EP0400874A1 - Multifunktionale viskositätsindexmodifizierende Additive, hergestellt aus Amidoaminen - Google Patents

Multifunktionale viskositätsindexmodifizierende Additive, hergestellt aus Amidoaminen Download PDF

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Publication number
EP0400874A1
EP0400874A1 EP90305579A EP90305579A EP0400874A1 EP 0400874 A1 EP0400874 A1 EP 0400874A1 EP 90305579 A EP90305579 A EP 90305579A EP 90305579 A EP90305579 A EP 90305579A EP 0400874 A1 EP0400874 A1 EP 0400874A1
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EP
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Prior art keywords
molecular weight
composition according
ethylene copolymer
amine
carboxylic acid
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EP90305579A
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English (en)
French (fr)
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EP0400874B1 (de
Inventor
Antonio Gutierrez
Robert Dean Lundberg
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/083—Dibenzyl sulfide
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02—Macromolecular compounds obtained by reactions of monomers involving only 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
    • 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
    • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2221/043—Polyoxyalkylene ethers with a thioether group
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • 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

Definitions

  • the invention relates to oil soluble polymeric compositions of matter useful as multifunctional viscosity index improver additives, particular viscosity index improver-dispersant additives, for oleaginous compositions such as fuel and lubricating oil compositions, and to oleaginous compositions containing said additives.
  • V.I.-dispersant oil additive The concept of derivatizing V.I. improving high molecular weight ethylene copolymers, with acid moieties such as maleic anhydride, followed by reaction with an amine to form a V.I.-dispersant oil additive is known as indicated by the following patents.
  • U.S. Pat. No. 3,316,177 teaches ethylene-propylene-diene, which are heated to elevated temperatures in the presence of oxygen so as to oxidize the polymer and cause its reaction with maleic anhydride which is present during the oxidation. The resulting polymer can then be reacted with alkylene polyamines.
  • U.S. Pat. No. 4,089,794 teaches grafting the ethylene copolymer with maleic anhydride using peroxide in a lubricating oil solution, wherein the grafting is preferably carried out under nitrogen, followed by reaction with polyamine.
  • U.S. Pat. No. 4,137,185 teaches reacting C, to C 30 monocarboxylic acid anhydrides, and dicarboxylic anhydrides, such as acetic anhydride, succinic anhydride, etc. with an ethylene copolymer reacted with maleic anhydride and a polyalkylene polyamine to inhibit cross linking and viscosity increase due to further reaction of any primary amine groups which were initially unreacted.
  • U.S. Pat. No. 4,144,181 is similar to 4,137,185 in that it teaches using a sulfonic acid to inactivate the remaining primary amine groups when a maleic anhydride grafted ethylene-propylene copolymer is reacted with a polyamine.
  • U.S. Pat. No. 4,169,063 reacts an ethylene copolymer in the absence of oxygen and chlorine at temperatures of 150° to 250' C with maleic anhydride followed by reaction with polyamine.
  • a number of prior disclosures teach avoiding the use of polyamine having two primary amine groups to thereby reduce cross-linking problems which become more of a problem as the number of amine moieties added to the polymer molecule is increased in order to increase dispersancy.
  • German Published Application No. P3025274.5 teaches an ethylene copolymer reacted with maleic anhydride in oil using a long chain alkyl hetero or oxygen-containing amine.
  • U.S. Pat. No. 4,132,661 grafts ethylene copolymer, using peroxide and/or air blowing, with maleic anhydride and then reacts with a primary-tertiary diamine.
  • U.S. Pat. No. 4,160,739 teaches an ethylene copolymer which is grafted, using a free-radical technique, with alternating maleic anhydride and a second polymerizable monomer such as methacrylic acid, which materials are reacted with an amine having a single primary, or a single secondary, amine group.
  • U.S. Pat. No. 4,171,273 reacts an ethylene copolymer with maleic anhydride in the presence of a free-radical initiator and then with mixtures of C4 to C12 n-alcohol and amine such as N-aminopropylmorpholine or dimethylamino propyl amine to form a V.I.-dispersant pour depressant additive.
  • U.S. Pat. No. 4,219,432 teaches maleic anhydride grafted ethylene copolymer reacted with a mixture of an amine having only one primary group together with a second amine having two or more primary groups.
  • German published application No. 2753569.9 shows an ethylene copolymer reacted with maleic anhydride by a free-radical technique and then reacted with an amine having a single primary group.
  • German published application No. 2845288 grafts maleic anhydride on an ethylene-propylene copolymer by thermal grafting at high temperatures and then reacts with amine having one primary group.
  • French published application No. 2423530 teaches the thermal reaction of an ethylene copolymer with maleic anhydride at 150 C to 210° C followed by reaction with an amine having one primary or secondary group.
  • U.S. Patent No. 4,517,104 discloses polymeric viscosity index (V.I.) improver-dispersant additive for petroleum oils, particularly lubricating oils, comprising a copolymer of ethylene with one or more C 3 to C 28 alpha-olefins, preferably propylene. which has been grafted with acid moieties such as maleic anhydride using a free radical initiator in a solvent such as lubricating oil, and then reacted with a carboxylic acid component including hydrocarbyl substituted succinic anhydride or acid having 12-400 carbon atoms in said hydrocarbyl group or long chain monocarboxylic acid, and a polyamine having two or more primary amine groups.
  • V.I. polymeric viscosity index
  • the grafted polymer may be reacted with said acid component prereacted with said polyamine to form salts, amides. imides, etc. and then reacted with said grafted olefin polymer. These reactions can permit the incorporation of varnish inhibition and dispersancy into the ethylene copolymer while inhibiting cross-linking or gelling.
  • U.S. Patent No. 4.632,769 discloses oil soluble viscosity index improving ethylene copolymers, such as copolymers of ethylene and propylene. reacted or grafted with ethylenically unsaturated carboxylic acid moieties, preferably maleic anhydride moieties, and then reacted with polyamines having two or more primary amine groups and a C 22 to C 28 olefin carboxylic acid component. These reactions can permit the incorporation of varnish inhibition and dispersancy into the ethylene copolymer while inhibiting cross-linking or gelling.
  • U.S. Patent 2,921,085 relates to the preparation of beta-aminopropionamides by reaction of an alkyl amine with an acrylate to form an alkyl aminopropionate and reaction of the latter compound with an amine.
  • the resulting compounds are disclosed to have utility as surface active agents, specifically as emulsifying, wetting, foaming and detergent agents.
  • U.S. Patent 3,337,609 relates to adducts of hydroxyalkyl alkylene polyamines and acrylates.
  • the resulting adducts are added to polyepoxides to provide compositions which are suitable for use as a barrier coating for polyethylene surfaces, and for additional end uses, such as in molding.
  • the adducts are disclosed to be useful as catalysts in resin preparation and as corrosion inhibitors in water systems for ferrous metals.
  • U.S. Patent 3,417,140 relates to the preparation of amido-amine compositions, which are useful as epoxy resin curing agents, by reacting a polyalkylene polyamine and a fatty amine (comprising a mono- or diamine having as one of the substituents on a nitrogen atom a hydrocarbyl radical having 8 to 24 carbon atoms) with an alpha-beta unsaturated carbonylic compound. It is disclosed that this reaction occurs through the Michael addition of an amine group across the unsaturated group of the carbonylic compound and through the condensation of an amine group with the carbonylic group.
  • U.S. Patent 3.247,163 also relates to curing agents for polyepoxide compositions, which curing agents are prepared by reacting an organic amine and an acrylate.
  • U.S. Patent 3.445.441 relates to amino-amido polymers characterized by being a reaction product of at least a polyamine and an acrylate type compound, such as methyl or ethyl acrylate, and methyl or ethyl methacrylate.
  • the patent states that the polymers are useful in a wide variety of applications, such as floculating agents, water clarifying additives, corrosion inhibitors in oil and gas wells, and as lube oil additives.
  • the polymers may be derivitized, including acylation with monocarboxylic acids and polycarboxylic acids, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, for example, diglycolic, phthalic, succinic, etc., acids.
  • U.S. Patent 3,903,003 relates to lubricating compositions containing an amido-amine reaction product of a terminally carboxylated isoprene polymer which is formed by reacting a terminally carboxylated substantially completely hydrogenated polyisoprene having an average molecular weight between about 20,000 and 250,000 and a nitrogen compound of the group consisting of polyalkylene amines and hydroxyl polyalkylene amines.
  • U.S. Patent 4,493,771 relates to scale inhibiting with compounds containing quaternary ammonium and methylene phosphonic acid groups. These compounds are derivatives of polyamines in which the amine hydrogens have been substituted with both methylene phosphonic acid groups or their salts and hydroxypropyl quaternary ammonium halide groups.
  • the patent discloses that any amine that contains reactive amino hydrogens can be utilized, for example, polyglycol amines, amido-amines, oxyacylated amines, and others.
  • U.S. Patent 4,459,241 contains a similar disclosure to U.S. Patent 4,493,771.
  • the materials of the present invention are an improvement over those of the aforediscussed prior disclosures because of their'effectiveness and their ability to provide enhanced lubricating oil dispersancy.
  • compositions of matter useful as multifunctional viscosity, index improvers for oleaginous compositions including fuel and lubricating oil compositions, comprising high molecular weight ethylene copolymers, such as ethylene-a-olefin copolymers, reacted or grafted with ethylenically unsaturated carboxylic acid materials, such as maleic anhydride, and reacted with an amido-amine.
  • high molecular weight ethylene copolymers such as ethylene-a-olefin copolymers
  • carboxylic acid materials such as maleic anhydride
  • the amido-amine is characterized by being a reaction product of at least one polyamine and an a-, ⁇ - unsaturated compound of the formula wherein X is sulfur or oxygen, Y is -OR°, -SR 4 , or -NR 4 (R 5 ), and R', R 2 , R 3 , R 4 and R 5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
  • compositions of matter of the instant invention comprise high molecular weight, i.e., at least 15,000 number average molecular weight, copolymers of ethylene, preferably copolymers of ethylene and at least one other C 3 to C 28 alpha-olefin such as propylene, reacted or grafted with ethylenically unsaturated carboxylic acid material to form a grafted ethylene copolymer, followed by reaction with an amido-amine.
  • These materials are useful as multifunctional viscosity index improver additives, particularly viscosity index improver-dispersant additives for oleaginous compositions such as fuel and lubricating oil compositions.
  • Oil soluble ethylene copolymers used in the invention are those capable of modifying or improving the viscosity index of oleaginous compositions, particularly lubricating oil compositions, i.e., polymers useful as V.I. improvers. Therefor, they generally will have a number-average molecular weight ( W n ) of greater than about 10,000, preferably at least about 15,000. These copolymers preferably have number average molecular weights of from about 15,000 to about 500,000, more preferably about 20,000 to about 300,000, and most preferably from about 30,000 to about 150,000. These V.I.
  • improvers will generally have a narrow range of molecular weight, as determined by the ratio of weight-average molecular weight ( M W ) to number-average molecular weight ( Mn).
  • M W weight-average molecular weight
  • Mn number-average molecular weight
  • Polymers having a M W ; M n of less than 10, preferably less than 7, and more preferably 4 or less are most desirable.
  • Mn and ( M W / Mn) are measured by the well known techniques of vapor phase osmometry (VPO), membrane osmometry and gel permeation chromatography.
  • VPO vapor phase osmometry
  • membrane osmometry membrane osmometry
  • gel permeation chromatography gel permeation chromatography
  • Post synthesis treatment such as extrusion at elevated temperature and under high shear through small orifices, mastication under elevated temperatures, thermal degradation, fractional precipitation from solution, etc. may also be used to obtain narrow ranges of desired molecular weights and to break down higher molecular weight polymer to different molecular weight grades for V.I. use.
  • These polymers are prepared from ethylene and ethylenically unsaturated hydrocarbons including cyclic, alicyclic and acyclic, containing from 3 to 28 carbons, e.g. 2 to 18 carbons.
  • These ethylene copolymers may contain from 15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to 85 wt. %, preferably 20 to 70 wt. % of one or more C 3 to C 28 , preferably C 3 to C 18 more preferably C 3 to C 8 , unsaturated hydrocarbons, preferably alpha olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt.
  • Copolymers of ethylene and propylene are most preferred.
  • copolymer as used herein includes terpolymers. tetrapolymers. etc., of ethylene, said C3-28 alpha-olefin and. or a non-conjugated diolefin or mixtures of such diolefins which may also be used.
  • the amount of the non-conjugated diolefin will generally range from about 0.5 to 20 mole percent, preferably about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present.
  • non-conjugated dienes that may be used as the third monomer in the terpolymer include:
  • the carboxylic acid material which is grafted to or reacted with the ethylene copolymer to form the grafted ethylene copolymer is preferably ethylenically unsaturated, preferably monounsaturated.
  • carboxylic acid material and can be either a monocarboxylic or dicarboxylic acid material.
  • the dicarboxylic acid materials include (i) monounsaturated C4 to C 10 dicarboxylic acid wherein (a) the carboxyl groups are vicinyl, i.e., located on adjacent carbon atoms, and (b) at least one, preferably both. of said adjacent carbon atoms are part of said monounsaturation; and (ii) derivatives of (i) such as anhydrides or C.
  • the monocarboxylic acid materials include (i) monounsaturated C 3 to C ⁇ 0 monocarboxylic acid wherein the carbon-carbon bond is conjugated to the carboxy qroup, i.e., of the structure and (ii) derivatives of (i) such as C, to C s alcohol derived monoesters of (i).
  • the monounsaturation of the monounsaturated carboxylic acid material becomes saturated.
  • acrylic acid becomes an ethylene copolymer substituted propionic acid
  • methacrylic acid becomes an ethylene copolymer substituted isobutyric acid.
  • Exemplary of such unsaturated mono- and dicarboxylic acids, or anhydrides and thereof include fumaric acid, itaconic acid, maleic acid. maleic anhydride. chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, etc.
  • Preferred carboxylic acid materials are the dicarboxylic acid anhydrides. Maleic anhydride or a derivative thereof is particularly preferred as it does not appear to homopolymerize appreciably but grafts onto the ethylene copolymer to give two carboxylic acid functionalities. Such preferred materials have the generic formula wherein R and R are independently hydrogen or a halogen.
  • various unsaturated comonomers may be grafted on the ethylene copolymer together with the unsaturated carboxylic acid material.
  • Such graft monomer systems may comprise one or a mixture of comonomers different from said unsaturated carboxylic acid material, and which contain only one copolymerizable double bond and are copolymerizable with said unsaturated acid component.
  • such comonomers do not contain free carboxylic acid groups and are esters containing alpha-ethylenic unsaturation in the acid or alcohol portion; hydrocarbons, both aliphatic and aromatic, containing , alpha-ethylenic unsaturation, such as the Ca-C, alpha olefins, for example hexene, nonene, dodecene, etc.; styrenes, for example styrene, alpha-methyl styrene, p-methyl styrene, butyl styrene, etc.; and vinyl monomers, for example vinyl acetate, vinyl chloride, vinyl ketones such as methyl and ethyl vinyl ketone, and nitrogen containing vinyl monomer such as vinyl pyridine and vinyl pyrrolidine, etc.
  • Comonomers containing functional groups which may cause crosslinking, gelation or other interfering reactions should be avoided, although minor amounts of such comonomers (up to about
  • the components of the graft copolymerizable system are used in a ratio of unsaturated carboxylic acid material monomer component to comonomer component of about 1:4 to 4:1, preferably about 12 to 2:1 by weight.
  • the grafting of the ethylene copolymer with the carboxylic acid material may be by any suitable method, such as thermally by the "ene” reaction, using copolymers containing unsaturation, such as ethylene-propylene-diene polymers either chlorinated or unchlorinated, or more preferably it is by free-radical induced grafting in solvent, preferably in a mineral lubricating oil as solvent.
  • the radical grafting is preferably carried out using free radical initiators such as peroxides, hydroperoxides, and azo compounds and preferably those which have a boiling point greater than about 100° C. and which decompose thermally within the grafting temperature range to provide said free radicals.
  • free-radical initiators are azobutyro-nitrile, 2,5-dimethyl-hex-3-yne-2, 5 bis-tertiary-butyl peroxide (sold. as Lupersol 130) or its hexane analogue, di-tertiary butyl peroxide and dicumyl peroxide.
  • the initiator is generally used at a level of between about 0.005% and about 1%, based on the total weight of the polymer solution, and temperatures of about 150 to 220 C.
  • the ethylenically unsaturated carboxylic acid material such as maleic anhydride
  • the aforesaid carboxylic acid material and free radical initiator are generally used in a weight percent ratio range of 1.0:1 to 30:1, preferably 3.0:1 to 6:1.
  • the initiator grafting is preferably carried out in an inert atmosphere, such as that obtained by nitrogen blanketing. While the grafting can be carried out in the presence of air, the yield of the desired graft polymer is generally thereby decreased as compared to grafting under an inert atmosphere substantially free of oxygen.
  • the grafting time will usually range from about 0.1 to 12 hours, preferably from about 0.5 to 6 hours, more preferably 0.5 to 3 hours.
  • the graft reaction will be usually carried out to at least approximately 4 times, preferably at least about 6 times the half-life of the free-radical initiator at the reaction temperature employed, e.g. with 2,5-dimethyl hex-3-yne-2, 5-bis(t-butyl peroxide) 2 hours at 160 C. and one hour at 170 C., etc.
  • the copolymer solution is first heated to grafting temperature and thereafter said unsaturated carboxylic acid material and initiator are added with agitation, although they could have been added prior to heating.
  • the excess acid material can be eliminated by an inert gas purge. e.g. nitrogen sparging.
  • the carboxylic acid material that is added is kept below its solubility limit in the polymer solution, e.g. below about 1 wt. %. preferably below 0.4 wt. % or less, of free maleic anhydride based on the total weight of polymer-solvent solution. e.g. ethylene copolymer mineral lubricating oil solution. Continuous or periodic addition of the carboxylic acid material along with an appropriate portion of initiator, during the course of the reaction, can be utilized to maintain the carboxylic acid below its solubility limits, while still obtaining the desired degree of total grafting.
  • the maleic anhydride or other carboxylic acid material used will be grafted onto both the polymer and the solvent for the reaction.
  • Many solvents such as dichlorobenzene are relatively inert and may be only slightly grafted, while mineral oil will tend to be more grafted.
  • the exact split of graft between the substrate present depends upon the polymer and its reactivity, the reactivity and type of oil, the concentration of the polymer in the oil, and also upon the maintenance of the carboxylic acid material in solution during the course of the reaction and minimizing the presence of dispersed, but undissolved acid, e.g. the maleic anhydride.
  • the undissolved acid material appears to have an increased tendency to react to form oil insoluble materials as opposed to dissolved acid material.
  • the split between grafted oil and grafted polymer may be measured empirically from the infrared analyses of the product dialyzed into oil and polymer fractions.
  • the grafting is preferably carned out in a mineral lubricating oil which need not be removed after the grafting step but can be used as the solvent in the subsequent reaction of the graft polymer with the amine material and as a solvent for the end product to form the lubricating additive concentrate.
  • the oil having attached, grafted carboxyl groups, when reacted with the amine material will also be converted to the corresponding derivatives.
  • the solution grafting step when carried out in the presence of a high temperature decomposable peroxide can be accomplished without substantial degradation of the chain length (molecular weight) of the ethylene containing polymer. This can be an advantage as opposed to high temperature thermal reactions which depend on degradation to apparently form free radical reactive sites. Measurement of molecular weights and degradation can be evaluated by determination of the thickening efficiency (T.E.) of the polymer as will later be described.
  • T.E. thickening efficiency
  • the amount of carboxylic acid material used in the grafting reaction is an amount which is effective to provide a grafted ethylene copolymer which upon further reaction with an amido-amine as described hereinafter provides a material exhibiting the properties of a multifunctional viscosity index improver additive, more specifically a viscosity index improver-dispersant additive, i.e., a material having both V.I. improving and dispersancy properties in an oleaginous composition. That is to say, an amount which is effective to provide, upon reaction of the grafted ethylene copolymer with the amido amine, an oleaginous composition exhibiting improved viscometric and dispersancy properties.
  • this amount of grafting material e.g., moles of carboxylic acid material such as maleic anhydride
  • a grafted ethylene copolymer e.g., ethylene-alpha-olefin substituted carboxylic acid material such as ethylene- propylene substituted succinic anhydride, containing an average number of acid material moieties, e.g., succinic anhydride, grafted to or present on a 10,000 number average molecular weight segment of a mole of ethylene copolymer of at least about 0.1, preferably at least about 0.5, and more preferably at least about 1.
  • the maximum average number of grafted moieties present per 10,000 average number molecular weight segment of a mole of ethylene copolymer backbone should not exceed about 10, preferably about 7 and more preferably about 5.
  • the average number, moles, of grafted moieties present per mole of ethylene copolymer backbone is at least about 0.6, preferably at least about 0.8, and more preferably at least about 1.
  • the maximum average number of grafted moieties grafted to or present per mole of ethylene copolymer backbone should generally not exceed about 10, preferably about 7, and more preferably about 5.
  • a mole of grafted ethylene copolymer e.g., ethylene-propylene substituted succinic anhydride, containing an ethylene copolymer backbone such as an ethylene-propylene backbone having an average number molecular weight of 50,000 contains grafted to said backbone an average number of succinic anhydride moieties of from about 0.5 to about 50, preferably from about 0.6 to about 10.
  • an average number of succinic anhydride moieties of from about 0.5 to about 50, preferably from about 0.6 to about 10.
  • from about 0.2 to about 12 preferably from about 0.4 to about 6 moles of said carboxylic acid material are charged to the reactor per mole of ethylene copolymer charged.
  • ethylene copolymer reacts with the carboxylic acid material, e.g., maleic anhydride, to produce a grafted ethylene copolymer, e.g., ethylene-propylene substituted succinic anhydride.
  • the resultant reaction product mixture therefore, contains reacted or grafted ethylene copolymer, e.g., ethylene-propylene substituted succinic anhydride, unreacted or ungrafted ethylene copolymer, and unreacted grafting material, e.g., maleic anhydride.
  • the unreacted ethylene copolymer is typically not removed from the reaction product mixture, and the reaction product mixture, generally stripped of any unreacted grafting material, is utilized as is or is employed for further reaction with the amine as described hereinafter.
  • Characterization of the average number of moles of carboxylic acid material, e.g., maleic anhydride, which have reacted per mole of ethylene copolymer charged to the reaction (whether it has undergone reaction or not) is defined herein as the average number of grafted moieties grafted to or present per mole of ethylene copolymer backbone. This number is defined solely with reference to the resulting reaction product mixture. Although the amount of said unreacted ethylene copolymer contained in the resulting reaction product mixture can be subsequently modified, i.e., increased or decreased by techniques known in the art, such modifications do not alter the average number of grafted moieties as defined above.
  • the term grafted ethylene copolymer is intended to refer to the reaction product mixture whether it has undergone such modification or not.
  • the amido-amine comprises a reaction product of at least a polyamine and an alpha, beta ethylenically unsaturated compound of formula (I) above.
  • the polyamines useful in this invention comprise polyamines, most preferably polyalkylene polyamines, of about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms and about 1 to 12, preferably 2 to 12, more preferably 3 to 12, and most preferably at least 5 (e.g., 5 to 9) nitrogen atoms in the molecule.
  • These amines may be hydrocarbyl amines or may be hydrocarbyl amines including other groups, e.g, hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably 1 to 3 hydroxy groups are particularly useful.
  • Preferred amines are aliphatic saturated amines, including those of the general formulas: wherein R, R , R and R are independently selected from alkylene radicals; and C, to C, alkylamino C 2 to C 6 alkylene radicals; and wherein R can additionally comprise a moiety of the formula: wherein R is as defined above, and wherein s and s can be the same or a different number of from 2 to 6, preferably 2 to 4; and t and t can be the same or different and are numbers of from 0 to 10, preferably 2 to 7, and most preferably about 3 to 7, with the proviso that the sum of t and t is not greater than 15.
  • R, R', R", R''', s, s , t and t be selected in a manner sufficient to provide the compounds of Formulas II and III with typically at least one primary or secondary amine group, preferably at least two primary or secondary amine groups. This can be achieved by selecting at least one of said R, R', R or R groups to be hydrogen or by letting t in Formula III be at least one when R is H or when the IV moiety possesses a secondary amino group.
  • the most preferred amine of the above formulas are represented by Formula III and contain at least two primary amine groups and at least one. and preferably at least three, secondary amine groups.
  • Non-limiting examples of suitable amine compounds include: 1,2-diammoethane: 1.3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene tnamine: triethylene tetramine; tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine: di-(1,2-propylene)triamine; di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-ammoethyl) ethylene diamine; N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine: N-dodecyl-1,3-propane diamine; aminopropane; N,N-di-(2-aminoethyl) ethylene di
  • amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane. and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula (V): wherein p, and p 2 are the same or different and are each integers of from 1 to 4, and n n2 and n 3 are the same or different and are each integers of from 1 to 3.
  • Non-limiting examples of such amines include 2-pentadecyl imidazoline: N-(2-aminoethyl) piperazine; etc.
  • one process for preparing alkylene amines involves the reaction of an involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetramine, tetraethylene pentamine and isomeric piperazines.
  • alkylene dihalide such as ethylene dichloride or propylene dichloride
  • ammonia such as ethylene triamine, triethylenetetramine, tetraethylene pentamine and isomeric piperazines.
  • Low cost poly-(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H'', "Polyamine 400", “Dow Polyamine E-100", etc.
  • the alkylene groups in either formula (VI) or (VII) may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 carbon atoms.
  • the polyoxyalkylene polyamines of formulas (VI) or (VII) above may have average molecular weights ranging from about 200 to about 4000 and preferably from about 400 to about 2000.
  • the preferred polyoxyalkylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2000.
  • the polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company. Inc. under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
  • any polyamine whether aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., can be employed provided it is capable of adding across the acrylic double bond and amidifying with for example the carbonyl group (-C(O)-) of the acrylate-type compound of formula I, or with the thiocarbonyl group (-C(S)-) of the thioacrylate-type compound of formula I.
  • the alpha, beta ethylenically unsaturated compounds employed in this invention comprise at least one member selected from the group consisting of alpha, beta ethylenically unsaturated compounds of the formula: wherein X is sulfur or oxygen, Y is -OR 4 , -SR 4 , or -NR 4 (R 5 ), and R 1 , R 2 , R 3 , R 4 and R s are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.
  • R', R 2 , R 3 , R 4 or R 5 are hydrocarbyl
  • these groups can comprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl or heterocyclic, which can be substituted with groups which are substantially inert to any component of the reaction mixture under conditions selected for preparation of the amido-amine.
  • substituent groups include hydroxy, halide (e.g., Cl, Fl, I, Br), -SH and alkylthio.
  • R' through R 5 are alkyl
  • such alkyl groups can be straight or branched chain, and will generally contain from 1 to 20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms.
  • alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like.
  • R' through R 5 the aryl group will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).
  • the alkaryl group will generally contain from about 7 to 20 carbon atoms, and preferably from 7 to 12 carbon atoms. Illustrative of such alkaryl groups are tolyl, methylphenyl, o-ethyltolyl, and m-hexyltolyl.
  • the aryl component generally consists of phenyl or (C 1 to C 6 ) alkyl-substituted phenol and the alkyl component generally contains from 1 to 12 carbon atoms, and preferably from 1 to 6 carbon atoms.
  • aralkyl groups examples include benzyl, o-ethylbenzyl, and 4-isobutylbenzyl.
  • R' and R 5 are cycloalkyl
  • the cycloalkyl group will generally contain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms.
  • Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, and cyclododecyl.
  • the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which on or more ring carbon atoms is replaced by oxygen or nitrogen.
  • heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofuryl, pyrazinyl and 1,4-oxazinyl.
  • alpha, beta ethylenically unsaturated carboxylate compounds employed herein have the following formula: wherein R 1 , R 2 , R 3 , and R 4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha, beta-ethylenically unsaturated carboxylate compounds of formula VIII are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2- heptenoic acid, 3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl 2-propenoate, methyl 2-butenoate, ethyl 2-hexers of
  • alpha, beta ethylenically unsaturated carboxylate thioester compounds employed herein have the following formula: wherein R 1 , R 2 , R 3 , and R 4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha, beta-ethylenically unsaturated carboxylate thioesters of formula IX are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate, isopropylmercapto 2- decenoate, phenylmercapto 2-pentenoate, tertiary butylmercapto 2-propenoate.
  • alpha, beta ethylenically unsaturated carboxyamide compounds employed herein have the following formula: wherein R', R 2 , R 3 . R 4 and R 5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha, beta-ethylenically unsaturated carboxyamides of formula X are 2-butenamide, 2-hexenamide.
  • alpha, beta ethylenically unsaturated thiocarboxylate compounds employed herein have the following formula: wherein R', R 2 , R3, and R 4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha. beta-ethylenically unsaturated thiocarboxylate compounds of formula XI are 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid, 3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid.
  • alpha, beta ethylenically unsaturated dithioic acid and acid ester compounds employed herein have the following formula: wherein R 1 , R 2 , R 3 , and R 4 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha, beta-ethylenically unsaturated dithioic acids and acid esters of formula XII are 2-butendithioic acid, 2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2- heptendithioic acid, 3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid, 3-cyclohexyl-2-butendithioic acid, 2-methyl-2-butendithioic acid, 2-propyl-2-propendithioic acid, 2-isopropyl-2-hexendithioic acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclohexyl-2-methyl-2-pentendithioic acid, 2-propendithioic acid, methyl 2-propendithioate, methyl 2-methyl 2-proendithioate, methyl 2-butendithioate, ethyl 2-hexendithioate, isoprop
  • alpha, beta ethylenically unsaturated thiocarboxyamide compounds employed herein have the following formula: wherein R', R 2 , R 3 , R 4 and R s are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above.
  • alpha, beta-ethylenically unsaturated thiocarboxyamides of formula XIII are 2-butenthioamide, 2-hexenthioamide, 2-decenthioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-butenthioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-butenthioamide, 2-methyl-2-butenthioamide, 2-propyl-2-propenthioamide, 2-isopropyl-2-hexenthioamide, 2,3-dimethyl-2-butenthioamide, 3-cyclohexyl-2-methyl-2-pententhioamide, N-methyl 2-butenthioamide, N,N-diethyl 2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl 2-propenthioamide, N-octadecyl 2-propenthioamide
  • Preferred compounds for reaction with the polyamines in accordance with this invention are lower alkyl esters of acrylic and (lower alkyl) substituted acrylic acid.
  • Illustrative of such preferred compounds are compounds of the formula: where R 3 is hydrogen or a C 1 to C 4 alkyl group, such as methyl, and R 4 is hydrogen or a C, to C4 alkyl group, capable of being removed so as to form an amido group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl, hexyl, etc.
  • these compounds are acrylic and methacrylic esters such as methyl, ethyl or propyl acrylate, methyl, ethyl or propyl methacrylate.
  • the selected alpha, beta-unsaturated compound comprises a compound of formula I wherein X is oxygen
  • the resulting reaction product with the polyamine contains at least one amido linkage (-C(O)N ⁇ ) and such materials are herein termed "amido-amines.”
  • the selected alpha, beta unsaturated compound of formula I comprises a compound wherein X is sulfur
  • the resulting reaction product with the polyamine contains thioamide linkage (-C(S)N ⁇ ) and these materials are herein termed "thioamido-amines.”
  • amido-amines although it will be understood that such discussion is also applicable to the thioamido-amines.
  • amido-amine formed varies with reaction conditions. For example, a more linear amido-amine is formed where substantially equimolar amounts of the unsaturated carboxylate and polyamine are reacted. The presence of excesses of the ethylenically unsaturated reactant of formula I tends to yield an amido-amine which is more cross-linked than that obtained where substantially equimolar amounts of reactants are employed. Where for economic or other reasons a cross-linked amido-amine using excess amine is desired, generally a molar excess of the ethylenically unsaturated reactant of about at least 10%, such as 10-300%, or greater, for example, 25-200%, is employed.
  • an excess of carboxylated material should preferably be used since a cleaner reaction ensues.
  • a molar excess of about 10-100% or greater such as 10-50%, but preferably an excess of 30-50%, of the carboxylated material. Larger excess can be employed if desired.
  • amido-amine adducts so formed are characterized by both amido and amino groups.
  • they may be represented by units of the following idealized formula: wherein the R's'', which may be the same or different, are hydrogen or a substituted group, such as a hydrocarbon group, for example. alkyl, alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which, for example, may be aryl, cycloalkyl, alkyl, etc., and n is an integer such as 1-10 or greater.
  • the amido-amine adducts preferably contain an average of form 1 to 3 amido groups per molecule of the amido-amine adduct.
  • cross-linked polymers may also be formed by employing certain conditions since the polymer has labile hydrogens which can further react with either the unsaturated moiety by adding across the double bond or by amidifying with a carboxylate group.
  • amido-amines of this invention are not cross-linked to any substantial degree, and more preferably are substantially linear.
  • the polyamine reactant contains at least one primary amine (and more preferably from 2 to 4 primary amines) group per molecule. and the polyamine and the unsaturated reactant of formula I are contacted in an amount of from about 1 to 10, more preferably from about 2 to 6, and most preferably from about 3 to 5, equivalents of primary amine in the polyamine reactant per mole of the unsaturated reactant of formula I.
  • the reaction between the selected polyamine and acrylate-type compound is carried out at any suitable temperature. Temperatures up to the decomposition points of reactants and products can be employed. In practice, one generally carries out the reaction by heating the reactants below 100' C, such as 80-90 C. for a suitable period of time, such as a few hours. Where an acrylic-type ester is employed, the progress of the reaction can be judged by the removal of the alcohol in forming the amide. During the early part of the reaction alcohol is removed quite readily below 100 C in the case of low boiling alcohols such as methanol or ethanol. As the reaction slows, the temperature is raised to push the polymerization to completion and the temperature may be raised to 150 C toward the end of the reaction. Removal of alcohol is a convenient method of judging the progress and completion of the reaction which is generally continued until no more alcohol is evolved. Based on removal of alcohol, the yields are generally stoichiometric. In more difficult reactions, yield of at least 95% are generally obtained.
  • reaction of an ethylenically unsaturated carboxylate thioester of formula IX liberates the corresponding HSR 4 compound (e.g., H 2 S when R° is hydrogen) as a by-product
  • reaction of an ethylenically unsaturated carboxyamide of formula X liberates the corresponding HNR 4 (R s ) compound (e.g., ammonia when R 4 and R s are each hydrogen) as by-product.
  • reaction time involved can vary widely depending on a wide variety of factors. For example, there is a relationship between time and temperature. In general, lower temperature demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to 10 hours will be employed.
  • the reaction can be run without the use of any solvent.
  • a solvent such as water
  • any suitable solvent can be employed, whether organic or inorganic, polar or non-polar.
  • TEPA tetraethylene pentaamine
  • the grafted high molecular weight ethylene copolymer preferably in solution, such as an oil solution, containing 5 to 95 wt.%, preferably 5 to 30 wt. %, and more preferably 10 to 20 wt.% of said grafted ethylene copolymer, is readily reacted with the amido-amine by introducing the amido amine into said grafted ethylene copolymer containing solution and heating at a temperature of from about 100°C to 250 C, preferably from 125 to 175 C, for from about 1 to 10 hours, usually about 2 to about 6 hours.
  • the heating is preferably carried out, in the case of ethylene copolymer substituted dicarboxylic acid material, to favor formation of imides or mixtures of imides and amides rather than amides and salts.
  • heating is preferably carried out to favor formation of amides rather than salts. Removal of water assures completion of the imidation / amidation reaction. Reaction ratios can vary considerably, depending upon the reactants, amounts of excess, type of bonds formed, etc.
  • ethylene copolymer substituted monocarboxylic or dicarboxylic acid moiety content e.g., grafted succinic anhydride content
  • amido amine reactant e.g., amine
  • An example of the reaction of an amido amine reactant with ethylene copolymer substituted dicarboxylic acid material is the reaction of ethylene-propylene copolymer substituted succinic anhydride (EPSA) with a poly amido-amine having two terminal -NH 2 groups, which can be illustrated as follows: wherein x and y are each integers of from 0 to 10, with the proviso that the sum of x + y is at least 1, e.g., 1 to 20.
  • ESA ethylene-propylene copolymer substituted succinic anhydride
  • An example of the reaction of an amido-amine reactant with an ethylene copolymer substituted monocarboxylic acid material is the reaction of ethylene-propylene copolymer substituted propionic acid (EPA) with a poly amido-amine having two terminal -NH 2 groups, which can be illustrated as follows: wherein x and y are each integers of from 0 to 10, with the proviso that the sum of x + y is at least 1. e.g., 1 to 20 and wherein Z' and Z 2 are the same or different and are each moieties of the formula:
  • amido-amine reactant can be employed alone or in admixture with any of the above described amines, such as the polyalkylene polyamines, useful in preparing the amido-amine reactant.
  • the ethylene copolymer substituted mono- or dicarboxylic acid material and amido-amine will be contacted for a time and under conditions sufficient to react substantially all of the pnmary nitrogens in the amido-amine reactant.
  • the progress of this reaction can be followed by infra-red analysis.
  • This reaction can be conducted in a polar or non-polar solvent, e.g., xylene, toluene, benzene, and the like, and is preferably conducted in the presence of a mineral or synthetic lubricating oil.
  • a polar or non-polar solvent e.g., xylene, toluene, benzene, and the like, and is preferably conducted in the presence of a mineral or synthetic lubricating oil.
  • the grafted high molecular weight ethylene copolymer is reacted with the amido-amine and a carboxylic acid component or with the preformed reaction products, e.g., salts, amides, imides, of said amido-amine and carboxylic acid component.
  • the carboxylic acid component includes: hydrocarbyl substituted dicarboxylic acid or anhydride, preferably succinic anhydride or acid, having 12 to 49 carbons, preferably 16 to 49 carbons in said hydrocarbyl group; long chain monocarboxylic acid of the formula RCOOH where R is a hydrocarbyl group of about 50 to about 400 carbons; and long chain hydrocarbyl substituted dicarboxylic acid or anhydride, preferably succinic anhydride or acid, having from about 50 to about 400 carbons in said hydrocarbyl group.
  • the preferred carboxylic acid component is the long chain hydrocarbyl substituted dicarboxylic acid or anhydride, preferably succinic acid or anhydride, having from about 50 to about 400 carbon atoms in said hydrocarbyl group.
  • Said hydrocarbyl groups are essentially aliphatic and include alkenyl and alkyl groups.
  • the longer chain acids and anhydrides are preferred, particularly when the grafting reaction is carried out in lubricating oil.
  • the about C 50 -C 400 hydrocarbyl subtituted dicarboxylic acid or anhydride includes the reaction product of the C 50 -C 400 hydrocarbon polymer, generally a polyolefin, with (i) monounsaturated C4. to C 10 dicarboxylic acid wherein (a) the carboxyl groups are vicinyl, i.e., located on adjacent carbon atoms, and (b) at least one, preferably both, of said adjacent carbon atoms are part of said monounsaturation; or with (ii) derivatives of (i) such as anhydrides of (i).
  • the monounsaturation of the dicarboxylic acid, anhydride, etc. becomes saturated.
  • maleic anhydride becomes a hydrocarbyl substituted succinic anhydride.
  • the polyolefin reacts with the unsaturated acid or derivative and the hydrocarbyl substituted dicarboxylic acid material will contain unreacted polyolefin.
  • the unreacted polyolefin is typically not removed from the reaction mixture (because such removal is difficult and would be commercially infeasible) and the product mixture. stripped of any unreacted monounsaturated C 4 . to C, dicarboxylic acid or anhydride, is employed as the carboxylic acid component.
  • Characterization of the average number of moles of dicarboxylic acid or anhydride, which have reacted per mole of polyolefin charged to the reaction (whether it has undergone reaction or not) is defined herein as functionoality. Said functionality is based upon (i) determination of the saponification number of the resulting product mixture using potassium hydroxide; and (ii) the number average molecular weight of the polymer charged using techniques well known in the art. Functionality is defined solely with reference to the resulting product mixture. Although the amount of said reacted polyolefin contained in the resulting product mixture can be subsequently modified, i.e., increased or decreased by techniques known in the art, such modifications do not alter functionality as defined above.
  • the term C 50 -C 400 hydrocarbyl substituted dicarboxylic acid material is intended to refer to the product mixture whether it has undergone such modification or not.
  • the functionality of the C 50 -C 400 hydrocarbyl substituted dicarboxylic acid material will be typically at least about 0.5, preferably at least about 0.8, and most preferably at least about 0.9 and will vary typically from about 0.5 to about 2.8 (e.g., 0.6 to 2), preferably from about 0.8 to about 1.4, and most preferably from about 0.9 to about 1.3.
  • Such unsaturated dicarboxylic acids or anhydrides thereof are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, etc.
  • Cso to about C 400 olefin polymers for reaction with the unsaturated dicarboxylic acids or derivatives thereof are polymers comprising a major molar amount of C 2 to Cio, e.g., C 2 to C 5 monoolefin.
  • Such olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, etc.
  • the polymers can be homopolymers such as polyisobutylene, as well as copolymers of two or more of such olefins such as copolymers of: ethylene and propylene; butylene and isobutylene; propylene and isobutylene; etc.
  • copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is a C4 to C 18 non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.
  • a minor molar amount of the copolymer monomers e.g., 1 to 10 mole %
  • a C4 to C 18 non-conjugated diolefin e.g., a copolymer of isobutylene and butadiene; or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.
  • the olefin polymer may be completely saturated, for example an ethylene-propylene copolymer made by a Ziegler-Natta synthesis usig hydrogen as a moderator to control molecular weight.
  • the olefin polymers used will usually have number average molecular weights within the range of about 700 and about 5,600, more usually between about 800 and about 3000. Particularly useful olefin polymers have number average molecular weights within the range of about 900 and about 2500 with approximately one terminal double bond per polymer chain.
  • An especially useful starting material is polyisobutylene.
  • the number average molecular weight for such polymers can be determined by several known techniques. A convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information, see W. W. Yau, J. J. Kirkland and D> D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979.
  • olefin polymer and the dicarboxylic acid or derivative may be simply heated together as disclosed in U.S. Patents 3,361,673 and 3,401,118 to cause a thermal "ene" reaction to take place.
  • the olefin polymer can be first halogenated, for example, chlorinated or brominated to about 1 to 8 wt. %, preferably 3 to 7 wt.
  • % chlorine, or bromine based on the weight of polymer, by passing the chlorine or bromine through the polyolefin at a temperature of 60 to 250' C, e.g. 120 to 160' C, for about 0.5 to 10, preferably 1 to 7 hours.
  • the halogenated polymer may then be reacted with sufficient unsaturated acid or derivative at 100 to 250 C, usually about 180 to 235 C, for about 0.5 to 10, e.g. 3 to 8 hours, so the product obtained will contain the desired number of moles of the unsaturated acid or derivative per mole of the halogenated polymer. Processes of this general type are taught in U.S. Patents 3,087,936; 3,172,892; 3,272,746 and others.
  • the olefin polymer, and the unsaturated acid or derivative are mixed and heated while adding chlorine to the hot material.
  • Processes of this type are disclosed in U.S. Patents 3,215,707; 3,231,587; 3,912,764; 4,110,349; and in U.K. 1,550,219.
  • halogen about 65 to 95 wt. % of the polyolefin, e.g. polyisobutylene will normally reacted with the dicarboxylic acid or derivative.
  • the acid component is polyisobutenyl succinic anhydride.
  • amido-amine and carboxylic acid component may be pre-reacted, with the acid being generally attached to the amido-amine through salt, imide, amide, or other linkages so that a primary or secondary amine group of the amido-amine is still available for reaction with the acid moieties of the grafted high molecular weight ethylene copolymer.
  • a convenient source of these pre-reacted materials are the lubricating oil dispersant, provided they retain primary amine groups capable of further reaction with the grafted ethylene copolymer, described in EP-A-0319229 and EP-A-0368548.
  • the grafted high molecular weight ethylene copolymer is reacted with the amido-amine and carboxylic acid component or pre-reacted amido-amine-carboxylic acid component substantially as described hereinafore for the reaction of the grafted high molecular weight ethylene copolymer with the amido-amine.
  • a reaction mixture containing the grafted high molecular weight ethylene copolymer, e.g., ethylene-propylene substituted succinic anhydride, and carboxylic acid component, e.g., polyisobutylene substituted succinic anhydride is prepared by admixing these two reactants, and the amido-amine is then introduced into this reaction mixture and the reaction is carried out as described hereinafore.
  • the carboxylic acid component and amido-amine may be added substantially simultaneously to a reaction mixture containing the grafted high molecular weight ethylene copolymer.
  • the amount of the carboxylic acid component utilized is an amount sufficient to provide about 0.5 to about 4, preferably from about 1 to about 2 moles of said carboxylic acid component per molar amount of the carboxylic acid moieties present in the grafted ethylene copolymer.
  • a grafted ethylene-propylene copolymer of about 40,000 Mn i.e., a thickening efficiency of about 2.1 g and averaging 4 succinic anhydride groups per molecule
  • about 4 moles of polyisobutenyl succinic anhydride would preferably be used per mole of grafted copolymer.
  • compositions of matter of the instant invention i.e., grafted ethylene copolymers reacted with the amido-amine
  • the adduct may be post-reacted or post-treated with C, - C 30 monocarboxylic acids or anhydrides, preferably acetic anhydride, or unsubstituted or C, -C 30 monocarboxylic monocarboxylic acids or anhydrides, preferably acetic anhydride, or unsubstituted or C, to C 23 hydrocarbyl substituted dicarboxylic acid anhydrides as disclosed in U.S. Patent No. 4,137,185, incorporated herein by reference: and the sulfonic acids of U.S. Patent No. 4,144,181, incorporated herein by reference.
  • the multifunctional viscosity index improvers of this invention can be used alone or in admixture with other viscosity index improvers or dispersants.
  • the other viscosity index improvers or viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters. These other viscosity modifiers may also be derivatized, as by grafting with a carboxylic acid material of the type described hereinafore and thereafter reacting with a polyamine of the type described hereinafore as a polyol, to include other properties or functions, such as the addition of dispersancy properties.
  • oil soluble viscosity modifying polymers will generally have number average molecular weights of from 10 3 to 10 6 , preferably 10 4 to 10 6 , e.g., 20,000 to 250,000, as determined by gel permeation chromatography or osmometry.
  • suitable hydrocarbon polymers include homopolymers and copolymers of two or more monomers of C 2 to C 3c , e.g. C 2 to C 8 olefins, including both alpha olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc. Frequently they will be of ethylene with C 3 to C 30 olefins, particularly preferred being the copolymers of ethylene and propylene.
  • polystyrene e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof.
  • the polymer may be degraded in molecular weight, for example by mastication, extrusion, oxidation or thermal degradation, and it may be oxidized and contain oxygen.
  • derivatized polymers such as post-grafted interpolymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol, or amine, e.g. an alkylene polyamine or hydroxy amine, e.g. see U.S. Patent Nos. 4,089,794; 4,160,739; 4,137,185; or copolymers of ethylene and propylene reacted or grafted with nitrogen compounds such as shown in U.S. Patent Nos. 4,068,056; 4,068,058; 4,146.489 and 4,149,984.
  • the preferred hydrocarbon polymers are ethylene copolymers containing from 15 to 90 wt.% ethylene, preferably 30 to 80 wt.% of ethylene and 10 to 85 wt.%, preferably 20 to 70 wt.% of one or more C 3 to C 28 , preferably C 3 to C ⁇ 8 , more preferably C 3 to C a , alpha-olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt.%, as determined by X-ray and differential scanning calorimetry. Copolymers of ethylene and propylene are most preferred.
  • alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc. include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, etc.; also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc., and mixtures thereof.
  • Terpolymers, tetrapolymers, etc., of ethylene, said C 3 - 2s alpha-olefin, and a non-conjugated diolefin or mixtures of such diolefins may also be used.
  • the amount of the non-conjugated diolefin generally ranges from about 0.5 to 20 mole percent, preferably from about 1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin present.
  • the polyester V.I. improvers are generally polymers of esters of ethylenically unsaturated C 3 to C 8 mono- and dicarboxylic acids such as methacrylic and acrylic acids, maleic acid, maleic anhydride, fumaric acid, etc.
  • unsaturated esters examples include those of aliphatic saturated mono alcohols of at least 1 carbon atom and preferably of from 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like and mixtures thereof.
  • esters include the vinyl alcohol esters of C 2 to C 22 fatty or mono carboxylic acids, preferably saturated such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like and mixtures thereof. Copolymers of vinyl alcohol esters with unsaturated acid esters such as the copolymer of vinyl acetate with dialkyl fumarates, can also be used.
  • the esters may be copolymerized with still other unsaturated monomers such as olefins, e.g. 0.2 to 5 moles of C 2 - C 20 aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification.
  • unsaturated monomers such as olefins, e.g. 0.2 to 5 moles of C 2 - C 20 aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification.
  • olefins e.g. 0.2 to 5 moles of C 2 - C 20 aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification.
  • copolymers of styrene with maleic anhydride esterified with alcohols and amines
  • ester polymers may be grafted with, or the ester copolymerized with, polymerizable unsaturated nitrogen-containing monomers to impart dispersancy to the V.I. improvers.
  • suitable unsaturated nitrogen-containing monomers include those containing 4 to 20 carbon atoms such as amino substituted olefins as p-(beta-diethylaminoethyl)styrene; basic nitrogen-containing heterocycles carrying a polymerizable ethylenically unsaturated substituent, e.g.
  • the vinyl pyridines and the vinyl alkyl pyridines such as 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinyl-pyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and 2-butyl-1-5-vinyl-pyridine and the like.
  • N-vinyl lactams are also suitable, e.g. N-vinyl pyrrolidones or N-vinyl piperidones.
  • the vinyl pyrrolidones are preferred and are exemplified by N-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.
  • Dispersants maintain oil insolubles, resulting from oxidation during use, in suspension in the fluid thus preventing sludge flocculation and precipitation as deposition on metal parts.
  • Suitable dispersants include alkyl succinimides, the reaction product of oil-soluble polyisobutylene succinic anhydride with polyamines such as tetraethylene pentamine, and borated salts thereof.
  • Such dispersants are disclosed, inter alia, in Belgium Patent No. 658,236 and U.S. Patent No. 3,272,746.
  • dispersants include the esters derived from long chain hydrocarbon substituted dicarboxylic acid material and hydroxy compounds such as monohydric and polyhydric alcohols or aromatic compounds such as phenols and naphthols, etc.
  • the polyhydric alcohols are the most preferred hydroxy compound and preferably contain from 2 to about 10 hydroxy radicals, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to about 8 carbon atoms.
  • polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
  • the ester dispersant may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, I.cydohexane.3.ol, and oleyl alcohol.
  • unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, I.cydohexane.3.ol, and oleyl alcohol.
  • Still other classes of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxy-alkylene, oxy-arylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals.
  • the ester dispersant may be di-esters of dicarboxylic acids (e.g., succinic acid or anhydride) or acidic esters, i.e., partially esterified succinic acids; as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxyl radicals. Mixtures of the above illustrated esters likewise are contemplated within the scope of this invention.
  • dicarboxylic acids e.g., succinic acid or anhydride
  • acidic esters i.e., partially esterified succinic acids
  • polyhydric alcohols or phenols i.e., esters having free alcohols or phenolic hydroxyl radicals.
  • the ester dispersant may be prepared by one of several known methods as illustrated for example in U.S. Patent 3,381,022.
  • the ester dispersants may also be borated, similar to the nitrogen containing dispersants.
  • Hydroxyamines which can be reacted with the polymer-substituted monocarboxylic acid materials to form dispersants include 2-aminO-1-butanol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline.
  • nucleophilic reactants suitable for reaction with the polymer-substituted monocarboxylic acid materials includes amines, alcohols, and compounds of mixed amine and hydroxy containing reactive functional groups, i.e., amino-alcohols.
  • THAM tris(hydroxymethyl) amino methane
  • the multifunctional viscosity index improvers of the present invention can be incorporated into a lubricating oil in any convenient way. Thus, they can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentration of the multifunctional viscosity index improvers. Such blending into the additional lube oil can occur at room temperature or elevated temperatures.
  • the multifunctional viscosity index improvers can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with a lubricating oil basestock to obtain the final formulation.
  • Such multifunctional viscosity index improver concentrates will typically contain (on an active ingredient (A.I.) basis) from about 3 to about 45 wt.%, and preferably from about 10 to about 35 wt.%, multifunctional viscosity index improver additive, and typically from about 30 to 90 wt.%, preferably from about 40 to 60 wt.%. base oil, based on the concentrate weight.
  • A.I. active ingredient
  • the lubricating oil basestock for the multifunctional viscosity index improver typically is adapted to perform a selected function by the incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).
  • the amounts of the multifunctional viscosity improver additives of the instant invention which are incorporated into an oleaginous composition, e.g., lubricating oil, is an amount which is effective to improve the viscometric properties, e.g., viscosity index, of said oleaginous composition and impart dispersancy thereto, i.e., a viscosity improving and dispersant effective amount.
  • this amount is from about 0.01 to about 20, preferably from about 0.1 to about 10, and more preferably from about 0.2 to about 5 weight percent, based on the weight of the oleaginous composition.
  • the oleaginous composition into which the multifunctional viscosity improvers or modifiers of the instant invention are incorporated or added include lubricating oil compositions, e.g., automatic transmission fluids, heavy duty oils suitable for gasoline and diesel engines, etc.
  • the multifunctional viscosity improvers of this invention may be added to the oleaginous composition in the form of an oil concentrate.
  • oil concentrate contains from about 5 wt.% up to about 49 wt.%, preferably 7 to 25 wt.%, of the multifunctional viscosity improver in oil, e.g., mineral lubricating oil.
  • the fully formulated oil compositions, or the oil concentrate may optionally contain other conventional additives such as pour point depressants, antiwear agents, antioxidants, other viscosity index improvers. dispersants, corrosion inhibitors, anti-foaming agents, detergents, rust inhibitors, friction modifiers, and the like.
  • Corrosion inhibitors also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition.
  • Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide.
  • oxidation inhibitors or antioxidants useful in this invention comprise oil-soluble copper compounds.
  • the copper may be blended into the oil as any suitable oil soluble copper compound.
  • oil soluble it is meant that the compound is oil soluble under normal blending conditions in the oil or additive package.
  • the copper compound may be in the cuprous or cupric form.
  • the copper may be in the form of the copper dihydrocarbyl thio- or dithio-phosphates.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid.
  • Examples of same thus include do to C, fatty acids, such as stearic or palmitic acid, but unsaturated acids such as oleic or branched carboxylic acids such as napthenic acids of molecular weights of from about 200 to 500, or synthetic carboxylic acids, are preferred, because of the improved handling and solubility properties of the resulting copper carboxylates.
  • oil-soluble copper dithiocarbamates of the general formula (RR,NCSS)nCu (where n is 1 or 2 and R and R, are the same or different hydrocarbyl radicals containing from 1 to 18, and preferably 2 to 12, carbon atoms, and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R, groups are alkyl groups of from 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc.
  • the total number of carbon atoms i.e., R and R, will generally be about 5 or greater. Copper sulphonates, phenates, and acetylacetonates may also be used.
  • Exemplary of useful copper compounds are copper Cul and/or Cull salts of alkenyl succinic acids or anhydrides.
  • the salts themselves may be basic, neutral or acidic. They may be formed by reacting (a) polyalkylene succinimides (having polymer groups of M of 700 to 5,000) derived from polyalkylenepolyamines, which have at least one free carboxylic acid group, with (b) a reactive metal compound.
  • Suitable reactive metal compounds include those such as cupric or cuprous hydroxides, oxides, acetates, borates, and carbonates or basic copper carbonate.
  • these metal salts are Cu salts of polyisobutenyl succinic anhydride, and Cu salts of polyisobutenyl succinic acid.
  • the selected metal employed is its divalent form, e.g., Cu+2.
  • the preferred substrates are polyalkenyl succinic acids in which the alkenyl group has a molecular weight greater than about 700.
  • the alkenyl group desirably has a M n from about 900 to 1,400, and up to 2,500, with a M n of about 950 being most preferred.
  • polyisobutylene succinic anhydride or acid is especially preferred.
  • These materials may desirably be dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) of the metal bearing material. Heating may take place between 70. and about 200 °C. Temperatures of 110°C to 140°C are entirely adequate. It may be necessary, depending upon the salt produced, not to allow the reaction to remain at a temperature above about 140" C for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.
  • a solvent such as a mineral oil
  • the copper antioxidants e.g., Cu-polyisobutenyl succinic anhydride, Cu-oleate, or mixtures thereof
  • Cu-polyisobutenyl succinic anhydride e.g., Cu-polyisobutenyl succinic anhydride, Cu-oleate, or mixtures thereof
  • Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the temperature at which the fluid will flow or can be poured.
  • Such additives are well known.
  • those additives which usefully optimize the low temperature fluidity of the fluid are C s -Cis dialkylfumarate vinyl acetate copolymers, polymethacrylates, and wax naphthalene.
  • Foam control can be provided by an antifoamant of the polysiloxane type, e.g., silicone oil and polydimethyl siloxane.
  • Anti-wear agents reduce wear of metal parts.
  • Representatives of conventional antiwear agents are zinc dialkyldithiophosphate and zinc diaryldithiosphate.
  • Detergents and metal rust inhibitors include the metal salts of sulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates and other oil soluble mono- and di-carboxylic acids.
  • Highly basic (viz, overbased) metal salts such as highly basic alkaline earth metal sulfonates (especially Ca and Mg salts) are frequently used as detergents. Representative examples of such materials, and their methods of preparation, are found in EP-A-0208560.
  • compositions when containing these conventional additives are typically blended into the base oil in amounts which are effective to provide their normal attendant function.
  • Representative effective amounts of such additives are illustrated as follows:
  • additive concentrates comprising concentrated solutions or dispersions of the multifunctional viscosity improver (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture being referred to here in as an additive package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the concentrate or additive-package will typically be formulated to contain the dispersant additive and optional additional additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant.
  • the products of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive- packages containing active ingredients in collective amounts of typically from about 2.5 to about 80%, and preferably from about 5 to about 60%, and most preferably from about 8 to about 49% by weight additives in the appropriate proportions with the remainder being base oil.
  • the final formulations may employ typically about 10 wt. % of the additive-package with the remainder being base oil.
  • weight percents expressed herein are based on active ingredient (a.i.) content of the additive, and or upon the total weight of any additive-package, or formulation which will be the sum of the a.i. weight of each additive plus the weight of total oil or diluent.
  • compositions of matter useful as multifunctional viscosity modifiers or improvers are oil-soluble, dissolvable in oil with the aid of a suitable solvent, or are stably dispersible materials.
  • Oil-soluble, dissolvable, or stably dispersible does not necessarily indicate that the materials are soluble, dissolvable, miscible, or capable of being suspended in oil in all proportions. It does mean, however, that the additives, for instance, are soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed.
  • the additional incorporation of other additives may also permit incorporation of higher levels of a particular copolymer hereof, if desired.
  • Example 1 The procedure of Example 1 is repeated except that the 148 grams of 1,3-propane diamine are replaced with 203 grams (2 moles) of diethylene triamine. Analysis of the resulting amido-amine product indicates 4.48 meq. of primary nitrogen per gram of sample and 25.85% nitrogen.
  • Example 1 The procedure of Example 1 is repeated except that the 148 grams of 1,3-propane diamine are replaced with 292 grams (2 moles) of triethylene triamine. Analysis of the resulting amido-amine product indicates 3.67 meq. of primary nitrogen per gram of sample and 26.76% nitrogen.
  • Example 1 The procedure of Example 1 is repeated except that the 148 grams of 1,3-propane diamine are replaced with 378 grams (2 moles) of tetraethylene pentamine. Analysis of the resulting amido-amine product indicates 4.39 meq. of primary nitrogen per gram of sample and 28.3% nitrogen.
  • Into a reactor vessel are charged 200 grams of a 20 wt. % oil solution of succinic-anhydride grafted ethylene-propylene copolymer (containing about 43 wt.% ethylene and 57% wt.% propylene, the ethylene-propylene backbone having a M n of about 80,000, and having a thickening efficiency of about 1.2), 21.3 grams of polyisobutenyl succinic anhydride (having a succinic anhydride to polyisobutenyl mole ratio of 1.04, a polyisobutylene M n of about 960, ASTM Saponification Number of 112, and 90 wt.% active ingredient, i.e., polyisobutenyl succinic anhydride, the remainder being primarily unreacted polyisobutylene), and 130 grams of S130N mineral oil.
  • succinic-anhydride grafted ethylene-propylene copolymer containing about 43 wt.%
  • the reactor vessel is blanketed with nitrogen and heated to 175°C for one-half hour. To this reactor vessel are then added 4.12 grams of amido-amine prepared in accordance with the procedure of Example 1. The reaction mixture is nitrogen stripped for 3 hours at 175' C. At the end of this period the reaction mixture is cooled to 100°C and is discharged from the reaction vessel.
  • Example 5 The procedure of Example 5 is repeated except that the 4.12 grams of the amido-amine prepared in accordance with the procedure of Example 1 are replaced with 9.02 grams of amido-amine prepared in accordance with the procedure of Example 2.
  • Example 5 The procedure of Example 5 is repeated except that the 4.12 grams of the amido-amine prepared in accordance with the procedure of Example 1 are replaced with 11.0 grams of amido-amine prepared in accordance with the procedure of Example 3.
  • Example 5 The procedure of Example 5 is repeated except that the 4.12 grams of the amido-amine prepared in accordance with the procedure of Example 1 are replaced with 9.2 grams of amido-amine prepared in accordance with the procedure of Example 4.
  • Thickening efficiency is defined as the ratio of the weight percent of a polyisobutylene (sold as an oil solution by Exxon Chemical Company as Paratone N), having a Staudinger molecular weight of 20,000. required to thicken a solvent-extracted neutral mineral lubricating oil, having a viscosity of 150 SUS at 37.8 C, a viscosity index of 105 and an ASTM pour point of 0°F. (Solvent 150 Neutral) to a viscosity of 12.4 centistokes at 98.9 C to the weight percent of a test copolymer required to thicken the same oil to the same viscosity at the same temperature.
  • the thickening efficiency is approximately proportional to the 0.75 power of the weight-average molecular weight.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP90305579A 1989-05-30 1990-05-22 Multifunktionale viskositätsindexmodifizierende Additive, hergestellt aus Amidoaminen Expired - Lifetime EP0400874B1 (de)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
EP0596567A1 (de) * 1992-11-06 1994-05-11 AGIP PETROLI S.p.A. Polymeradditive für Schmieröle
US5672573A (en) * 1996-04-10 1997-09-30 Exxon Chemical Patents Inc. Amicloamine derivatives of carboxylic and thiocarboxylic-functionalized hydrocarbon polymers
WO2021018467A1 (en) * 2019-07-29 2021-02-04 Clariant International Ltd Wax inhibitors with improved flowability
CN114875412A (zh) * 2022-05-19 2022-08-09 西安交通大学 一种多核无定型固体缓蚀剂的制备方法

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US4240804A (en) * 1978-01-24 1980-12-23 Sherex Chemical Company, Inc. Alkyl acrylate adducts of polyamines, ether amines and ether polyamines
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EP0146162A2 (de) * 1981-05-06 1985-06-26 Exxon Research And Engineering Company Verfahren zur Herstellung eines Äthylencopolymer-Viskositätsindexverbesserer-Dispergierzusatzes, der in Ölzusammensetzungen verwendbar ist
EP0319229A2 (de) * 1987-11-30 1989-06-07 Exxon Chemical Patents Inc. Von Amidoaminen abgeleitete Dispersant-Additive

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US2568876A (en) * 1949-11-14 1951-09-25 Socony Vacuum Oil Co Inc Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides
US3445441A (en) * 1965-03-25 1969-05-20 Petrolite Corp Amino-amido polymers
US3448049A (en) * 1967-09-22 1969-06-03 Rohm & Haas Polyolefinic succinates
US3630902A (en) * 1969-07-23 1971-12-28 Chevron Res Lubricant additives derived from catalytically polymerized reaction products of succinimides and unsaturated monocarboxylic acids or anhydrides
US4240804A (en) * 1978-01-24 1980-12-23 Sherex Chemical Company, Inc. Alkyl acrylate adducts of polyamines, ether amines and ether polyamines
EP0146162A2 (de) * 1981-05-06 1985-06-26 Exxon Research And Engineering Company Verfahren zur Herstellung eines Äthylencopolymer-Viskositätsindexverbesserer-Dispergierzusatzes, der in Ölzusammensetzungen verwendbar ist
EP0145369A2 (de) * 1983-11-21 1985-06-19 Exxon Research And Engineering Company Viskositätsindexmodifikator-Dispergierungsmittel aus Äthylenmischpolymerisaten und ihre Verwendung in Ölzusammensetzungen
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Publication number Priority date Publication date Assignee Title
EP0596567A1 (de) * 1992-11-06 1994-05-11 AGIP PETROLI S.p.A. Polymeradditive für Schmieröle
US5425888A (en) * 1992-11-06 1995-06-20 Agip Petroli S.P.A. Polymeric additive for lubricating oils
US5672573A (en) * 1996-04-10 1997-09-30 Exxon Chemical Patents Inc. Amicloamine derivatives of carboxylic and thiocarboxylic-functionalized hydrocarbon polymers
WO2021018467A1 (en) * 2019-07-29 2021-02-04 Clariant International Ltd Wax inhibitors with improved flowability
US11981876B2 (en) 2019-07-29 2024-05-14 Clariant International Ltd Wax inhibitors with improved flowability
CN114875412A (zh) * 2022-05-19 2022-08-09 西安交通大学 一种多核无定型固体缓蚀剂的制备方法
CN114875412B (zh) * 2022-05-19 2023-03-10 西安交通大学 一种多核无定型固体缓蚀剂的制备方法

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AU623525B2 (en) 1992-05-14
CA2015063A1 (en) 1990-11-30
BR9002543A (pt) 1991-08-13
EP0400874B1 (de) 1993-04-21
AU5599290A (en) 1990-12-06
DE69001389T2 (de) 1993-08-19

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