CN102268317B - Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same - Google Patents

Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same Download PDF

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Publication number
CN102268317B
CN102268317B CN2011101892197A CN201110189219A CN102268317B CN 102268317 B CN102268317 B CN 102268317B CN 2011101892197 A CN2011101892197 A CN 2011101892197A CN 201110189219 A CN201110189219 A CN 201110189219A CN 102268317 B CN102268317 B CN 102268317B
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Prior art keywords
lubricating oil
additive
oil additive
alkyl
carbon atom
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Expired - Fee Related
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CN2011101892197A
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Chinese (zh)
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CN102268317A (en
Inventor
八木下和宏
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Eneos Corp
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Nippon Oil Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/06—Metal salts
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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    • C10M169/06—Mixtures of thickeners and additives
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    • 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
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    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • 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
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    • 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
    • C10M2207/0285—Overbased salts thereof used as base material
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
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Abstract

A lubricating oil additive which is obtained by imparting oil solubility to (A) a specific phosphorus compound metal salt insoluble or sparingly soluble in lubricating oils by dissolving or reacting the salt (A) in or with (B) an amine compound. A lubricating oil composition containing the additive, and a process for producing the additive and the composition.

Description

Lubricating oil additive comprises the lubricating oil composition of this additive and this additive and composition manufacturing method
Technical field
The present invention relates to lubricating oil additive, more specifically to by making metal-salt insoluble or that not too be dissolved in the phosphorus compound in the lubricating base oil be dissolved in the lubricating oil additive that wherein obtains, comprise the lubricating oil composition of this additive, and produce this additive and method for compositions.
Background technology
From recent demand, as the minimizing of resources effective utilization, waste oil and the reduction of cost that the user bears, people are than more need long change oil (Long drain oils) in the past.
The present inventor finds, for the transsexual energy of the length that improves lubricating oil, include the single thiophosphate ester group compound that sulphur reduces in the molecule or in molecule, do not comprise the phosphate-based compound of sulphur or the metal-salt of phosphonic acid ester, rather than sulfur-bearing resistance to wears and the low sulfur content lubricating oil composition of antioxidant such as zinc dialkyl dithiophosphate, have base number retention property and oxidative stability that good causing produces long transsexual energy, keep resistance to abrasion simultaneously and can show high temperature detergency and low friction performance.The inventor has submitted patent application to these inventions, is respectively Japanese patent application 2002-015351 and 2002-246975.
Though zinc dialkyl dithiophosphate is liquid at normal temperatures, but the metal-salt of these phosphorus compounds but is solid at normal temperatures, so the problem that they exist is that not only processing property is poor, and the solvability in lubricating oil is low, perhaps need spend long time when they will dissolve.Therefore, the feasible lubricating oil composition that is difficult to contain at industrial mass production effectively these phosphorus compound metal-salts of these problems.
Consider above-mentioned condition, the present invention aims to provide a kind of metal-salt liquefaction that makes the phosphorus compound that solvability is low in lubricating oil in order to can be dissolved in wherein effectively in short duration, thereby has good performance as the method for the lubricating oil composition of long metal-salt transsexual energy, that contain specific phosphorus compound industrial production effectively.
Summary of the invention
Carried out deep research in order to address the above problem, the result is to have finished the present invention according to following discovery: namely by making aforesaid phosphorus compound be dissolved in the amine compound in advance or reaction with it, can improve its solvability in lubricating oil.
That is to say, the object of the present invention is to provide a kind of lubricating oil additive, it is to be dissolved in (B) amine compound or to react with it by the metal-salt that makes (A) at least one class be selected from the phosphorus compound of being represented by following formula (1), (2) and (3) to prepare:
Figure BSA00000533179300021
Wherein, X 1, X 2And X 3Be oxygen or sulphur independently of one another, condition is to have at least one to be oxygen in them, R 11, R 12And R 13Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them;
Figure BSA00000533179300022
Wherein, X 4, X 5, X 6And X 7Be oxygen or sulphur independently of one another, condition is to have at least three to be oxygen in them, R 14, R 15And R 16Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; With
Figure BSA00000533179300023
Wherein, X 8, X 9And X 10Be oxygen or sulphur independently of one another, condition is to have at least two to be oxygen in them, R 17, R 18And R 19Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; A is 0 or 1 integer; And the phosphorus compound of formula (1)-(3) between the X-R key, can comprise by-(OR ') nThe group of-expression, wherein R ' is the alkylidene group that contains 1-4 carbon atom, n is the integer of 1-10.
In lubricating oil additive of the present invention, the X in the formula (1) 1, X 2And X 3, the X in the formula (2) 4, X 5, X 6And X 7, and the X in the formula (3) 8, X 9And X 10Be preferably oxygen all.
The preferred at least one class of the metal of component (A) is selected from the metal of lithium, magnesium, calcium and zinc.
Component (B) is the amine compound that at least one class is selected from amido antioxidant, fatty amine and ashless dispersant and derivative thereof.
The a kind of of lubricating oil additive of the present invention prepares by component (A) is dissolved in the amido antioxidant.
Lubricating oil additive of the present invention a kind of by making component (A) or above-mentioned lubricating oil additive and aliphatic amide prepared in reaction.
Lubricating oil additive of the present invention a kind of by make component (A) or any above-mentioned lubricating oil additive and ashless dispersant and/or its derivatives reaction the preparation.
In above-mentioned lubricating oil additive, the reaction ratio of aliphatic amide or ashless dispersant or derivatives thereof and component (A) preferably be in mass 0.15 or more than.
Ashless dispersant and derivative thereof be those when measuring with the salt acid system base number be 5mgKOH/g or above compound.
The derivative of ashless dispersant is preferably the boron compound derivative of ashless dispersant.
Lubricating oil additive of the present invention is to obtain by the additive blend that any above-mentioned slip additive and at least one class is selected from lubricating base oil, antioxidant, ashless dispersant, metal detergent, friction modifiers, anti-wear agent, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, dyestuff and viscosity index improver.
It is a kind of by the lubricating oil composition with any above-mentioned lubricating oil additive and lubricating base oil blend generation that the present invention also provides.
In addition, the invention provides a kind of method for preparing lubricating oil additive, it is by making (A) at least one class select the metal-salt of the phosphorus compound of free style (1), (2) and (3) expression to be dissolved in (B) amine compound or react with it and realize.
It is a kind of by above-mentioned slip additive and lubricating oil blend being prepared the method for lubricating oil composition that the present invention also provides.
Below will be described in more detail the present invention.
The example of component (A) comprises, by making the phosphorus compound and the metal base reaction that is selected from metal oxide, metal hydroxides, metal carbonate and metal chloride by following formula (1), (2) or (3) expression, so as to neutralize part or all remaining acid-hydrolysis and the salt that obtains:
Figure BSA00000533179300041
Wherein, X 1, X 2And X 3Be oxygen or sulphur independently of one another, condition is to have at least one to be oxygen in them, R 11, R 11And R 13Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them;
Figure BSA00000533179300042
Wherein, X 4, X 5, X 6And X 7Be oxygen or sulphur independently of one another, condition is to have at least three to be oxygen in them, R 14, R 15And R 16Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; With
Figure BSA00000533179300043
Wherein, X 8, X 9And X 10Be oxygen or sulphur independently of one another, condition is to have at least two to be oxygen in them, R 17, R 18And R 19Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be that hydrogen and a are 0 or 1 integers in them.
The phosphorus compound of formula (1)-(3) between the X-R key, can or can comprise by-(OR ') nThe group of-expression, wherein R ' contains 1-4, and the alkylidene group of preferred 1 or 2 carbon atom, n are 1-10, the integer of preferred 1-4.In order to improve resistance to abrasion and extreme pressure property, preferably between the X-R key, do not exist-(OR ') nThe compound of-group.
The specific examples of the metal in the above-mentioned metal base comprises basic metal such as lithium, sodium, potassium, and caesium; Alkaline-earth metal such as calcium, magnesium, and barium; And heavy metal such as zinc, copper, iron, lead, nickel, silver, manganese, and molybdenum.In the middle of these metals, preferably basic metal such as lithium and sodium; Alkaline-earth metal such as magnesium and calcium, and zinc, most preferably zinc.
The number of contained OH in the valency of metal and the phosphorus compound or SR group is depended in the structural variation of the metal-salt of above-mentioned phosphorus compound.Therefore, the structure to the phosphorus compound metal-salt does not apply special restriction.For example, when 1 mole of zinc oxide and 2 mole of phosphoric acid diester (having an OH group) reaction, still also may there be polymerizable molecular in the compound that our conjecture obtains having the structure that is expressed from the next as main component:
Figure BSA00000533179300051
Another example is that when 1 mole of zinc oxide and 1 mole of phosphoric acid monoesters (having two OH groups) reaction, still also may there be polymerizable molecular in the compound that our conjecture obtains having the structure that is expressed from the next as main component:
Be used for R 11-R 19The specific examples of the alkyl that contains 1-30 carbon atom comprise alkyl, cycloalkyl, thiazolinyl, the cycloalkyl that alkyl replaces, aryl, the aryl that alkyl replaces, and aralkyl.
The example of alkyl comprises straight or branched alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl.
The example of cycloalkyl comprises the cycloalkyl with 5-7 carbon atom, as cyclopentyl, and cyclohexyl, and suberyl.The example of alkyl-cycloalkyl comprises the alkyl-cycloalkyl with 6-11 carbon atom, as methylcyclopentyl, and dimethylcyclopentyl, the first and second basic ring amyl groups, diethyl cyclopentyl, methylcyclohexyl, Dimethylcyclohexyl, the first and second basic ring hexyls, diethyl cyclohexyl, methyl suberyl, the dimethyl suberyl, the first and second basic ring heptyl and diethyl suberyl, wherein alkyl can be connected on the optional position of cycloalkyl.
The example of thiazolinyl comprises butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, the decene base, undecenyl, laurylene base, the tridecylene base, tetradecene base, ten pentaene bases, the hexadecylene base, 17 thiazolinyls and octadecylene base, all these all can be straight or brancheds, and the position of its pair key can change.
The example of aryl comprises phenyl and naphthyl.The example of alkylaryl comprises those with 7-18 carbon atom, as tolyl, and xylyl, the ethylbenzene base, propyl group phenyl, butyl phenyl, the amyl group phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, the undecyl phenyl, and dodecylphenyl, wherein alkyl can be straight or branched, and can be connected on the optional position of aryl.
The example of aralkyl comprises those with 7-12 carbon atom, as benzyl, and styroyl, hydrocinnamyl, the benzene butyl, benzene amyl group and benzene hexyl, wherein alkyl can be straight or branched.
Be used for R 11-R 19The alkyl with 1-30 carbon atom preferably have the alkyl of 1-30 carbon atom and have the aryl of 6-24 carbon atom, the alkyl that more preferably has 3-18 carbon atom, the alkyl that more preferably has 4-10 carbon atom, in order to improve resistance to abrasion and extreme pressure property, especially preferably has the alkyl of 4-6 carbon atom.
The example of the phosphorus compound of formula (1) comprises phosphorous acid, single thiophosphorous acid and dithio phosphorous acid; The phosphorous acid monoesters, single thiophosphorous acid monoesters and dithio phosphorous acid monoesters, each all has the alkyl of the above-mentioned 1-30 of a containing carbon atom; The phosphorous acid diester, single thiophosphorous acid diester and dithio phosphorous acid diester, every kind of alkyl that all has two the above-mentioned 1-30 of containing carbon atoms; And composition thereof.
In the present invention, X in the preferred formula (1) 1, X 2And X 3In two or more be oxygen, more preferably X 1, X 2And X 3All be oxygen.
The example of the phosphorus compound of formula (2) comprises phosphoric acid and single thiophosphate; Phosphate monoester and single thiophosphate monoesters, each all has the alkyl of the above-mentioned 1-30 of a containing carbon atom; Phosphodiester and single thiophosphate diester, every kind of alkyl that all has two the above-mentioned 1-30 of containing carbon atoms; With its mixture.
In the present invention, X in the preferred formula (2) 4-X 7All be oxygen.
The example of the phosphorus compound of formula (3) comprises phosphonic acids and single phosphonothionic acid, and each all has the alkyl of the above-mentioned 1-30 of a containing carbon atom; Phosphonate monoester and single phosphonothionic acid monoesters, every kind of alkyl that all has two the above-mentioned 1-30 of containing carbon atoms; And composition thereof.
In the present invention, X in the preferred formula (3) 8-X 10All be oxygen.
Component (A) be preferably selected from phosphorous acid diester with two alkyl or aryls that contain 3-18 carbon atom and zinc-, molybdenum-, calcium-, magnesium-or the salt of lithium alkali; Have the phosphodiester of two alkyl or aryls that contain 3-18 carbon atom and zinc-, molybdenum-, calcium-, magnesium-or the salt of lithium alkali; With the phosphonic acids alkyl or aryl monoesters with two alkyl or aryls that contain 3-18 carbon atom and zinc-, molybdenum-, calcium-, magnesium-or the salt of lithium alkali.
The component of one or more types (A) blend arbitrarily.
In that there is no particular limitation aspect the preparation method of phosphorus compound metal-salt of the present invention, because they can be prepared by any universal method.Zinc salt for phosphodiester, be by phosphorus compound and 0.1-2 mole with 2 moles of formulas (2), preferred 0.5-1 mole, the zinc alkali of preferred especially 0.8-0.98 mole, as zinc oxide, zinc hydroxide, zinc carbonate and zinc chloride, 0.2-2 rise, preferred 0.5-1.5 rises organic solvent and 0.05-1 liter, preferred 0.1-0.5 premium on currency mixes, and at 40-100 ℃, under preferred 60-90 ℃ the temperature reacting by heating 0.5-10 hour, obtained in preferred 1-6 hour.Remove water and leach after the organic solvent, with solvent vacuum distilling.The zinc salt of phosphate monoester is by with above-mentioned identical method, with phosphorus compound and the 0.2-4 mole of 2 moles of formulas (2), and preferred 1-2 mole, preferred especially 1.6-1.96 mole zinc alkali obtains as zinc oxide, zinc hydroxide, zinc carbonate and zinc chloride.There is no particular limitation concerning organic solvent.The example of organic solvent comprises usually known those, as alcohol, and hexane, benzene, toluene, dimethylbenzene and naphthane, and compound and lubricating base oil with aromatic nucleus.
In the present invention, the neutralization ratio of phosphorus compound metal-salt is preferably 50% or higher, and more preferably 80% or higher, preferred especially 90% or higher.The compound that obtains in this way, as di-(2-ethylhexyl)phosphoric acid zinc, two (2-ethylhexyl) single thiophosphate zinc, di-(2-ethylhexyl)phosphoric acid calcium, dibutylphosphoric acid zinc, with 1,3-dimethylbutyl zinc phosphate be white solid, at lubricating base oil, do not comprise in the additive of component (B) or very low with regard to the solvability in the lubricating oil composition that itself does not comprise component (B) like that.Therefore, although any above-claimed cpd can be dissolved in this base oil, additive or the composition when being in the state following time that is dissolved in the organic solvent, when the distillation organic solvent, may be precipitated out.In addition, although any above-claimed cpd (energy) is heated and simultaneously with contain component (B) or lubricating base oil, component (B) and other lubricating oil compositions that does not comprise its additive and mix, it is dissolved fully need take a long time.Therefore, must remove by filter insoluble phosphorus compound metal-salt in case of necessity, this causes the industrial production of the additive planned or lubricating oil composition not too effective.
Example for the preparation of the additive method of component (A) comprises, the method of Dorinson (ASLE Trans., 22 (2), 190 (1967)), method (the Analyt.Chem. of Handley, 35,991-995 page or leaf (1963)) disclosed method and among Japanese Patent publication 42-12646,5-29357 and Japanese Patent Laid-Open Publication 5-222068 and the 8-245656.Preferably mix with organic solvent before mix with component (B) or be dissolved in wherein with the solid-state component that obtains (A).In the above method of enumerating, can mix with component (B) without distilling out the component (A) that organic solvent just obtains.Alternatively, can be at first above-mentioned material for component (A) be mixed, and then with component (B) or its any substance reaction.
Component of the present invention (B) is amine compound.The example of this amine compound comprises various amine compound.The example of preferred ingredients (B) comprises the amido antioxidant, fatty amine and ashless dispersant and/or its derivative.
(B-1) example of amido antioxidant comprises various aromatic amine compounds, and preferred examples comprises generally well-known those of lubricating oil of will can be used for, as alkyl diphenyl base amine, alkyl naphthylamines, phenyl-a-naphthylamine, and alkyl phenyl-alpha-naphthylamine.Preferably those are the compounds of liquid to these amido antioxidants at normal temperatures.Why preferably using these amido antioxidants, is because they have extremely high solvability to component (A).The alkyl of above-mentioned antioxidant has 1-30, and preferred 3-20, preferred especially 4-10 carbon atom, the replacement number of alkyl is 1-4, preferred 1 or 2.
Ashless dispersant is preferably at least one class and is selected from (B-2) succinimide, (B-3) benzylamine, (B-4) polyamines and polyamines and alkyl-or the compound of the Mannich reaction products of thiazolinyl-phenol, formaldehyde and derivative of these compounds.
The base number of above-mentioned ashless dispersant and/or its derivative (measuring according to the salt acid system) is preferably 5mgKOH/g or higher, more preferably 10mgKOH/g or higher, especially preferably 20mgKOH/g or higher.The base number meaning of measuring with the salt acid system refers to the value according to the potentiometric determination of JIS K2501 the 6th part.
(B-2) specific examples of succinimide comprises the compound that is expressed from the next:
Figure BSA00000533179300091
In formula (4), R 21Be to have 12-400, preferred 60-200, the alkyl or alkenyl of preferred especially 70-150 carbon atom, a is the integer of 1-5, preferred 2-4.
In formula (5), R 22And R 23Be to have 12-400 independently of one another, preferred 60-200, the alkyl or alkenyl of preferred especially 70-150 carbon atom, especially preferably polybutylene-based, b is the integer of 0-4, preferred 1-3.
Succinimide is divided into suc as formula (4) represented monotype succinimide (wherein succinyl oxide is added to an end of polyamines by imidization) with suc as formula (5) represented dimorphism succinimide (wherein succinyl oxide is added to the two ends of polyamines by imidization).In the present invention, the succinimide of this two type and its mixture all can be used as component (B-2).
There is no particular limitation for the method for preparing above-mentioned succinimide.For example, a kind of method of using is, to under 100-200 ℃ temperature, react the polybutylene-based succinimide that obtains by polybutene or the polyisobutene (5-100 mole % wherein has the terminal vinylidene structure) that makes chlorination or polybutene and the maleic anhydride of therefrom fully having removed chlorine and fluorine, with polyamines such as diethylenetriamine, Triethylenetetramine (TETA), tetren or penten reaction.Under the situation of preparation double amber imide, can make the above polybutylene-based succinimide that obtains almost to be the amount (mol ratio) and polyamines reaction of polyamines twice, and under the situation of the single succinimide of preparation, this polybutylene-based succinimide can be with the amount identical with polyamines (mol ratio) and its reaction.In the middle of these succinimides, preferred polybutylene-based double amber imide is because they can make the lubricating composition of gained have oxidative stability and sludge dispersiveness.
(B-3) specific examples of benzylamine comprises the compound that is expressed from the next:
Figure BSA00000533179300101
In formula (6), R 24Be to have 12-400, preferred 60-200, the alkyl or alkenyl of preferred especially 70-150 carbon atom, c is the integer of 1-5, preferred 2-4.
Benzylamine can react to obtain alkylphenol by making polyolefine such as oligomerization of propene thing, polybutene or ethene-alpha-olefin copolymer and phenol, then alkylphenol and formaldehyde, polyamines such as Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or pentaethylene hexamine is carried out Mannich reaction and obtains.
(B-4) specific examples of polyamines comprises the compound that is expressed from the next:
R 25-NH-(CH 2CH 2NH) d-H (7)
In formula (7), R 25Be to have 12-400, preferred 60-200, the alkyl or alkenyl of preferred especially 70-150 carbon atom, d is the integer of 1-5, preferred 2-4.
This polyamines can be by with polyolefine such as oligomerization of propene thing, polybutene or ethene-alpha-olefin copolymer chlorination and make the polyolefine of chlorination and ammonia or polyamines such as quadrol, Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or pentaethylene hexamine react to prepare.
The specific examples of the derivative of ashless dispersant comprises the compound by the various modifications that nitrogenous compound (B-2)-(B-4) and boron compound, oxygen-containing organic compound, sulfocompound or two or more these combination of compounds arbitrarily reacted neutralize or amino and/or the imino-amidation of all or part of remnants obtained.
The example of boron compound comprises boric acid, borate, and boric acid ester.The specific examples of boric acid comprises boric acid, methyl-boron-dihydroxide, and tetraboric acid.Boratory example comprises an alkali metal salt, alkaline earth salt or the ammonium salt of boric acid.Boratory particular instance comprises lithium tetraborate such as methyl-boron-dihydroxide lithium, lithium tetraborate, five lithium tetraborates and peroxyboric acid lithium; Sodium tetraborate such as methyl-boron-dihydroxide sodium, hypoboric acid sodium, sodium tetraborate, sodium pentaborate, six Sodium Tetraboratees and eight Sodium Tetraboratees; Potassium borate such as methyl-boron-dihydroxide potassium, potassium tetraborate, potassium pentaborate, six potassium borates and eight potassium borates; Lime borate such as methyl-boron-dihydroxide calcium, hypoboric acid calcium, tetraboric acid DFP, tetraboric acid five calcium and six lime borates; Magnesium borate such as methyl-boron-dihydroxide magnesium, hypoboric acid magnesium, tetraboric acid three magnesium, tetraboric acid five magnesium and magnesium hexaborate; With ammonium borate such as methyl-boron-dihydroxide ammonium, tetraboric acid ammonium, ammonium pentaborate and eight ammonium borates.
The example of boric acid ester comprises boric acid and preferably contains the ester of the fatty alcohol of 1-6 carbon atom.The particular instance of boric acid ester comprises the boric acid mono-methyl, trimethyl borate, trimethyl borate, boric acid mono ethyl ester, boric acid diethyl ester, triethyl borate, boric acid list propyl ester, boric acid dipropyl, tripropoxy-boron, boric acid mono, boric acid dibutylester, and tributyl borate.
The preferred derivative that uses by succinimide and any above-mentioned boron compound reaction are obtained is because they can make the lubricating oil composition of gained have thermotolerance and oxidative stability.There is no particular limitation for the equivalence ratio (B/N equivalence ratio) of nitrogen and boron.But the B/N equivalence ratio is preferably 1 or lower, more preferably 0.7 or lower, preferred especially 0.5 or lower, because this derivative is easy to and component (A) forms complex compound.
The particular instance of oxygen-containing organic compound comprises the monocarboxylic acid that contains 1-30 carbon atom, as formic acid, and acetic acid, oxyacetic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, lauric acid, tridecylic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, natural pearls acid, stearic acid, oleic acid, nondecylic acid, and eicosanoic acid; The poly carboxylic acid that contains 2-30 carbon atom, as oxalic acid, phthalic acid, trimellitic acid, pyromellitic acid and its acid anhydrides with and ester cpds; The oxyalkylene that contains 2-6 carbon atom; And hydroxyl (gathering) oxyalkylene carbonic ether.By making this oxygen-containing organic compound carry out aforesaid reaction, amino or imino-all or part of in arbitrary formula (4)-(7) compound probably have the structure that is expressed from the next:
In formula (8), R 26Be hydrogen, contain alkyl, thiazolinyl or the alkoxyl group of 1-24 carbon atom, perhaps by-O-(R 27O) mThe hydroxyl that H represents (gathering) oxyalkylene group, wherein R 27Be the alkylidene group that contains 1-4 carbon atom, m is the integer of 1-5.
Especially preferably use component (B-2)-(B-4) and its derivative, because we estimate, these components can by with component (A) reacting forming complex, therefore can stable existence in lubricating oil additive or lubricating oil composition, thereby shorten time of preparation lubricating oil composition.In the middle of component (B-2)-(B-4) and its derivative, preferably (B-2) succinimide and/or its derivative and the derivative by with boron compound component (B-2)-(B-4) modification being obtained, they particularly preferably are the derivative that component (B-2) modification is obtained by with boron compound, because can improve thermotolerance, oxidative stability and the extreme pressure property of lubricating oil additive of the present invention or lubricating oil composition.
The example that is used as other amine compound of component (B) comprises the alkylamine with the straight or branched alkyl that contains 1-30 carbon atom, as methylamine, and ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, heptadecyl-amine, stearylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, the Di-Octyl amine nonyl amine, didecylamine, two heptadecyl-amines, two n-Laurylamines, diamin, two tetradecylamines, two pentadecyl amines, two cetylamines, two heptadecylamine (HDA)s, two octadecane amine, thyl methyl amine, first propylamine, the first butylamine, second propylamine, second butylamine, third butylamine, penta methylamine, own methylamine, heptan methylamine, hot methylamine, the ninth of the ten Heavenly Stems methylamine, the last of the ten Heavenly stems methylamine, undecyl methylamine, dodecyl methyl amine, the tridecyl methylamine, tetradecyl methylamine, pentadecyl methylamine, the hexadecyl methylamine, heptadecyl methylamine, octadecyl methyl amine, Trimethylamine 99, ethyl dimethyl amine, propyl-dimethyl amine, the butyl dimethyl amine, hexyl dimethyl amine, octyldimethyl amine, the decyl dimethyl amine, undecyl dimethyl amine and octadecyl dimethyl amine; Alkenyl amine with the straight or branched thiazolinyl that contains 2-30 carbon atom, as vinyl amine, propenyl amine, butenyl amine, octenyl amine, oleyl amine, the octenyl methylamine, decene ylmethyl amine, laurylene ylmethyl amine, octadecylene ylmethyl amine, the octenyl dimethyl amine, decene base dimethyl amine, laurylene base dimethyl amine and octadecylene base dimethyl amine; Have the cycloalkyl that contains 3-30 carbon atom, alkyl or alkenyl cycloalkyl aliphatic cyclic amine (these alkyl and thiazolinyl can be straight chain or side chain and be positioned at arbitrarily on the position), as hexahydroaniline, methyl cyclohexylamine, and ethyl cyclohexylamine; Alkanolamine with the straight or branched alkanol groups that contains 1-30 carbon atom, as carbinolamine, thanomin, Propanolamine, butanolamine, amylalcohol amine, hexanol amine, enanthol amine, octanol amine, nonyl alcohol amine, decyl alcohol amine, lauryl alcohol amine, stearyl alcohol amine, methanol amine, methyl alcohol Propanolamine, methyl alcohol butanolamine, ethanol propanol amine, ethanol and butanol amine and propyl alcohol butanolamine; Alkylene diamines with the alkylene that contains 1-30 carbon atom, as methylene diamine, quadrol, propylene diamine, and butanediamine; Polyamines such as Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine, and pentaethylene hexamine; Heterogeneous ring compound, as has a heterogeneous ring compound that is connected to the alkyl or alkenyl that contains 8-20 carbon atom on above-mentioned illustrative monoamine, diamines and the polyamines, the undecyl diethylamide is specifically arranged, the undecyl diethanolamine, the dodecyl dipropanolamine, oil base diethanolamine, oil base propylene diamine, with the stearyl tetraethylenepentamine, and N-hydroxyethyl oil-based imidazoline; Its oxyalkylene addition compound; With its mixture.
In the middle of these amine compound, preferred examples comprises having the 8-20 of containing, the fatty amine of the alkyl or alkenyl of preferred 12-18 carbon atom, this amine can be straight chain or side chain, as decyl amine, amino dodecane, tridecyl amine, heptadecyl-amine, stearylamine, oleyl amine, stearylamine, decyl dimethyl amine, undecyl diethylamide, undecyl diethanolamine, undecyl dimethyl amine, tridecyl dimethyl amine, heptadecyl dimethyl amine, octadecyl dimethyl amine, oil base dimethyl amine and stearyl dimethyl amine.
Use fatty amine, the preferred fat monoamine can make the lubricating oil additive that further has excellent friction reduction effect between metal parts as component (B).In the middle of component (B), special preferred aliphat tertiary amine is because can prepare more excellent lubrication oil additive of extreme pressure property with them.
In the present invention, above-mentioned amine compound a kind of or two or more mixture can be used as component (B).
The example of the preferred embodiments of the invention comprises the following stated:
(1) comprises the lubricating oil additive of the mixture of component (A) and amido antioxidant;
(2) lubricating oil additive that obtains of the lubricating oil additive by making component (A) or above (1) and ashless dispersant and/or its derivatives reaction;
(3) react the lubricating oil additive that obtains by lubricating oil additive and the aliphatic amide that makes component (A) or above (1);
(4) lubricating oil additive that obtains by the mixture reaction that makes component (A) and amido antioxidant and ashless dispersant and/or its derivative; With
(5) lubricating oil additive that obtains by the mixture reaction that makes component (A) and amido antioxidant and aliphatic amide.
We guess, in the lubricating oil additive of above (1), the residing state of component (A) is, it is dissolved in the amido antioxidant, and in the lubricating oil additive of above (2)-(5), component (A) is liquefied by forming complex compound with aliphatic amide or ashless dispersant and/or its derivative.
For the present invention, preferred lubricating oil additive comprises those of (2)-(5), the more preferably lubricating oil additive of (2) and (4).
There is no particular limitation for preparation process lubricant oil additive of the present invention, as long as component (A) can be dissolved in or can react with component (B).Preferably, the prior component (A) of mixing with above-mentioned organic solvent or being dissolved in is wherein mixed with component (B), stirs then, in case of necessity organic solvent is distilled.There is no particular limitation for mixing and stirring condition.Mixing and stirring are preferably carried out under 15-150 ℃ temperature, and more preferably 30-120 ℃, preferred 40-90 ℃ especially.Consider security reason, preferably mix and be stirred in the boiling point of selected organic solvent or be lower than under its boiling point and carry out.The time of mixing and stirring was preferably 5 minutes-5 hours, and more preferably 20 minutes-3 hours, preferred especially 30 minutes-1 hour.The distillation of organic solvent is undertaken by the method such as vacuum distilling, and lasts till always and steam solvent.The slip additive of the present invention that obtains like this comprises usually with regard to phosphorus, in the total mass of additive, and 0.5-20 quality %, the component (A) of preferred 1-10 quality %.
For preparation during lubricating oil additive of the present invention component (A) there is no particular limitation with (B) ratio of mixture.Component (A) and component (B) are with 1 mass parts: the mixed of 0.1-30 mass parts, preferred 1 mass parts: 0.15 mass parts or more than, more preferably 1 mass parts: 0.2 mass parts or more than, more preferably 1 mass parts in addition: 0.3 mass parts or more than, even more preferably 1 mass parts: 0.5 mass parts or more than, preferred especially 1 mass parts: 0.8 mass parts or more than and preferred 1 mass parts: 10 mass parts or following, more preferably 1 mass parts: 5 mass parts or following.If the component of 1 mass parts (A) and 0.15 mass parts or above component (B), particularly aliphatic amide or ashless dispersant and/or its derivatives reaction, the gained lubricating oil additive will be dissolved in the lubricating base oil at an easy rate, even it also is like this when joining wherein separately.
Lubricating oil additive of the present invention is a kind of alkaline additive, it has as the transsexual energy of the defined length of base number retention property and oxidative stability, the resistance to abrasion that keeps lubricating oil composition simultaneously, and can be advantageously used in and make its high temperature detergency with raising and low friction performance.But, in order further to improve the performance characteristic of gained lubricating oil composition, this lubricating oil additive can be selected from the additive mixing of antioxidant, ashless dispersant, metal detergent, friction modifiers, anti-wear agent, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, dyestuff and viscosity index improver with at least one class.In case of necessity, can add a small amount of lubricating base oil in order to regulate the viscosity of lubricating oil additive of the present invention.In this case, according to the desired properties of gained lubricating oil composition, lubricating oil additive of the present invention can provide with the form of its additive-package of mixing with any above-mentioned various additives wherein.Thereby can obtain lubricating oil composition useful on the cost and simplified by this additive-package is mixed with lubricating base oil for the preparation of the method for lubricating oil composition.Lubricating oil composition of the present invention can additive of the present invention joins in the lubricating base oil (perhaps being the lubricating oil that comprises other various additives in case of necessity) with lubricating oil additive of the present invention or the additive-package that various additives mix by inciting somebody to action wherein, and at 15-150 ℃, preferred 40-120 ℃, under preferred 60-90 ℃ the temperature its mixing and stirring are made especially.
There is no particular limitation for the amount that joins the lubricating oil additive of the present invention in lubricating base oil or the lubricating oil composition.Lower limit amount is preferably with regard to phosphorus, in the total mass 0.005 quality % of composition, and more preferably 0.01 quality %, preferred especially 0.02 quality %, upper limit amount is preferably 0.4 quality %, more preferably 0.2 quality %, preferred especially 0.1 quality %.
The lubricating base oil of forming lubricating oil composition of the present invention and the above-mentioned additive that will add where necessary except lubricating oil additive of the present invention below will be described.
There is no particular limitation to being used for lubricating base oil of the present invention.Therefore, can use general mineral and synthetic base oil for lubricating oil.
The particular instance of mineral base oil comprises can be undertaken arbitrarily that one or more are selected from those base oils that solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing and hydrorefined processing obtain by the lubricating oil distillate that obtain the topped oil vacuum distilling that is produced by crude oil atmospheric distillation; The isomerized mineral oil of wax; With the base oil by GTL WAX (gas-liquid wax) isomerization is obtained.
Although there is no particular limitation for total aromaticity content of mineral base oil, be preferably 15 quality % or still less, more preferably 10 quality % or still less, more preferably 5 quality % or still less also, preferred especially 2 quality % or still less.Not preferred total aromaticity content surpasses the base oil of 15 quality %, because the oxidative stability of gained lubricating oil composition will be very poor.
The aromatic fraction content that the term of Shi Yonging " total aromaticity content " expression is here measured according to ASTM D2549.Aromatic fraction comprises alkylbenzene; Alkylnaphthalene; Anthracene, phenanthrene and its alkylate; 4 or the above phenyl ring compound of condensation each other wherein; And compound such as pyridine, quinoline, phenol and naphthols with assorted aromatic nucleus.
Although there is no particular limitation for the sulphur content of mineral base oil, be preferably 0.01 quality % or still less, more preferably 0.005 quality % or still less, preferred especially 0.001 quality % or still less.Can obtain having the lubricating oil composition of the transsexual energy of good length by the sulphur content that reduces mineral base oil.
The particular instance of ucon oil comprises polybutene and its hydride; Poly-alpha-olefin such as 1-octene oligopolymer and 1-decene oligopolymer and its hydride; Diester such as pentanedioic acid two (tridecyl) ester, hexanodioic acid two-2-(ethyl hexyl) ester, diisodecyl adipate, hexanodioic acid two (tridecyl) ester and cebacate two-2-(ethyl hexyl) ester; Polyol ester such as trimethylolpropane caprylate, TriMethylolPropane(TMP) pelargonate, tetramethylolmethane-2-ethylhexanoate and tetramethylolmethane pelargonate; Three esters such as neopentyl glycol; Aromatics synthetic oil such as alkylnaphthalene, alkylbenzene, and aromatic ester; With and composition thereof.
Any in above-mentioned mineral base oil or the synthetic base oil or the mixture that is selected from two or more types of these base oils can be used for the present invention.For example, being used for base oil of the present invention can be one or more mineral base oils or synthetic base oil, perhaps the mixing oil of one or more mineral base oils and one or more synthetic base oils.
Although there is no particular limitation to being used for the kinematic viscosity of lubricating base oil of the present invention under 100 ℃, be preferably 20mm 2/ s or lower, more preferably 10mm 2/ s or lower and preferred 1mm 2/ s or higher, more preferably 2mm 2/ s or higher.Preferably do not surpass 20mm 100 ℃ of following kinematic viscosity 2The lubricating base oil of/s because the low temperature viscosity characteristic of gained lubricating oil composition will be damaged, preferably is not lower than 1mm 100 ℃ of following kinematic viscosity simultaneously yet 2The lubricating base oil of/s is because the lubricity of gained lubricating oil composition will be big and relatively poor in the vaporization losses of lubricating the inadequate oil film formation ability in position and base oil owing to it.
The vaporization losses that is used for base oil of the present invention by NOACK evaporation assay determination the time, will be preferably 20 quality % or lower, more preferably 16 quality % or lower, preferred especially 10 quality % or lower.Not preferred NOACK vaporization losses surpasses the lubricating base oil of 20 quality %, because the vaporization losses of base oil will be very big in the gained lubricating oil composition, if and composition is as internal combustion (IC) engine lubricating oil, sulphur compound in the composition, phosphorus compound or metal will accumulate on the exhaust gas purification device together with base oil so, will cause disadvantageous effect to the exhaust gas purification performance like this.Here the term of Shi Yonging " NOACK evaporation " is defined as according to ASTM D5800 and measures, and is retained under 250 ℃ the temperature when oil and 20mmH 2The pressure of O (196Pa) is in the time of following 1 hour, and 60 restrain the loss amount of lubricating oil sample.
Although there is no particular limitation to the viscosity index of used lubricating base oil, in order to obtain the good viscosity characteristics from low temperature to high temperature, be preferably 80 or higher, more preferably 100 or higher, also more preferably 120 or higher.The preferred viscosities index is not lower than 80 lubricating base oil, because it will damage the low temperature viscosity characteristic of gained lubricating oil composition.
The example of antioxidant comprise be used for lubricating oil except illustration as the amido antioxidant of component (B) those antioxidants, as phenol-or metal matrix antioxidant.The adding of any antioxidant can further improve the transsexual energy of length of gained lubricating oil composition.
The example of phenol-based anti-oxidants comprises:
4,
4,4 '-two (2,6 di t butyl phenols),
4,4 '-two (2-methyl-6-tert butyl phenol),
2,
2,2 '-methylene-bis (4-methyl-6-tert butyl phenol),
4,
4,4 '-isopropylidene two (2,6 di t butyl phenol),
2,2 '-methylene-bis (4-methyl-6-nonyl phenol),
2,2 '-isobutyl fork base two (4,6-xylenol),
2,
2,6-di-t-butyl-4-cresols,
2,6-di-t-butyl-4-ethylphenol,
2,4 dimethyl-6-tert.-butyl phenol,
2,6-, two uncles-alpha, alpha-dimethyl amino-p-cresol,
2,6-di-t-butyl-4-(N, N '-dimethylaminomethyl phenol),
4,4 '-sulfo-two (2-methyl-6-tert butyl phenol),
4,4 '-sulfo-two (3 methy 6 tert butyl phenol),
2,2 '-sulfo-two (4-methyl-6-tert butyl phenol),
Two (3-methyl-4-hydroxyl-5-tertiary butyl benzyl) sulfide,
Two (3,5-di-t-butyl-4-acrinyl) sulfide,
2,2 '-sulfo-diethylidene two [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester],
Tridecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester,
Tetramethylolmethane-four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester],
Octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester,
Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, and
The fatty acid ester that the 3-methyl-5-tertiary butyl-4 hydroxyphenyl replaces.
Can use the mixture of two or more these antioxidants.
The example of ashless dispersant comprises those of with regard to component (B) example.Preferred these ashless dispersants that use are in order to further improve sludge dispersiveness, high temperature detergency and the oxidative stability of gained lubricating oil composition.
The example of metal detergent comprises basic metal or alkaline earth metal sulfonate, basic metal or alkaline-earth metal salicylate, basic metal or alkaline-earth metal phenolate and basic metal or alkaline earth metal phosphonate salt.Known base number is that the metal detergent normal, alkaline or that cross alkalization of 0-500mgKOH/g can be used for the present invention.The alkali-metal example of here mentioning comprises sodium and potassium.The example of the alkaline-earth metal of here mentioning comprises calcium and magnesium.Preferred calcium and the magnesium of using especially preferably uses calcium.Although than there is no particular limitation, it is 1-20 quality % normally for the metal of these metal detergents.Yet, in order further to improve the gained lubricating oil composition at high temperature and base number retention property and high temperature detergency in the presence of NOx, metal detergent preferably its metal than being adjusted to 2.3 or lower basic metal or alkaline-earth metal salicylate, or metal than be 1.5 or lower basic metal or alkaline-earth metal salicylate with metal than for the basic metal of 1-20 or alkaline-earth metal salicylate mixture.Here the term of Shi Yonging " metal ratio " is represented by " content (mol%) of the content (mol%) of the valency X metallic element of metallic element in the metal detergent/soap base group ", wherein metallic element is calcium, magnesium etc., soap base group be sulfonic group, salicyl, etc.
The example of friction modifiers comprises molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenumdisulphide, long-chain fat family amine, longer chain fatty acid, long chain fatty acid ester, long chain fatty acids amides, and long chain aliphatic.
The example of the anti-wear agent except component (A) comprises phosphoric acid, phosphate monoester, phosphodiester, phosphotriester, phosphorous acid, the phosphorous acid monoesters, phosphorous acid diester, tris phosphite, its amine salt, zinc dithiophosphate, zinc dithiocarbamate, disulphide, the fat of alkene sulfide and sulfuration and oily.Preferred anti-wear agent is those anti-wear agents that do not comprise sulphur.
The example of sanitas comprise benzotriazole-, azimido-toluene-, thiadiazoles-and imidazo-5-yl-compound.
The example of rust-preventive agent comprises petroleum sulfonates, alkylbenzene sulfonate, dinonylnaphthalene sulfonic acid salt, alkenyl succinic acid ester, and polyol ester.
The example of emulsion splitter comprises polyglycol-Ji nonionic surface active agent such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether and polyxyethylated naphthyl ether.
The example of metal passivator comprises tetrahydroglyoxaline, pyrimidine derivatives, alkyl thiadiazoles, Thiotax, benzotriazole and its derivative, 1,3,4-thiadiazoles polysulfide, 1,3,4-thiadiazolyl group-2,5-two (dialkyl dithio amino formates), 2-(alkyl dithio) benzoglyoxaline, and β-(neighbour-carboxyl dibenzylsulfide generation) propionitrile.The additive that thiazole and thiadiazoles have resistance to abrasion in can the present composition.
The example of defoamer comprises polysiloxane, fluorosilicone, and fluoroalkyl ether.
The example of viscosity index improver comprises non-dispersive liquid type viscosity index improver, is selected from polymkeric substance or the multipolymer of the monomer of various methacrylic esters or its hydride as one or more; Dispersion liquid type viscosity index improver is as the multipolymer of the various methacrylic esters that further comprise nitrogen compound; Wherein alpha-olefin can be non-dispersive liquid-or the dispersion liquid type ethene-alpha-olefin copolymer of propylene, 1-butylene or 1-amylene or its hydride; Polyisobutene or its hydride; The phenylethylene-dialkene multipolymer of hydrogenation; The phenylethylene-maleic anhydride ester copolymer; With polyoxyethylene alkylphenyl ethene.
Must consider its shear stability when selecting the molecular weight of these viscosity index improvers.Specifically, the number-average molecular weight of non-dispersive liquid or dispersion liquid type polymethacrylate is 5,000-1,000,000, and preferred 100,000-900,000.The number-average molecular weight of polyisobutene or its hydride is 800-5,000, and preferred 1,000-4,000.The number-average molecular weight of ethene-alpha-olefin copolymer or its hydride is 800-500,000, and preferred 3,000-200,000.
In the middle of these viscosity index improvers, use ethene-alpha-olefin copolymer or its hydride to help to form the special excellent lubrication oil compositions of shear stability.One or more compounds that are selected from above-mentioned viscosity index improver can be with amount mixing arbitrarily.
(comprise that wherein these additives are with the situation of the form adding of additive-package) when these additives join in the lubricating oil composition of the present invention, the amount of each all is selected from the total mass 0.005-5 quality % in composition in antioxidant, anti-wear agent, friction modifiers, inhibiter, rust-preventive agent and the emulsion splitter except component (A).The amount of each is selected from 0.1-10 quality % in ashless dispersant and the metal detergent.The amount of metal passivator is selected from 0.005-1 quality %.The amount of defoamer is selected from 0.0005-1 quality %, and the amount of viscosity index improver then is selected from 0.1-20 quality %.
In the present invention, comprise 0.3 quality % or following, preferred 0.1 quality % or following, more preferably 0.01 quality % or following sulphur or do not comprise the amount that the lubricating oil composition of sulphur can be by reducing sulfur-containing additive basically or do not use this class additive to obtain.
Lubricating oil additive of the present invention and lubricating oil composition are preferred for oil engine, as two-or the gasoline of four-wheel automobile-, diesel oil-and gas-engine, generator, steamer, etc.
Lubricating oil additive and lubricating oil composition are particularly preferred for oil engine, be 50 quality ppm or still less especially for using low sulfur content fuel such as sulphur content, preferred 30 quality ppm or still less, preferred especially 10 quality ppm or gasoline still less, gasol or kerosene or sulphur content are in the gas blowing engine of 1 quality ppm or fuel still less (LPG, Sweet natural gas, the hydrogen that is substantially free of sulphur, dme, alcohol, GTL etc.).In addition, lubricating oil additive of the present invention can improve the transsexual energy of length of lubricating oil composition, keep its resistance to abrasion simultaneously, therefore suitable as requiring to have in the lubricating oil of this performance, as being used for drive system as lubricating oil automatic or manual transmission, the lubricating oil that is used for wet brake, hydraulic efficiency oil, turbine oil, compressor oil, bearing refrigeration oil, etc.
Preferred forms of the present invention
Hereinafter, will be described in more detail the present invention by following examples and comparative example, these should not be considered to be limiting the scope of the invention.
Embodiment 1-13
According to the following prescription that provides, preparation lubricating oil additive A-M (embodiment 1-13).
(1) preparation of phosphorus compound metal-salt
(a) 0.196 mole of zinc oxide and 0.4 mole of phosphoric acid dibutylester are mixed in 200 milliliters of hexanes and 40 ml waters, and under 80 ℃ temperature, stirred 4 hours.Remove the water of gained mixture.Filter after the hexane layer, with the hexane vacuum distilling in the filtrate, thereby obtain dibutylphosphoric acid zinc (white solid, phosphorus content: 13.2 quality %, zinc content: 13 quality %).We guess that the gained compound comprises compound with following structure as main component:
Figure BSA00000533179300211
(b) except using list/two (1, the 3-dimethyl) mixture of butyl phosphoric acid ester replaces outside the dibutyl phosphate, repeat above (a) identical program, thereby obtain list/two (1, the 3-dimethyl) mixture (white solid of butyl phosphoric acid zinc, phosphorus content: 13.8 quality %, zinc content: 18.7 quality %).We guess that mixture that the gained compound comprises the compound with following structure is as main ingredient:
Figure BSA00000533179300212
(c) except using calcium hydroxide to replace zinc oxide and using di(2-ethylhexyl)phosphate (2-ethylhexyl) ester to replace the dibutyl phosphate, repeat above (a) identical program, thereby obtain di-(2-ethylhexyl)phosphoric acid calcium (white solid, phosphorus content: 9.1 quality %, calcium contents: 5.8 quality %).
(d) except using di(2-ethylhexyl)phosphate (2-ethylhexyl) ester to replace the dibutyl phosphate, repeat above (a) identical program, thereby obtain di-(2-ethylhexyl)phosphoric acid zinc (white solid, phosphorus content: 8.8 quality %, zinc content: 9.1 quality %).
In addition, use various material to carry out above-mentioned identical program, thereby obtain the following compound that neutralization ratio is 95-98%.All these compounds all are solid at normal temperatures.
(e) mixture of list/two (normal-butyl) zinc phosphate,
(f) mixture of list/di-(2-ethylhexyl)phosphoric acid zinc,
(g) mixture of list/two (n-octyl) zinc phosphate,
(h) mixture of list/two (isodecyl) zinc phosphate,
(i) mixture of list/two (dodecyl) zinc phosphate,
(j) mixture of list/two (isotridecyl) zinc phosphate,
(k) mixture of list/two (oleyl) zinc phosphate,
(l) mixture of list/two (stearyl) zinc phosphate,
(m) mixture of list/di-(2-ethylhexyl)phosphoric acid ester calcium,
(n) di-(2-ethylhexyl)phosphoric acid magnesium,
(o) mixture of list/di-(2-ethylhexyl)phosphoric acid magnesium,
(p) di-(2-ethylhexyl)phosphoric acid lithium,
(q) single (2-ethylhexyl)-2-ethylhexyl phosphoric acid zinc
(2) preparation of the mixed additive A-D of the metal-salt of phosphorus compound and amido antioxidant (embodiment 1-4)
(A) 500 grams are being obtained in (1)-(a) after white solid is dissolved in 1 kilogram of hexane, to wherein adding 500 gram alkyl diphenyl base amine (alkyl: butyl and octyl group), and under 40 ℃ temperature, mixing and stirred 30 minutes.With hexane vacuum distilling, thereby had mobile viscosity additives A (phosphorus content: 6.6 quality %) at normal temperatures.
(B) the white solid that in using (1)-(b), obtains, repeat above (A) identical program, thereby had mobile viscosity additives B (phosphorus content: 6.9 quality %) at normal temperatures.
(C) the white solid that in using (1)-(c), obtains, repeat above (A) identical program, thereby had mobile viscosity additives C (phosphorus content: 4.55 quality %) at normal temperatures.
(D) the white solid that in using (1)-(d), obtains, repeat above (A) identical program, thereby had mobile viscosity additives D (phosphorus content: 4.4 quality %) at normal temperatures.
(3) preparation of the mixed additive E-H of the metal-salt of phosphorus compound and ashless dispersant (embodiment 5-8)
(E) after the white solid that obtains in 200 grams (1)-(a) is dissolved in 1 kilogram of hexane, with the commercially available polybutylene-based succinimide base ashless dispersant SB (molecular weight of polybutylene-based group: 1300 of 800 grams, nitrogen content: 1.3 quality %, boron content: 0.5 quality %, base number (salt acid system): 24mgKOH/g) join in the solution and under 40 ℃ temperature the heating and stirred 30 minutes.With hexane vacuum distilling, thereby had mobile viscosity additives E (phosphorus content: 2.64 quality %) at normal temperatures.
(F) the white solid that in using (1)-(b), obtains, repeat above (E) identical program, thereby had mobile viscosity additives F (phosphorus content: 2.76 quality %) at normal temperatures.
(G) the white solid that in using (1)-(c), obtains, repeat above (E) identical program, thereby had mobile viscosity additives G (phosphorus content: 1.82 quality %) at normal temperatures.
(H) the white solid that in using (1)-(d), obtains, repeat above (E) identical program, thereby had mobile viscosity additives H (phosphorus content: 1.76 quality %) at normal temperatures.
Use the metal-salt of the phosphorus compound of (e)-(q) to repeat above-mentioned identical program with commercially available polybutylene-based succinimide base ashless dispersant SB, thereby had mobile viscosity additives (e at normal temperatures SB-q SB).
(4) preparation of the mixed additive I-M of amido antioxidant and ashless dispersant (embodiment 9-13)
(I) additive A that obtains in 400 grams (2)-(A) is joined among the commercially available polybutylene-based succinimide base ashless dispersant SB of 600 grams, and heating and stir 1 hour under 80 ℃ temperature, thereby had mobile additive I (phosphorus content: 2.64 quality %) at normal temperatures.
(J) additive B that obtains in 400 grams (2)-(B) is joined among the commercially available polybutylene-based succinimide base ashless dispersant SB of 600 grams, and heating and stir 1 hour under 80 ℃ temperature, thereby had mobile additive J (phosphorus content: 2.76 quality %) at normal temperatures.
(K) addition of C that obtains in 400 grams (2)-(C) is joined among the commercially available polybutylene-based succinimide base ashless dispersant SB of 600 grams, and heating and stir 1 hour under 80 ℃ temperature, thereby had mobile additive K (phosphorus content: 1.82 quality %) at normal temperatures.
(L) the additive D that obtains in 400 grams (2)-(D) is joined among the commercially available polybutylene-based succinimide base ashless dispersant SB of 600 grams, and heating and stir 1 hour under 80 ℃ temperature, thereby had mobile additive L (phosphorus content: 1.76 quality %) at normal temperatures.
(M) with the additive A that obtains in 100 grams (2)-(A), the commercially available polybutylene-based succinimido ashless dispersant SB of 400 grams, 400 gram calcium salicylate base purification agent (calcium contentss: 6.2 quality %, metal ratio: 2.7), with 100 gram octyl group-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester mixes under the temperature be incorporated in 80 ℃ heating and stirs 1 hour, thereby is had mobile additive M (phosphorus content: 0.66 quality %, calcium contents: 2.5 quality %) at normal temperatures.
(5) preparation of the mixed additive N-U of the mixture of the metal-salt of phosphorus compound and amine compound or amine compound and amido antioxidant (embodiment 14-21)
(N) be dissolved in 100 and restrain oneself after the alkane 50 grams being obtained dibutylphosphoric acid zinc in (1)-(a), to wherein adding 50 gram oleyl amines, and under 40 ℃ temperature, mix and stirred 30 minutes.With hexane vacuum distilling, thereby be liquid and transparent additive N (phosphorus content: 6.6 quality %) at normal temperatures.
(O) except using n-Laurylamine to replace repeating (N) identical program, thereby being liquid and transparent additive O (phosphorus content: 6.6 quality %) at normal temperatures the oleyl amine.
(P) except using the undecyl dimethyl amine to replace repeating (N) identical program, thereby being liquid and transparent additive P (phosphorus content: 6.6 quality %) at normal temperatures the oleyl amine.
(Q) (alkyl: mixture butyl octyl) replaces repeating (N) identical program, thereby being liquid and transparent additive Q (phosphorus content: 6.6 quality %) at normal temperatures the oleyl amine except using 10 gram oleyl amines and 40 gram alkyl diphenyl base amine.
(R) (alkyl: mixture butyl octyl) replaces repeating (N) identical program, thereby being liquid and transparent additive R (phosphorus content: 6.6 quality %) at normal temperatures the oleyl amine except using 10 gram n-Laurylamines and 40 gram alkyl diphenyl base amine.
(S) except using outside list/two (1, the 3-dimethylbutyl) zinc phosphate that obtains in 50 grams (1)-(b), repeat (N) identical program, thereby be liquid and transparent additive S (phosphorus content: 6.9 quality %) at normal temperatures.
(T) except using the di-(2-ethylhexyl)phosphoric acid zinc that obtains in 50 grams (1)-(d), 25 gram undecyl dimethyl amines, outside 25 gram alkyl diphenyl base amine (alkyl: butyl and octyl group), (N) the identical program of repetition, thus be liquid and transparent additive T (phosphorus content: 4.4 quality %) at normal temperatures.
(U) the di-(2-ethylhexyl)phosphoric acid magnesium that in using 50 grams (1)-(n), obtains, repeat (N) identical program, thereby be liquid and transparent additive U at normal temperatures.
Estimate gained lubricating oil additive A-U (embodiment 1-21) by storage stability test, but both do not observed precipitation, do not observe muddiness again.
Embodiment 22-57 and comparative example 1-12
According to the prescription shown in the following table 1-3, use lubricating oil additive A-M (embodiment 1-13) to prepare lubricating oil composition of the present invention (embodiment 22-57).In the preparation, estimate the solvability of each additive by dissolubility test.Dissolubility test be by composition at normal temperatures sample introduction in mixing vessel, and after sample mixed under 80 ℃ temperature in heating with under stirring, estimate in each scheduled time that the dissolved state (whether having insoluble substance) of the additive that comprises in each composition carries out.
In order to compare, prepare lubricating oil composition (comparative example 1-12) according to the prescription shown in the following table 4 with universal mode.In the same way composition is estimated by identical dissolubility test.The results are shown in table 1-4.
Figure BSA00000533179300261
Figure BSA00000533179300271
Figure BSA00000533179300281
Figure BSA00000533179300291
Figure BSA00000533179300301
Figure BSA00000533179300311
Figure BSA00000533179300321
Figure BSA00000533179300331
Apparent from the result shown in the table 1-3, the insoluble substance that comprises the lubricating oil composition of lubricating oil additive of the present invention disappeared after 16 hours, because their dissolvings fully.In addition, shown in table 2 and 3, each self-contained use ashless dispersant disappears after 2 hours as the insoluble substance in the composition (embodiment 34-57) of the additive of the present invention of component (B), and has dissolved in short duration.Also confirm, can not occur the problem of any relevant stability in storage with these lubricating oil compositions.Also confirmation, even dialkyl group single thiophosphate zinc (footnote 7 in the table 4) also can become oil-soluble in the mode identical with additive of the present invention, thereby generates lubricating oil composition in the short period of time.
In addition, the additive e that in above (3), obtains SB-q SBDissolve in table with the additive N-U that in above (5), obtains and be called footnote 1 among the 1-3), 2) and 3) lubricating base oil in.The result is that insoluble substance dissolved fully in 2 hours and disappears.
On the contrary, as shown in table 4, when the metal-salt of phosphorus compound heats with lubricating base oil and other additives (comparative example 1-12) and stirs, even after 16 hours, still there is insoluble substance and can not dissolves fully.The time period of length is dissolved these insoluble substances fully in addition to need cost.
Do not use boric acid modified polybutylene-based succinimide base ashless dispersant SA (polybutylene-based molecular weight: 1300, nitrogen content: 1.6 quality %, boron content: 0 quality %, (the salt acid system: 24mgKOH/g) the commercially available polybutylene-based succinimido ashless dispersant SB (additive E-M of the present invention) that uses among the replacement embodiment 5-13 obtains other lubricating oil additives of the present invention to base number.Comprise this additive-treated oil composition and have the similar result of result who reaches with the present invention as mentioned above.
Confirmed already, its resistance to abrasion of lubricating oil composition of the present invention is equal to the composition that uses zinc dialkyl dithiophosphate, and it is by the transsexual energy of length of oxidative stability, base number retention property and high temperature detergency definition, low friction performance, anti-copper corrosion performance etc. can have significant improvement, and can to generate sulphur content be 0.3 quality % or lower, preferred 0.1 quality % or lower, more preferably 0.01 quality % or lower especially preferably is substantially free of the lubricating oil composition of sulphur.Also confirm, lubricating oil composition of the present invention can, particularly using sulphur content is that 10 quality ppm or lower gasoline or sulphur content are to realize above-mentioned performance in the oil engine of 1 quality ppm or lower Sweet natural gas.
Industrial applicibility
Lubricating oil additive of the present invention can make the wherein salt that comprises in additive metal-salt insoluble or that not too be dissolved in the phosphorus compound in the lubricating oil be dissolved in wherein fully in short duration.Especially, be dissolved in or when preparing lubricating oil composition with additive that amine compound such as ashless dispersant or aliphatic amide reaction obtain when using by the metal-salt that makes phosphorus compound in advance, can be similar to general lubricating oil composition, in short duration, generate described composition.Therefore, the present invention can provide obviously can be used for mass production have above-mentioned premium properties lubricating oil composition lubricating oil additive and prepare the method for this additive.

Claims (15)

1. lubricating oil additive comprises the mixture of the succinimide of component (A) and boration, and wherein said component (A) is the compound of the metal-salt of at least a phosphorus compound that is selected from following formula (1), (2) and (3) expression:
Figure FSB00001076228800011
Wherein, X 1, X 2And X 3Be oxygen or sulphur independently of one another, condition is to have at least one to be oxygen in them, R 11, R 12And R 13Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them;
Figure FSB00001076228800012
Wherein, X 4, X 5, X 6And X 7Be oxygen or sulphur independently of one another, condition is to have at least three to be oxygen in them, R 14, R 15And R 16Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; With
Figure FSB00001076228800013
Wherein, X 8, X 9And X 10Be oxygen or sulphur independently of one another, condition is to have at least two to be oxygen in them, R 17, R 18And R 19Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; A is 0 or 1 integer; And the phosphorus compound of formula (1)-(3) between the X-R key, can comprise by-(OR ') nThe group of-expression, wherein R ' is the alkylidene group that contains 1-4 carbon atom, n is the integer of 1-10.
2. the lubricating oil additive of claim 1 further comprises the lubricating oil additive of the lubricating oil additive that comprises following (1), (2), (3), (4) or (5):
(1) comprises the lubricating oil additive of the mixture of component (A) and amido antioxidant;
(2) lubricating oil additive that obtains of the lubricating oil additive of above by making (1) and succinimide and/or its derivatives reaction;
(3) react the lubricating oil additive that obtains by lubricating oil additive and the aliphatic monoamine that makes component (A) or above (1);
(4) lubricating oil additive that obtains by the mixture reaction that makes component (A) and amido antioxidant and succinimide and/or its derivative; With
(5) lubricating oil additive that obtains by the mixture reaction that makes component (A) and amido antioxidant and aliphatic monoamine,
Wherein said component (A) is the compound of the metal-salt of at least a phosphorus compound that is selected from following formula (1), (2) and (3) expression:
Figure FSB00001076228800021
Wherein, X 1, X 2And X 3Be oxygen or sulphur independently of one another, condition is to have at least one to be oxygen in them, R 11, R 12And R 13Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them;
Figure FSB00001076228800022
Wherein, X 4, X 5, X 6And X 7Be oxygen or sulphur independently of one another, condition is to have at least three to be oxygen in them, R 14, R 15And R 16Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; With
Figure FSB00001076228800023
Wherein, X 8, X 9And X 10Be oxygen or sulphur independently of one another, condition is to have at least two to be oxygen in them, R 17, R 18And R 19Be hydrogen or the alkyl that contains 1-30 carbon atom independently of one another, condition is to have at least one to be hydrogen in them; A is 0 or 1 integer; And the phosphorus compound of formula (1)-(3) between the X-R key, can comprise by-(OR ') nThe group of-expression, wherein R ' is the alkylidene group that contains 1-4 carbon atom, n is the integer of 1-10,
Wherein said amido antioxidant is at least a following compound that is selected from: alkyl diphenyl base amine, and the alkyl naphthylamines, phenyl-a-naphthylamine and alkyl phenyl-alpha-naphthylamine,
Described aliphatic monoamine is at least a following compound that is selected from: the alkylamine that contains 1-30 carbon atom alkyl is arranged, the alkenyl amine that contains 2-30 carbon atom thiazolinyl is arranged, the aliphatic cyclic amine that each cycloalkyl that contains 3-30 carbon atom, alkyl or alkenyl cycloalkyl are arranged has the alkanolamine and the derivative thereof that contain 1-30 carbon atom triacontanol group.
3. according to the lubricating oil additive of claim 1 or 2, the X in its Chinese style (1) 1, X 2And X 3, the X in the formula (2) 4, X 5, X 6And X 7, and the X in the formula (3) 8, X 9And X 10All be oxygen.
4. according to each lubricating oil additive of claim 1-3, wherein the metal of component (A) is at least a metal that is selected from lithium, magnesium, calcium and zinc.
5. according to the lubricating oil additive of claim 2, the reaction ratio of wherein said aliphatic monoamine or succinimide or derivatives thereof and component (A) be in mass 0.15 or more than.
6. according to the lubricating oil additive of claim 2, wherein said succinimide or derivatives thereof is that the base number of measuring by the salt acid system is 5mgKOH/g or above compound.
7. according to the lubricating oil additive of claim 2, the derivative of wherein said succinimide is the boron compound derivative of succinimide.
8. according to the lubricating oil additive of claim 2, wherein aliphatic monoamine is tertiary amine.
9. lubricating oil additive, it comprises each lubricating oil additive and at least one class additive of being selected from lubricating base oil, antioxidant, ashless dispersant, metal detergent, friction modifiers, anti-wear agent, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, dyestuff and viscosity index improver of claim 1-8.
10. lubricating oil additive, it comprises lubricating oil additive and the lubricating base oil of claim 9.
11. lubricating oil composition, it comprises among the claim 1-10 each lubricating oil additive, and lubricating base oil and at least one class are selected from the additive of antioxidant, ashless dispersant, metal detergent, friction modifiers, anti-wear agent, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, dyestuff and viscosity index improver.
12. according to the lubricating oil composition of claim 11, wherein said composition contains 0.3 quality % or following sulphur, is as the criterion in total composition.
13. according to the lubricating oil composition of claim 11 or 12, it is the oil engine of 50 quality ppm or lower low sulfur content fuel that wherein said composition be used for to use sulphur content.
14. prepare the method for lubricating oil additive, comprise that the lubricating oil additive with claim 9 mixes with lubricating oil.
15. prepare the method for lubricating oil composition, comprise each lubricating oil additive among the claim 1-10 is mixed with the additive that lubricating base oil and at least one class are selected from antioxidant, ashless dispersant, metal detergent, friction modifiers, anti-wear agent, sanitas, rust-preventive agent, emulsion splitter, metal passivator, defoamer, dyestuff and viscosity index improver.
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