CN1261550C - Viscosity growth inhibition in oil additive concentrates - Google Patents

Viscosity growth inhibition in oil additive concentrates Download PDF

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Publication number
CN1261550C
CN1261550C CNB028237277A CN02823727A CN1261550C CN 1261550 C CN1261550 C CN 1261550C CN B028237277 A CNB028237277 A CN B028237277A CN 02823727 A CN02823727 A CN 02823727A CN 1261550 C CN1261550 C CN 1261550C
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oil
methyl
acid
enriched material
amine
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CN1596296A (en
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K·戴克
T·E·纳莱斯尼克
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CHRUPTON CORP
Lanxess Solutions US Inc
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CHRUPTON CORP
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/09—Treatment with nitrogen containing compounds
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

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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)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A method is disclosed for inhibiting the rate of viscosity growth in an oil concentrate of a VI-dispersant prepared form a copolymer of ethylene and at least one C3-C16 alpha olefin, wherein said copolymer has been grafted with at least one unsaturated carboxylic acid-containing material, further reacted with an amount of a polyamine sufficient to neutralize said acid containing material, or at least one unsaturated nitrogen-containing material, comprising blending a primary antioxidant into said concentrate as a top treatment or as a displacement for an equal amount of diluting oil.

Description

Viscosity in the inhibited oil multifunctional additive for lubricating oils increases
Background of invention
1. invention field
The present invention relates to be used for the polymer viscosity index improver/dispersant additives enriched material of lubricating oil.More particularly, the present invention relates to suppress to be used for method oil compositions, grafting and amine-functionalized hydrocarbon polymer enriched material medium viscosity rate of rise.
2. background technology
The known higher molecular weight hydrocarbon polymer, for example ethylene copolymer, particularly ethylene-propylene copolymer can be used as and be used for oil compositions, and particularly the viscosity index of lubricating oil composition (VI) is improved additive.These VI improving agents can further react to form multi-functional VI improving agent.Multi-functional VI improving agent is a kind of like this material, and it not only improves the VI performance of oil, and gives dispersiveness, with the sludge that may form in work of suspension lubricating oil or the use and suppress carbon distribution in the engine.When storing with the oil concentrate form, the viscosity of these enriched materials may sharply increase in time.
United States Patent (USP) 3,928,497 have described a kind of method for preparing the ethene polymers or the multipolymer of graft modification, this method is included in radical initiator and exists down, in the aromatic solvent that alkyl replaces, but make ethene polymers or multipolymer and can with the derivatives reaction of the graft copolymerization of the dicarboxylic acid of its graft copolymerization or dicarboxylic acid, it is characterized in that reaction is to carry out adding the dicarboxylic acid or derivatives thereof gradually in the solvent that has initial ethene polymers or multipolymer when.
United States Patent (USP) 4,089,794 have described derived from about 2 to 98wt% ethene and one or more C 3To C 28The ethylene copolymer of alpha-olefin, ethylene-propylene copolymer for example, but this multipolymer is in the presence of the radical initiator of pyrolytic decomposition, under inert atmosphere, carry out solution graft copolymerization with ethylenic unsaturated carboxylic acid material at elevated temperatures, subsequently with can form carboxyl polymers grafted derivative with the multifunctional substance reaction of carboxyl reaction, this polymer derivant has good engine sludge and carbon distribution control behavior in fuel and lubricating oil, wherein above-mentioned can be (a) polyamines for example with the multifunctional material of carboxyl reaction, or (b) polyvalent alcohol, or (c) oxyamine, or their mixture.If molecular weight surpasses 10,000, these polymkeric substance also can be used as multifunctional viscosity index improver so.
United States Patent (USP) 4,219,432 disclose ethylene copolymer oil-soluble, derivatize, and it derives from about 2 to 98wt% ethene and one or more C 3To C 28Alpha-olefin such as propylene, but this ethylene copolymer is in the presence of the radical initiator of pyrolytic decomposition, under inert atmosphere, high temperature descends and ethylenic unsaturated dicarboxylic acid material carries out grafting, preferably carry out solution graft copolymerization, subsequently at first with the amino amine compound reaction of the uncle of only containing primary amino group of 0.1 to 0.9 molar equivalent, form the imide group, second step and the α that contains at least two primary amine groups of 0.1 to 0.9 molar equivalent then, ω-primary diamines, for example poly-(alkylene amines) forms carboxyl grafted polymerization imide intermediate as the diethylenetriamine reaction, generally be the succinimide intermediate, the 3rd step and C 1-C 30The acid anhydrides of hydrocarbon replacing acid, preferred acetic anhydride produces oil-soluble, the stable amide derivatives of described polyamines, and the oil solution of described amide derivatives is characterised in that thus, and viscosity changes minimum after the standing storage.The useful number-average molecular weight of described multipolymer is in about 700 to 500,000 scopes; Yet,, it is reported so that these multipolymers can be used as and improved the active multifunctional viscosity index improver of sludge-dispersing agent if molecular weight is 10,000 to 500,000.If the multipolymer of these derivatizes is handled with oil-soluble alkyl replacing acid (the chain alkyl aryl sulfonic acid of the preferred average about 20-40 of side chain carbon number), it is said that they will generate the hydrocarbon enriched material of no turbidity, can be used as the additive solution that is used for lubricating oil.
United States Patent (USP) 4,517,104 disclose ethylene copolymer oil-soluble, that improve viscosity index, as the multipolymer of ethene and propylene and the multipolymer of ethene, propylene and diolefine etc., they and ethylenic unsaturated carboxylic acid part, preferred maleic anhydride partial reaction or grafting, and with polyamines that contains two or more primary amine groups and carboxyl acid component (preferred alkylene polyamine and alkenyl succinic anhydrides such as polyisobutenyl succinic anhydride) reaction.Perhaps, the grafted ethylene copolymer can with the salt of described polyamines that has formed and acid constituents, acid amides, imide etc. (imide of preferred alkylene polyamine and alkenyl succinic anhydrides) reaction.These reactions allegedly can suppress to cause the crosslinked of viscosity increase, muddiness or gel simultaneously with carbon distribution rejection and the dispersed ethylene copolymer of introducing.Above-mentioned graft reaction can be by heating in mineral lubricating oils, perhaps more preferably carry out with radical initiator such as superoxide, described acid constituents this moment preferably also is used for stablizing the insoluble compound that side reaction forms, for example with the oil molecule of the maleic anhydride graft of amine reaction, suppress muddy thus and form, particularly when preparing the oil concentrate of the VI-dispersant additives that is used for joining subsequently lubricating oil.
United States Patent (USP) 4,693,838 have described hydrocarbon polymer such as ethylene copolymer, and they can be in the presence of radical initiator such as superoxide, in synthetic hydrocarbon lubricating oil, with unsaturated nitrogen containing monomer or unsaturated carboxylic acid reaction.Directly can be used as the VI-dispersant additives of the additive, particularly lubricating oil composition of oil compositions with nitrogen containing monomer grafted multipolymer.Can further react with the polymkeric substance of carboxylic acid reaction, also form multi-functional VI-dispersant additives with amine or amino alcohol.
United States Patent (USP) 4,735,736 disclose allegedly and can be used as the VI improving agent, oil-soluble hydrocarbon polymer, ethylene copolymer for example, optimal ethylene-propylene copolymer, it is with unsaturated acid material such as maleic anhydride graft, preferably by solid-state grafting, subsequently with polyamines, preferred tertiary-primary amine reaction, and handle and/or reaction with monoamine.The gained material is used for oil compositions such as lubricating oil, as the viscosity index improver with sludge dispersing property.Monoamine is handled and has allegedly been suppressed the viscosity growth of described additive when storing.
United States Patent (USP) 4,808,325 disclose dispersion agent and the Mannich composition that improves VI, it is said that said composition is not easy to increase in the storage process medium viscosity, said composition comprises a kind of physical mixture by the preparation of mixed phenol compound and Mannich condensation product, and described Mannich condensation product is to be obtained by the Mannich reaction that the polymkeric substance of oxidation, amine and formaldehyde generate reagent.
United States Patent (USP) 5,211,865 and 5,273,671 have described the oily composition that has allegedly improved antioxidant property, lubricating oil composition particularly, it contains the viscosity index improver-dispersion agent of viscosity index improvement amount, described viscosity index improver-dispersion agent is made up of the reaction product of following component: (a) with ethylenic unsaturated carboxylic acid material grafted with 1 or 2 acid or anhydride moiety, comprise at least a C of about 15 to 90wt% ethene and about 10 to 85wt% 3-C 28Alpha-olefin, number-average molecular weight are about 5,000 to 500,000 oil-soluble ethylene multipolymer; (b) contain the organic polyamine that at least two primary aminos are rolled into a ball; (c) aldehyde; (d) have on the heterocycle at least one-the heterocyclic nitrogen reagent of N (H)-group; With optional, (e) the dicarboxylic acid material that effectively provides the high functionality long chain hydrocarbon of amount of the VI improving agent-dispersion agent of the low temperature viscosity performance that shows improvement to replace, this material functionality is at least 1.2.
Mishra, M.K. wait the people at Polymer Science (Symp.Proc.Polym.1991) the 2nd volume, the 6994-699 page or leaf (is published by Tata McGraw-Hill, New Delhi India) has studied the viscosity characteristics of the ethylene-propylene copolymer solution that contains 58 to 80mol% ethene among the Specialty Olefin Copolymers in Oil Additives in.They have reported that in-10 to 50 ℃ of scopes the limiting viscosity of amorphous copolymer and equivalent hydrodynamic volume change minimum.On the contrary, for the partial crystallization multipolymer that contains 80mol% ethene, above-mentioned performance is fallen suddenly under the low temperature.They have also discussed the application of some multi-functional olefin copolymer based on ethylene-propylene (OCP) as viscosity index improver, and this improving agent is given machine oil with dispersing property and antioxidant property.They have reported that the Engine Block Test performance of the machine oil that contains these polyfunctional poly compounds is better than containing the oil of commercially available OCP VI improving agent.
Also referring to Kuczkowski, people's such as J.A Polymer-Bound Antioxidants, Rubber Chemistry and Technology, 57:621-651 (1984).
Above disclosed content by reference integral body be combined in herein.
The invention summary
According to the present invention, in the presence of radical initiator such as superoxide, hydrocarbon polymer such as ethene-alpha-olefin copolymer and terpolymer and be preferably dissolved in suitable solvent such as alkylbenzene, mineral oil, synthetic oil and/or aromatic ester in unsaturated carboxylic acid reaction.After carboxylic acid reaction, this polymkeric substance further forms multi-functional VI-dispersant additives with amine or amino alcohol reaction.Hydrocarbon polymer such as ethene-alpha-olefin copolymer and terpolymer also can react with unsaturated nitrogen containing monomer similarly.Then,, be also referred to as enriched material, be used as the additive that is used for oil compositions, the VI-dispersant additives in the lubricating oil composition with a certain amount of this graft copolymer of thinning oil blended.Then, these enriched materials mix with primary antioxidant, with their viscosity rate of rise of obvious inhibition.Described primary antioxidant is amine or phenols in essence preferably, and dissolves in the described multifunctional additive for lubricating oils.Preferred phenolic antioxidant is 2,6 di tert butyl 4 methyl phenol (BHT); Preferred amine antioxidants comprises alkylated diphenylamine and alkylation phenyl-Alpha-Naphthyl amine.Even in the dispersion agent enriched material, sneak into the oxidation inhibitor of little percentage composition, for example in the about 0.1wt% of enriched material weight, preferred about 0.25wt% is extremely up to 5wt% or more, shown in the oven ageing result, also providing significant advantage aspect the long-term viscosity stability of dispersant additives enriched material.
More particularly, the present invention relates to suppress the method for the oil concentrate medium viscosity rate of rise of VI-dispersion agent, comprise with the top and handle (top treatment) or replace the mode of the thinning oil of equivalent that primary antioxidant is sneaked in the described enriched material that described VI-dispersion agent is by ethene and at least a C 3-C 16The copolymer of alpha-olefin, wherein said multipolymer and at least a material grafting that contains unsaturated carboxylic acid, and further react with the polyamines that contains at least one primary amine.
On the other hand, the present invention relates to suppress the method for the oil concentrate medium viscosity rate of rise of VI-dispersion agent, comprise with the top and handle or replace the mode of the thinning oil of equivalent that primary antioxidant is sneaked in the described enriched material that described VI-dispersion agent is by ethene and at least a C 3-C 16The copolymer of alpha-olefin, wherein said multipolymer and at least a nitrogenous unsaturated material grafting.
The description of preferred embodiment
The present invention provides dispersion agent-viscosity index improver by following method: in the presence of radical initiator, in oily thinner, with the unsaturated acid solution graft copolymerization to high molecular weight hydrocarbon polymer, then further with this product and amine or polyol reaction.Even high molecular weight hydrocarbon polymer also has high viscosity under the grafting temperature, need dilution when therefore handling.After the unsaturated acid grafting, can add mineral (or synthetic) lubricating oil to form final multifunctional additive for lubricating oils, if perhaps product will further be reacted, for example form functionalized derivative, mineral (or synthetic) lubricating oil can be as another kind of thinner to carry out addition reaction and to be formed with the multifunctional additive for lubricating oils of usefulness so.This enriched material is carried out the top of primary antioxidant and handle, so that the viscosity rate of rise of enriched material is reduced to minimum in the storage process.
When carrying out in being grafted on mineral lubricating oils, this oil does not need to be removed after the grafting step, but can be as subsequently the graftomer solvent with the reaction of amine material, and as the solvent formation lubricating oil additive concentrate of final product.
Suitable hydrocarbon diluent comprises olefin polymer and alkylbenzene.Suitable polyolefine comprises derived from single ethylenic unsaturated olefin, and is preferred 3 to 18, for example the monomeric liquid polyolefine of the alkene-1 of 3 to 12 carbon atoms, its number-average molecular weight (Mn) is 200 to 10,000, for example 300 to 3000,350 to 1300 molal weights most preferably.Suitable polyolefine comprises poly-C 3-C 4Olefin polymer, particularly molecular weight are 200 to about 2000, for example 400 to 1300, and 500 to 900 polyisobutene according to appointment, poly decene, C 6To C 18The polymkeric substance of the mixture of alpha-olefin, etc.
Suitable liquid alkylbenzene is list and polyalkylbenzene, comprises that wherein each alkyl can have 1 to 300, and as list and many alkylated benzenes of 10 to 30 carbon atoms, wherein preferred molecular weight is 200 to 800 dialkyl benzene.
Be used to implement polymkeric substance of the present invention and generally have about 5000 to about 500,000, preferred 10,000 to 200,000,20,000 to 100,000 number-average molecular weight more preferably from about, and have narrow molecular weight usually.
The example of suitable hydrocarbon polymer comprises C 2-C 16, preferred C 2-C 8The homopolymer of alkene and two or more monomeric multipolymers, described alkene not only comprises alpha-olefin but also comprise internal olefin, can be straight or branched, aliphatics, aromatics, alkyl aromatic, cyclic aliphatic etc.Preferably, they are ethene and C 3-C 16The multipolymer of alkene is more preferably the multipolymer of ethene and propylene.Operable other hydrocarbon comprises vinylbenzene, butylene, iso-butylene, C 6With high alpha-olefin, atactic isoprene, divinyl etc.
Preferred polymkeric substance is by ethene and the preparation of ethylenic unsaturated hydrocarbons, and described ethylenic unsaturated hydrocarbons comprises and contains 3 to 16 carbon atoms, the ring-type of preferred 3 to 8 carbon atoms, alicyclic and acyclic material.These ethylene copolymers can contain 15 to 90wt% ethene, and preferred 30 to 80wt% ethene and 10 are to 85wt%, one or more C of preferred 20 to 70wt% 3-C 16, preferred C 3-C 8Alpha-olefin.The multipolymer of ethene and propylene is most preferred.Be fit to replace propylene to form multipolymer, perhaps be fit to be used in combination other alpha-olefin that forms terpolymer, tetrapolymer etc. and comprise 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene etc. with ethene and propylene; Also comprise the side chain alpha-olefin, for example 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 5-methylpentene-1,4,4-dimethyl-1-amylene and 6-methyl heptene-1 etc. and their mixture.
Term " polymer " " be intended to comprise multipolymer, terpolymer, tetrapolymer etc.Be used to implement polymkeric substance of the present invention and can comprise one or more non-conjugated diene hydrocarbon.The ethene that for example exists in hydrocarbon and the total amount of alpha-olefin, the amount of non-conjugated diene hydrocarbon is generally about 0.5 to 20mol%, and preferred about 1 to about 7mol%.
The representative example of operable non-conjugated diene comprises 1, the 4-hexadiene, 1, the 5-heptadiene, 1, the 6-octadiene, the 5-methyl isophthalic acid, the 4-hexadiene, 3,7-dimethyl-1, the 6-octadiene, 3,7-dimethyl-1, the 7-octadiene, the mixed isomers of dihydromyrcene and dihydro isopropyltoluene, 1, the 4-cyclohexadiene, 1, the 5-cyclooctadiene, 1,5-encircles 12 carbon diene, 4 vinyl cyclohexene, 1-allyl group-4-isopropylidene hexanaphthene, 3-allyl group-cyclopentenes, 4-allyl group tetrahydrobenzene, 1-pseudoallyl-4-(4-butenyl) hexanaphthene, 4,4 '-the dicyclopentenyl diene, 4,4 '-two cyclohexenyl diene, tetrahydroindene, the methyl tetrahydroindene, Dicyclopentadiene (DCPD), two ring (2.2.1) heptan-2, the 5-diene, the ethyl norbornylene, 5-methylene radical-6-methyl-2-norbornylene, 5-methylene radical-6,6-dimethyl-2-norbornylene, 5-propenyl-2-norbornylene, 5-(3-cyclopentenyl)-2-norbornylene, 5-cyclohexylidene-2-norbornylene, norbornadiene, Deng.
The compound that can be grafted on the hydrocarbon polymer preferably contains 3 to 10 carbon atoms, has the ethylenic degree of unsaturation, have at least one, preferred two hydroxy-acid groups or anhydride group, perhaps can be by change the polar group of this carboxyl into as oxidation or hydrolysis.Because therefore the not obvious homopolymerization of maleic anhydride or derivatives thereof but be connected to two carboxylic acid functionals are provided on the polymkeric substance is preferred.Other example comprise chloromaleic acid acid anhydride, itaconic anhydride, hemic acid anhydrides, toxilic acid, fumaric acid, above-mentioned substance monoesters, etc.
As United States Patent (USP) 4,160,739 and 4,161,452 instructed like that, various other unsaturated comonomers can be grafted on the hydrocarbon polymer with described unsaturated acid component.Can use one or more to be different from described unsaturated acid component, but contain the two keys of copolymerization, and can with this comonomer of unsaturated acid component copolymerization.This comonomer does not generally contain the free hydroxy-acid group, but can be to contain α in acid or alcohol moiety, the ester of β-ethylenic degree of unsaturation; Contain α, the hydrocarbon of β-ethylenic degree of unsaturation (comprising aliphatic hydrocarbon and aromatic hydrocarbon), for example C 4-C 12Alpha-olefin is as iso-butylene, hexene, nonene, dodecylene etc.; Styrenic, for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, to sec-butylbenzene ethene etc.; And vinyl monomer, for example vinyl acetate, vinylchlorid, methyl vinyl ketone, ethyl vinyl ketone, etc.
Well-known nitrogenous unsaturated compound can be used for preparing the polymkeric substance as oil additive.These monomers can be grafted on the hydrocarbon polymer, and except other, comprise those with 6 to 30 carbon atoms and 1 to 4 nitrogen-atoms.
The example of this nitrogen containing monomer comprises dimethylaminoethyl methacrylate, the vinylformic acid dimethylamino ethyl ester, N-(1,1-dimethyl-3-oxo butyl) acrylamide, N-(1,2-dimethyl-1-ethyl-3-oxo butyl) acrylamide, N-(1,3-phenylbenzene-1-methyl-3-oxopropyl) acrylamide, N-(1-methyl isophthalic acid-phenyl-3-oxo butyl) Methacrylamide, N, N-diethylamino ethyl acrylamide, 2-hydroxyethyl acrylamide, acrylamide, N-dimethylaminopropyl Methacrylamide, the N-caprolactam, the N-vinyl pyrrolidone, N-vinyl sulphur pyrrolidone, 3-methyl isophthalic acid-vinyl pyrrolidone, 4-methyl isophthalic acid-vinyl pyrrolidone, 5-methyl isophthalic acid-vinyl pyrrolidone, 3-ethyl-1-vinyl pyrrolidone, 3-butyl-1-vinyl pyrrolidone, 3,3-dimethyl-1-vinyl pyrrolidone, 4,5-dimethyl-1-vinyl pyrrolidone, the 2-vinyl pyridine, 4-vinylpridine, 2-methyl-5-vinylpyrine, 2-methyl-4-vinylpridine, 2-vinyl-5-ethylpyridine, 2-vinyl-6-picoline, etc.
Grafting utilizes one or more radical initiators to carry out, described initiator is a Diisopropyl azodicarboxylate, 2 for example, the 5-dimethyl-oneself-3-alkynes-2,5-two (tert-butyl peroxide) or its hexane homologue, ditertiary butyl peroxide, dicumyl peroxide, etc.Initiator is superoxide preferably, and in the gross weight of polymers soln, its consumption generally between about 0.005% to about 1%, about 25 ℃ to 250 ℃ of temperature, preferred about 100 ℃ to 250 ℃.
In the weight of initial soln, the consumption of ethylenic unsaturated carboxylic acid material (it is maleic anhydride preferably) is generally about 0.05% to about 10%, preferred 0.1% to 4.0%.The weight ratio of used carboxylic acid material and radical initiator was generally about 3: 1 to about 30: 1, preferred about 1: 1 to about 6: 1.
The initiator grafting is preferably carried out under the inert atmosphere atmosphere that for example nitrogen shrouds.Although grafting can be carried out in the presence of air, and to carry out grafting under the inert atmosphere of oxygen and compare being substantially devoid of, the output of the graftomer of hope generally reduces.The grafting time was generally about 0.1 to 12 hour, and preferred about 0.5 to 10 hour, more preferably 0.5 to 3 hour.
Described polymers grafted can be used reactant known in the art and condition in the mode of routine, reacts with suitable amine.Useful amine compound comprise contain in the molecule have an appointment 2 to about 60, preferred about 3 to about 20 total carbon atoms and about 1 to about 12, preferred about 2 monoamine and polyamines to about 7 nitrogen-atoms.These amine can be alkylamines, or contain the alkylamine of other group such as alkoxyl group, amido, imidazolinyl etc.
Useful amine comprises 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1, the 6-diamino hexane, diethylenetriamine, Triethylenetetramine (TETA), tetren, 1, the 2-propylene diamine, two-(1, the 2-propylidene) diamines, two-(1, the 2-propylidene) triamine, two-(1, the 3-propylidene) triamine, N, N-dimethyl-1, the 3-diaminopropanes, N, N-two (2-aminoethyl) quadrol, N, N-two (2-hydroxyethyl)-1, the 3-propylene diamine, 3-dodecyloxy-propylamine, N-dodecyl-1, the 3-propylene diamine, Tutofusin tris, diisopropanolamine (DIPA), diethanolamine, trolamine, single-, two-and three-tallow amine, N-(3-aminopropyl) morpholine, 3-dodecyloxy propylamine, N-(2-aminoethyl) morpholine, the 2-aminopyridine, 2-methylamino pyridine, 3-methylamino pyridine, thiazolamine, 2-amino-2-thiazoline, the 2-aminopyrimidine, the 2-aminobenzothiazole, methyl isophthalic acid-phenyl hydrazine, to morpholino aniline, N-aminopropyl imidazoles and its variant, N-aminopropyl pyrrolidone and its variant, N-aminopropyl piperidines and its variant, thiodiphenylamine and its variant, etc.
The amine that particularly preferably to be any other amido of having a primary amine group and existing be tertiary amine group.This has suppressed crosslinked, has higher acidity and work as polymkeric substance, and for example 0.1 milliequivalent/when the g polymkeric substance was above, crosslinked was particularly important.Can use and contain have an appointment 70wt% or the more mixture that only contains the amine of a primary amine or secondary amine group and have the amine of two or more primary amine or secondary amine group on a small quantity.The acidity that is lower than 0.1 milliequivalent/g polymkeric substance is to crosslinked more insensitive, and can use and have two or more active groups this moment, i.e. primary amine group or secondary amine group, perhaps primary amine group and secondary amine group, the perhaps amine of a primary amine group and an alcohol radical.
In hydrocarbon polymer weight, the consumption of amine is generally about 0.1 to about 10wt%, and preferred about 0.5 to about 5wt%.Amine is preferably to use by forming the needed amount of acid amides, imide or salt neutralizing acid part.
Preferably, the feasible dicarboxylic acid that the polyamine/equivalent mole of 1 to 2 mole of participation reaction is arranged of the consumption of amine.For example, for average 4 maleic anhydride groups of grafting on each molecule, number-average molecular weight is 40,000 ethylene-propylene copolymer, preferred per molecule grafted ethylene-propylene copolymer uses the amine of about 4 to 8 molecules.
Use the acidic moiety polymers grafted, preferably have an appointment 5 to solution generally containing up to 50wt%, preferred 10 to 30wt% polymkeric substance, by at about 100 ℃ to 250 ℃, heating is about 0.5 to about 10 hours under preferred about 120 ℃ to 230 ℃ temperature, preferred about 1 to about 6 hours, can easily react with amine.Preferably heat to help the formation of imide and acid amides.According to the type of reactant, excessive what, the key that forms etc., reaction can be very big than changing.
In a preferred embodiment, about multipolymer of 5 to 95% is dissolved in 95 to 5wt% the solvent, with forming solution in about 0.05 to 10wt% the unsaturated materials of solution weight and about initiator of 0.005 to 10wt%.Then, after the grafting step, add in about 40 to 500wt% mineral of solution weight or ucon oil, adding subsequently is enough to the amine of described acid that neutralizes, and heats 0.5-10 hour under 100 ℃ to 250 ℃ temperature.
Used oxidation inhibitor is primary antioxidant in the invention process, as amine oxidation inhibitor and hindered phenol.
Amine oxidation inhibitor can be the diarylamine that hydrocarbon replaces, for example the pentanoic antioxidant material of aryl, alkyl, alkaryl and aralkyl replacement.The indefiniteness example of the pentanoic that commercially available hydrocarbon replaces comprises the vinylbenzeneization or the alpha-methyl styrene diphenylamines of octyl groupization, nonylated and the heptyl diphenylamines and the para-orientation of replacement.The pentanoic that the hydrocarbon of sulfur-bearing replaces, for example p-(p-tolylsulfonyl amino)-pentanoic also is considered to the part in this kind antioxidant.
Can be used to implement the diarylamine that hydrocarbon of the present invention replaces can represent with following general formula:
Ar-NH-Ar′
Wherein, Ar and Ar ' are independently selected from aryl, and wherein at least one is preferably replaced by at least one alkyl.Aryl can be for example phenyl, xenyl, terphenyl, naphthyl, anthryl, phenanthryl etc.Alkyl substituent can be for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, their isomer etc.
The diarylamine that preferred hydrocarbon replaces is a United States Patent (USP) 3,452, those disclosed in 056 and 3,505,225, and their disclosed contents are combined in herein by reference.The diarylamine that preferred hydrocarbon replaces can be represented by following general formula:
Wherein,
R 1Be selected from phenyl and p-methylphenyl;
R 2And R 3Be independently selected from methyl, phenyl and p-methylphenyl;
R 4Be selected from methyl, phenyl, p-methylphenyl and neo-pentyl;
R 5Be selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-; With
R 6It is methyl.
Wherein, R 1To R 5Be independently selected from group shown in the formula I, R 7Be selected from methyl, phenyl and p-methylphenyl;
X is selected from methyl, ethyl, C 3-C 10Secondary alkyl, α, the group of the metal-salt of alpha-alpha-dimethyl phenmethyl, Alpha-Methyl phenmethyl, chlorine, bromine, carboxyl and carboxylic acid, wherein said metal is selected from zinc, cadmium, nickel, lead, tin, magnesium and copper; And
Y is selected from hydrogen, methyl, ethyl, C 3-C 10The group of secondary alkyl, chlorine and bromine.
Wherein,
R 1Be selected from phenyl or p-methylphenyl;
R 2And R 3Be independently selected from methyl, phenyl and p-methylphenyl;
R 4Be to be selected from hydrogen, C 3-C 10The primary, the second month in a season and tertiary alkyl, and C 3-C 10The group of alkoxyl group, it can be a straight or branched; And
X and Y are independently selected from hydrogen, methyl, ethyl, C 3-C 10The group of secondary alkyl, chlorine and bromine.
Figure C0282372700133
Wherein,
R 9Be selected from phenyl and p-methylphenyl;
R 10It is the group that is selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-;
R 11It is the group that is selected from methyl, phenyl and p-methylphenyl.
Wherein,
R 12Be selected from phenyl or p-methylphenyl;
R 13Be selected from methyl, phenyl and p-methylphenyl;
R 14Be selected from methyl, phenyl, p-methylphenyl and 2-phenyl isobutyl-; And
R 15Be selected from hydrogen, α, alpha-alpha-dimethyl phenmethyl, Alpha-Methyl diphenyl-methyl, trityl group and a, α, p-Three methyl Benzene methyl.
It is as follows to be used for typical chemical of the present invention:
Figure C0282372700142
Type i V
R 9Be phenyl, R 10And R 11It is methyl.
In the pentanoic that above-mentioned preferred hydrocarbon replaces, the pentanoic of the replacement of following formula is particularly preferred:
Wherein, R 16And R 17It is methyl or phenyl.R wherein 16And R 17The compound that all is methyl is 4,4 '-two (α, alpha-alpha-dimethyl phenmethyl) pentanoic, wherein R 16And R 17The compound that all is phenyl is 4,4 '-two (Alpha-Methyl phenmethyl) pentanoic.
The second class amine oxidation inhibitor comprises diarylamine and alkenolic reaction product.The diarylamine aliphatic ketone reaction product that can be used for herein is disclosed in United States Patent (USP) 1,906,935; 1,975,167; In 2,002,642 and 2,562,802.Briefly, these products are in the presence of suitable catalyst, obtain by reaction between diarylamine and the aliphatic ketone (preferred acetone), and the preferred pentanoic of described diarylamine, it can have one or more substituting groups on each aryl if desired.Except pentanoic, other suitable diarylamine reactant comprises dinaphthylamine, p-nitrodiphenylamine, 2,4-dinitro diphenylamine, mutual-amido two polyaniline, p-hydroxydiphenylamine etc.Except acetone, other useful reactive ketone thing comprises methylethylketone, metacetone, Mono Chloro acetone, Dichloro acetone etc.
Preferred diarylamine-aliphatic ketone reaction product is (NAUGAED A, the Uniroyal Chemical) that the condensation reaction by pentanoic and acetone obtains, for example according to United States Patent (USP) 2,562, and 802 described conditions.Commercially available product is shallow brown-green powder, or green brown flap, and fusion range is 85 ℃ to 95 ℃.
The amine that the 3rd class is suitable comprises N, the Ursol D that N '-hydrocarbon replaces.Hydrocarbon substituent can be replacement or unsubstituted alkyl or aryl.Unless explanation especially in addition, used herein term " alkyl " comprises cycloalkyl.Representative substances is:
N-phenyl-N '-cyclohexyl-Ursol D;
N-phenyl-N '-sec-butyl-Ursol D;
N-phenyl-N '-sec.-propyl-Ursol D;
N-phenyl-N '-(1, the 3-dimethylbutyl)-Ursol D;
N, N '-two (1,4-dimethyl amyl group)-Ursol D;
N, N '-phenylbenzene-Ursol D;
Blended diaryl-right-N, N '-two (1-ethyl-3-aminomethyl phenyl)-Ursol D; With
N, N '-two (1-methylheptyl)-Ursol D.
Last class amine oxidation inhibitor comprises that based on quinoline particularly polymeric 1,2-dihydro-2,2, the material of 4-trimethylquinoline.Representational material comprises polymeric 2,2,4-trimethylammonium-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethylammonium-1,2-dihydroquinoline, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihydroquinoline etc.
It is preferably oil-soluble to be particularly useful for implementing hindered phenol of the present invention.
The example of useful hindered phenol comprises 2,4-dimethyl-6-octyl group-phenol, 2,6-di-tert-butyl-4-methy phenol (being Yoshinox BHT), 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 2,2 '-methylene radical two (4-ethyl-6-tert.-butyl phenol), 2,4-dimethyl-6-the tertiary butyl-phenol, 4-methylol-2, the 6-DI-tert-butylphenol compounds, β (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane base ester, 2,6-two (octadecyl)-4-methylphenol, 2,4, the 6-pseudocuminol, 2,4,6-triisopropyl phenol, 2,4, the 6-tri-butyl-phenol, the 2-tertiary butyl-4, the 6-xylenol, 2,6-methyl-4-two (dodecyl) phenol, three (3,5-di-t-butyl-4-hydroxyl isocyanuric acid ester and three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane.
Other useful oxidation inhibitor comprises 3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate, octadecyl-3, and the 5-di-t-butyl-(NAUGARD 76, UniroyalChemical for 4-hydroxyl hydrogenated cinnamate; IRGANOX 1076, Ciba-Geigy), (IRGANOX 1010, Ciba-Geigy) for methane in four { methylene radical (3,5-di-t-butyl-4-hydroxyl-hydrogenated cinnamate) }, 1,2-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide) hydrazine (IRGANOX MD 1024, Ciba-Geigy), 1,3,5-three (3,5-di-t-butyl-4-hydroxybenzene methyl)-and s-triazine-2,4,6 (1H, 3H, 5H) (IRGANOX 3114, Ciba-Geigy) for triketone, 2,2 '-{ ethyl-3-(3 for oxamido-two, the 5-di-tert-butyl-hydroxy phenyl) } propionic ester (NAUGARD XL-1, Uniroyal Chemical), 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzene methyl)-s-triazine-2,4,6-(1H, 3H, 5H) (CYANOX 1790 for triketone, American Cyanamid Co.), 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxybenzene methyl) benzene (ETHANOX 330, Ethyl Corp.), 3,5-di-t-butyl-4-hydroxyl phenylpropionic acid and 1,3,5-three (2-hydroxyethyl)-5-triazine-2,4,6 (1H, 3H, 5H)-three esters and two (3,3-two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid) glycol ester of triketone.
The another kind of hindered phenol that can be used in the invention process is a polyphenol, it contains three or more the phenolic group groups that replace, for example (IRGANOX 1010, Ciba-Geigy) with 1 for four { methylene radical (3,5-di-t-butyl-4-hydroxyl-hydrogenated cinnamate) } methane, 3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxybenzene methyl) benzene (ETHANOX 330, Ethyl Corp.).
Can clearer understanding advantage of the present invention and key character from the following examples.
Embodiment
Graft copolymer used in the invention process can be according to United States Patent (USP) 4,693,838; 4,517,104 or 3,928, the similar method preparation of those methods described in 497.
After graft reaction is finished, add sufficient amount of solvent neutral oil 100 (SN100, a kind of paraffinic mineral oil), polymer content is diluted to 50% so that handle.
Second step, under nitrogen atmosphere, with the polymkeric substance of the maleinization in the oil with the stirring of equal amounts of S N100 oil and be heated to 160 ℃.The amine of the maleic anhydride equimolar amount of then using and adding neutralizes, and nitrogen purging is 3 hours then, to remove the water that generates in the reaction process.Cool off each product then, and filter with 100 mesh sieves.
Preparation embodiment
According to such sample for preparing two series of describing in detail among embodiment 1 to 7 and the embodiment 8 to 14.Except sneaking into the oxidation inhibitor with different levels, the method for the sample of two series of preparation is identical.Used oxidation inhibitor is 2,6 di tert butyl 4 methyl phenol (BHT) and alkylating pentanoic (Naugalube 438L), and they all are that Uniroyal Chemical Company provides.
Series A
Embodiment 1
125g maleic anhydride grafted polymer (rubber) is lubricated in the thinning oil at 375g, under mechanical stirring, be heated to 160 ℃, simultaneously mixture is maintained under the nitrogen atmosphere, in the wherein said maleic anhydride grafted polymer, polymeric substrate contains have an appointment 57mol% ethene and 43mol% propylene, number-average molecular weight is about 27,000, on it grafting the maleic anhydride of 2.9w%.In case reach temperature, continue 160 ℃ of following remix 1 hour.
N-3-aminopropyl morpholine (5.33g) is joined in the oil solution of polymkeric substance, under mechanical stirring, under nitrogen purging, react more than 4 hours in 160 ℃.To contain the reaction mixture cooling and the filtration of the graftomer of derivatize then.One duplicate samples is put into glass jar, and the kinematic viscosity of specimen under 210 (about 99 ℃) with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 2
A sample of the product of embodiment 1 is mixed with the 2,6 di tert butyl 4 methyl phenol (BHT) of 0.5wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 3
A sample of the product of embodiment 1 is mixed with the BHT of 1.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 4
A sample of the product of embodiment 1 is mixed with the BHT of 3.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 5
A sample of the product of embodiment 1 is mixed with the alkylated diphenylamine of 0.5wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 6
A sample of the product of embodiment 1 is mixed with the alkylated diphenylamine of 1.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 7
A sample of the product of embodiment 1 is mixed with the alkylated diphenylamine of 3.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Following table has shown the result of stability study.
Embodiment Initial viscosity 3 months viscosity The increase of 3 months viscosity Increased in 3 months (%) 6 months viscosity The increase of 6 months viscosity Increased in 6 months (%)
1 548 730.5 182.5 33.3 839 291 53.1
2 534 629 95 17.8 672 138 25.8
3 523 599 76 14.5 637 114 21.8
4 475 535 60 12.6 572 97 20.4
5 540 590 50 9.3 606 66 12.2
6 530 576.5 46.5 8.8 596 66 12.5
7 503 540 37 7.4 566 63 12.5
Series B
Embodiment 8
125g maleic anhydride grafted polymer (rubber) is lubricated in the thinning oil at 375g, under mechanical stirring, be heated to 160 ℃, simultaneously mixture is maintained under the nitrogen atmosphere, in the wherein said maleic anhydride grafted polymer, polymeric substrate is made up of about 57mol% ethene and 43mol% propylene, number-average molecular weight is about 24,000, on it grafting the maleic anhydride of 2.9w%.In case reach temperature, continue 160 ℃ of following remix 1 hour.
N-3-aminopropyl morpholine (5.33g) is joined in the oil solution of polymkeric substance, under mechanical stirring, under nitrogen purging, react more than 4 hours in 160 ℃.To contain the reaction mixture cooling and the filtration of the graftomer of derivatize then.One duplicate samples is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 9
A sample of the product of embodiment 8 is mixed with the BHT of 0.1wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 10
A sample of the product of embodiment 8 is mixed with the BHT of 0.25wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 11
A sample of the product of embodiment 8 is mixed with the BHT of 3.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 12
A sample of the product of embodiment 8 is mixed with the alkylated diphenylamine of 0.1wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 13
A sample of the product of embodiment 8 is mixed with the alkylated diphenylamine of 0.25wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Embodiment 14
A sample of the product of embodiment 8 is mixed with the alkylated diphenylamine of 3.0wt%.This sample is put into glass jar, and the kinematic viscosity of specimen under 210 with the residuum sealing, is put into 65 ℃ of baking ovens and is carried out stability test then.
Table 2
Embodiment Initial viscosity 3 months viscosity The increase of 3 months viscosity Increased in 3 months (%) 6 months viscosity The increase of 6 months viscosity Increased in 6 months (%)
8 353.3 407 53.7 15.2 429.7 76.4 21.6
9 352.6 386.6 34 9.6 393.5 40.9 11.6
10 352.8 380.6 27.8 7.9 389.1 36.3 10.3
11 337.4 358.5 21.1 6.3 367.1 29.7 8.8
12 353.6 375.4 21.8 6.2 380.3 26.7 7.6
13 355.1 369.7 14.6 4.1 371.7 16.6 4.7
14 353.7 363.6 9.9 2,8 370 16.3 4.6
From the sample of top two series, as can be seen, in basic enriched material (embodiment 1 and 8), add the growth that primary antioxidant (phenols or amine antioxidants) can significantly limit multifunctional additive for lubricating oils viscosity in the storage process.
In view of making multiple change and modification under the premise without departing from the spirit of the present invention, so should understand protection scope of the present invention with reference to following claim.

Claims (10)

1. a method that suppresses the oil concentrate medium viscosity rate of rise of VI-dispersion agent comprises that described VI-dispersion agent is by ethene and at least a C to push up processing or to replace the mode of the thinning oil of equivalent that primary antioxidant is sneaked in the described enriched material 3-C 16The copolymer of alpha-olefin, wherein said multipolymer and at least a material grafting that contains unsaturated carboxylic acid, and with the polyamines or the amino alcohol reaction of the amount of the described acid that is enough to neutralize.
2. according to the process of claim 1 wherein in enriched material weight, the content of primary antioxidant is 0.1wt% at least.
3. according to the process of claim 1 wherein that primary antioxidant is a phenolic antioxidant.
4. according to the method for claim 3, wherein in enriched material weight, phenolic antioxidant joins in the enriched material with 0.25% to 5.0% level.
5. according to the process of claim 1 wherein that primary antioxidant is an amine antioxidants.
6. according to the method for claim 5, wherein in enriched material weight, amine antioxidants joins in the enriched material with 0.25% to 5.0% level.
7. a method that suppresses the oil concentrate medium viscosity rate of rise of VI-dispersion agent comprises that described VI-dispersion agent is by ethene and at least a C to push up processing or to replace the mode of the thinning oil of equivalent that primary antioxidant is sneaked in the described enriched material 3-C 16The copolymer of alpha-olefin, wherein said multipolymer is with at least a undersaturated nitrogenous substances grafting.
8. according to the method for claim 7, wherein in enriched material weight, the content of primary antioxidant is 0.1wt% at least.
9. according to the method for claim 7, wherein primary antioxidant is a phenolic antioxidant.
10. according to the method for claim 7, wherein primary antioxidant is an amine antioxidants.
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