CN1958759A - Lubricating oil composition - Google Patents
Lubricating oil composition Download PDFInfo
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- CN1958759A CN1958759A CNA2006101646204A CN200610164620A CN1958759A CN 1958759 A CN1958759 A CN 1958759A CN A2006101646204 A CNA2006101646204 A CN A2006101646204A CN 200610164620 A CN200610164620 A CN 200610164620A CN 1958759 A CN1958759 A CN 1958759A
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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
- C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
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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
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/019—Shear stability
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/069—Linear chain compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- 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
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- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/02—Reduction, e.g. hydrogenation
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- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/09—Treatment with nitrogen containing compounds
Abstract
An internal combustion engine crankcase lubricating oil composition has a phosphorus content of not greater than 0.09 mass % a metal detergent additive system comprising one or more metal salts of organic carboxylic acids, and a viscosity index improver comprising a linear diblock copolymer, one block being derived from a vinyl aromatic hydrocarbon monomer and one block being derived from a diene monomer.
Description
The present invention relates to the lubricating oil composition (or lubricant) of crank case of internal combustion engine, relate more specifically to be applicable to piston engines, in particular for gasoline (spark ignition) and the lubricated composition of diesel oil (ignition) piston engines; And relate to the purposes that additive in this kind composition is used to reduce abrasion.
Crankcase lubricant is to be used for the generally lubricated oil of oil engine, wherein crank case sump generally be positioned at engine crankshaft below, round-robin lubricating oil returns wherein.Well-known is to comprise in the crankcase oil being used for multi-purpose additive.
In order to improve the weather resistance of exhaust gas treatment catalyst, need and/or require to reduce the level of phosphorus in the crankcase lubricant.But the consumption that reduces the phosphorus-containing lubricant additive can increase engine wear.
Also being well known that provides salicylate Base Metal sanitising agent as the additive in the crankcase lubricant.
EP-A-1338643 (' 643) has described and has contained overbased calcium salicylate or magnesium salicylate and have crankcase lubricant less than 50ppm phosphorus.' 643 described to this contain calcium salicylate and not an example of phosphorated lubricant test to measure average cam wear, it is reported that this average abrasion is in ILSAC GF-3 engine limit of measurement scope.
' problem in 643 is that wherein preparaton can show bad cam and tappet rod for valve wearing and tearing.Cam adds that tappet rod for valve wearing and tearing are one of program IIIG test parameters, and it has simulated high-speed cruising in high relatively ambient temperature conditions process for the API classification SM test carried out, ILSAC classification GF-4 test and it in the hot conditions process.
The present invention, and as digital proof shown in the present specification, the preparaton that contains specific viscosity index improver by employing has overcome this problem surprisingly.
First aspect, the invention provides a kind of crank case of internal combustion engine lubricating oil composition, its phosphorus concentration of representing with phosphorus atom that has is no more than 0.09 quality % based on the quality of oil compositions, and described composition comprises following component or by following component is mixed:
(A) oil with lubricant viscosity of main consumption;
(B) as the little metal sanitising agent system of additive, it comprises the metal-salt of one or more organic carboxyl acids; And
(C) comprise the viscosity index improver of linear diblock copolymer, this Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock comprises that at least one mainly can be by the vinyl aromatic monomer block that the block that obtains and at least one mainly can be derived and be obtained by diene monomers of deriving.
Second aspect the invention provides the method for the oil engine of a kind of lubricated ignition or spark ignition, and this method comprises to the lubricating oil composition of engine supply according to first aspect present invention.
The third aspect, the invention provides the purposes as the defined viscosity index improver of first aspect present invention, it is no more than the lubricating oil composition of 0.08 quality % in order to improve the wearing and tearing of lubricated cam of crank case of internal combustion engine and tappet rod for valve by having the phosphorus concentration represented with phosphorus atom based on the quality of lubricating oil composition.
The phosphorus content that can have according to lubricating oil composition of the present invention based on the quality of oil compositions at least greater than 0.005 quality %, preferred at least 0.01 quality %, and be no more than 0.08 quality %.
The total basicnumber (TBN) that can have according to lubricating oil composition of the present invention is 2-9, is preferably 4-8.
Preferably, lubricating oil composition of the present invention is low viscous oil compositions, for example satisfies the multi-grade oil composition of SAE 0W-X or SAE 5W-X feature, wherein the X typical example as in 20,30 and 40 any.
Following word or wording in this specification sheets if you are using, will have the following meaning:
" activeconstituents " or " a.i. " is meant the additive material that is not thinner or solvent;
" comprise " or similar word explanation exists described feature, step or integral body or component, do not exist or add one or more other features, step, integral body, component or their group but do not get rid of; Wording " by ... form " or " substantially by ... form " or similar saying can be included in " comprising " or similarly within the saying, wherein " substantially by ... form " allow to comprise the material that can not influence the composition characteristic that it was applied in itself;
" main consumption " is meant the 50 quality % that surpass composition;
" on a small quantity " is meant the 50 quality % that are lower than composition;
" TBN " is meant the total basicnumber of measuring by ASTM D2896.
In addition, in this manual:
" phosphorus content " measured by ASTM D5185;
" sulfate ash content " is measured by ASTM D874;
" sulphur content " measured by ASTM D2622;
" KV100 " is meant the kinematic viscosity under 100 ℃ that measure by ASTM D445.
What it is also understood that is that preferred plan and the used various components of conventional scheme all can be reacted under preparation, storage or working conditions basically, and the present invention also provides the product that can be got or obtain by any described reaction.
The bound of any amount, scope and the ratio that should be understood that herein in addition to be proposed can make up independently.
,, be described in more detail now following if suitable for feature about each and all aspect of the present invention:
Oil (A) with lubricant viscosity
This is known as base oil or base-material sometimes is the main liquid ingredient that wherein blend has additive and possible other oily compositions.
Base oil can be selected from natural (plant, animal or mineral) and synthetic lubricating oil and their mixture.Its viscosity can for example change in the scope of gas engine oil, mineral lubricating oils, automotive oil and heavy-duty diesel oil to heavy lubricating oil distillating mineral oil from lightweight.Oil viscosity is generally 2-30mm under 100 ℃
2s
-1, 5-20mm especially
2s
-1
Natural lubricating oil comprises paraffinic hydrocarbons, naphthenic hydrocarbon and the blended alkane-cycloalkane mineral lubricating oils that animal oil and vegetables oil (for example Viscotrol C and lard), petroleum liquid lubricating oil and hydrofining solvent are handled.The oil with lubricant viscosity that derives from coal and shale also can be used as base oil.
Ucon oil comprises hydrocarbon ils for example polymeric and poly-mutually alkene (for example polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly-(1-hexene), poly-(1-octene), poly-(1-decene)); Alkylbenzene (for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene); Polyphenol (for example biphenyl, terphenyl, alkylating polyphenol); And alkylating phenyl ether and alkylating diphenyl sulfide and derivative, analogue and homologue.
The ucon oil that other classes are suitable comprises the ester of dicarboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, alkenyl propanedioic acid) and various alcohol (for example butanols, hexanol, dodecanol, 2-Ethylhexyl Alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol).The object lesson of these esters comprises the 2-ethylhexyl diester of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, fumaric acid di-n-hexyl ester, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid two (eicosyl) ester, linoleic acid dimer and by with the complex ester of 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acid reaction formation etc.
The ester that can be used as synthetic oil comprises that also those are by C
5-C
12Monocarboxylic acid and polyvalent alcohol and polyol ethers be the ester that makes of neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol, tripentaerythritol for example.
Not refining, refining and again purified oil can be used for composition of the present invention.Unrefined oil is that those are directly by natural or synthetic source obtains without the oil that is further purified processing.For example, the shale oil that directly obtains by destructive distillation operation, the petroleum oil that directly obtains by distillation or the ester oil that directly obtains by esterification process and be exactly unrefined oil without further handling what use.Purified oils is similar to unrefined oil, except they are further handled to improve one or more performances in one or more purification steps.Many such purification techniques, for example distillation, solvent extraction, acid or alkali extraction, filtration and diafiltration are known for those skilled in the art.Purified oil obtains by the refining oil that will be similar to those methods of being used to obtain refining oil and be applied to come into operation again.Such again refining oil be also referred to as recovered oil or handling oil again, its usually the technology of the degradation production approval by exhausted additive and oil carry out extra process.
Other examples of base oil be gas to liquid (" GTL ") base oil, promptly base oil can be the oil that derives from the synthetic hydrocarbon of Fischer-Tropsch, described hydrocarbon adopts the Fischer-Tropsch catalyzer to make by the synthetic gas that comprises hydrogen and carbon monoxide.These hydrocarbon need further processing so that as base oil usually.For example, they can pass through hydroisomerizing; Hydrocracking and hydroisomerizing; Dewaxing; Or method well known in the art such as hydroisomerizing and dewaxing is carried out.
Base oil can be to be group I-V according to API EOLCS 1509 defining classifications.Preferably derive from one or more the base oil of group III, IV and V.
Oil with lubricant viscosity is main consumption, in conjunction with minor amounts of additives (B) and (C), and if necessary, also has for example described below one or more to help additive to constitute said composition.This preparation is by directly being added to additive in this oil or adding so that additive disperses or dissolves finishes by the form with its enriched material.Can by well known to a person skilled in the art any method before adding other additives, with it simultaneously or after it, additive is added in the oil.
Terminology used here " oil soluble " or " oil is diffusible " or other similar terms must not represent that this compound or additive are solvable with any ratio, solubilized, solvablely mix or can suspend or be suspended in the oil.But, but they are meant that really for example described compound or additive degree solvable or stable dispersion in oil is enough to make that they can be to the effect of the employed environment performance of oil expectation.In addition, if necessary, additionally introduce other additives and also can allow to introduce the more special additive of a large amount.
Metal detergent system (B)
Metal detergent is to reduce additive that engine inner carrier settling forms and it can have sour neutrality, and terminology used here " sanitising agent " is defined as can provide one of above-mentioned two kinds of functions or whole two kinds of materials with function in lubricating oil composition.They are based on metal " soap ", and just the metal-salt of acidic organic compound sometimes is called tensio-active agent, and it generally includes the polar head that has long hydrophobic tail.
As mentioned above, described metal detergent system comprises the metal-salt of one or more organic carboxyl acids.
Preferred carboxylic acid is the aromatic carboxylic acid; More preferably aromatic carboxylic acid's salt constitutes whole metal detergent systems.
Described aromatic carboxylic acid's aromatics part can contain heteroatoms for example nitrogen-atoms and Sauerstoffatom, but preferably only contains carbon atom and hydrogen atom, for example six or more carbon atom.Benzene is the preferred construction part.
This aromatic carboxylic acid can be contained one or more aromatics parts that condense or be connected by alkylidene bridge, for example one or more phenyl ring.
The carboxyl structure part can be connected on the aromatic structure part directly or indirectly, preferably is directly connected on the carbon atom of aromatic structure part, as the carbon atom on the phenyl ring.
More preferably the aromatic structure part also contains second functional group on the carbon atom that directly or indirectly is connected to the aromatic structure part, for example hydroxyl.
The preferred example of described aromatic carboxylic acid is a Whitfield's ointment, for example the Whitfield's ointment of alkyl replacement." alkyl " is meant and contains hydrogen atom and carbon atom and the direct group that is keyed to the molecule remainder by carbon atom basically; It can contain one or more heteroatomss, as long as do not impair the alkyl character of group in essence.
This salt can with for example phenolate complexing and can be the form of hydroxy benzoate of other tensio-active agents.Can there be alkylphenol.US-A-5808145, EP-A-0933417 and EP-A-0985726 have described the example of such complex compound.
Metal is preferably alkaline-earth metal for example calcium and magnesium.
The metal-salt of the organic carboxyl acid that other classes are useful is the metal-salt that contains phenol unit and unitary linearity of Whitfield's ointment and ring compound, sometimes is called " Whitfield's ointment calixarene ".Such sanitising agent for example is described among EP-A-0708171, WO 99/0025677, WO 02/0072529 and the WO 03/0018728.
If described aromatic carboxylic acid is a Whitfield's ointment, each salicylate replaces for alkyl suitably, for example with independently, contain 8-30 carbon atom and it can be linearity, branching or the replacement of cyclic alkyl.As the example of alkyl can mention as follows: octyl group, nonyl, decyl, dodecyl, pentadecyl, octadecyl, eicosyl, docosyl, tricosyl, ceryl, triacontyl, Dimethylcyclohexyl, ethyl cyclohexyl, methyl cyclohexane ylmethyl and cyclohexyl ethyl.
Preferably whole basically metal detergent systems are calcium salicylate, and it contains other metal detergents except that calcium salicylate of a small amount of or non-quantitative at most in other words on this meaning.More preferably there are not or more preferably do not exist fully metal phenates and metal sulfonate in the metal detergent system substantially.
Suitably, calcium salicylate, if you are using, it is 50-4000ppm that the quality based on lubricating oil composition is provided, the calcium atom of preferred 100-3000ppm quality.
Detergent additive in this sanitising agent system can be neutral or overbasic, and is preferably overbasic.Suitably, its TBN that can have is 15 or 60-600, is preferably 100-450.
Viscosity index improver (C)
The viscosity index improver or the VI improving agent that are used for the present invention practice are linear Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks, and it comprises that at least one is mainly by vinyl aromatic monomer derive block that obtains and the block that at least one is mainly derived and obtained by diene monomers.Useful vinyl aromatic monomer comprises those vinyl naphthalenes of replacing of the vinylbenzene that replaces of aryl, vinylbenzene, vinyl naphthalene, alkyl that alkoxyl group replaces etc. for example that contain 8-16 carbon atom.Diene or diolefine comprise two and are usually located at the two keys of 1,3 conjugated.Contain the alkene of two keys more than two, sometimes be called polyenoid, also be considered within " diene " used herein definition.Useful diene comprises and contains about 12 carbon atoms of 4-, those of preferred 8-16 carbon atom, for example 1,3-divinyl, isoprene, piperylene, methylpentadiene, phenyl butadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1, the 3-octadiene, preferred 1,3-butadiene and isoprene.
The linear block copolymers that is used for the present invention's practice can be represented by following general formula:
A-B
Wherein:
A is the polymeric blocks of mainly being derived and being obtained by vinyl aromatic monomer;
B is the polymeric blocks of mainly being derived and being obtained by conjugate diene monomer.
Also comprise the taper linear block copolymers of representing by following general formula in the definition " linear diblock copolymer ":
A-A/B-B
Wherein:
A is the polymeric blocks of mainly being derived and being obtained by vinyl aromatic monomer;
B is the polymeric blocks of mainly being derived and being obtained by conjugated diene monomer;
A/B is the taper segment of being derived and being obtained by vinyl aromatic monomer and conjugated diene monomer.
In polymer blocks Composition Aspects " mainly " the used herein meaning is the 85 weight % that are at least block in the polymer blocks for the amount of the monomer of main ingredient or monomer type.
Polymkeric substance with the diolefine preparation will contain the olefinic degree of unsaturation, and preferably this base polymer is hydrogenated.When polymkeric substance is hydrogenated, can use any technology well known in the art to finish hydrogenation.For example, finish hydrogenation and can be to use for example US patent 3,113,986 and 3,700,633 methods of being instructed make olefinic degree of unsaturation and aromatics degree of unsaturation all be transformed (by saturated), perhaps can be for example as US patent 3,634,595, US3,670,054; US 3,700,633 and Re 27,145 instructed like that, optionally finish hydrogenation, make most of olefinic degree of unsaturation be had only seldom or do not have the aromatics degree of unsaturation to be transformed by conversion.Any of these methods can be used for also that hydrogenation only contains the olefinic degree of unsaturation and the polymkeric substance that do not contain the aromatics degree of unsaturation.
Segmented copolymer can comprise the mixture of the above-mentioned linear polymer with different molecular weight and/or differing ethylene base aromatics part content, and the mixture with linear diblock copolymer of different molecular weight and/or differing ethylene base aromatics part content.When being used to produce the engine oil of preparation,,, can preferably use two or more different polymkeric substance than single polymkeric substance according to the rheological property that will give product.
The number-average molecular weight that described segmented copolymer can have is being 200,000-1,500,000.Preferred number-average molecular weight is 350,000-900,000.The amount of the aromatic vinyl part of multipolymer preferably accounts for the 5-40 weight % of multipolymer.For this analog copolymer, its acceptable number-average molecular weight is 85,000-300,000.
Useful segmented copolymer comprises with those of body, suspension, solution or emulsion preparation.As known in the art, monomer polymerization is produced hydrocarbon polymer can use free radical, positively charged ion and anionic initiator or polymerizing catalyst, and the transition-metal catalyst and metallocene-type (being also referred to as " the single active center ") catalyzer that for example are used for Ziegler-Natta are realized.
Preferably, described linear diblock copolymer is at least aly to contain polystyrene block and by the derive linear diblock copolymer of the block that obtains of isoprene, divinyl or its mixture.More preferably, described linear diblock copolymer is at least a linear diblock copolymer that is selected from hydrogenant phenylethylene/butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and hydrogenant styrene/isoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.Preferably, the shear stability index value that the program according to ASTM D6278-98 that described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock has (being called Kurt-Orban (KO) or DIN small-scale test) is measured is 2-50%, 5-50% (30 circulations) more preferably, and derive by isoprene and obtain and 10-60 quality % is derived by divinyl and obtains by derive 40-90 quality % that the block of the described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that obtains contains of diene.
Alternatively, the VI improving agent that is used for the present invention practice can have and gives the nitrogen-containing functional group of VI improving agent with the dispersion agent ability.A trend in the industry is to use such " multi-functional " VI improving agent to come instead of part or whole dispersion agent in lubricant.Can be by structure division that will nitrogenous or hydroxyl, preferably nitrogenous structure division is grafted on the polymer main chain of VI improving agent and nitrogen-containing functional group is added on the polymeric VI improving agent (functionalized).The method that nitrogenous structure division is grafted on the polymkeric substance is well known in the art, and comprises, for example, in the presence of the radical initiator in the presence of pure or the solvent polymkeric substance is contacted with nitrogenous structure division.Described radical initiator can by shear (as in forcing machine) or add the thermal free radical initiator precursor for example hydrogen peroxide produce.
The amount of nitrogenous grafted monomer depends on the character of matrix polymer and to a certain extent to the requirement of this graftomer dispersion force level.In order to give star-like and linear copolymer with dispersing characteristic, the amount of grafted nitrogen containing monomer is suitably 0.4-2.2 weight % based on the gross weight of graftomer, is preferably 0.5-1.8 weight %, most preferably is 0.6-1.2 weight %.
Method and suitable nitrogenous grafted monomer that nitrogen containing monomer is grafted on the main polymer chain are known and are described in for example US patent 5,141,996, WO98/13443, WO99/21902, US patent 4,146,489, US patent 4,292,414 and US patent 4,506,056 in.(also referring to Gaylord and Mehta at J.PolymerScience, Part A:Polymer Chemistry, Vol.26,1189-1198 (1988); J.Polymer Science, Polymer Letters, Vol.20,481-486 (1982) and J.Polymer Science, Polymer Letters, Vol.21, the paper that 23-30 (1983) delivers and Gaylord, Mehta and Metha are published in J.AppliedPolymer Science, Vol.33, on the 2549-2558 (1987)
Degradaation and Crosslinking of Ethylene-Propylene Copolymer Rubber on Reaction with Maleic Anhydride And/or Peroxides(degraded of ethylene-propylene copolymer rubber the time and crosslinked) with maleic anhydride and/or peroxide reactions.
The component of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of the present invention is that commodity can get.The example of commercial vinylbenzene/hydrogenated isoprene linear diblock copolymer comprises the Infmeum SV140 that derives from Infineum USA L.P. and Infineum UK Ltd.
TM, Infineum SV150
TMWith Infineum SV160
TMDerive from the Lubrizol 7318 of LubrizolCorporation; Derive from the Septon 1001 of Septon Company of America (KurarayGroup) company
TMWith Septon 1020
TMSuitable vinylbenzene/1,3-butadiene hydrogenated block copolymer by BASF AG with trade name Glissoviscal
TMSell.
The amount that described viscosity index improver provides can be 0.01-20 quality % based on the quality of described lubricating oil composition, is preferably 1-10 quality %.
Other additives
Can also there be other additives in the lubricating oil composition of the present invention, for example following additive.
Ashless dispersant, its comprise have can with the oil soluble polymeric hydrocarbon main chain for the treatment of the mutually associating functional group of discrete particles.Generally speaking, dispersion agent comprises usually by the bridge joint group and is connected to amine, alcohol, acid amides or ester polar structure part on the main polymer chain.Ashless dispersant can for example be selected from: the monocarboxylic acid that long chain hydrocarbon replaces and oil soluble salt, ester, amino ester, acid amides, imide and the azoles quinoline of dicarboxylic acid or their acid anhydrides; The thio carboxy acid ester derivative of long chain hydrocarbon; Long chain aliphatic hydrocarbon with the polyamines that is directly connected on it; And by the phenol of long-chain replacement and the Mannich condensation product of formaldehyde and polyalkylene polyamine condensation formation.
Anti-friction decreases agent, and it can comprise dialkyl phosphorodithioic acid metal-salt, and wherein said metal can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel, copper, or preferably, zinc.
Can be according to technique known, by making one or more alcohol or phenol and P
2S
5Reaction at first forms dialkyl phosphorodithioic acid (DDPA), then with metallic compound with among the DDPA that forms and prepare dialkyl phosphorodithioic acid metal-salt.For example, phosphorodithioic acid can be made by the mixture reaction that makes primary alconol and secondary alcohol.Perhaps, can prepare multiple phosphorodithioic acid, the alkyl on one of them is a secondary alcohol on characteristic fully, and the alkyl on another is primary alconol fully on characteristic.Can use any alkalescence or neutral metallic compound to prepare metal-salt, but the most frequently used be oxide compound, oxyhydroxide and carbonate.Commercial additive often contains excessive metal, is because used excessive alkaline metal cpds in neutralization reaction.
Oil soluble salt that preferred dialkyl zinc dithiophosphate (ZDDP) is the dialkyl phosphorodithioic acid and available following general formula are represented:
Wherein R and R ' can for identical or different, contain 1-18, preferred 2-12 carbon atom and comprise for example alkyl of alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic groups of group.Be the alkyl of 2-8 carbon atom especially preferably as R and R ' group.Therefore, described group can for example be 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, the total number of carbon atoms in the described phosphorodithioic acid (being R and R ') is typically about 5 or more.Therefore, described dialkyl zinc dithiophosphate can comprise zinc dialkyl dithiophosphate.
Be no more than 0.09 quality % in order to be restricted to by the amount that ZDDP introduces the phosphorus in the lubricating oil composition, the amount that joins the ZDDP in the lubricating oil composition should preferably be no more than about 1.1-1.3 quality % based on the lubricating oil composition total mass.
Oxidation retarder or antioxidant, it can reduce the in use rotten tendency of base-material, this rotten can by oxidation products for example the sludge on the metallic surface and lacquer deposit and increase by viscosity be confirmed.As US4, described in 867,890, such oxidation retarder comprises hindered phenol, aromatic amine, has preferred C
5-C
12The alkaline earth salt of the alkylphenol thioester of alkyl group side chain, nonyl phenol sulfurated lime, ashless oil soluble phenates and sulfuration phenates, phosphorus sulfuration or sulfurized hydrocarbon, phosphide, thiocarbamate metal-salt and oil-soluble copper compounds.
Can use friction modifiers, it comprises and reduces frictional coefficient and thereby improved the boundary lubrication agent addition agent of saving of fuel.Example comprises the organic friction modifiers of ester group, for example the fatty acid partial ester of polyvalent alcohol XU 61518.10 for example; With the organic friction modifiers of amido.Further example be make molybdenumdisulphide for example wherein molybdenum for example be the sedimentary additive of organic molybdenum of double-core or three kernel form.
Can use rust-preventive agent, it is selected from the group of being made up of nonionic polyalkylene oxide polyvalent alcohol and ester, polyalkylene oxide phenols and negatively charged ion alkylsulphonic acid.
Can use the corrosion inhibitor of copper and plumbous load, but not require usually in the preparaton of the present invention.Common this compound is thiadiazole polysulphide, its derivative and the polymkeric substance that contains 5-50 carbon atom.The derivative of 1,3,4 thiadiazoles normally, for example in US patent 2,719,125,2,719, those that describe in 126 and 3,087,932.Other materials similar are described in US patent 3,821,236,3,904, in 537,4,097,387,4,107,059,4,136,043,4,188,299 and 4,193,882.Other additives are sulfo-and poly-sulfo-sulphenamides of thiadiazoles, and for example the UK patent specification 1,560, those described in 830.Benzotriazole derivatives also belongs to the scope of examples of such additives.When comprising these compounds in the described lubricating oil composition, the amount that they exist preferably is no more than 0.2 quality % of activeconstituents.
Can use a small amount of emulsion breaking component.Preferred emulsion breaking component is described in EP330, in 522.It obtains by making alkylene oxide and the adducts reaction that obtains by di-epoxide and polyol reaction.The consumption of demulsifying compound should be no more than 0.1 quality % of activeconstituents.0.001-0.05 the treatment rate of quality % activeconstituents (treatrate) is suitable.
Pour point reducer is called the mobile improving agent of lubricating oil in addition, has reduced the minimum temperature that fluid flow maybe can be toppled over.This additive is very known.These additives that improved the fluid low-temperature fluidity are typically fumaric acid C
8-C
18Dialkyl/vinyl acetate copolymer, poly-alkylmethacrylate etc.
The chemical compound lot of the antifoams of polysiloxane type that can be by comprising silicone oil for example or polydimethylsiloxane provides foam control.
Lubricating oil composition of the present invention is except viscosity index improver (C), also can choose wantonly and contain VI improvement material, as ethylene-propylene or other olefin copolymers (OCP) VI improving agent, perhaps random or linear three block copolymer, or be derived from the random star-like or star block copolymer of vinyl-arene and diene.Such other VI improving agents are known and commercial getting.Preferably, viscosity index improver (C) is unique VI improving agent used in the lubricating oil composition.
Various independent additives can be incorporated in the base-material in any suitable manner.Therefore, every kind of component can be by it is dispersed or dissolved in base-material or the base oil blend with required concentration and directly is added in base-material or the base oil blend.Blend can be carried out under the temperature of envrionment temperature or rising.
Preferably except viscosity modifier and pour point reducer, all additives all are blended in the enriched material described here as additive-package, it is blended into makes finished lubricants in the base-material then.Usually concentrated solution is mixed with the additive that contains appropriate amount, in order to the base lubricant of concentrated solution and predetermined amount in conjunction with the time required concentration is provided in final preparaton.
Described concentrated solution is preferably according to US 4,938, and the method described in 880 makes.
Final crankcase lubricating oil composition can use 2-20 quality %, preferably 4-18 quality % and most preferably concentrated solution or the additive-package of 5-17 quality %, and surplus is a base-material.Preferably, the sulfate ash concentration that lubricating oil composition of the present invention has is no more than 1.0 quality % and/or is no more than 0.3 quality % with the sulphur concentration that sulphur atom is represented, more preferably no more than 0.2 quality %.
Engine
The present invention is applicable to the oil engine scope, for example two strokes of ignition and spark ignition or the reciprocating type engine of four-stroke.Example comprises and is used to generate electricity, the engine of locomotive and ship's machinery and heavy road truck; The heavy non-highway that for example can be used for agricultural, building and mining industry is with engine and be used for the engine of light-duty commercial affairs and passenger car applications.
Embodiment
The present invention now will describe especially with the following examples, and this embodiment does not limit the scope of the claims.
The 5W30 lubricating oil composition (or lubricant) of two kinds of full formulas is with method blend well known in the art.
Each lubricant formulation is become to have identical kinematic viscosity under 100 ℃, and comprises or contain:
The calcium salicylate detergent additive, TBN160 produces the calcium atom of 0.114 quality %;
Phosphorus content is 0.05 quality %;
Polymer content is 0.9 quality %; With
Dispersion agent, antiwear agents, antioxidant, friction modifiers and other additives of the same amount that the preparation lubricating oil composition is conventional used.
The difference of described two kinds of lubricants is:
Lubricant 1, lubricant of the present invention comprises isoprene/vinylbenzene linear diblock copolymer of 6 quality % as viscosity index improver in containing the 130N group I base-material of 1.9 quality % polymethacrylate LOFI.Having the styrene content that a multipolymer that is derived from the block of a cinnamic block and a hydrogenated polyisoprene has is that 35 quality % and number-average molecular weight (with the vinylbenzene determination of equivalent) are 130,000; With
Lubricant A with reference to lubricant, comprises the star copolymer of 15 quality % as viscosity index improver in 130N group I base-material.Described star copolymer has hydrogenant polyisoprene arm and total number-average molecular weight (with the vinylbenzene determination of equivalent) is 360,000.
According to each cam and the tappet rod for valve wearing and tearing of the described two kinds of lubricants of program IIIG experimental test.Described test adopts 1996 General Motors 3800cc series II, water-cooled, 4 circulations, V-6 gasoline engine as testing apparatus.Program IIIG test engine is overhead valve design (OHV) and uses single camshaft to operate inlet valve and blast gate by push rod and hydraulic valve tappet with slip-driven layout.Use unleaded gas and oil, engine is initial oil level program (oil-leveling procedure) operation 10 minutes, then through slowly rising to speed and loading condiction in 15 minutes.Described then engine is at 125bhp, 3, the operation 100 hours down of the oil temperature of 600rpm and 150 ℃, with 20 hours interval interrupt in order to check oil level.
After the off-test, measure the wearing and tearing of cam lobe and tappet rod for valve.It is as follows with the micron to be that unit representation is that average cam adds the result of valve tappet wearing and tearing, and wherein Ce Shi acceptability limit is 60 microns of maximums.
Lubricant 1:57.2
Lubricant A:291.7
The result proves that A compares with lubricant, uses linear diblock viscosity index improver remarkably to produce better polishing machine in generally acknowledging engine test in lubricant 1.
Claims (11)
1, a kind of crank case of internal combustion engine lubricating oil composition, its phosphorus concentration of representing with phosphorus atom that has is no more than 0.09 quality % based on the quality of oil compositions, and described composition comprises following component or makes by mixing following component:
(A) oil with lubricant viscosity of main consumption;
(B) as the little metal sanitising agent system of additive, it comprises the metal-salt of one or more organic carboxyl acids; And
(C) comprise the viscosity index improver of linear diblock copolymer, this Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock comprises that at least one mainly can be by the vinyl aromatic monomer block that the block that obtains and at least one mainly can be derived and be obtained by diene monomers of deriving.
2, oil compositions as claimed in claim 1, wherein said linear diblock copolymer are at least a at least one polystyrene block and Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks that is derived from the block of isoprene, divinyl or its mixture of containing.
3, oil compositions as claimed in claim 2, wherein said linear diblock copolymer are at least a Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks that is selected from the group of being made up of hydrogenant phenylethylene/butadiene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and hydrogenant styrene/isoprene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock.
4, as claim 2 or 3 described oil compositionss, the shear stability index value that wherein said Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock has is 2-50% (30 circulation), and the 40-90 quality % that the polydiene block of described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock comprises is derived from isoprene and 10-60 quality % derived from butadiene.
5, as each described oil compositions of claim 1-4, the shear stability index value that wherein said Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock has is 5-25% (30 circulation).
6, as each described oil compositions of claim 1-5, the sulfate ash concentration that it has is no more than 1.0 quality %.
7, as each described oil compositions of claim 1-6, its sulphur concentration of representing with sulphur atom that has is no more than 0.3 quality %, preferably is no more than 0.2 quality %.
8, as each described oil compositions of claim 1-7, the metal-salt of wherein said organic carboxyl acid is overbasic alkaline earth metal salicylates.
9, as each described oil compositions of claim 1-8, it comprises further that except (B) with (C) one or more are selected from the additive of dispersion agent, sanitising agent, antioxidant, antiwear agents, friction modifiers, corrosion inhibitor, pour point reducer, demulsifying compound and antifoams.
10, the method for the oil engine of a kind of lubricated ignition or spark ignition, it comprises to this engine supply as each described lubricating oil composition of claim 1-9.
11, as the purposes of each defined viscosity index improver among the claim 1-5, it is used to improve the wearing and tearing of lubricated cam of crank case of internal combustion engine and tappet rod for valve by lubricating oil composition, and described lubricating oil composition has the quality of representing with phosphorus atom based on lubricating oil composition and is no more than the phosphorus concentration of 0.09 quality % and comprises as claim 1,7 and 8 each defined metal detergent systems.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05270076.2 | 2005-11-03 | ||
| EP05270076 | 2005-11-03 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102252407A Division CN103333730A (en) | 2005-11-03 | 2006-11-03 | Lubricating oil compositions |
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| CN1958759A true CN1958759A (en) | 2007-05-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2006101646204A Pending CN1958759A (en) | 2005-11-03 | 2006-11-03 | Lubricating oil composition |
| CN2013102252407A Pending CN103333730A (en) | 2005-11-03 | 2006-11-03 | Lubricating oil compositions |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2013102252407A Pending CN103333730A (en) | 2005-11-03 | 2006-11-03 | Lubricating oil compositions |
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| Country | Link |
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| US (1) | US20070099802A1 (en) |
| JP (2) | JP5348834B2 (en) |
| CN (2) | CN1958759A (en) |
| AT (1) | ATE552328T1 (en) |
| CA (1) | CA2567180C (en) |
| ES (1) | ES2380949T3 (en) |
| SG (1) | SG131927A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161927A (en) * | 2010-02-23 | 2011-08-24 | 英菲诺姆国际有限公司 | A lubricating oil composition |
| CN102575434A (en) * | 2010-03-31 | 2012-07-11 | 曼泰克株式会社 | Contamination inhibitor composition |
| CN106635320A (en) * | 2007-12-10 | 2017-05-10 | 凯密特尔有限公司 | Formulation of a metalworking fluid |
| CN111334357A (en) * | 2020-04-14 | 2020-06-26 | 无锡中石油润滑脂有限责任公司 | Mineral oil lithium-based lubricating grease and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090156442A1 (en) * | 2007-12-17 | 2009-06-18 | Laurent Chambard | Lubricant Compositions With Low HTHS for a Given SAE Viscosity Grade |
| CN102549215B (en) * | 2010-03-31 | 2013-04-17 | 曼泰克株式会社 | Contamination inhibitor composition |
| FR2980799B1 (en) * | 2011-09-29 | 2013-10-04 | Total Raffinage Marketing | LUBRICATING COMPOSITION FOR MARINE ENGINE |
| EP2607461B1 (en) * | 2011-12-21 | 2018-01-17 | Infineum International Limited | Marine engine lubrication |
| US9506009B2 (en) | 2014-05-29 | 2016-11-29 | Exxonmobil Research And Engineering Company | Lubricating oil compositions with engine wear protection |
| FR3057273B1 (en) * | 2016-10-07 | 2020-02-21 | Total Marketing Services | LUBRICATING COMPOSITION FOR MARINE ENGINE OR STATIONARY ENGINE |
| MX2021006002A (en) | 2018-11-26 | 2021-07-06 | Shell Int Research | Fuel compositions. |
| FR3108620B1 (en) * | 2020-03-25 | 2022-09-09 | Total Marketing Services | Use of hydrogenated styrene diene polymer to reduce particulate emissions |
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| BE759713A (en) * | 1969-12-12 | 1971-06-02 | Shell Int Research | BLOCK COPOLYMERS AS VISCOSITY INDEX IMPROVING AGENTS |
| US3772196A (en) * | 1971-12-03 | 1973-11-13 | Shell Oil Co | Lubricating compositions |
| US4073737A (en) * | 1976-04-19 | 1978-02-14 | Exxon Research & Engineering Co. | Hydrogenated copolymers of conjugated dienes and when desired a vinyl aromatic monomer are useful as oil additives |
| US5310490A (en) * | 1991-03-13 | 1994-05-10 | Exxon Chemical Products Inc. | Viscosity modifer polymers |
| US6083888A (en) * | 1997-09-16 | 2000-07-04 | Shell Oil Company | Dispersant viscosity index improvers |
| US6103673A (en) * | 1998-09-14 | 2000-08-15 | The Lubrizol Corporation | Compositions containing friction modifiers for continuously variable transmissions |
| US6303550B1 (en) * | 1998-11-06 | 2001-10-16 | Infineum Usa L.P. | Lubricating oil composition |
| CA2374501A1 (en) * | 1999-05-24 | 2000-11-30 | The Lubrizol Corporation | Mineral gear oils and transmission fluids |
| WO2001046352A1 (en) * | 1999-12-22 | 2001-06-28 | The Lubrizol Corporation | Lubricants with the combination of a molybdenum compound, a phosphorus compounds and dispersants |
| US6715473B2 (en) * | 2002-07-30 | 2004-04-06 | Infineum International Ltd. | EGR equipped diesel engines and lubricating oil compositions |
| US6784143B2 (en) * | 2001-05-11 | 2004-08-31 | Infineum International Ltd. | Lubricating oil composition |
| US6583092B1 (en) * | 2001-09-12 | 2003-06-24 | The Lubrizol Corporation | Lubricating oil composition |
| JP4889179B2 (en) * | 2002-08-27 | 2012-03-07 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| US20040235682A1 (en) * | 2003-05-22 | 2004-11-25 | Chevron Oronite Company Llc | Low emission diesel lubricant with improved corrosion protection |
-
2006
- 2006-10-11 AT AT06122139T patent/ATE552328T1/en active
- 2006-10-11 ES ES06122139T patent/ES2380949T3/en active Active
- 2006-10-30 US US11/554,240 patent/US20070099802A1/en not_active Abandoned
- 2006-11-02 JP JP2006299214A patent/JP5348834B2/en active Active
- 2006-11-03 CN CNA2006101646204A patent/CN1958759A/en active Pending
- 2006-11-03 CA CA2567180A patent/CA2567180C/en active Active
- 2006-11-03 CN CN2013102252407A patent/CN103333730A/en active Pending
- 2006-11-03 SG SG200607664-0A patent/SG131927A1/en unknown
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- 2013-02-28 JP JP2013039243A patent/JP2013100556A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635320A (en) * | 2007-12-10 | 2017-05-10 | 凯密特尔有限公司 | Formulation of a metalworking fluid |
| CN102161927A (en) * | 2010-02-23 | 2011-08-24 | 英菲诺姆国际有限公司 | A lubricating oil composition |
| CN102161927B (en) * | 2010-02-23 | 2017-06-23 | 英菲诺姆国际有限公司 | Lubricant oil composite |
| CN102575434A (en) * | 2010-03-31 | 2012-07-11 | 曼泰克株式会社 | Contamination inhibitor composition |
| CN102575434B (en) * | 2010-03-31 | 2013-05-29 | 曼泰克株式会社 | Contamination inhibitor composition |
| CN111334357A (en) * | 2020-04-14 | 2020-06-26 | 无锡中石油润滑脂有限责任公司 | Mineral oil lithium-based lubricating grease and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE552328T1 (en) | 2012-04-15 |
| JP2007126669A (en) | 2007-05-24 |
| ES2380949T3 (en) | 2012-05-21 |
| CA2567180A1 (en) | 2007-05-03 |
| US20070099802A1 (en) | 2007-05-03 |
| JP5348834B2 (en) | 2013-11-20 |
| CA2567180C (en) | 2011-05-17 |
| SG131927A1 (en) | 2007-05-28 |
| JP2013100556A (en) | 2013-05-23 |
| CN103333730A (en) | 2013-10-02 |
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