %, preferred 1.0 quality % at the most, more preferably the SASH content of 0.8 quality % at the most.
7. according to the lubricating oil composition of above-mentioned arbitrary claim, wherein at least 10% of composition TBN, preferably at least 15%, more preferably at least 20% ashless tbn sources that stems from the compound that comprises at least a formula (I) is measured according to ASTM D-4379.
8. according to the lubricating oil composition of above-mentioned arbitrary claim, have the sulphur content less than 0.4 quality, and the phosphorus of 1200ppm at the most.
9. for the preparation of the enriched material according to the lubricating oil composition of above-mentioned arbitrary claim, described enriched material comprises about 2.5 compounds to the formula (I) described in about 30 one or more claims 1 of quality %; About 10 to about 40 quality % nitrogenous dispersion agents; About 2 to about 20 quality % amine antioxidantss, phenolic antioxidant, molybdenum compound or their mixture; About 5 to 40 quality % purification agents; With about 2 to about 20 quality % metal dialkyl dithiophosphates.
10. the compound of formula (I):
Figure FDA00002212455400021
R wherein 1, R 2, R 3, R 4And R 5Represent independently alkyl or do not contain the substituted alkyl of aryl substituent.
Do not improve simultaneously the method for SASH content 11. improve the TBN of lubricating oil composition, the method comprises in described lubricating oil composition adds one or more compounds according to claim 10.
12. compound according to claim 10 is as the purposes in ashless lubricating oil composition TBN source.
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