CN101084295B - Corrosion inhibition - Google Patents

Corrosion inhibition Download PDF

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Publication number
CN101084295B
CN101084295B CN2005800438087A CN200580043808A CN101084295B CN 101084295 B CN101084295 B CN 101084295B CN 2005800438087 A CN2005800438087 A CN 2005800438087A CN 200580043808 A CN200580043808 A CN 200580043808A CN 101084295 B CN101084295 B CN 101084295B
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lubricating composition
composition according
amine
oil
corrosion inhibitor
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CN101084295A (en
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R·J·麦卡蒂
M·博耶
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Lubrizol Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

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

Abstract

The present invention provides a lubricating composition containing (a) an oil of lubricating viscosity; (b) a corrosion inhibitor; and (c) an antiwear agent comprising at least one of (i) polyhydric alcohol with oxyalkylene groups, (ii) a fatty amine, or (iii) mixtures thereof, wherein the lubricating composition has a total sulphated ash content of less than 0.8 wt %. The invention further provides for the use of the lubricating composition in an internal combustion engine.

Description

The lubricating composition that comprises corrosion inhibitor
Technical field
The present invention relates to corrosion inhibition in the low lubricating composition of sulfated ash total content.The invention still further relates to the purposes of this lubricating composition in explosive motor.
Background of invention
Corrosion inhibitor is known, and has been used in the various lubricant formulations.But corrosion inhibitor rarely has in the lubricant that is used in engine lubricant for example, because known their resistance to wear performances of chemical agent, particularly zinc dialkyl dithiophosphate (ZDDP) of influence unfriendly.Therefore, the disappearance of corrosion inhibitor causes corrosion to increase.On the contrary, the existence of corrosion inhibitor can reduce wear resistance, causes wearing and tearing to increase.
Therefore, advantageously lubricating composition has acceptable corrosion inhibition and wear resistance.The invention provides lubricating composition with acceptable corrosion inhibition and wear resistance.
Lubricating composition provided by the invention comprises:
(a) has the oil of lubricant viscosity;
(b) corrosion inhibitor; With
(c) antiwear agents, it comprises that (i) has the polyvalent alcohol of oxyalkylene group, (ii) aliphatic amide, or (iii) at least a in their mixture,
Wherein the sulfate ash content of this lubricating composition is lower than 0.8wt%.
Detailed Description Of The Invention
The invention provides a kind of lubricating composition as defined above.
In one embodiment, the sulfated ash total content of this lubricating composition is 0.75wt% or lower, 0.7wt% or lower, 0.65wt% or lower, 0.6wt% or lower, or 0.5wt% or lower.The example of the OK range of sulfated ash total content comprises 0.01wt%-0.68wt%, or 0.1wt%-0.63wt%, or 0.2wt%-0.55wt%.
In one embodiment, the phosphorus content of this lubricating composition is 900ppm or lower, 800ppm or lower, or 750ppm or lower.The example of OK range comprises the phosphorus of 50ppm-850ppm, the phosphorus of 100ppm-700ppm, or the phosphorus of 150ppm-500ppm.
In one embodiment, the sulphur content of this lubricating composition is lower than 3000ppm, 2000ppm or lower, 1500ppm or lower, or 1000ppm or lower.The example of OK range comprises 50ppm-1750ppm, or the sulphur of 50ppm-2000ppm, the sulphur of 200ppm-1250ppm or the sulphur of 300ppm-900ppm.
Oil with lubricant viscosity
This lubricating oil composition comprises natural oil or the synthetic oil with lubricant viscosity, is derived from hydrocracking, hydrogenation, hydrorefined oil and unpurified, purified and the oil re-refined and composition thereof.
Natural oil comprises animal oil, vegetables oil, mineral oil and composition thereof.Synthetic oil comprises the liquid ester of hydrocarbon ils, silicon-based oil and phosphoric acid.Synthetic oil can make to the liquid synthesis technique by fischer-tropsch gas, and can be the oil of other gas to liquid.In one embodiment, polymer composition of the present invention is useful in gas in the oil of liquid.Fischer-tropsch hydrocarbon or wax often can hydroisomerizations.
Oil with lubricant viscosity can also be the oil as defined among American Petroleum Institute (API) the Base Oil Interchangeability Guidelines.In one embodiment, the oil with lubricant viscosity comprises API I, II, III, IV, V, VI family or its mixture; In another embodiment, comprise API I, II, III family or its mixture.If have the oil of lubricant viscosity is API II, III, IV, V or VI family oil, and the API I family oil that then can also exist accounts for the 40wt% at the most of lubricating oil, in another embodiment the highest 5wt% at the most.
In one embodiment, amount with oil of lubricant viscosity is the 15wt%-99.9wt% of composition, be the 30wt%-98.9wt% of composition in another embodiment, being the 40wt%-97.9wt% of composition in another embodiment, is the 50wt%-94.5wt% of composition in another embodiment.
Corrosion inhibitor
This lubricating composition comprises corrosion inhibitor.
In one embodiment, corrosion inhibitor is a polyvalent alcohol.In one embodiment, corrosion inhibitor comprises the polyvalent alcohol with oxyalkylene group.In one embodiment, corrosion inhibitor comprises having the unitary polyvalent alcohol of oxyalkylene group monomer.This polyvalent alcohol is aliphatic series, cyclic aliphatic, aromatics or heterocyclic often.This polyvalent alcohol can be selected from the cycloaliphatic alcohol of aliphatic series replacement, the aromatic alcohol that aliphatic series replaces, the heterocyclic alcohol that aliphatic series replaces, the fatty alcohol of cyclic aliphatic replacement, the aromatic alcohol that cyclic aliphatic replaces, the heterocyclic alcohol that cyclic aliphatic replaces, the fatty alcohol of heterocyclic substituted, the cycloaliphatic alcohol of heterocyclic substituted, aromatic alcohol or its mixture of heterocyclic substituted.
This polyvalent alcohol comprises 2-10 usually, 2-6 is individual or 2-4 hydroxyl.This polyvalent alcohol can derived from contain up to 150, up to 100, up to 75 or up to the polyglycol of 50 oxyalkylene groups.The oxyalkylene group can exist with repeating unit, and amount is 2-150 repeating unit or 2-125 repeating unit, a 4-90 repeating unit or 6-45 repeating unit.Each oxyalkylene group can comprise many carbon atoms independently, and 2-8 is individual, 2-5 is individual or 3-4 is individual.In one embodiment, the oxyalkylene group comprises 3 or 4 carbon atoms.
Other example of polyvalent alcohol comprises glycol, for example ethylene glycol, propylene glycol, butyleneglycol, tetramethylolmethane, N.F,USP MANNITOL, Sorbitol Powder, glycerine, two glycerine, triglycerin, four glycerine, tetrahydroxybutane, 2-methylol-2-methyl isophthalic acid, ammediol (trimethylolethane), 2-ethyl-2-(methylol)-1, ammediol (TriMethylolPropane(TMP)), 1,2,4-hexanetriol and composition thereof.
The example of suitable polyvalent alcohol corrosion inhibitor comprises and can be purchased from BASF Or
Figure S05843808720070622D000032
100-20B,
Figure S05843808720070622D000033
100-30B,
Figure S05843808720070622D000034
100-50B,
Figure S05843808720070622D000035
100-85B,
Figure S05843808720070622D000036
100-120B or
Figure S05843808720070622D000037
The polyalkylene glycol of 100-150B (all can be purchased from Dow).
Figure S05843808720070622D000038
Corrosion inhibitor is that pour point is very low, viscosity index is high has an oxyalkylene group, promptly poly--or the polyvalent alcohol of oligomeric-oxyalkylene group.Typically,
Figure S05843808720070622D000039
Corrosion inhibitor comprises the homopolymer or the multipolymer of propylene oxide.
Figure S05843808720070622D0000310
Corrosion inhibitor is described in greater detail among the product manual Form No.118-01453-0702AMS of Dow Chemical Company announcement.This product manual is entitled as " SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications ".
When this corrosion inhibitor comprise have poly--or during the polyvalent alcohol of oligomeric-oxyalkylene group, the free oxygen alkylidene group comprises 50wt% or 65wt% or 80wt% or the group with 3-8 carbon atom of 95wt% at least at least at least at least usually.In some cases, many oxyalkylene groups can be oxyethane, and condition is this corrosion inhibitor oil-soluble.
In one embodiment, this corrosion inhibitor comprises aliphatic amide or acid amides, for example saturated the or undersaturated alkylated amines or derivatives thereof of oil soluble.In one embodiment, this amine is monoamine; In another embodiment, this amine is polyamines.In one embodiment, this aliphatic amide has-NH 2End group.
The example of suitable fat amine comprises reaction product or its mixture of oleyl amine, octylame octanoate or for example oleic lipid acid and polyamines.
In another embodiment, this corrosion inhibitor comprises the condensation product of dodecylene Succinic Acid or acid anhydrides.
In one embodiment, this corrosion inhibitor can be identical with metal deactivators, i.e. benzotriazole, 1,2, the derivative of 4-triazole, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline or 2-alkyl dithio benzothiazole.Benzotriazole cpd can be substituted on one of them position of the 1-on its ring or 2-or 4-or 5-or 6-or 7-position.Alkyl comprises 1-30,1-15 is individual or 1-7 carbon atom.The example of benzotriazole comprises the tolyl benzotriazole.
The amount of this corrosion inhibitor in lubricating composition often is 0.01-10wt%, is 0.01-5wt% in one embodiment, is 0.02-2wt% in another embodiment, is 0.05-1wt% in yet another embodiment.This corrosion inhibitor can be used alone or in combination.
Antiwear agents
This lubricating composition comprises antiwear agents.In one embodiment, antiwear agents is the hydrocarbyl dithiophosphoric acid metal-salt.In one embodiment, alkyl is the alkyl or cycloalkyl with 1-30 carbon atom, has 3-10 carbon atom in another embodiment, has 3-8 carbon atom in yet another embodiment.
Described metal comprises monovalence, divalence or trivalent metal, is divalence in one embodiment, is divalent transition metal in another embodiment.In one embodiment, this metal is a zinc; In another embodiment, this metal is calcium or barium.
The example of hydrocarbyl dithiophosphoric acid metal-salt comprises dialkyl zinc dithiophosphate (often being called ZDDP, ZDP or ZDTP).The example of suitable hydrocarbyl dithiophosphoric acid zn cpds can comprise the reaction product of heptylization or octyl groupization or nonylated phosphorodithioic acid and quadrol, morpholine or its mixture.
In interchangeable embodiment, this antiwear agents is ashless, i.e. this antiwear agents containing metal (with before other component is mixed) not.This metal-free antiwear agents is amine salt often.This ashless antiwear agents often comprises and comprises sulphur, phosphorus, boron or its blended atom.
This amine is primary amine, secondary amine, tertiary amine or its mixture often.It is 2-30 that primary amine and/or secondary amine often comprise at least one carbonatoms, is 8-26 in one embodiment, is 10-20 in another embodiment, is the alkyl of 11-18 in yet another embodiment.
The example that is applicable to the primary amine among the present invention comprises ethamine, propylamine, butylamine, 2 ethyl hexylamine, octylame and n-Laurylamine.Suitable fat primary amine comprises n-octyl amine, n-Decylamine, n-dodecane amine, n-tetradecane amine, n-hexadecane amine, Octadecane amine and oleyl amine.Other aliphatic amide that is suitable for comprises commercially available aliphatic amide, for example
Figure S05843808720070622D000051
Amine (Akzo Chemicals, Chicago, the product of Illinois), for example Armeen C, Armeen O, Armeen OL, ArmeenT, Armeen HT, ArmeenS and Armeen SD, wherein alphabetical label is relevant with fat group, for example cocoyl, oleyl, tallow or stearyl.
The example of suitable secondary amine comprises dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, methyl ethyl-amine, ethyl butyl amine and ethyl amylamine.This secondary amine can be cyclammonium, for example piperidines, piperazine and morpholine.
This amine can also be uncle's aliphatic primary amine.This fat base contains 2-30 carbon atom often, in one embodiment 6-26 carbon atom, the alkyl of 8-24 carbon atom in another embodiment.This primary t-alkyl-amine is monoamine often, for example TERTIARY BUTYL AMINE, uncle's hexylamine, 1-methyl isophthalic acid-aminocyclohexane, tert-Octylamine, uncle's decyl amine, uncle's n-Laurylamine, uncle's tetradecylamine, uncle's cetylamine, uncle's octadecane amine, uncle's tetracosane amine and uncle's octacosane amine.
The mixture of amine also can be with in the present invention.Particularly suitable amine mixt is Primene81R and Primene JMT.Primene 81R and Primene JMT are (by Rohm﹠amp; The Haas production and selling) is C respectively 11-C 14The mixture of primary t-alkyl-amine and C 18-C 22The mixture of primary t-alkyl-amine.
This ashless antiwear agents can also comprise phosphoric acid ester or its salt; Dialkyl dithiophosphate or its salt; Phosphorous acid ester/salt; The ester of phosphoric acid, ether and acid amides or its mixture.
Other is ashless, and the antiwear agents compound comprises the ashless antiwear additive of sulfur-bearing, this reagent is the compound that contains the sulfo-carbamate, for example thiocarbamate, thiocarbamate acid amides, thiocarbamate ether, alkylidene group coupling thiocarbamate and two (S-alkyl dithio carbamyl) disulfide.
This compound that contains dithiocarbamate can be by making dithiocarbamic acid or salt and unsaturated compound reaction.This compound that contains dithiocarbamate also can make by amine, dithiocarbonic anhydride and unsaturated compound are reacted simultaneously.Usually, this is reflected under 25 ℃-125 ℃ the temperature and carries out.United States Patent (USP) 4,758,362 and 4,997,969 have described dithio carbamate compounds and preparation method thereof.
The aliphatic amide that is suitable for comprises commercially available aliphatic amide, for example Amine (AkzoChemicals, Chicago, the product of Illinois), for example Armeen C, the ArmeenO of Akzo, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein alphabetical label is relevant with fat group, for example cocoyl, oleyl, tallow or stearyl.
In replaceable embodiment of the present invention, this ashless antiwear agents can be the monoesters of polyvalent alcohol and aliphatic carboxylic acid (containing the acid of 12-24 carbon atom often).The monoesters of this polyvalent alcohol and aliphatic carboxylic acid often is the form of mixtures with the sunflower wet goods, it can be with the 5-95% of friction modifiers mixture weight, be 10-90% in one embodiment, be 20-85% in another embodiment, be present in this mixture for 20-80% in yet another embodiment.The aliphatic carboxylic acid (particularly monocarboxylic acid) that forms this ester is those acid that comprise 12-24 carbon atom, comprises 14-20 carbon atom in one embodiment.The example of carboxylic acid comprises dodecylic acid, stearic acid, lauric acid, mountain Yu's acid and oleic acid.
Polyvalent alcohol comprises more alcohol of glycol, three pure and mild alcoholic extract hydroxyl group numbers.Polyvalent alcohol comprises ethylene glycol, comprises two, three and TEG; Propylene glycol comprises two, three and four propylene glycol; Glycerol; Butyleneglycol; Hexylene glycol; Sorbitol Powder; Arabitol; N.F,USP MANNITOL; Sucrose; Fructose; Glucose; Cyclohexane diol; Tetrahydroxybutane; And tetramethylolmethane, comprise two and tripentaerythritol.This polyvalent alcohol is Diethylene Glycol, triethylene glycol, glycerol, Sorbitol Powder, tetramethylolmethane or Dipentaerythritol often.
It is believed that the commercially available monoesters that is called " glyceryl monooleate " comprises chemical glyceryl monooleate and 35 ± 5% the glycerol dioleate of 60 ± 5wt% and is lower than 5% trioleate and oleic acid.The amount of above-mentioned monoesters calculates based on actual amount, the correction of existing polyol monoesters in any this mixture.
In one embodiment of the present invention, this antiwear agents is a boric acid ester.This boric acid ester can make by boron compound and at least a compound reaction that is selected from epoxy compounds, halohydrin compound, epihalohydrin compound, alcohol and composition thereof.Usually this alcohol comprises monohydroxy-alcohol, dibasic alcohol, trivalent alcohol or high-grade alcohol more.
The boron compound that is fit to this boric acid ester of preparation comprises that boric acid (comprises metaboric acid HBO 2, ortho-boric acid H 3BO 3With tetraboric acid H 2B 4O 7), boron oxide, boron trioxide and boron alkyl acid esters.This boric acid ester can also be made by halogenation boron.This boric acid ester also comprises at least one alkyl that often has about 30 carbon atoms of about 8-.
The amount of this antiwear agents in this lubricating composition often is 0.01-20wt%, be 0.01-10wt% in one embodiment, being 0.01-5wt% in one embodiment, is 0.02-4wt% in another embodiment, is 0.05-2.5wt% in yet another embodiment.This antiwear agents can be used alone or in combination.
Other performance additive
Composition of the present invention also randomly comprises at least a other performance additive.This other performance additive comprises metal deactivators, purification agent, dispersion agent, viscosity modifier, friction modifiers, dispersant viscosity modifiers, anti-extreme pressure agent, antioxidant, froth suppressor, emulsion splitter, pour point reducer, sealing swelling agent (seal swelling agent) and composition thereof.
The total amount of other performance additive in lubricating composition is 0wt%-25wt%, is 0.01wt%-20wt% in one embodiment, is 0.1wt%-15wt% in another embodiment, is 0.5wt%-10wt% in another embodiment.Though can there be one or more other performance additive, these other performance additive exist with the amount that differs from one another usually.
If the present invention is with the form (it can mix to form final lubricant wholly or in part with other oil) of enriched material, then the amount of every kind of above-mentioned additive and other performance additive is higher about 5 or 10 times than institute specified value.The corresponding minimizing of amount of oil.
Viscosity modifier
In one embodiment, this lubricating composition also comprises viscosity modifier.Viscosity modifier comprises ester or its mixture of styrene butadiene rubbers, ethylene-propylene copolymer, hydrogenated styrene-isoprene copolymer, hydrogenated isoprene polymkeric substance, polyoxyethylene alkylphenyl ethene, polyolefine, poly-alkylmethacrylate and maleic anhydride-styrene copolymers.In one embodiment, polymer viscosifier is poly-(methyl) acrylate.
The weight-average molecular weight of polymer viscosifier (Mw) is at least 10,000, is at least 15,000 in another embodiment, is at least 25,000 in another embodiment, is at least 35,000 in another embodiment.The Mw of polymer viscosifier does not generally have the upper limit, but Mw is less than 2,000,000, in another embodiment less than 500,000, in another embodiment less than 150,000 in one embodiment.The example of Mw OK range comprises being 12 in one embodiment, 000-1, and 000,000, be 20 in another embodiment, 000-300,000, be 30 in another embodiment, 000-75,000.
Antioxidant comprises molybdenum dithiocarbamate, olefine sulfide, hindered phenol, pentanoic; Purification agent comprises neutral or overbasic, the newton-type or the salt non newtonian type, alkalescence of basic metal, alkaline-earth metal and transition metal and one or more substrates.This substrate generally comprises substituted phenol (formation phenates), disulfide-bridged substituted phenol (forming the sulfuration phenates), sulfonic acid (forming sulfonate (TBN is the calcium sulfonate detergents of 300-500 or 330-450 often)), carboxylic acid (formation carboxylate salt), phosphoric acid (formation phosphoric acid salt), list and/or phosphorodithioic acid (formation thiophosphate), saligenol, alkyl salicylate (formation alkylsalicylate), salixarate.Dispersion agent comprises that N-replaces long chain alkenyl succinimides and reprocessed product thereof; Reprocessed dispersion agent comprises those that react by succinyl oxide, nitrile, epoxide, boron compound and phosphorus compound with urea, thiocarbamide, dimercaptothiodiazole, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon replacement.Can also use to comprise benzotriazole, 1,2 metal deactivators of the derivative of 4-triazole, benzoglyoxaline, 2-alkyl dithio benzoglyoxaline or 2-alkyl dithio benzothiazole.
Anti-wear agent comprises organic thioether and polythioether, for example benzyl disulfide, two (benzyl chloride base) disulfide, dibutyl four thioethers, di-t-butyl polythioether, di-t-butyl thioether, sulfuration Diels-Alder adducts or alkyl sulfenyl N ' N-dialkyl dithio amino formate; Anti-extreme pressure (EP) agent comprises chlorinated wax, organic thioether and polythioether, for example benzyl disulfide, two (benzyl chloride base) disulfide, dibutyl four thioethers, sulfurized Witconol 2301, sulfenyl phenolate, sulfuration limonene, sulfuration terpenes and sulfuration Diels-Alder adducts, phosphosulfurized hydrocarbon, thiocarbamate metal-salt, for example dioctyl zinc dithiocarbamate and heptyl dibasic phenol acid barium; Friction modifiers comprises the ester of aliphatic amide, for example boration glyceryl ester, fatty phosphorous acid ester, fatty acid amide, fat epoxide, boration fat epoxide, alkoxylated fats amine, boration alkoxylated fats amine, the metal-salt of lipid acid, fatty tetrahydroglyoxaline, carboxylic acid and the condensation product of polyalkylene polyamine, the amine salt of alkylphosphonic acid carboxylic acid; Dispersant viscosity modifiers (often being called DVM) comprises functionalised polyolefin, for example by the functionalized ethylene-propylene copolymer of the reaction product of maleic anhydride and amine, by amine-functionalized polymethacrylate, or with the esterification styrene-maleic anhydride copolymer of amine reaction.
Can also use other performance additive in the present composition, froth suppressor for example comprises the multipolymer of ethyl propenoate and 2-ethylhexyl acrylate and optional vinyl-acetic ester; Emulsion splitter comprises trialkyl phosphates, polyoxyethylene glycol, polyethylene oxide, poly(propylene oxide) and (epoxy ethane-epoxy propane) polymkeric substance; Pour point reducer comprises ester, polymethacrylate, polyacrylic ester or the polyacrylamide of maleic anhydride-styrene; The sealing swelling agent comprises Exxon Necton-37 TM(FN1380) and Exxon Minerals Seal Oil (FN3200).
Method
Lubricating composition of the present invention can make by comprising the method for mixing following material:
(a) has the oil of lubricant viscosity;
(b) corrosion inhibitor; With
(c) antiwear agents,
Wherein the sulfated ash total content of this lubricating composition is lower than 0.8wt%.
In one embodiment, mixing condition is generally 15 ℃-130 ℃, is 20 ℃-120 ℃ in one embodiment, is 25 ℃-110 ℃ in another embodiment; Time is 30 seconds-48 hours, is 2 minutes-24 hours in one embodiment, is 5 minutes-16 hours in another embodiment; Pressure is 86.4kPa-266kPa (650mmHg-2000mmHg), is 91.8kPa-200kPa (690mmHg-1500mmHg) in one embodiment, is 95.1kPa-133kPa (715mmHg-1000mmHg) in another embodiment.
This method randomly comprises mixes other above-mentioned performance additive.Optional performance additive can be successively, add separately or as enriched material.
Industrial application
Lubricating composition of the present invention is applicable to explosive motor, for example diesel-fueled engine, gasoline engines, natural gas fueled engines or blend gasoline/alcohol engine.In one embodiment, explosive motor is a diesel-fueled engine, is gasoline engines in another embodiment.
In one embodiment, the invention provides a kind of method of lubricated explosive motor, comprise to it lubricant that comprises composition described herein is provided.The use of said composition can be given one or more corrosion inhibition and wear resistances.
In one embodiment, the invention provides the purposes of the polyvalent alcohol of the monomeric unit that comprises oxyalkylene group as the corrosion inhibitor in the lubricating composition with 2-8 carbon atom.
The following examples are used for illustrating the present invention.These embodiment are non-exhaustive, are not intended to limit scope of the present invention.
Embodiment
Oleyl amine corrosion inhibitor in the reference embodiment 1:API III-th family oil
Reference embodiment 1 is mixed into by other additive that 12.1wt% viscosity modifier, 11.4wt% is comprised the significant quantity antiwear agents and comprises that viscosity is 4.3mm 2s -1Nexbase TMOil the oil with lubricant viscosity in and make.The sulfated ash total content of said composition is greater than 1wt%, and phosphorus content is greater than 960ppm, and sulphur content is greater than 3000ppm.
Oleyl amine corrosion inhibitor in the reference embodiment 2:API III-th family oil
Reference embodiment 2 is identical with reference embodiment 1, except additionally mixed 0.5wt% oleyl amine.
Oleyl amine corrosion inhibitor in the reference embodiment 3:API IV family oil
Reference embodiment 3 makes by 0.5wt% oleyl amine and 9wt% viscosity modifier, 14.2wt% being comprised other additive of significant quantity antiwear agents is mixed in the oil with lubricant viscosity that comprises 49.9wt%PAO-6.The sulfated ash total content of said composition is greater than 1wt%, and phosphorus content is greater than 960ppm, and sulphur content is greater than 3000ppm.
Embodiment 1
Embodiment 1 passes through 0.1wt%
Figure S05843808720070622D000111
Corrosion inhibitor is mixed into that to comprise viscosity be 4.3mm 2s -1Nexbase TMOil, 12.1wt% viscosity modifier, 11.4wt% comprise in the lubricating composition of other additive of significant quantity antiwear agents and make.The sulfated ash total content of said composition is less than 0.08wt%, and phosphorus content is less than 960ppm, and sulphur content is less than 3000ppm.
Embodiment 2
Embodiment 2 is identical with embodiment 1, except
Figure S05843808720070622D000112
The amount of corrosion inhibitor is 0.2wt%.
Embodiment 3
Embodiment 3 is identical with embodiment 1, except corrosion inhibitor is the 0.1wt% oleyl amine.
Embodiment 4
Embodiment 4 is identical with embodiment 3, except the amount of oleyl amine is 0.2wt%.
Embodiment 5
Embodiment 5 is identical with embodiment 1, except corrosion inhibitor is 0.1wt%
Figure S05843808720070622D000113
100-120B.
Embodiment 6
Embodiment 6 is identical with embodiment 5, except corrosion inhibitor is 0.2wt%
Figure S05843808720070622D000114
100-120B.
Test 1:PV1401 corrosion test
PV1401 is that the Volkswagen corrosion prevents test.This test request is immersed in steel plate in the oil with lubricant viscosity, drains the oil on the plate subsequently, then plate is suspended in the sealing moist chamber of 50 ℃ and 100% humidity.Then analyze this plate, to determine etching extent by extent of corrosion being categorized as the listed 1-5 of table 1 rank.
Table 1
Extent of corrosion Significance Describe
1 Not corrosion Whole surface does not change
2 Microcorrosion Maximum 5 rust spot/surfaces
3 Mild corrosion 5% surface corrosion at the most
4 The moderate corrosion The 5-20% surface corrosion
5 The severe corrosion 20% above surface corrosion
All data show that the ash oontent of sulphating of the present invention is that 0.8wt% or lower lubricating composition have improved corrosion-inhibiting than the analogous composition of sulfate ash content more than 1wt%, and can influence wear resistance sharply.
In a word, the invention provides and in the engine lubricant of protosulfate ash content, have corrosion inhibition and lubricating composition abrasion resistance.
Above-mentioned every piece of document is incorporated herein by reference.In embodiment, or have in addition outside the explanation, the data of the amount of designated substance, reaction conditions, molecular weight, carbonatoms etc. all are interpreted as and can be limited by " pact " in this specification sheets.Except as otherwise noted, every kind of chemical substance or composition that this paper mentions should be interpreted as the commercial grade material, and it can comprise isomer, by product, derivative and be generally understood as other this material that exists in the commercial grade material.But the amount of every kind of chemical composition does not comprise any solvent or thinning oil, and these may routine be present in the commercial grade material, except as otherwise noted.It is to be understood that the amount of bound as herein described, scope and ratio restriction can independently be made up.Similarly, the scope of each key element of the present invention and amount can be used with the scope or the amount of any other key element.As used herein, all scopes all allow component to comprise the thinning oil that often is used as the normally commercial known quantity of carrying object.
As used herein, term " basically by ... form " allow to comprise not the material of fundamental sum new features that can the described composition of substantial effect.As used herein, any one in the class (or tabulation) can be got rid of in the Accessory Right requirement.
As used herein, term " hydrocarbyl substituent " or " hydrocarbyl group " are by well known to a person skilled in the art that ordinary meaning uses.Particularly, it refers to have the carbon atom that is directly connected on the molecule other parts, and mainly is the group of hydrocarbon feature.The example of alkyl comprises:
Hydrocarbon substituent, promptly aliphatic series (for example alkyl or alkenyl), alicyclic (for example cycloalkyl, cycloalkenyl group) substituting group and aromatics-, the aromatic substituent of aliphatic series-and alicyclic-replace, and wherein the another part by this molecule forms the ring family substituting group of ring (for example two substituting group Cheng Huan) together;
The hydrocarbon substituent that replaces, the substituting group that promptly comprises non-alkyl, these non-alkyl do not change this substituent basic hydrocarbon characteristic (for example halogen (particularly chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulphur oxygen base) in this explanation;
Assorted substituting group promptly has in this explanation in the basic hydrocarbon feature, comprises the substituting group of non-carbon atom in ring that is made of carbon atom or chain.Heteroatoms comprises sulphur, oxygen, nitrogen; The substituting group that comprises pyridyl, furyl, thienyl and imidazolyl.Usually, in this alkyl, be no more than 2, be no more than 1 non-hydrocarbon substituent in one embodiment for per 10 carbon atoms existence; Usually, in this alkyl, there is not non-hydrocarbon substituent.

Claims (12)

1. lubricating composition comprises:
(a) has the oil of lubricant viscosity;
(b) antiwear agents; With
(c) comprise the unitary polyvalent alcohol corrosion inhibitor of oxyalkylene group monomer,
The sulfated ash total content of wherein said lubricating composition is lower than 0.8wt%,
Wherein said corrosion inhibitor comprises the oxyalkylene group, and the 65wt% at least of wherein said oxyalkylene group has 3-8 carbon atom.
2. lubricating composition according to claim 1, wherein said polyvalent alcohol comprise 2-150 oxyalkylene group.
3. lubricating composition according to claim 1 and 2, wherein said oxyalkylene group comprises 3 or 4 carbon atoms.
4. lubricating composition according to claim 1, wherein the sulfated ash total content is 0.7wt% or lower.
5. lubricating composition according to claim 1, the phosphorus content of wherein said composition are 900ppm or lower.
6. lubricating composition according to claim 1, the sulphur content of wherein said composition are 50ppm-2000ppm.
7. lubricating composition according to claim 1, the phosphorus content of wherein said lubricating composition are 100ppm-700ppm, and the sulphur content of described lubricating composition is lower than 3000ppm.
8. lubricating composition according to claim 1, wherein said antiwear agents comprises the hydrocarbyl dithiophosphoric acid metal-salt.
9. lubricating composition according to claim 1 also comprises viscosity modifier.
10. lubricating composition according to claim 9, the Mw of wherein said viscosity modifier are 20,000-300,000.
11. lubricating composition according to claim 1, wherein said corrosion inhibitor exists with the amount of the 0.01-10wt% of described lubricating composition.
12. the method for a lubricated explosive motor, comprise to explosive motor provide comprise according to claim 1-11 in each the lubricant of lubricating composition.
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