CN1826401A - Lubricating oil composition with antiwear performance - Google Patents

Lubricating oil composition with antiwear performance Download PDF

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Publication number
CN1826401A
CN1826401A CNA2004800208894A CN200480020889A CN1826401A CN 1826401 A CN1826401 A CN 1826401A CN A2004800208894 A CNA2004800208894 A CN A2004800208894A CN 200480020889 A CN200480020889 A CN 200480020889A CN 1826401 A CN1826401 A CN 1826401A
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alkyl
lubricating oil
mixture
composition
oil composition
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B·J·布特克
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Lubrizol Corp
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Lubrizol 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
    • 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
    • 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
    • C10M141/10—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 phosphorus-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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/14—Metal deactivation
    • 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
    • C10N2030/66—Hydrolytic stability
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Abstract

The present invention relates to a lubricating oil composition containing: (1) an antiwear package comprising: (a) a hydrocarbyl phosphate and amine salt thereof; and (b) an alkylene coupled adduct of a hydrocarbyl substituted dithiophosphoric acid and a alpha,beta-unsaturated carbonyl containing compound; (2) an antioxidant package comprising: (a) a hydrocarbyl diphenylamine; and (b) a sterically hindered phenol; (3) a metal deactivator; and (4) an oil of lubricating viscosity. The invention further relates to the process to make the lubricating oil composition and its use in industrial fluids especially hydraulic fluids.

Description

Lubricating oil composition with abrasion resistance
Invention field
The present invention relates to a kind of lubricating oil composition, it comprises: (1) contains the wear-resistant molectron of following material: (a) alkyl phosphate and its amine salt; (b) phosphorodithioic acid that replaces of alkyl and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl; (2) contain the anti-oxidant molectron of following material: (a) alkyl pentanoic; (b) sterically hindered phenol; (3) metal passivator; (4) lubrication viscosity oil.The invention still further relates to method and its purposes in industrial fluids of this lubricating oil composition of preparation.
Background of invention
Protect lubricating oil composition to avoid the life-span that the oxidation degradation can improve lubricating oil significantly by the oxidation retarder component of selecting suitable surplus.When oxygen invasion and attack petroleum fluids oxidation can take place, this can cause the viscosity and the sedimental formation that increase in this fluid.Oxidising process can promote in oil to form greasy filth and to the destruction of lubricating oil viscosity characteristic.
Come the protective money metal surface to avoid wearing and tearing demoting by the anti-wear agent of in lubricating oil composition, selecting suitable surplus and can increase the life-span of metallic surface significantly.Anti-wear agent can form film on the metallic surface, it can prevent contacting of metal and metal, thereby causes reducing abrasion loss.Known anti-wear agent is derived from the compound zinc dialkyl dithiophosphate (ZDDP) for example that contains ash content usually.Yet many commercial runs adopt high temperature and/or high pressure, and this makes the compound that contains ash content decompose in lubricating oil composition.In addition, owing to contain the compound decomposition of ash content and discharge for example zinc of divalent metal, therefore these divalent metals can with for example alkenyl succinic anhydride and alkenyl succinimide reaction of other performance additive that exist, thereby produce greasy filth and other particulate matters that can cause filter stoppage.If industrial fluids contains from pollutent or other performance additive other divalent metals of calcium or magnesium purification agent for example, then equally filter stoppage may take place.
In the trial that overcomes the filter stoppage problem relevant, in lubricating oil composition, developed the surrogate that does not contain ash content with the industrial fluids that contains ash content.Yet the known composition that does not contain ash content is highly acidic and hydrolytically unstable normally.
U.S. Patent application 2002/0010103A1 has disclosed a kind of lubricating oil composition, and it has base oil and more a spot of (a) at least a P contained compound that is selected from phosphoric acid ester, thiophosphatephosphorothioate and its amine salt of more amount; (b) phosphorous acid ester (phosphorus acid ester) and its amine salt; (c) be selected from least a compound of alkenyl succinimide, alkenyl succinic acid ester, benzylamine and its derivative.Said composition contains the alkenyl succinic anhydride or derivatives thereof, and it can cause the greasy filth of filter stoppage with the divalent metal reaction of contamination level with formation.
International open WO02/053687A2 has disclosed a kind of lubricating oil composition, and it comprises: (a) triaryl phosphate; (b) propionic acid of β-dithio phosphorylated and (c) base oil.This lubricating oil composition provides abrasion resistance and a small amount of ash content.English Patent No.1,415,964 have disclosed a kind of lubricating oil with following composition: dissolve in thiophosphoric acid (phosphorothionic acid) three esters of hydrocarbon ils and (b) monoesters or the diester of at least a (i) triaryl phosphate and phosphate amine salt.Yet the lubricating oil that contains the triaryl phosphate anti-wear agent is known to have high activation temperature, so their validity under lesser temps and/or low load is lower.
U.S. Patent No. 5,531,911 have disclosed a kind of metal-free hydraulic fluid, the rust-preventive agent that it contains the phosphorus anti-wear agent and prepares by amine and sulfonic acid reaction.Yet, improved the stability of formed emulsion when hydraulic fluid is mixed with water by the rust-preventive agent of amine and sulfonic acid prepared in reaction.
Wish to obtain a kind of lubricating oil composition that contains the metal-free performance additive that to give good wear-resistant and/or antioxidant levels.The invention provides a kind of lubricating oil composition that contains the metal-free performance additive that to give good wear-resistant and/or antioxidant levels.
Wish to obtain a kind of unwanted sedimental lubricating oil composition that can improve industrial fluids viscosity that prevents to form.The invention provides a kind of prevent from the to form settling of unwanted meeting raising industrial fluids viscosity and/or the lubricating oil composition that does not contain ash content of greasy filth.
Wish to obtain a kind of lubricating oil composition that prevents that filter stoppage and greasy filth from forming.The invention provides a kind of lubricating oil composition that prevents that filter stoppage and greasy filth from forming.
Wish to obtain a kind of lubricating oil composition that can under wide temperature and/or load range, operate.The invention provides a kind of lubricating oil composition that can under wide temperature and/or load range, operate.
Wish to obtain a kind of lubricating oil composition of hydrolysis-stable.The invention provides a kind of lubricating oil composition with stability to hydrolysis.
Summary of the invention
The invention provides a kind of lubricating oil composition, it comprises:
(1) contain the wear-resistant molectron of following material:
(a) alkyl phosphate and its amine salt; With
(b) phosphorodithioic acid that replaces of alkyl and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl;
(2) contain the anti-oxidant molectron of following material:
(a) alkyl pentanoic; With
(b) sterically hindered phenol;
(3) metal passivator; With
(4) lubrication viscosity oil.
In one embodiment, the invention provides a kind of mentioned above not containing substantially to the lubricating oil composition of containing metal positively charged ion, particularly divalent metal not.In one embodiment, the invention provides a kind of mentioned above not containing substantially to the lubricating oil composition that does not contain the rust-preventive agent for preparing by amine and sulfonic acid reaction.
The present invention further provides a kind of method for preparing lubricating oil composition, it comprises: metal passivator, anti-oxidant molectron, wear-resistant molectron and the non-essential at least a additive that is selected from antifoams, emulsion splitter, viscosity modifier, rust-preventive agent, pour point depressant and combination thereof are mixed and/or be dissolved in base oil and/or the thinning oil.
Lubricating oil composition of the present invention give can be good wear-resistant and/or antioxidant levels.Lubricating oil composition of the present invention can reduce the formation of filter stoppage settling and greasy filth.Lubricating oil composition of the present invention has stability to hydrolysis.
Detailed Description Of The Invention
The invention provides a kind of lubricating oil composition, it comprises:
(1) contain the wear-resistant molectron of following material:
(a) alkyl phosphate and its amine salt; With
(b) phosphorodithioic acid that replaces of alkyl and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl;
(2) contain the anti-oxidant molectron of following material:
(a) alkyl pentanoic; With
(b) sterically hindered phenol;
(3) metal passivator; With
(4) lubrication viscosity oil.
In one embodiment, the invention provides a kind of mentioned above not containing substantially to not containing metal positively charged ion, the particularly divalent metal lubricating oil composition of calcium, magnesium or its mixture for example.In one embodiment, the invention provides a kind of mentioned above not containing substantially to the lubricating oil composition that does not contain the rust-preventive agent for preparing by amine and sulfonic acid reaction.
Wear-resistant molectron
This wear-resistant molectron contains alkyl phosphate and its amine salt that can be expressed from the next:
J wherein 1, J 2, J 3, J 4Be oxygen or sulphur independently, J 1, J 2, J 3, J 4In preferably at least 1, more preferably at least 2 even more preferably at least 3, most preferably all be oxygen.In one embodiment, J 1, J 2And J 3All be oxygen, J 4Be sulphur.In one embodiment, J 1, J 2, J 3And J 4All be oxygen.
R 1And R 2Be hydrogen or alkyl independently, preferably, described alkyl is alkyl, cycloalkyl, aryl or its mixture.In one embodiment, described alkyl is alkyl or its mixture.When alkyl is alkyl, alkyl chain can be branching or line style, but line style preferably.R 1And R 2Contain and have an appointment 4～about 30, preferred about 8～about 25, more preferably from about 10～about 20, most preferably from about 13～about 19 carbon atoms.In one embodiment, R 1Be hydrogen and R 2Be alkyl, in another embodiment, R 1And R 2It all is alkyl.
Suitable R 1And R 2Example include, but not limited to lauryl, myristyl, palmityl, stearyl, hexadecyl, oil base and its mixture.In one embodiment, R 1And R 2All be hexadecyl, in another embodiment, R 1And R 2It all is oil base.In one embodiment, R 1And R 2It is the mixture of hexadecyl and oil base.
R 3, R 4And R 5Be hydrogen or alkyl independently, and can be line style or branching, preferably branching.This alkyl contains has an appointment 1～about 30, preferred about 4～about 24 even more preferably from about 6～about 20, most preferably from about 8～about 16 carbon atoms.In one embodiment, R 3, R 4And R 5It all is alkyl.In one embodiment, R 3And R 4Be alkyl and R 5Be hydrogen.In one embodiment, R 3And R 4Be hydrogen and R 5It is alkyl.
Be applicable to R 3, R 4And R 5The example of alkyl comprise, but be not limited to butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, n-hexyl, Sec-Hexyl, n-octyl, the 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, the octadecylene base, nonadecyl, eicosyl, different nonyl, isodecyl, different undecyl, different-dodecyl, different-tridecyl, different-tetradecyl, different-pentadecyl, different-hexadecyl, different-heptadecyl, different-octadecyl, different-the octadecylene base, different-nonadecyl, different-eicosyl or its mixture.Be applicable to R 3, R 4And R 5Preferred group comprise, but be not limited to n-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, different-nonyl, different-decyl, different-undecyl, different-dodecyl, different-tridecyl, different-tetradecyl, different-pentadecyl, different-hexadecyl and its mixture.
In one embodiment, described alkyl phosphate and its amine salt are by (a) C 14-C 18Alkylation phosphoric acid and (b) the reaction formation of nonyl primary amine.
In one embodiment, described alkyl phosphate and its amine salt are C 14-C 18Alkylation phosphoric acid with Primene 81R (by Rohm ﹠amp; Haas produces and sells, and it is C 11-C 14The mixture of primary t-alkyl-amine) reaction product of salify processing.
The amount that described alkyl phosphate and its amine salt exist is about 0.01～about 5wt% of lubricating oil composition, preferred about 0.1～about 1.5wt%, even more preferably from about 0.2～about 1wt%, most preferably from about 0.25～about 0.75wt%.
Described wear-resistant molectron further contains the phosphorodithioic acid of the alkyl replacement that can be expressed from the next and contains α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl:
J wherein 5, J 6, J 7, J 8Be sulphur or oxygen independently, condition is at least one, preferably at least two be sulphur.In one embodiment, J 5, J 6All be oxygen, J 7And J 8All be sulphur.
R 6And R 7Be hydrogen or alkyl independently, preferably, described alkyl is alkyl, cycloalkyl, aryl or its mixture; Most preferably be alkyl.When alkyl is alkyl, alkyl chain can be branching or line style, but branching preferably.R 6And R 7Can contain and have an appointment 4～about 30, preferred about 5～about 25, more preferably from about 5～about 20, most preferably from about 6～about 19 carbon atoms.In one embodiment, R 6Be hydrogen and R 7Be alkyl, in another embodiment, R 6And R 7It all is alkyl.
Suitable example R 6And R 7Include, but not limited to butyl, amyl group, hexyl, heptyl, octyl group, iso-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and its mixture.Preferably, R 6And R 7Include, but not limited to heptyl, octyl group, iso-octyl, nonyl, decyl and its mixture.In one embodiment, R 6Be hydrogen and R 7It is iso-octyl.In one embodiment, R 6Be iso-octyl and R 7Be hydrogen.In another embodiment, R 6And R 7It all is iso-octyl.
R 8And R 9Be hydrogen or alkyl independently, preferably, described alkyl is to contain 1 usually～alkyl of about 30, preferred 1～about 20, more preferably 1～about 10, most preferably 1～about 5 carbon atoms.In one embodiment, R 8And R 9All being hydrogen, all is alkyl in another embodiment, and R in another embodiment 8And R 9It is the mixture of hydrogen and alkyl.
R 10And R 11Can be hydrogen or alkyl independently.Described alkyl can contain 1～about 5, preferred 1～about 3,1～2 carbon atom most preferably.In one embodiment, R 10Be hydrogen.In one embodiment, R 10It is methyl.In one embodiment, R 10It is the mixture of hydrogen and methyl.In one embodiment, R 11Be hydrogen.
R 12Can be hydrogen, alkylene or randomly contain ehter bond contain the oxygen alkylene.Described alkylene contains 1～about 30, preferred 1～about 20, more preferably 1～about 10, most preferably 1～about 5 carbon atoms.In one embodiment, R 12It is methylene radical.In one embodiment, R 12Be hydrogen.
R when existing 13Can be hydrogen or alkyl, be preferably alkyl.N can be 1 or 2, and condition is m+n=2, except when R 12Beyond during for hydrogen.Preferably n be 2 and m be 0.M can be 0 or 1, and condition is m+n=2, except when R 12Beyond during for hydrogen.
T can be-S-,-O-or-NR 14R 14Can be hydrogen or alkyl.Described alkyl can be to contain 1～alkyl of about 25, preferred 1～about 18, more preferably 1～about 12, most preferably 1～about 6 carbon atoms.R 14Suitable example can include, but not limited to methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and its mixture.In one embodiment, R 14Be hydrogen.
At one especially in the available embodiment, T is NR in the formula (IIa) 14Thereby forming can be by the compound of formula (IIb) expression:
J wherein 5, J 6, J 7, J 8, R 6, R 7, R 8, R 9, R 10And R 11As defined above.
In one embodiment, the described α that contains, the compound of beta-unsaturated carbonyl is selected from: methylene-bisacrylamide, methylene-bis Methacrylamide, acrylamide, Methacrylamide, vinylformic acid, methacrylic acid, acrylate, methacrylic ester and its mixture.
In one embodiment, the described α that contains, the compound of beta-unsaturated carbonyl do not contain acrylate, methacrylic ester and its mixture; And can be selected from: methylene-bisacrylamide, methylene-bis Methacrylamide, acrylamide, Methacrylamide, vinylformic acid, methacrylic acid and its mixture.
In one embodiment, the described α that contains, the compound of beta-unsaturated carbonyl are selected from methylene-bisacrylamide, methylene-bis Methacrylamide and its mixture.Preferably, the described α that contains, the compound of beta-unsaturated carbonyl are methylene-bisacrylamide or its mixture.This contains α, and the compound of beta-unsaturated carbonyl can be used alone or in combination.
The phosphorodithioic acid that alkyl replaces and contain α, the suitable example of the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl comprises, but be not limited to the adducts of the methylene-coupled of diisooctyl phosphorodithioic acid and acrylamide, the adducts of the methylene-coupled of diisooctyl phosphorodithioic acid and Methacrylamide, the adducts of the methylene-coupled of diisooctyl phosphorodithioic acid and ethyl propenoate, the adducts of the methylene-coupled of diisooctyl phosphorodithioic acid and Jia Jibingxisuanyizhi, the adducts of the methylene-coupled of dinonyl phosphorodithioic acid and acrylamide, the adducts of the methylene-coupled of dinonyl phosphorodithioic acid and Methacrylamide, the adducts of the methylene-coupled of dinonyl phosphorodithioic acid and ethyl propenoate, the adducts of the methylene-coupled of dinonyl phosphorodithioic acid and Jia Jibingxisuanyizhi, with its mixture.In one embodiment, the phosphorodithioic acid that alkyl replaces and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl is the adducts of the methylene-coupled of diisooctyl phosphorodithioic acid and acrylamide.
The phosphorodithioic acid that alkyl replaces and contain α, the suitable example of the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl comprises, but be not limited to the adducts of diisooctyl phosphorodithioic acid and methylene-bisacrylamide, the adducts of diisooctyl phosphorodithioic acid and methylene-bis Methacrylamide, the adducts of diisooctyl phosphorodithioic acid and ethyl propenoate, the adducts of diisooctyl phosphorodithioic acid and Jia Jibingxisuanyizhi, the adducts of dinonyl phosphorodithioic acid and methylene-bisacrylamide, the adducts of dinonyl phosphorodithioic acid and methylene-bis Methacrylamide, the adducts of dinonyl phosphorodithioic acid and ethyl propenoate, the adducts of dinonyl phosphorodithioic acid and Jia Jibingxisuanyizhi, with its mixture.In one embodiment, the phosphorodithioic acid that alkyl replaces and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl is the adducts of diisooctyl phosphorodithioic acid and methylene-bisacrylamide.
The phosphorodithioic acid that alkyl replaces and contain α, the amount that the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl exists is about 0.01～about 5wt% of lubricating oil composition, preferred about 0.02～about 1.5wt%, even more preferably from about 0.03～about 1wt%, most preferably from about 0.04～about 0.5wt%.
Anti-oxidant molectron
Described anti-oxidant molectron contains the alkyl pentanoic that can be expressed from the next:
Figure A20048002088900141
R wherein 15Can be identical or different, and be hydrogen or alkyl independently, preferably aralkyl or alkyl or its mixture.Described aralkyl contains has an appointment 5～about 20, preferred about 6～about 10 carbon atoms.Described alkyl can be line style or branching, preferably branching; Described alkyl contains has an appointment 1～about 24, preferred about 2～about 18, most preferably from about 4～about 12 carbon atoms; Z is 0,1,2 or 3 independently, and condition is that at least one aromatic ring contains alkyl.The suitable example of alkyl pentanoic includes, but not limited to pentanoic, decyl diphenylamine and its mixture of pentanoic, nonyl diphenylamine, the octyl diphenylamine of two nonylated, the pentanoic of two octyl groupizations, two decylizations.In one embodiment, described alkyl pentanoic is the pentanoic of two nonylated.This alkyl pentanoic can be used alone or in combination.
The amount that described alkyl pentanoic exists is about 0.01～about 5wt% of lubricating oil composition, preferred about 0.03～about 1.5wt%, even more preferably from about 0.05～about 1wt%, most preferably from about 0.1～about 0.5wt%.
Described anti-oxidant molectron further contains the sterically hindered phenol that can be expressed from the next:
Figure A20048002088900142
R wherein 16And R 17Be to contain to have an appointment 1～about 24, preferred about 4～about 18, the most preferably from about 4～branching of about 12 carbon atoms or alkyl of line style independently.
R 16And R 17Can be straight chain or branched chain; Preferred branched.Preferably, described phenol is that the butyl that contains two tertiary butyls replaces.Q is hydrogen or alkyl, and can with position or contraposition between the OH group becomes, but preferred contraposition.V can be 1,2 or 3, is preferably 1 or 2, even more preferably 1.The example of suitable alkyl includes, but not limited to 2-ethylhexyl, normal-butyl, dodecyl and its mixture.In one embodiment, R 16And R 17It all is the tertiary butyl.
The suitable example that is derived from the sterically hindered phenol of formula (IV) comprises, but be not limited to, 2, the 6-DI-tert-butylphenol compounds, 4-methyl-2, the 6-DI-tert-butylphenol compounds, 4-ethyl-2, the 6-DI-tert-butylphenol compounds, 4-propyl group-2,6 di t butyl phenol, 4-butyl-2,6 di t butyl phenol, 2, the 6-DI-tert-butylphenol compounds, 4-amyl group-2, the 6-DI-tert-butylphenol compounds, 4-hexyl-2,6 di t butyl phenol, 4-heptyl-2,6 di t butyl phenol, 4-(2-ethylhexyl)-2, the 6-DI-tert-butylphenol compounds, 4-octyl group-2, the 6-DI-tert-butylphenol compounds, 4-nonyl-2,6 di t butyl phenol, 4-decyl-2,6 di t butyl phenol, 4-undecyl-2, the 6-DI-tert-butylphenol compounds, 4-dodecyl-2, the 6-DI-tert-butylphenol compounds, 4-tridecyl-2,6 di t butyl phenol, 4-tetradecyl-2,6 di t butyl phenol and its mixture.
In one embodiment, described sterically hindered phenol is 2,6 di t butyl phenol and its mixture.In one embodiment, described sterically hindered phenol is 4-(2-ethylhexyl)-2,6 di t butyl phenol and its mixture.In one embodiment, described sterically hindered phenol is 4-dodecyl-2,6 di t butyl phenol and its mixture.
Be applicable to those that other optional sterically hindered phenol of the present invention include, but are not limited to be expressed from the next:
Figure A20048002088900151
Or
R wherein 18, R 19, R 20, R 21, R 22, R 23Be straight chain or branched chain, and contain and have an appointment 4～about 18, preferred about 4～about 12 carbon atoms.Preferably, described phenol is that butyl replaces.R 24And R 25Be hydrogen or alkyl independently; Preferably, R 24And R 25Be aralkyl, alkyl or its mixture independently.Described alkyl can be line style or branching, preferably line style.R 24And R 25Usually in the contraposition of-OH group.Described aralkyl or alkyl contain 1 usually～about 15, preferred 1～about 10, more preferably 1～about 5 carbon atoms.Bridged group Y includes, but are not limited to-CH 2-(methylene bridge) or-CH 2OCH 2-(ether bridge) and its mixture.
The example of the sterically hindered phenol of methylene-bridged comprises, but be not limited to 4,4 '-methylene-bis (the 6-tertiary butyl-ortho-cresol), 4,4 '-methylene-bis (2-tert-pentyl-ortho-cresol), 2,2 '-methylene-bis (4-methyl-6-tert butyl-phenol), 4,4 '-methylene-bis (2,6-di-t-butyl-phenol) and its mixture.
In one embodiment, described sterically hindered phenolic antioxidant can be expressed from the next:
R wherein 26, R 27And R 28Can be identical or different, and be to contain to have an appointment 2～about 22, preferred about 2～about 18, the more preferably from about 4～straight chain of about 8 carbon atoms or alkyl of branching.The specific examples of alkyl includes, but not limited to 2-ethylhexyl, normal-butyl, dodecyl and its mixture.In one embodiment, R 27And R 28Be the tertiary butyl, R 26It is normal-butyl.
Sterically hindered phenol of the present invention can be used alone or in combination.The amount that sterically hindered phenol of the present invention exists is about 0.01～about 5wt% of lubricating oil composition, preferred about 0.03～about 1.5wt%, even more preferably from about 0.05～about 1wt%, most preferably from about 0.1～about 0.5wt%.
Metal passivator
The present invention further comprises metal passivator, and it can be used for neutralizing and promotes the katalysis of the metal of oxidizing reaction in the lubricating oil.The example of metal passivator comprises; but be not limited to 1,2,4-triazole species, benzimidazoles, 2-alkyl disulfide group benzo imidazoles, 2-alkyl disulfide group benzo thiazoles, 2-(N; N-dialkyl group disulfide group formamyl) benzothiazoles, 2; two (alkyl-disulfide group)-1,3 of 5-, 4-thiadiazole, 2; two (the N of 5-; N-dialkyl group disulfide group formamyl)-1,3, derivative and its mixture of 4-thiadiazole, 2-alkyl disulfide group-5-dimercaptothiodiazole class, benzotriazole category.In one embodiment, described metal passivator is the derivative of benzotriazole.In one embodiment, described metal passivator is 2, two (alkyl-disulfide group)-1,3 of 5-, 4-thiadiazoles.This metal passivator can be used in combination separately or with other metal passivators.
The alkyl derivative of benzotriazole contains the hydrocarbyl substituent on one or more following ring positions: 1-or 2-or 4-or 5-or 6-or 7-.Described alkyl contains 1～about 30, preferred 1～about 15, more preferably 1～about 7 carbon atoms.In one embodiment, described metal passivator is a tolyl-triazole.In one embodiment, substituted alkyl benzotriazole can further react with aldehyde and secondary amine on 4-or 5-or 6-or 7-position, and can be expressed from the next:
Figure A20048002088900171
Wherein said reaction product can form carbon-nitrogen bond on ring position 1-or 2-.In one embodiment, described carbon-nitrogen bond is on ring position 1-.R 29Can be that hydrogen or contain has an appointment 1～alkyl or its mixture of about 30, preferred about 1～about 15, more preferably from about 1～about 7 carbon atoms.In one embodiment, R 29Be hydrogen.In one embodiment, R 29It is methyl.
R 30Be derived from the aldehyde of this reaction, and can be hydrogen or the alkyl that contains 1～about 7, more preferably 1～about 4, most preferably 1～about 2 carbon atoms usually.In one embodiment, R 30Be hydrogen.The example of suitable aldehyde includes, but not limited to formaldehyde, acetaldehyde, propionic aldehyde and its mixture.In one embodiment, described aldehyde is formaldehyde, and it can be monomeric a, polymeric (paraformaldehyde) or in the aqueous solution; Preferably, described formaldehyde is in the aqueous solution.
R 31And R 32Be derived from the amine of this reaction, and be hydrogen or alkyl independently, preferably, R 31And R 32It all is alkyl.Alkyl contains 1～and about 22, more preferably from about 2～about 18, and more preferably from about 4～about 16,6～about 14 carbon atoms most preferably from about.The suitable example of amine includes, but not limited to dimethylamine, diethylamine, dipropyl amine, diallylamine, diisobutylamine, diisobutylene amine, diamylamine, diamyl enamine, dibenzylamine, dinaphthylamine, two-2 ethyl hexylamine and its mixture.In one embodiment, described amine is two-2 ethyl hexylamine.This amine can be used in combination separately or with other amine.
The examples for compounds that is suitable for the formula that is derived from (VIII) of making metal passivator comprises, but be not limited to, N, two (the heptyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, N, two (the nonyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, N, two (the decyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, N, two (the undecyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, N, two (the dodecyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine, N, two (2-the ethylhexyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine and its mixture.In one embodiment, described metal passivator is N, two (2-the ethylhexyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine.
In one embodiment, described metal passivator is 2, two (alkyl-disulfide group)-1,3 of 5-, 4-thiadiazoles.2, two (alkyl-disulfide group)-1,3 of 5-, the alkyl of 4-thiadiazoles contains 1～about 30, preferred about 2～about 25, more preferably 4～about 20, most preferably from about 6～about 16 carbon atoms.Suitable 2, two (alkyl-disulfide group)-1,3 of 5-, the example of 4-thiadiazoles comprises, but be not limited to, 2, two (the uncle's octyl group disulfide groups)-1,3 of 5-, the 4-thiadiazoles, 2, two (the uncle's nonyl disulfide groups)-1,3 of 5-, 4-thiadiazoles, 2, two (the uncle's decyl disulfide groups)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-undecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-dodecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-tridecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-tetradecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-pentadecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-hexadecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-heptadecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-octadecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-nonadecyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, 2, two (uncles-eicosyl disulfide group)-1,3 of 5-, the 4-thiadiazoles, with its mixture.Preferably 2,5-two (uncle's nonyl disulfide groups)-1,3,4-thiadiazoles and its mixtures.
The amount that described metal passivator exists is about 0.0001～about 5wt% of lubricating oil composition, preferred about 0.0003～about 1.5wt%, even more preferably from about 0.0005～about 0.5wt%, most preferably from about 0.001～about 0.2wt%.
Lubrication viscosity oil
Lubricating oil composition of the present invention include, but not limited to the natural oil of natural oil, synthetic oil, lubricant viscosity and synthetic oil mixture, be derived from hydrocracking, hydrogenation, hydrorefined oil, not refining oil, refining oil and refining oil and its mixture again.
Refining oil is not need (perhaps needing few) to be further purified direct those that obtain of processing usually from natural or synthetic source.
Refining oil is with refining oil is not similar, except they are further handled to improve one or more performances with one or more purification steps.Purification technique is known in the art, and comprises solvent extraction, second distillation, acid or alkali extraction, filtration, diafiltration etc.
Refining oil is known as recovered oil or reprocessed oils again again, and it obtains by similar those methods that are used to obtain refining oil, and the further processing by the technology that is intended to remove useless additive and oil decomposition product usually.
Natural oil comprises, but be not limited to, animal oil, vegetables oil (for example Viscotrol C, lard), mineral lubricating oils for example petroleum liquid and solvent treatment or acid-treated alkanes, cycloalkane or blended alkane-cycloalkane mineral lubricating oils and be derived from coal or the oil of shale and its mixture.
Ucon oil includes, but not limited to hydrocarbon ils for example polymerization and poly-mutually alkene (for example polybutene, polypropylene, propylene isobutylene copolymers); Poly-(1-hexene), poly-(1-octene), poly-(1-decene) and its mixture; Alkylbenzene (for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two-(2-ethylhexyl) benzene; Polyphenyl (for example biphenyl, terphenyl, alkylating polyphenyl); Alkylating phenyl ether and alkylating diphenyl sulfide and derivative, analogue and homologue and its mixture.
Based on for example poly-alkyl of the oil of silicon-, poly-aryl-, poly-alkoxyl group-, or poly-aryloxy-silicone oil and silicic acid ester oil comprise the synthetic lubricant (for example tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four-(2-ethylhexyl) ester, silicic acid four-(4-methyl hexyl) ester, silicic acid four-(right-tert-butyl-phenyl) ester, hexyl-(4-methyl-2-pentyloxy) sily oxide, poly-(methyl) siloxanes and poly-(aminomethyl phenyl) siloxanes) of another available types.In one embodiment, described lubrication viscosity oil is not siliceous.
Other ucon oil includes, but not limited to the liquid ester (for example Tritolyl Phosphate, trioctyl phosphate and decane phosphonic diethyl ester) and the polymeric tetrahydrofuran (THF) of phosphorated acid.Synthetic oil can prepare by Fischer-Tropsch reaction, and can be the fischer-tropsch hydrocarbon or the wax of hydroisomerization usually.
Lubrication viscosity oil also can define as regulation in the API (API) " Base OilInterchangeability Guidelines ".5 basic oils are as follows: the I class, and sulphur content＞0.03wt%, and/or＜the 90wt% saturates, viscosity index 80～120; The II class, sulphur content≤0.03wt% and 〉=the 90wt% saturates, viscosity index 80～120; The III class, sulphur content≤0.03wt% and 〉=the 90wt% saturates, viscosity index 〉=120; The IV class, all poly-alpha olefinss (PAO ' s); With the V class, all are not included in other materials in I, II, III or the IV class.In one embodiment, described lubrication viscosity oil comprises I, II, III, IV, V class oil or its mixture of API, and preferably I, II, III class oil or its mixture of API.
The amount that described lubrication viscosity oil exists is about 34～about 99.96wt% of lubricating oil composition, preferred about 74.8～about 99.8wt%, even more preferably from about 80.6～about 99.5wt%, most preferably from about 84.7～about 99.2wt%.Lubrication viscosity oil can use separately or with its mixture.In one embodiment, the amount of described lubrication viscosity oil existence is about 98.9wt% of lubricating oil composition.
Performance additive
Randomly, said composition can comprise at least a performance additive that is selected from following material: rust-preventive agent, antifoams, emulsion splitter, friction modifiers, viscosity modifier, pour point depressant and its mixture.
Rust-preventive agent
Rust-preventive agent is known and comprises, but be not limited to, the amine salt of carboxylic acid is octylame octylate, laurylene base succsinic acid or acid anhydrides and the lipid acid for example condensation product and the thiazolinyl alkenyl succinic acid that contains 8～about 24 carbon atoms of having an appointment and the alcohol half ester of polyoxyethylene glycol for example wherein of polyalkylene polyamine such as Triethylenetetramine (TETA) of oleic acid and polyamine for example for example.This rust-preventive agent can be used alone or in combination.
Another kind of rust-preventive agent is amine and the reaction product that contains the compound of sulfonic acid group.Described amine can be selected from: monoamine, polyamine and its mixture.Described amine can be saturated, unsaturated, acyclic, ring-type, aromatics, line style, branching and its mixture.The amine of typical types can include, but not limited to alkene monoamine (alkylenemonoamine), heterocycle monoamine, alkylene polyamine, heterocyclic polyamines and its mixture.
The amine of particularly useful type is alkylene polyamine, preferred ethylidene polyamines.The example of suitable ethylidene polyamines includes, but not limited to ethylene diamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, polyamine distillation bottoms and its mixture.
Be applicable to that the compound that contains sulfonic acid group of the present invention can be saturated, unsaturated, acyclic, ring-type, aromatics, line style, branching and its mixture.The suitable examples for compounds that contains sulfonic acid group comprises, but be not limited to naphthene sulfonic acid, Witco 1298 Soft Acid, two-Witco 1298 Soft Acid, dinonyl Phenylsulfonic acid, hexadecyl chlorobenzenesulfonic acid, dilauryl beta-naphthalenesulfonic-acid and its mixture that list-eicosyl replaces.
The compound that contains sulfonic acid of another adequate types can by with chlorsulfonic acid, nitro-naphthalene-monosulfonic acid, paraffin sulfonic acid, hexadecyl pentamethylene sulfonic acid, lauryl hexanaphthene sulfonic acid and its mixture process number-average molecular weight (Mn) about 500～about 5000, preferred about 800～about polybutene of 3000, more preferably from about 1000～about 2000 prepares.
The compound that contains sulfonic acid of another adequate types can by with chlorsulfonic acid, nitro-naphthalene-monosulfonic acid, paraffin sulfonic acid, hexadecyl pentamethylene sulfonic acid, lauryl hexanaphthene sulfonic acid and its mixture process number-average molecular weight (Mn) about 300～about 1500, preferred about 400～about polyethylene of 1000, most preferably from about 500～about 900 prepares.
In one embodiment, composition of the present invention does not contain the rust-preventive agent for preparing by amine and the compound reaction that contains sulfonic acid group substantially.In another embodiment, composition of the present invention does not contain substantially to not containing rust-preventive agent.
The amount that described rust-preventive agent exists is 0 of lubricating oil composition～about 5wt%, preferred about 0.001～about 1.5wt%, even more preferably from about 0.002～about 1wt%, most preferably from about 0.0025～about 0.75wt%.
Antifoams
Antifoams is known and includes, but not limited to organo-siloxane for example dimethyl siloxane or polysiloxane, poly-acetic ester, polyacrylic ester or its mixture.This antifoams can be used alone or in combination.
The example of antifoams includes, but not limited to gather multipolymer and its mixture of (ethyl propenoate), poly-(2-EHA), poly-(ethyl acetate), 2-EHA and ethyl propenoate.In one embodiment, described antifoams is the multipolymer of 2-EHA and ethyl propenoate.
The amount that described antifoams exists is 0 of lubricating oil composition～about 5wt%, preferred about 0.005～about 0.1wt%, even more preferably from about 0.007～about 0.05wt%, most preferably from about 0.01～about 0.03wt%.Emulsion splitter
Emulsion splitter is known and includes, but not limited to diamines or polyamine and its mixture of the derivative of propylene oxide, oxyethane, polyoxyalkylene alcohol, alkylamine, amino alcohol, order and the reacting ethylene oxide of oxyethane or replacement.This emulsion splitter can be used alone or in combination.
The example of emulsion splitter includes, but not limited to trialkyl phosphates, polyoxyethylene glycol, polyethylene oxide, poly(propylene oxide), (epoxy ethane-epoxy propane) multipolymer and its mixture.In one embodiment, described emulsion splitter is a PEP-101.
The amount that described emulsion splitter exists is 0 of lubricating oil composition～about 5wt%, preferred about 0.0005～about 0.05wt%, even more preferably from about 0.0007～about 0.01wt%, most preferably from about 0.001～about 0.005wt%.
Pour point depressant
Pour point depressant is known and comprises, but be not limited to, the terpolymer of the vinyl acetate of condensation product, carboxylic acid vinyl ester polymer and the lipid acid of the ester of maleic anhydride-styrene copolymers, polymethacrylate, polyacrylic ester, polyacrylamide, halo paraffin and aromatic substance, ethylene-ethyl acetate copolymer, dialkyl group fumarate, alkylphenol formaldehyde condensation resins, alkyl vinyl ether and its mixture.Preferred pour point depressant includes, but are not limited to ester, polymethacrylate, Viscoplex  1-153, polyacrylic ester and its mixture of maleic anhydride-styrene copolymers.This pour point depressant can be used alone or in combination.
The amount that described pour point depressant exists is about 0～about 5wt% of lubricating oil composition, preferred about 0.005～about 0.5wt%, even more preferably from about 0.007～about 0.1wt%, most preferably from about 0.01～about 0.05wt%.
Friction modifiers
This lubricating oil can contain friction modifiers in addition.The available friction modifiers comprises, but be not limited to, the condensation product of the oxyalkylated aliphatic amide of fatty amine, ester (especially glyceryl ester for example XU 61518.10), the glyceryl ester of boronation, fatty phosphorous acid ester, fatty acid amide, fat epoxide, the fat epoxide of boronation, oxyalkylated aliphatic amide, boronation, metal-salt, sulfurized alkene, fatty tetrahydroglyoxaline, carboxylic acid and the polyalkylene polyamine of lipid acid, the amine salt of alkylphosphonic acid carboxylic acid and the friction modifiers that contains molybdenum for example the dithiocarbamate molybdenum, and composition thereof.Preferred friction modifiers comprises condensation product of fatty amine, ester (especially glyceryl ester), sulfurized alkene, fatty tetrahydroglyoxaline, carboxylic acid and polyalkylene-polyamines and composition thereof.This friction modifiers can be used alone or in combination.
The amount that described friction modifiers exists is about 0～about 6wt% of lubricating oil composition, preferred about 0.05～about 1wt%, even more preferably from about 0.1～about 0.75wt%, most preferably from about 0.2～about 0.5wt%.
Viscosity modifier
Viscosity modifier is known and comprises, but be not limited to ester and its mixture of the multipolymer of styrene butadiene rubbers, ethylene-propylene copolymer, polyisobutene, hydrogenant styrene-isoprene polymkeric substance, hydrogenant free radical isoprene copolymer, polymethacrylate, polyacrylic ester, polyoxyethylene alkylphenyl ethene, alkenyl aryl conjugated diene copolymer, polyolefine, polyalkyl methacrylate, maleic anhydride-styrene copolymers.Preferred viscosity modifier comprises ester and its mixture of polyacrylic ester, polyalkyl methacrylate, maleic anhydride-styrene copolymers.This viscosity modifier can be used alone or in combination.
The amount that described viscosity modifier exists is about 0～about 20wt% of lubricating oil composition, preferred about 0.03～about 16wt%, even more preferably from about 0.1～about 14wt%, most preferably from about 0.2～about 12wt% existence.
Method
The present invention further provides a kind of method for preparing lubricating oil composition, it may further comprise the steps: at first at elevated temperatures at least a metal passivator or its mixture are blended in alkyl phosphate and its amine salt up to described metal passivator substantially or dissolving fully.This temperature is about 40 ℃～about 110 ℃, preferred about 50 ℃～95 ℃, and most preferably from about 55 ℃～about 85 ℃.Described mixture was kept about at a certain temperature 30 seconds～about 24 hours, preferred about 2 minutes～about 8 hours, most preferably from about 5 minutes～about 4 hours time.Pressure is about 93.3kPa～about 266.7kPa (about 700mmHg～about 2000mmHg), preferably about 100kPa～about 133.3kPa (about 750mmHg～about 1000mmHg), most preferably from about 103kPa～about 120kPa (about 775mmHg～about 900mmHg).
Basically the mixture of all first steps is joined the phosphorodithioic acid that alkyl replaces and contains α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl and being selected from the anti-oxidant molectron of alkyl pentanoic, sterically hindered phenol or its mixture to form mixture.The compound of gained mixture successively, add alone or in combination.This mixture is handled under about 20 ℃～about 140 ℃, preferred about 25 ℃～85 ℃, most preferably from about 30 ℃～about 65 ℃ temperature.With this mixture 93.3kPa～about 266.7kPa (about 700mmHg～about 2000mmHg), preferably about 94.6kPa～about 133.3kPa (about 710mmHg～about 1000mmHg), most preferably from about handle under the pressure of 96kPa～about 120kPa (about 720mmHg～about 900mmHg).This mixture was kept about 1 minute～about 3 days, preferred about 5 minutes～about 8 hours, most preferably from about 10 minutes～about 4 hours time.
By any known method basically the mixture of all second steps add and be mixed in described lubrication viscosity oil, base oil, thinning oil or its mixture to form lubricating oil composition.
This method randomly comprises: the performance additive that will be selected from rust-preventive agent, antifoams, emulsion splitter, viscosity modifier, pour point depressant and its mixture joins in the mixture of step (2), step (3) or its combination.
In one embodiment, the present invention is the form of enriched material, wherein described wear-resistant molectron, described anti-oxidant molectron, described metal passivator and non-essential performance additive are joined all or basically in lubricating oil, base oil, thinning oil or its mixture of all or a part, and when prepare using with lubricating oil, base oil, thinning oil or the merging of its mixture of remaining real mass, obtain the finished product fluid.
A kind of method for preparing the enriched material of lubricating oil composition, it may further comprise the steps:
(1) at least a metal passivator is blended in alkyl phosphate and its amine salt; With
(2) will be basically institute in steps the goods of (1) add and be mixed into the phosphorodithioic acid that alkyl replaces successively, alone or in combination and contain α, in the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl and all basically anti-oxidant molectron that is selected from alkyl pentanoic, sterically hindered phenol and its mixture with the formation mixture; With
(3) the described lubricating oil of enough shares, base oil, thinning oil or its mixture are added and be mixed in the gained mixture of step (2) to form the enriched material of described lubricating oil composition.
If the present invention is with the form of enriched material, then the amount of thinning oil be described lubricating oil composition enriched material less than about 50wt%, preferably less than about 30wt%, be more preferably less than about 15wt%, most preferably less than about 10wt%.In one embodiment, the amount of described thinning oil existence is about 5.5wt% of the enriched material of described lubricating oil composition.
Industrial application
Lubricating oil composition of the present invention is used for industrial fluids, hydraulic fluid, turbine oil, turning oil and its combination.
In one embodiment of the invention, lubricating oil composition can be used for turbine oil.The use of this lubricating oil composition can reduce the formation that the steam turbine middle filtrator stops up settling and greasy filth.This lubricating oil composition further can provide good wear-resistant and/or antioxidant levels.This lubricating oil composition has good stability to hydrolysis.
Following examples provide explanation of the invention.Yet should be understood that these embodiment are non-exhaustive and are not used to limit the scope of the invention.
Specific embodiments
Embodiment
Embodiment 1
Prepare hydraulic fluid in the following manner: with the C of (a) about 0.53wt% 14-C 18The reaction product of alkylating phosphoric acid and Primene 81R; (b) adducts of the methylene-coupled of the diisooctyl phosphorodithioic acid of about 0.1wt% and acrylamide; (c) pentanoic of two nonylated of about 0.196wt%; (d) 2,6 di t butyl phenol of about 0.196wt%; (e) tolyl-triazole of about 0.005wt%; (f) multipolymer of the 2-EHA of about 0.02wt% and ethyl propenoate; What (g) thinning oil of about 0.049wt% was mixed into that about 100g contains the 35wt% that has an appointment is down 11.90mm at 100 ℃ 2s -1(cSt) I class base oil and about 65wt% are 5.2mm down at 100 ℃ 2s -1In the base oil of I class base oil (cSt).
Embodiment 2
This hydraulic fluid is identical with embodiment's 1, is 5.8mm except described base oil contains descending at 100 ℃ of the 40wt% that has an appointment 2s -1(cSt) II class base oil and about 60wt% are 11.5mm down at 100 ℃ 2s -1(cSt) outside the Viscoplex  1-153 of II class base oil and the about 0.02wt% of adding.
Embodiment 3
This hydraulic fluid is identical with embodiment's 1, is 5.3mm except described base oil contains descending at 100 ℃ of the 90wt% that has an appointment 2s -1(cSt) I class base oil and about 10wt% are 12.1mm down at 100 ℃ 2s -1(cSt) outside I class base oil and described metal passivator tolyl-triazole exist with about 0.002wt%.
Embodiment 4
This hydraulic fluid is identical with embodiment's 1, except described metal passivator is 2, two (the uncle's nonyl sulfenyls)-1,3 of 5-, the 4-thiadiazoles and exist with about 0.005wt% outside.
Embodiment 5
This hydraulic fluid is identical with embodiment's 1, except described metal passivator is N, two (2-the ethylhexyl)-ar-methyl isophthalic acid H-benzotriazoles of N--1-methylamine and exist with about 0.01wt% outside.
Test 1:ASTM D665
The rust-preventing characteristic of ASTM D665 experimental measurement oil in the presence of water.To not comprise that the steel nail spiral of wide about 68mm of threaded part and the about 12.7mm of diameter is on the plastics upholder.Steel nail is immersed in the beaker of about 30ml distilled water and about 300ml oil.Beaker placed the oil bath that is maintained at about under 60 ℃ and with about 24 hours of the contents stirred of beaker.Measure the amount of corrosion/rusty stain.Use synthetic sea water and new steel nail to repeat this process.
All embodiment have passed through the D665 test.Embodiment 1～5 has from the lubricating oil composition of enough protections of metal passivator, anti-oxidant molectron and the acquisition of wear-resistant molectron and by described distilled water and synthetic sea water nail evaluation (pin rating).
Test 2:ASTM D2619
The stability to hydrolysis of ASTM D2619 experimental measurement hydraulic fluid in the presence of water.The mixture of about 75g oil and about 25g water is placed the pressure-type beverage bottle together with about 13mm * about 51mm, the weighing clean copper sample in pact ± 0.2mg.This bottle is placed baking oven and it is rotated under about 5rpm, be heated to about 93 ℃ and kept about 48 hours simultaneously.With this bottle cooling and will place the conical centrifuge tube of 100ml except the content the described copper sample, and about 10 minutes of centrifugation under 1500rpm.The sample decantation separating water outlet and emulsion layer, and is passed through membrane filtration.Clean sample with about 25ml distilled water.Repeat sample cleans up to cleaning thing litmus paper is become neutral.Write down the changes in weight of copper sample and measure oily total acid value according to ASTM D974.For good hydraulic fluid, Denison Hydraulics Limits HF-0 requires in the total acidity that contains aqueous phase less than about 4mg KOH.The maximum reduction value of copper sample weight is about 0.20mg/cm 2The result of gained is that the weight reduction value of copper sample and total acidity are:
Table 1:ASTM D2619 result
Embodiment The weight reduction value (mg/cm of copper sample 2) Total acid value (mg KOH)
1 0.15 1.68
2 0.03 2.24
3 0.02 2.24
4 0 1.68
5 0.04 2.53
All samples has all passed through the D2619 test.Generally speaking, test shows that this lubricating oil composition has the enough performances that are derived from described metal passivator, anti-oxidant molectron and wear-resistant molectron and provides and avoid wearing and tearing and the protection of oxidation and have the total acidity that is lower than 4mg KOH.
Although explained the present invention, should be understood that for those skilled in the art, when reading specification sheets, multiple improvement of the present invention will become obvious.Therefore will be appreciated that in this disclosed the present invention and do not mean that and covered those improvement that for example fall in the appended claims book scope.

Claims (20)

1. lubricating oil composition, it comprises:
(1) contain the wear-resistant molectron of following material:
(a) alkyl phosphate and its amine salt; With
(b) phosphorodithioic acid that replaces of alkyl and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl;
(2) contain the anti-oxidant molectron of following material:
(a) alkyl pentanoic; With
(b) sterically hindered phenol;
(3) metal passivator; With
(4) lubrication viscosity oil.
2. the composition of claim 1, wherein said alkyl phosphate and its amine salt are expressed from the next:
Figure A2004800208890002C1
J wherein 1, J 2, J 3, J 4Be oxygen or sulphur independently; R 1And R 2Be hydrogen or alkyl independently; R 3, R 4And R 5Be hydrogen or alkyl independently.
3. the composition of claim 1, the phosphorodithioic acid that wherein said alkyl replaces and contain α, the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl is expressed from the next:
Wherein:
J 5, J 6, J 7, J 8Be sulphur or oxygen independently, condition is J 5, J 6, J 7, J 8In at least one be sulphur;
N is 1 or 2, and condition is m+n=2, except when R 12Beyond during for hydrogen;
M is 0 or 1, and condition is m+n=2, except when R 12Beyond during for hydrogen;
R 6, R 7, R 8And R 9Be hydrogen or alkyl independently;
R 10And R 11Be hydrogen or alkyl independently;
R 12Be hydrogen, alkylene or randomly contain ehter bond contain the oxygen alkylene;
R 13Be hydrogen or alkyl; With
T is-S-,-O-or-NR 14, R wherein 14Be hydrogen or alkyl.
4. the composition of claim 3, the wherein said α that contains, the compound of beta-unsaturated carbonyl is selected from: methylene-bisacrylamide, methylene-bis Methacrylamide, acrylamide, Methacrylamide, vinylformic acid, methacrylic acid, acrylate, methacrylic ester and its mixture.
5. the composition of claim 1, wherein said alkyl pentanoic is expressed from the next:
R wherein 15Can be identical or different, and be hydrogen or alkyl independently; With z be 0,1,2 or 3 independently, condition is that at least one aromatic ring contains alkyl.
6. the composition of claim 1, wherein said sterically hindered phenol can be expressed from the next:
Figure A2004800208890003C2
R wherein 16And R 17Be alkyl independently; Q is hydrogen or alkyl; With v be 1,2 or 3.
7. the composition of claim 1, wherein said metal passivator are to contain the benzotriazole derivatives that alkyl replaces, and described alkyl replaces at least one that comprises in the following ring position: 1-or 2-or 4-or 5-or 6-or 7-.
8. the composition of claim 1, wherein said metal passivator is 2, two (the alkyl disulfide groups)-1,3 of 5-, 4-thiadiazoles.
9. the composition of claim 1, I, the II that wherein said viscosity lubricating oil is API, III class oil or its mixture.
10. the composition of claim 1, it further comprises at least a following performance additive that is selected from: rust-preventive agent, antifoams, emulsion splitter, friction modifiers, viscosity modifier, pour point depressant and its mixture.
11. the composition of claim 1, the amount that wherein said alkyl phosphate and its amine salt exist is about 0.01～about 5wt% of lubricating oil composition;
The phosphorodithioic acid that alkyl replaces and contain α, the amount that the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl exists is about 0.01～about 5wt% of lubricating oil composition; The amount that wherein said alkyl pentanoic exists is about 0.01～about 5wt% of lubricating oil composition; The amount that wherein said sterically hindered phenol exists is about 0.01～about 5wt% of lubricating oil composition; The amount that wherein said metal passivator exists is about 0.0001～about 5wt% of lubricating oil composition; And the amount that wherein said lubrication viscosity oil exists is about 34～about 99.96wt% of lubricating oil composition.
12. the composition of claim 11, it further comprises performance additive, and the amount that wherein said rust-preventive agent exists is about 0～about 5wt% of lubricating oil composition; Wherein the amount of antifoams existence is about 0～about 5wt% of lubricating oil composition; The amount that wherein said emulsion splitter exists is about 0～about 5wt% of lubricating oil composition; The amount that wherein said pour point depressant exists is about 0～about 5wt% of lubricating oil composition; The amount that wherein said friction modifiers exists is about 0～about 6wt% of lubricating oil composition; And the amount that wherein said viscosity modifier exists is about 0～about 20wt% of lubricating oil composition.
13. a method for preparing lubricating oil composition, it may further comprise the steps:
(1) at least a metal passivator is blended in alkyl phosphate and its amine salt; With
(2) will be basically institute in steps the goods of (1) add and be mixed into the phosphorodithioic acid that alkyl replaces successively, alone or in combination and contain α, in the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl and all basically anti-oxidant molectron that is selected from alkyl pentanoic, sterically hindered phenol and its mixture with the formation mixture; With
(3) the gained mixture of step (2) is added and be mixed in lubrication viscosity oil or its mixture.
14. the method for claim 13, it comprises that further the performance additive that will be selected from rust-preventive agent, antifoams, emulsion splitter, viscosity modifier, pour point depressant and its mixture joins in the mixture of step (2), step (3) or its combination.
15. a method for preparing the enriched material of lubricating oil composition, it may further comprise the steps:
(1) at least a metal passivator is blended in alkyl phosphate and its amine salt; With
(2) will be basically institute in steps the goods of (1) add and be mixed into the phosphorodithioic acid that alkyl replaces successively, alone or in combination and contain α, in the alkylidene group link coupled adducts of the compound of beta-unsaturated carbonyl and all basically anti-oxidant molectron that is selected from alkyl pentanoic, sterically hindered phenol and its mixture with the formation mixture; With
(3) lubricating oil of enough shares, base oil, thinning oil or its mixture are added and be mixed in the gained mixture of step (2) to form the enriched material of lubricating oil composition.
16. the method for claim 15, it comprises that further the performance additive that will be selected from rust-preventive agent, antifoams, emulsion splitter, viscosity modifier, pour point depressant and its mixture joins in the mixture of step (2), step (3) or its combination.
17. the method for claim 15, it further comprises described enriched material is joined in lubricating oil, base oil, thinning oil or its mixture of final share, thereby obtains the finished product fluid.
18. the lubricating oil composition as industrial fluids, hydraulic fluid, turbine oil, turning oil and its combination, it comprises the lubricating oil composition of claim 1.
19. a lubricating oil composition that is used for hydraulic fluid, it comprises the composition of claim 1.
20. according to the lubricating oil composition that is used for hydraulic fluid of claim 19, wherein said hydraulic fluid has at least a performance that is selected from following type: the filter stoppage settling of reduction and the formation of greasy filth, good wear-resistant level, good antioxidant levels, good stability to hydrolysis.
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