EP0000648B1 - Additifs stabilisés pour lubrifiants à base de copolymères d'éthylène greffés imidés, procédé pour leur préparation, procédé pour stabiliser des additifs pour lubrifiants à base du copolymère d'éthylène greffé imidé et compositions d'huiles lubrifiantes comprenant l'additif stabilisé - Google Patents

Additifs stabilisés pour lubrifiants à base de copolymères d'éthylène greffés imidés, procédé pour leur préparation, procédé pour stabiliser des additifs pour lubrifiants à base du copolymère d'éthylène greffé imidé et compositions d'huiles lubrifiantes comprenant l'additif stabilisé Download PDF

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Publication number
EP0000648B1
EP0000648B1 EP78300173A EP78300173A EP0000648B1 EP 0000648 B1 EP0000648 B1 EP 0000648B1 EP 78300173 A EP78300173 A EP 78300173A EP 78300173 A EP78300173 A EP 78300173A EP 0000648 B1 EP0000648 B1 EP 0000648B1
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Prior art keywords
ethylene
acid
anhydride
oil
copolymer
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English (en)
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EP0000648A1 (fr
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John Brooke Gardiner
James Zielinski
Robert Leroy Elliott
Stanley James Brois
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • 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
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • 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
    • C10M2215/086—Imides
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2215/30—Heterocyclic compounds
    • 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
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound

Definitions

  • This invention relates to stable polymeric dispersant additives and viscosity-index improvers for lubricating oils. More particularly, this invention relates to viscosity-stable solutions of substantially saturated polymers comprising ethylene and one or more C 3 to C 28 alpha-olefins, preferably propylene, which have been grafted in the presence of a free radical initiator with an ethylenically-unsaturated dicarboxylic acid material, preferably at an elevated temperature and in an inert atmosphere, and thereafter reacted first with a polyamine, preferably an alkylene polyamine, having at least two primary amino groups, such as diethylene triamine, and then with an anhydride of an organic acid, to form multifunctional polymeric reaction products characterized by viscosity-stabilising activity in mineral oil solutions.
  • a polyamine preferably an alkylene polyamine, having at least two primary amino groups, such as diethylene triamine, and then with an anhydride of an organic acid
  • Ashless dispersants for lubricating oil compositions are known to enhance the sludge dispersing ability of said compositions see for example United States Patent 3374174.
  • One type of dispersant is generally derived from a hydrocarbon-substituted dicarboxylic acid material such as an alkenyl succinic acid or anhydride reacted with a nitrogen-containing material.
  • United Kingdom Patent Specification 1,018,982 discloses the reaction of said alkenyl succinic anhydride with a 2-imidazoline or pyrimidine (the latter is obtained by the reaction of a carboxylic acid, e.g. acetic acid and an alkylene polyamine, e.g. diethylene triamine) to provide a sludge dispersant for lubricating oils.
  • a carboxylic acid e.g. acetic acid
  • an alkylene polyamine e.g. diethylene triamine
  • Patent 3,415,750 discloses polyalkenyl succinicimido imidazolines and bis-imidazolines which can be used as said ashless detergents.
  • the imidazoline is first prepared by the sequential reaction of a polyalkylene polyamine with a carboxylic acid or its anhydride, e.g. acetic, which product is thereafter reacted with a polyalkenyl succinic anhydride as is described in Column 3 lines 9 to 15 and in Examples 4 to 6.
  • U.S. Patent 3,216,936 teaches that it is advantageous to ensure that the reaction product of a mixture of a hydrocarbon-substituted succinic acid, a monocarboxylic acid and an alkylene polyamine does not come from an intermediate reaction product of said monocarboxylic acid and said amine in order to avoid destroying the sludge dispersant activity of the final reaction product.
  • the reactions of this patent being sequential as is shown at column 5 lines 28 to 33.
  • Belgian Patent 843,360 teaches the production of soluble, sludge-dispersing additives for hydrocarbon fuels and lubricating oils by the free-radical induced grafting in solution of an ethylenically-unsaturated dicarboxylic acid material, such as maleic anhydride, onto a substantially saturated copolymer comprising ethylene and at least one other alpha-olefin at an elevated temperature to provide, without substantial polymer degradation, a useful precursor copolymer which can be subsequently reacted with a carboxylic acid reacting polyfunctional material, such as a polyamine or a hydroxyamine or mixtures of these, to form multifunctional polymeric imidated derivatives having particular utility as engine sludge and varnish control additives for lubricating oils.
  • an ethylenically-unsaturated dicarboxylic acid material such as maleic anhydride
  • the present invention therefore provides an oil-soluble ethylene polymeric viscosity index improver containing in the range of from 0.001 to 8 wt. % of nitrogen, which improver has been formed by grafting an ethylenically unsaturated dicarboxylic acid or anhydride onto an ethylene copolymer comprising 30 to 80 wt. % ethylene and 20 to 70 wt.
  • % C 3 to C 28 alpha olefin reacting said grafted ethylene copolymer with polyamine of 2 to 60 carbons and 2 to 12 nitrogens and having at least two primary amine groups, wherein essentially one of said primary amine groups reacts with an acid moiety of said grafted ethylene copolymer characterised in that said imidization reaction product is then reacted with an anhydride of an organic carboxylic acid having a C, to C 30 hydrocarbyl group to thereby stabilize the resulting ethylene polymeric viscosity index improver and inhibit viscosity increase upon ageing.
  • the present invention also provides process for improving the viscosity stability of an oil additive concentrate consisting essentially of a hydrocarbon solvent and from .1 to 50 wt. %, based on the total weight of said concentrate, of an imidated grafted ethylene/C 3- C,, alpha-olefin copolymeric viscosity index improver containing_from 0.001 to 8 wt. % of nitrogen and having a molecular weight (M n ) of 700 to 500,000 and a Mv/Mn ratio of less than 7, said viscosity index improver being formed by grafting maleic anhydride onto an ethylene copolymer comprising 30 to 80 wt. % ethylene and 20 to 70 wt.
  • an oil additive concentrate consisting essentially of a hydrocarbon solvent and from .1 to 50 wt. %, based on the total weight of said concentrate, of an imidated grafted ethylene/C 3- C,, alpha-olefin copolymeric viscosity index
  • the reaction appears to be an acylation of pendant primary amine groups by their reaction with the organic acid anhydride which can be represented as follows:
  • This acylation of the free primary amino group with the anhydride produces an amide structure which limits the multifunctionalized copolymers property of solution chain extension thereby inhibiting viscosity increase of oil solutions containing the additives of the invention.
  • the mineral oil compositions of the invention can be further reacted with an oil-soluble hydrocarbyl substituted acid having from about 10 to 70 carbon atoms having a pK of less than about 2.5, preferably a polymethylene substituted benzene sulfonic acid, said polymethylene substituent having from 18-40, optimally 24 to 32 carbons, in an amount of from about 0.01 wt. % to 8 wt. % at a temperature within the range of about 150°C. to about 200°C. and for a period from about 0.1 hour to about 20 hours, e.g. for 1 hour at 190°C.
  • This further step results in an additive oil composition of improved viscosity stability which has no visually perceptible haze.
  • the ethylene copolymers to be grafted contain from about 30 to 80 wt. % preferably 38 to 70 wt. % of ethylene, and 20 to 70 wt. % of one or more C 3 to C,,, preferably C 3 to C 18 , more preferably C 3 to C 8 , alpha-olefins, e.g. propylene.
  • Such copolymers preferably have a degree of crystallinity of less than 25 wt.
  • M n number average molecular weight in the range of about 700 to about 500,000, preferably 10,000 to 250,000, as determined by vapor phase osmometry (VPO) or membrane osmometry.
  • VPO vapor phase osmometry
  • 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 include 1-butene, 1-pentene, 1-hexene, 1-octene; also branched-chain alpha-olefins, such as 5-methylpentene-1 and 6-methylheptene-1 and mixtures thereof.
  • Terpolymers of ethylene, said alpha-olefin and a non-conjugated diolefin or mixtures of such diolefins may also be used.
  • the amount of the non-conjugated diolefin ranges 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.
  • diolefins include cyclopentadiene, 2-methytene-5-norbornene, non-conjugated hexadiene, or any other alicyclic or aliphatic non-conjugated diolefin having from 6 to 15 carbon atoms per molecule, such as 2-methyl or ethyl norbornadiene, 2,4-dimethyl-2-octadiene, 3-(2-methyl-1-propene) cyclopentene, ethylidene norbornene, etc.
  • ethylene copolymers this term including terpolymers, may be prepared using the well-known Ziegler-Natta catalyst compositions as described in U.K. Patent 1,397,994.
  • Such polymerization may be effected to produce the ethylene copolymers by passing 0.1 to 15, for example, 5 parts of ethylene; 0.05 to 10, for example, 2.5 parts of said higher alpha-olefin, typically propylene; and from 10 to 10,000 parts of hydrogen per million parts of ethylene; into 100 parts of an inert liquid solvent containing (a) from about 0.0017 to 0.017, for example, 0.0086 parts of a transition metal principal catalyst, for example, VOCI 3 ; and (b) from about 0.0084 to 0.084, for example, 0.042 parts of cocatalyst, e.g. (CZHS)3AIZCI3; at a temperature of about 25°C. and a pressure of 60 psig for a period of time sufficient to effect optimum conversion, for example, 15 minutes to one-half hour; all parts being parts by weight.
  • an inert liquid solvent containing (a) from about 0.0017 to 0.017, for example, 0.0086 parts of a transition metal principal catalyst
  • These materials which are grafted (attached) onto the copolymer contain at least one ethylenic bond and two, carboxylic acid groups or the anhydride or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
  • Maleic anhydride or a derivative thereof is preferred as it does not appear to homopolymerize appreciably but grafts onto the ethylene copolymer or terpolymer to give two carboxylic acid functionalities.
  • Such preferred materials have the generic formula wherein R,and R 2 are hydrogen or a halogen. Suitable examples additionally include chloromaleic anhydride, itaconic anhydride, or the corresponding dicarboxylic acids, such as maleic acid or fumaric acid or their monoesters.
  • the free-radical induced grafting of ethylenically unsaturated carboxylic acid materials in solvents, such as benzene, is known in the art (see U.S. Patent 3,236,917).
  • the grafting according to the process of this invention is carried out at an elevated temperature in the range of 100°C. to 250°C., preferably 120 to 190°C., and more preferably 150 to 180°C., e.g. above 160°C., in a solvent, preferably a mineral lubricating oil solution containing, e.g. 1 to 50, preferably 5 to 30 wt. %, based on the initial total oil solution, of the ethylene polymer and under an inert environment.
  • the grafting is carried out in the presence of a high-temperature decomposable compound capable of supplying free radicals at said elevated temperature.
  • the free-radical initiators which may be used are peroxides, hydroperoxides, and azo compounds which have a boiling point greater than about 100°C. and decompose thermally within the grafting temperature range to provide said free radicals.
  • Representative of these free-radical initiators are azobutyronitrile and 2,5-dimethyl-hex-3-yne-2,5 bis-tertiary-butyl peroxide, commercially sold as Lupersol (Registered Trade Mark) 130 or its hexane analogue.
  • the initiator is preferably used at a level of between about 0.005% and about 1%, based on the total weight of the polymer solution.
  • the ethylenically unsaturated carboxylic acid material e.g. maleic anhydride
  • the aforesaid carboxylic acid material and free radical initiator are used in a weight percent ratio range of 1.0:1 to 30:1, preferably 2.0:1 to 7:1, more preferably 3.0:1 to 6:1.
  • the grafting is carried out in an inert atmosphere, such as by nitrogen blanketing. While the grafting can be carried out in the presence of air, the yield of the desired graft polymer is decreased as compared to grafting under an inert atmosphere.
  • the inert environment should be substantially free of oxygen.
  • the grafting time is generally 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 is 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.
  • the copolymer solution is first heated to grafting temperature and thereafter said carboxylic acid material and initiator are added with agitation although they could have been added prior to heating.
  • any excess acid material may be eliminated by an inert gas purge, e.g. nitrogen sparging.
  • the maleic anhydride or other carboxylic acid material used is grafted onto both the polymer and the solvent for the reaction.
  • the wt. % grafted onto the polymer is normally greater than the amount grafted onto the oil due to greater reactivity of the polymer to grafting.
  • the exact split between the two materials depends upon the polymer and its reactivity, the reactivity and type of oil, and also the concentration of the polymer in the oil. The split can be measured empirically from the infrared analyses of product dialyzed into oil and polymer fractions and measuring the anhydride peak absorbance in each.
  • the grafting is preferably carried 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 polyfunctional material and as a solvent for the end product to form the concentrate.
  • Useful polyamines for reaction with the grafted ethylene-containing polymers are those which have at least two primary amino groups, hereafter designated poly(primary amines), i.e. one group to react with the dicarboxylic acid moiety to form the imido linkage and one more group to react with the organic acid anhydride whereby an amide is formed.
  • poly(primary amines) can be represented by the formula wherein R represents an alkylene group, an alkylene imino group, a hydrocarbyl group, a saturated ring structure, an unsaturated ring structure or a nitrogen containing heterocyclic ring structure.
  • the useful poly(primary amines) include poly(primary amines) of about 2 to 60, e.g.
  • amines may be hydrocarbyl poly-(primary amines) or may be hydrocarbyl poly(primary amines) including other groups, e.g., cyano groups, amide groups, imidazoline groups, and the like.
  • Preferred amines are aliphatic saturated poly-(primary amines), including those of the general formula: wherein R and R' are independently selected from hydrogen, amino alkylene radicals, and C, to C 12 alkylamino C 2 to C 6 alkylene radicals, s is a number of from 2 to 6, preferably 2 to 4, and t is a number of from 0 to 10, preferably 2 to 6.
  • Suitable amine compounds include ethylene diamine, diaminomethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, 1,2-propylene diamine, di-( 1,2-propylene) triamine, di-(1,3-propyiene) triamine, di-(1,4-butylene) triamine and N,N-di-(2-aminoethyl) ethylene diamine.
  • amine compounds include alicyclic diamines such as 1,4-di-(aminoethyl) cyclohexane and heterocyclic nitrogen compounds, such as N-amino-alkyl piperazines of the general formula: wherein G is an omega-aminoalkylene radical of from 1 to 3 carbon atoms and p is an integer of from 1 to 4.
  • N,N'-di-(2-aminomethyl) piperazine is N,N'-di-(2-aminomethyl) piperazine.
  • alkylene amines Commercial mixtures of amine compounds may advantageously be used.
  • one process for preparing alkylene amines involves the reaction of an alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of 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 a complex mixture of alkylene groups
  • Low cost poly(ethylene amines) compounds having a composition approximating tetraethylene pentamine are available commercially under the trade name Polyamine 400.
  • Still other polyamines separated by hetero atom chains such as polyethers or sulfides can be used.
  • the grafted polymer preferably in solution, can be readily reacted with said poly(primary amine) and mixtures thereof by admixture together and heating at a temperature of from about 100°C. to 250°C. for from 10 minutes to 30 hours, preferably 10 minutes to 10 hours, usually about 15 minutes to about 3 hours. It is preferred to use 0.01 to 2.5 mole, more preferably 0.5 to 1.0 mole, of the poly-(primary amine) per mole of grafted carboxylic material, such as maleic anhydride.
  • the reaction of diethylene triamine with the grafted ethylene-containing polymer occurs in 15 minutes or less at 170°C. with a nitrogen blanket.
  • the solution grafting step is carried out in the presence of a high temperature decomposable peroxide and is accomplished without significant degradation of the chain length (molecular weight) of the ethylene-containing polymer. Measurement of molecular weights and degradation can be evaluated by determination of the thickening efficiency of the polymer.
  • T.E. Thickening efficiency
  • a polyisobutylene sold as an oil solution by Exxon Chemical Co. as Paratone (Registered Trade Mark) N
  • Paratone Registered Trade Mark
  • T.E. is related to (M n ) and is a convenient, useful measurement for the formulation of lubricating oils of various grades.
  • grafted carboxyl e.g. maleic anhydride
  • the imidization reaction product contains in the range of 0.001 to 8, preferably 0.01 to 2, wt. % nitrogen and preferably has a M " in the range of 700 to 500,000, preferably 700 to 250,000.
  • the imidization reaction product is readily reacted with the organic acid anhydride to achieve imidation of the imidized grafted ethylene copolymer.
  • Suitable organic acid anhydrides include anhydrides of monocarboxylic and dicarboxylic acids represented by the structure and wherein Z is selected from alkylene, arylene and alkenylene and contains from 2 to 10 carbon atoms.
  • anhydrides of the monocarboxylic acids the anhydrides of the following aliphatic monocarboxylic acids are representative.
  • amidation of the imide grafted ethylene copolymer which imidization reaction was preferentially carried out in a mineral oil solution, can be preferentially conducted as a continuation of the imidization reaction by subsequently injecting the organic acid anhydride directly into the system. If desired, amidation can be a separate non-integrated reaction step.
  • the reaction is in an oil solution a sufficient amount of the organic acid anhydride is introduced into the heated solution containing the imidized grafted ethylene copolymer and the reaction carried on for a period of 0.25 to 8 hours at a temperature ranging from 50 to 250°C., a temperature of about 100 to 200°C. being preferred. In order to fully complete the reaction, it is useful to utilize a slight excess, i.e.
  • the amidation process step is preferentially conducted on an imidized graft ethylene copolymeric mineral oil solution wherein the excess poly(primary amine) e.g. alkylene polyamine is reduced to a level of less than about 0.05, optimally less than about 0.02, weight percent free (unreacted) amine.
  • poly(primary amine) e.g. alkylene polyamine
  • the amidation reaction can be monitored by differential infrared analysis of the reaction medium. Differential infrared analysis involves absorption comparison of a sample of the starting material placed in the reference beam with a test sample placed in the sample beam using matched cells. It has been found that amidation results in the development of maximum absorption at an amide band of 1650-1670 cm-' whereas the acid absorption band of between 1720 and 1740 cm-' first increases and then decreases as the reaction is completed since the excess anhydride and acid byproducts responsible for acid absorption are depleted through removal. The best method of monitoring completion of the amidation of the imide grafted ethylene copolymer is to continue the reaction until absorption at the 1650-1670 cm- 1 band is at a maximum.
  • the mineral oil additive composition containing the ethylene copolymer dispersant additives usually contain from about .1 to about 50 wt.% based upon the total weight of the hydrocarbon solution of the amidated-imidated, grafted ethylene copolymer additive.
  • these oil additive compositions are found to be hazy because they contain a hazing material derived from homopolymerization of the grafted moieties and/or low molecular weight polar species insoluble in oil. It is therefore useful to treat the composition by adding at least a haze-removing amount of an oil-soluble acid having a pK of less than about 2.5, e.g. a dialkylbenzene sulfonic acid.
  • the treatment of the haze-containing oil composition is carried out at a temperature of about room temperature to about 250°C., preferably from about 150 to about 200°C. and for a time period of about 0.1 hour up to about 20 hours, preferably from 0.5 to about 3 hours.
  • the oil-soluble acid preferably has a pK of from about 0.001 to about 2.5, optimally from about 0.1 to about 2.
  • the term pK or the purpose of this disclosure is used herein to express the extent of the dissociation of the acid used to treat the haze causing substance.
  • pK can be defined as the negative logarithm of the base 10 of the equilibrium constant for the dissociation of the oil-soluble strong acid.
  • Useful acids which eliminate the hazing property of the hazing substance are represented by oil-soluble derivatives of alkyl carboxylic acids, such as isostearic acid, maleic acid, malonic acid, phosphoric acid, thiophosphoric acids, phosphonic acid, thiophosphonic acids, phosphinic acid, thio- phosphinic acids, sulfonic acid, sulfuric acid, sulfinic acid and alpha-substituted halo- or nitro- or nitrilo- carboxylic acids wherein the oil solubilizing group or groups are hydrocarbyl and containing from about 3 to about 70, preferably from about 18 to 40, optimally 25 to 32 carbon atoms.
  • oil-soluble sulfonic acids which are typically alkarly sulfonic acids.
  • alkylaryl sulfonic acids generally have from 9 to 76, preferably 24 to 46, total carbons.
  • the alkyl substituent or substituents preferably have 18 to 40, optimally 24 to 32, total carbons.
  • alkyl mono-aryl sulfonic acids are those acids that are formed by alkylating benzene with oligomers of propylene or C 4 -C 10 1-alkenes containing 20 to 40 carbon atoms and thereafter sulfonating the resulting alkylate.
  • the class of compounds may thus be identified as the polyalkyl benzene sulfonic acids.
  • An especially preferred compound is the octacosyl benzene sulfonic acid wherein the alkyl radical is derived from a nominal 28 carbon propylene oligomer.
  • a wide range, e.g. 0.001 to 50 wt. %, preferably 0.005 to 20%, of the oil-soluble nitrogen containing graft polymers treated in accordance with this invention can be incorporated into about a major amount of an oleaginous material, such as a lubricating oil or hydrocarbon fuel.
  • an oleaginous material such as a lubricating oil or hydrocarbon fuel.
  • the treated polymer concentrations are within the range of about 0.01 to 20 wt. % e.g., 0.1 to 15.0 wt. %, preferably 0.25 to 10.0 wt.%, of the total composition.
  • the lubricationg oils to which the products of this invention can be added include not onfy hydrocarbon oil derived from petroleum, but also include synthetic lubricating oils such as esters of dibasic acids and complex esters made by esterification of monobasic acids, polyglycols, dibasic acids and alcohols.
  • amidated-imidated graft polymers of the invention may be utilized in a concentrate form, e.g., from about 10 wt. % to about 50 wt. %, preferably 15 to 49 wt. % in oil, e.g., mineral lubricationg oil, for ease of handling.
  • oil e.g., mineral lubricationg oil
  • the above concentrates and lubricating oil compositions may contain other conventional additives, such as dyes, pour point depressants, antiwear agents, antioxidants, other viscosity-index improvers, dispersants and the like.
  • the solution was heated to 154°C (310°F) during a period of 2 hours and 15 minutes; 6 kilograms of Lupersol 130 (2,5-dimethyl hex-3-yne-2,5-bis-tertiary butyl peroxide) was added in three equal charges over a 2 hour and 50 min. period. Excess maleic anhydride was stripped out with N 2 over 2 hours,and 20 minutes. 20 kg of diethylene triamine (DETA) was charged and allowed to react for 1.5 hrs. Excess DETA was stripped with vacuum and N 2 for 6 hours. The resulting material was diluted with S130N to 14 wt. % polymer and cooled. The final material had about 0.262 wt. % DETA incorporated.
  • DETA diethylene triamine
  • the resulting copolymer solution had a color of 5 with a haze reading of 108 nephelos (unchanged from the starting material), as measured on a naphelometer purchased from Kohlmann Industries, Maywood, III and identified as Model 9.
  • This material had a viscosity'of 1543 centistokes (1543 x 10- 6 m 2 -S -1 ) at 99°C (210°F), active ingredient of 15.42 wt. % by dialysis, N wt. % of 0.12% (0.49 wt. % N on polymer), flash point of 420°F. and T.E. of 1.43.
  • % gave a 12.8 cs. 99°C (210°F) viscosity, 13% sonic shear breakdown, a pour point (with 0.4 wt. % of a vinyl acetate/fumerate pour depressant) of less than ­35°C., and a -18°C (0°F) viscosity of 2.53 Pa.s. (25.3 poise) in a Cold Cranking Simulator (ASTM) method.
  • ASTM Cold Cranking Simulator
  • Example 1 product 300 grams was charged into a 4-necked 1 liter flask and heated to 125°C. while stirring and N 2 blanketing. 1 gram of acetic anhydride was added and reacted for 1 hour. The mixture was stripped for 1 hour at 125°C. The temperature was then raised to 170°C. and 3 grams of C 24 ave. alkylbenzene sulfonic acid were added. Reaction continued for 4 hours. The haze was reduced from 108 (initial) to 16 nephelos.
  • Acid anhydrides are known not to react with tertiary amines. However, they may react with secondary amines. From the stoichiometry of the reaction of acetic anhydride with an imide made from DETA, as derived from their amide measurements, only the primary amine, not the secondary amine, reacts in this case.
  • a 15W50 SAE crankcase oil formulation was made up using 12.5 wt. % of the oil concentrate of Example 2, 2 volume % of the ashless dispersant additive, 1.1 volume % of an overbased magnesium sulfonate, 0.8 volume % of overbased calcium phenate, 0.5 volume % of an antioxidant, and 1.43 volume % of a zinc dialkyldithiophosphate and a mineral lubricating oil blend of base stocks.
  • a formulation was made up in the same manner replacing the oil concentrate of Example 2 with the same weight percent of the oil concentrate of Example 1.

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  • Health & Medical Sciences (AREA)
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Claims (16)

1. Agent polymérique éthylénique soluble dans l'huile, améliorant l'indice de viscosité, contenant une proportion de 0,001 à 8% en poids d'azote, cet agent ayant été formé par greffage d'un acide ou anhydride dicarboxylique à non-saturation éthylénique sur un copolymère d'éthylène comprenant 30 à 80 % en poids d'éthylène et 20 à 70% en poids d'une alpha-oléfine en C3 à C.28' réaction dudit copolymère d'éthylène greffé avec une polyamine de 2 à 60 atomes de carbone et de 2 à 12 atomes d'azote et portant au moins deux groupes amino primaires, dont essentiellement l'un desdits groupes amino primaires réagit avec une portion acide dudit copolymère éthylénique greffé, caractérisé en ce que le produit de la réaction d'imidation est amené à réagir avec un anhydride d'un acide carboxylique organique portant un groupe hydrocarbyle en C, à C30 pour stabiliser ainsi l'agent polymérique éthylénique résultant améliorant l'indice de viscosité et pour inhiber l'élévation de viscosité lors du vieillissement.
2. Agent améliorant l'indice de viscosité suivant la revendication 1, dans lequel le copolymère éthylénique est un copolymère éthlène-propylène ayant une moyenne en nombre du poids moléculaire de 700 à 500 000.
3. Procédé de production d'un agent polymérique améliorant l'indice de viscosité, qui consiste à greffer en solution une matière acide dicarboxylique organique à non-saturation éthylénique sur un copolymère formé de 30 à 80% en poids d'éthylène et de 20 à 70% en poids d'au moins une alpha-oléfine en C3 à C28 à une température de 100 à 250°C dans un solvant sous une atmosphère inerte dépourvue d'oxygène, en présence d'un initiateur de radicaux libres pouvant se décomposer à haute température et étant utilisé dans un rapport de pourcentages en poids de la matière acide dicarboxylique organique à non-saturation éthylénique à l'initiateur de radicaux libres de 1,0:1 à 30:1, ce polymère greffé étant ensuite transformé par réaction avec une alkylènepolyamine ayant 2 à 60 atomes de carbone et 2 à 12 atomes d'azote et ayant au moins deux groupes amino primaires, caractérisé en ce que ledit produit d'imidation est ensuite amené à réagir avec 0,5 à 2,5 moles d'un anhydride d'un acide carboxylique organique ayant un groupe hydrocarbyle en C, à C30 par groupe amino primaire dans ledit produit.
4. Procédé suivant la revendication 3, dans lequel ledit copolymère est un copolymère d'éthylène et de propylène ayant 38 à 70% en poids d'éthylène, la matière acide dicarboxylique est l'anhydride d'acide maléique, le greffage de la solution est conduit en utilisant comme solvant une huile lubrifiante minérale, la polyamine est la diéthylènetriamine et l'anhydride en proportion de 0,5 à 2,5 moles consiste en anhydride acétique.
5. Procédé suivant les revendications 3 ou 4, dans lequel la solution résultant de ladite réaction avec 0,5 à 2,5 moles d'anhydride est traitée avec un acide alkylarylsulfonique soluble dans l'huile contenant 9 à 76 atomes de carbone à une température allant de la température ambiante à 250°C.
6. Procédé suivant la revendication 5, dans lequel l'acide sulfonique est un acide (alkyle en C24 en moyenne)-benzènesulfonique.
7. Compositon d'huile lubrifiante, comprenant une quantité dominante d'une huile lubrifiante dans laquelle est dissoute au moins une quantité améliorant l'indice de viscosité d'un agent polymérique éthylénique soluble dans l'huile améliorant l'indice de viscosité suivant la revendication 1.
8. Composition suivant la revendication 7, dans laquelle l'agent améliorant l'indice de viscosité est présent en une quantité de 0,1 à 50% en poids sur la base du poids total de ladite composition.
9. Composition suivant les revendications 7 ou 8, dans laquelle l'agent améliorant l'indice de viscosité est préparé par greffage en solution d'une matière acide dicarboxylique à non-saturation éthylénique sur un copolymère formé de 30 à 80% en poids d'éthylène et de 20 à 70% en poids d'au moins une alpha-oléfine en Ca à C28 à une température de 100 à 250°C, en présence d'un initiateur de radicaux libres décomposable à haute température ayant un point d'ébullition de plus de 100°C, ledit polymère greffé est ensuite transformé par réaction avec une alkylènepolyamine ayant 3 à 20 atomes de carbone et 2 à 6 atomes d'azote et un produit ayant une activité de dispersion de la boue, puis amené à réagir avec 0,5 à 2,5 moles dudit anhydride par groupe amino primaire dudit produit.
10. Composition suivant la revendication 9, dans laquelle ledit copolymère est un copolymère d'éthylène et de propylène ayant 38 à 70% en poids d'éthylène et est présent dans ladite composition en une quantité allant de 0,1 à 15% en poids, ladite matière acide dicarboxylique est l'anhydride d'acide maléique, ledit greffage en solution est conduit en utilisant comme solvant une huile lubrifiante minérale, ladite polyamine est la diéthylène-triamine et ledit anhydride en proportion de 0,5 à 2,5 moles est l'anhydride acétique.
11. Composition suivant les revendications 7 à 10, dans laquelle la solution résultante de ladite réaction avec lesdites 0,5 à 2,5 moles d'anhydride est traitée avec un acide alkylarylsulfonique soluble dans l'huile contenant 9 à 76 atomes de carbone à une température allant de la température ambiante à 250°C pour inhiber le développement d'un trouble.
12. Composition suivant la revendication 11, dans laquelle ledit acide sulfonique est un acide (alkyle en C24 en moyenne)-benzènesulfonique.
13. Procédé pour améliorer la stabilité de la viscosité d'un concentré d'additifs pour huile principalement formé d'un solvant hydrocarboné et de 0,1 à 50% en poids, sur la base du poids total dudit concentré, d'un agent améliorant l'indice de viscosité, copolymère d'éthylène et d'une alpha-oléfine en C3 à C28 greffé avec un imide, contenant 0 001 à 8% en poids d'azote et ayant un poids moléculaire (Mn) de 700 à 500 000 et un rapport M p/M n inférieur à 7, ledit agent améliorant l'indice de viscosité étant formé par greffage d'anhydride maléique sur un copolymère d'éthylène comprenant 30 à 80% en poids d'éthylène et 20 à 70% en poids de ladite alpha-oléfine en C3 à C28, suivi de la réaction desdites portions d'anhydride maléique avec une polyamine de 2 à 60 atomes de carbone et de 2 à 12 atomes d'azote et portant au moins deux groupes amino primaires, au moins certains des groupes amino primaires restant intacts, ledit procédé étant caractérisé par l'étape de réaction dudit concentré avec un anhydride d'acide carboxylique organique à substituant hydrocarbyle ayant 2 à 30 atomes de carbone par addition dudit anhydride d'acide en une quantité apportant un excès d'au moins 5% sur la base de la concentration en groupes amino primaires dans ledit concentré et maintien dudit concentré à une température allant de 50 à 250°C et pendant une période de 0,25 à 8 heures, puis élimination de la totalité de l'anhydride n'ayant pas réagi et des sous-produits de la réaction tout en maintenant ledit concentré dans un milieu inerte et anhydre.
14. Procédé suivant la revendication 13, dans lequel ledit concentré contient moins de 0,02% en poids d'alkylènepolyamine n'ayant pas réagi, ledit anhydride d'acide à substituant hydrocarbyle est l'anhydride acétique et ladite température est maintenue jusqu'à ce qu'une absorption maximale à 1650-1670 cm-' soit trouvée égale à un maximum par l'analyse infrarouge différentielle, et ladite élimination est effectuée par passage d'un courant d'azote jusqu'à ce que l'absorption soit minimale à 1720 cm-'.
15. Procédé suivant les revendications 13 ou 14 dans lequel il y a en outre une étape de traitement dudit concentré avec un acide fort, à substituant hydrocarbyle, soluble dans l'huile, contenant un groupement se dissociant en hydrogène qui a un pK inférieur à 2,5 et qui contient 3 à 70 atomes de carbone, à une température allant de la température ambiante à 250°C.
16. Procédé suivant la revendication 15, dans lequel ledit acide fort est un acide benzène- sulfonique dialkylé présent en une quantité allant de 0,1 à 2,5 équivalents molaires par équivalent molaire de matière azotée introduite sur le copolymère greffé améliorant l'indice de viscosité et ledit traitement est conduit à une température allant de 20 à 250°C pendant une période allant de 0,1 à 20 heures.
EP78300173A 1977-07-28 1978-07-20 Additifs stabilisés pour lubrifiants à base de copolymères d'éthylène greffés imidés, procédé pour leur préparation, procédé pour stabiliser des additifs pour lubrifiants à base du copolymère d'éthylène greffé imidé et compositions d'huiles lubrifiantes comprenant l'additif stabilisé Expired EP0000648B1 (fr)

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US05/819,846 US4137185A (en) 1977-07-28 1977-07-28 Stabilized imide graft of ethylene copolymeric additives for lubricants
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JPS629158B2 (fr) 1987-02-26
US4137185A (en) 1979-01-30
IT7825666A0 (it) 1978-07-13
EP0000648A1 (fr) 1979-02-07
CA1118548A (fr) 1982-02-16
BR7804856A (pt) 1979-03-13
JPS5425903A (en) 1979-02-27
AU521057B2 (en) 1982-03-11
DE2861753D1 (en) 1982-06-03
AU3764778A (en) 1980-01-03

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