EP0051998B1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

Info

Publication number
EP0051998B1
EP0051998B1 EP81305297A EP81305297A EP0051998B1 EP 0051998 B1 EP0051998 B1 EP 0051998B1 EP 81305297 A EP81305297 A EP 81305297A EP 81305297 A EP81305297 A EP 81305297A EP 0051998 B1 EP0051998 B1 EP 0051998B1
Authority
EP
European Patent Office
Prior art keywords
composition
acid
dispersant
ester
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81305297A
Other languages
German (de)
English (en)
Other versions
EP0051998A1 (fr
Inventor
Harold Shaub
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0051998A1 publication Critical patent/EP0051998A1/fr
Application granted granted Critical
Publication of EP0051998B1 publication Critical patent/EP0051998B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid 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
    • C10M2215/02—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
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • 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
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • This invention relates to a storage stable lubricating oil composition having improved anti-friction properties.
  • crankcase motor oils Known ways to solve the problem of energy losses due to high friction e.g., in crankcase motor oils include the use of synthetic ester base oils which are expensive and the use of insoluble molybdenum sulfides which have the disadvantage of giving the oil composition a black or hazy appearance.
  • a lubricating oil composition involves a composition containing an additive combination of an oil soluble friction reducing ester component derived from esterification of a polycarboxylic acid with a glycol and a zinc dihydrocarbyl dithiophosphate.
  • This type of composition is disclosed in U.S. Patent 4,105,571 which notes that while a lubricating composition containing the additive packages of such ester and zinc thiophosphate components provides excellent anti-friction and anti-wear properties, it presents compatibility and stability problems.
  • ashless dispersant containing a high molecular weight aliphatic hydrocarbon oil solubilizing group attached thereto to the composition, and preferably predispersing either the ester and/or zinc thiophosphate components prior to their addition to the remainder of the composition.
  • ashless dispersants may contain hydroxyl groups as noted in the patent.
  • lubricating oil compositions containing an additive combination of an ester of a polycarboxylic acid and a glycol or glycerol plus zinc dihydrocarbyl dithiophosphate can be made storage stable and have particularly improved friction reducing properties when an ashless dispersant containing a selected amount of free hydroxyl is used.
  • composition of this invention which includes an additive combination of (1) an ester of a polycarboxylic acid with a glycol or glycerol (2) a zinc dihydrocarbyl dithiophosphate and (3) an ashless dispersant containing a high molecular weight aliphatic hydrocarbon oil solubilizing group attached thereto and a selected amount of free hydroxyl groups.
  • a storage stable lubricating oil composition with improved friction reducing properties is provided by a composition
  • a composition comprising a major portion of lubricating oil, from about 0.01 to 1.0 parts by weight of an ester of a polycarboxylic acid with a glycol or glycerol, from 0.01 to 5.0 parts by weight of zinc dihydrocarbyl dithiophosphate and from 0.1 to 20 parts by weight of an hydroxyl containing ashless dispersant having a high molecular weight aliphatic hydrocarbon oil solubilizing group attached thereto, said dispersant containing from 0.35 to 1.8 millimoles (mM) of free hydroxyl per gram of dispersant, all weights based on 100 parts by weight of said lubricating oil composition.
  • mM millimoles
  • the present invention relates to a storage stable lubricating oil composition having particularly improved friction reducing properties comprising an additive combination of an ester of a polycarboxylic acid and a glycol or glycerol, zinc dihydrocarbyl dithiophosphate and an ashless dispersant containing a selected amount of free hydroxyl groups.
  • the oil soluble friction reducing ester component used in the composition of this invention generally, can be any hydroxy substituted oil soluble ester of a polycarboxylic acid.
  • esters of the type illustrated by the foregoing formulas can be obtained by esterifying a polycarboxylic acid, or a mixture of such acids, with a diol or mixture of such diols.
  • the polycarboxylic acid used in preparing the ester may be an aliphatic saturated or unsaturated acid and will generally have a total of about 24 to about 90, preferably about 24 to about 60 carbon atoms and about 2 to about 4, preferably about 2 to about 3 and more preferably about 2 carboxylic acid groups with at least about 9 up to about 42 carbon atoms, preferably about 12 to about 42 and more preferably about 16 to about 22 carbon atoms between the carboxylic acid groups.
  • the oil insoluble glycol which is reacted with the polycarboxylic acid may be an alkane diol, i.e. alkylene glycol or an oxa-alkane diol, i.e. polyalkylene glycol, straight chain or branched.
  • the alkane diol may have from about 2 to about 12 carbon atoms and preferably about 2 to about 5 carbon atoms in the molecule and the oxa-alkane diol will, generally, have from about 4 to about 200, preferably about 4 to about 100 carbon atoms.
  • the oxa-alkane diol (polyalkylene glycol) will, of course, contain periodically repeating groups of the formula: wherein R may be H, CH 3 , C 2 H 5 or C 3 H 7 , and x is 2 to 100, preferably 2 to 25.
  • the preferred alkane diol or alkylene glycol is ethylene glycol and the preferred oxa-alkane diol or polyalkylene glycol is diethylene glycol.
  • glycerol may also be used in preparing the ester of polycarboxylic acid and it is contemplated that such component will also include its higher molecular weight analogues.
  • esters as set forth above can be effectively used, best results are, however, obtained with such compounds wherein the carboxyl groups of the polycarboxylic acid are separated from each other by from about 16 to about 22 carbon atoms and wherein the hydroxy groups are separated from the closest carboxyl group by from about 2 to about 12 carbon atoms.
  • Particularly desirable results have been obtained with additives prepared by esterifying a dimer of a fatty acid particularly those containing conjugated unsaturation with a polyhydroxy compound.
  • dimers are, of course, clearly taught in U.S. Patent 3,180,832 which was granted on April 27, 1965 and U.S.
  • the preferred hydroxy-substituted ester lubricity additives useful in the present invention will be the reaction product of a dimerized fatty acid, such as those illustrated, and an oil insoluble glycol and may be produced by various techniques.
  • the preferred acid dimers are the dimers of linoleic acid, oleic acid or the mixed dimer of linoleic and oleic acids, which may also contain some monomer as well as trimer.
  • Other specifically satisfactory glycols in addition to ethylene glycol and polyethylene glycol are, for example, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol and the like.
  • the zinc dihydrocarbyl dithiophosphates useful in the present invention are salts of dihydrocarbyl esters of dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be 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 Rand R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-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 in the dithiophosphoric acid will average about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphates which are useful in the compositions of the present invention may be prepared in accordance with known techniques by first esterifying a dithiophosphoric acid usually by reaction of an alcohol or phenol with P Z S S and then neutralizing the dithiophosphoric acid ester with a suitable zinc compound such as zinc oxide.
  • a suitable zinc compound such as zinc oxide.
  • the alcohol or mixtures of alcohols containing from 1 to 18 carbon atoms may be used to effect the esterification.
  • the hydrocarbon portion of the alcohol may, for example, be a straight or branched chain alkyl or alkenyl group, or a cycloaliphatic or aromatic group.
  • Other natural products containing alcohols such as the alcohols derived from wool fat, natural waxes and the like may be used.
  • alcohols produced by the oxidation of petroleum hydrocarbon products as well as the Oxo-alcohols produced from olefins, carbon monoxide and hydrogen may be employed.
  • Further aromatic compounds such as alkylated phenols of the type n-butyl phenol, tertiaryamyl phenol, diamyl phenol, tertiary octyl phenol, cetyl phenol, petroleum phenol and the like as well as the corresponding naphthols may be employed in like manner.
  • the diester is then neutralized with a suitable basic zinc compound or a mixture of such compounds.
  • a suitable basic zinc compound or a mixture of such compounds.
  • any compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • any lubricating oil ashless dispersant containing a high molecular weight aliphatic hydrocarbon oil solubilizing group attached thereto and the selected amount of free hydroxyl groups can be used in the composition of this invention. More particularly, said dispersant will contain from about 0.35 to about 1.8 millimoles of free hydroxyl per gram of dispersant, preferably from about 0.5 to about 1.5 and more preferably about 0.7 to about 1.3 millimoles of free hydroxyl per gram of dispersant.
  • the gram weight is of active dispersant, i.e. it does not include the carrier or lubricating oil in which the dispersant is diluted or otherwise dispersed.
  • hydroxyl content in the dispersant is the essential feature of this invention since it has surprisingly been found that controlling hydroxyl content per gram of active dispersant results in significantly lower engine friction. Additionally, there is a minimum amount of hydroxyl content which must be maintained in the dispersant in order to retain composition stability. Accordingly, it is essential that the dispersant contain a selected amount of free hydroxyl content as described herein to provide a lubricating composition with improved friction reducing properties while retaining its stability.
  • a variety of compounds may be used as the ashless dispersant in the composition of this invention provided they have a suitable high molecular weight aliphatic hydrocarbon oil solubilizing group attached thereto and most important a selected amount of free hydroxyl groups.
  • Dispersant compounds of this type include esters of mono and polycarboxylic acids with polyhydric alcohols, phenols and naphthols as well as nitrogen containing compounds containing the necessary hydroxyl content as previously noted. It is contemplated that mixtures and a wide variety of compounds may be utilized as the ashless dispersant or ashless dispersant system in this invention provided the necessary functionality is available, particularly the selected amount of free hydroxyl content.
  • the ashless dispersant of this invention may comprise a mixture of a hydroxylated and non-hydroxylated compound provided the necessary functionality as defined herein is satisfied. Accordingly, the term ashless dispersant as used throughout this application is intended to include such mixtures and combination of compounds thereof.
  • the different dispersants which can be used in this invention are characterized by a long chain hydrocarbon group or groups, which may be attached, e.g. to the acid, so the acid contains a total of about 50to about 400 carbon atoms, said acid being attached, e.g. to an amine and/or ester group or both.
  • Ester containing ashless dispersants of this invention can be derived from polyhydric aliphatic alcohols or polyhydric aromatic hydroxyl containing compounds such as phenols and naphthols.
  • the polyhydric alcohols and aromatic compounds used will preferably contain from 2 to about 10 hydroxy radicals and are illustrated by ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene radicals contain from about 2 to about 8 carbon atoms.
  • resorcinol catechol, p,p'-dihydroxybiphenyl, 4,4'-methylene bis-phenol, di (hydroxyphenyl) oxide, and di (hydroxyphenyl) sulfide.
  • Other useful polyhydric compounds include glycerol, mono-oleate of glycerol, pentaerythritol, trimethylol propane, 9,10-dihydroxystearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4 hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, and 1,2-cyclohexanediol.
  • Carbohydrates such as sugars, starches, cellulose, etc., likewise may yield appropriate esters as exemplified by flucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde, and galactose.
  • An especially preferred class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterified with a monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oil acid.
  • a monocarboxylic acid having from about 8 to about 30 carbon atoms
  • octanoic acid oleic acid
  • stearic acid stearic acid
  • linoleic acid dodecanoic acid or tall oil acid
  • Examples of such partially esterified polyhydric alcohols are the mono-oleate of glycerol, monosterate of glycerol, di- dodecanote of erythritol.
  • the ester dispersant of this invention may also be derived from unsaturated alcohols, ether-alcohols, and amino alcohols including for example: oxy-alkylene, oxy-arylene, amino-alkylene, and amino-arylene substituted alcohols.
  • Such compounds include di (hydroxyethyl) amine, tri (hydroxypropyl) amine, N,N,N,N-tetrahydroxytrimethylenediamine, 2-amino-2-methyl-1,3 propanediol, 2-amino-2-ethyl-1,3-propanediol, tris (hydroxymethyl) amino-methane, etc.
  • the particular dispersants used in this invention contain a long chain hydrocarbon group which will generally have about 50 to about 400 carbon atoms and preferably will be derived from an alkenyl succinic acid/anhydride where the alkenyl radical will have a molecular weight of at least about 900 and preferably at least about 1200 and more preferably at least about 1300.
  • dispersants having the above identified characteristics can be used in this invention some of which are disclosed in U.S. Patents 4,105,571; 3,542,678; 3,522,179; 3,542,680; 3,632,511; and 3,804,763. Methods for preparing such dispersants are generally well known and are also disclosed in the noted patents.
  • Some particularly preferred dispersant combinations include 1) a combination of a polyisobutenyl succinic anhydride, a hydroxy compound e.g. pentaerythritol and a polyoxyalkylene polyamine e.g. polyoxypropylenediamine and a polyalkylene polyamine e.g.
  • the zinc dihydrocarbyl dithiophosphate will be used in the lubricating composition at a concentration within the range of about 0.01 to about 5 parts by weight per 100 parts of lubricating oil composition and preferably from about 0.5 to about 1.5.
  • the polycarboxylic acid/glycol or glycerol ester will be used at a concentration of about 0.01 to about 2.0, preferably about 0.05 to about 1.0 and more preferably 0.05 to 0.5 parts by weight per 100 parts of lubricating oil composition and the ashless dispersant will be employed at a concentration of about 0.1 to about 20 and preferably about 0.5 to about 10 parts by weight per 100 parts of lubricating oil composition.
  • the lubricating oil liquid hydrocarbons which may be used include the mineral lubricating oils and the synthetic lubricating oils and mixtures thereof.
  • the synthetic oils will include diester oils such as di(2-ethylhexyl) sebacate, azelate and adipate; complex ester oils such as those formed from dicarboxylic acids, glycols and either monobasic acids or monohydric alcohols; silicone oils; sulfide esters; organic carbonates; and other synthetic oils known to the art.
  • additives may be added to the oil compositions of the present invention to form a finished oil.
  • Such additives may be the conventionally used additives including oxidation inhibitors such as phenothiazine or phenyl a-naphthylamine; rust inhibitors such as lecithin or sorbitan monoleate; detergents such as barium phenates; pour point depressants such as copolymers of vinyl acetate with fumaric acid esters of coconut oil alcohols; viscosity index improvers such as olefin copolymers, polymethacrylates; etc.
  • oxidation inhibitors such as phenothiazine or phenyl a-naphthylamine
  • rust inhibitors such as lecithin or sorbitan monoleate
  • detergents such as barium phenates
  • pour point depressants such as copolymers of vinyl acetate with fumaric acid esters of coconut oil alcohols
  • a particularly useful additive is the basic alkaline earth metal salts of an organic sulfonic acid, generally a petroleum sulfonic acid or a synthetically prepared alkaryl sulfonic acid.
  • an organic sulfonic acid generally a petroleum sulfonic acid or a synthetically prepared alkaryl sulfonic acid.
  • the most useful products are those prepared by the sulfonation of suitable petroleum fractions with subsequent removal of acid sludge and purification.
  • Synthetic alkaryl sulfonic acids are usually prepared from alkylated benzenes such as the Friedel-Crafts reaction product of benzene and a polymer such as tetrapropylene.
  • Suitable acids may also be obtained by sulfonation of alkylated derivatives of such compounds as diphenylene oxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydro naphthalene and the like.
  • Basic alkaline earth metal sulfonates are generally prepared by reacting an alkaline earth metal base, e.g. lime, magnesium oxide, magnesium alcoholate with C0 2 in the presence of sulfonic acid or neutral metal sulfonates, ordinarily the calcium, magnesium or barium salts.
  • alkaline earth metal base e.g. lime, magnesium oxide, magnesium alcoholate
  • neutral metal sulfonates ordinarily the calcium, magnesium or barium salts.
  • These neutral salts in turn may be prepared from the free acids by reaction with the suitable alkaline earth metal base, or by double decomposition of an alkali metal sulfonate, which methods are well known in the art. Further details are described in U.S. Patent No. 3,562,159.
  • composition of this invention is particularly useful when metal containing additives such as the normal and basic metal phenates, sulfonates or sulfurized phenates are used since such components have been known to cause compatibility problems in more conventional type lubricant compositions.
  • the above described additive package may be used in conventional base oils with other conventional additives. While the components can generally be added in their normal and conventional manner, it is a preferred embodiment of this invention to keep the zinc dihydrocarbyl dithiophosphate and polycarboxylic acid/glycol or glycerol ester components apart from one another until at least one of such components has been predispersed as described in U.S. 4,105,571. This will help to maintain a storage stable and compatible composition.
  • predispersed it is meant that the ester component or the zinc component or both separately are mixed with the ashless dispersant, which may be in oil solution, until the solution is generally clear.
  • Formulations were prepared using a 10W-40SE quality automotive engine oil containing 1.5% by weight, based on the total lubricating oil weight, of zinc dialkyl dithiophosphate (80% active ingredient in diluent mineral oil) in which the alkyl groups were a mixture of such groups having between 4 and 5 carbon atoms and made by reacting P 2 S 5 with a mixture of about 65% isobutyl alcohol and 35% of amyl alcohol; 0.1 % by weight, based on the total lubricating oil weight of an ester formed by esterification of a dimer acid of linoleic acid and diethylene glycol and having the formula:
  • This additive is actually a mixture of the structure shown plus higher molecular weight repeating units (polymers) of this material.
  • Dispersants containing different amounts of free hydroxyl contents were used in the different lubricating formulations as described below:
  • the dispersants noted above were added to the 10W-40SE crankcase oil along with the other additives and a rust inhibitor, i.e. overbased magnesium sulfonate, a detergent and a VI improver, i.e. an ethylene-propylene copolymer.
  • a rust inhibitor i.e. overbased magnesium sulfonate
  • a detergent and a VI improver i.e. an ethylene-propylene copolymer.
  • compositions all exhibited storage stability and compatibility over an extended period and were further tested for relative friction using a ball on cylinder test.
  • the apparatus used in the ball on cylinder test is described in the Journal of the American Society of Lubrication Engineers, entitled “ASLE Transactions", Vol. 4 pages 1-11, 1961.
  • the apparatus consists basically of a fixed metal ball loaded against a rotating cylinder.
  • the weight on the ball and the rotation of the cylinder can be varied during any given test or from test to test.
  • the time of any given test can be varied.
  • steel on steel is used at a constant load, a constant rpm and a fixed time and in each of the tests of this example, a 4 Kg load, 0.26 rpm and 70 minutes was used.
  • the actual friction was determined from the power actually required to effect rotation and the relative friction determined by ratioing the actual load to that of a standard.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (11)

1. Composition d'huile lubrifiante comprenant, pour 100 parties en poids, une proportion majeure d'huile lubrifiante, un total de 0,01 à 2,0 parties en poids d'un ou plusieurs esters d'un polyacide carboxylique et d'un glycol ou de glycérol et un total de 0,1 à 5,0 parties en poids d'un ou plusieurs dihydrocarbyl dithiophosphates de zinc, contenant en outre un total de 0,1 à 20 parties en poids d'un ou plusieurs dispersants sans cendres contenant des groupes hydroxyles et sur lesquels est fixé un groupe aliphatique de poids moléculaire élevé solubilisant dans l'huile, caractérsé en ce que ce dispersant (ces dispersants) contient (contiennent) 0,35 à 1,8 millimoles de groupes hydroxyles libres par gramme d'ingrédient actif (d'ingrédients actifs) du dispersant.
2. Composition selon la revendication 1, caractérisée en ce que ce dispersant contient 0,5 à 1,5 millimoles de groupes hydroxyles libres par gramme d'ingrédient actif (d'ingrédients actifs) du dispersant.
3. Composition selon la revendication 1 ou 2, caractérisée en ce que ce dispersant est un dérivé d'un acide ou d'un anhydride alkényl succinique dans lequel le groupe alkényle a un poids moléculaire d'au moins 900.
4. Composition selon la revendication 1 ou 2, caractérisée en ce que ce dispersant est un acide ou un anhydride alkényl succinique contenant de l'azote ou est un ester d'un acide ou d'un anhydride alkényl succinique et de polyalcools, de polyphénols ou de polynaphtols.
5. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que l'ester (les esters) de polyacide(s) carboxylique(s) est formé (sont formés) à partir d'un diacide carboxylique ayant 9 à 42 atomes de carbone entre les groupes acides carboxyliques et d'un glycol choisi parmi les alcane diols ayant 2 à 12 atomes de carbone et les oxa-alcane diols ayant 4 à 200 atomes de carbone.
6. Composition selon la revendication 4, caractérisée en ce que l'ester (les esters) de polyacide(s) carboxyliques est formé (sont formés) à partir d'un acide dimère d'un acide gras conjugé ayant 16 à 22 atomes de carbone entre les groupes acides carboxyliques.
7. Composition selon la revendication 6, caractérisée en ce que cet ester est formé par estérification d'un acide dimère de l'acide linoléique par le diéthylèneglycol.
8. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que les groupes dihydrocarbyles du dérivé du zinc sont des groupes alkyles de 2 à 8 atomes de carbone.
9. Composition selon l'une quelconque des revendications précédentes, contenant en outre un additif contenant un métal, comprenant un phénate, un sulfonate ou un phénate sulfuré de métal normal ou basique.
10. Procédé de préparation de la composition lubrifiante définie dans l'une quelconque des revendications précédentes, caractérisée en ce que l'on disperse préalablement le dihydrocarbyle dithiophosphate de zinc ou l'ester de polyacide carboxylique ou les deux séparément dans au moins une certaine quantité du dispersant avant de les incorporer à la composition d'huile lubrifiante.
11. Procédé pour diminuer le frottement dans un moteur à combustion interne comprenant la lubrification du moteur par emploi de la composition d'huile lubrifiante revendiquée dans l'une quelconque des revendications 1 à 9.
EP81305297A 1980-11-10 1981-11-06 Composition d'huile lubrifiante Expired EP0051998B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US20531480A 1980-11-10 1980-11-10
US205314 1980-11-10

Publications (2)

Publication Number Publication Date
EP0051998A1 EP0051998A1 (fr) 1982-05-19
EP0051998B1 true EP0051998B1 (fr) 1985-04-10

Family

ID=22761700

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81305297A Expired EP0051998B1 (fr) 1980-11-10 1981-11-06 Composition d'huile lubrifiante

Country Status (4)

Country Link
EP (1) EP0051998B1 (fr)
JP (1) JPS57108194A (fr)
CA (1) CA1159436A (fr)
DE (1) DE3169874D1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4952328A (en) * 1988-05-27 1990-08-28 The Lubrizol Corporation Lubricating oil compositions
US4981602A (en) * 1988-06-13 1991-01-01 The Lubrizol Corporation Lubricating oil compositions and concentrates
US4938881A (en) * 1988-08-01 1990-07-03 The Lubrizol Corporation Lubricating oil compositions and concentrates
US4957649A (en) * 1988-08-01 1990-09-18 The Lubrizol Corporation Lubricating oil compositions and concentrates
JP5318395B2 (ja) * 2007-10-31 2013-10-16 株式会社ファンケル ダイマージリノール酸ジエチレングリコールオリゴマーエステル含有油性組成物
JP5137786B2 (ja) * 2007-11-21 2013-02-06 株式会社ファンケル ダイマージリノール酸ジエチレングリコールオリゴマーエステル含有クレンジング化粧料
US9732301B2 (en) * 2014-11-05 2017-08-15 Infineum International Limited Power transmitting fluids with improved materials compatibility
GB201718527D0 (en) * 2017-11-09 2017-12-27 Croda Int Plc Lubricant formulation & friction modifier additive
JP6501003B1 (ja) 2018-01-17 2019-04-17 千住金属工業株式会社 はんだ付け用樹脂組成物、やに入りはんだ、フラックスコートはんだ及び液状フラックス

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1271877B (de) * 1963-04-23 1968-07-04 Lubrizol Corp Schmieroel
US3216936A (en) * 1964-03-02 1965-11-09 Lubrizol Corp Process of preparing lubricant additives
US4105571A (en) * 1977-08-22 1978-08-08 Exxon Research & Engineering Co. Lubricant composition

Also Published As

Publication number Publication date
DE3169874D1 (en) 1985-05-15
JPS57108194A (en) 1982-07-06
CA1159436A (fr) 1983-12-27
EP0051998A1 (fr) 1982-05-19

Similar Documents

Publication Publication Date Title
US4479883A (en) Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates
US4105571A (en) Lubricant composition
US4455243A (en) Succinimide complexes of borated fatty acid esters of glycerol and lubricating oil compositions containing same
CA2171536C (fr) Compositions de lubrification avec qualites antioxydantes ameliorees
US4376711A (en) Lubricant composition
EP0217591B1 (fr) Catéchols monoalcoylés en C18 à C24 normalement liquides
EP0389573A1 (fr) Compositions et concentres d'huile lubrifiante.
EP0382806A1 (fr) Compositions et concentres d'huile lubrifiante.
US4394277A (en) Method for improving fuel economy of internal combustion engines using borated sulfur-containing 1,2-alkane diols
US4629578A (en) Succinimide complexes of borated alkyl catechols and lubricating oil compositions containing same
EP0051998B1 (fr) Composition d'huile lubrifiante
GB2103651A (en) Reduction of fuel consumption of internal combustion engines and composition therefor
US4629577A (en) Method for improving fuel economy of internal combustion engines
US4617134A (en) Method and lubricant composition for providing improved friction reduction
EP0322235B1 (fr) Dithiophosphates
US4684473A (en) Lubricant oil composition with improved friction reducing properties
US4153562A (en) Antioxidants for low ash and medium ash lubricating oils
CA1273344A (fr) Complexes de type succinimide d'alkylcatechols borates et produits lubrifiants contenant ceux-ci
US4394276A (en) Method for improving fuel economy of internal combustion engines using sulfur-containing alkanediols
US11697785B2 (en) Lubricant composition for a gas engine
CA1224470A (fr) Complexes de succinimide et d'esters d'acides gras bores et de glycerol; compositions lubrifiantes qui en renferment
US5739089A (en) Dihydrocarbyl dithiophosphates
US4362636A (en) Crankcase lubricant and method for improving fuel economy of internal combustion engines utilizing same
CA1340717C (fr) Dithiophosphates dihydrocarbyles
US5703262A (en) Process for the preparation of dithiophosphoric acids

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19821112

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 3169874

Country of ref document: DE

Date of ref document: 19850515

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19871130

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19890731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19890801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST