CN1179025C - High graft multi-functional olefinic copolymer viscosity index improver - Google Patents
High graft multi-functional olefinic copolymer viscosity index improver Download PDFInfo
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- CN1179025C CN1179025C CNB98126977XA CN98126977A CN1179025C CN 1179025 C CN1179025 C CN 1179025C CN B98126977X A CNB98126977X A CN B98126977XA CN 98126977 A CN98126977 A CN 98126977A CN 1179025 C CN1179025 C CN 1179025C
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Abstract
The present invention provides a new additive containing a highly-grafted multifunctional olefin copolymer which comprises a copolymer derived from grafts prepared from ethylene, at least one C3 to C23 alpha-monoolefin and optional polyene, and amine, wherein the copolymer of the ethylene and at least one C3 to C23 alpha-monoolefin has been grafted with the olefin copolymer of 0.3 to 0.75 carboxyl per 1000 number-average molecular weight unit, and the number-average molecular weight of the olefin copolymer is from 20000 150000. The present invention also provides a lubricating oil concentrate and a lubricating oil composition containing the additive.
Description
The present invention relates to the multifunctional lubricating agent addition agent of high graft, be used as the viscosity index improver of improvement in the time of in being used in lubricating oil composition.The invention still further relates to the method that prolongs the lubricant drain intervals and improve fuel economy and fuel economy weather resistance.
About in lubricating oil composition, using polymeric additive, this area that a lot of disclosed documents are arranged.Ethylene-propylene copolymer and ethene-alpha-olefin non-conjugated diene trimer have further been derived and are provided difunctional performance that such lubricating oil additive just is described in lubricating oil composition.
U.S.P4,089,794 discloses by ethene and one or more C
3-C
28Alpha-olefin and the grafting of ethylene unsaturated carboxylic acid's substance solution, then with the multi-functional material that the has carboxyl ethylene copolymer that obtains of polyamines, polyvalent alcohol or azanol reaction for example, this reaction product is used as sludge and the paint film control additive in the lubricating oil.
U.S.P4,137,185 disclose a kind of stable imines grafted ethylene copolymer additive that is used for lubricant.
U.S.P4,146,489 disclose a kind of graft copolymer, wherein skeleton polymer is the trimer that molten ethylene-propylene copolymer of oil or ethylene-propylene diene are used the modification of grafted monomer C-vinyl pyridine or N-vinyl pyrrolidone, and a kind of dispersant viscosity index improvers that is used for lubricating oil is provided.
U.S.P4,320,019 disclose a kind of multifunctional lubricating additive, and this additive is by ethene and C
3-C
8The multipolymer of α-monoolefine and olefin carboxylic acid's acylation reaction form the intermediate product of acylation reaction, and it prepares with the amine reaction then.
U.S.P4,340,689 disclose and a kind of the function organic group have been grafted to method on ethylene copolymer or the ethylene-propylene-diene trimer.
U.S.P4,357,250 disclose a kind of multipolymer and a kind of olefin carboxylic acid by " alkene " reaction then with the reaction product of monoamine polyamine mixture reaction.
U.S.P4,382,007 disclose a kind of dispersant viscosity index improvers, and this improving agent is by the ethylene-propylene polymkeric substance of polyamines deutero-dispersion agent and oxidation or ethylene-propylene diene trimer prepared in reaction.
U.S.P4,144,181 disclose a kind of polymeric additive that is used for fuel and lubricant, and this additive comprises and polyamines, polyvalent alcohol or azanol reaction, last grafted ethylene copolymer of reacting with an alkarylsulphonic acid.
WO96/39477 has proposed multigrade lubricating oil, and this lubricating oil comprises low saturated basic material, the ashless dispersant that is less than 3% quality and viscosity modifier.The document is not mentioned the multi-functional viscosity index improver of high graft of the present invention.
WO94/13763 discloses the multi-functional viscosity modifier of blended ethylene.The document is not mentioned the multi-functional viscosity index improver of high graft of the present invention.
U.S.P4,863,623 have mentioned multi-functional olefinic copolymer viscosity index improver.This patent is not mentioned the relation of functional and molecular weight of the multi-functional viscosity index improver of high graft of the present invention.
U.S.P5,075,383 discloses a kind of method for preparing dispersion agent and antioxidant olefin copolymer additives, and wherein owing to the shearing of machinery, the grafting of radical is accompanied by the reduction of the molecular weight of multipolymer.
U.S.P5,556,923 disclose addition deutero-EPR or EPDM oil solution.This patent is not mentioned the relation of functional and molecular weight of the multi-functional viscosity index improver of high graft of the present invention.
An object of the present invention is to provide a kind of multi-functional composition of olefin copolymer of new high graft.
Another object of the present invention provides the multi-functional of a kind of high graft lubricating oil composition is effectively improved the lubricant additive of viscosity index, dispersiveness and antioxidant property, and can prolong drain intervals and improve fuel economy and fuel economy weather resistance.
Of the present invention also have a purpose to provide a kind of new lubricating oil composition, the enriched material that this lubricating oil composition contains the multi-functional olefin copolymer additives of high graft of the present invention and new additive of the present invention is provided.
The multi-functional olefin copolymer of new high graft of the present invention comprises olefin copolymer of (1) acidylate and the reaction product that (2) are selected from following polyamine compounds, and wherein the olefin copolymer of this acidylate comprises ethene and C
3-C
23Alpha-olefin and optional unconjugated diene or the multipolymer or the trimer of triolefin, grafted ethene unsaturated carboxylic acid reactant therein, the grafting amount is 0.3-0.75 carboxyls of per 1000 number-average molecular weight units (Mn):
(a) the N-aryl phenylenediamine of representing by following formula:
Wherein, R
1Be hydrogen ,-NH-aryl ,-NH-aralkyl ,-NH-alkyl, or have the side chain or the straight chain group of 4-24 carbon atom, this group can be an alkyl, alkenyl, alkoxyl group, aralkyl, alkaryl, hydroxyalkyl, or aminoalkyl group; R
2Be-NH
2, CH
2-(CH
2)
n-NH
2, CH
2-aryl-NH
2, wherein n is the value of 1-10; R
3Be hydrogen, have the alkyl of 4-24 carbon atom, alkenyl, alkoxyl group, aralkyl, alkaryl;
(b) be selected from aminothiazole, aminobenzothiazole, the aminothiazole of amino diazosulfide and aminoalkyl group thiazole;
(c) aminocarbazole of representing by following formula:
Wherein, R and R
1Represent hydrogen, or have the alkyl of 1-14 carbon atom, alkenyl, or alkoxyl group;
(d) amino indole of representing by following formula:
Wherein, R represents hydrogen, or has the alkyl of 1-14 carbon atom;
(e) amino-pyrroles of representing by following formula:
Wherein, R is divalent alkylidene group and the R with 2-6 carbon atom
1Be hydrogen or alkyl with 1-14 carbon atom;
(f) the Aminoindazole ketone of representing by following formula:
Wherein, R is hydrogen or the alkyl with 1-14 carbon atom;
(g) the amino thiohydroxy triazole of representing by following formula:
Wherein, R can not exist or be selected from alkyl, alkenyl, the C of aralkyl or aryl
1-C
10The straight or branched alkyl;
(h) the amino white pyridine of representing by following formula:
Wherein, R is hydrogen or alkyl or the alkoxyl group with 1-14 carbon atom;
(i) aminoalkyl group imidazoles, 1-(2-amino-ethyl) imidazoles for example, 1-(3-aminopropyl) imidazoles; With
(j) aminoalkyl group morpholine, for example 4-(3-aminopropyl) morpholine.
This new lubricant compositions of the present invention comprises the multi-functional olefinic copolymer of the high graft of the oil of lubricant viscosity and significant quantity.
Can be used for the polymkeric substance or the copolymer matrix of the multi-functional olefinic copolymer additive of this new high graft of the present invention by ethene and propylene production, perhaps it can be by ethene and at least a at C
3-C
23Higher alkene in the alhpa olefin scope prepares.
Being used for preferred polymkeric substance of the present invention is ethene and one or more C
3-C
23The multipolymer of alhpa olefin.The multipolymer of ethene and propylene is most preferred.Other be fit to be used for replacing propylene to form multipolymer or be used in ethene and the mixture of propylene in form trimeric alhpa olefin and comprise 1-butylene, 1-amylene, 1-hexene, 1-octene and vinylbenzene; α, ω-diolefine for example 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene; The side chain alpha-olefin is 4-methyl butene-1 for example, 5-methylpentene-1 and 6-methyl heptene-1; With their mixture.
Can use the 3rd component to prepare to be often referred to the more complicated polymeric matrix of multipolymer customized.The 3rd component that generally is used for preparing copolymer matrix is the polyenoid monomer that is selected from non-conjugated diene and triolefin.The non-conjugated diene component is that those of 5-14 carbon atom are arranged on chain.Preferably the feature of this diene monomers is to have vinyl and can comprise ring-type and dicyclic compound in its structure.Representational diene comprises 1,4-hexadiene, 1, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene and 1,6-octadiene.In the preparation multipolymer, can use mixture more than a kind of diene.The preferred non-conjugated diene that is used to prepare terpolymer or copolymer matrix is 1, the 4-hexadiene.
Three olefinic constituents will have at least 2 unconjugated double bonds and have on chain until 30 carbon atoms.The general triolefin that is used to prepare multipolymer of the present invention is 1-isopropylidene-3 α, 4,7, and 7 α-tetrahydroindene, 1-isopropylidene Dicyclopentadiene (DCPD), dihydro-different Dicyclopentadiene (DCPD) and 2-(2-methylene radical-4 methyl-3-pentenyl) [2.2.1] dicyclo-5-heptene.
Ethylene-propylene or high alpha-olefin multipolymer can be by about 15-80 mole % ethene and about 85-20 mole %C
3-C
23Alpha-olefin is formed, and preferred mol ratio is about 35-75 mole % ethene and about 65-25 mole %C
3-C
23Alpha-olefin, preferred ratio are 50-70 mole % ethene and about 50-30 mole %C
3-C
23Alpha-olefin, most preferred ratio are 55-65 mole % ethene and about 45-35 mole %C
3-C
23Alpha-olefin.
The various terpolymers of above-mentioned polymkeric substance can contain non-conjugated diene or the triolefin of the 0.1-10 mole % that has an appointment.
Polymeric matrix, be ethylene copolymer or terpolymer, be that the molten number-average molecular weight of oil is about 20,000-150, the polymkeric substance of 000 straight or branched, this number-average molecular weight are to measure by gel permeation chromatography and common standard verification, and its preferred number-average molecular weight is 30,000-110,000.
Used term polymer and multipolymer are general comprises ethylene copolymer, terpolymer or interpolymer.These materials can contain a spot of other olefinic monomer, as long as the basic feature of these ethylene copolymers does not have great change.
The polyreaction that is used for forming ethene-alpha-olefin copolymer matrix usually is to carry out in the presence of the Ziegler-Narta of routine or metallocene catalyst system.Polymerisation medium is not special, can comprise solution, slurry or gas phase process that the those skilled in the art of this area know.When using solution polymerization, this solvent can be any suitable unreactive hydrocarbons solvent, and this solvent is a liquid under the condition of the reaction of alpha-olefine polymerizing; The example of satisfied hydrocarbon solvent comprises the straight-chain paraffin with 5-8 carbon atom, and hexane is preferred.Aromatic hydrocarbons, preferred aromatic hydrocarbons has single phenyl ring, for example benzene, toluene etc.; With the saturated cyclic hydrocarbon of proximate boiling spread, be specially suitable with above-mentioned straight-chain paraffin and aromatic hydrocarbons.Selected solvent can be a kind of mixture of and multiple above-mentioned hydrocarbon.When using slurry polymerization, be used for preferably liquid propene of polymeric liquid phase.What meet the requirements is that polymerisation medium does not have matrix, and this matrix can influence catalyst component.
Then the undersaturated carboxylic acid material of ethene is grafted on the ethylene copolymer that forms acidylate on the specified polymer backbone.Be suitable for being grafted on these carboxylic acid reaction things on the ethylene copolymer and contain at least one ethylenic linkage and at least one, preferred 2 carboxylic acids or its acid anhydrides or a polar group, this group can transform into said carboxyl by oxidation or hydrolysis.Preferably the carboxylic acid reaction thing is selected from vinylformic acid, methacrylic acid, styracin, Ba Dousuan, toxilic acid, fumaric acid and methylene-succinic acid reactant.More preferably the carboxylic acid reaction thing is selected from toxilic acid, fumaric acid, the mixture of maleic anhydride or two or three in the middle of them.The maleic anhydride or derivatives thereof generally is most preferred, because can buy on its market and reaction easily.Methylene-succinic acid or its acid anhydride are preferred under the situation of unsaturated ethylene alkene copolymer or terpolymer, because it has reductive trend in radical grafted process, form the interlinkage structure.
What this ethylene unsaturated carboxylic acid's material was general can provide every one or two carboxyl of molar reactive thing to this graftomer.Be that methyl methacrylate can provide carboxyl of per molecule to graftomer, and maleic anhydride can provide two carboxyls of per molecule to graftomer.
The amount that is grafted to the carboxylic acid reaction thing on the specified polymer backbone will provide a polymer backbone 0.3-0.75 carboxyl of per 1000 number-average molecular weight units, preferred per 1000 number-average molecular weight 0.3-0.5 carboxyl.For example, Mn is 6-10 carboxyl grafting of the every polymer chain of copolymer matrix of 20000, or the 3-5 mole maleic anhydride grafting of every moles of polymer.Mn is 30-50 carboxyl grafting of the every polymer chain of multipolymer of 100000, or the 15-25 mole maleic anhydride grafting of every polymer chain.Functional minimum is to reach minimum satisfied dispersed amount.Have been noted that if any, the amount of above-mentioned maximum function additional dispersing property be very little, other performance of this additive may be adversely affected.
When in extruding machine or enhancing mixed device, form this graft reaction of acylated olefin copolymer general in the presence of auxiliary free-radical initiator, in solution or in body, carry out.When this polymerization is when carrying out in hexane solution, as at U, S, P4,340,689,4,670,515 and 4,948, described in 842, in hexane, carry out graft reaction and be economy easily, these documents are classified reference as at this.The feature of resulting polymkeric substance intermediate product is have the carboxylic acid acidylate in its structure random functional.
In the batch process that forms acylated olefin copolymer; this olefin copolymer is added to rubber or device of plastic processing for example in extruding machine, enhancing mixed machine or the masticator; be heated to 150-400 ℃, be added to ethylene unsaturated carboxylic acid's reactant and free-radical initiator in the fused polymkeric substance respectively and make grafting.According to U, S, P5,075,383, this reaction is at random carried out under the blended condition, makes to shear and the ethylene copolymer grafting, and the document is classified reference as at this.This processing units is usually used nitrogen purging, preventing the polymkeric substance oxidation, and incidental by product of emitting unreacted reactant and graft reaction.The residence time in this processing units will be enough to provide desired acidylate degree, and feasible multipolymer by this acidylate of emptying purifying.After the emptying stage, can at random be added to mineral lubricating oils or ucon oil in the processing units, to dissolve the multipolymer of this acidylate.
Can be used for this ethylene unsaturated carboxylic acid's material of grafting comprises superoxide, hydroperoxide, peresters to the free-radical initiator on the polymer backbone, also comprise azo-compound, preferably those boiling points greater than 100 ℃ and in the grafting temperature range thermolysis compound of radical is provided.The representational example of these free-radical initiators is azo butyronitrile, dicumyl peroxide, 2,5-dimethylhexane-2, and 5-pair-tert-butyl peroxide and 2, the 5-dimethyl-oneself-3-alkynes-2,5-pair-tert-butyl peroxide.By the weight of reaction mixture, the consumption of this initiator is about 0.005%-1% (weight).
Make other method well known in the art of ethylene-olefin copolymer and ethylene unsaturated carboxylic acid's reactant reaction, for example halogenating reaction, heat or " alkene (ene) " reaction or their combination can be used for replacing the radical grafting method.These reactions are carried out in mineral oil or body usually, by under inert atmosphere at 250-400 ℃ of reacting by heating thing, to avoid producing radical or oxidized byproduct." alkene " reaction is preferred grafting method when ethylene-olefin copolymer contains unsaturated materials.In order to reach high graft amount of the presently claimed invention, every 1000Mn0.3-0.5 carboxyl just may need the free radical graft reaction to follow or be somebody's turn to do " alkene " or the reaction of hot joining branch.
Have this polymkeric substance intermediate product of carboxylic acid acidylate function and be selected from following polyamine compounds reaction:
(a) the N-aryl phenylenediamine of representing by following formula:
Wherein, R
1Be hydrogen ,-NH-aryl ,-NH-aralkyl ,-NH-alkyl, or have the side chain or the straight chain group of 4-24 carbon atom, this group can be an alkyl, alkenyl, alkoxyl group, aralkyl, alkaryl, hydroxyalkyl, or aminoalkyl group; R
2Be-NH
2, CH
2-(CH
2)
n-NH
2, CH
2-aryl-NH
2, wherein n is the value of 1-10; R
3Be hydrogen, have the alkyl of 4-24 carbon atom, alkenyl, alkoxyl group, aralkyl, alkaryl;
(b) by aminothiazole, aminobenzothiazole, the aminothiazole that amino diazosulfide and aminoalkyl group thiazole are formed;
(c) aminocarbazole of representing by following formula:
Wherein, R and R
1Represent hydrogen, or have the alkyl of 1-14 carbon atom, alkenyl or alkoxyl group;
(d) amino indole of representing by following formula:
Wherein, R represents hydrogen, or has the alkyl of 1-14 carbon atom;
(e) amino-pyrroles of representing by following formula:
Wherein, R is divalent alkylidene group and the R with 2-6 carbon atom
1Be hydrogen or alkyl with 1-14 carbon atom;
(f) the Aminoindazole ketone of representing by following formula:
Wherein, R is hydrogen or the alkyl with 1-14 carbon atom;
(g) the amino thiohydroxy triazole of representing by following formula:
Wherein, R can not exist or be selected from alkyl, alkenyl, the C of aralkyl or aryl
1-C
10The straight or branched alkyl;
(h) the amino white pyridine of representing by following formula:
Wherein, R is hydrogen or alkyl or the alkoxyl group with 1-14 carbon atom;
(i) aminoalkyl group imidazoles, 1-(2-amino-ethyl) imidazoles for example, 1-(3-aminopropyl) imidazoles; With
(j) aminoalkyl group morpholine, for example 4-(3-aminopropyl) morpholine.
Being used for particularly preferred polyamines of the present invention is N-aryl phenylenediamine, N-phenyl phenylenediamine more especially, N-phenyl-1 for example, 4-phenylenediamine, N-phenyl-1,3-phenylenediamine and N-phenyl-1,2-phenylenediamine.
Preferably this polyamines only contains a primary amine groups, so that avoid the coupling and/or the gelling of this olefin copolymer.
Being grafted with the polymeric matrix intermediate product of carboxylic acid acidylate function and the reaction between the specified polyamine compounds thereon preferably is performed as follows: the solution of heated polymerizable thing matrix under inert conditions, general then under the blended condition polyamine compounds being added in the solution of this heating carried out this reaction.Usually use a kind of oil solution that is heated to this polymeric matrix of 140-175 ℃, keep this solution simultaneously under nitrogen protection.This polyamine compounds is added in this solution and under specified condition reacts.
General, this polyamine compounds is dissolved in the tensio-active agent, and is added to mineral lubricating oils or ucon oil or contains in the solvent solution of olefin copolymer of this acidylate.Press U.S.P5,384,371 introduced like that, in 120-200 ℃ scope, under inert gas purge, under agitation heat this solution, the document is classified reference as at this.This reaction is carried out in the reactor that stirs under nitrogen purging usually.But, also can be added to downstream area to the surfactant soln of this polyamine compounds at the graft reaction-discharging area of twin-screw extrusion reactor.
The olefin copolymer and the polyamines reacted surface promoting agent that can be used for carrying out acidylate comprise; but be not limited thereto; those of following feature are arranged: (a) with mineral lubricating oils or the compatible dissolubility property of ucon oil, (b) polarity that can not change the boiling point of oil flash and vapour pressure characteristic and (c) be suitable for dissolving this polyamines.The tensio-active agent of suitable such type comprises the reaction product of aliphatic series and aromatic hydroxy compound and oxyethane, propylene oxide or their mixture.These tensio-active agents are called aliphatic series or phenol alkoxy compound usually.Representational example is SURFONIC
N-40, N-60, L-24-5, L-46-7 (Huntsman Chemical Company), Neodol
23-5 and 25-7 (Shell Chemical Company) and Tergitol
Tensio-active agent (UnionCarbide).Preferred surfactants comprise contain functional group for example-OH, can with those tensio-active agents of the olefin copolymer of acidylate reaction.
The amount of used tensio-active agent depends in part on the ability that it dissolves this polyamines.General, the concentration of used polyamines is 5-40% (weight).Institute is displaced or except enriched material discussed above, also can add tensio-active agent respectively, so that the total amount of the tensio-active agent in the finished product additive is 10% (weight) or still less.
Can join the mode of the multi-functional olefin copolymer of high graft of the present invention in the lubricating oil with any routine.So, can directly join the multi-functional olefin copolymer of this high graft in the lubricating oil, disperse or dissolve this multipolymer in lubricating oil with the amount of desired concentration.Can be added in the lubricating oil at following such mixture of the temperature of room temperature or raising.In addition, the multi-functional olefin copolymer of this high graft can with suitable oily molten solvents/diluents (for example benzene, dimethylbenzene, toluene, lubricating base oil and petroleum fractions) blending, form enriched material, this enriched material and lubricating oil blending obtain final product then.What such multifunctional additive for lubricating oils was general will contain (by active ingredient (A.I.)) about 3-45% (weight), the multi-functional olefin copolymer additives of preferred about 10-35% (weight) high graft and general about 20-90% (weight), preferably about 40-60% (weight) base oil (by the weight of enriched material).
In the lubricating oil composition that uses base oil, wherein additive is dissolved or dispersive, finds the main effectiveness of the multi-functional olefin copolymer product of high graft of the present invention.These base oils can be natural or synthetic base oil or their mixture.The base oil that is fit to be used for to prepare lubricating oil composition of the present invention comprises that those are used as spark ignition and compression-ignition engine usually, for example the base oil of the crankcase oil of automobile and truck engine, peculiar to vessel and rail diesel engine etc.Be used in and/or be fit to be used as in routine and use additive agent mixture of the present invention also can obtain favourable result in the base oil of power transmission liquid, heavy loading hydraulic liquid, fluid-link steering liquid etc.It also may be favourable adding compositions of additives of the present invention at gear oil, industrial lubricant, pump in lubricating oil and other lubricating oil composition.
Usually contain the other additive that these needed characteristics of filling a prescription will be provided in these lubricant formulas.In the middle of the additive of these types, comprise other viscosity index improver, antioxidant, sanitas, purification agent, dispersion agent, pour point depressant, anti-wear agent, suds suppressor, emulsion splitter and friction improver.
In the preparation lubricant formula, usually hydrocarbon ils for example in mineral lubricating oils or other the suitable solvent form with 10-80% (weight) active ingredient enriched material additive is added.Usually these enriched materials can with every part of weight to form for example automobile-used oil additive component 3-100 of crankcase of finished lubricants, for example lubricating oil dilution of 5-40 weight part.Certainly, the purpose of enriched material is to make it possible to handle various reluctant materials, and impel the dissolving or be dispersed in the final blended thing.Therefore, the multi-functional olefin copolymer of this high graft generally uses with the form of for example enriched material of the 10-50% in lubricating oil distillate (weight).
The multi-functional olefin copolymer of high graft of the present invention usually will be to comprise that with the oil that contains lubricant viscosity the mixture of the lubricating base oil of natural lubricating oil, ucon oil and their mixture uses.
Natural oil comprises animal oil and vegetables oil (for example Viscotrol C, lard), liquid petroleum and hydrorefined, solvent treatment or acid-treated paraffinic base, cycloalkyl and blended paraffin-naphthenic mineral lubricating oil.The oil of the lubricant viscosity that is obtained by coal or resinous shale also can be used as base oil.Be used for ucon oil of the present invention and comprise usually any at the used a variety of oil of ucon oil, it comprises, but be not limited thereto, poly-alpha olefins, alkylating aromatic hydrocarbons, epoxy alkane polymkeric substance, interpolymer, multipolymer and their mixture, wherein terminal hydroxyl groups is by improvement such as esterification, etherificates, the ester of dicarboxylic acid and silicon-based oil.
The invention still further relates to the method for the economical life of the economy of improving automobile fuel and fuel, wherein said method comprises above-mentioned lubricating oil composition joined in the crankcase of automobile and with it drives.
In addition, consider a kind of method that prolongs the oil draining period of lubricant in the automobile.This method comprises above-mentioned lubricating oil composition joined in the crankcase of automobile and with it drives.
Also consideration improves the method for the low-temperature performance of lubricating oil.Said method comprises mixes the oil of lubricant viscosity with the multi-functional olefin copolymer of above-mentioned high graft.
The multi-functional olefin copolymer of high graft of the present invention can aftertreatment, so that provide special lubricant applications needed additional performance.Post-processing technology is well known in the art, comprises boronation, phosphorylation and maleinization.
The following examples illustrate the preparation method of the multi-functional olefin copolymer of high graft of the present invention.
Example I((0.36 carboxyl/1000Mn) multi-functional viscosity modifier) of preparation high graft
With the identical described in the following embodiments multi-functional hydrocarbon copolymer of general method preparation.In the presence of solvent, prepare the ethylene-propylene copolymer of acidylate to the ethylene-propylene copolymer skeleton by radical grafting maleic anhydride.The number-average molecular weight of the ethylene-propylene copolymer of this acidylate by gel permeation chromatography is about 40,000.The mol ratio of reaction conditions and maleic anhydride and ethylene-propylene copolymer is such, and promptly 7.2 moles maleic anhydride is grafted on the skeleton of olefin copolymer.In order to form the ethylene-propylene copolymer of this acidylate, this just is equivalent to polymer backbone (i.e. 2 * 7.2=14.4 carboxyl/40,000 Mn=0.36 carboxyls/1000Mn) of 0.36 carboxyl/1000Mn.At 160 ℃, in the presence of tensio-active agent, the ethylene-propylene copolymer of this acidylate and N-phenyl-1, about 6 hours of 4-phenylenediamine (NPPDA) reaction.The add-on of this NPPDA will be enough to make in theory and all grafted carboxyl reactions.
Example II((0.71 carboxyl/1000Mn) multi-functional viscosity modifier) of preparation high graft
With the method identical with embodiment 1, the multi-functional viscosity modifier of the high graft of preparation embodiment 2.But, add the maleic anhydride of capacity, so that 14.2 moles maleic anhydride is grafted on the skeleton of olefin copolymer.In order to form the ethylene-propylene copolymer of this acidylate, this just is equivalent to polymer backbone (i.e. 2 * 14.2=28.4 carboxyl/40,000 Mn=0.71 carboxyls/1000Mn) of 0.71 carboxyl/1000Mn.At 160 ℃, in the presence of tensio-active agent, the ethylene-propylene copolymer of this acidylate and N-phenyl-1, about 6 hours of 4-phenylenediamine (NPPDA) reaction.The add-on of this NPPDA will be enough to make in theory and all grafted carboxyl reactions.
Comparative Example I(preparation has the multi-functional viscosity modifier of 0.16 carboxyl/1000Mn)
With the method identical with example I, the multi-functional viscosity modifier of preparation comparative example 1.But, add the maleic anhydride of capacity, so that 3.2 moles maleic anhydride is grafted on the skeleton of olefin copolymer.In order to form the ethylene-propylene copolymer of this acidylate, this just is equivalent to polymer backbone (i.e. 2 * 3.2=6.4 carboxyl/40,000 Mn=0.16 carboxyls/1000Mn) of 0.16 carboxyl/1000Mn.At 160 ℃, in the presence of tensio-active agent, the ethylene-propylene copolymer of this acidylate and N-phenyl-1, about 6 hours of 4-phenylenediamine (NPPDA) reaction.The add-on of this NPPDA will be enough to make in theory and all grafted carboxyl reactions.
The enhanced performance that the multi-functional olefin copolymer of the high graft of table 1 explanation the application of the invention obtains.Embodiment A, the olefin copolymer that contains embodiment 1, Comparative examples A, contain multi-functional viscosity modifier according to the WO-A-94/13763 preparation, can buy from Exxon Chemical Company, have in the lubricant formula of SAE 15W-50 automotive engine oil, the mineral oil basis oil of identical peace and quiet inhibitor component and ashless dispersant by dividing other viscosity modifier to join identical containing, prepare the product of embodiment A and Comparative examples A.The oil of these full formulas of test the results are shown in table 1 in Peugeot XUD 11ATE test.This Peugeot XUD 11ATE test illustrates that additive is to the effect of viscosity controller in the passenger vehicle diesel engine.
Table 1 test-results
| Test | The ACEA grade | Embodiment A | Comparative examples A | |
| B2 | B3 | |||
| The piston index | 42min | 46min | 50.0 | 40.9 |
| Viscosity increases | 200max | 125max | 20 | 214 |
| Sludge | R&R | R&R | 9.2 | 7.6 |
| Performance | B3 | Failure | ||
Result by table 1 can significantly find out, in XUD 11ATE test, the oil (embodiment 1) that contains the full formula of viscosity index improver of the present invention has reached the highest performance (being B3), and in this test, the oil (Comparative examples A) that contains the full formula of the multi-functional viscosity modifier of buying on the market is failed.These data show, for the viscosity controller in the passenger vehicle diesel engine, viscosity modifier of the present invention has significantly and the advantage that is not expected to.This viscosity controller has the advantage of following persistence to lubricant: the pump-conveying property of improvement, the oil draining period of improving wearing and tearing, improving fuel economy and improving prolongation.
Table 2 explanation, the performance that the multi-functional olefin copolymer of the high graft of the application of the invention is enhanced.Implement B, the olefin copolymer that contains embodiment 1, comparative example B, contain multi-functional viscosity modifier according to the WO-A-94/13763 preparation, can buy from Exxon Chemical Company, have in the lubricant formula of SAE 10W-40 automotive engine oil, the mineral oil basis oil of identical peace and quiet inhibitor component and ashless dispersant by dividing other viscosity modifier to join identical containing, prepare the product of Embodiment B and comparative example B.The oil of these full formulas of test the results are shown in table 2 in Peugeot TU3M HTPD test.This Peugeot TU3M HTPD test illustrates that additive is to viscosity controller and the sedimentary effect of high temperature in the passenger vehicle petrol motor.
Table 2 TU3M HTPD result
| Test | The ACEA grade | Embodiment B | Comparative example B | |
| A2 | A3 | |||
| The piston ring bonding | ＞9.0 | ＞9.0 | 9.8 | 9.3 |
| Piston ring bonding＞9.0 | 0max | 0max | 0 | 2 |
| The piston paint film | ＞60 | ＞65 | 81.6 | 61.5 |
| Viscosity increases | ＜40 | ＜40 | 39.3 | 15.0 |
| Performance | A3 | Failure | ||
Result by table 2 can significantly find out, in TU3M HTPD test, the oil (embodiment 1) that contains the full formula of viscosity index improver of the present invention has reached the highest performance (being A3), and in this test, the oil (comparative example B) that contains the full formula of the multi-functional viscosity modifier of buying on the market is failed.These data show that for viscosity controller and high temperature piston deposit, the multi-functional viscosity modifier of high graft of the present invention has tangible and wonderful advantage.Good performance in this test shows, the abrasion protection that improves in the long oil draining period and increase the ability of the oil draining period that prolongs, with the similar recipe ratio that contains the viscosity modifier outside the scope of the invention, be because than circlet and line wearing and tearing.
The result of table 3 explanation VE sludge and paint film and cold starting simulation meter (CCS).The multi-functional viscosity modifier of the high graft of example I and viscosity modifier relatively are added to respectively in the identical lubricant formula that contains the SAE 10W-30 mineral oil basis oil with identical peace and quiet inhibitor component, the Mannich dispersant of having bought on the market of 4% (weight) is added in the comparison oil, and only the Mannich dispersant of 2% (weight) is added in the oil of Embodiment C, the oil of Embodiment C contains the viscosity modifier of embodiment 1 preparation.Be present in this comparison viscosity modifier among the comparative example C according to the described preparation of above-mentioned Comparative Example I, so that 0.16 carboxyl is provided, i.e. 0.08 maleic anhydride mole, the copolymer matrix of every 1000Mn.Comparative example C contains 0.84% the copolymer matrix that derives from the comparison viscosity modifier, and Embodiment C contains viscosity index improver of the present invention, contains the copolymer matrix of 0.91% the viscosity modifier that derives from embodiment 1.It as reduction the direct result of the obvious reduction (2 pairs 4%) of the dispersion dosage of allowing by the special dispersing agent performance of the multi-functional viscosity modifier of the high graft of embodiment 1 by the represented low temperature viscosity of cold starting simulation meter test.
Table 3
| Embodiment C | Comparative example C | |
| CCS 20℃ | 3020 | 3300 |
| Average sludge (9.0 minutes) | 9.23 | 9.32 |
| Average paint film (5.0 minutes) | 6.31 | 6.07 |
Can significantly find out by top data, the composition that contains viscosity modifier of the present invention and the composition that contains the viscosity modifier outside the scope of the invention relatively also show comparable VE sludge and paint film even contain the oil that viscosity modifier of the present invention only contains the viscosity modifier of the Mannich dispersant of half amount of comparative example C and comparative example 1.In addition, significantly as can be seen, the oil that contains viscosity modifier of the present invention and the similar oil ratio that contains the viscosity modifier outside the scope of the invention demonstrate improved (promptly reducing) CCS.By this improvement of low-temperature performance, people just can prepare contain a spot of or even do not have unconventional, i.e. synthetic oil, the lubricating oil composition of poly-alpha olefins for example, and still satisfy the performance requriements of described crankcase oil.The mineral oil of a large amount that can use more that is not expected to is prepared lubricating oil of the present invention and is not reduced performance, and just making has bigger formulation flexibility and cost saving.
The dispersing agent performance of product of the present invention is set forth in the following table 4.It is dispersed to use sludge dispersivity test (SDT) to measure.This test determination dispersion agent suspends and the ability of desludging thin layer with blotting paper.When using the dispersion agent candidate, remove 2 rings of formation that deoil with blotting paper, ring constitutes the sludge that is passed on by dispersion agent in this, and this outer shroud comprises base oil.The effect of this dispersion agent is by the definition of the ratio of the diameter of the diameter of interior ring and outer shroud.For specific candidate, the high more then performance as the candidate of dispersion agent of this ratio is good more.In each test, the additive of 6% (weight) is mixed with the used oil of extreme of 94% VE testing of engine.This used oil, when 149 ℃ of store overnight, obtain 30-35% by on blotting paper not the diameter of the interior ring of dispersive sludge take advantage of 100 dispersivenesses that define with the ratio of the diameter of outer oil ring.
Table 4 sludge dispersivity test
| Additive | SDT result |
| Comparative Example I | 33 |
| Example I | 54 |
| Example II | 60 |
Result in the above-mentioned table 4 shows that the additive outside the product of the present invention and the scope of the invention compares, and demonstrates excellent dispersion properties (being higher SDT result).
When fluid film is thinned to boundary lubrication just taking place when being enough to make that relative metallic surface is interact with each other, just increases when this interacts to rub when taking place.In engine, the increase of friction just makes fuel economy reduce.
This boundary friction of fluidic can use the reciprocal equipment of high frequency (High Frequency ReciprocatingRig) (HFRR) to measure.This HFRR crosses plate by ball of vibration in the sample box that contains the 1-2ml sample to be operated.Can control vibrational frequency, ball horizontal throw path length, be added to load and test temperature on the ball.By controlling these parameters, can measure fluidic boundary friction performance.
New polymeric additive of the present invention and comparison dispersion agent are blended in the SAE 5W-30 full formula automotive engine oil." Predicting Seq.VI and VIA Fuel Economy from Laboratory Bench Test " byC.Bovington, identical condition described in the V.Anghel and H.A.Spikes (SAE Technical Paper 961142), be under the condition of 4N load, 1mm path length, 20Hz frequency, use HFRR to measure these fluidic boundary friction performances.Measure frictional behaviour at 130 ℃.
Table 5 explanation, with contain be less than 0.3-0.5 carboxyl/1000Mn multi-functional multipolymer relatively, the multi-functional multipolymer of new high graft of the present invention is joined the improvement of resulting boundary friction result in the automotive engine oil.As mentioned above, lower boundary friction result represents the fuel economy improved.Used in the following embodiments multi-functional olefinic copolymer viscosity modifier is the ethylene-propylene copolymer of number-average molecular weight about 40000, and this number-average molecular weight is to measure by gel permeation chromatography with by the general standard verification that the method for the above embodiments I and Comparative Example I is prepared.Table 5 has been listed the mole number of the carboxyl of every 1000Mn, the amount and the boundary friction result of ethylene-propylene copolymer viscosity index improver.Embodiment 1-16 contains the low-molecular-weight olefin copolymer dispersion agent of having bought on the market, has also listed used amount among each embodiment in the table.The Mannich dispersant that contains 2.0% routine among the embodiment 9-16 in addition.
All test oils all are based on the passenger vehicle automotive engine oil of SAE 5W-30 full formula.This oil is to prepare with the purification agent of having bought on the market, ZDDP, oxidation inhibitor, defoamer, pour point depressant, rust-preventive agent, viscosity index improver, friction improver and dilution treated oil.
Table 5, border friction result
| Embodiment # | Carboxyl/1000Mn olefin copolymer skeleton | Amount | Additional dispersion agent | The border friction |
| 1 * | 0.16 | 6.8 | 2.0 | 0.1012 |
| 2 * | 0.16 | 8.0 | 2.0 | 0.0990 |
| 3 * | 0.16 | 6.0 | 5.0 | 0.1003 |
| 4 * | 0.16 | 8.0 | 5.0 | 0.1011 |
| Mean boundary friction/% reduces 1 0.1004/0％ | ||||
| 5 | 0.36 | 6.0 | 2.0 | 0.0974 |
| 6 | 0.36 | 8.0 | 2.0 | 0.0974 |
| 7 | 0.36 | 6.0 | 5.0 | 0.0969 |
| 8 | 0.36 | 8.0 | 5.0 | 0.0990 |
| Mean boundary friction/% reduces 1 0.0977/2.7％ | ||||
| 9 * | 0.16 | 6.8 | 2.0 | 0.1076 |
| 10 * | 0.16 | 8.0 | 2.0 | 0.1094 |
| 11 * | 0.16 | 6.0 | 5.0 | 0.1075 |
| 12 * | 0.16 | 8.0 | 5.0 | 0.1084 |
| Mean boundary friction/% reduces 2 0.1082/0％ | ||||
| 13 | 0.36 | 6.0 | 2.0 | 0.1052 |
| 14 | 0.36 | 8.0 | 2.0 | 0.1047 |
| 15 | 0.36 | 6.0 | 5.0 | 0.1050 |
| 16 | 0.36 | 8.0 | 5.0 | 0.1053 |
| Mean boundary friction/% reduces 2 0.1050/2.9％ | ||||
| 17 * | 0.16 | 8.0 | 0 | 0.1090 |
| 18 | 0.36 | 8.0 | 0 | 0.1035 |
| % reduces 3 5.0％ | ||||
*Comparative example
1: with contain the percentage ratio that more low grafted oil ratio reduces than boundary friction, embodiment 1-4
2: with contain the percentage ratio that more low grafted oil ratio reduces than boundary friction, embodiment 9-12
3: the percentage ratio that reduces than the boundary friction of the oil of embodiment 18 with the oil ratio of embodiment 17
Data by top table can significantly be found out, therefore be less than 0.3-0.75 carboxyl/1000Mn and be oil compositions (the embodiment 1-4 of the olefin copolymer outside the scope of the invention with containing to have, 9-12 and 17) relatively, multi-functional olefin copolymer (the embodiment 5-8 that contains high graft of the present invention, 13-16 and 18) demonstrate improved (promptly reducing) boundary friction, it shows the economy of having improved above-mentioned fuel.
In practice, the present invention is easy to carry out sizable variation.Therefore, the invention is not restricted to above-mentioned certain embodiments.On the contrary, the present invention comprises the equivalent that obtains legally in the spirit and scope of appended claim.
The patentee does not want all disclosed embodiments are all dedicated to the public, does not want to make the degree of any disclosed improvement and change not fall within the scope of the claims on literal yet, and they are considered to a part of the present invention under the principle that is equal to.
Claims (3)
1. the multi-functional olefinic copolymer viscosity modifier of a high graft; it contains the reaction product of the olefin copolymer and the polyamines of acidylate; wherein; the amount of this polyamines is enough to the olefin copolymer reaction with all acidylates; the olefin copolymer of this acidylate contains a kind of olefin copolymer; olefin copolymer of per 1000 number-average molecular weight units is grafted with the 0.3-0.75 carboxyl on it, and wherein the number-average molecular weight of this olefin copolymer is 20000-150000.
2. according to the multi-functional olefinic copolymer viscosity modifier of the high graft of claim 1, wherein, this olefin copolymer is ethene and one or more C
3-C
23The multipolymer of alpha-olefin.
3. according to the multi-functional olefinic copolymer viscosity modifier of the high graft of claim 1, wherein, this polyamines is selected from:
(a) the N-aryl phenylenediamine of representing by following formula:
Wherein: R
1Be hydrogen ,-the NH-aryl ,-the NH-aralkyl ,-NH-alkyl or have the side chain or the straight chain group of 4-24 carbon atom, this group can be alkyl, alkenyl, alkoxyl group, aralkyl, alkaryl, hydroxyalkyl or aminoalkyl group; R
2Be-NH
2, CH
2-(CH
2)
n-NH
2Or CH
2-aryl-NH
2, wherein n represents 1-10; R
3Be hydrogen, have alkyl, alkenyl, alkoxyl group, aralkyl or the alkaryl of 4-24 carbon atom;
(b) be selected from a kind of aminothiazole of aminothiazole, aminobenzothiazole, amino diazosulfide and aminoalkyl group thiazole;
(c) aminocarbazole of representing by following formula:
Wherein: R and R
1Represent hydrogen, or have alkyl, alkenyl or the alkoxyl group of 1-14 carbon atom;
(d) amino indole of representing by following formula:
Wherein, R represents hydrogen or has the alkyl of 1-14 carbon atom;
(e) amino-pyrroles of representing by following formula:
Wherein, R is divalent alkylidene group and the R with 2-6 carbon atom
1Be hydrogen or alkyl with 1-14 carbon atom;
(f) the Aminoindazole ketone of representing by following formula:
Wherein, R is hydrogen or the alkyl with 1-14 carbon atom;
(g) the amino thiohydroxy triazole of representing by following formula:
Wherein, R can not exist or C
1-C
10The straight or branched alkyl, be selected from alkyl, alkenyl, aralkyl or aryl;
(h) the amino pyridine of representing by following formula:
Wherein, R is hydrogen or alkyl or the alkoxyl group with 1-14 carbon atom;
(i) be selected from the aminoalkyl group imidazoles of 1-(2-amino-ethyl) imidazoles and 1-(3-aminopropyl) imidazoles; With
(j) 4-(3-aminopropyl) morpholine.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100851397A CN100523152C (en) | 1998-12-10 | 1998-12-10 | Oil concentrate containing improved viscosity index improver and lubricating oil composition |
| CNB98126977XA CN1179025C (en) | 1998-12-10 | 1998-12-10 | High graft multi-functional olefinic copolymer viscosity index improver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB98126977XA CN1179025C (en) | 1998-12-10 | 1998-12-10 | High graft multi-functional olefinic copolymer viscosity index improver |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100851397A Division CN100523152C (en) | 1998-12-10 | 1998-12-10 | Oil concentrate containing improved viscosity index improver and lubricating oil composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1256305A CN1256305A (en) | 2000-06-14 |
| CN1179025C true CN1179025C (en) | 2004-12-08 |
Family
ID=5229830
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB98126977XA Expired - Lifetime CN1179025C (en) | 1998-12-10 | 1998-12-10 | High graft multi-functional olefinic copolymer viscosity index improver |
| CNB2004100851397A Expired - Lifetime CN100523152C (en) | 1998-12-10 | 1998-12-10 | Oil concentrate containing improved viscosity index improver and lubricating oil composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100851397A Expired - Lifetime CN100523152C (en) | 1998-12-10 | 1998-12-10 | Oil concentrate containing improved viscosity index improver and lubricating oil composition |
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| Country | Link |
|---|---|
| CN (2) | CN1179025C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7253231B2 (en) * | 2005-01-31 | 2007-08-07 | Afton Chemical Corporation | Grafted multi-functional olefin copolymer VI modifiers and uses thereof |
| CN101376860B (en) * | 2007-08-27 | 2011-02-09 | 中国石油化工股份有限公司 | Lubricating oil viscosity index improver, preparation thereof and lubricant oil |
| US8415284B2 (en) * | 2009-11-05 | 2013-04-09 | Afton Chemical Corporation | Olefin copolymer VI improvers and lubricant compositions and uses thereof |
| US8865633B2 (en) * | 2011-08-24 | 2014-10-21 | Afton Chemical Corporation | Gear oil compositions |
| US20180171258A1 (en) * | 2016-12-16 | 2018-06-21 | Afton Chemical Corporation | Multi-Functional Olefin Copolymers and Lubricating Compositions Containing Same |
| CN115161122B (en) * | 2022-06-22 | 2023-03-21 | 烟台德高石油有限公司 | Online cleaning agent for wind power hydraulic system and preparation method thereof |
-
1998
- 1998-12-10 CN CNB98126977XA patent/CN1179025C/en not_active Expired - Lifetime
- 1998-12-10 CN CNB2004100851397A patent/CN100523152C/en not_active Expired - Lifetime
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|---|---|
| CN100523152C (en) | 2009-08-05 |
| CN1616614A (en) | 2005-05-18 |
| CN1256305A (en) | 2000-06-14 |
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