CN101245278B - Lubricant formulations with improved antiwear properties - Google Patents

Lubricant formulations with improved antiwear properties Download PDF

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Publication number
CN101245278B
CN101245278B CN2007103035784A CN200710303578A CN101245278B CN 101245278 B CN101245278 B CN 101245278B CN 2007103035784 A CN2007103035784 A CN 2007103035784A CN 200710303578 A CN200710303578 A CN 200710303578A CN 101245278 B CN101245278 B CN 101245278B
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lubricant compositions
lubricant
compound
acid
magnesium
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CN101245278A (en
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W·Y·林
M·T·德林
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Afton Chemical 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Abstract

A lubricated surface, a method for reducing wear between moving parts, and lubricants, and lubricant additive concentrates containing a wear reducing agent. The lubricated surface contains a base oil of lubricating viscosity and an amount of at least one hydrocarbon soluble magnesium compound effective to provide a reduction in surface wear greater than a reduction surface wear for a lubricant composition devoid of the magnesium compound. The lubricant composition contains no more than about 0.05 wt. % phosphorus and is devoid of calcium detergents.

Description

Be used to improve the additive and the lubricant formulations of abrasion resistance
Technical field
Embodiment described in the literary composition relates to the molten magnesium additive of particular oils and this magnesium additive are used to improve the prescription abrasion resistance in lubricating oil preparation application.
Background technology
Bus engine oil of future generation and heavy duty diesel engine oil will need suitable abrasion resistance, and have the p and s of lower level in prescription, to reduce the pollution of stricter pollution control device.As everyone knows, the additive of sulfur-bearing and phosphorus gives processed oil with abrasion resistance, and may endanger or otherwise reduce the effectiveness of pollution control device.
For many years, zinc dialkyl dithiophosphate (" Zn DDPs ") uses in lubricating oil.ZnDDPs has good abrasion resistance equally and has tested by cam wear, for example Seq IVA and TU3 wear testing.Many patents have been delivered preparation and the use of Zn DDPs, comprise United States Patent (USP) 4,904,401; 4,957,649; 6,114,288, all these quotes in full to do reference at this.
The anti-wear agent of sulfur-bearing is well-known equally, comprises the many sulphur of dialkyl; Olefine sulfide; Natural and synthetic sulfide aliphatic acid ester; Three thioketones (trithione); Sulfuration thienyl derivative; Sulfuration terpene (terpene); Sulfuration polyenoid (sulfurized polyenes); Sulfuration Diels-Alder adducts, or the like.Especially, concrete example comprises sulfide isobutene, sulfuration diisobutylene, sulfuration triisobutene, the many sulphur of dicyclohexyl, the many sulphur of hexichol, the many sulphur of dibenzyl, the many sulphur of dinonyl, and the mixture of the many sulphur of di-t-butyl, for example mixture of di-t-butyl trithio, di-t-butyl four sulphur and di-t-butyl five sulphur.In above-mentioned substance, olefine sulfide is used for many application.The preparation method of olefine sulfide is disclosed in United States Patent (USP) 2,995,569; 3,673,090; 3,703,504; 3,703,505; In 3,796,661 and 3,873,454.Also usefully be disclosed in United States Patent (USP) 4,654, the derivative of the olefine sulfide in 156.Other sulfur-bearing wear preventive additive is disclosed in United States Patent (USP) 4,857,214; In 5,242,613 and 6,096,691.
Need a kind of slip additive, it provides outstanding abrasion resistance and has mated more with the pollution control device that is used for automobile and diesel engine.
Summary of the invention
According to preamble, disclosed exemplary embodiment provides lubricated surface in the literary composition, is used to reduce the method for wearing and tearing between the moving-member, and lubricant (lubricant) and contain the slip additive concentrated solution of the depressant that weares and teares.Lubricated surface comprises the base oil of lubricant viscosity, and the solvable magnesium compound of a certain amount of at least a hydrocarbon, compares the reduction surface abrasion that does not have the lubricant compositions that magnesium compound exists, and it provides the reduction of bigger surface abrasion effectively.Lubricant compositions comprises the phosphorus that is no more than about 0.05wt%, and is substantially free of the calcium sanitising agent.
In an exemplary embodiment, a kind of vehicle with moving-member is provided, wherein said vehicle comprises the lubricant that is used for lubricated moving-member.This lubricant is the oil of lubricant viscosity, wherein has a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided, compare the reduction surface abrasion of the moving-member that does not have the lubricant compositions that magnesium compound exists, it provides the reduction of the surface abrasion of bigger moving-member effectively.Lubricant compositions comprises the phosphorus that is no more than about 0.05wt%, and calcic sanitising agent not substantially.
In another embodiment, (full formulated) lubricant compositions of a kind of full allotment is provided, the base oil component that comprises lubricant viscosity, and a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided, it provides the wearing and tearing greater than the wearing and tearing reduction amount of the lubricant compositions that does not have magnesium compound to reduce effectively.Lubricant compositions comprises the phosphorus that is no more than about 500ppm, and calcic sanitising agent not substantially.
Another one embodiment of the present invention provides a kind of slip additive concentrated solution, is used for providing improved abrasion resistance to lubricant compositions.Described concentrated solution is calcium containing compound not substantially, and has a kind of alkyl carrier fluid, and the solvable magnesium compound of a certain amount of at least a hydrocarbon, and it is enough to provide about magnesium of 120 to about 2000ppm to the lubricant compositions that contains described concentrated solution.
As above sketch, embodiment of the present invention provides a kind of antiwear additive that comprises the solvable magnesium compound of hydrocarbon, it can obviously improve the abrasion resistance of lubricant compositions, therefore can reduce the quantity of p and s antiwear additive under the requirement that guarantees suitable abrasion resistance.Additive can mix with oleaginous fluid, and described fluid is applied to the surface to reduce surface abrasion.In other was used, additive can provide with the form of the lubricant compositions of full allotment.Described additive is intended to satisfy the GF-4 standard of the present bus engine oil that proposes and the PC-10 standard of heavy duty diesel engine oil especially.
Composition described in the literary composition and method are particularly useful for reducing the pollution of pollution control device on the Motor vehicles, or alternatively, described composition is applicable to the performance of improving antiwear agents in the lubricant formulations.The further feature of described composition and method and advantage can be proved by the reference following detailed, and following detailed is used for the illustration as the embodiment of the present invention each side, is not to be used to limit the embodiment described in the literary composition.
General description before it should be understood that and detailed description afterwards all are demonstration and explanation, are intended to provide the further explanation of embodiment of the present invention and claim.
Embodiment
In one embodiment, provide a kind of magnesium compound as the component in the lubricating oil composition.Magnesium compound comprises the solvable magnesium compound of hydrocarbon, and it is selected from sulfonic acid magnesium, phenol magnesium, magnesium salicylate and their mixture.
Term " hydrocarbon is solvable " means this compound and suspends on substantially or be dissolved in the hydrocarbon material, as reaction or the complexing by magnesium compound and hydrocarbon material." hydrocarbon " that uses in the literary composition means with various combinations and comprises in numerous compounds of carbon, hydrogen and/or oxygen any.
Term " alkyl " means the group that has the carbon atom that is directly connected to the molecule remainder and have main hydrocarbon feature.The example of alkyl comprises:
(i) hydrocarbon substituent, promptly, aliphatic series (for example, alkyl or (chain) thiazolinyl), alicyclic (for example, cycloalkyl, cycloalkenyl group) substituting group, and aromatics-, the aromatic substituent of aliphatic series-and alicyclic-replace, and ring substituents, wherein ring is (for example, two substituting groups together forms alicyclic group) of finishing by another part of molecule;
(ii) substituted hydrocarbon substituent, promptly, substituting group comprises non-hydrocarbyl group, and described non-hydrocarbyl group does not change main hydrocarbon substituent (for example, halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkane sulfydryl, nitro, nitroso-group and sulphur oxygen base) with regard to this paper describes;
(iii) assorted substituting group, that is, substituting group, it with regard to this paper describes, comprises non-carbon (atom) in ring of being made of carbon atom except that (otherwise) it and chain when having main hydrocarbon feature.Heteroatoms comprises sulphur, oxygen, nitrogen, and has contained substituting group for example pyridyl, furyl, thienyl and imidazolyl.Usually, for per ten carbon atoms in the alkyl, exist to be no more than two, typically to be no more than one non-hydrocarbon substituent; Usually, in alkyl, will there be non-hydrocarbon substituent.
Desirably, magnesium compound is alkalescence or high alkalinity (overbased) magnesium salts, and it contains excessive magnesium cation.Usually, alkalescence or high alkalinity salt can have at the most the metal ratio of (up to) about 40, and more specifically, can have about 2 to about 30 or 40 metal ratio.
The normally used method for preparing alkalescence (or high alkalinity) magnesium salts is included in when surpassing about 50 ℃, adds the mineral oil solution of the excessive metal neutralizing agent of hot acid and stoichiometry (for example metal oxide, oxyhydroxide, carbonate, supercarbonate, sulfide etc.).In addition, can in high alkalinity process (overbasing process), use various promotor to help the introducing of excess metal.These promotor comprise compound such as aldehydes matter, for example the various polycondensation products of phenol, naphthols, alkylphenol, thiophenol, sulphurized alkyl phenols and formaldehyde and aldehydes matter; Alcohols, for example methyl alcohol, 2-propyl alcohol, octanol, cellosolve Trivalin SF, ethylene glycol, stearyl alcohol and hexalin; Amine, for example aniline, phenylenediamine, thiodiphenylamine, Phenyl beta naphthylamine and n-Laurylamine, etc.
Magnesium salts deutero-acidic organic compound can be at least a sulfur acid (sulfur acid), carboxylic acid, phosphoric acid (phosphorus acid) or (benzene) phenol or their mixture.Sulfur acid can be sulfonic acid, thiosulfonic acid,-sulfinic acid, sulfenic acid, partial ester sulfuric acid, sulfurous acid and thiosulfuric acid.Sulfonic acid is suitable especially to be used to prepare the solvable magnesium compound of hydrocarbon.
The sulfonic acid that is used to prepare component (B) comprises those that following formula is represented:
R xT (SO 3H) y(1) and
R 1(SO 3H) y (2)
In these general formulas, R 1Be cycloaliphatic hydrocarbon or hydrocarbon basically (essentially hydrocarbon) group that aliphatic series or aliphatic series replace, it does not have alkynes unsaturation (acetylenic unsaturation) and comprises about at the most 60 carbon atoms.Work as R 1When being aliphatic series, it comprises usually at least about 15 carbon atoms; When being the cycloaliphatic groups of aliphatic series replacement, aliphatic substituting group contains usually altogether at least about 12 carbon atoms.R 1Example be the cycloaliphatic groups that alkyl, (chain) thiazolinyl and alkoxyalkyl and aliphatic series replace, wherein aliphatic substituting group is alkyl, (chain) thiazolinyl, alkoxyl group, alkoxyalkyl, carboxyalkyl or the like.Usually, cyclic aliphatic nuclear (nucleus) is derived from naphthenic hydrocarbon or cycloolefin for example pentamethylene, hexanaphthene, tetrahydrobenzene or cyclopentenes.R 1Particular instance be hexadecyl cyclohexyl, dodecyl cyclohexyl, hexadecyl oxygen base ethyl, octadecylene base and derived from the group of oil, saturated and unsaturation paraffin (paraffin wax) and olefin polymer (it comprises polymerization monoolefine and diolefin, and each olefin monomer unit contains 2-8 the carbon atom of having an appointment).R 1--NH--,--O--or--S--that yet can comprise other substituting group for example phenyl, cycloalkyl, hydroxyl, sulfydryl, halogen, nitro, amino, nitroso-group, lower alkoxy, low-grade alkane hydrosulfuryl, carboxyl, carbalkoxy (carbalkoxy), oxo or sulfo-or for example be interrupted group is not as long as its basic hydrocarbon feature has destroyed.
R in the general formula I is hydrocarbon or hydrocarbyl group basically normally, and it does not have the alkynes unsaturation and comprises about 4 to about 60 aliphatic carbon atoms, for example, and aliphatic hydrocarbon group such as alkyl or (chain) thiazolinyl.But this compound also can comprise substituting group or be interrupted group, and for example those are above-named, and prerequisite is to have kept its basic hydrocarbon feature.Usually, R 1Or any non-carbon atom that exists among the R does not account for more than 10% of its gross weight.
In the superincumbent general formula, T is a kind of nucleolus, and it can be derived from aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or is derived from heterogeneous ring compound for example pyridine, indoles or isoindole.Usually, T is a kind of aromatic hydrocarbon nuclear, especially benzene or naphthalene nuclear.
More than subscript x in various be 1 at least, 1-3 normally.The mean value of subscript r and y is the about 1-2 of per molecule, normally 1.
Usually, sulfonic acid is an alkarylsulphonic acid of mahogany acid or synthetic preparation.In mahogany acid, the most useful product is those by the sulfonation of suitable petroleum fractions, the product removing acid sludge and purify and prepare subsequently.Synthetic an alkarylsulphonic acid is usually by alkylated benzenes, for example benzene and polymkeric substance for example the Friedel-Crafts reaction product of tetrapropylene (tetrapropylene) prepare.Be the example that is used to prepare the sulfonic acid of the solvable magnesium compound of hydrocarbon described in the literary composition below.These sulfonic acid comprise, but be not limited to, mahogany acid (mahoganysulfonic acid), bright stock sulfonic acid (bright stock sulfonic acid), vaseline sulfonic acid (petrolatum sulfonicacid), the naphthene sulfonic acid that single wax (monowax) and many wax (polywax) replace, the hexadecyl chlorobenzenesulfonic acid, the hexadecyl sulfocarbolic acid, hexadecyl phenol disulfide sulfonic acid (cetylphenol disulfide sulfonic acid), n-Hexadecane oxygen Ji Xinji (cetoxycapryl) Phenylsulfonic acid, double hexadecyl thianthrene sulfonic acid, the dilauryl beta-naphtholsulfonic acid, dioctyl (capryl) nitro-naphthalene-monosulfonic acid, saturated paraffin sulfonic acid, unsaturation paraffin sulfonic acid, the paraffin sulfonic acid that hydroxyl replaces, four-pib sulfonic acid, four-amylene sulfonic acid, chloro paraffin sulfonic acid, the paraffin sulfonic acid that nitroso-group replaces, petronaphthalene sulfonic acid, hexadecyl cyclopentyl sulfonic acid, dodecyl cyclohexyl sulfonic acid, the cyclohexyl sulfonic acid that single wax or many wax replace, Witco 1298 Soft Acid, " alkylide dimer (dimmer alkylate) " sulfonic acid, or the like.
Wherein alkyl comprises the Phenylsulfonic acid of the alkyl replacement of at least 8 carbon atoms, comprises dodecylbenzene " end (bottoms) " sulfonic acid, is useful especially.The latter be by with tetrapropylene or tri-isobutylene alkylation on phenyl ring, to introduce 1,2,3 or higly branched chain C more 12The acid of substituent benzenesulfonamide derivative.At the bottom of the dodecylbenzene, mainly the mixture of list or two dodecylbenzenes can obtain as byproduct from the household detergent manufacturing.The analogous products that obtain at the bottom of the alkylation that forms during linear alkyl benzene sulphonic acid (LAS, the linear alkyl sulfonate) preparation also can be used to prepare the sulfonate described in the literary composition (sulfonate).
Suitably, aromatics list and polycarboxylic acid that the carboxylic acid that can prepare the solvable magnesium compound of hydrocarbon comprises aliphatic series, cyclic aliphatic and do not have the alkynes unsaturation to exist, comprise cyclohexylenedinitrilotetraacetic acid of chaulmoogric acid, alkyl or (chain) alkenyl substituted of naphthenic acid (naphthenic acid), alkyl or (chain) alkenyl substituted and the aromatic carboxylic acid of alkyl or (chain) alkenyl substituted.Common aliphatic acid contains has an appointment 8 to about 50, and preferred about 12 to about 25 carbon atoms.Cyclic aliphatic and aliphatic carboxylic acid are especially suitable, and they can be saturated or unsaturated.Concrete example comprises 2 ethyl hexanoic acid, linolenic acid (linolenic acid), the toxilic acid that tetrapropylene replaces, docosoic acid (behenic acid), Unimac 5680, n-nonanoic acid (pelargonic acid), capric acid (capric acid), Zoomeric acid (palmitoleic acid), linolic acid (linoleic acid), lauric acid, oleic acid (oleic acid), ricinolic acid (ricinoleic acid), undecanoic acid (undecyclic acid), the dioctyl Cyclopentane carboxylic acid, tetradecanoic acid (myristic acid), dilauryl naphthane carboxylic acid (dilauryldecahydronaphthalenecarboxylic aicd), octadecyl-octahydro indene carboxylic acid (stearyl-octahydroindenecarboxylic acid), palmitinic acid (palmitic acid), alkyl and (chain) alkenyl succinic acid, the acid that vaseline or chloroflo oxidation form, and two or more carboxylic acids such as tall oil acid (tall oilacid), the commercially available mixture that gets of sylvic acid (rosin acid) etc.
The solvable magnesium compound of hydrocarbon also can prepare from phenols; That is, has the compound that is directly connected to the hydroxyl on the aromatic ring.The term that uses in the literary composition " phenols " comprises having a compound that is connected to the hydroxyl on the aromatic ring, for example pyrocatechol (catechol), Resorcinol (resorcinol) and the Resorcinol (hydroquinone) of surpassing.Also comprise alkylphenol for example cresols (cresol) and diethylstilbestrol (ethylphenol), and (chain) thiazolinyl phenol.What especially be suitable for is to have the phenol that at least one contains the alkyl substituent of have an appointment 3 to 100 and preferred about 6 to 50 carbon atoms, for example heptan phenol, octyl phenol, 4-dodecylphenol, tetrapropylene alkylating phenol (tetrapropene-alkylated phenol), octadecyl phenol and polybutylene-based phenol (polybuenylphenol).Have the phenol that surpasses an alkyl substituent and can use equally, but monoalkyl phenol is more suitable, because they are easy to obtain and prepare simple.
The polycondensation product of above-mentioned phenol and at least a rudimentary aldehydes or ketones also is useful, and term " rudimentary " expression aldehyde and ketone have and is no more than 7 carbon atoms.Suitable aldehyde comprises formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral and phenyl aldehyde.The reactant of producing aldehyde is suitable equally, for example the methanol solution (methyl formcel) and the paraldehyde (paraldehyde) of paraformaldehyde, trioxane, methylol (methylol), formaldehyde.
The amount of the solvable magnesium compound of hydrocarbon also can change in the lubricant of demonstration embodiment, and the useful amount in the lubricating oil composition of any specific can be determined easily by those skilled in the art.The amount of the magnesium compound that contains in the lubricant described herein can about 0.15 weight % to about 2.0 weight % or higher between change.The amount of the magnesium compound that comprises in the described oil compositions is the amount that is enough to provide the resistance to abrasion of expectation.
In the preparation of lubricating oil preparation, usually additive is introduced in the hydrocarbon ils for example mineral lubricating oils, or other suitable solvent with the form of 1 to 99wt% activeconstituents concentrated solution.Usually forming final lubricant, for example in the crankcase engine oil, can add these concentrated solutions with the additive-package of lubricating oil/1 weight part of 0.05 to 10 weight part.Certainly, the purpose of concentrated solution is for the processing that makes various materials becomes not too difficult and thorny, and promotes dissolving and dispersion in final mixture.
The lubricant compositions of the solvable magnesium compound preparation of above-mentioned hydrocarbon is used in the various application.For compression ignition engine and spark ignition engine, be desirable to lubricant compositions and meet or surpass GF-4 or the API-CI-4 standard of being announced.Lubricant compositions according to aforementioned GF-4 or API-CI-4 standard comprises base oil and oil additive bag, thereby the lubricant of full allotment is provided.The base oil that is used for lubricant of the present invention is a lubrication viscosity oil, and it is selected from natural lubricating oil, ucon oil and their mixture.This base oil comprises that common usefulness acts on those of crankcase oil of the oil engine of spark ignition and ignition (as automobile and truck engine, boats and ships and rail diesel engine etc.).
Natural oil comprises animal oil and vegetables oil (for example, Viscotrol C, lard), hydrogenation, solvent treatment or the acid-treated mineral lubricating oils of liquid petroleum (liquidpetroleum oils) and alkane, cycloalkanes and mixing alkane-cycloalkanes type.Oil derived from the lubricant viscosity of coal and shale also is useful base oil.Ucon oil used in the exemplary embodiment of the present invention comprises one of numerous normally used synthetic hydrocarbon oils, it includes but not limited to, poly-alpha-olefin, alkylaromatic (alkylated aromatics), alkylene oxide polymer, interpolymer (interpolymers), multipolymer (copolymers) and its derivative, the terminal hydroxyl ester by modifications such as esterification, etherificate, dicarboxylic acid and silicon-based oil here.
The lubricant of full allotment comprises additive-package usually, is called dispersant or DI bag in the literary composition, and it will provide desired characteristic in the preparation.For example, suitable DI wraps in United States Patent (USP) 5,204, is described in 012 and 6,034,040.Wherein, included additive types can be dispersion agent, friction modifiers, sealing toughener (seal swell agents), antioxidant, suds suppressor, smoothing agent (lubricityagents), rust-preventive agent (rust inhibitor), inhibiter (corrosion inhibitor), emulsion splitter, viscosity index improver in the additive-package, or the like.In these components some are well known to a person skilled in the art, and use with additive described in the literary composition and composition with convention amount usually.
Dispersion agent
Another component of lubricant compositions is the dispersion agent of at least a polyalkylene compound deriving.The number-average molecular weight of polyalkylene compound can be about 400 to about 5000 or bigger.Spendable dispersion agent includes but not limited to, amine, alcohol, acid amides or ester polarity part, and it often is connected on the main polymer chain by bridged group.Dispersion agent for example can be selected from United States Patent (USP) 3,697, and 574 and 3,736, the Mannich described in 357 (Mannich) dispersion agent; United States Patent (USP) 4,234,435 and 4,636, the ashless succinimide dispersants described in 322; United States Patent (USP) 3,219,666,3,565,804 and 5,633, the amine dispersion agent described in 326; United States Patent (USP) 5,936,041,5,643,859 and 5,627, the Koch dispersion agent described in 259, and United States Patent (USP) 5,851,965; 5,853,434 and 5,792, the polyalkylene succinimide dispersants described in 729.
Specially suitable dispersion agent is the polyalkylene succinimide dispersants of polyisobutene (PIB) compound deriving.Dispersion agent can be the number-average molecular weight scope between about 800 to about 3000 and the mixture of the dispersion agent of reactive PIB content between about 50 to about 60%.The total amount of dispersion agent can be the about 10wt% of about 1-of lubricant compositions gross weight in the lubricant compositions.
Friction modifiers
Can comprise oily molten friction modifiers in the lubricating oil composition described in the literary composition.That this friction modifiers can be selected from is nitrogenous, do not have nitrogen and/or do not have the amine friction modifiers.Usually, the consumption of friction modifiers can be lubricating oil composition about 0.02 to 2.0wt%.Preferably, use 0.05-1.0wt%, more preferably, the friction modifiers of 0.1-0.5wt%.
The example of operable this nitrogenous friction modifiers includes but not limited to, tetrahydroglyoxaline, acid amides, amine, succinimide, oxyalkylated amine, oxyalkylated ether amine, amine oxide, amidoamines (amidoamine), nitrile, trimethyl-glycine (betaine), quaternary amine, imide, amine salt, aminoguanidine (guanadine), alkanolamide, or the like.
This friction modifiers can comprise alkyl, and it can be selected from straight chain, side chain or aromatic hydrocarbyl or their mixture, and can be saturated or unsaturated.Alkyl mainly is made up of carbon and hydrogen, but can contain one or more heteroatomss for example sulphur or oxygen.From 12 to 25 carbon atoms of suitable alkyl scope and can be saturated or unsaturated.Those straight-chain alkyls more preferably.
Exemplary friction modifiers comprises the acid amides of polyamines.This compound can have straight-chain alkyl, saturated or unsaturated or their mixture, and contain and be no more than about 12 to about 25 carbon atoms.
Other exemplary friction modifiers comprises oxyalkylated amine and oxyalkylated ether amine, and most preferably oxyalkylated amine contains 2 moles of alkylene oxides/1 mole of nitrogen of having an appointment.This compound can have straight-chain alkyl, saturated or unsaturated or their mixture.They contain and are no more than about 12 to about 25 carbon atoms, and can contain one or more heteroatoms in hydrocarbon chain.The ether amine of the amine of ethoxylation and ethoxylation is specially suitable nitrogenous friction modifiers.Amine and acid amides can itself be used or with boron compound for example the form of the adducts of boron oxide, halogenation boron, metaborate (metaborate), boric acid or single, double or trialkylboron acid esters or reaction product use.
Can comprise the organic compound that following formula is represented as the ashless organic polysulfide of friction modifiers, for example fatty or the polyolefinic sulfide of oil wherein exists the sulphur atom group with two or more adjacency or sulphur atom of combining in the molecular structure.
R 2-S x-R 3
Figure S2007103035784D00091
OHC-R 4-S-S-R 5-CHO
R 2-C(O)O-R 4-S-S-R 5-OC(O)-R 3
R 2-OC(S)-S-S-C(S)O-R 3
Figure S2007103035784D00093
Figure S2007103035784D00094
In the following formula, R 2And R 3Represent straight chain, side chain, alicyclic or aromatic hydrocarbyl independently, wherein optionally comprise straight chain, side chain, alicyclic unit and aromatic units in any combination way.Can contain unsaturated key, but saturated hydrocarbyl is expected.Among them, expectation is alkyl, aryl, alkaryl, phenmethyl and alkylbenzene methyl especially.
R 3And R 4Represent the alkyl with two binding sites of straight chain, side chain, alicyclic or aromatics independently, and wherein optionally comprise straight chain, side chain, alicyclic unit and aromatic units in any combination way.Can contain unsaturated key, but the expectation of saturated hydrocarbyl.Among them, expectation is alkylidene group especially.
R 6And R 7Represent the straight or branched alkyl independently.Subscript " x " and " y " represent 2 or bigger integer independently.
For example, what can mention specifically, is sulfuration whale oil (sperm oil), sulfuration firpene oil (pinene oil), sulfuration soya-bean oil (soybean oil), sulfurized polyolefin, dialkyl disulphides, dialkyl polysulfide, dibenzyl disulfide, 2-tertiary butyl disulphide, polyolefine polysulfide, thiadiazole (thiadiazole) type compound for example dialkyl group polythioalkane base thiadiazole (bis-alkyl polysulfanyl thiadiazole) and sulfuration phenol.In these compounds, expectation be dialkyl polysulfide, dibenzyl disulfide and thiadiazole type compound.Particularly preferably be dialkyl group polythioalkane base thiadiazole.
For slip additive, can use metallic compound as having the calcium phenylate of polysulfide key.But because this compound has big frictional coefficient, the use of this compound may be always unsuitable.On the contrary, above-mentioned organic polysulfide can be metal-free ashless compound, and is keeping demonstrating excellent performance aspect the low-friction coefficient for a long time with other friction modifiers coupling the time.
When with sulphur (S), calculate with respect to the lubricant compositions total amount, the addition of above-mentioned ashless organic polysulfide (hereinafter abbreviating " polysulfide " as) is generally 0.1-0.3wt% between 0.01 to 0.4wt%, desirably be 0.2-0.3wt%.If addition is less than 0.01wt%, just be difficult to reach desired effects, yet if it surpasses 0.4wt%, the danger that just has corrosive wear to increase.
Can be used for organic, ashless (the no metal) of lubricating oil composition disclosed herein, no nitrogen friction modifiers is normally known, comprises the ester that carboxylic acid and acid anhydride and alkanol or diol reaction form, wherein said lipid acid is specially suitable carboxylic acid.Other useful friction modifiers generally includes covalently bound terminal polar group (for example carboxyl or hydroxyl) to oleophylic (oleophilic) hydrocarbon chain.The ester of carboxylic acid and acid anhydride and alkanol is described in United States Patent (USP) 4,702, in 850.The friction modifiers that particularly preferred and magnesium compound is united use is an ester, for example single oleic acid glyceryl ester (GMO, glycerol monooleate).
Above-mentioned friction modifiers is included in the lubricant compositions disclosed herein with significant quantity and makes when combining with magnesium compound, composition can pass through high-frequency reciprocating testing table wear testing (HFRR, high frequency reciprocating rig wear test) reliably.For example, contain the friction modifiers that can add q.s in the magnesium lubricating oil composition, thereby obtain to be less than the average HFRR wearing and tearing scar (wear scar) of about 100 square microns.Usually, for desired effects is provided, based on the gross weight of lubricating oil composition, the amount of the friction modifiers of interpolation can be that about 0.25wt% is to about 2.0wt% (AI).
Antiwear agents
Dialkyl phosphorodithioic acid metal-salt antiwear agents can be united with magnesium compound and added in the described lubricating oil composition of exemplary embodiment.This antiwear agents comprises dialkyl phosphorodithioic acid metal-salt, and wherein metal can be alkali or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc.Zinc salt is most commonly used in the lubricating oil.
Dialkyl phosphorodithioic acid metal-salt can comprise at first forming dialkyl phosphorodithioic acid (DDPA) according to known technology preparation, plants alcohol or phenol and P by one or more usually 2S 5Reaction and realizing is used in the metallic compound and formed DDPA then.For example, phosphorodithioic acid can be made by the mixture reaction of primary alconol and secondary alcohol.Alternatively, multiple phosphorodithioic acid can be produced, and wherein the alkyl on a kind of is secondary fully (the entirely secondary) that belongs in nature, and the alkyl on other is being uncle (the entirely primary) that belong to fully in nature.In order to make metal-salt, can use any alkalescence or neutral metal compound, still the most frequently used is oxide compound, oxyhydroxide and carbonate.Because use excessive alkaline metal cpds in the neutralization reaction, the additive that commerce can get often contains excessive metal.
Normally used dialkyl zinc dithiophosphate (ZDDP) is the oily dissolved salt of dialkyl phosphorodithioic acid, and can be expressed from the next:
Figure S2007103035784D00111
R wherein 8And R 9Can be identical or different alkyl, contain 1 to 18, common 2 to 12 carbon atoms, and comprise group for example alkyl, (chain) thiazolinyl, aryl, aralkyl, alkaryl and cycloaliphatic radical.Preferred R 8And R 9It is the alkyl of 2 to 8 carbon atoms.Therefore, group can be, for example, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, amyl group, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butyl phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.In order to obtain oil soluble, (that is R, of the total number of carbon atoms in the phosphorodithioic acid 8And R 9) will normally about 5 or more.Therefore, the dialkyl zinc dithiophosphate can comprise zinc dialkyl dithiophosphate.
In order to limit quantity that ZDDP introduces phosphorus in the lubricating oil composition to being no more than 0.1wt% (1000ppm) phosphorus, ideally, the amount that adds the ZDDP in the lubricating oil composition should be no more than about 1.0wt%, based on the total amount of lubricating oil composition.With contain magnesium sanitising agent bonded words, be no more than about 500ppm ideally from the quantity of the phosphorus of the ZDDP in the lubricating oil, more desirably, about 250 to about 500ppm phosphorus, so that the wearing and tearing scar result of the best is provided.
Other additive, for example described below, also may reside in the described herein lubricating oil composition.
Viscosity modifier
The function of viscosity modifier (VM) is to give high temperature and cryogenic operability to lubricant.The VM that uses can be unifunctional, and is perhaps multi-functional.
The multi-functional viscosity modifier that has the dispersion agent function equally also is known.Suitable viscosity modifier is a polyisobutene, the multipolymer of ethene and propylene and high alpha-olefin, polymethacrylate (polymethacrylates), poly-alkylmethacrylate (polyalkylmethacrylates), alkylmethacrylate polymer, the multipolymer of unsaturation dicarboxylic acid and vinyl compound, the interpolymer of vinylbenzene and acrylate, and styrene/isoprene, the partial hydrogenation multipolymer of phenylethylene/butadiene and isoprene/butadiene, and the partial hydrogenation homopolymer of divinyl and isoprene and isoprene/Vinylstyrene (partiallyhydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene).
Oxidation retarder
Oxidation retarder or antioxidant have reduced the rotten during use trend of base stock (base stock), and this going bad may be by mud (sludge) shape or lacquer (varnish) the shape throw out and the viscosity increase proof of oxidation products such as metallic surface.This oxidation retarder comprises hindered phenol, has C 5-C 12The alkaline earth salt of the alkylphenol monothioester of alkyl group side chain, sulfuration nonylphenol calcium, the molten phenates of no putty oil and sulfuration phenates, phosphoric acid sulfuration (phosphosulfurized) or sulfuration (sulfurized) hydrocarbon, phosphide (phosphorus esters), metal thiocarbamate and United States Patent (USP) 4, the molten copper compound of disclosed oil in 867,890.
Rust-preventive agent
Can use rust-preventive agent, it is selected from nonionic polyoxyalkylene polyols and its ester, polyoxyalkylene phenol, and the negatively charged ion alkylsulphonic acid.
Inhibiter
Can use cupric and plumbous inhibiter, still, not need usually for the preparation of disclosed embodiment.Common this compound is the thiadiazole polysulfide that contains 5 to 50 carbon atoms, their derivative and its polymkeric substance.Be typically: 1,3,4 thiadiazole derivatives, for example United States Patent (USP) 2,719, and 125; Those disclosed in 2,719,126 and 3,087,932; Other materials similar is described in United States Patent (USP) 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; In 4,188,299 and 4,193,882.Other additive is the sulfo-and the polythio sulfinyl amine (sulfenamide) of thiadiazole, and for example british patent specification 1,560, those disclosed in 830.Benzotriazole derivatives also belongs to this additive.When comprising these compounds in lubricating composition, their content is no more than the active ingredient of 0.2wt% usually.
Emulsion splitter
Can use a spot of breakdown of emulsion component.The breakdown of emulsion component that is suitable for is described among the EP 330,522.The reaction of the adducts that the breakdown of emulsion component can obtain by the reaction of alkylene oxide and di-epoxide and polyvalent alcohol makes.The breakdown of emulsion components contents of using can be no more than 0.1 quality % active ingredient.0.001-0.05 the processing rate of the active ingredient of quality % (treat rate) is suitable.
Pour point reducer
Pour point reducer is called the mobile improving agent of lubricating oil again, reduces the minimum temperature that fluid will flow or can be come down in torrents.These additives are known.These representatives that improve the additive of fluid low-temperature fluidity are C 8-C 18Dialkyl group fumaric acid esters/vinyl acetate copolymer, poly-alkylmethacrylate etc.
Antifoams
Can provide foam control by chemical compound lot, described compound comprises polysiloxane type antifoams, for example, and silicone oil or polydimethylsiloxane.
Some above-mentioned additives can provide multiple effect; Therefore for example, single additive can be used as dispersion agent-oxidation retarder.This method is to further describe known the needs.
Independent additive can add in the base stock in any suitable method.Therefore, each component can directly be added in base stock or the base oil blend by it being dispersed or dissolved in base stock or base oil blend under the expectation concentration level.Can under room temperature or high temperature, carry out this blend.
The magnesium compound additive can directly add in the lubricating oil composition.But, in one embodiment, use a kind of basic inertia, be generally the organic thinner of liquid, for example mineral oil, synthetic oil, petroleum naphtha, alkylation (for example, C 10-C 13Alkyl) benzene, toluene or dimethylbenzene dilute them, form a kind of additive concentrating liquid.The amount of the magnesium compound that common these concentrated solutions contain is the about 100wt% of about 1wt%-, is the about 90wt% of about 10wt%-in one embodiment.
The base oil that is applicable to the described composition of preparation, additive and concentrated solution herein can be selected from any in synthetic or natural oil or their mixture.Synthetic base oil comprises alkyl ester, the poly-alpha olefins of dicarboxylic acid, polyoxyethylene glycol and alcohol, comprises the organic ester of polybutene, alkylbenzene, phosphoric acid, and silicone oil.Natural foundation oil comprises mineral generation, and it can change with regard to its natural origin (crude source) widely, and for example, they are alkane, naphthenic or mix alkane-naphthenic.Usually, basic oil viscosity at 100 ℃, is the about 15cSt of about 2.5-, ideally, and the about 11cSt of about 2.5-.
Therefore, operable used base oil can be selected from any in the I-V family base oil of American Petroleum Institute (API) (API) base oil interchangeability criterion (American Petroleum Institute (API) Base Oil Interchaneability Guidelines) regulation.Described base oil family is as follows:
Figure S2007103035784D00141
1The I-III of family is the basic oil plant of mineral oil
Used additive can be sneaked in the base oil individually or in the mode of various sub-portfolios in the described herein composition of preparation.But, preferably use additive concentrating liquid (that is, additive adds thinner, for example hydrocarbon solvent) to sneak into all components simultaneously.The use of additive concentrating liquid has utilized, when with the additive concentrating liquid form time, and the intermiscibility that combination provided of component.Equally, the use of concentrated solution has reduced the blend time, has reduced the possibility of blend error.
Embodiment provides a kind of lubricating oil that is used for oil engine, and wherein the concentration of the solvable magnesium compound of hydrocarbon of Jia Ruing is lower, and the element magnesium meter according in oil provides about 120-the magnesium of about 2000ppm.In one embodiment, magnesium compound exists with competent amount in lubricant compositions, thereby about 250-is provided the magnesium of about 1500ppm, and in further embodiment, the magnesium metal of the about 1000ppm of about 450-.
Embodiment given below is all respects that embodiment is described for example, in any form embodiment is not limited.
Embodiment
Prepare the lubricant compositions of 12 kinds of full allotments, and used the polishing machine of high-frequency reciprocating testing table (HFRR) comparative composition.In the HFRR test, steel ball oscillates with respect to the steel disk that is immersed in the oil, speed 20Hz, and amplitude is 1mm.Between ball and dish, applied 7 newton (～1.0GPa) load, and test was carried out a hour at 120 ℃.After the test, use available from Precision Devices, Inc., Middleton, the MICRO ANALYZER 2000 of Wisconsin measures the marks on surface of the wearing and tearing scar on the HFRR dish.The cross-sectional area of wearing and tearing scar can be reported by analyzer under 700 gram loads and 120 ℃ of conditions.Also listed the standard deviation of wearing and tearing scar observed value in the table.Each lubricant compositions contains conventional DI bag, and it provides the lubricant compositions of about 9wt%.The sanitising agent, dispersion agent, antiwear additive, friction modifiers, antifoams and the antioxidant that comprise convention amount in the DI bag.Preparation also comprises a small amount of or does not have ZDDP and 0.35 or do not have single oleic acid glyceryl ester friction modifiers.Sample 1-4 does not contain ZDDP, and contains calcium or magnesium sanitising agent.Sample 5-8 contains the ZDDP of 0.05wt%, and contains calcium or magnesium sanitising agent.Sample 9-12 contains the ZDDP of 0.025wt%, and contains calcium or magnesium sanitising agent.Following table has provided preparation and result:
Table
Composition Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6
ZnDDP?wt％ 0 0 0 0 0.05 0.05
The magnesium sanitising agent Do not have Have Do not have Have Do not have Have
The calcium sanitising agent Have Do not have Have Do not have Have Do not have
Single oleic acid glyceryl ester wt% 0 0 0.35 0.35 0 0
Physical data
Wearing and tearing scar (square micron) on the HFRR 22 32 154 218 103 47
The standard deviation of wearing and tearing scar 2 0 2 2 8 12
Composition Sample 7 Sample 8 Sample 9 Sample 10 Sample 11 Sample 12
ZnDDP?wt％ 0.05 0.05 0.025 0.025 0.025 0.025
The magnesium sanitising agent Do not have Have Do not have Have Do not have Have
The calcium sanitising agent Have Do not have Have Do not have Have Do not have
Single oleic acid glyceryl ester wt% 0.35 0.35 0 0 0.35 0.35
Physical data
Wearing and tearing scar (square micron) on the HFRR 177 136 30 28 103 55
The standard deviation of wearing and tearing scar 23 15 8 1 11 13
Shown in above-mentioned result, compare sample 5,7,9 and 11 with calcic sanitising agent and ZDDP preparation, produced lower wearing and tearing scar with the sample 6,8,10 and 12 that contains magnesium sanitising agent and ZDDP preparation.Compare the lubricant (sample 5-8) that contains 0.05wt%ZDDP, the lubricant (sample 9-12) that contains 0.025wt%ZDDP has produced minimum wearing and tearing scar.
More specifically, sample 1 and 3 is compared sample 2 and 4 and has been produced lower wearing and tearing scar, and this has illustrated that when ZDDP does not exist calcareous sanitising agent is compared magniferous sanitising agent and prevented wearing and tearing better.Compare the wear results of sample 3 and 4 and the result of sample 1 and 2, the wear resistance of calcium and magnesium sanitising agent has been disturbed in the interpolation that the surfactivity friction modifiers has been described.But friction modifiers is that the fuel efficiency performance of raising oil is necessary, and will be generally comprised within the oil of full allotment.
Surprisingly, compare sample 5 and 7, sample 6 and 8 has produced lower wearing and tearing scar respectively, contains the magnesium sanitising agent though exist in sample 6 and 8.Compare sample 5 to 8, the sample 9 to 12 that contains ZDDP has still less produced even lower wearing and tearing scar.In addition, the existence of the single oleic acid glyceryl ester in the sample 12 has prevented wearing and tearing with containing the magnesium sanitising agent, than the sample 11 with the preparation of calcic sanitising agent, better effects if.
Desirably, the magnesium compound that contains the solvable magnesium compound form of hydrocarbon of the about 2000ppm of 120-that has an appointment will make it possible to reduce conventional phosphorus or sulphur antiwear agents, thereby improve the performance of the pollution control equipment on the vehicle, reach similar or better wear resistance or benefit simultaneously.
A great number of U.S. patents has been quoted in many places at this specification sheets.These citing documents are quoted in full in this specification sheets, just list in this article in full as it.
Aforesaid embodiment can allow bigger change in practice.Therefore, these embodiments are not used in and limit particular instance mentioned above.But aforementioned embodiments is in the spirit and scope of the claims that comprise admissible its Equivalent of law.
The patentee is not intended to any disclosed embodiment is dedicated to the public, and may not fall into the situation of the scope of claim with regard to any disclosed variation or change on literal, and they are considered to its part under doctrine of equivalents.
In a word, the present invention is embodied in the following main points:
Put 1 one kinds of lubricated surfaces that comprise lubricant compositions, described lubricant compositions contains the base oil of lubricant viscosity, and the solvable magnesium compound of at least a hydrocarbon of some amount, reduction surface abrasion than the lubricant compositions that does not have magnesium compound, it provides the reduction of bigger surface abrasion effectively, and wherein lubricant compositions comprises the phosphorus that is no more than about 0.05wt%.
Put 2 and will put 1 described lubricated surface, wherein lubricated surface comprises engine drive device (engine drive train).
Put 3 and will put 1 described lubricated surface, wherein lubricated surface comprises the internal surface or the assembly of oil engine.
Put 4 and will put 1 described lubricated surface, wherein lubricated surface comprises the internal surface or the assembly of compression ignition engine.
Put 5 and will put 1 described lubricated surface, wherein magnesium compound comprises sulfonic acid magnesium.
Put 6 and will put 2 described lubricated surfaces, wherein sulfonic acid magnesium comprises the overbased sulfonate (overabased sulfonate) of (TBN) scope between about 300 to about 500 that have total basicnumber.
Put 7 and will put 1 described lubricated surface, wherein in lubricant compositions, the phosphorus content scope from about 250 to about 500ppm.
Put 8 and will put 1 described lubricated surface, wherein lubricant compositions also comprises the friction modifiers of no metal, and it is selected from glycerine ester and amine compound.
Put 9 one kinds and comprise the Motor vehicles that to put 1 described lubricated surface.
Put 10 and will put 1 described lubricated surface, wherein the weight range of the solvable magnesium compound of hydrocarbon in lubricant compositions is from the about 2.0wt% of about 0.15wt%-.
Put 11 1 kinds of vehicles, described vehicle has moving-member and comprises the lubricant that is used for lubricated this moving-member, described lubricant comprises oil and a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided of lubricant viscosity, reduction surface abrasion than the moving-member of the lubricant compositions that does not have magnesium compound, it provides the reduction of the surface abrasion of bigger moving-member effectively, and wherein lubricant compositions comprises the phosphorus that is no more than about 500ppm.
Put 12 and will put 11 described vehicles, wherein magnesium compound comprises sulfonic acid magnesium.
Put 13 and will put 12 described vehicles, wherein sulfonic acid magnesium comprises the overbased sulfonate of (TBN) scope between about 300 to about 500 that have total basicnumber.
Put 14 and will put 11 described vehicles, wherein in lubricant compositions, the phosphorus content scope from about 250 to about 500ppm.
Put 15 and will put 11 described vehicles, wherein lubricant compositions also comprises the friction modifiers of no metal, and it is selected from glycerine ester and amine compound.
Put 16 and will put 11 described vehicles, wherein the weight range of the magnesium compound in lubricant compositions is from the about 2.0wt% of about 0.15wt%-.
Put 17 and will put 11 described vehicles, wherein moving-member comprises large diesel engine.
Put the lubricant compositions of 18 1 kinds of full allotments, the base oil component that comprises lubricant viscosity, and a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided, it provides the wearing and tearing greater than the wearing and tearing reduction amount of the lubricant compositions that does not have magnesium compound to reduce effectively, wherein lubricant compositions comprises the phosphorus that is no more than about 500ppm, and does not have calcium sanitising agent and organic molybdenum.
Put 19 and will put 18 lubricant compositions, wherein lubricant compositions comprises low ash, low-sulfur and the low-phosphorous lubricant composition that is suitable for compression ignition engine.
Put 20 and will put 18 lubricant compositions, wherein magnesium compound comprises the overbased magnesium sulphonates of (TBN) scope between about 300 to about 500 that have total basicnumber.
Put 21 and will put 18 lubricant compositions, wherein in lubricant compositions, the phosphorus content scope from about 250 to about 500ppm.
Put 22 and will put 18 lubricant compositions, also comprise the friction modifiers of no metal, it is selected from glycerine ester and amine compound.
Put 23 and will put 18 lubricant compositions, wherein the weight range of the magnesium compound in lubricant compositions is from the about 2.0wt% of about 0.15wt%-.
Select 24 1 kinds of slip additive concentrated solutions, be used for providing improved abrasion resistance to lubricant compositions, described concentrated solution is calcic and comprise the alkyl carrier fluid not substantially, and the solvable magnesium compound of a certain amount of at least a hydrocarbon, it is enough to provide about 120-the magnesium of about 2000ppm to the lubricant compositions that contains described concentrated solution.
Put 25 and will put 24 additive concentrating liquid, wherein magnesium compound comprises the overbased magnesium sulphonates of (TBN) scope between about 300 to about 500 that have total basicnumber.
Put 26 1 kinds of lubricant compositions that comprise base oil and will put 24 described additive concentrating liquids.
Put 27 1 kinds of methods with the lubricated moving-member of lubricating oil of the abrasion resistance that demonstrates increase, described method comprise use comprise base oil and substantially not the lubricant compositions of calcareous antiwear additive as the lubricating oil of one or more moving-member, described antiwear additive comprises the alkyl carrier fluid, and the solvable magnesium compound of a certain amount of hydrocarbon, it is enough to provide about magnesium of 120 to about 2000ppm in lubricating oil.
Put 28 and will put 27 method, wherein moving-member comprises the moving-member of engine.
Put 29 and will put 28 method, wherein engine is selected from compression ignition engine and spark ignition engine.
Put 30 and will put 28 method, wherein engine comprises the oil engine with crankcase, and wherein lubricating oil comprises the crankcase oil (crankcase oil) that exists in the base chamber.
Put 31 and will put 27 method, wherein lubricating oil comprises the drive unit lubricant (drive train lubricant) that exists in the drive unit (drive train) of the vehicle that contains engine.
Put 32 and will put 27 method, wherein lubricating oil also comprises the friction modifiers of no metal, and it is selected from glycerine ester and amine compound.

Claims (9)

1. lubricated surface that comprises lubricant compositions, described lubricant compositions contains the base oil of lubricant viscosity, be selected from the friction modifiers of no metal of glycerine ester and amine compound and the solvable magnesium compound of at least a hydrocarbon of some amount, reduction surface abrasion than the lubricant compositions that does not have magnesium compound, it provides the reduction of bigger surface abrasion effectively, wherein lubricant compositions comprises the phosphorus that is no more than 0.05wt%, and lubricant compositions does not have calcium and organic molybdenum.
2. the described lubricated surface of claim 1, wherein magnesium compound comprises sulfonic acid magnesium.
3. the described lubricated surface of claim 2, wherein sulfonic acid magnesium comprises having the overbased sulfonate of total basicnumber TBN scope between 300 to 500.
4. the described lubricated surface of claim 1, wherein in lubricant compositions, the phosphorus content scope from 250 to 500ppm.
5. vehicle, described vehicle has moving-member and comprises the lubricant that is used for lubricated this moving-member, described lubricant comprises the oil of lubricant viscosity, be selected from friction modifiers and a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided of the no metal of glycerine ester and amine compound, reduction surface abrasion than the moving-member of the lubricant compositions that does not have magnesium compound, it provides the reduction of the surface abrasion of bigger moving-member effectively, wherein lubricant compositions comprises the phosphorus that is no more than 500ppm, and lubricant compositions does not have calcium and organic molybdenum.
6. the described vehicle of claim 5, wherein the weight range of the magnesium compound in lubricant compositions is from 0.15wt%-2.0wt%.
7. the lubricant compositions of a full allotment, the base oil component that comprises lubricant viscosity, be selected from friction modifiers and a certain amount of antiwear agents that the solvable magnesium compound of a certain amount of at least a hydrocarbon is provided of the no metal of glycerine ester and amine compound, it provides the wearing and tearing greater than the wearing and tearing reduction amount of the lubricant compositions that does not have magnesium compound to reduce effectively, wherein lubricant compositions comprises the phosphorus that is no more than 500ppm, and does not have calcium and organic molybdenum.
8. slip additive concentrated solution, be used for providing improved abrasion resistance to lubricant compositions, described concentrated solution is calcic and do not contain organic molybdenum compound and comprise the alkyl carrier fluid not substantially, be selected from the friction modifiers and the solvable magnesium compound of a certain amount of at least a hydrocarbon of the no metal of glycerine ester and amine compound, it is enough to provide the magnesium of 120-2000ppm to the lubricant compositions that contains described concentrated solution.
9. method with the lubricated moving-member of the lubricating oil of the abrasion resistance that demonstrates increase, described method comprises that use comprises base oil, be selected from the calcic and do not contain the lubricating oil of the lubricant compositions of organic molybdenum compound not substantially of the friction modifiers of no metal of glycerine ester and amine compound and antiwear additive as one or more moving-member, described antiwear additive comprises the alkyl carrier fluid, and the solvable magnesium compound of a certain amount of hydrocarbon, it is enough to provide 120 to 2000ppm magnesium in lubricating oil.
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