CN101161799A - Lubricating oil compositions - Google Patents

Lubricating oil compositions Download PDF

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Publication number
CN101161799A
CN101161799A CNA2007101809687A CN200710180968A CN101161799A CN 101161799 A CN101161799 A CN 101161799A CN A2007101809687 A CNA2007101809687 A CN A2007101809687A CN 200710180968 A CN200710180968 A CN 200710180968A CN 101161799 A CN101161799 A CN 101161799A
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quality
polymkeric substance
derived
unit
lubricating oil
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K-L·特塞
J·埃默特
J·G·班塞尔
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Infineum International Ltd
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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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2020/075—Dendrimers
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Lubricating oil compositions and viscosity index (VI) improver concentrates containing combinations of first polymers that are amorphous ethylene alpha-olefin copolymers; and second polymers that are star polymers, the arms of which are derived from diene, and optionally vinyl aromatic hydrocarbon monomer, wherein the star polymers have a Shear Stability Index (SSI) of from about 1% to about 35% (30 cycle).

Description

Lubricating oil composition
Technical field
The present invention relates to lubricating oil composition with the viscosity index improver composition preparation of fusion.More specifically, the present invention relates to comprise the oil of lubricant viscosity of main amount and the lubricating oil composition of viscosity index improver composition, described viscosity index improver composition contains at least two kinds of polymerization viscosity index improvers, and this lubricating oil composition provides improved viscosity (particularly at low temperatures) and shear stability simultaneously.
Background technology
The lubricating oil composition that is used for crankcase machine oil comprises base oil and the improvement lubricants performance of minor amount and the additive of its useful life of prolongation of main amount.Crankcase lubricating oil composition contains the polymeric component that is useful on improvement machine oil viscosity usually,, provides multi-grade oil thus, for example SAE 5W-30,10W-30,10W-40 and 15W-40 that is.These viscosity are improved material and often are called viscosity index (VI) improving agent, can improve the viscosity of lubricating oil preparation under comparatively high temps (usually above 100 ℃), and can excessively not improve the high shear rate viscosity under lesser temps (-10 to-35 ℃ usually).These oil-soluble polymers compare with other component with base oil and have higher molecular weight usually (＞100,000M n).The known type that is suitable as the polymkeric substance of lubricating oil composition viscosity index improver comprises ethylene, polymethacrylate, has Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and radial copolymer and the hydrogenant isoprene line style and the star polymer of vinyl aromatic blocks and hydrogenation polydiene block.
When using in a small amount, the lubricating oil composition viscosity index improver has advantageously improved the viscosity (have high thickening efficiency TE) of lubricating oil composition under comparatively high temps, reduced the opposing (by " CCS " performance measurement) of lubricating oil to engine cold-start, and antagonism using time tool degradation and molecular weight reduction (having low shear stability index SSI).In addition, because the viscosity index property improved polymkeric substance is fed in the lubricant blending machine with enriched material (wherein this viscosity index property improved polymkeric substance dilutes in oil) form usually, then this enriched material is mixed in the relatively large oil so that required lubricant product to be provided, therefore, further preferably, the viscosity index property improved polymkeric substance can be mixed in the enriched material but do not cause enriched material to have too high kinetic viscosity with relatively large.Some polymkeric substance have excellent above-mentioned some performance, but the one or more deficiencies in other performance.
Amorphous olefin copolymer (OCP) is a class VI improving agent.Traditionally, OCP is the multipolymer of ethene and propylene monomer (EPM) and optional diene monomers (EPDM).Amorphous OCP has utmost point low-crystallinity or does not have degree of crystallinity, and to the selection relative insensitivity of base oil and pour point reducer.But for given shear stability index (30 circulation SSI), amorphous OCP provides relatively poor thickening efficiency (TE) in oil.
Hypocrystalline OCP shows improved TE for given SSI, and still, the crystallographic property of this analog copolymer causes intermolecular and intramolecular interaction, and this causes the formation of network.Even the formation of this class network at room temperature also causes the difficulty in the operation of multipolymer enriched material, and the interaction between this analog copolymer and the base oil may cause poor low temperature viscosity, for example high MRV viscosity and scanning Brookfield gelation index value.
Star polymer is the 3rd class VI improving agent.The arm of star polymer derived from diene and randomly, vinyl aromatic monomer.OCP compares with hypocrystalline, and star polymer provides improved TE and SSI (30 circulation).But, when the cycle number of the test that is used to measure SSI increases (having ratified 90 circulation shear stability tests (ASTM D7109) in 2004), contain the kinetic viscosity (kv of the solution of star polymer 100) continue reduction, and contain the kv of the solution of OCP 100Near the asymptote value (referring to Shear Stability Index of Viscosity Modifiers-Effect of Polymer Architecture, people such as Huang deliver Singapore, 2002 on 8th Annual Fuels and Asian Conference andExhibition).
If the high total thickening efficiency that not only has star polymer and enriched material processing property, but also lubricating oil composition with shear stability of the low temperature viscosity of amorphous or hypocrystalline OCP and prolongation can be provided, then be favourable.
The open WO 96/17041 of the PCT on June 6th, 1996 discloses some adulterant of star-branched styrene-isoprene polymkeric substance and ethylene.The disclosure has been described and added a certain amount of ethylene in star-branched styrene-isoprene polymkeric substance, the dimensional stability of star shape branch copolymer can be effectively improved, thereby the star shape branch copolymer of stable solid heap (bale) form can be formed.
The United States Patent (USP) 4,194,057 on March 18th, 1980 discloses the viscosity index property the improved composition of the combination that contains certain class lower molecular weight aromatic vinyl/conjugated diolefine Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and ethylene.Aromatic vinyl/conjugated diolefine Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock that this patent has been described described type is insoluble to oil, and has improved solubility with the fusion of ethylene, and can form polymer concentrates.
The open WO 2004/087849 of the PCT on October 14th, 2004 discloses and has contained the high ethylene content ethylene of selecting type and the aromatic vinyl/diene Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock viscosity index improver composition with the adulterant of certain proportion fusion, according to description, this provides good low-temperature performance and weather resistance.
Brief summary of the invention
According to a first aspect of the invention, the oil of the lubricant viscosity that comprises main amount and the lubricating oil composition of viscosity index (VI) improver composition are provided, this viscosity index (VI) improver composition comprises first polymkeric substance and second polymkeric substance, first polymkeric substance is to comprise the amorphous or semi-crystalline ethylene alpha-olefin copolymer that is no more than 66 quality % units derived from ethylene, second polymkeric substance comprises star polymer, its arm derived from diene and, randomly, vinyl aromatic monomer, wherein star polymer has about 1% to about 35% shear stability index (SSI) (30 circulation).
According to a second aspect of the invention, provide the lubricating oil composition of first aspect, wherein first polymkeric substance and second polymkeric substance existed to about 20: 80 quality % ratio with about 80: 20.
According to a third aspect of the invention we, provide first or the lubricating oil composition of second aspect, it further comprises derived from number-average molecular weight (M n) the nitrogenous dispersion agent of polyene greater than about 1500.
According to a forth aspect of the invention, the lubricating oil composition of first, second or the third aspect is provided, wherein the base oil of this lubricating oil composition has about at least 80% saturates content, and described lubricating oil composition contains and is less than about 0.4 quality % sulphur, is less than about 0.12 quality % phosphorus and is less than about 1.2 quality % sulfate ashes.
According to a fifth aspect of the invention, provide and comprised thinning oil, the VI improving agent enriched material of first polymkeric substance and second polymkeric substance, first polymkeric substance is that degree of crystallinity is lower than 1.0% amorphous ethylene alpha-olefin copolymer, second polymkeric substance comprises star polymer, its arm derived from diene and, randomly, vinyl aromatic monomer, wherein star polymer has about 1% to about 35% shear stability index (SSI) (30 circulation), and wherein the total amount of polymkeric substance (comprising first polymkeric substance and second polymkeric substance at least) is at least 5 quality % of enriched material total mass in the enriched material.
Understand other and further purpose, advantage and feature of the present invention with reference to following specification sheets.
Detailed Description Of The Invention
Available ethene-alpha-olefin copolymer (OCP) comprises by vinyl monomer and the amorphous OCP of at least a other alpha-olefin comonomer synthetic in the practice of the present invention.Among the present invention among the available OCP OCP average quality % (hereinafter referred to as " ethylene content ") derived from diene can be low to moderate about 20 quality %, preferably be not less than about 25 quality %; More preferably be not less than about 30 quality %.Maximum ethylene content can be about 66 quality %.Preferably, the ethylene content of OCP is about 25 to 55 quality %, more preferably about 35 to 55 quality %.
For the ethylene-propylene copolymer that contains 35 quality % to 85 quality % ethene, ethylene content can be measured by ASTM-D3900.When being higher than 85 quality %, can use ASTM-D2238 to obtain methyl concentration, for ethylene-propylene copolymer, it is associated with ethene per-cent in the mode of determining.When the comonomer beyond the use propylene, do not have the ASTM test that covers big ethylene content scope; But, can use proton and carbon-13 nuclear-magnetism spectrometries to measure the composition of this base polymer.These are the time not need the absolute technology of calibrating in operation, and all nuclears of given element all produce identical effect to this spectrum.ASTM test for ethylene-propylene copolymer does not have the ethylene content scope of covering, and for any ethylene-propylene copolymer, can use above-mentioned nuclear magnetic resonance method yet.
" degree of crystallinity " is meant:
Degree of crystallinity (%)=(melting heat of (being total to) polymkeric substance, unit: J/g)/292 J/g * 100; Wherein measure melting heat, and 292J/g is that poly melting heat is (referring to SAE PaperNo.971696 by DSC; " Evaluation of Polyolefin Elastomers Produced by ConstrainedGeometry Chemistry as Viscosity Modifiers for Engine Oil ", people such as McGirk (1997)).
As mentioned above, ethene-alpha-olefin copolymer is made of ethene and at least a other alpha-olefin.Described " other " alpha-olefin generally includes those that contain 3 to 18 carbon atoms, for example propylene, 1-butylene, 1-amylene or the like.The alpha-olefin that preferably has 3 to 6 carbon atoms, particularly for economic reasons.Most preferred OCP is those that are made of ethene and propylene.
As known to the skilled person, ethene and more the multipolymer of high-grade alpha-olefin (for example propylene) can randomly comprise other polymerisable monomer.Typical these other monomers are non-conjugated dienes, for example following non-limitative example:
A. straight chain acyclic dienes, for example: 1, the 4-hexadiene; 1, the 6-octadiene;
B. side chain acyclic dienes, for example: 5-methyl isophthalic acid, 4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1, the mixed isomers of 7-octadiene and dihydromyrcene (dihydro-mycene) and dihydro ocimene (dihydroocinene);
C. the alicyclic diene of monocycle, for example: 1; 1, the 5-cyclooctadiene; With 1,5-cyclododecane diene; With
D. many alicyclic condensed ring of ring and bridged ring diene, for example: tetrahydroindene; The methyl tetrahydroindene; Dicyclopentadiene (DCPD); Dicyclo-(2,2,1)-heptan-2, the 5-diene; Alkenyl, alkylidene group, cycloalkenyl group and ring alkylidene group norbornylene, for example 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene; 5-cyclohexylene-2-norbornylene.
Be usually used in preparing in the non-conjugated diene of these multipolymers, the diene that contains at least one two key in the strain ring is preferred.Most preferred diene is 5-ethylidene-2-norbornene (ENB).When having diene, its amount (by weight) in multipolymer can be for greater than 0% to about 20%; Be preferably greater than 0% to about 15%; Most preferably greater than 0% to about 10%.Available OCP VI improving agent is preferably and contains the ethylene-propylene copolymer that is less than 2% diene units in the practice of the present invention.
The molecular weight of available OCP can change in big scope according to the present invention, because number-average molecular weight (M n) be low to moderate the viscosity that about 2,000 ethylene copolymer can influence oleaginous composition.Preferred minimum value M nBe about 10,000; Most preferred minimum value is about 20,000.Maximum value M nCan be as high as about 12,000,000; Preferred maximum is about 1,000,000; Most preferred maximum value is about 750,000.For available OCP among the present invention, especially preferred number-average molecular weight scope is about 15,000 to about 500,000; Preferably approximately 20,000 is to about 250,000; More preferably about 25,000 to about 150,000.Term used herein " number-average molecular weight " is meant the number-average molecular weight that records by gel permeation chromatography (" GPC ") with polystyrene standards.
Available OCP is included in those that make in body, suspension, solution or the milk sap.As known in the art, can use free radical, positively charged ion and anionic initiator or polymerizing catalyst, for example be used for the transition-metal catalyst of Z-N and metallocene-type (be also referred to as " single " center ") catalyzer, make monomer polymerization produce hydrocarbon polymer.
" thickening efficiency " (" TE ") represented the ability of the polymkeric substance of per unit mass with oily thickening, and is meant:
Figure S2007101809687D00061
Wherein c is polymer concentration (a polymkeric substance gram number/100 gram solution), kv Oil+polymkeric substanceBe the kinetic viscosity of polymkeric substance in reference oil, kv OilIt is the kinetic viscosity of reference oil.
The polymkeric substance that " shear stability index " (" SSI ") measured as the VI improving agent keeps the ability of thickening power during use in crankcase lubricant, and has represented the anti-degradation of polymkeric substance under working conditions.SSI is high more, and the stability of polymkeric substance is low more, i.e. its easy more degradation.SSI is meant the viscosity loss per-cent that is caused by polymkeric substance, and following calculating:
Figure S2007101809687D00062
Kv wherein FreshBe the kinetic viscosity of solution before degradation that contains polymkeric substance, kv AfterBe the kinetic viscosity of solution after degradation that contains polymkeric substance.Traditionally, use ASTM D6278-98 (being called Kurt-Orban (KO) or DIN testing bed test) to measure SSI.With the dissolving in suitable base oil (for example, solvent extraction 150 neutrality) of the polymkeric substance in the test, 100 ℃ of relative viscosities that are issued to 9 to 15 centistokes, and with testing apparatus pumping 30 circulation of gained fluid by stipulating in the ASTM D6278-98 rules.As mentioned above, 90 circulation shear stability tests (ASTM D7109) have been ratified in 2004.
" viscosity loss " measured the VI polymkeric substance and keep the ability of thickening power in use in the lubricant of preparation, and is defined as:
Viscosity loss (%)=kv Fresh-kv Used/ kv Fresh* 100
" cold cranking simulator " (" CCS ") measures the cold start characteristics of crankcase lubricant, and uses the technical measurement described in the ASTM D5293-92 traditionally.
OCP of the present invention preferably have about 15 to about 60%, preferably approximately 20% to about 55%, more preferably about 25% to about 50% SSI (30 circulation).OCP of the present invention preferably have about 1.5 to about 4.0, preferably approximately 1.6 to about 3.3, more preferably about 1.7 to about 3.0 TE.
In a preferred embodiment, OCP VI improving agent of the present invention is amorphous ethylene-propylene copolymer or the multipolymer adulterant of SSI (30 circulation) for about 20 to about 55%.More preferably, this class OCP VI improving agent is made via ziegler-natta catalyzed and is contained about 40 quality % to about 55 quality % ethene, or makes via (metallocenes) catalysis of single center and contain about 35 quality % to about 55 quality % ethene.
In the practice of the present invention available star (or radial) polymkeric substance or multipolymer have a plurality of derived from diene and, randomly, the arm of aromatic monomer, and have about 1% to about 35% shear stability index (SSI) (30 circulations).Diene or diolefine contain two two keys, concern the conjugation location with 1,3 usually.Contain the alkene of two keys more than two, be called polyenoid sometimes, also be taken into account in the definition of " diene " used herein.The available diene comprises and contains 4 to those of about 12 carbon atoms, for example 1,3-divinyl, isoprene, m-pentadiene, methylpentadiene, phenyl butadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, wherein 1,3-butadiene and isoprene and composition thereof are preferred.The preferred isoprene monomer that can be used as the precursor of multipolymer of the present invention can be used as 1,4-or 3, and 4-tectonic element and composition thereof is incorporated polymkeric substance into.Preferably, most of isoprene is as 1, and 4-incorporates polymkeric substance in the unit, for example surpass about 60 weight %, more preferably surpass about 80 weight %, for example about 80 to 100 weight %, most preferably surpass about 90 weight %, for example about 93 weight % to 100 weight %.The preferred divinylic monomer that can be used as the precursor of multipolymer of the present invention can be used as 1,2-or 1, and the 4-tectonic element is incorporated polymkeric substance into.Preferably, at least about 70 weight %, for example about at least 75 weight %, more preferably about at least 80 weight %, for example about at least 85 weight %, most preferably about at least 90 weight %, for example the divinyl of 95 weight % to 100 weight % is as 1,4-incorporates polymkeric substance in the unit.
The available vinyl aromatic monomer comprises and contains 8 to those of about 16 carbon atoms, for example the vinyl naphthalene that replaces of the vinylbenzene that replaces of aryl, vinylbenzene, vinyl naphthalene, alkyl that alkoxyl group replaces etc.Diene or diolefine contain two two keys, concern the conjugation location with 1,3 usually.Contain the alkene of two keys more than two, be called polyenoid sometimes, also be taken into account in the definition of " diene " used herein.The available diene comprises and contains 4 to those of about 12 carbon atoms, for example 1,3-divinyl, isoprene, m-pentadiene, methylpentadiene, phenyl butadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, wherein 1,3-butadiene and isoprene are preferred.
The arm of star polymer can be diene homopolymer, for example polyisoprene; The multipolymer of two or more diene, for example isoprene-butadiene multipolymer; Or diene and another monomeric multipolymer, for example isoprene-styrol copolymer.
The arm of star polymer also can be a segmented copolymer, the sort of shown in for example following general formula:
A z-(B-A) y-B x
Wherein:
A is the polymeric blocks that mainly comes from vinyl aromatic monomer;
B is the polymeric blocks that mainly comes from conjugate diene monomer;
X and z are independently for equaling 0 or 1 number; And
Y is 1 to about 15 integer.
The arm of star polymer also can be the taper line-type block polymer, the sort of shown in for example following general formula:
A-A/B-B
Wherein:
A is the polymeric blocks that mainly comes from vinyl aromatic monomer;
B is the polymeric blocks that mainly comes from conjugate diene monomer;
A/B is the tapered block of derived from ethylene base aromatic monomer and conjugate diene monomer.
In the description of this paper about the polymer blocks composition, " mainly " of use is meant as the appointment monomer of main ingredient in this polymer blocks or the monomer type amount with at least 85 weight % of this block weight and exists.
Preferably, form reactive polymer, form the arm of star polymer thus via anionoid polymerization.Have been found that anionoid polymerization provides and has narrow molecular weight distribution (M w/ M n) multipolymer, for example molecular weight distribution is less than about 1.2.
As is well known with as United States Patent (USP) 4,116, disclosed in 917, reactive polymer can prepare as the basic metal of anionic initiator or the anionic solution polymerization in the presence of the basic metal hydrocarbon (for example sodium naphthalene) by the mixture of conjugate diene monomer.Preferred initiator is lithium hydrocarbon or single lithium hydrocarbon.Suitable lithium hydrocarbon comprises unsaturated compound, for example allyl group lithium, methylallyl lithium; Aromatic substance, for example phenyl lithium, tolyl lithium, xylyl lithium and naphthyl lithium, particularly lithium alkylide, for example lithium methide, lithium ethide, propyl lithium, butyllithium, amyl group lithium, hexyl lithium, 2-ethylhexyl lithium and n-hexadecyl lithium.S-butyl lithium is preferred initiator.Initiator can be chosen wantonly with additional monomer in two or more stages, added in the polyblend.Reactive polymer is that ethylenic is undersaturated.
Forming the solvent that reactive polymer uses therein is the inert liq solvent, hydro carbons for example, aliphatic hydrocrbon for example, for example pentane, hexane, heptane, octane, 2-ethyl hexane, nonane, decane, hexanaphthene, methylcyclohexane or aromatic hydrocarbons, for example benzene, toluene, ethylbenzene, dimethylbenzene, diethylbenzene, propylbenzene.Hexanaphthene is preferred.Also can use the mixture of hydro carbons, for example lubricating oil.
Carrying out the polymeric temperature can change in wide region, for example from approximately-50 ℃ to about 150 ℃, 20 ℃ to about 80 ℃ of preferably approximatelies.Reaction should be carried out in inert atmosphere, for example nitrogen, and can choose wantonly under pressure, for example about 0.5 to about 10 the crust pressure under carry out.
The initiator concentration that is used to prepare reactive polymer also can change in wide region, and by the desired molecule amount decision of reactive polymer.
In order to form star polymer, the reactive polymer that forms via preceding method reacts with the polyene-based coupling agent in additional reactions steps.The polyene-based coupling agent that can form star polymer is known for many years, and for example at United States Patent (USP) 3,985, describes to some extent in 830.The polyene-based coupling agent normally has the compound of at least two non-conjugated thiazolinyls.This class group is typically connected on the identical or different electrophilic residue (for example aromatic nucleus).This compounds has following character: this thiazolinyl can independently react with different reactive polymers at least, is different from traditional conjugated diolefine polymerisable monomer in this respect, for example divinyl, isoprene, or the like.Can use pure or technical grade polyene-based coupling agent.This compounds can be aliphatic series, aromatics or heterocyclic.The example of aliphatic cpd comprises many vinyl and polyenoid propylacetylene, diacetylene, phosphoric acid ester and phosphoric acid salt, and dimethacrylate/salt, for example the dimethacrylate ethyl.The example of suitable heterogeneous ring compound comprises divinyl pyridine and divinyl thiophene.
Preferred coupling agent is the polyene-based aromatic substance, most preferably many vinyl aromatic compounds.The example of this compounds comprises by at least two alkenyl substituted aromatic substance of (preferably directly being connected with it), for example benzene,toluene,xylene, anthracene, naphthalene and durol.Object lesson comprises many vinyl benzenes, for example divinyl, trivinyl and tetrem alkenyl benzene; Divinyl, trivinyl and tetrem thiazolinyl neighbour-,-and right-dimethylbenzene, divinyl naphthalene, divinyl ethylbenzene, divinyl biphenyl, diisobutylene base benzene, di isopropenylbenzene and diisopropenyl biphenyl.Preferred aromatic substance is formula A-(CH=CH 2) xShown those, wherein A is the optional aromatic proton that replaces, x is at least 2 integer.Vinylstyrene, particularly between Vinylstyrene, be most preferred aromatic substance.Can use pure or technical grade Vinylstyrene (containing other monomer, for example vinylbenzene and ethyl styrene).Coupling agent can mix use with the monomer (for example vinylbenzene or ring-alkylated styrenes) that adds of a small amount of increase nuclear size.In this case, nuclear can be described as gathering (dialkylene coupling agent/monoalkenyl aromatic compounds) nuclear, for example poly-(Vinylstyrene/monoalkenyl aromatic compounds) nuclear.
The polyene-based coupling agent should add in the reactive polymer after monomer polymerization is finished substantially, and promptly coupling agent should only add after nearly all monomer has changed into reactive polymer.
The amount of the polyene-based coupling agent that adds can change in wide region, but preferably, every mole of unsaturated reactive polymer uses at least 0.5 mole of coupling agent.Every mole of reactive polymer about 1 to about 15 moles, preferably approximately 1.5 to about 5 moles amount are preferred.This amount (can add in two or more stages) is generally the amount that is enough to the reactive polymer of about at least 80 quality % to 85 quality % is changed into star polymer.
Linked reaction can be carried out in the solvent identical with living polymerization.Linked reaction can be carried out under the temperature in wide region, and for example 0 ℃ to 150 ℃, 20 ℃ to about 120 ℃ of preferably approximatelies.Reaction can be carried out to the pressure of about 10 crust in inert atmosphere (for example nitrogen) and at about 0.5 crust.
The star polymer of Xing Chenging is characterised in that the dense core or the nuclear of crosslinked poly-(polyene-based coupling agent) and is the many from examining outward extending arm of line style unsaturated polymer substantially thus.The number of arm can noticeable change, but is typically about 4 to 25.
Can make then in any suitable manner with the hydrogenation of gained star polymer.Can use hydrogenation catalyst, for example copper or molybdenum compound.Also can use the catalyzer that contains precious metal or contain the compound of precious metal.Preferred hydrogenation catalyst contain periodictable group VIII base metal or contain non-noble metal compound, i.e. iron, cobalt, particularly nickel.The object lesson of preferred hydrogenation catalyst comprises Raney nickel and the nickel on diatomite.Specially suitable hydrogenation catalyst is those that obtain by the organic compound reaction that makes metal hydrocarbon based compound and arbitrary group VIII metallic iron, cobalt or nickel, wherein the compound of back contains at least a as English Patent 1, the organic compound that is connected with atoms metal via Sauerstoffatom described in 030,306.Preferably by making trialkylaluminium (triethyl aluminum (Al (Et for example 3)) or triisobutyl aluminium) react the hydrogenation catalyst of acquisition with organic acid nickel salt (for example di-isopropyl Whitfield's ointment nickel, nickel naphthenate, 2 ethyl hexanoic acid nickel, di-tert-butyl benzoic acid nickel, the nickel salt of the alkene saturated mono carboxylic acid that the reaction in the presence of acid catalyst obtains with carbon monoxide and water by having 4 to 20 carbon atoms in the molecule) or with enol nickel or phenol nickel (for example nickel salt of acetonyl-acetone nickel, butylbenzene ethyl ketone).Suitable hydrogenation catalyst is well known to a person skilled in the art, aforementioned list limit anything but.
The hydrogenation of star polymer should be in solution, carrying out in the inert solvent during hydrogenation carries out.Stable hydrocarbon and saturated hydrocarbon mixtures are suitable.Advantageously, the solvent phase of hydrogenation solvent when carrying out polymerization with.Suitably, at least 50%, preferred at least 70%, more preferably at least 90%, most preferably at least 95% initial alkene formula nonsaturation is hydrogenated.
Then by any mode easily (for example passing through evaporating solvent) from carry out the hydrogenant solvent with recovered in solid form hydrogenant star polymer.Perhaps, oil (for example lubricating oil) can be added in the solution, and from the mixture that forms thus, remove solvent so that enriched material to be provided.Suitable enriched material contains the hydrogenant star polymer VI improving agent of about 3 quality % to about 25 quality %, preferably approximately 5 quality % to about 15 quality %.
In the practice of the present invention the available star polymer can have about 10,000 to 700,000, the number-average molecular weight of preferably approximately 30,000 to 500,000.Term used herein " number-average molecular weight " is meant the number-average molecular weight that records by gel permeation chromatography (" GPC ") with polystyrene standards after hydrogenation.It may be noted that importantly that when using this method to measure the number-average molecular weight of star polymer the number-average molecular weight that calculates is because the three-dimensional structure of star polymer and less than actual molecular weight.
In a preferred embodiment, star polymer of the present invention is derived from about 75% to about 90% isoprene and about 10% to about 25% divinyl, and surpass 80% butadiene unit be incorporate into 1, the 4-adduct.In another preferred embodiment, star polymer of the present invention comprises derived from about 30 to about 80%1,2-incorporate into about 20 to about 70%1, the amorphous butadiene unit of the divinyl that 4-incorporates into.In another preferred embodiment, star polymer is derived from isoprene, divinyl or its mixture, and further contains about 5 to about 35% styrene units.
Randomly, the VI improving agent of one or both used types can have the nitrogen-containing functional group that makes the VI improving agent have the dispersion agent ability in the practice of the present invention.A kind of trend in the industry is to use this class " multi-functional " VI improving agent to substitute some or all of dispersion agents in lubricant.Can be by with the residue of nitrogenous or hydroxyl, preferred nitrogenous residue grafted to the polymeric skeleton of VI improving agent (functionalized) and in polymerization VI improving agent, add nitrogen-containing functional group.Is as known in the art with nitrogenous residue grafted to the method on the polymkeric substance, and comprises and for example make polymkeric substance and nitrogenous residue contact (pure ground or in the presence of solvent) in the presence of the radical initiator.Radical initiator can produce by shearing (as in forcing machine) or adding thermal free radical initiator precursor (for example hydrogen peroxide).
The amount of nitrogenous grafted monomer is somewhat dependent upon the character of substrate polymer and the dispersed level that graftomer is needed.In order to make star and linear copolymers all have dispersiveness, gross weight based on graftomer, the amount of grafted nitrogen containing monomer is preferably about 0.4 to about 2.2 weight %, and preferably approximately 0.5 is to about 1.8 weight %, and most preferably about 0.6 to about 1.2 weight %.
Nitrogen containing monomer is grafted to method on the polymer backbone and suitable nitrogenous grafted monomer is known, and at for example United States Patent (USP) 5,141,996, WO98/13443, WO99/21902, United States Patent (USP) 4,146,489, United States Patent (USP) 4,292,414 and United States Patent (USP) 4,506,056 in be described, also referring to J Polymer Science, Part A:Polymer Chemistry, the 26th volume, 1189-1198 page or leaf (1988); J.Polymer Science, Polymer Letters, the 20th volume, 481-486 page or leaf (1982) and J.Polymer Letters, the 21st rolls up, 23-30 page or leaf (1983), all give Gaylord and Mehta and Degradation and Cross-linking of Ethylene-Propylene Copolymer Rubber on Reaction with Maleic Anhydride and/or PeroxidesJ.AppliedPolymer Science, the 33rd volume, 2549-2558 page or leaf (1987) is given Gaylord, Mehta and Mehta.
Amorphous OCP of the present invention and star polymer component can obtain as commodity independently.Can be available from the Infineum V534 of Infineum USA L.P. and Infineum UK Ltd. TMWith Infineum V501 TMIt is the example of commercially available amorphous OCP.Other example of commercially available amorphous OCP VI improving agent comprises can be available from the Lubrizol 7065 of The Lubrizol Corporation TMWith Lubrizol 7075 TMCan be available from the Jilin0010 of PetroChina Jilin Petrochemical Company TMWith can be available from the NDR0135 of Dow Elastomers L.L.C TMThe example that SSI is equal to or less than 35 commercially available star polymer VI improving agent is can be available from the Infineum SV200 of Infineum USA L.P. and Infineum UK Ltd. TMOther example that SSI is equal to or less than 35 commercially available star polymer VI improving agent comprises equally can be available from the Infineum SV250 of Infineum USA L.P. and InfineumUK Ltd. TMWith Infineum SV270 TM
Composition of the present invention contains that quality % ratio is about 80: 20 to about 20: 80, preferably approximately 35: 65 to about 65: 35, more preferably about 45: 55 to about 55: 45 specific OCP and star polymer.Polymer composition of the present invention can provide with the chemical combination solid polymer adulterant form of dimensional stabilizing, or with in oil, contain about 3 to about 20 quality %, preferably approximately 6 is to about 16 quality %, more preferably the about 9 enriched material forms to about 12 quality % polymkeric substance provide.Perhaps, enriched material of the present invention can comprise about 0.6 to about 16.0 quality %, preferably approximately 2.1 to about 10.4 quality %, more preferably about 4.0 to about amorphous OCP of 6.6 quality % and about 2.1 to about 10.4 quality %, preferably approximately 4.0 is to about 6.6 quality % star polymers.
This class enriched material can contain polymer blend as unique additive, or can further contain other additive, particularly other polymeric additive, and for example the mobile improving agent (" LOFI ") of lubricating oil is also referred to as pour point reducer (" PPD ") usually.Use LOFI or PPD to reduce can flow minimum temperature in the time of maybe can toppling over of fluid, and this class additive is known.Typical this class additive is C 8To C 18Dialkyl group fumarate/vinyl acetate copolymer, polymethacrylate and phenylethylene/maleic anhydride ester copolymer.Enriched material of the present invention can contain about 0 to about 5 quality %LOFI.Preferably, about at least 98 quality % of enriched material of the present invention, more preferably about at least 99.5 quality % are VI improving agent, LOFI and thinning oil.
This class VI improving agent enriched material can by use known technology with VI improving agent polymkeric substance and, randomly, LOFI is dissolved in thinning oil and prepares.When dissolved solids VI improving agent polymkeric substance when forming enriched material, the high viscosity of polymkeric substance can cause the dispersiveness of difference in thinning oil.In order to promote dissolving, usually by for example polymkeric substance granulation, chopping, grinding or efflorescence being improved the surface-area of polymkeric substance.Also can heat the temperature that improves thinning oil by for example using steam or deep fat.When diluent temperatures improved a lot (for example to being higher than 100 ℃), heating should be shrouded (N for example at rare gas element 2Or CO 2) under carry out.Also can use the mechanical energy that for example in forcing machine or masticator, polymkeric substance is applied to improve the temperature of polymkeric substance.Polymer temperature can be brought up to and be higher than 150 ℃; Polymer temperature preferably shrouds down at rare gas element and improves.Also can for example pass through to stir or stir (at reactor or in groove) by stirring enriched material, or the dissolving by using recycle pump to come auxiliary polyalcohol.Also can be used in combination two or more aforementioned techniques arbitrarily.Also can be by forming enriched material with oil exchange polymer solvent (normally volatile hydrocarbon, for example propane, hexane or hexanaphthene).This exchange can for example use distillation tower to realize, to guarantee staying any polymer solvent hardly.
For the lubricant for preparing fully is provided, solid copolymer or VI improving agent enriched material can be dissolved in the oil of the lubricant viscosity of main amount with the suit additive that contains lubricant additive other necessity or required.According to the lubricant for preparing fully of the present invention can in oil, comprise about 0.4 to about 2.5 quality %, preferably approximately 0.6 is to about 1.7 quality %, more preferably about 0.8 polymer composition of the present invention to about 1.2 quality %.Perhaps, the lubricant for preparing fully according to the present invention can comprise about 0.1 to about 2.0 quality %, preferably approximately 0.2 is to about 1.1 quality %, more preferably about 0.4 to about 0.7 quality % OCP and about 0.1 to about 2.0 quality %, preferably approximately 0.2 be to the star polymer of about 1.1 quality %.
The oil of available lubricant viscosity can be selected from natural oil, synthetic oil and composition thereof in the practice of the present invention.
Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard); Liquid petroleum and hydrorefined, solvent treatment or acid-treated alkane type, cycloalkanes type and mixing alkane-cycloalkanes type mineral oil.Derived from the oil of the lubricant viscosity of coal or shale also as the available base oil.
Ucon oil comprises hydrocarbon ils and halo hydrocarbon ils, for example the alkene of polymerization and copolymerization (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); Many benzene (for example biphenyl, terphenyl, alkylating poly-phenol); With alkylating phenyl ether and alkylating diphenyl sulfide and their derivative, analogue and homologue.
Alkylene oxide polymer and multipolymer and terminal hydroxyl thereof have constituted another kind of known synthetic oil by the derivative of modifications such as esterification, etherificate.These are with the polyoxyalkylene polymers of making by the polymerization of oxyethane or propylene oxide, the alkyl and the aryl ethers (for example molecular weight is 1000 the poly-Isopropanediol ether of methyl, or molecular weight is 1000 to 1500 polyoxyethylene glycol phenyl ether) of polyoxyalkylene polymers; With their monocarboxylate and polycarboxylate, for example acetic ester of Tetraglycol 99, blended C 3-C 8Fatty acid ester and C 13The oxoacid diester.
Another adequate types of synthetic oil comprises the ester of dicarboxylic acid (for example phthalic acid, succsinic acid, alkyl succinic acid and alkenyl succinic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linolic acid two polymkeric substance, propanedioic acid, alkyl propanedioic acid, thiazolinyl propanedioic acid) and various alcohol (for example butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, monoalkyl ethers of diethylene glycol, propylene glycol).The example of this class ester comprises the own diester of 2-ethyl of Polycizer W 260, sebacic acid two (2-ethylhexyl) ester, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate (DOP), didecyl phthalate, sebacic acid 2 alkyl esters, linoleic acid dimer and passes through the complexing ester of the reaction formation of 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 5To C 12Those that monocarboxylic acid and polyvalent alcohol and polyol ester are made, for example neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and tripentaerythritol.
Based on the oil of silicon, for example many alkyl-silicone oils, polyaryl silicone oil, many alkoxyl groups silicone oil or many aryloxy silicone oil and silicic acid ester oil have constituted another available types of synthetic lubricant; This class oil comprises tetraethyl orthosilicate, silicic acid four isopropyl esters, silicic acid four-(2-ethylhexyl) ester, silicic acid four-(4-methyl-2-ethylhexyl) ester, silicic acid four (to tert-butyl-phenyl) ester, six-(4-methyl-2-ethylhexyl) sily oxide, poly-(methyl) siloxanes and poly-(aminomethyl phenyl) siloxanes.Other ucon oil comprises the liquid ester (for example Tritolyl Phosphate, trioctyl phosphate, decylphosphonic acid diethyl ester) and the polymerizing tetrahydrofuran of phosphorated acid.
The oil of available lubricant viscosity can comprise the adulterant of one or more I classes, II class, III class, IV class or V class oil or above-mentioned oil in the practice of the present invention.The definition of oil used herein and API (API) publication " Engine Oil Licensing and Certification System ", Industry Services Department, the 14 edition, in December, 1996, described the same in the appendix 1,1998 year 12 months.Described publication is with the following classification of oil:
A) use the test method of table 1 regulation, I class oil contains and is less than 90% saturates and/or more than 0.03% sulphur, and has more than or equal to 80 and less than 120 viscosity index.
B) use the test method of table 1 regulation, II class oil contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and has more than or equal to 80 and less than 120 viscosity index.
Although be not the independent type of API approval, viscosity index is commonly referred to as " II+ class " oil greater than about 110 II class oil.
C) use the test method of table 1 regulation, III class oil contains more than or equal to 90% saturates and is less than or equal to 0.03% sulphur, and has the viscosity index more than or equal to 120.
D) IV class oil is polyalphaolefin (PAO).
E) V class oil is all other base oils that are not included in I, II, III or the IV class.
Character Test method
Saturates ASTM D2007
Viscosity index ASTM D2270
Sulphur ASTM D4294
Preferably, measure by Noack test (ASTM D5880), the oil volatility of lubricant viscosity is less than or equal to about 40%, for example be less than or equal to about 35%, preferably be less than or equal to approximately 32%, for example be less than or equal to approximately 28%, be more preferably less than or equal about 16%.Preferably, the oil viscosity index (VI) of lubricant viscosity is at least 100, preferably at least 110, and more preferably greater than 120.
Except VI improving agent and LOFI, the lubricant for preparing fully contains many other performance improvement additives usually, and they are selected from ashless dispersant, metallic or form washing composition, anti-wear agent, oxidation retarder or antioxidant, friction improver and fuel economy agent and the stablizer or the emulsifying agent of ash content.Traditionally, when the preparation lubricant, be provided at VI improving agent and/or a VI improving agent and a LOFI in the concentrated suit to the makers-up, and in one or more additional combinations that all the other additives are provided in the suit that concentrate, this is commonly referred to as DI (dispersion agent-inhibitor) suit.
The available dispersion agent comprises nitrogenous, ashless (no metal) dispersion agent among the present invention, and they are known can effectively reduce that the settling in gasoline and diesel engine forms when using in adding lubricating oil to the time.Ashless dispersant of the present invention comprise have can with the oil soluble polymerization long-chain skeleton for the treatment of divided particles bonded functional group.Usually, this class dispersion agent has with polymer backbone amine, amine-alcohol or the acid amides polar residues that is connected (usually via bridging group).Ashless dispersant can for example be selected from the monocarboxylic acid of long chain hydrocarbon replacement and oil soluble salt, ester, amino ester, acid amides, imide He the oxazoline of poly carboxylic acid or its acid anhydride; Carbothioic acid ester/the salt derivative of long chain hydrocarbon; Long chain aliphatic hydrocarbon with direct connected polyamines residue; The Mannich condensation product that forms with the phenol that replaces by long-chain and formaldehyde and polyalkylenepolyamines condensation.
Preferably improving disperser composition that the property multipolymer uses with VI of the present invention is the monocarboxylic acid that replaces derived from polyalkenyl or the nitrogenous dispersion agent of dicarboxylic acid, acid anhydride or ester, and it is polyalkenyl residue about 1500 to 3000, preferably approximately 1800 to 2500 that this dispersion agent has number-average molecular weight.Further preferably derived from number-average molecular weight be about 1800 to 2500 polyalkenyl residue and each thiazolinyl residue have about 1.2 to about 1.7, be preferably greater than about 1.3 to about 1.6, most preferably greater than about 1.3 succinimide dispersants (medium functionality dispersion agent) to about 1.5 functional groups (forming the residue of monocarboxylic acid or dicarboxylic acid).Functionality (F) can be determined according to following formula:
F＝(SAP×M n)/((112,200×A.I.)-(SAP×98))
Wherein SAP is saponification value (promptly restraining the KOH milligram number that consumes in the neutralization fully at acid groups in the reaction product that contains succsinic acid according to what ASTM D94 measured 1); M nIt is the number-average molecular weight of raw material olefin polymkeric substance; A.I. be the activeconstituents per-cent (rest part is unreacted alkene polymkeric substance, succinyl oxide and thinner) that contains the reaction product of succsinic acid.
Usually, each residue that generates monocarboxylic acid or dicarboxylic acid can react with nucleophilic group (amine, alcohol, acid amides or ester polar residues), and the functional group's number among the carboxylic acid acylating agent of polyalkenyl replacement has determined the quantity of the nucleophilic group in the final dispersion agent.
The preferred dispersing agent composition is the composition that comprises at least a polyalkenyl succinimide, this polyalkenyl succinimide is the succinyl oxide (for example PIBSA) that replaces of polyalkenyl and the reaction product of polyamines (PAM), its have about 0.65 to about 1.25, preferably approximately 0.8 to about 1.1, about 0.9 to about 1 coupling ratio most preferably.In this article, " coupling ratio " can be defined as be the succinyl among the PIBSA and the ratio of the primary amine group in the polyamine reactants.
Dispersion agent is preferably non-polymeric (for example being single succinimide or two succinimides).Dispersion agent of the present invention can be by as United States Patent (USP) 3,087, the traditional way boration of general description in 936,3,254,025 and 5,430,105.By using boron compound, for example the ester of boron oxide, halogenation boron, boric acid and boric acid is handled the dispersion agent that contains acyl group nitrogen, realizes the boration of dispersion agent easily.
Dispersion agent can be to be enough to make nitrogen, preferably approximately 0.10 that lubricating oil composition contains at least 0.08 weight % to about 0.18 weight %, more preferably the amount of about 0.115 to about 0.16 weight %, most preferably about 0.12 to about 0.14 weight % nitrogen exists.
Can add in the present composition with other additive that satisfies the specified property requirement is washing composition, metal antirusting agent, inhibiter, oxidation retarder, friction improver, antifoams, anti-wear agent and pour point reducer.The more detailed below argumentation of some of them.
Washing composition metallic or the formation ash content both had been used as washing composition to reduce or the removal settling, and again as acid neutralizing agent or rust-preventive agent, reduction is worn and torn and corrosion and prolongation engine life thus.Washing composition comprises polar head and long hydrophobic tail usually, and wherein polar head comprises the metal-salt of acidic organic compound.This salt can contain the almost metal of stoichiometric quantity, and in this case, they are commonly referred to as normal salt or neutral salt, and has 0 to 80 total basicnumber or TBN (can measure by ASTM D2896) usually.Can incorporate a large amount of metal base into by making excess metal compound (for example oxide compound or oxyhydroxide) and sour gas (for example carbonic acid gas) reaction.Gained high alkalinity washing composition comprises the neutral washing composition, and it is as metal matrix (for example carbonate) micellar skin.This class high alkalinity washing composition can have 150 or higher TBN, has 250 to 450 or higher TBN usually.
The dialkyl dithiophosphate metal-salt is usually as anti-wear agent and antioxidant.Metal can be basic metal or alkaline-earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.Zinc salt is most frequently used in the lubricating oil, and can be prepared as follows according to known technology: at first form dialkyl phosphorodithioic acid (DDPA) (usually by one or more alcohol or phenol and P 2S 5Reaction forms), use in the zn cpds then and formed DDPA.For example, can make phosphorodithioic acid by the mixture reaction that makes primary and secondary alcohol.Perhaps, can prepare multiple phosphorodithioic acid, the alkyl on wherein a kind of is a sechy-drocarbyl in nature fully, and the alkyl on other is uncle's alkyl in nature fully.In order to make zinc salt, can use any alkalescence or neutral zn cpds, but the most normal use oxide compound, oxyhydroxide and carbonate.Commercial additive is usually owing to using the excesses of basic zn cpds to contain excess zinc in neutralization reaction.
Oxidation retarder or antioxidant have reduced the mineral oil trend of deterioration in use.The oxidisability deterioration can raise by the sludge in the lubricant, lacquer deposit on the metallic surface and viscosity and show.This class oxidation retarder comprises hindered phenol, has preferred C 5To C 12The alkaline earth salt of the alkylphenol thioester of alkyl group side chain, sulfuration of nonyl phenol sulfurated lime, oil soluble phenates and sulfurized phenates, phosphorus or sulfurized hydrocarbon, phosphorated ester, thiocarbamate metal-salt, as United States Patent (USP) 4, oil-soluble copper compounds described in 867,890 and molybdate compound and arylamine.
Known friction improver comprises oil-soluble organo-molybdenum compound.This class organic-molybdenum friction improver also provides antioxidant and anti-wear agent effect for lubricating oil composition.The example of this class oil-soluble organo-molybdenum compound comprises dithiocar-bamate, dithiophosphates, phosphonodithious acid salt, xanthogenate, sulfo-xanthogenate, sulfide etc. and their mixture.Particularly preferably be molybdenum dithiocarbamate, dialkyl dithiophosphate, Alkylxanthates and alkylthio xanthogenate.
Other known friction improves the monoglyceride that material comprises higher fatty acid, for example XU 61518.10; The ester of long-chain poly carboxylic acid and dibasic alcohol, for example butanediol ester of dimerization unsaturated fatty acids; The oxazoline compound; Replace monoamine, diamines and alkyl ether amine, for example ethoxylated tallow amine and ethoxylation tallow ether amine with alkoxylated alkyl group.
Can pass through polysiloxane type antifoams, for example silicone oil or polydimethylsiloxane provide foam control.
Some above-mentioned additives can provide multiple effect; Therefore, for example, single additive can serve as dispersion agent-oxidation retarder.This method is known, and need not be described in further detail at this.
The additive that may also must comprise the viscosity stability that keeps adulterant.Therefore, although the additive of polar functionalities has been realized suitable low viscosity in the premix stage, observe, some compositions viscosity when long-time the storage raises.Effectively the additive that raises of this viscosity of control comprise preamble described be used to prepare ashless dispersant, by functionalized long chain hydrocarbon with the reaction of monocarboxylic acid or dicarboxyl acid or anhydride.
In the time of in being used in crankcase lubricant, the typical significant quantity of this class additional additives is as follows:
Additive Quality % (wide region) Quality % (preferably)
Ashless dispersant 0.1-20 1-8
Metal detergent 0.1-15 0.2-9
Inhibiter 0-5 0-1.5
The metal dialkyl dithiophosphate 0.1-6 0.1-4
Antioxidant 0-5 0.01-2
Pour point reducer 0.01-5 0.01-1.5
Antifoams 0-5 0.001-0.15
Auxiliary anti-wear agent 0-1.0 0-0.5
Friction improver 0-5 0-1.5
Base oil Surplus Surplus
Passenger vehicle diesel lubrication oil (PCDO) composition that the present invention prepares fully preferably have less than about 0.4 quality %, for example less than about 0.35 quality %, be more preferably less than about 0.03 quality %, for example less than the sulphur content of about 0.15 quality %.Preferably, the Noack volatility of the PCDO for preparing fully (oil of lubricant viscosity adds all additives) is no more than 13, for example is no more than 12, preferably is no more than 10.The PCDOs that the present invention prepares fully preferably has the phosphorus that is no more than 1200ppm, for example is no more than the phosphorus of 1000ppm, or is no more than the phosphorus of 800ppm.The PCDOs that the present invention prepares fully preferably has about 1.0 quality % or lower sulfate ash (SASH) content.
The large diesel engine that the present invention prepares fully (HDD) lubricating oil composition preferably have less than about 1.0 quality %, for example less than about 0.6 quality %, be more preferably less than about 0.4 quality %, for example less than the sulphur content of about 0.15 quality %.Preferably, the Noack volatility of the HDD lubricating oil composition for preparing fully (oil of lubricant viscosity adds all additives) is no more than 20, for example is no more than 15, preferably is no more than 12.The HDD lubricating oil composition that the present invention prepares fully preferably has the phosphorus that is no more than 1600ppm, for example is no more than the phosphorus of 1400ppm, or is no more than the phosphorus of 1200ppm.The HDD lubricating oil composition that the present invention prepares fully preferably has about 1.0 quality % or lower sulfate ash (SASH) content.
Further understand the present invention with reference to the following example.Except as otherwise noted, all wt per-cent shown in this article is all based on activeconstituents (AI) content of additive, and/or based on the gross weight of any suit additive or formulation (its oil for the AI weight of each additive adds and/or the thinner gross weight and).
Embodiment
Embodiment 1
The various polymerization VI improving agents and the VI improving agent adulterant of the 1 weight % polymers soln form of test in thinning oil, thus shear stability index or SSI (30 circulations measured; ASTMD628-98); And thickening efficiency, or TE.
VII-1 is number-average molecular weight (M n) be 360,000 and comprise the commercially available star polymer of at least 5 arms; Its each arm is the hydrogenant isoprene.
VII-2 is number-average molecular weight (M n) be 460,000 and comprise the commercially available star polymer of at least 5 arms; Its each arm is that styrene content is vinylbenzene-hydrogenated isoprene multipolymer of about 4 quality %.
VII-3 is content and the number-average molecular weight (M with derived from ethylene of 46.2 quality % n) be the commercially available amorphous OCP of 67,700 ziegler-natta catalyzed.
VII-4 is content and the number-average molecular weight (M with derived from ethylene of 43.8 quality % n) be the commercially available amorphous OCP of 44,800 metallocene catalyst.
VII-5 is content and the number-average molecular weight (M with derived from ethylene of 65.9 quality % n) be 39,200 commercially available hypocrystalline OCP.
VII-6 is content and the number-average molecular weight (M with derived from ethylene of 48.1 quality % n) be 44,000 commercially available amorphous OCP.
Table 1
Component The VII-type Ethylene content (quality %) 30 preceding kv of circulation KO 100 Kv behind 30 circulation KO 100 SSI(％) TE
VII-1 Star N/A * 9.15 9.11 0.9 1.91
VII-2 Star N/A * 11.25 10.47 11.9 2.51
VII-3 Amorphous OCP Z-N 46.2 10.37 8.45 34.0 2.27
VII-4 Amorphous OCP metallocenes 43.8 10.66 8.62 34.3 2.35
VII-5 Hypocrystalline OCP 65.9 9.61 8.64 19.8 2.05
VII-6 Amorphous OCP Z-N 48.1 11.53 ** 10.10 21.0 1.72
*Non-availability
*The solution that contains 1.5 quality % polymkeric substance; All other solution contain 1.0 quality % polymkeric substance
Use above-mentioned VI improving agent with commercial laundering agent inhibitor (DI) suit and the mobile improving agent (LOFI) of lubricating oil, thus a series of 15W40 level of following fusion lubricating oil composition (all amounts are represented as quality %):
Table 2
Component Embodiment 1 (contrast) Embodiment 2 (contrast) Embodiment 3 (invention) Embodiment 4 (invention)
The DI suit 16.20 16.20 16.20 16.20
LOFI 0.20 0.20 0.20 0.20
Base oil 83.01 83.13 83.01 83.01
VII-5 0.59 --- --- ---
VII-2 --- 0.47 --- ---
VII-1 and VII-3 (55/45) --- --- 0.59 ---
VII-1 and VII-4 (55/45) --- --- --- 0.59
Amount to 100.00 100.00 100.00 100.00
The viscosity of evaluation and test above-mentioned materials; The result is as follows:
Table 3
Embodiment VII handles (polymer quality %) kv 100 (cST) Kv loss (%) behind 90 circulation KO MRV is in 25 ℃ (cp) CCS is in 20 ℃ (cp)
Embodiment 1 0.59 14.18 8.7 21322 7771
Embodiment 2 0.47 14.33 17.0 23251 7262
Embodiment 3 0.59 14.12 5.9 25508 7918
Embodiment 4 0.59 14.22 9.0 26663 7629
Use above-mentioned VI improving agent with commercial laundering agent inhibitor (DI) suit and the mobile improving agent (LOFI) of lubricating oil, thus a series of 15W40 level of following fusion lubricating oil composition (all amounts are represented with quality %):
Table 4
Component Embodiment 5 (contrast) Embodiment 6 (contrast) Embodiment 7 (contrast) Embodiment 8 (invention)
The DI suit 11.80 11.80 11.80 11.80
LOFI 0.20 0.20 0.20 0.20
Base oil 87.35 87.66 87.12 87.28
VII-2 0.65 --- --- ---
VII-5 --- 0.74 --- ---
VII-6 --- --- 0.88 ---
VII-1 and VII-3 (40/60) --- --- --- 0.72
Amount to 100.00 100.00 100.00 100.00
The viscosity of evaluation and test above-mentioned materials; The result is as follows:
Table 5
Embodiment VII handles (polymer quality %) kv 100 (cST) Kv loss (%) behind 90 circulation KO MRV is in 25 ℃ (cp) CCS is in 20 ℃ (cp) Maximum gelation index **
Embodiment 5 0.65 14.05 19.7 26300 6250 4.1
Embodiment 6 0.74 13.90 10.8 20700 6180 12.2
Embodiment 7 0.88 13.92 9.8 26800 6870 4.7
Embodiment 8 0.72 13.90 10.8 28100 6500 4.0
*The maximum gelation index (ASTM 5133) of scanning Brookfield
Shown in the comparison of table 3, according to the substantially invariable kv of being combined in of VI improving agent of the present invention 100Provide down and the suitable low-temperature performance that provides by independent hypocrystalline OCP and star polymer, and compared improved shear stability with star polymer.Simultaneously, shown in the comparison of table 5, according to the substantially invariable kv of being combined in of VI improving agent of the present invention 100Under provide compare with amorphous OCP improved thickening efficiency and with VII/ base oil that hypocrystalline OCP greatly reduces interact (showing as lower gelation index).
The disclosure of all patents as herein described, article and other material is all quoted through this application in full and is incorporated this specification sheets into.Comprising shown in this paper and the claims, by or the description of the composition that constitutes by multiple specified ingredients substantially should be regarded as also comprising composition by will described multiple specified ingredients mixing making.Principle of the present invention, preferred embodiment and operator scheme have been described in aforementioned specification.What the applicant submitted is their invention, but is not considered as being subjected to the restriction of disclosed particular, because disclosed embodiment is considered to exemplary and nonrestrictive.Can under the situation that does not depart from essence of the present invention, make variation by those skilled in the art.

Claims (25)

1. lubricating oil composition, the oil and viscosity index (VI) improver composition that comprise the lubricant viscosity of main amount, this viscosity index (VI) improver composition comprises first polymkeric substance and second polymkeric substance, first polymkeric substance comprises degree of crystallinity and is not higher than about 1.0% amorphous ethylene-alpha olefin copolymer or ethylene-alpha-olefin-diene terpolymer, second polymkeric substance comprises star polymer, the arm of this star polymer derived from diene and, randomly, vinyl aromatic monomer, wherein star polymer has about 1% to about 35% shear stability index (SSI) (30 circulation).
2. lubricating oil composition as claimed in claim 1, wherein first polymkeric substance and second polymkeric substance existed to about 20: 80 quality % ratio with about 80: 20.
3. lubricating oil composition as claimed in claim 2, wherein said first polymkeric substance are to have to be less than 2% the unitary ethylene-propylene copolymer derived from diene.
4. lubricating oil composition as claimed in claim 3, wherein said ethylene-propylene copolymer are that shear stability index (SSI) is about 20% to about 50% amorphous copolymer.
5. lubricating oil composition as claimed in claim 4, the polymerization of wherein said ethylene-propylene copolymer via ziegler-natta catalyzed, and contain about 40 quality % to about 55 quality % ethene.
6. lubricating oil composition as claimed in claim 4, the polymerization of wherein said ethylene-propylene copolymer via (metallocenes) catalysis of single center, and contain about 35 quality % to about 50 quality % ethene.
7. lubricating oil composition as claimed in claim 2, wherein said second polymkeric substance is a hydropolymer, its derived from comprise diene units and, randomly, the arm link coupled polyenoid linking agent of vinyl aromatic units.
8. lubricating oil composition as claimed in claim 7, wherein said diene units comprise divinyl, isoprene or its mixture.
9. lubricating oil composition as claimed in claim 8, wherein said second polymkeric substance comprises about 75 to about 90 quality % unit and about 10 unit to about 25 quality % derived from butadiene derived from isoprene, the unit of described derived from butadiene that wherein surpasses about 80 quality % is as 1, and the 4-adduct is incorporated into.
10. lubricating oil composition as claimed in claim 8, wherein said second polymkeric substance comprises divinyl, and wherein about 30 to about 80 quality % butadiene unit is as 1, and the 2-adduct is incorporated into, and about 20 to about 70 quality % butadiene unit is as 1, and the 4-adduct is incorporated into.
11. lubricating oil composition as claimed in claim 8, wherein said second polymkeric substance further comprise about 0 to about 35 quality % derived from cinnamic unit.
12. lubricating oil composition as claimed in claim 2, wherein said first polymkeric substance are the ethylene-propylene amorphous copolymers with SSI of about 20% to about 50%; And described second polymkeric substance comprises about 75 to about 90 quality % the unit derived from the derived from butadiene of the unit of isoprene and about 10 to about 25 quality %; The unit of described derived from butadiene that surpasses about 80 quality % is as 1, and the 4-adduct is incorporated into; And described second polymkeric substance has about 1% to about 15% SSI.
13. lubricating oil composition as claimed in claim 1 further comprises derived from number-average molecular weight (M n) the nitrogenous dispersion agent of polyene greater than about 1500.
14.VI improving agent enriched material, comprise thinning oil, first polymkeric substance and second polymkeric substance, first polymkeric substance is that degree of crystallinity is not higher than 1.0% amorphous ethylene alpha-olefin copolymer, second polymkeric substance comprises star polymer, its arm derived from diene and, randomly, vinyl aromatic monomer, wherein star polymer has about 1% to about 35% shear stability index (SSI) (30 circulation), wherein, comprise at least in the enriched material that the total amount of the polymkeric substance of described first polymkeric substance and described second polymkeric substance is at least 5 quality % based on the total mass of enriched material.
15. VI improving agent enriched material as claimed in claim 14, wherein first polymkeric substance and second polymkeric substance existed to about 20: 80 quality % ratio with about 80: 20.
16. VI improving agent enriched material as claimed in claim 15, wherein said first polymkeric substance are to have to be less than 2% the unitary ethylene-propylene copolymer derived from diene.
17. VI improving agent enriched material as claimed in claim 16, wherein said ethylene-propylene copolymer are shear stability indexes (SSI) is about 20% to about 50% amorphous copolymer.
18. VI improving agent enriched material as claimed in claim 17, the polymerization of wherein said ethylene-propylene copolymer via ziegler-natta catalyzed, and contain about 40 quality % to about 55 quality % ethene.
19. VI improving agent enriched material as claimed in claim 17, the polymerization of wherein said ethylene-propylene copolymer via (metallocenes) catalysis of single center, and contain about 35 quality % to about 55 quality % ethene.
20. VI improving agent enriched material as claimed in claim 15, wherein said second polymkeric substance is a hydropolymer, its derived from comprise diene units and, randomly, the arm link coupled polyenoid linking agent of vinyl aromatic units.
21. VI improving agent enriched material as claimed in claim 20, wherein said diene units comprises divinyl, isoprene or its mixture.
22. VI improving agent enriched material as claimed in claim 20, wherein said second polymkeric substance comprises about 75 to about 90 quality % unit and about 10 unit to about 25 quality % derived from butadiene derived from isoprene, the unit of described derived from butadiene that wherein surpasses about 80 quality % is as 1, and the 4-adduct is incorporated into.
23. VI improving agent enriched material as claimed in claim 20, wherein said second polymkeric substance comprises butadiene unit, wherein about 30 to about 80 quality % butadiene unit is as 1, the 2-adduct is incorporated into, and about 20 to about 70 quality % butadiene unit is as 1, and the 4-adduct is incorporated into.
24. VI improving agent enriched material as claimed in claim 21, wherein said second polymkeric substance further comprise about 5 to about 35 quality % derived from cinnamic unit.
25. VI improving agent enriched material as claimed in claim 15, wherein said first polymkeric substance are the ethylene-propylene amorphous copolymers with SSI of about 35% to about 50%; And described second polymkeric substance comprises about 75 to about 90 quality % the unit derived from the derived from butadiene of the unit of isoprene and about 10 to about 25 quality %; The unit of described derived from butadiene that surpasses about 80 quality % is as 1, and the 4-adduct is incorporated into; And described second polymkeric substance has about 1% to about 15% SSI.
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