CN1596296A - Viscosity growth inhibition in oil additive concentrates - Google Patents

Viscosity growth inhibition in oil additive concentrates Download PDF

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CN1596296A
CN1596296A CNA028237277A CN02823727A CN1596296A CN 1596296 A CN1596296 A CN 1596296A CN A028237277 A CNA028237277 A CN A028237277A CN 02823727 A CN02823727 A CN 02823727A CN 1596296 A CN1596296 A CN 1596296A
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concentrate
antioxidant
ethylene
oil
primary
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CN1261550C (en
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K·戴克
T·E·纳莱斯尼克
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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

Inhibiting viscosity build in oil additive concentrates
Background
1. Field of the invention
The present invention relates to polymeric viscosity index improver/dispersant additive concentrates for lubricating oils. More particularly, the present invention relates to a method for inhibiting the rate of viscosity increase in grafted and amine functionalized hydrocarbon polymer concentrates for oil compositions.
2. Background of the invention
High molecular weight hydrocarbon polymers, such as ethylene copolymers, particularly ethylene-propylene copolymers, are known to be useful as Viscosity Index (VI) improving additives for oil compositions, particularly lubricating oil compositions. These VI improvers can be further reacted to form multifunctional VI improvers. Multifunctional VI improvers are materials that not only improve the VI properties of the oil, but also impart dispersancy to suspend sludge that may form during operation or use of the lubricating oil and inhibit carbon deposition in the engine. When stored as oil concentrates, the viscosity of these concentrates can increase dramatically over time.
Us patent 3,928,497 describes a process for the preparation of graft-modified ethylene polymers or copolymers which comprises reacting an ethylene polymer or copolymer with a dicarboxylic acid or a graft-copolymerizable derivative of a dicarboxylic acid graft-copolymerizable therewith in an alkyl-substituted aromatic hydrocarbon solvent in the presence of a free-radical initiator, characterized in that the reaction is carried out while gradually adding the dicarboxylic acid or derivative thereof to the solvent in which the starting ethylene polymer or copolymer is present.
U.S. Pat. No. 4,089,794 describes ethylene derivatives derived from about 2 to 98 wt% ethylene and one or more C3To C28Ethylene copolymers of alpha-olefins, such as ethylene-propylene copolymers, solution grafted with ethylenically unsaturated carboxylic acid species at elevated temperature in the presence of a free radical initiator which is decomposable at high temperature under an inert atmosphere, and subsequently reacted with a polyfunctional carboxylic acid species which is reactive with carboxyl groupsThe materials react to form carboxyl grafted polymer derivatives having good engine sludge and soot control behavior in fuels and lubricating oils, wherein the above mentioned multifunctional materials which can react with carboxyl groups are for example (a) polyamines, or (b) polyols, or (c) hydroxylamines, or mixtures thereof. These polymers may also be used as multifunctional viscosity index improvers if the molecular weight exceeds 10,000.
U.S. patent 4,219,432 discloses oil-soluble, derivatized ethylene copolymers derived from about 2 to 98 weight percent ethylene and one or more C3To C28Alpha-olefins such as propylene, the ethylene copolymers being grafted, preferably solution grafted, with ethylenically unsaturated dicarboxylic acid species at elevated temperature in the presence of a thermally decomposable free radical initiator under an inert atmosphere at elevated temperature and subsequently reacted first with 0.1 to 0.9 molar equivalents of a tertiary amino amine compound containing only one primary amino group to form imido groups, and then reacted in a second step with 0.1 to 0.9 molar equivalents of an alpha, omega-primary diamine containing at least two primary amino groups, for example a poly (alkyleneamine) such as diethylenetriamine, to form a carboxyl grafted polymeric imide intermediate, typically a succinimide intermediate, and in a third step with a C1-C30The anhydride of the hydrocarbon-substituted acid, preferably acetic anhydride, reacts to produce an oil-soluble, stable amide derivative of the polyamine, whereby the oil solution of the amide derivative is characterized by minimal viscosity change upon long-term storage. Useful number average molecular weights of the copolymer range from about 700 to 500,000; however, if the molecular weight is 10,000 to 500,000, these copolymers are reported to act as multifunctional viscosity index improvers which increase the activity of the sludge dispersant. If these derivatized copolymers are treated with an oil-soluble hydrocarbyl-substituted acid, preferably a long chain alkyl aryl sulfonic acid having an average side chain carbon number of about 20 to 40, they are said to produce a haze-free hydrocarbon concentrate useful as an additive solution for lubricating oils.
U.S. patent 4,517,104 discloses oil soluble, viscosity index improving ethylene copolymers, such as copolymers of ethylene and propylene and copolymers of ethylene, propylene and dienes, and the like, reacted or grafted with ethylenically unsaturated carboxylic acid moieties, preferably maleic anhydride moieties, and reacted with polyamines containing two or more primary amine groups and carboxylic acid components, preferably alkylene polyamines and alkenyl succinic anhydrides such as polyisobutenyl succinic anhydride. Alternatively, the grafted ethylene copolymer may be reacted with an already formed salt, amide, imide, or the like (preferably an imide of an alkylene polyamine and an alkenyl succinic anhydride) of the polyamine and acid component. These reactions are said to be capable of introducing carbon deposit inhibiting properties and dispersibility into the ethylene copolymer while inhibiting crosslinking which causes viscosity increase, cloudiness or gelation. The above grafting reaction may be carried out in a mineral lubricating oil by heating, or more preferably with a free radical initiator such as a peroxide, in which case the acid component preferably also serves to stabilize insoluble compounds formed by side reactions, for example maleic anhydride grafted oil molecules reacted with amines, thereby suppressing haze formation, especially when preparing an oil concentrate for the VI-dispersant additive to be subsequently added to the lubricating oil.
U.S. patent 4,693,838 describes hydrocarbon polymers such as ethylene copolymers which can be reacted with unsaturated nitrogen-containing monomers or unsaturated carboxylic acids in the presence of free radical initiators such as peroxides in synthetic hydrocarbon lubricating oils. The copolymers directly grafted with nitrogen-containing monomers can be used as additives for oil compositions, in particular as VI-dispersant additives for lubricating oil compositions. The polymer reacted with the carboxylic acid may be further reacted with an amine or amino alcohol to also form the multifunctional VI-dispersant additive.
U.S. patent 4,735,736 discloses oil soluble hydrocarbon polymers said to be useful as VI improvers, for example ethylene copolymers, preferably ethylene-propylene copolymers, grafted with an unsaturated acid material such as maleic anhydride, preferably by solid state grafting, followed by reaction with a polyamine, preferably a tertiary-primary amine, and treatment and/or reaction with a monoamine. The resulting material is used in oil compositions such as lubricating oils as viscosity index improvers having sludge dispersancy properties. Monoamine treatment is said to inhibit the viscosity build of the additive on storage.
U.S. patent 4,808,325 discloses dispersants and VI improving Mannich compositions which are said to be less susceptible to viscosity increase during storage and which comprise a physical mixture prepared by combining a phenolic compound and a Mannich condensation product resulting from a Mannich reaction of an oxidized polymer, an amine and a formaldehyde-generating agent.
U.S. patents 5,211,865 and 5,273,671 describe oil-containing compositions, particularly lubricating oil compositions, said to have improved oxidation resistance properties, containing a viscosity index improving amount of a viscosity index improver-dispersant comprised of the reaction product of: (a) grafted with an ethylenically unsaturated carboxylic acid species having 1 or 2 acid or anhydride moieties, comprising about 15 to 90 wt% ethylene and about 10 to 85 wt% of at least one C3-C28An alpha-olefin, oil-soluble ethylene copolymer having a number average molecular weight of about 5,000 to 500,000; (b) an organic polyamine containing at least two primary amino groups; (c) an aldehyde; (d) a heterocyclic nitrogen reagent having at least one-N (H) -group on the heterocycle; and optionally, (e) a high functionality long chain hydrocarbon substituted dicarboxylic acid material having a functionality of at least 1.2 in an amount effective to provide a VI improver-dispersant exhibiting improved low temperature viscosity properties.
The viscosity behavior of ethylene-propylene copolymer solutions containing from 58 to 80 mol% of ethylene was investigated by Mishra, M.K. et al in Polymer Science (Symp. Proc. Polymer.1991), Vol.2, page 6994-699 (published by Tata McGraw-Hill, New Delhi, India) by Specialty Olefin Copolymers in Oil Additives. They report that the intrinsic viscosity and equivalent hydrodynamic volume of the amorphous copolymer change very little in the range of-10 to 50 ℃. In contrast, for a partially crystalline copolymer containing 80 mol% ethylene, the above properties drop sharply at low temperatures. They also discuss the use of certain ethylene-propylene based multifunctional Olefin Copolymers (OCP) as viscosity index improvers which impart dispersancy and antioxidancy properties to engine oils. They reported that engine oils containing these multifunctional polymers performed better in engine testing than oils containing commercially available OCP VI improvers.
See also Kuczkowski, J.A et al, Polymer-Bound influences, Rubber Chemistry and Technology, 57: 621-651(1984).
The disclosure above is incorporated by reference herein in its entirety.
Brief description of the invention
According to the present invention, hydrocarbon polymers such as ethylene-alpha-olefin copolymers and terpolymers are reacted with unsaturated carboxylic acids preferably dissolved in suitable solvents such as alkylbenzenes, mineral oils, synthetic oils and/or aromatic esters in the presence of a free radical initiator such as a peroxide. After reaction with the carboxylic acid, the polymer is further reacted with an amine or amino alcohol to form the multifunctional VI-dispersant additive. Hydrocarbon polymers such as ethylene-alpha-olefin copolymers and terpolymers may also be similarly reacted with unsaturated nitrogen-containing monomers. The graft copolymer, also referred to as a concentrate, mixed with an amount of diluent oil is then used as an additive in oil compositions, particularly as a VI-dispersant additive in lubricating oil compositions. These concentrates are then mixed with primary antioxidants to significantly inhibit their rate of viscosity increase. The primary antioxidant is preferably amine or phenol in nature and is soluble in the additive concentrate. Preferred phenolic antioxidants are 2, 6-di-tert-butyl-4-methylphenol (BHT); preferred aminic antioxidants include alkylated diphenylamines and alkylated phenyl-alpha-naphthylamines. Even incorporation of small percentages of antioxidant, for example about 0.1 wt%, preferably from about 0.25 wt% up to 5 wt% or more by weight of the concentrate, into the dispersant concentrate provides significant advantages in the long term viscosity stability of the dispersant additive concentrate as indicated by the oven aging results.
More particularly, the invention relates to a method for inhibiting the rate of viscosity increase in an oil concentrate of a VI-dispersant consisting of ethylene and at least one C, comprising admixing a primary antioxidant to said concentrate as the primary treatment (topembodied) or in place of an equivalent amount of diluent oil3-C16Copolymers of alpha-olefins, wherein the copolymers are grafted with at least one unsaturated carboxylic acid containing material and further reacted with a polyamine containing at least one primary amine.
In another aspect, the invention relates to a method of inhibiting the rate of viscosity increase in an oil concentrate of a VI-dispersant consisting essentially of ethylene and at least one C, comprising admixing a primary antioxidant to said concentrate as the primary treatment or in place of an equal amount of diluent oil3-C16An alpha-olefin copolymer, wherein the copolymer is grafted with at least one nitrogen-containing unsaturated material.
Description of the preferred embodiments
The present invention provides a dispersant-viscosity index improver by the following method: unsaturated acid solutions are grafted onto high molecular weight hydrocarbon polymers in an oil diluent in the presence of a free radical initiator, and the product is then further reacted with an amine or polyol. High molecular weight hydrocarbon polymers have high viscosity even at grafting temperatures and therefore require dilution for handling. After grafting with the unsaturated acid, a mineral (or synthetic) lubricating oil can be added to form the final additive concentrate, or if the product is to be further reacted, e.g., to form a functionalized derivative, the mineral (or synthetic) lubricating oil can be used as another diluent to carry out additional reactions and form useful additive concentrates. The concentrate is subjected to a primary treatment of primary antioxidants to minimize the rate of viscosity increase of the concentrate during storage.
When grafting is carried out in a mineral lubricating oil, the oil need not be removed after the grafting step, but rather can be used as a solvent for the subsequent reaction of the grafted polymer with the amine species and form a lubricating oil additive concentrate as a solvent for the final product.
Suitable hydrocarbon diluents include olefin polymers and alkylbenzenes. Suitable polyolefins include alkene-1-units derived from monoethylenically unsaturated olefins, preferably from 3 to 18, for example from 3 to 12, carbon atomsLiquid polyolefins in bulk having a number average molecular weight (Mn) of 200 to 10,000, for example 300 to 3000, most preferably 350 to 1300, molar weight. Suitable polyolefins include poly C3-C4Olefin polymers, in particular polyisobutenes having a molecular weight of from 200 to about 2000, for example from 400 to 1300, such as from about 500 to 900, polydecenes, C6To C18Polymers of mixtures of alpha-olefins, and the like.
Suitable liquid alkylbenzenes are mono-and polyalkylbenzenes including mono-and polyalkylated benzenes in which each alkyl group may have from 1 to 300, such as from 10 to 30 carbon atoms, with dialkylbenzenes having a molecular weight of from 200 to 800 being preferred.
The polymers useful in the practice of the present invention generally have a number average molecular weight of from about 5000 to about 500,000, preferably from 10,000 to 200,000, more preferably from about 20,000 to 100,000, and generally have a narrow molecular weight.
Examples of suitable hydrocarbon polymers include C2-C16Preferably C2-C8Homopolymers of olefins, including both alpha-olefins and internal olefins, and copolymers of two or more monomers, which may be linear or branched, aliphatic, aromatic, alkylaromatic, cycloaliphatic, and the like. Preferably, they are ethylene and C3-C16Copolymers of olefins, more preferably copolymers of ethylene and propylene. Other hydrocarbons that may be used include styrene, butylene, isobutylene, C6And higher alpha-olefins, atactic isoprene, butadiene, and the like.
Preferred polymers are prepared from ethylene and ethylenically unsaturated hydrocarbons including cyclic, alicyclic and acyclic species containing from 3 to 16 carbon atoms, preferably from 3 to 8 carbon atoms. These ethylene copolymers may contain from 15 to 90% by weight of ethylene, preferably from 30 to 80% by weight of ethylene, and from 10 to 85% by weight, preferably from 20 to 70% by weight, of one or more C3-C16Preferably C3-C8An alpha-olefin. Copolymers of ethylene and propylene are most preferred. Suitable for forming copolymers in place of propylene or in combination with ethylene and propylene to form terpolymers, quaterpolymersOther alpha-olefins of copolymers and the like include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like; also included are branched alpha-olefins such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4-dimethyl-1-pentene, 6-methylheptene-1, and the like, and mixtures thereof.
The term "polymer" is intended to include copolymers, terpolymers, tetrapolymers, and the like. The polymers used in the practice of the present invention may include one or more non-conjugated dienes. The amount of non-conjugated diolefin is generally about 0.5 to 20 mol%, preferably about 1 to about 7 mol%, based on the total amount of hydrocarbons, e.g., ethylene and alpha-olefins, present.
Representative examples of non-conjugated dienes that may be used include 1, 4-hexadiene, 1, 5-heptadiene, 1, 6-octadiene, 5-methyl-1, 4-hexadiene, 3, 7-dimethyl-1, 6-octadiene, 3, 7-dimethyl-1, 7-octadiene, mixed isomers of dihydromyrcene and dihydrocymene, 1, 4-cyclohexadiene, 1, 5-cyclooctadiene, 1, 5-cyclododecadiene, 4-vinylcyclohexene, 1-allyl-4-isopropylidenecyclohexane, 3-allyl-cyclopentene, 4-allylcyclohexene, 1-isopropenyl-4- (4-butenyl) cyclohexane, 4 '-dicyclopentadienyl diene, 1, 4' -octadien, 4, 4' -bicyclohexene diene, tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo (2.2.1) hepta-2, 5-diene, ethyl norbornene, 5-methylene-6-methyl-2-norbornene, 5-methylene-6, 6-dimethyl-2-norbornene, 5-propenyl-2-norbornene, 5- (3-cyclopentenyl) -2-norbornene, 5-cyclohexylene-2-norbornene, norbornadiene, and the like.
The compounds which can be grafted onto the hydrocarbon polymer preferably contain from 3 to 10 carbon atoms, have ethylenic unsaturation, carry at least one, preferably two, carboxylic acid groups or anhydride groups, or can be converted into polar groups of such carboxylic groups, for example by oxidation or hydrolysis. Maleic anhydride or its derivatives are preferred because they do not significantly homopolymerize but rather are linked to the polymer to provide two carboxylic acid functional groups. Other examples include chloromaleic anhydride, itaconic anhydride, hemic anhydride, maleic acid, fumaric acid, monoesters of the foregoing, and the like.
Various other unsaturated comonomers can be grafted onto the hydrocarbon polymer along with the unsaturated acid component as taught in U.S. patent 4,160,739 and 4,161,452. One or more kinds of such comonomers which are different from the unsaturated acid component, contain a copolymerizable double bond, and are copolymerizable with the unsaturated acid component may be used. Such comonomers generally do not contain free carboxylic acid groups, but may be esters containing α, β -ethylenic unsaturation in the acid or alcohol moiety; hydrocarbons containing alpha, beta-ethylenic unsaturation (including aliphatic and aromatic hydrocarbons), e.g. C4-C12Alpha-olefins such as isobutylene, hexene, nonene, dodecene, and the like; styrenes such as styrene, α -methylstyrene, p-sec-butylstyrene, etc.; and vinyl monomers such as vinyl acetate, vinyl chloride, methyl vinyl ketone, ethyl vinyl ketone, and the like.
It is well known that nitrogen-containing unsaturated compounds can be used to prepare polymers for use as oil additives. These monomers may be grafted onto the hydrocarbon polymer and include, among others, those having from 6 to 30 carbon atoms and from 1 to 4 nitrogen atoms.
Examples of such nitrogen-containing monomers include dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N- (1, 2-dimethyl-1-ethyl-3-oxobutyl) acrylamide, N- (1, 3-diphenyl-1-methyl-3-oxopropyl) acrylamide, N- (1-methyl-1-phenyl-3-oxobutyl) methacrylamide, N-diethylaminoethyl acrylamide, 2-hydroxyethyl acrylamide, N-dimethylaminopropyl methacrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-butylpyrrolidone, N-butylmethacrylamide, N-butyl, N-vinylthiopyrrolidone, 3-methyl-1-vinylpyrrolidone, 4-methyl-1-vinylpyrrolidone, 5-methyl-1-vinylpyrrolidone, 3-ethyl-1-vinylpyrrolidone, 3-butyl-1-vinylpyrrolidone, 3-dimethyl-1-vinylpyrrolidone, 4, 5-dimethyl-1-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-4-vinylpyridine, 2-vinyl-5-ethylpyridine, 2-vinyl-6-methylpyridine, and the like.
Grafting is carried out using one or more free radical initiators such as azobisisobutyronitrile, 2, 5-dimethyl-hex-3-yne-2, 5-bis (t-butyl peroxide) or its hexane homolog, di-t-butyl peroxide, dicumyl peroxide, and the like. The initiator is preferably a peroxide and is generally used in an amount of between about 0.005% and about 1% by weight of the total polymer solution at a temperature of about 25 ℃ to 250 ℃, preferably about 100 ℃ to 250 ℃.
The ethylenically unsaturated carboxylic acid species, which is preferably maleic anhydride, is generally used in amounts of from about 0.05% to about 10%, preferably from 0.1% to 4.0%, by weight of the initial solution. The weight ratio of carboxylic acid species to free radical initiator employed is generally from about 3: 1 to about 30: 1, preferably from about 1: 1 to about 6: 1.
The initiator grafting is preferably carried out under an inert atmosphere, for example under a nitrogen blanketing atmosphere. Although grafting may be carried out in the presence of air, the yield of the desired graft polymer is generally reduced as compared to grafting carried out under an inert atmosphere substantially free of oxygen. The grafting time is generally from about 0.1 to 12 hours, preferably from about 0.5 to 10 hours, more preferably from 0.5 to 3 hours.
The grafted polymer may be reacted with the appropriate amine in a conventional manner using reactants and conditions known in the art. Useful amine compounds include mono-and polyamines containing from about 2 to about 60, preferably from about 3 to about 20 total carbon atoms and from about 1 to about 12, preferably from about 2 to about 7 nitrogen atoms in the molecule. These amines may be hydrocarbyl amines, or hydrocarbyl amines containing other groups such as alkoxy, amido, imidazolinyl, and the like.
Useful amines include 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1, 2-propanediamine, bis- (1, 2-propylene) diamine, bis- (1, 2-propylene) triamine, bis- (1, 3-propylene) triamine, N-dimethyl-1, 3-diaminopropane, N-bis (2-aminoethyl) ethylenediamine, N-bis (2-hydroxyethyl) -1, 3-propanediamine, 3-dodecyloxy-propylamine, N-dodecyl-1, 3-propanediamine, tris (hydroxymethyl) aminomethane, di (tert-butyl-methyl-amino-propane), di (tert-butyl-ethyl) -1, 3-propanediamine, di (butyl-ethyl-methyl-amino-propane, di, Diisopropanolamine, diethanolamine, triethanolamine, mono-, di-and tri-tallow amine, N- (3-aminopropyl) morpholine, 3-dodecyloxypropylamine, N- (2-aminoethyl) morpholine, 2-aminopyridine, 2-methylaminopyridine, 3-methylaminopyridine, 2-aminothiazole, 2-amino-2-thiazoline, 2-aminopyrimidine, 2-aminobenzothiazole, methyl-1-phenylhydrazine, p-morpholinoaniline, N-aminopropylimidazole and its variants, N-aminopropylpyrrolidone and its variants, N-aminopropylpiperidine and its variants, phenothiazine and its variants, and the like.
Particularly preferred are amines bearing one primary amine group and any other amine group present is a tertiary amine group. This inhibits cross-linking, which is particularly important when the polymer has a relatively high acidity, for example above 0.1 meq/g polymer. Mixtures containing about 70 wt% or more of amines containing only one primary or secondary amine group and a small amount of amines with two or more primary or secondary amine groups can be used. Acidity of less than 0.1 meq/g of polymer is less susceptible to crosslinking, in which case amines with two or more reactive groups, i.e. primary or secondary, or primary and secondary, or one primary and one alcohol group may be used.
The amine is generally used in an amount of about 0.1 to about 10 wt%, preferably about 0.5 to about 5 wt%, based on the weight of the hydrocarbon polymer. The amine is preferably used in an amount necessary to neutralize the acid moiety by forming an amide, imide, or salt.
Preferably, the amine is used in an amount such that there are 1 to 2 moles of polyamine participating in the reaction per equivalent mole of dicarboxylic acid. For example, for an ethylene-propylene copolymer having a number average molecular weight of 40,000 onto which an average of 4 maleic anhydride groups per molecule are grafted, it is preferable to use about 4 to 8 molecules of amine per molecule of the grafted ethylene-propylene copolymer.
The polymer grafted with acidic moieties, preferably in a solution generally containing from about 5 up to 50 wt%, preferably 10 to 30 wt% of the polymer, can be readily reacted with the amine by heating at a temperature of from about 100 ℃ to 250 ℃, preferably from about 120 ℃ to 230 ℃, for from about 0.5 to about 10 hours, preferably from about 1 to about 6 hours. Heating is preferably performed to facilitate imide and amide formation. The reaction ratio may vary greatly depending on the reactants, the amount of excess, the type of bond formed, etc.
In a preferred embodiment, about 5 to 95% of the copolymer is dissolved in 95 to 5 wt% of a solvent to form a solution with about 0.05 to 10 wt% of the unsaturated species and about 0.005 to 10 wt% of the initiator, based on the weight of the solution. Next, after the grafting step, about 40 to 500 wt% of a mineral or synthetic lubricating oil, based on the weight of the solution, is added followed by an amine sufficient to neutralize the acid and heated at a temperature of 100 ℃ to 250 ℃ for 0.5 to 10 hours.
The antioxidants used in the practice of the present invention are primary antioxidants such as amine antioxidants and hindered phenols.
The amine antioxidant can be a hydrocarbon-substituted diarylamine, such as aryl, alkyl, alkaryl, and aralkyl substituted diphenylamine antioxidant materials. Non-limiting examples of commercially available hydrocarbon-substituted diphenylamines include substituted octylated, nonylated and heptylated diphenylamines and para-substituted styrenated or alpha-methylstyrene-ated diphenylamines. Sulfur-containing hydrocarbon-substituted diphenylamines, such as p- (p-toluenesulfonylamino) -diphenylamine, are also considered part of this class of antioxidants.
Hydrocarbon-substituted diarylamines that can be used in the practice of the present invention can be represented by the following general formula:
Ar-NH-Ar′
wherein Ar and Ar' are independently selected from aryl groups, at least one of which is preferably substituted with at least one alkyl group. Aryl groups can be, for example, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, and the like. The alkyl substituent may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isomers thereof, and the like.
Preferred hydrocarbon-substituted diarylamines are those disclosed in U.S. Pat. Nos. 3,452,056 and 3,505,225, the disclosures of which are incorporated herein by reference. Preferred hydrocarbon-substituted diarylamines can be represented by the following general formula:
Figure A0282372700121
wherein,
R1selected from phenyl and p-tolyl;
R2and R3Independently selected from methyl, phenyl and p-tolyl;
R4selected from methyl, phenyl, p-tolyl and neopentyl;
R5selected from the group consisting of methyl, phenyl, p-tolyl, and 2-phenylisobutyl; and
R6is methyl.
Wherein R is1To R5Independently selected from the group shown in formula I, R7Selected from methyl, phenyl and p-tolyl;
x is selected from methyl, ethyl, C3-C10A group of secondary alkyl groups, α -dimethylbenzyl groups, α -methylbenzyl groups, chlorine, bromine, carboxyl groups, and metal salts of carboxylic acids, wherein the metals are selected from zinc, cadmium, nickel, lead, tin, magnesium, and copper; and
y is selected from hydrogen, methyl, ethyl, C3-C10Secondary alkyl, chloro and bromo.
Wherein,
R1selected from phenyl or p-tolyl;
R2and R3Independently selected from methyl, phenyl and p-tolyl;
R4is selected from hydrogen, C3-C10Primary, secondary and tertiary alkyl groups, and C3-C10A radical of alkoxy, which may be linear or branched; and
x and Y are independently selected from hydrogen, methyl, ethyl, C3-C10Secondary alkyl, chloro and bromo.
Wherein,
R9selected from phenyl and p-tolyl;
R10is a group selected from methyl, phenyl, p-tolyl and 2-phenylisobutyl;
R11is a group selected from methyl, phenyl and p-tolyl.
Figure A0282372700141
Wherein,
R12selected from phenyl or p-tolyl;
R13selected from methyl, phenyl and p-tolyl;
R14selected from the group consisting of methyl, phenyl, p-tolyl, and 2-phenylisobutyl; and
R15selected from hydrogen, alpha-dimethylbenzyl, alpha-methyldiphenylmethyl, triphenylmethyl and α, α, p-trimethylbenzyl.
Typical chemicals used in the present invention are as follows:
Figure A0282372700142
Figure A0282372700152
type IV
R9Is phenyl, R10And R11Is methyl.
Among the above preferred hydrocarbon-substituted diphenylamines, substituted diphenylamines of the formula are particularly preferred:
wherein R is16And R17Is methyl or phenyl. Wherein R is16And R17The compound being both methyl is 4, 4' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine in which R is16And R17The compound that is both phenyl is 4, 4' -bis (alpha-methylbenzyl) diphenylamine.
The second class of amine antioxidants includes the reaction products of diarylamines and aliphatic ketones. Diarylamine aliphatic ketone reaction products useful herein are disclosed in U.S. patent nos. 1,906,935; 1,975,167, respectively; 2,002,642 and 2,562,802. Briefly, these products are obtained by reaction between a diarylamine, preferably diphenylamine, which may, if desired, bear one or more substituents on each aryl group, and an aliphatic ketone, preferably acetone, in the presence of a suitable catalyst. In addition to diphenylamine, other suitable diarylamine reactants include dinaphthylamine, p-nitrodiphenylamine, 2, 4-dinitrodiphenylamine, p-aminodiphenylamine, p-hydroxydiphenylamine, and the like. In addition to acetone, other useful ketone reactants include methyl ethyl ketone, diethyl ketone, monochloroacetone, dichloroacetone, and the like.
Preferred diarylamine-fatty ketone reaction products are obtained from the condensation reaction of diphenylamine and acetone (NAUGAED A, Uniroyal Chemical), for example, under the conditions described in U.S. Pat. No. 2,562,802. The commercial product is a light brown-green powder, or green-brown flakes, with a melting range of 85 ℃ to 95 ℃.
A third class of suitable amines includes N, N' -hydrocarbon substituted p-phenylenediamines. The hydrocarbon substituent may be a substituted or unsubstituted alkyl or aryl group. The term "alkyl" as used herein includes cycloalkyl unless otherwise specified. Representative substances are:
N-phenyl-N' -cyclohexyl-p-phenylenediamine;
N-phenyl-N' -sec-butyl-p-phenylenediamine;
N-phenyl-N' -isopropyl-p-phenylenediamine;
N-phenyl-N' - (1, 3-dimethylbutyl) -p-phenylenediamine;
n, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine;
n, N' -diphenyl-p-phenylenediamine;
mixed diaryl-p-N, N' -bis (1-ethyl-3-methylphenyl) -p-phenylenediamine; and
n, N' -bis (1-methylheptyl) -p-phenylenediamine.
The last class of amine antioxidants includes substances based on quinolines, in particular polymeric 1, 2-dihydro-2, 2, 4-trimethylquinolines. Representative materials include polymeric 2, 2, 4-trimethyl-1, 2-dihydroquinoline, 6-dodecyl-2, 2, 4-trimethyl-1, 2-dihydroquinoline, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, and the like.
Hindered phenols particularly useful in the practice of the present invention are preferably oil soluble.
Examples of useful hindered phenols include 2, 4-dimethyl-6-octyl-phenol, 2, 6-di-tert-butyl-4-methylphenol (i.e., butylated hydroxytoluene), 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 2, 4-dimethyl-6-tert-butylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, n-octadecyl beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl acetate, and mixtures thereof, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-trimethylphenol, 2, 4, 6-triisopropylphenol, 2, 4, 6-tri-tert-butylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-methyl-4-didodecylphenol, tris (3, 5-di-tert-butyl-4-hydroxyisocyanurate and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Other useful antioxidants include 3, 5-di-tert-butyl-4-hydroxyhydrocinnamate, octadecyl-3, 5-di-tert-butyl-4-hydroxyhydrocinnamate (NAUGARD 76, Uniroyal chemical; IRGANOX 1076, Ciba-Geigy), tetrakis { methylene (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate) } methane (IRGANOX 1010, Ciba-Geigy), 1, 2-bis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine (IRGAMD 1024, Ciba-Geigy), 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -s-triazine-2, 4, 6(1H, 3H, 5H) trione (IRGANOX 3114, Ciba-Geigy), 2, 2' -oxamido bis { Ethyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) } propionate (NAUGARD XL-1, Uniroyal Chemical), 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -s-triazine-2, 4, 6- (1H, 3H, 5H) trione (CYANOX 1790, American Cyanamid Co.), 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (ETHANOX 330, Ethyl Corp.), 3, 5-di-tert-butyl-4-hydroxyhydrocinnamic acid with 1, 3, 5-tris (2-hydroxyethyl) -5-triazine-2, triesters of 4, 6(1H, 3H, 5H) -trione and ethylene glycol bis (3, 3-bis (4-hydroxy-3-tert-butylphenyl) butyrate).
Another class of hindered phenols that can be used in the practice of the present invention are polyphenols that contain three or more substituted phenol groups, such as tetrakis { methylene (3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate) } methane (IRGANOX 1010, Ciba-Geigy) and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (ETHANOX 330, Ethyl Corp.).
The advantages and important features of the present invention will be more clearly understood from the following examples.
Examples
The graft copolymers used in the practice of the present invention can be prepared according to the methods described in U.S. patent nos. 4,693,838; 4,517,104 or 3,928,497, in a manner analogous to those described above.
After the grafting reaction is complete, sufficient solvent neutral oil 100(SN100, a paraffinic mineral oil) is added to dilute the polymer content to 50% for ease of handling.
In a second step, the maleated polymer in oil is stirred with an equivalent amount of SN100 oil and heated to 160 ℃ under a nitrogen atmosphere. Then, neutralization was carried out with an amine in an equimolar amount to the added maleic anhydride, followed by nitrogen purging for 3 hours to remove water generated during the reaction. The products were then cooled and filtered through a 100 mesh screen.
Preparation examples
Two series of samples were prepared as detailed in examples 1 to 7 and examples 8 to 14. The procedure for preparing the two series of samples was identical except that the antioxidant was mixed at different levels. The antioxidants used were 2, 6-di-tert-butyl-4-methylphenol (BHT) and alkylated diphenylamine (Naugalube 438L), both of which are available from Uniroyal Chemical Company.
Series A
Example 1
125g of a maleic anhydride-grafted polymer (rubber) in which the polymer base material contains about 57 mol% of ethylene and 43 mol% of propylene and has a number average molecular weight of about 27,000 to which 2.9 w% of maleic anhydride was grafted, was heated to 160 ℃ in 375g of lubricating diluent oil with mechanical stirring while maintaining the mixture under a nitrogen atmosphere. Once the temperature was reached, mixing was continued for an additional 1 hour at 160 ℃.
N-3-aminopropylmorpholine (5.33g) was added to an oil solution of the polymer and reacted at 160 ℃ for 4 hours or more with mechanical stirring under a nitrogen purge. The reaction mixture containing the derivatized graft polymer is then cooled and filtered. A sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210F (about 99 c) and the residue was then sealed and placed in a 65 c oven for stability testing.
Example 2
A sample of the product of example 1 was mixed with 0.5 weight percent 2, 6-di-tert-butyl-4-methylphenol (BHT). The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 3
A sample of the product of example 1 was mixed with 1.0 wt.% BHT. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 4
A sample of the product of example 1 was mixed with 3.0 wt.% BHT. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 5
A sample of the product of example 1 was mixed with 0.5 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 6
A sample of the product of example 1 was mixed with 1.0 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 7
A sample of the product of example 1 was mixed with 3.0 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
The following table shows the results of the stability study.
Examples Initial viscosity Viscosity at 3 months Increase in viscosity for 3 months 3 month increase (%) Viscosity at 6 months Increase in viscosity for 6 months 6 month increase (%)
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
Example 8
125g of a maleic anhydride-grafted polymer (rubber) in which the polymer base material consists of about 57 mol% of ethylene and 43 mol% of propylene, has a number-average molecular weight of about 24,000, onto which 2.9 w% of maleic anhydride has been grafted, was heated to 160 ℃ in 375g of lubricating diluent oil with mechanical stirring while maintaining the mixture under a nitrogen atmosphere. Once the temperature was reached, mixing was continued for an additional 1 hour at 160 ℃.
N-3-aminopropylmorpholine (5.33g) was added to an oil solution of the polymer and reacted at 160 ℃ for 4 hours or more with mechanical stirring under a nitrogen purge. The reaction mixture containing the derivatized graft polymer is then cooled and filtered. A sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210F, then the residue was sealed and placed in a 65 c oven for stability testing.
Example 9
A sample of the product of example 8 was mixed with 0.1 wt.% BHT. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 10
A sample of the product of example 8 was mixed with 0.25 wt.% BHT. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 11
A sample of the product of example 8 was combined with 3.0 wt.% BHT. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 12
A sample of the product of example 8 was mixed with 0.1 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 13
A sample of the product of example 8 was mixed with 0.25 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
Example 14
A sample of the product of example 8 was mixed with 3.0 wt% of an alkylated diphenylamine. The sample was placed in a glass jar and the kinematic viscosity of the sample was tested at 210 ° F, then the residue was sealed and placed in a 65 ℃ oven for stability testing.
TABLE 2
Examples Initial viscosity Viscosity at 3 months Of 3 months viscosityIncrease of 3 month increase (%) Viscosity at 6 months Increase in viscosity for 6 months 6 month increase (%)
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
As can be seen from the above two series of samples, the addition of primary antioxidants (phenolic or aminic) to the base concentrate (examples 1 and 8) can significantly limit the increase in viscosity of the additive concentrate during storage.
In view of the many changes and modifications that can be made without departing from spirit of the invention, reference should be made to the appended claims for an understanding of the scope of the protection to be afforded the invention.

Claims (10)

1. A method of inhibiting the rate of viscosity increase in an oil concentrate of a VI-dispersant consisting essentially of ethylene and at least one C, comprising admixing a primary antioxidant into said concentrate as the principal treatment or as a replacement for an equivalent amount of diluent oil3-C16Copolymers of alpha-olefins, wherein the copolymer is grafted with at least one unsaturated carboxylic acid containing material and reacted with a polyamine or aminoalcohol in an amount sufficient to neutralize the acid.
2. The method of claim 1 wherein the antioxidant is present in an amount of at least about 0.1% by weight based on the weight of the concentrate.
3. The method of claim 1, wherein the primary antioxidant is a phenolic antioxidant.
4. A process according to claim 3 wherein the phenolic antioxidant is added to the concentrate at a level of from 0.25% to 5.0% by weight of the concentrate.
5. The method of claim 1, wherein the primary antioxidant is an amine antioxidant.
6. A process according to claim 5 wherein the aminic antioxidant is added to the concentrate at a level of from 0.25% to 5.0% by weight of the concentrate.
7. A method of inhibiting the rate of viscosity increase in an oil concentrate of a VI-dispersant consisting of ethylene and at least one C, comprising admixing a primary antioxidant into said concentrate as the primary treatment or as a replacement for an equal amount of diluent oil3-C16A copolymer of an alpha-olefin, wherein the copolymer is grafted with at least one unsaturated nitrogen-containing species.
8. The method of claim 7 wherein the antioxidant is present in an amount of at least about 0.1% by weight based on the weight of the concentrate.
9. The method of claim 7, wherein the primary antioxidant is a phenolic antioxidant.
10. The method of claim 7, wherein the primary antioxidant is an amine antioxidant.
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