CN1322103C - Lubricating oil composition for internal combustion engine - Google Patents

Lubricating oil composition for internal combustion engine Download PDF

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Publication number
CN1322103C
CN1322103C CNB028183746A CN02818374A CN1322103C CN 1322103 C CN1322103 C CN 1322103C CN B028183746 A CNB028183746 A CN B028183746A CN 02818374 A CN02818374 A CN 02818374A CN 1322103 C CN1322103 C CN 1322103C
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quality
acid
content
composition
carbon atoms
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CN1556846A (en
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白浜真一
山田恭久
栗原功
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Eneos Corp
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Nippon Oil Corp
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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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • 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
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2215/086—Imides
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • 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
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • 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
    • C10M2223/049—Phosphite
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/50—Emission or smoke controlling properties
    • 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
    • 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
    • C10N2040/253—Small diesel 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
    • C10N2040/255—Gasoline 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Lubricating oil compositions for internal combustion engines comprises a mineral and/or synthetic base oil, (A) a succinimide-based ashless dispersant in an amount of 0.08 to 0.40 percent by mass in terms of nitrogen, (B) a metallic detergent in an amount of 0.06 to 0.22 percent by mass in terms of metal element, (C) a zinc secondary alkyldithiophosphate in an amount of 0.04 to 0.08 percent by mass in terms of phosphorus, and (D) a phosphorus-containing ashless anti-wear agent in an amount of 0.01 to 0.04 percent by mass in terms of phosphorus and contains sulfated ashes derived from the metal elements in the composition in an amount of 0.3 to 1.0 percent by mass. The lubricating oil compositions are excellent in anti-wear properties and high-temperature detergency although they are decreased in ash content.

Description

Lubricant composition for internal combustion engine
Technical field
The present invention relates to lubricant composition for internal combustion engine, particularly be applicable to the low ash content diesel engine oil of the diesel motor of being furnished with exhaust gas post-treatment device.
Background technology
Under the background of whole world environmental problem, various countries are strict year by year to the deflated management.Especially, the amount of NOx and suspended particulate (SPM) in the diesel engine exhaust of urgent need reduction at present.Considered so far to reduce diesel engine exhaust such as high pressure blow smelting operation, exhaust cycle system (EGR), oxide catalyst, diesel particulate filter (DPF) and NOx sorption reducing catalyst with some measure.
Known these reduce in the deflated measure, shorten the work-ing life of the oxide catalyst that especially uses in exhaust gas post-treatment device, NOx absorbing catalyst and DPFs to depend on used lubricated oil composition.For example, use comprise known can lubricated oil condition as the zinc dialkyl dithiophosphate (hereinafter being called " ZnDTP ") of anti-wear agent or antioxidant under, be accumulated in catalyst surface or the strainer by ZnDTP deutero-zinc oxide and zinc phosphate in the combustion processes, thus the purifying property of infringement exhaust gas post-treatment device.Therefore, wish in being furnished with the cylinder oil of above-mentioned exhaust gas post-treatment device, not add ZnDTP or make the amount of ZnDTP minimum as far as possible.Similar to ZnDTP, be accumulated as ash content by metallo-detergent deutero-metal sulfate and metal oxide, thereby may bring the problems referred to above.
But particularly be furnished with lubricating oil in the diesel motor of EGR because a large amount of soots pollute diesel motors, ZnDTP and metallo-detergent content reduce and will cause the valve wearing and tearing and the detergency of piston is descended.Thereby, be to reduce ZnDTP and metallo-detergent content, must study the detergency that the minimizing of compensation ZnDTP and metallo-detergent brought and the new measure of resistance to abrasion decline.As the lubricating oil composition of the diesel motor that is used to be furnished with exhaust gas post-treatment device, JP-A-2000-256690 proposes its sulfate ash content and reduces to 0.7% (quality) or lower diesel engine oil composition.
The purpose of this invention is to provide even under the condition of a large amount of soot pollution lubricating oil, also can show low ash content diesel engine oil enhanced resistance to abrasion and high temperature detergency, that be applicable to the diesel motor of being furnished with exhaust gas post-treatment device.
Summary of the invention
To in addition under the situation that ZnDTP and metallo-detergent content reduce, also can keep the diesel engine oil of resistance to abrasion and high temperature detergency to carry out after extensive investigations and the research, even discovery when reducing ZnDTP and metallo-detergent amount, mix specific ashless dispersant and specific phosphorous ash-free antiwear agent, and the fatty acid amide that mixes specified quantitative alternatively can obtain also to be shown the lubricating oil composition of splendid resistance to abrasion and high temperature detergency by the soot pollution, thereby finish the present invention.
The invention provides a kind of internal combustion engine lubrication oil compositions, comprise that mineral and/or synthetic base oil, (A) are that the succinimido ashless dispersant, (B) of 0.08 to 0.40% (quality) is that the metallo-detergent, (C) of 0.06 to 0.22% (quality) is the secondary alkyl zinc dithiophosphate of 0.04 to 0.08% (quality) by phosphorus content and (D) is the phosphorous ash-free antiwear agent of 0.01 to 0.04% (quality) by phosphorus content by metal element content by nitrogen content, and contain 0.3 to 1.0% (quality) by the metallic element deutero-sulfated ash in the composition.
In addition, the present invention also provides a kind of internal combustion engine lubrication oil compositions, comprise mineral and/or synthetic base oil, (A) by nitrogen content be the succinimido ashless dispersant of 0.08 to 0.40% (quality), (B) be the metallo-detergent of 0.06 to 0.22% (quality) by metal element content, (C) by phosphorus content be the secondary alkyl zinc dithiophosphate of 0.02 to 0.08% (quality), (D) by phosphorus content be the phosphorous ash-free antiwear agent of 0.01 to 0.04% (quality), (E) content is the fatty acid amide of 0.01 to 2.0% (quality), and contain 0.3 to 1.0% (quality) by the metallic element deutero-sulfated ash in the composition.
In the lubricating oil composition of the present invention, component (B) is preferably the alkaline-earth metal salicylate.Component (D) is preferably and is selected from phosphoric acid ester and amine salt thereof; At least a compound with phosphorous acid ester and amine salt thereof.Lubricating oil composition of the present invention is preferred for being furnished with the diesel motor of exhaust gas post-treatment device.
Detailed Description Of The Invention
Be described in more detail below the present invention.
The used lubricating base oil of the present invention does not have particular restriction, as long as they are to be used for the base oil of lubricating oil composition usually as base oil, no matter be mineral base oil or synthetic base oil.
The example of mineral base oil comprises and can obtain by one or more refining process that the lubricating oil distillate that crude oil atmospheric distillation or vacuum distilling are produced is handled through the isomerization that be selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrofining and wax; With preferred use the isomerization processing of this lubricating oil distillate process hydrocracking, hydrofining or wax is obtained.
The specific examples of synthetic base oil comprises alkylnaphthalene; Alkylbenzene; Polybutene and hydride thereof; Poly-alpha-olefin such as 1-octene oligopolymer and 1-decene oligopolymer and hydride thereof; Diester such as pentanedioic acid two (13) ester, Octyl adipate, diisodecyl adipate, hexanodioic acid two (13) ester and dioctyl sebacate; Polyol ester such as trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate and tetramethylolmethane pelargonate; And composition thereof.In these synthetic base oils, preferably poly-alpha-olefin such as 1-octene oligopolymer and 1-decene oligopolymer and hydride thereof.
The used lubricating base oil of the present invention can be the arbitrary of above cited mineral or synthetic base oil or combination and two or the mixture of multi mineral base oil or synthetic base oil.Two or the ratio of mixture of multiple base oil can select arbitrarily.
Although total aromatic content of described base oil does not have particular restriction, be preferably 15% (quality) or lower, more preferably 13% (quality) or lower, more preferably 10% (quality) or lower also.It is poor that its total aromatic content is higher than the lubricating base oil oxidative stability of 15% (quality), and the base oil that total aromatic content is lower than 2% (quality) fully dissolved constituent (A) to (D).Thereby total aromatic content is preferably 2% (quality) or higher.The aromatic fraction content that ASTMD2549 measures is pressed in term used herein " aromatic content " representative.Aromatic fraction comprise alkylbenzene, alkylnaphthalene, anthracene, phenanthrene and alkylate thereof, wherein four or more phenyl ring each other condensation compound and aromatic heterocycle is arranged such as the compound of pyridine, quinoline, phenol and naphthols.
The kinematic viscosity of base oil does not have particular restriction.But the kinematic viscosity under 100 ℃ is preferably 2mm 2/ s or higher, more preferably 3mm 2/ s or higher, and be preferably 10mm 2/ s or lower, more preferably 8mm 2/ s or lower.Use 100 ℃ of following kinematic viscosity to be 2mm 2/ s or higher base oil because of it ability of enough formation oil films are arranged and the vaporization losses of base oil is rare under hot conditions helps the fabulous lubricating oil composition of production oilness, and uses 100 ℃ of following kinematic viscosity to be 10mm 2But/s or the lower little thereby little lubricating oil composition of friction resistance of base oil production resistance to flow in the lubricant housings.
The component of lubricating oil composition of the present invention (A) is that the succinimido ashless dispersant can be a double imide shown in single imide shown in the following formula (1), the following formula (2) and by organic acid or boric acid modified product:
Figure C0281837400061
In formula (1) and (2), R 1, R 2And R 3Be polybutylene-based independently, m and n are 2 to 5 integer independently.
R 1, R 2And R 3The polybutylene-based number-average molecular weight of representative be preferably 800 or bigger, more preferably 900 or bigger, preferred especially 1500 or bigger, be preferably on the other hand 3500 or littler, more preferably 2500 or littler.Number-average molecular weight is less than 800 the polybutylene-based detergency that will reduce the gained lubricating oil composition.And number-average molecular weight is greater than 3500 the polybutylene-based low-temperature fluidity that will reduce the gained lubricating oil composition.For reaching the effect that suppresses to form mud, preferred m and n are 3 or 4 independently.
Described polybutylene-basedly obtained by the polybutene of producing with the catalyst based polymerization of mixtures that makes 1-butylene and iso-butylene or highly purified iso-butylene of catalyzer such as aluminum chloride or boron fluoride, preferably wherein the chlorine of trace and fluorine have fully been removed.
The production method of succinimide does not have particular restriction shown in formula (1) or (2).For example, can produce by polyamines and the reaction of polybutylene-based succinimide, described polybutylene-based succinimide is chlorinated polybutylenes (preferably therefrom removing chlorine and fluorine fully) reaction acquisition under 100 to 200 ℃ temperature of 800 to 3500 by maleic anhydride and number-average molecular weight.The example of polyamines is diethylenetriamine, Triethylenetetramine (TETA), tetren and penten.
The example of the production method of boric acid modified succinimide be among JP-B-42-8013 and 42-8014, JP-A-51-52381 and the 51-130408 disclosed those.More specifically, can by make polyamines and polybutylene-based succsinic acid (acid anhydride) and boron-containing compound such as boric acid, boric acid ester or borate solvent comprise mix during alcohol, organic solvent are as hexane or dimethylbenzene or lubricating base oil lighting end and heat under proper condition as described in mixture obtain boric acid modified succinimide.The boron content of the boron modification succinimide of Huo Deing is generally 0.1 to 4.0% (quality) in this way.
The lower limit content of component (A) is counted 0.08% (quality), preferred 0.10% (quality), preferred especially 0.12% (quality) based on the total amount of the present composition by nitrogen.Upper limit content is counted 0.4% (quality), preferred 0.3% (quality) based on the total amount of composition by nitrogen.The component (A) that is less than 0.08% (quality) can not make resulting composition that enough high temperature detergencies are arranged, and will destroy the low-temperature fluidity of resulting composition more than the component (A) of 0.4% (quality).
The component of internal combustion (IC) engine lubricating oil of the present invention (B) is a metallo-detergent.Can be used for metallo-detergent of the present invention is any metallo-detergent that can be used for lubricating oil.Specific examples be selected from alkali or alkaline earth metal sulfonate, alkali or alkaline-earth metal phenates, alkali or alkaline-earth metal salicylate, and one or more alkali or the alkaline-earth metal-based washing agent of alkali or alkaline earth metal phosphonate salt.
Preferred alkali and alkaline earth metal sulfonate are that to make molecular weight be alkali and alkaline earth salt such as sodium, potassium, magnesium and calcium salt, preferably magnesium and the calcium salt of the alkyl aromatic sulfonic acid that obtains of 300 to 1500, preferred 400 to 700 Alkylaromatics sulfonation.
The specific examples of described alkyl aromatic sulfonic acid is mahogany acid and synthetic sulfonic acid.Mahogany acid can be the mahogany acid that contained Alkylaromatics sulfonation obtains in the lubricant cut by mineral oil or the mahogany acid of by-product when producing white oil.Synthetic sulfonic acid can be that alkylbenzene (can be the alkylbenzene factory by-product as the detergent raw material) sulfonation that makes the straight or branched alkyl obtains or make polyolefine be alkylated into benzene or make alkylnaphthalene sulfonation obtains as the dinonyl naphthalene.Being used to make these Alkylaromatics sulfonated sulphonating agents can be oleum and sulphuric anhydride.
The example of described alkali and alkaline-earth metal phenates is alkali and alkaline earth salt, particularly sodium, potassium, magnesium and the calcium salt of the Mannich reaction product of alkylphenol, alkylphenol sulfide or alkylphenol.Specific examples is those shown in the formula (3) to (5):
Figure C0281837400081
R wherein 11For have 4 to 30, the straight or branched alkyl of preferred 6 to 18 carbon atoms, M 1Be alkali or alkaline-earth metal, p is 1 or 2, if M 1Be basic metal, then p is 1, if M 1Be alkaline-earth metal, then p is 2;
Figure C0281837400082
R wherein 13, R 14, R 15And R 16Independently for have 4 to 30, the straight or branched alkyl of preferred 6 to 18 carbon atoms, M 2And M 3Be alkaline-earth metal independently, x is 1 or 2.
Be used for R 11And R 13To R 16The specific examples of alkyl be butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl.These alkyl can be straight or brancheds, can be primary, the second month in a season or tertiary alkyl.
Above-mentioned alkaline-earth metal is preferably calcium or magnesium, preferred especially calcium.
Alkali and alkaline-earth metal salicylate example be the alkali and the alkaline earth salt of alkyl salicylate, preferred sodium, potassium, magnesium and calcium salt.Specific examples is a compound shown in the following formula:
Figure C0281837400083
In the formula (6), R 17For have 4 to 30, the straight or branched alkyl of preferred 6 to 18 carbon atoms, M 4Be alkali or alkaline-earth metal, q is 1 or 2, if M 4Be basic metal, then q is 1, if M 4Be alkaline-earth metal, then q is 2.
Be used for R 17The specific examples of alkyl be butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, ceryl, heptacosyl, octacosyl, nonacosyl and triacontyl.These alkyl can be straight or brancheds, can be primary, the second month in a season or tertiary alkyl.
Above-mentioned alkaline-earth metal is preferably calcium or magnesium, preferred especially calcium.
Described alkali or alkaline earth metal sulfonate, alkali or alkaline-earth metal phenates and alkali or alkaline-earth metal salicylate can pass through the Mannich reaction product of alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, alkylphenol or alkyl salicylate is direct and alkali or alkaline earth metal alkali such as alkali or alkaline earth metal oxide or oxyhydroxide reaction acquisition.
The present invention preferably uses the alkaline-earth metal-based washing agent.Remove outside above-mentioned neutrality (normal salt) alkaline earth metal sulfonate, neutral alkaline-earth metal phenates and the neutral alkaline-earth metal salicylate, preferred washing agent is that described neutral alkaline earth metal sulfonate, neutral alkaline-earth metal phenates or neutral alkaline-earth metal salicylate heat alkali formula alkaline earth metal sulfonate, alkali formula alkaline-earth metal phenates and the alkali formula alkaline-earth metal salicylate that obtains with excessive alkaline earth salt or alkaline earth metal alkali in the presence of water; With alkaline earth metal hydroxides and carbonic anhydride or boric acid described neutral alkaline earth metal sulfonate, neutral alkaline-earth metal phenates or neutral alkaline-earth metal salicylate arbitrary in the presence of the reaction high alkaline alkaline earth metal sulfonate, high-alkaline base earth metals phenates and the high-alkaline base earth metals salicylate that obtain.
Above-mentioned an alkali metal salt, neutral alkaline earth salt, alkali formula alkaline earth salt, high-alkaline base earth metal salt, and composition thereof can be used for the present invention.Used alkali of the present invention and alkaline-earth metal-based washing agent generally are that base number is 0 to 500mgKOH/g.But obtain good especially high temperature detergency and resistance to abrasion under the condition that goes bad for polluting because of soot at lubricating oil, described base number is preferably 0 to 350mgKOH/g, more preferably 140 to 200mgKOH/g.The total basicnumber that JIS K2501 (1992) the 7th part " mensuration of petroleum products and lubricant-neutralization value " is measured by the perchloric acid potentiometric titration is pressed in term used herein " total basicnumber " representative.
Although metallo-detergent is purchased with the form of lubricated base oil lighting end dilution usually, preferably use the metallo-detergent of metal content in 1.0 to 20% (quality), preferred 2.0 to 16% (quality) scope.
The lower limit content of component (B) is counted 0.06% (quality), preferred 0.08% (quality) based on the total amount of composition by the metal element.The upper limit content of component (B) is counted 0.22% (quality), preferred 0.20% (quality), more preferably 0.18% (quality), preferred especially 0.1 4% (quality) based on the gross weight of composition by the metal element.The component (B) that is lower than 0.06% (quality) will be brought difficulty to the maintenance resistance to abrasion, and will increase the ash amount that accumulates on the exhaust gas post-treatment device more than the component (B) of 0.22% (quality).Among the present invention, preferably use the alkaline-earth metal salicylate for keeping splendid high temperature detergency and resistance to abrasion.
The component of internal combustion engine lubrication oil compositions of the present invention (C) is secondary alkyl zinc dithiophosphate.The specific examples of the used secondary alkyl zinc dithiophosphate of the present invention is a compound shown in the following formula:
Figure C0281837400101
In the formula (7), R 21, R 22, R 23, and R 24Independently for the secondary alkyl of 3 to 20 carbon atoms is arranged.The resistance to abrasion and the oxidative stability that are less than 3 carbon atoms or will destroy resulting composition more than the alkyl of 20 carbon atoms are arranged.
Described secondary alkyl is represented with following formula:
Figure C0281837400102
In the formula (8), R 25And R 26Independently for the straight or branched alkyl of 1 to 18 carbon atom, R are arranged 25And R 26Total carbon number be 2 to 19.
Be used for R 25And R 26The specific examples of alkyl be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl, all can be straight or branched.
The preferred embodiment of described secondary alkyl is sec.-propyl, 1-methyl-propyl and 1, and the 3-dimethylbutyl particularly preferably is 1, the 3-dimethylbutyl.
Can use one or more of above-mentioned secondary alkyl zinc dithiophosphate among the present invention.
The lower limit content of component (C) is counted 0.04% (quality), preferred 0.05% (quality) based on the total amount of the present composition by phosphorus.The upper limit content of component (C) is counted 0.08% (quality), preferred 0.07% (quality) based on the total amount of the present composition by phosphorus.The component (C) that is lower than 0.04% (quality) will be to keeping initial resistance to abrasion and follow-up resistance to abrasion to bring difficulty.Component (C) more than 0.08% (quality) will increase the ash amount that accumulates on the exhaust gas post-treatment device and destroy the high temperature detergency.
When using, the content of component (C) can reduce with back described component (E).In the case, the lower limit content of component (C) is counted 0.02% (quality), preferred 0.025% (quality) based on the total amount of the present composition by phosphorus.With regard to upper limit content, even reach 0.08% (quality) or lower, 0.05% (quality) or lower, 0.04% (quality) or lower or 0.035% (quality) or lower component (C) and help to produce the low ash content composition that can keep resistance to abrasion and splendid high temperature detergency.
The component of internal combustion engine lubrication oil compositions of the present invention (D) is phosphorous ash-free antiwear agent.The specific examples of described phosphorous ash-free antiwear agent be have 2 to 30, the phosphoric acid ester and the amine salt thereof of preferred 6 to 20 carbon atoms; And have 2 to 30, the phosphorous acid ester and the amine salt thereof of the alkyl of preferred 6 to 20 carbon atoms.One or more of available these compounds is as component (D).
The example that the alkyl of 2 to 30 carbon atoms is arranged is alkyl, cycloalkyl, alkyl-cycloalkyl, alkenyl, aryl, alkaryl and aralkyl.
The example of alkyl is ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, all can be straight or branched.
The example of cycloalkyl is that those of 5 to 7 carbon atoms are arranged, as cyclopentyl, cyclohexyl and suberyl.
The example of alkyl-cycloalkyl is that those of 6 to 11 carbon atoms are arranged, as methylcyclopentyl, dimethylcyclopentyl, methylethyl cyclopentyl, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, methylethyl cyclohexyl, diethyl cyclohexyl, methyl suberyl, dimethyl suberyl, methylethyl suberyl and diethyl suberyl, wherein the position of alkyl can change.
The example of alkenyl is butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl, dodecenyl succinic and vaccenic acid base, can be straight or branched and also position of double bond can change.
The example of aryl is phenyl and naphthyl.
The example of alkaryl is that those of 7 to 12 carbon atoms are arranged, and as tolyl, xylyl, ethylbenzene base, propyl phenyl, butylbenzene base, penta phenyl and own phenyl, alkyl wherein can be a straight or branched, and its position on aryl can change.
The example of aralkyl is that those of 7 to 12 carbon atoms are arranged, and as benzyl, styroyl, hydrocinnamyl, benzene butyl, benzene amyl group and benzene hexyl, alkyl wherein can be a straight or branched.
Be preferred for the phosphoric acid of component (D) and phosphorous acid ester and be oneself ester of mono alkyl phosphate such as phosphoric acid one propyl ester, monobutyl phosphate, phosphoric acid one pentyl ester, phosphoric acid, phosphoric acid one heptyl ester and phosphoric acid one monooctyl ester, alkyl wherein can be a straight or branched; Mono phosphoric acid ester (alkyl) aryl ester such as phosphoric acid one phenyl ester and phosphoric acid one toluene ester; Phosphate dialkyl ester such as di(2-ethylhexyl)phosphate propyl ester, dibutyl phosphate, di(2-ethylhexyl)phosphate pentyl ester, phosphoric acid dihexyl, di(2-ethylhexyl)phosphate heptyl ester and dioctylphosphoric acid ester, alkyl wherein can be straight or brancheds; Di(2-ethylhexyl)phosphate (alkyl) aryl ester such as diphenyl phosphate and xylenylphosphate; Trialkylphosphate such as tricresyl phosphate propyl ester, tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate and trioctyl phosphate, alkyl wherein can be straight or brancheds; Tricresyl phosphate (alkyl) aryl ester such as triphenylphosphate and Tritolyl Phosphate; Oneself ester of phosphorous acid mono alkyl ester such as phosphorous acid one propyl ester, phosphorous acid one butyl ester, phosphorous acid one pentyl ester, phosphorous acid, phosphorous acid one heptyl ester and phosphorous acid one monooctyl ester, alkyl wherein can be a straight or branched; Phosphorous acid list (alkyl) aryl ester such as phosphorous acid one phenyl ester and phosphorous acid one toluene ester; Dialkyl phosphite such as phosphorous acid dipropyl, dibutyl phosphite, phosphorous acid diamyl ester, phosphorous acid dihexyl, phosphorous acid two heptyl esters and dioctyl phosphite, alkyl wherein can be a straight or branched; Phosphorous acid two (alkyl) aryl ester such as phosphorous acid diphenyl ester and phosphorous acid diformazan phenyl ester; Trialkyl phosphite such as tricresyl phosphite propyl ester, tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite heptyl ester and tricresyl phosphite monooctyl ester, alkyl wherein can be a straight or branched; Tricresyl phosphite (alkyl) aryl ester such as triphenyl phosphite and tricresyl phosphite; And composition thereof.
The specific examples of the amine salt of phosphoric acid ester and phosphorous acid ester is to make phosplate, bisphosphate, single phosphorous acid ester or diphosphites and nitrogenous compound such as ammonia or the alkyl that contains 1-20 carbon atom is only arranged in its molecule or the reaction of the aminated compounds of the alkyl of hydroxyl obtains with all or part of remaining acid-hydrolysis that neutralizes.
The specific examples of described nitrogenous compound is an ammonia; Alkyl or alkenyl amine, alkyl wherein or alkenyl can be straight or brancheds, as Monomethylamine, monoethylamine, a propylamine, monobutylamine (MBA), an amylamine, a hexylamine, a heptyl amice, an octylame, a stearylamine, an oleyl amine, an allylamine, a butenylamine, an octene amine, single octadecenyl amine, dimethylamine, methyl ethyl-amine, diethylamine, methyl propylamine, ethyl propylamine, dipropyl amine, methylbutylamine, ethyl butyl amine, propyl group butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; Alkanolamine, alkanol groups wherein can be a straight or branched, as single carbinolamine, monoethanolamine, single Propanolamine, only son's hydramine, single amylalcohol amine, single hexanol amine, single enanthol amine, single octanol amine, single nonyl alcohol amine, dimethanolamine, methanol amine, diethanolamine, methyl alcohol Propanolamine, ethanol propanol amine, dipropanolamine, methyl alcohol butanolamine, ethanol and butanol amine, propyl alcohol butanolamine, two butanolamines, diamyl hydramine, two hexanol amine, two enanthol amine and two octanol amine; And composition thereof.
Among the present invention, preferably use the oleyl amine salt of triphenyl phosphite and acid phosphorous acid stearyl, because they can keep splendid resistance to abrasion and high temperature detergency.
Can use one or more of these components (D) among the present invention.The lower limit content of component (D) is counted 0.01% (quality), preferred 0.015% (quality) based on the total amount of lubricating oil composition of the present invention by phosphorus, and upper limit content is counted 0.04% (quality), preferred 0.035% (quality) based on the total amount of lubricating oil composition of the present invention by phosphorus.The component (D) that is lower than 0.01% (quality) will be brought difficulty to initial resistance to abrasion of maintenance and follow-up resistance to abrasion, and will greatly destroy the oxidative stability of gained lubricating oil composition more than the component (D) of 0.04% (quality).
The component of internal combustion engine lubrication oil compositions of the present invention (E) is a fatty acid amide.Although the lipid acid of described fatty acid amide can be straight or branched and saturated or unsaturated fatty acids, its alkyl or alkenyl have 6 to 30, preferred 9 to 24, more preferably 12 to 20 carbon atoms.There are the alkyl that is less than 6 carbon atoms or the lipid acid of alkenyl will destroy the solubility of component (E), will destroy resistance to abrasion and have more than those of the alkyl of 30 carbon atoms or alkenyl.
The specific examples of described lipid acid is the straight or branched saturated fatty acid, as caproic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, margaric acid, octadecanoic acid, nondecylic acid, arachic acid, heneicosanoic acid, docosoic acid, tricosanic acid, Lignoceric acid, pentacosoic acid, hexacosanoic acid, carboceric acid, octocosoic acid, montanic acid and triacontanoic acid; With the straight or branched unsaturated fatty acids, its position of double bond can change, as heptenoic acid, octylenic acid, nonenoic acid, decylenic acid, undecylenic acid, dodecenoic acid, tridecylenic acid, tetradecenoic acid, pentadecylenic acid, hexadecylenic acid, heptadecenoic acid, octadecenoic acid, jecoleic acid, eicosenoic acid, heneicosene acid, Decosahedaenoic acid, tricosenoic acid, tetracosenoic acid, Timnodonic Acid, hexacosenoic acid, cerotene acid, two octadecenoic acids, two jecoleic acids and lumequeic acid.
The specific examples that is used for the fatty acid amide of component (E) is the acid amides that the arbitrary and nitrogenous compound of the above lipid acid of enumerating or its acyl chlorides such as ammonia and molecule only have the aminated compounds reaction of the alkyl of the alkyl that contains 1-20 carbon atom or hydroxyl to obtain.
The specific examples of described nitrogenous compound is an ammonia; Alkylamine, alkyl wherein can be a straight or branched, as Monomethylamine, monoethylamine, a propylamine, monobutylamine (MBA), an amylamine, a hexylamine, a heptyl amice, an octylame, dimethylamine, methyl ethyl-amine, diethylamine, methyl propylamine, ethyl propylamine, dipropyl amine, methylbutylamine, ethyl butyl amine, propyl group butylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices and Di-Octyl amine; Alkanolamine, alkanol groups wherein can be a straight or branched, as single carbinolamine, monoethanolamine, single Propanolamine, only son's hydramine, single amylalcohol amine, single hexanol amine, single enanthol amine, single octanol amine, single nonyl alcohol amine, dimethanolamine, methanol amine, diethanolamine, methyl alcohol Propanolamine, ethanol propanol amine, dipropanolamine, methyl alcohol butanolamine, ethanol and butanol amine, propyl alcohol butanolamine, two butanolamines, diamyl hydramine, two hexanol amine, two enanthol amine and two octanol amine; And composition thereof.
Among the present invention, preferably use stearic amide and amine hydroxybenzene, because their initial resistance to abrasion is fabulous and can keep resistance to abrasion.
Use component (E) can reduce the content of component (C) in the internal combustion engine lubrication oil compositions of the present invention.The lower limit content of component (E) is 0.01% (quality), preferred 0.05% (quality) based on the total amount of the present composition, and upper limit content is 2.0% (quality), preferred 1.0% (quality) based on the total amount of the present composition.The component (E) that is lower than 0.01% (quality) will be brought difficulty to the maintenance resistance to abrasion, and will destroy the stability in storage of resulting composition more than the component (E) of 2.0% (quality).
Internal combustion engine lubrication oil compositions of the present invention contain 0.3 to 1.0% (quality) by metallic element deutero-sulfated ash.Described lower limit sulfate ash content is preferably 0.4% (quality), more preferably 0.45% (quality), more preferably 0.50% (quality) also.Described upper limit sulfate ash content is preferably 0.8% (quality), more preferably 0.65% (quality), preferred especially 0.6% (quality).The sulfate ash content that is lower than 0.3% (quality) as previously described will be to keeping resistance to abrasion bring difficulty, and the sulfate ash content that is higher than 1.0% (quality) has disadvantageous effect such as ash content in accumulation on the exhaust gas post-treatment device with take place to stop up particularly in DPF due to ash content.
When needing, can in lubricating oil composition of the present invention, add in addition ashless dispersant of various additives such as component (A), component (C) and (D) in addition anti-wear agent, component (E) friction modifiers, antioxidant, rust-preventive agent, non-emulsifying agent, metal passivator and defoamer in addition on the degree that realize the object of the invention not influencing.
The example of component (A) ashless dispersant in addition is to have at least one to contain the alkyl of 40 to 400 carbon atoms or the benzylamine and the derivative thereof of alkenyl in the per molecule; And have at least one to contain the alkyl of 40 to 400 carbon atoms or the polyamines and the derivative thereof of alkenyl in the per molecule.
Component (C) and (D) in addition the example of friction modifiers be thiophosphite that 1 to 3 sulphur atom is arranged in thiophosphatephosphorothioate that 1 to 4 sulphur atom is arranged in sulfur-based compound such as the per molecule, the per molecule, its amine salt, disulphide, alkene sulfide, dithiocarbamate, and sulfurized fat and oil.Although can add uncle's zinc dialkyl dithiophosphate and diaryl zinc dithiophosphate, lubricating oil composition of the present invention preferably only contains at the defined zinc dithiophosphate of component (C).
Component (E) friction modifiers in addition is molybdenum dithiocarbamate, molybdenum dithiophosphate, the fatty acid ester and the aliphatic amine of the alkyl of 6 to 30 carbon atoms are arranged.
Examples of antioxidants be various phenol-, amine-and sulphur-based compound.
The example of rust-preventive agent is alkenyl succinate and polyol ester.
The example of non-emulsifying agent is polyalkylene glycol base nonionogenic tenside such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether and polyxyethylated naphthyl ether.
The example of metal passivator be benzotriazole-, benzoglyoxaline-, benzothiazole-and thiadiazoles-based compound.
The example of defoamer is dimethyl polysiloxane and polyacrylic ester.
Internal combustion engine lubrication oil compositions of the present invention contains in addition the ashless dispersant of component (A) that is respectively 0.01 to 5% (quality), component (C) and (D) in addition anti-wear agent, component (E) friction modifiers, antioxidant, rust-preventive agent and non-emulsifying agent in addition, 0.005 metal passivator to 1% (quality), 0.0005 to the defoamer of 1% (quality), based on the total amount of composition.
Preferred forms
Below, describe the present invention in more detail with Comparative Examples with the following Examples, but should not be considered as limiting the scope of the invention.
Embodiment 1 to 7 and Comparative Examples 1 to 6
Press the various lubricating oil compositions of formulation shown in table 1 (embodiment 1 to 7) and 2 (Comparative Examples 1 to 6), and estimate by following benchmark test.Table 1 and 2 also illustrates the result of these tests.
(1) high speed four-ball test
1) uses the fresh lubricating oil composition
Make carbon black and each lubricating oil composition blending of 3% (quality), stirred 10 minutes with 25000rpm with homogenizer.Press ASTM D417-82 (Shell high speed four-ball wear test) under the load of the rotating speed of 80 ℃ temperature, 1800rpm and 30kg each test oil of test 30 minutes to measure grinding defect diameter.
2) use rotten lubricating oil composition
By " mensuration of internal combustion (IC) engine lubricating oil-oxidation stability test " (Indiana StirringOxidation Test (ISOT), JIS K2514) under 165.5 ℃ temperature, forced in 24 hours each composition rotten after, make 3% (quality) thus the test oil that goes bad of carbon black and each rotten oil compositions blending preparation.Described rotten test oil is carried out wearing test same as described above measure grinding defect diameter.
(2) heat pipe experiment
Estimate the high temperature detergency of each lubricating oil composition with the heat pipe experiment instrument HT-201 of Komatsu Engineering (K.K.) manufacturing.In this test, making each composition sample is that the air Continuous Flow of 10ml/min is crossed the soft glass pipe that heats with scorching hot of fine aluminium with the flow of 0.3ml/hr under 290 ℃ temperature with flow.After the described Glass tubing of petroleum ether, estimated the high temperature detergency by the deposition that produces on the pipe internal surface based on 10 minutes.The internal surface of 10 fens expression clear, colorless (not having deposition), and 0 fen expression black non transparent surface.Estimate the Glass tubing that the internal surface in 0 to 10 scope is arranged with reference to the standard pipe of producing by scoring with 0.5.Under 290 ℃ temperature, scoring be 6 or higher lubricating oil to be considered as detergency fabulous.
Table 1
Embodiment
1 2 3 4 5 6 7
Base oil/mineral oil 1) Surplus Surplus Surplus Surplus Surplus Surplus Surplus
(A) succinimido ashless dispersant 2)(N concentration: quality %) 8.0 0.13 8.0 0.13 8.0 0.13 8.0 0.13 8.0 0.13 8.0 0.13 8.0 0.13
(B) alkaline-earth metal washing agent calcium salicylate 3)Calcium sulphonate 4)Calcium phenylate 5) 2.0 0.8 1.2 2.0 2.0 2.0 2.0
(C) secondary alkyl zinc dithiophosphate 6)(P concentration: quality %) 0.95 0.068 0.95 0.068 0.95 0.068 0.95 0.068 0.95 0.068 0.70 0.050 0.40 0.029
(D) phosphorous ash-free antiwear agent phosphorous acid ester 7)The amine salt of phosphorous acid ester 8)Phosphate ester acid 9)(P concentration: quality %) 1.0 0.025 1.0 0.025 1.0 0.025 0.8 0.024 0.5 0.031 0.6 0.015 0.5 0.013
(E) fatty acid amide 10) 0.3
Other additive 11) 2.6 2.6 2.6 2.6 2.6 2.6 2.6
Ca concentration: quality % Zn concentration: quality % P concentration: quality % N concentration: quality % sulfate ash content: quality % 0.12 0.074 0.093 0.18 0.62 0.10 0.074 0.093 0.18 057 0.11 0.074 0.093 0.18 0.61 0.12 0.074 0.092 0.17 0.62 0.12 0.074 0.099 0.17 0.62 0.12 0.055 0.065 0.18 0.59 0.12 0.031 0.041 0.17 0.56
(1) high speed four-ball wear test grinding defect diameter (fresh oil): mm grinding defect diameter (pressing the rotten oil of ISOT): mm 0.35 0.36 0.35 0.40 0.36 0.41 0.36 0.36 0.35 0.40 0.35 0.35 0.36 0.40
(2) heat pipe experiment scoring (290 ℃, 16h) 7.5 7.0 7.0 7.0 7.0 75 8.0
Table 2
Comparative Examples
1 2 3 4 5 6
Base oil/mineral oil 1) Surplus Surplus Surplus Surplus Surplus Surplus
(A) succinimido ashless dispersant 2)(N concentration: quality %) 8.0 0.13 8.0 0.13 3.0 0.05 8.0 0.13 8.0 0.13 8.0 0.13
(B) alkaline-earth metal washing agent calcium salicylate 3)Calcium sulphonate 4)Calcium phenylate 5) 0.7 0.3 2.0 2.0 2.0 2.0
(C) swollen alkyl zinc dithiophosphate 6)(P concentration: quality %) 0.95 0.068 0.95 0.068 0.95 0.068 0.95 0.068 0.000 0.4 0.029
(D) phosphorous ash-free antiwear agent phosphorous acid ester 7)The amine salt of phosphorous acid ester 8)Phosphate ester acid 9)(P concentration: quality %) 1.0 0.025 1.0 0.025 1.0 0.025 0.0 1.0 0.025 0.5 0.013
(E) fatty acid amide 10)
Other additive 11) 2.6 2.6 2.6 2.6 2.6 2.6
Ca concentration: quality % Zn concentration: quality % P concentration: quality % N concentration: quality % sulfate ash content: quality % 0.04 0.074 0.093 0.18 0.37 0.04 0.074 0.093 0.18 0.36 0.12 0.074 0.093 0.10 0.62 0.12 0.074 0.068 0.17 0.62 0.12 0.0 0.025 0.18 0.49 0.12 0.031 0.041 0.17 0.55
(1) high speed four-ball wear test grinding defect diameter (fresh oil): mm grinding defect diameter (pressing the rotten oil of ISOT): mm 0.34 0.70 0.34 0.70 0.34 0.39 0.71 0.79 0.67 0.75 0.66 0.69
(2) heat pipe experiment scoring (290 ℃, 16h) 7.5 7.5 2.5 7.0 7.0 8.0
In the table 1 and 2 1) to 11) as follows:
1) hydrorefined mineral oil (kinematic viscosity: 4mm 2@100 ℃ of/s (), viscosity index: 120)
2) boration double focusing butenyl succinimide (dimorphism, polybutylene-based number-average molecular weight: 1300, nitrogen content: 1.6 quality %, boron content: 0.5 quality %)
3) overbased calcium salicylate calciferous (base number: 166, calcium contents: 5.8 quality %, sulfate ash content: 19.7 quality %)
4) high alkaline calcium sulfonate calciferous (base number: 320, calcium contents: 12.5 quality %, sulfate ash content: 42.5 quality %)
5) high alkalinity phenol calcium calciferous (base number: 250, calcium contents: 9.25 quality %, sulfate ash content: 31.5 quality %)
6) zinc dialkyl dithiophosphate (zinc content: 7.8 quality %, phosphorus content: 7.2 quality %, alkyl: 1,3-dimethylbutyl)
7) triphenyl phosphite (phosphorus content: 3.0 quality %)
8) the oleyl amine salt of acid phosphorous acid stearyl (phosphorus content: 2.5 quality %, nitrogen content: 0.35 quality %)
9) acid phosphoric acid iso stearyl ester (phosphorus content: 6.2 quality %)
10) oleylamide (iodine number: 80-90)
11) phenol-based anti-oxidants, amido antioxidant and polymethacrylate type viscosity index improver
From result shown in table 1 and 2 as seen, although the ash oontent of internal combustion engine lubrication oil compositions of the present invention is low, they show splendid resistance to abrasion and high temperature detergency.Especially, even very high resistance to abrasion is also arranged on the turn, and keep almost identical resistance to abrasion with new oil.
On the contrary, the content of component (B) than the composition of the much lower Comparative Examples 1 of the present invention specified amount and 2 on the turn the back resistance to abrasion descend.The composition of the Comparative Examples 3 that the content of component (A) is more much lower than the present invention specified amount fails to obtain enough high temperature detergencies.The composition that does not contain the composition of component (D) or Comparative Examples (C) 4 and 5 and component (C) the content Comparative Examples 6 more much lower than the present invention specified amount fails to obtain enough resistance to abrasions.
Industrial applicibility
Wear resistence and high temperature detergency are fabulous although lubricant composition for internal combustion engines of the present invention contains a small amount of ash content, particularly also show fabulous wear resistence when fresh even after going bad because of the soot pollution. Thereby, lubricant oil composite of the present invention is preferred for being furnished with the Diesel engine of exhaust gas post-treatment device such as EGR, oxidation catalyst, NOx sorption reducing catalyst or DPF, can be used as generator and marine diesel engine, gas engine and two or four-wheel car with petrol engine lubricating oil.

Claims (4)

1. lubricant composition for internal combustion engine, comprise mineral and/or synthetic base oil, (A) by nitrogen content be the succinimido ashless dispersant of 0.08 to 0.40 quality %, (B) be the metallo-detergent of 0.06 to 0.22 quality % by metal element content, (C) by phosphorus content be the secondary alkyl zinc dithiophosphate that 3 to 20 carbon atoms are arranged of 0.04 to 0.08 quality %, (D) by phosphorus content be the phosphorous ash-free antiwear agent of 0.01 to 0.04 quality %, described phosphorous ash-free antiwear agent is selected from the phosphoric acid ester and the amine salt thereof of 2 to 30 carbon atoms or the phosphorous acid ester and the amine salt thereof of 2 to 30 carbon atoms is arranged, and contain 0.3 to 1.0 quality % by the metallic element deutero-sulfated ash in the composition.
2. lubricant composition for internal combustion engine, comprise mineral and/or synthetic base oil, (A) by nitrogen content be the succinimido ashless dispersant of 0.08 to 0.40 quality %, (B) be the metallo-detergent of 0.06 to 0.22 quality % by metal element content, (C) by phosphorus content be the secondary alkyl zinc dithiophosphate that 3 to 20 carbon atoms are arranged of 0.02 to 0.08 quality %, (D) by phosphorus content be the phosphorous ash-free antiwear agent of 0.01 to 0.04 quality %, described phosphorous ash-free antiwear agent is selected from the phosphoric acid ester and the amine salt thereof of 2 to 30 carbon atoms or the phosphorous acid ester and the amine salt thereof of 2 to 30 carbon atoms is arranged, (E) content is the fatty acid amide of 0.01 to 2.0 quality %, its fatty acid residue is alkyl or the alkenyl that 6 to 30 carbon atoms are arranged, and contain 0.3 to 1.0 quality % by the metallic element deutero-sulfated ash in the composition.
3. claim 1 or 2 lubricating oil composition, wherein component (B) is the alkaline-earth metal salicylate.
4. claim 1 or 2 the application of lubricating oil composition in being furnished with the diesel motor of exhaust gas post-treatment device.
CNB028183746A 2001-09-20 2002-09-06 Lubricating oil composition for internal combustion engine Expired - Fee Related CN1322103C (en)

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