CN100523155C

CN100523155C - Hydrocarbyl dispersants and compositions containing the dispersants

Info

Publication number: CN100523155C
Application number: CNB2004100922424A
Authority: CN
Inventors: J·T·洛珀; D·A·文豪斯; W·Y·林
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2003-11-06
Filing date: 2004-11-05
Publication date: 2009-08-05
Anticipated expiration: 2024-11-05
Also published as: EP1531176A2; US20050101496A1; CA2484558A1; EP1531176A3; SG112028A1; AR046825A1; JP2005139448A; CN1626633A; BRPI0404819A

Abstract

A dispersant for use as a lubricant additive, a lubricant composition and a method for improving engine performance. The dispersant includes at least one member selected from the group consisting of hydrocarbyl-substituted succinimides, hydrocarbyl-substituted amines, and Mannich base adducts derived from hydrocarbyl-substituted phenols condensed with aldehydes and amines. The hydrocarbyl substituent is composed of a polymerization product of a raffinate I stream and isobutylene having a number average molecular weight ranging from about 500 to about 3000 as determined by gel permeation chromatography and more than about 70 mol percent of the polymerization product having a terminal vinylidene group.

Description

Alkyl dispersion agent and the composition that contains described dispersion agent

Technical field

The following discloses content relates to dispersion agent, crankcase dispersion agent, the crankcase lubricant composition that is used for field of lubricant and uses novel wear reduction lubricant compositions to improve the method for motor performance.

Background technology

Dispersion agent is a kind of important additive for lubricant compositions.Dispersion agent remains suspended state with impurity and settling, makes it possible to by filtration or other method it be removed from system, rather than is deposited on the built-in motor parts.

Be used for the dispersion agent of field of lubricant in routine, polymerization Mannich base, alkylamine adducts and hydrocarbyl succinic acid derivative demonstrate the excellent properties for described field.Such as having described phenol that the Mannich base dispersion agent normally replaces by alkyl and aldehyde and amine prepared in reaction in United States Patent (USP) 3539633,3697574,3704308,3736535,3736357,4334085 and 5433875.

According to the description in the United States Patent (USP) 5071919 of authorizing DeGonia etc., hydrocarbyl succinic acidic group dispersion agent is by using the alkene will for example, and maleic anhydride, acid, ester or halogenide alkylation produce with the formation acylating agent.Acylating agent and amine reaction subsequently forms dispersion agent.Preferred alkene is polyisobutene (polyisobutene), also can be described as polyisobutene (polyisobutylene).

Except a large amount of dispersion agents that are used for field of lubricant, also need improved dispersion agent, especially for the dispersion agent in crankcase lubricant field.

Summary of the invention

In the embodiment of this paper, provide a kind of as dispersion agent, the lubricant compositions of lubricant additive and the method that is used to improve motor performance.Described dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and at least a by with in the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation.By gel permeation chromatography, hydrocarbyl substituent is made up of the polymerisate of number-average molecular weight in about 3000 scopes of about 500-of raffinate stream I and iso-butylene, and has inferior ethene end group above the polymerisate of about 70mol%

In another embodiment, a kind of lubricant additive of being made up of first dispersion agent and second dispersion agent is provided, described first dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and at least a by with in the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation, and second dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and a kind of by with in the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation.According to the mensuration of gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of first dispersion agent has is in the scope of about 1500-about 2500.According to the mensuration of gel permeation chromatography, the number-average molecular weight that second dispersion agent has is in the scope of about 500-about 1200.

In an embodiment again, provide a kind of method that in the oil engine of vehicle, reduces engine deposits.This method comprises uses a kind of lubricant compositions that contains lubricant and lubricant additive to be used for oil engine as crankcase oil.Lubricant additive package is drawn together first dispersion agent and second dispersion agent, described first dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and at least a by with in the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation, and second dispersion agent comprises succinimide that alkyl replaces, amine that alkyl replaces and a kind of by with in the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation.According to the mensuration of gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of first dispersion agent has is in the scope of about 1500-about 2500.According to the mensuration of gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of second dispersion agent has is in the scope of about 500-about 1200.Lubricant additive is to be enough to reduce engine deposits and to provide at least the amount by grade (pass rating) to be present in the lubricant compositions in the engine deposits experiment.

The advantage of embodiment described herein has been to provide the improvement dispersion agent that is used for lubricant compositions, has contained the lubricant compositions of this improvement dispersion agent and use this improved lubricant to improve the method for motor performance.Dispersion agent in the lubricating oil is thermolysis and oxidation products, suspends such as cigarette ash and mud, and reduces or hindered the formation of settling on lubricated surface.The additive that is used to wear away the dispersion agent that lowers additive and is the hydrocarbyl substituent that provides by the polymerisate that has by raffinate stream I and iso-butylene provides.Dispersion agent helps to meet or surpasses the GF-4 specification of passenger vehicle with machine oil like this.

Dispersion agent described herein is particularly suitable for diesel engine and petrol motor with crankcase lubricant, as the dispersion agent of mechanical transmission liquid, as the continuous variable gear oil additive and as the component of hydraulic efficiency oil.The further feature of this dispersion agent and advantage will become apparent with reference to following detailed description, and described description is the simplification of preferred embodiment, but is not limited to embodiment described herein.

Embodiment

The term of Shi Yonging " hydrocarbyl substituent " or " alkyl " use well known to a person skilled in the art conventional sense herein.Specifically be meant the group that carbon atom is connected directly to the rest part of molecule and has main hydrocarbon feature.The example of alkyl comprises:

(1) hydrocarbon substituent, promptly aliphatic series (for example, alkyl or alkenyl), alicyclic (for example, cycloalkyl, cycloalkenyl group) aromatic substituent of substituting group and aromatics, aliphatic series and alicyclic replacement, and cyclic substituents, wherein ring constitutes (for example, two substituting groups form alicyclic radical) by another part of molecule;

(2) hydrocarbon substituent of Qu Daiing promptly contains the substituting group (for example, halogen (mainly being chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl) that does not change the non-alkyl of main hydrocarbon substituent in this article;

(3) assorted substituting group promptly in this article, has main alkyl feature simultaneously and contain atom (in addition, described ring or chain are made up of carbon atom) substituting group outside the carbon in ring or chain.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises the substituting group such as pyridyl, furyl, thienyl and imidazolyl.Generally speaking, per ten carbon atoms in the alkyl are no more than two with existence, preferably are no more than a non-hydrocarbon substituent; Usually in alkyl, will there be non-hydrocarbon substituent.

In hydrocarbyl substituent, alkene especially is preferred for the hydrocarbyl substituent of at least a dispersion agent.Alkene generally is be C by the cracking hydrocarbon stream basically to produce such as iso-butylene ₄The hydrocarbon mixture of hydrocarbon makes.For example, the C 4 fraction of pyrolysis method (streamcracker) generation comprises C ₄Paraffins and C4 alkene, major part is an iso-butylene.From logistics, remove divinyl and acetylene basically by extra selective hydration or extractive distillation technology.The logistics that obtains is called " raffinate I ", is applicable to that polyisobutene (PIB) is synthetic and has following typical case's composition basically: 44-49% iso-butylene, 24-28%1-butylene, 19-21%2-butylene, 6-% normal butane, 2-3% Trimethylmethane.The composition of raffinate stream I can change according to operational condition.Purifying raffinate stream I provides pure basically iso-butylene product.

Up to now, being used for preparing lubricant and oil compositions mainly is from the isobutene polymerisation deutero-with the small molecular weight PIB of dispersion agent.The vinylidene content that products therefrom generally has is the about 60 weight % of about 50 weight %-that account for polymerisate.In the alkylation process of preparation succsinic acid adducts, amine adduct or alkylphenol adducts, vinylidene content is reactive influential for PIB's.

The hydrocarbon substituent of being made by the polymerization of mixtures of raffinate I and iso-butylene is better than the polyisobutene (PIB) that only produced by iso-butylene.For example, described hydrocarbon substituent is because its vinylidene content and obviously reactive higher than PIB.The vinylidene content of the polyblend of raffinate I and iso-butylene is usually above about 70 weight %.Polyblend described herein also provides the alkyl polymeric chain of the carbon atom that comprises that gem-dimethyl carbon atom, mesomethylene carbon atom, the carbon atom of monomethyl replacement, single ethyl replace.On the contrary, the polymerization of relative purer isobutene reaction thing only provides the mixture of gem-dimethyl carbon atom and mesomethylene carbon atom.

Preferred polymerisate is to provide with the about 65 weight % raffinate I of about 55-that contain at least about 40 weight % iso-butylenes by the about 45 weight % iso-butylenes of the about 35-of polymerization.The vinylidene content that the polymerisate that obtains has is about 70 weight %, and preferably the number-average molecular weight by gel permeation chromatography is that about 500-is about 3000, preferably about 500-about 2500.The number-average molecular weight of macromolecule polymerisate is in the scope of about 1500-about 2500 relatively.The number-average molecular weight of small molecular weight polymerisate is in the scope of about 500-about 1200 relatively.Macromolecule and small molecular weight polymerisate all can be used for preparing the dispersion agent that is applicable to field of lubricant.

Be used to form that the polyreaction of polymerisate normally carries out in the presence of conventional Z-N or metallocene catalyst system.Polymerisation medium can comprise and well known to a person skilled in the art solution, slurry, or vapor phase process.When adopting solution polymerization, solvent can be to be used for being any suitable unreactive hydrocarbons solvent of liquid under the reaction conditions of polymerization of Alpha-olefin; The example of the hydrocarbon solvent that is fit to comprises the straight chain paraffins with 5-8 carbon atom, preferred hexane.Aromatic hydrocarbons preferably has the aromatic hydrocarbons of a benzene nucleus, such as benzene and toluene; And boiling point is especially suitable near the saturated cyclic hydrocarbons of above-mentioned straight chain paraffins and aromatic hydrocarbons boiling point.Selected solvent can be the mixture of one or more above-mentioned hydrocarbon.When adopting slurry polymerization, be used for preferably propylene liquid of polymeric liquid phase.Wish that polymerisation medium does not contain the material that disturbs catalyst component.

Improved disperser composition can comprise the dispersion agent that uses the above polymerisate of describing as alkyl to make.Other disperser composition comprises at least the first and second dispersion agents, described dispersion agent is selected from respectively, but be not limited to, ashless dispersant is such as the succinimide of alkyl replacement, the amine that alkyl replaces and the Mannich base adducts that is produced by the alkyl substituted phenol with the aldehyde condensation.According to gel permeation chromatography, the number-average molecular weight that first dispersion agent preferably has is in the scope of about 1500-about 2500.According to gel permeation chromatography, the number-average molecular weight that second dispersion agent preferably has is in the scope of about 500-about 1200.In particularly preferred embodiments, first dispersion agent is the dispersion agent of aftertreatment, and second dispersion agent comprises the hydrocarbyl substituent that is polymerized by above-mentioned raffinate I and isobutene mixture.

The amber acylation agent that uses alkyl to replace prepares the succinimide that alkyl replaces.The amber acylation agent that alkyl replaces includes but not limited to the amber carboxylic acid halides (especially acid fluoride and chloride of acid) that hydrocarbyl substituted succinic, hydrocarbyl substituted succinic acid anhydride, alkyl replace; and the ester of hydrocarbyl substituted succinic and lower alcohol (for example the highest contain 7 carbon atoms those), promptly can play the compound that the alkyl of carboxylic acylating agent effect replaces.In these compounds, the mixture of general preferred use hydrocarbyl substituted succinic and hydrocarbyl substituted succinic acid anhydride and described acid and acid anhydrides, the succinyl oxide that preferred especially alkyl replaces.

The acylating agent that alkyl replaces is by the suitable polyolefine of molecular weight (with or without chlorine) and maleic anhydride prepared in reaction.Similarly the carboxylic acid reaction thing can be used for preparing acylating agent.Described reactant includes but not limited to toxilic acid, fumaric acid, oxysuccinic acid, tartrate, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, ethyl maleic anhydride, dimethyl maleic anhydride, ethyl toxilic acid, dimethyl maleic acid, hexyl toxilic acid etc., comprises corresponding carboxylic acid halides and rudimentary aliphatic ester.

The hydrocarbyl substituted succinic acid anhydride is normally by under the about 275 ℃ temperature of about 175-, and the mixture of heating maleic anhydride and aliphatic olefin prepares.The molecular weight of alkene can change according to the expectation purposes of the succinyl oxide that replaces.Usually, the succinyl oxide of replacement will have the alkyl of 8-500 carbon atom.But the succinyl oxide that is used to prepare the replacement of lubricating oil dispersant has the alkyl of about 40-500 carbon atom usually.The dispersion agent that alkyl contains about 8-150 carbon atom is called as " small molecular weight dispersion agent relatively " at this moment.And alkyl contains the dispersion agent of maximum 500 carbon atoms of about 150-and is called as " relatively macromolecule dispersion agent " at this moment.For the unusual succinyl oxide of the replacement of macromolecule, reference number average molecular weight (Mn) is then more accurate, this is owing to be used to prepare the alkene of the succinyl oxide of these replacements and can comprise by the small molecular weight olefinic monomer, the mixture of the different molecular weight component that obtains such as ethene, propylene and isobutene polymerisation.

The mol ratio of maleic anhydride and alkene can alter a great deal.For example, can more preferably change in the scope of 1:1-3:1 at 5:1-1:5.For alkene, such as number-average molecular weight 500-7000, preferred 800-3000 or higher polyisobutene and ethene-alpha-olefin copolymer, maleic anhydride be preferably with the excessive use of stoichiometry, for example 1.1-3 mole maleic anhydride/every mole of alkene.Unreacted maleic anhydride can be evaporated from reaction mixture.

The hydrocarbyl substituted succinic acid anhydride comprises by under the reaction conditions known in the art, the poly-alkyl or the polyalkenyl succinic anhydrides of the prepared in reaction of maleic anhydride and required polyolefine or chlorinatedpolyolefins.For example, can be according to the description of United States Patent (USP) 3361673,3676089 and 5454964, by the such succinyl oxide of the reaction for preparation of polyolefine and maleic anhydride.Perhaps can be according to for example description of United States Patent (USP) 3172892, the succinyl oxide that the prepared in reaction by chloro polyolefine and maleic anhydride replaces.For example, in United States Patent (USP) 4234435,5620486 and 539330, can find the further argumentation of relevant hydrocarbyl substituted succinic acid anhydride.General these hydrocarbyl substituents will contain 40-500 carbon atom.

Polyalkenyl succinic anhydrides can be converted into poly-alkyl succinic anhydride such as catalytic hydrogenation by using the conventional reduction condition.For catalytic hydrogenation, preferred catalyzer is that carbon carries palladium.Can use similar reductive condition equally, the polyalkenyl succinimide is converted into poly-alkyl succinimide.

Poly-alkyl on the succinyl oxide of Shi Yonging or polyalkenyl substituting group are normally by polyolefin derivative herein, and described polyolefine is a monoolefine, and 1-monoolefine particularly is such as the polymkeric substance or the multipolymer of ethene, propylene and butylene.The preferred monoolefine that uses has about 24 carbon atoms of 2-, more preferably from about 3-12 carbon atom.Preferred monoolefine comprises propylene, butylene, especially iso-butylene, 1-octene and 1-decene.Polyolefine by described monoolefine preparation comprises polypropylene, polybutene, polyisobutene and the poly-alpha olefins that is prepared by 1-octene and 1-decene.

Dispersion agent can pass through, for example hydrocarbyl substituted succinic or acid anhydrides and amine prepared in reaction.Preferred amine is selected from polyamines and oxyamine.The example of operable polyamines includes but not limited to aminoguanidine bicarbonate (AGBC), diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA) and heavy polyamines.Heavy polyamines is to comprise a small amount of rudimentary polyamines oligopolymer, such as TEPA and PEHA, but mainly is to have 7 or more a plurality of nitrogen-atoms, 2 or more primary amine/per molecules and the polyalkylenepolyamines mixture that more gos deep into branching than conventional polyamine mixture.

The polyamines that also is applicable to preparation dispersion agent described herein comprises N-aryl phenylenediamine, such as N-phenyl phenylenediamine, and N-phenyl-1 for example, 4-phenylenediamine, N-phenyl-1,3-phenylenediamine and N-phenyl-1,2-phenylenediamine; The aminothiazole class is such as aminothiazole, aminobenzothiazole, amino diazosulfide and aminoalkyl group thiazole; The aminocarbazole class; The amino indole class; Aminopyrrole; Amino-indazole quinoline ketone; The amino mercapto triazole species; Aminopyridines; The aminoalkyl group imidazoles is such as 1-(2-amino-ethyl) imidazoles, 1-(3-aminopropyl) imidazoles; And the aminoalkyl group morpholine, such as 4-(3-aminopropyl) morpholine.These polyamines have been described in United States Patent (USP) 4863623 and 5075383 in more detail.Described polyamines can provide extra advantage for end product, such as resistance to wearing with anti-oxidant.

Other polyamines that is used to form the succinimide that alkyl replaces comprises the instruction according to United States Patent (USP) 5634951 and 5725612, has the polyamines of at least one uncle or secondary amino group and at least one uncle's amino in molecule.The example of the polyamines that is fit to comprises N, N; N "; N "-tetraalkyl two alkylene triamine (two amino and center secondary amino groups of end uncle), N, N; N "; N "-tetraalkyl three alkylidene group tetramines (end uncle amino, two amino and end primary aminos of inner uncle), N, N, N ', N "; N " '-five alkyl three alkylidene group tetramines (end uncle amino, two amino and end secondary amino groups of inner uncle), three (dialkyl aminoalkyl) aminoalkyl group methane compounds such as (three amino and end primary aminos of end uncle), wherein alkyl is identical or different, and generally contains respectively and be no more than about 12 carbon atoms, wherein preferably contains 1-4 carbon atom respectively.Most preferably these alkyl are methyl and/or ethyl.The preferred polyamine reactant of this class comprises dimethylamino propylamine (DMAPA) and N methyl piperazine.

Be applicable to herein oxyamine comprise contain at least a can with the primary amine of hydrocarbyl substituted succinic or anhydride reaction or compound, oligopolymer or the polymkeric substance of secondary amine.Be applicable to that oxyamine herein comprises N-aminoethyl ethanolamine (AEEA), aminopropyl diethanolamine (APDEA), thanomin, diethanolamine (DEA), the propenoxylated hexamethylene-diamine of part (for example HMDA-2PO or HMDA-3PO), 3-amino-1,2-propylene glycol, three (methylol) aminomethane and 2-amino-1, ammediol.

The mol ratio of amine and hydrocarbyl substituted succinic or acid anhydrides is preferably in the scope of the about 2.5:1 of 1:1-.The mol ratio of special preferred amines and hydrocarbyl substituted succinic or acid anhydrides is in the scope of the about 2.0:1 of about 1.5:1-.

Above-mentioned dispersion agent for example can also be, according to the description in the United States Patent (USP) 5789353 of for example authorizing Scattergood, handle dispersion agent by using toxilic acid and boric acid, or, handle the aftertreatment dispersion agent that dispersion agent makes by using nonylphenol, formaldehyde and oxyacetic acid according to the description in the United States Patent (USP) 5137980 of for example authorizing DeGonia etc.

The Mannich base dispersion agent preferably has the substituent alkylphenol of chain alkyl usually on ring and one or more contain the aliphatic aldehyde (especially formaldehyde and derivative thereof) of about 7 carbon atoms of 1-and the reaction product of polyamines (especially polyalkylenepolyamines).Example of Mannich condensation product and preparation method thereof is referring to United States Patent (USP)

2,459,112; 2,962,442; 2,984,550; 3,036,003; 3,166,516; 3,236,770; 3,368,972; 3,413,347; 3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520; 3,539,633; 3,558,743; 3,586,629; 3,591,598; 3,600,372; 3,634,515; 3,649,229; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,872,019; 3,904,595; 3,957,746; 3,980,569; 3,985,802; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,083,699; 4,090,854; 4,354,950; With 4,485,023.

The preferred hydrocarbons source that is used to prepare Mannich polyamines dispersion agent is by saturated basically petroleum fractions and olefin polymer, preferably has those of polymer-derived of the monoolefine of about 6 carbon atoms of 2-.The hydrocarbon source is generally contained at least about 40, preferably at least about 50 carbon atoms so that dispersion agent has huge oil soluble.The olefin polymer of GPC number-average molecular weight between about 600-5000 preferably uses owing to reacting easily with low cost.But the macromolecule polymkeric substance also can use.Especially the hydrocarbon source of Shi Heing is isobutene polymer and the polymkeric substance made by the mixture of iso-butylene and raffinate stream I.

The preferred Mannich base dispersion agent Mannich ashless dispersant that to be the phenol that replaces by the about 1 mole of long chain hydrocarbon of condensation form with about 1-2.5 moles of formaldehyde and about 0.5-2 mole polyalkylenepolyamines.

The polymerized polyamines dispersion agent that is suitable as ashless dispersant is the polymkeric substance that contains alkaline amido and oil-soluble group (for example having the pendent alkyl groups at least about 8 carbon atoms).Described material is for example by various monomers, such as the alkene of methacrylic acid decyl ester, vinyl decyl ethers or relative macromolecule and the interpolymer of amino alkyl acrylates and the formation of aminoalkyl group acrylamide.In United States Patent (USP) 3329658,3449250,3493520,3519565,3666730,3687849 and 3702300, enumerated the example of polymerized polyamines dispersion agent.Preferred polymerized polyamines is a hydrocarbyl polyamine, and wherein alkyl is made up of the polymerisate of above-mentioned iso-butylene and raffinate stream I.Also can use PIB-amine and PIB-polyamines.

According to embodiment described herein, another component of disperser composition is the polyfunctional group viscosity index improver, all as known in the art and can buy from market.For example, instructed these products and preparation method thereof in the United States Patent (USP) 4732942,4863623,5075383,5112508,5238588 and 6107257, incorporated by reference respectively herein.

The viscosity index improver that the polyfunctional group viscosity index improver is preferably nitrogenous.The polyfunctional group viscosity index improver comprises nitrogenous or contains the ethylenically unsaturated aliphatic of oxygen and nitrogen or aromatic monomer and grafts on reaction product on the olefin copolymer.Be fit to nitrogenous or the ethylenically unsaturated monomer that contains oxygen and nitrogen comprise the N-vinyl imidazole, 1-vinyl-2-pyrrolinone (pyrrolidinone), the N-allyl imidazole, allyl amine, the 1-vinyl pyrrolidone, the 2-vinyl pyridine, 4-vinylpridine, N-methyl-N-vinyl acetamide, the diallyl methane amide, N-methyl-N-allyl group methane amide, N-ethyl-N-allyl group methane amide, N-cyclohexyl-N-allyl group methane amide, 4-methyl-5-vinylthiazole, N-allyl group diisooctyl thiodiphenylamine, 2-methyl isophthalic acid-vinyl imidazole, 3-methyl isophthalic acid-vinyl pyrazoles, N-vinyl purine, N-vinyl piperazine, N-vinyl succinimide, the vinyl piperidines, the vinyl morpholine, N-aryl phenylenediamine and composition thereof.

In United States Patent (USP) 4092255,4170561,4146489,4715975,4769043,4810754,5294354,5523008,5663126,5814586 and 6187721, instructed above-mentioned polyfunctional group multipolymer and preparation method thereof, incorporated by reference respectively herein.Wherein particularly preferred nitrogenous viscosity index improver is the ethylene-propylene copolymer and the N-aryl phenylenediamine of the maleic anhydride graft of number-average molecular weight in about 50000 scopes of about 5000-.The amount of the viscosity index improver in the embodiment in the lubricant compositions is being in the scope of the about 12 weight % of about 2-based on the lubricant compositions gross weight.

Non-dispersant viscosity index improver can be used for alternatives, or is used in combination with above-mentioned nitrogenous viscosity index improver.Described non-dispersant viscosity index improver includes, but are not limited to olefin copolymer, polyalkyl methacrylate and styrene-maleic acid ester.Wherein, preferred especially polyalkyl methacrylate.Viscosity index improver can generally be that the solution form of mineral oil solvent (normally strict purified mineral oil) provides with inert solvent.

The material that is applicable to viscosity index improver comprises the styrene-maleic acid ester, such as what can obtain from Lubrizol Corporation 3702,

3706 Hes

3715; Polyalkyl methacrylate is such as can (Darmstadt, Germany) commodity of Huo Deing are by name from ROHM GmbH

5543, 5548,

5549,

5550,

5551 Hes

5151, from Rohm ﹠amp; (Phliadelphia, Pa.) commodity of Huo Deing are by name for Haas Company

1277,

1265 Hes

1269, and from Ethyl Corporation (Richmond, Va.) commodity of Huo Deing are by name

5710VII; And olefin copolymer vi modifiers, such as what can obtain from Ethyl Corporation

5747VII,

5751VII,

5770VII and

5772VII, and obtain from Shell Chemical Company 200.Also can use mixture and the dispersion agent and the dispersion agent-antioxidant viscosity index improver of the said products.

As what enumerate herein, the dispersion agent of embodiment described herein comprises the dispersion agent that has derived from the relative big or relative small molecular weight of the alkyl of raffinate stream I and iso-butylene, or the mixture of the relative small molecular weight dispersion agent of the first relative macromolecule dispersion agent, and optional nitrogenous viscosity index improver with second.The Mannich base dispersion agent that phenol and formaldehyde and the polyalkylenepolyamines that first and second dispersion agents can be selected from succinimide that alkyl replaces respectively, replace by the condensation alkyl provides and the amine of alkyl replacement.Pass through gel permeation chromatography, preferably in the scope of about 1800-about 2500, at least a number-average molecular weight that has of first and second dispersion agents is preferably in the scope of about 500-about 1200 at least a number-average molecular weight that has of first and second dispersion agents.Most preferably at least a dispersion agent contains the alkyl derived from the polymerisate of iso-butylene and raffinate stream I.

The mixture of first and second dispersion agents can be made by mixing each component in a conventional manner.The preferred about 30-about 70 weight %s of macromolecule dispersion agent to account for the mixed dispersant gross weight, most preferably from about the amount of the about 65 weight % of 45-is present in the mixture.Therefore, the small molecular weight dispersion agent is the about 30 weight % of about 70-to account for the mixed dispersant gross weight preferably, and most preferably from about the amount of the about 45 weight % of 35-is present in the mixture.Dispersion agent total amount in the lubricant formulations is preferably about 10% at about 1-of lubricant formulations gross weight, more preferably from about in the scope of the about 6 weight % of 3-.

Following examples are used for simplified embodiment, but also limit embodiment never in any form.In following examples, use to contain the lubricant of different dispersion agents and mixture of dispersing agents, and carry out Sequence IIIG engine test, to measure sedimentation velocity with weighting piston deposit (WPD) expression.The lubricant that is used for all flow processs is Group II and Group III lubricating oil, promptly from 50wt%Ultra-SVHV14 Group III, 20wt% Conoco110N Pure-Performance Group II and the 30wt% Conoco 225N Pure-Performance Group II of S-Oils.Following dispersion agent is used for following examples:

644 dispersion agents are 1000MW _NPIBSA adds polyamines.

646 dispersion agents are 1300MW _NPIBSA adds polyamines.

1921 dispersion agents are 2100MW _NPIBSA add with nonyl phenol, formaldehyde and oxyacetic acid is reprocessed and the SA/PIB mol ratio greater than about 1.1 polyamines.

Above-mentioned dispersion agent is all from Richmond, and the Ethyl Corporation of Virginia obtains." PIBSA " is defined as polyisobutylene succinic acid or acid anhydrides." SA/PIB " is than the ratio that is succsinic acid or acid anhydrides mole number and PIB mole number in the PIBSA adducts.

Table 1

Shown in above-mentioned embodiment, mixture of dispersing agents (embodiment 2,3 and 4) has better WPD grade than the oil compositions that only contains relative macromolecule dispersion agent (embodiment 1).According to the foregoing description, when relative small molecular weight dispersion agent during with relative macromolecule dispersant (embodiment 2 and 4) obtained optimum.

The performance of other dispersion agent that expectation obtains from Ethyl Corporation mixture of dispersing agents and described herein similar.For example, following dispersion agent also can obtain from Ethyl Corporation.

643 dispersion agents are 1300MW _NPIBSA adds polyamines, wherein uses maleic anhydride and boric acid aftertreatment dispersion agent.

1919 dispersion agents are 2100MW _NPIBSA adds the polyamines that uses nonyl phenol, formaldehyde and oxyacetic acid aftertreatment.

1932 dispersion agents are 2100MW _NPIBSA adds that SA/PIB compares the polyamines greater than about 1.1.

7049 dispersion agents are 2100MW _NPIB-phenol Mannich reaction products.

Mixture of dispersing agents can be made shown in following table 2, and it is the representative mixture for prepare and use herein only, and constitutes the restriction to embodiment never in any form.

Table 2

Be applicable to that the base oil that uses can be selected from any synthetic or natural oil in the preparation lubricating oil composition, or its mixture.The synthetic base oil comprises alkyl ester, polyoxyethylene glycol and alcohols, the poly-alpha olefins of dicarboxylic acid, comprises the organic ester and the silicone oil of polybutene, alkylbenzene, phosphoric acid.Natural base oil comprises the mineral lubricating oils of thick wide material sources, and for example alkane belongs to, cycloalkanes belongs to or blended alkane genus-cycloalkanes belongs to.The viscosity that base oil has usually is 100 ℃ and is the about 15cSt of about 2.5-, the about 11cSt of preferably about 2.5-down.

The base oil that can be used for preparing lubricant compositions described herein can be selected from any base oil of the Groups I-V that stipulates among Americanpetroleum Institute (API) the Base Oil Interchangebility Guideline.Described base oil group is as follows:

Base oil Group ¹Sulphur (wt%) saturates (wt%) viscosity index

Group I〉0.03 and/or＜90 80-120

Group II≤0.03 and 〉=90 80-120

Group III≤0.03 and 〉=90 〉=120

All poly-alpha olefinss of Group IV (PAO)

All are not included among the Group I-IV those Group V

¹Base oil Group I-III is a mineral oil based feed.

Base oil can be selected from the mixture of natural oil, synthetic oil or natural and synthetic oil.Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard) and mineral lubricating oils, such as the alkane of liquid petroleum lubricating oil and solvent treatment or acid treatment belong to, cycloalkanes belongs to or alkane genus-cycloalkanes belongs to mixture type mineral lubricating oils.Also be fit to by coal or shale derived oil.Synthetic lubricating oil comprises hydrocarbon ils, such as the alkene (for example polybutene, polypropylene, propylene isobutylene copolymers etc.) of polymerization and copolymerization, poly-(1-hexene), poly-(1-octene), poly--(1-decene) etc. and composition thereof; Alkylbenzene (for example dodecylbenzene, tetradecyl benzene, dinonyl benzene, two (2-ethylhexyl) benzene etc.), polyphenyl (for example biphenyl, terphenyl, alkylating polyphenyl etc.), alkylating phenyl ether and alkylating diphenyl sulfide, and derivative, analogue and homologue etc.

Wherein the alkylene oxide polymer of modification such as esterified, etherificate of terminal hydroxy group and interpolymer and derivative thereof have constituted another kind of known available ucon oil.The example of this class oil is the alkyl or aryl ether (for example molecular-weight average is that about 1000 methyl-poly-Isopropanediol ether, molecular weight are the phenyl ether of the polyoxyethylene glycol of about 500-1000, the diethyl ether of polypropylene glycol that molecular weight is about 1000-1500 etc.) by the oil of polymerization of ethylene oxide or propylene oxide production, these polyoxyalkylene polymers, or its list or polycarboxylate, for example acetic ester, blended C ₃-C ₈The C of fatty acid ester or Tetraglycol 99 ₁₃The oxygen acid diester.

Another kind of operable ucon oil comprises the ester of dicarboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid, alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid etc.) and various alcohol (for example butanols, hexanol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol etc.).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, sebacic acid dioctyl ester, nonane diacid diisooctyl ester, nonane diacid diiso decyl ester, phthalic acid didecyl ester, the two eicosyl esters of sebacic acid, linoleic acid dimer, by the complex ester of reaction formation such as 1 mole of sebacic acid and 2 moles of Tetraglycol 99s and 2 moles of 2 ethyl hexanoic acids.

The ester that can be used as synthetic oil also comprises by C ₅-C ₁₂Monocarboxylic acid and polyvalent alcohol and polyol ethers, those that make such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol etc.

As mentioned above, base oil can be poly-alpha olefins (PAO).General poly-alpha olefins is derived from the monomer with about 20 or about 16 carbon atoms of about 6-of about 4-about 30 or about 4-.The example of useful PAO comprise by deutero-such as octene, decene or its mixture those.PAO can have 100 ℃ down about 15 for about 2-, or about 3-is about 12, or the viscosity index of the about 8cSt of about 4-.Can use poly-alpha olefins and composition thereof, the mixture of mineral oil and above-mentioned poly-alpha olefins.

Base oil can be the oil derived from the synthetic hydrocarbon of Fischer-Tropsch.The synthetic hydrocarbon of Fischer-Tropsch is to use the Fischer-Tropsch catalyzer, by containing H ₂Make with the synthetic gas of CO.This hydrocarbon requires further processing usually, to be used as base oil.Hydrocarbon can be by using United States Patent (USP) 6103099 or 6180575 disclosed method hydrogenation isomerizations; Use United States Patent (USP) 4943672 or 6096940 disclosed method hydrocracking and hydrogenation isomerizations; Use the dewaxing of United States Patent (USP) 5882505 disclosed methods; Or use United States Patent (USP) 6013171,6080301 or 6165949 disclosed method hydrogenation isomerization and dewaxings.

No matter above-mentioned open type refining, refining and the oil of re-refining are natural or synthetic oil (and wherein two or more mixture), all can be used for lubricating base oil.Unrefined oil is to be handled and direct those that obtain without being further purified by natural or synthetic source.For example, unrefined oil can be the shale oil that directly obtained by retorting operation, the petroleum oil that directly obtained by primary distillation or directly obtain and need not further handling the ester oil that promptly uses by esterification.Treated oil is except also handling to improve one or more characteristics through one or more purification steps, and is similar with unrefined oil.Many such purification techniques are well known by persons skilled in the art, such as solvent extraction, second distillation, acid or alkali extraction, filtration, infiltration etc.Rerefined oils is to be applied to the treated oil that is used to use and to obtain by being similar to the method that is used to obtain treated oil.This rerefined oils also can be described as reprocessing or handling oil again, and often further processes by the technology that is used to remove useless additive, pollutent or oily cleavage product.

The additive that is used to prepare composition described herein can be sneaked into base oil separately or in the mode of various secondary mixtures.But, preferably use additive concentrating liquid whole components to be sneaked into simultaneously (being that additive adds thinner) such as hydrocarbon solvent.Using additive concentrating liquid is the consistency of having utilized component to provide with the mixing of additive concentrating liquid form.The use concentrated solution has also reduced the time of sneaking into and has reduced and mixed the possibility of makeing mistakes.

An embodiment relates to the method that reduces wear in oil engine, wherein said method comprises that use contains the lubricating oil of dispersion agent described herein or mixture of dispersing agents as crankcase oil, be used for described oil engine, wherein with according to same way as and in oil do not contain dispersion agent or the mixture of dispersing agents, use the described engine of identical crankcase oil operation to compare, described dispersion agent exists with the amount that is enough to reduce wear in the oil engine that uses described crankcase oil operation.Therefore, in order to reduce wear, dispersion agent or mixture of dispersing agents are present in the lubricating oil with the amount of the 0.1-3 weight % that accounts for oily gross weight usually.Can comprise the wearing and tearing of cam wear and elevating lever by the representative wear type that uses composition described herein to reduce.In other embodiments, lubricant compositions described herein also can be used as or is formulated as gear oil, hydraulic efficiency oil, mechanical transmission liquid etc.

Many places are with reference to a large amount of United States Patent (USP)s in this manual.Herein fully with described these cited literature 2 hereby incorporated by reference with writing.

Above-mentioned embodiment is retrofited easily in practice.Therefore, embodiment is not limited to the above specific embodiments of enumerating.Otherwise above embodiment comprises its equivalent that obtains according to law, falls in the purport and scope of claims.

The patentee does not wish that disclosed technical scheme is reluctant for the public, and open can a word land the scope that falls into claim to any remodeling or modification, it can be thought based on doctrine of equivalents in this.

Claims

1. dispersion agent as lubricant additive, comprise and be selected from the succinimide that alkyl replaces, the amine that alkyl replaces and at least a by with the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation, wherein hydrocarbyl substituent is made up of the polymerisate of raffinate stream I and iso-butylene, pass through gel permeation chromatography, the number-average molecular weight of this polymerisate is in the 500-3000 scope, and the polymerisate that surpasses 70mol% has inferior ethene end group and wherein said polymerisate to be provided and comprises the gem-dimethyl carbon atom, the mesomethylene carbon atom, the alkyl polymeric chain of the mixture of the carbon atom that the carbon atom that monomethyl replaces and single ethyl replace.

2. according to the dispersion agent of claim 1, wherein hydrocarbyl substituent is that 55-65wt% contains the raffinate stream I of 40wt% iso-butylene and the polymerisate of 35-45wt% iso-butylene at least.

3. lubricant compositions comprises the oil of lubricant viscosity and is the dispersion agent of the claim 1 of 0.1-10wt% based on the lubricant compositions gross weight.

4. lubricant additive, comprise first dispersion agent and be selected from succinimide that alkyl replaces, amine that alkyl replaces and by second dispersion agent with the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation, wherein first dispersion agent is the dispersion agent of claim 1.

5. lubricant compositions comprises the oil of lubricant viscosity and is the lubricant additive of the claim 4 of 0.1-10wt% based on the lubricant compositions gross weight.

6. lubricant additive comprises:

First dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and at least a by with the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation; With

Second dispersion agent comprises the succinimide that is selected from alkyl and replaces, amine that alkyl replaces and a kind of by with the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation,

Wherein according to gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of first dispersion agent has is in the scope of 1500-2500, and wherein according to gel permeation chromatography, the number-average molecular weight that second dispersion agent has in the scope of 500-1200 and

Wherein the hydrocarbyl substituent one of at least of this first and second dispersion agent comprises the polymerisate of raffinate stream I and iso-butylene.

7. lubricant compositions comprises the oil of lubricant viscosity and is the lubricant additive of the claim 6 of 0.1-10wt% based on the lubricant compositions gross weight.

8. the method for the moving-member of lubricated vehicles, this method comprise uses the lubricant compositions that contains lubricant and lubricant additive as lubricating oil, is used for and a plurality of moving-members of the vehicles, and wherein lubricant additive package is drawn together:

Wherein according to gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of first dispersion agent has is in the scope of 1500-2500, wherein according to gel permeation chromatography, the number-average molecular weight that second dispersion agent has is in the scope of 500-1200, wherein lubricant additive be present in the lubricant compositions with the amount of one or more moving-members of being enough to the lubricated vehicles and

9. the method for a lubricated moving-member comprises moving-member is contacted with the lubricant compositions that contains lubricant additive that wherein lubricant additive package is drawn together:

Wherein according to gel permeation chromatography, the number-average molecular weight that the hydrocarbyl substituent of first dispersion agent has is in the scope of 1500-2500, wherein according to gel permeation chromatography, the number-average molecular weight that second dispersion agent has is in the scope of 500-1200, wherein lubricant additive be present in the lubricant compositions with the amount that is enough to the dispersiveness of enhanced granule in lubricant compositions and

10. the method for the moving-member of lubricated vehicles, this method comprises that use contains the lubricant compositions of significant quantity lubricant and dispersant additives as lubricating oil, the one or more moving-members that are used for the vehicles, dispersion agent comprises the succinimide that is selected from the alkyl replacement, the amine that alkyl replaces and at least a by with the alkyl substituted phenol deutero-Mannich base adducts of aldehyde and amine condensation, wherein hydrocarbyl substituent is made up of the polymerisate of raffinate stream I and iso-butylene, wherein pass through gel permeation chromatography, the number-average molecular weight of this polymerisate is in the 500-3000 scope, and the polymerisate that surpasses 70mol% have inferior ethene end group and

Wherein said polymerisate provides the alkyl polymeric chain of the mixture of carbon atom that comprises gem-dimethyl carbon atom, mesomethylene carbon atom, monomethyl replacement and the carbon atom that single ethyl replaces.