CN102666817A - Lubricating composition - Google Patents

Lubricating composition Download PDF

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Publication number
CN102666817A
CN102666817A CN2010800483238A CN201080048323A CN102666817A CN 102666817 A CN102666817 A CN 102666817A CN 2010800483238 A CN2010800483238 A CN 2010800483238A CN 201080048323 A CN201080048323 A CN 201080048323A CN 102666817 A CN102666817 A CN 102666817A
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CN
China
Prior art keywords
lubricating composition
purification agent
koh
base oil
detergent
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CN2010800483238A
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Chinese (zh)
Inventor
J·L·加西亚奥赫达
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to CN201710068277.1A priority Critical patent/CN106811266A/en
Publication of CN102666817A publication Critical patent/CN102666817A/en
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
    • C10M157/06—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a sulfur-, selenium- or tellurium-containing compound
    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • 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
    • 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
    • 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
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/04—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
    • C10N2030/52—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
    • C10N2040/252—Diesel engines

Abstract

The present invention provides a lubricating composition at least comprising: a base oil; and a detergent; wherein the detergent comprises at least 30 mol%, based on the total amount of detergent, of a sulphonate detergent having a BlSI (Base Number) of from 0.1 to 80 mg KOH/ g; wherein the detergent comprises from 30 to 70 mol%, based on the total amount of detergent, of a phenate detergent; wherein the lubricating composition comprises at least 4 wt. % of detergent, based on the total weight of the composition; and wherein the lubricating composition has a TBN (total base number) (according to ASTM D 2896) of at least 10 mg KOH /g.

Description

Lubricating composition
Technical field
The present invention relates to a kind of lubricating composition, the lubricating composition of particularly under continuing high-load condition, using in the oil engine of operation, the lubricating composition of for example in marine diesel and power generation application, using.More particularly, the present invention relates to a kind of lubricant peculiar to vessel.
Technical background
Lubricant peculiar to vessel is well known in the art.For example; EP1086195 discloses a kind of marine cylinder oil compsn that contains lubricating base oil and overbased detergent component; The TBN of said compsn is that to be included in 100 ℃ of following viscosity be about 400 or bigger overbased calcium sulfonate for 180cSt at least and TBN for 50-90 and said purification agent component.
The lubricating composition of in oil engine, using will bear heavily stressed.The lubricity that importantly said lubricating composition can provide under various conditions, to help to keep engine washing, heat and oxidation-stabilized, wear-resisting, the corrosionproof protection that provides is also taken away heat from mover.
Because ship engine is moving near long-term under the loaded condition through the remote districts of being everlasting usually continuously, so the lubricating composition of using in the marine diesel will bear extra high stress.In addition, owing to often seldom or almost have no chance to change the lubricating composition in the ship engine, therefore hope that lubricating composition has the long life-span.
Will be appreciated that those movers that term " peculiar to vessel " is not limited in the water ballast container, use in the prior art.That is to say that said term also comprises the mover that is used for power generation application.These high-grade, fuel are effectively, slow and middling speed ship engine and stationary diesel engine operate under high pressure, high temperature and long stroke.
Summary of the invention
The settling that an object of the present invention is to improve the lubricating composition of particularly in oil engine such as marine diesel, using forms performance.
Another object of the present invention provides the alternative lubricating composition that in oil engine, uses.
The present invention can reach one or more above-mentioned or other purposes through a kind of lubricating composition is provided, and said lubricating composition comprises base oil and purification agent at least; Wherein said purification agent comprises at least in the purification agent total amount, and 30mol%BN (alkali number) is the sulfonate detergent of 0.1-80mg KOH/g; Wherein said purification agent comprises the phenates purification agent of 30-70mol% in the purification agent total amount; Wherein said lubricating composition comprises the purification agent of 4wt% at least in the lubricating composition gross weight; Be 10mg KOH/g (pressing ASTM D 2896) at least with the TBN (total alkali number) of wherein said lubricating composition.
It has surprisingly been found that now that according to the present invention lubricating composition of the present invention shows by DIN51392 and the definite improved settling formation control performance of Komatsu Hot Tube Test (Komatsu heat pipe method).
To not special MO, synthetic oil and natural deutero-ester such as the vegetables oil that limits and can use various routines easily of the base oil of in lubricating composition of the present invention, using.
The base oil of using in the present invention can comprise the mixture of one or more MO and/or one or more synthetic oils easily; Therefore, according to the present invention, term " base oil " can refer to contain the mixture of multiple base oil.MO comprises petroleum liquid and alkane, cycloalkanes or mixes the solvent treatment or the acid-treated mineral lubricating oils of alkane/cycloalkanes type that it can be further refining through unifining process and/or dewaxing.
The suitable base oils of in lubricating composition of the present invention, using is I-III class mineral base oil, IV class poly-alpha olefins (PAO), the Fisher-Tropsch derived base oil of I-III class and their mixture.
In the present invention, " I class ", " II class ", " III class " and " IV class " base oil refer to the lubricant base according to the I-IV class definition of American Petroleum Institute (API).These API are sorted in API publication 1509, the 15 editions, and appendix E defines in 2002 4 months.
Fisher-Tropsch derived base oil is known in the prior art.Term " Fisher-Tropsch derived " refers to that base oil is or derived from the sintetics of Fischer-Tropsch process.Fisher-Tropsch derived base oil also can be called GTL (gas is to liquid) base oil.The suitable Fisher-Tropsch derived base oil that can be used as the base oil of lubricating composition of the present invention easily is for example those disclosed in EP0776959, EP0668342, WO97/21788, WO00/15736, WO00/14188, WO00/14187, WO00/14183, WO00/14179, WO00/08115, WO99/41332, EP1029029, WO01/18156 and WO01/57166.
Synthetic oil comprises that hydrocarbon ils such as olefin oligomer (comprise and gather α-base oil; PAO), the wax isomer of dibasic acid esters, polyol ester, polyalkylene glycol (PAG), alkylnaphthalene and dewaxing.Can use the synthetic alkyl oil of selling with title " Shell XHVI " (trade mark) by Shell Group easily.
Being prepared in of poly-alpha olefins base oil (PAO) and they is known in the art.The preferred poly-alpha olefins base oil that can in lubricating composition of the present invention, use can be derived from straight chain C 2-C 32, preferred C 6-C 16Terminal olefin.Preferred especially raw material is 1-octene, 1-decene, 1-dodecylene and tetradecene for poly-alpha olefins.
In the gross weight of lubricating composition, the total amount of bonded base oil is preferably 60-99wt% in lubricating composition of the present invention, more preferably 65-98wt% and most preferably be 70-95wt%.
According to the preferred embodiments of the invention, said base oil comprises the II class base oil of 50wt% at least in the total amount of base oil, is preferably 60wt% at least, more preferably 70wt% at least.
Do not have to limit (as long as meeting the requirement of claim 1) and can use various conventional purification agents easily especially for the purification agent of in lubricating composition of the present invention, using.Term " purification agent " can refer to single purification agent, also can refer to contain the mixture of two kinds or more kinds of different purification agents.The instance of adaptable purification agent comprises oil-soluble neutrality and overbased sulfonates, phenates, sulfuration phenates, thio-phosphonates, salicylate and naphthenate and other oil-soluble metal carboxylate; Said metal is basic metal or earth alkali metal particularly, like sodium, potassium, lithium and particularly calcium and magnesium.Preferred metal detergent is a neutral and TBN (the total alkali number is pressed ASTM D 2896) is the overbased detergent of 450mg KOH/g at the most.Can use the compsn of purification agent, said purification agent can be that overbased detergent or neutral purification agent or both all have.
As noted earlier, in compsn of the present invention, said purification agent comprises at least by the total amount of purification agent that 30mol%BN (alkali number) is the sulfonate detergent of 0.1-80mg KOH/g.This sulfonate detergent with low relatively BN is known in the art.For example, WO96/26919 discloses low BN calcium sulphonate and preparation thereof.
According to the preferred embodiments of the invention, said purification agent comprises the sulfonate detergent of 35mol% at least, is preferably 40mol% at least, 45mol% at least more preferably, even 50mol% at least more preferably, most preferably 55mol% at least.Preferably said in addition sulfonate detergent has at the most 50mg KOH/g, the more preferably BN of 40mg KOH/g at the most.
As noted earlier, in compsn of the present invention, said purification agent comprises the phenates purification agent of 30-70mol% in the total amount of purification agent.Said purification agent preferably comprises the phenates purification agent of 35mol% at least; Said purification agent preferably comprises the phenates purification agent of 65mol% at the most, 60mol% at the most more preferably, even 55mol% at the most more preferably, and still 50mol% at the most more preferably most preferably is the phenates purification agent of 45mol% at the most.Preferably said in addition phenates purification agent is an overbased detergent, and its BN is 190mg KOH/g at least, is preferably at least 200, more preferably at least 220, most preferably be 240mg KOH/g at least.This purification agent is known in the art.
In the gross weight of lubricating composition, the total amount of purification agent is generally 35.0wt% at the most in compsn of the present invention.In the gross weight of compsn, compsn of the present invention comprises at least 4wt%, preferred 8wt% at least, the more preferably purification agent of 12wt% at least.
Lubricating composition of the present invention can also comprise one or more other additives, like inhibitor, anti-wear agent, dispersion agent, other purification agent, extreme-pressure additive, other friction modifier, viscosity modifier, pour point reducer, metal passivator, sanitas, emulsion splitter, skimmer, sealing compatilizer and additive thinner base oil etc.Preferably, except that purification agent, in compsn of the present invention, also there is dispersion agent at least; More preferably, there are dispersion agent and anti-wear agent at least.
In the gross weight of lubricating composition, the amount of above-mentioned additive is generally 0.01-35.0wt%, is preferably 0.5-30.0wt%.More preferably, lubricating composition of the present invention comprises any other additive that is different from one or more purification agents less than 5.0wt%.Preferably, said compsn does not contain except that one or more purification agents, one or more dispersion agents and one or more other additives anti-wear agent.
Because those skilled in the art are familiar with above-mentioned and other additive, therefore no longer go through here.The specific examples of these additives is at the Encyclopedia of for example Kirk-Othmer of Chemical Technology, the third edition, and the 14th volume is stated in the 477-526 page or leaf.
Preferably, total alkali number (TBN) value of said compsn is preferably 75mg KOH/g at the most, is preferably 70mg KOH/g at the most, 65mg KOH/g at the most more preferably, even 60mg KOH/g (specifically pressing ASTM D 2896 measures) at the most more preferably.The total alkali number (TBN) of said compsn value (pressing ASTM D 2896) is 10mg KOH/g at least.
In addition, the kinematic viscosity (press ASTM D 445) of preferably said compsn under 100 ℃ is greater than 5.6mm 2/ s and less than 21.9mm 2/ s is preferably greater than 12.5mm 2/ s is more preferably greater than 16.3mm 2/ s.
Lubricating composition of the present invention can prepare through mixing one or more additives and base oil easily.
In yet another aspect, the present invention provides lubricating composition of the present invention to improve the purposes that settling forms control performance (specifically pressing DIN51392 measures).
Lubricating composition of the present invention is generally used for lubrication equipment, but is particularly useful as the engine oil that is used for oil engine.These engine oils comprise bus engine, diesel motor, marine diesel, gas engine, two circulation and four-circulation motor etc. and particularly marine diesel.
The following embodiment of following reference describes the present invention, the scope that said embodiment does not limit the present invention in any way.
Embodiment
Lubricating oil composition
Be formulated in the various lubricating compositions that are used as marine cylinder oil in the marine diesel.
Table 1 has been listed the composition and the performance of the prescription of being tested; Component concentration is represented with wt% based on the prescription gross weight meter of preparation fully.
The marine diesel oil formula of all tests is all by SAE 50 formulated, and these prescriptions satisfy so-called SAE J 300 specifications (in January, 2009 revision, SAE represents Society of automotive engineers).The kinematic viscosity (press ASTM D 445) of the prescription of all tests under 100 ℃ is all greater than 16.3mm 2/ s and less than 21.9mm 2/ s.
The marine cylinder oil prescription of all tests all comprises the combination of base oil, cleaning agent composition and dispersion agent.
" base oil 1 " is the blend of I class base oil and bright stock, and (London UK) is commercially available with trade(brand)name " Catenex " by Shell Chemicals Ltd. for it.
" base oil 2 " is for comprising the base oil blend of thickening material and 75wt% I I class base oil; (San Ramon, CA USA) are commercially available with trade(brand)name " Chevron 600R " this blend by for example Chevron Products Company.
" purification agent 1 " is that 417mg KOH/g (by ASTM D 2896) and soap content are 236mM Ca for TBN 2+The overbased sulfonates purification agent, (Windsor UK) is commercially available with trade(brand)name " OLOA 249SX " by Chevron Oronite for it.
" purification agent 2 " is that 375mg KOH/g and soap content are 317mM Ca for TBN 2+The overbased sulfonates purification agent, (Liaoning China) is commercially available with trade(brand)name " T106 " by JinZhou KangTai Lubricant Additives Co.Ltd. for it.
" purification agent 3 " is that 246mg KOH/g and soap content are 397mM Ca for TBN 2+Parlkaline phenates purification agent, (Wickliffe, Ohio USA) are commercially available with trade(brand)name " Lubrizol 6499 " by Lubrizol for they.
" purification agent 4 " is that 250mg KOH/g and soap content are 282mM Ca for TBN 2+Parlkaline phenates purification agent, it is commercially available with trade(brand)name " OLOA 219C " by Chevron Oronite.
" purification agent 5 " is that 16mg KOH/g and soap content are 410mM Ca for TBN 2+Low BN sulfonate detergent, it is commercially available with trade(brand)name " OLOA 246S " by Chevron Oronite.
" purification agent 6 " is that 34mg KOH/g and soap content are 395mM Ca for TBN 2+Low BN sulfonate detergent, (Middlebury USA) is commercially available with trade(brand)name " LOBASE C-4503 " by Chemtura Corporat ion for it.
" purification agent 7 " is that 9mg KOH/g and soap content are 441mM Ca for TBN 2+The overbased sulfonates purification agent, it is commercially available with trade(brand)name " LOBASEC-4506 " by Chemtura Corporat ion.
" dispersion agent " is the polyisobutenyl succinimide of high MW, and (Richmond, VA USA) are commercially available with trade(brand)name " HiTEC " by Afton Chemical Corporation for they.
The compsn of embodiment 1-10 and Comparative Examples 1-2 is through using conventional lubricant combination process mixing base oil and purification agent, dispersion agent acquisition.
Pointed following method in the application table 1:
1The TBN value is pressed ASTM D 2896 and is confirmed;
2The purification agent content of each purification agent (or " soap content ") is at experience V.A.Zakupra and S.V.Timoshenko (All-Union Scientific-Research and Design Institute of the Petroleum Refining and Petrochemical Industry (VNIIPKnef tekhim); USSR) article " Separation of lube oil detergent additives on silica gel "; In Khimiya i TekhnologiyaTopliv i Masel; No.2, pp.48-52, February; Behind the separable programming of describing in 1980, the soap of using purification agent divides the TAN measurement (pressing ASTM D 664) of rate to confirm.The soap content value of being measured is with the equivalent mmole Ca of every kg detergent additives 2+Expression (referring to the top soap content of confirming to purification agent 1-7).Purification agent (mole) content of every kind of purification agent type (for example low BN sulphonate) multiply by through the contribution (wt%) of each detergent additives in the whole prescription and adds behind each purification agent content and obtain.
3The ratio of purification agent is confirmed through calculating (every kind of purification agent component is divided by sum), and is represented with mol%.In an embodiment, phenates ratio and sulphonate ratio and be 100%; The ratio of low BN sulphonate (being that BN is 0.1-80mg KOH/g, is preferably the sulphonate of 0.1-50mg KOH/g) is the part of sulphonate ratio.
4The nominal settling is based on the total settling value after testing by DIN 51392.When making reference, shown that nominal settling (rather than total settling) has reflected relative value better with Comparative Examples 3.
Figure BDA0000157406990000091
Wolf Strip test
In order to verify that settling of the present invention forms control performance, press DIN 51392 application Wolf Strip test procedures (test time 12 hours, the dish temperature is 280 ℃) and measure.In test, use following test condition: the oily flow of application 1 50ml in closed cycle; In the test process with oil with form of film under 280 ℃ with the pumping 12 hours on the movable detection band of the flow of 50 (± 5) ml/h, the inclination angle of the relative horizontal direction of wherein said band is 8 °.
The nominal settling that measures is listed in last table 1, and the result representes and has the relative quantity that the embodiment (being Comparative Examples 3) of high total sediment yield compares.
The test of Komatsu heat pipe
Form in the alternative test of control performance at checking settling of the present invention, use Komatsu heat pipe test procedure according to the vision grading of in Swiss Testing procedure No.STS Nr.452, explaining and measure.The high-temperature stability of Komatsu heat pipe test evaluation lubricant.The inner air of the thin glass capillary of heating upwards boost oil droplet and through Glass tubing on the varnish formation degree measure the film oxidation stability of lubricant, the final color of pipe press the scale of 0-10 and is graded.Grading 0 refers to that very heavy settling forms, and 10 fingers of grading still are clean Glass tubing at EOT.This method also has description in SAE paper 840262.The formation level of paint film has reflected oily high-temperature stability and in the high-temperature area of mover, has formed sedimental tendency during use in pipe.The grading that measures (under 290 and 320 ℃) provides in following table 2.
Table 2
Embodiment 2 Embodiment 3 Embodiment 5 Embodiment 6 Comparative Examples 1
290℃ 9.5 9.5 9.5 9.5 8.5
320℃ 5.0 5.0 8.5 8.5 Stop up
Discuss
Can find out that from table 1 when comparing with Comparative Examples 1-2, the settling of the present composition forms control performance and obviously improves.
The comparison that forms control performance from the settling of embodiment 1-10 can be found out; According to the present invention; Preferred wherein at least the purification agent of 40mol% be the embodiment of phenates purification agent (embodiment 1-7) for low BN sulfonate detergent (be that the BN number is 0.1-80, preferably be lower than 50mg KOH/g) and while greater than the purification agent total amount of 35mol%.In addition, embodiment 5 and 6 is preferred especially, because they have littler sediment yield.In addition, preferably base oil comprises the II class base oil of 50wt% at least.
Desirable settling of the present invention forms control performance and in the test of Komatsu heat pipe, has obtained affirmation (referring to table 2).Embodiment 2,3,5 and 6 is obtaining fabulous grading (is 9.5) in total grading 10 under 290 ℃; Under 320 ℃, still have and to accept (embodiment 2 and 3 is 5.0) value, and Comparative Examples 1 is not passed through test (obstruction) under 320 ℃ to good (embodiment 5 and 6 is 8.5).

Claims (10)

1. lubricating composition, said lubricating composition comprises:
Base oil; With
Purification agent;
Wherein said purification agent comprises at least in the purification agent total amount, and 30mol%BN (alkali number) is the sulfonate detergent of 0.1-80mg KOH/g;
Wherein said purification agent comprises the phenates purification agent of 30-70mol% in the purification agent total amount;
Wherein said lubricating composition comprises the purification agent of 4wt% at least in the lubricating composition gross weight; With
The TBN of wherein said lubricating composition (total alkali number) is 10mg KOH/g (pressing ASTMD 2896) at least.
2. the lubricating composition of claim 1, wherein said purification agent comprises the sulfonate detergent of 35mol% at least, is preferably 40mol% at least, and more preferably 45mol% at least most preferably is 50mol% at least.
3. claim 1 or 2 lubricating composition, wherein said sulfonate detergent has the BN of 50mg KOH/g at the most.
4. each lubricating composition of claim 1-3, wherein said purification agent comprises the phenates purification agent of 35mol% at least.
5. each lubricating composition of claim 1-4, wherein said phenates purification agent are that BN is 190mg KOH/g, preferred at least 200, more preferably at least 220, the overbased detergent of 240mg KOH/g at least most preferably at least.
6. each lubricating composition of claim 1-5, wherein said compsn comprises at least 8wt%, is preferably the purification agent of 12wt% at least in the gross weight of compsn.
7. each lubricating composition of claim 1-6, the TBN of wherein said compsn (total alkali number) value is 75mg KOH/g at the most, is preferably 70mg KOH/g at the most, more preferably 60mg KOH/g at the most.
8. each lubricating composition of claim 1-7, wherein said base oil comprises the II class base oil of 50wt% at least in the base oil total amount, is preferably 60wt% at least, more preferably 70wt% at least.
9. each lubricating composition of claim 1-8, wherein said compsn is a marine diesel engine oil.
10. each lubricating composition of claim 1-9 improves the purposes that settling forms control performance.
CN2010800483238A 2009-10-26 2010-10-26 Lubricating composition Pending CN102666817A (en)

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