EP0425367B1 - Additif surbasé pour huiles lubrifiantes renfermant un dérivé du cuivre ou un dérivé du cuivre et du bore, son procédé de préparation et compositions renfermant ledit additif - Google Patents

Additif surbasé pour huiles lubrifiantes renfermant un dérivé du cuivre ou un dérivé du cuivre et du bore, son procédé de préparation et compositions renfermant ledit additif Download PDF

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Publication number
EP0425367B1
EP0425367B1 EP90402981A EP90402981A EP0425367B1 EP 0425367 B1 EP0425367 B1 EP 0425367B1 EP 90402981 A EP90402981 A EP 90402981A EP 90402981 A EP90402981 A EP 90402981A EP 0425367 B1 EP0425367 B1 EP 0425367B1
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Prior art keywords
copper
additive
weight
additive according
overbased
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German (de)
English (en)
French (fr)
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EP0425367A1 (fr
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Henri Bourgognon
Pierre Hoornaert
Claude Rey
Christian Rodes
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Societe National Elf Aquitaine
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Societe National Elf Aquitaine
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more 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
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/063—Peroxides
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/105—Silica
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • 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
    • C10M2207/26—Overbased carboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • 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
    • C10N2010/02—Groups 1 or 11
    • 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

Definitions

  • This invention relates to overbased additives for lubricating oils containing a copper derivative or a copper and boron derivative, their preparation process and lubricant compositions containing said additives.
  • Overbased additives are alkali or alkaline earth metal salts of organic acids, overbased by carbonation with carbon dioxide.
  • the term overbased is used to designate the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the organic acid used.
  • the structure of the overbased additives is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation.
  • the micelles are stabilized by the alkali or alkaline earth metal salts of organic acids which have a detergent effect.
  • organic acid salts used in the overbased additives are generally the sulphonates, salicylates or sulfurized phenates, described respectively in US Patents 4,606,219, EP-A 279,493 and FR 2,305,494.
  • overbased additives are particularly useful in lubricants used in internal combustion engines of the "gasoline” type or of the "diesel” type.
  • overbased additives in particular overbased sulfonates have the disadvantage of significantly degrading the antioxidant performance of lubricant formulations.
  • additives according to the invention makes it possible to avoid this degradation and even to improve the resistance of lubricants to oxidation.
  • Multi-valent metals such as copper, molybdenum, iron and cobalt influence the oxidation of oils.
  • Copper for example, at concentrations below 50 ppm, catalyzes the oxidation of the lubricant. In the concentration range between 50 and 500 ppm, on the other hand it has an oxidation inhibiting effect.
  • Patent application EP-A-0024146 describes formulations containing such copper concentrations in the form of cupric oleate.
  • US Patent 4,715,974 describes the use in lubricants of copper salts of sulfurized unsaturated fatty acids.
  • US Patent 4,770,799 relates to the copper salts of succinic esters of substituted phenols.
  • Copper derivatives are also used in combination with amines, which in turn promote the decomposition of peroxides.
  • Oil-soluble copper salts such as copper oleate cannot be used in overbased additives.
  • the overbasing of a reaction mixture containing the copper oleate is not possible and the addition of the copper oleate to an overbased additive gives an unstable mixture.
  • Patent application EP-A-0225580 describes the introduction into an overbased additive of a copper carboxylate insoluble in hydrocarbons, the total number of carbons of which does not exceed six. These oil-insoluble copper carboxylates are found inside the micelles of the colloidal dispersion, in the same way as the alkali or alkaline earth metal carbonate, most often calcium carbonate.
  • the invention relates to an overbased additive for lubricating oils, composed of an alkali or alkaline earth metal carbonate dispersed in a diluent oil using a mixture of detergents, characterized in that said mixture contains at least one copper carboxylate. , derived from straight chain or branched C7 to C linéaire aliphatic carboxylic acids.
  • the copper carboxylate in the form of an association formed with an inorganic derivative of boron.
  • the presence of boron contributes to the antioxidant effect and improves the extreme pressure performance of the additive.
  • the copper carboxylates used are derived from aliphatic carboxylic acids with a linear or branched chain from C7 to C10, such as n-heptanoic acid, ethyl-hexanoic acid or n-decanoic acid. It may be advantageous to use mixtures of acids, obtained from alpha-olefins or rather from alpha-olefin cuts, by oxo synthesis. Among these mixtures of acids, mention may be made of C7 to C10 oxo acids branched in the alpha or beta position or else VERSATIC 10 acids, sold by SHELL. VERSATIC 10 acids are obtained by oxo reaction from a mixture of branched C9 olefins. They mainly consist of tertiary acids, with a trialkylacetic acid structure.
  • Copper carboxylates are generally obtained by reacting a carboxylic acid with cupric hydroxide or a mixture of cupric hydroxide and carbonate in an organic solvent. Copper carboxylates can also be prepared by displacing the sodium from a sodium carboxylate with a solution of a mineral salt of copper, such as cupric chloride.
  • the copper carboxylates can be prepared in the form of solids containing approximately 12 to 17% by weight of copper or in the form of a solution.
  • the solvent is preferably identical to that used for carbonation.
  • the associations of copper carboxylates with inorganic boron derivatives are prepared by reacting a solution of copper carboxylate with a solution of a mineral boron compound, such as ammonium borate, sodium tetraborate, metaborate sodium or boric anhydride.
  • a mineral boron compound such as ammonium borate, sodium tetraborate, metaborate sodium or boric anhydride.
  • the preferred boron compound is boric anhydride, B2O3.
  • the preferred solvent is a glycol ether, such as propylene glycol methyl ether.
  • the two solutions are mixed at a temperature in the region of 100 ° C., then the mixture is brought to reflux for at least one hour. After distillation of part of the solvents, a small amount of a glycol, such as butyl glycol, is optionally added. The concentration of the latter does not exceed 5% by weight of the final mixture.
  • the copper carboxylate / boron compound associations obtained contain between approximately 8 to 12% by weight of copper and 0.8 to 2% by weight of boron and are in the form of an intense blue solution, which very quickly crosses a membrane. latex dialysis machine.
  • the copper carboxylate or the copper-boron carboxylate association is used in mixture with a usual detergent of overbased additives.
  • detergents mention may be made of naphthenates, sulfonates, phenates, salicylates, phosphonates and alkali or alkaline earth thiophosphonates soluble in the hydrocarbon medium.
  • the sulfonic acids used for the preparation of the sulfonates can be of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum. Their structure does not correspond to a well defined formula but their average molecular weight must be at least equal to 300.
  • Synthetic sulfonic acids are prepared by alkylation of aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
  • aromatic compounds such as benzene, toluene, xylene or naphthalene with olefinic cuts and then by sulfonation of the alkylate obtained.
  • the structure of the alkyl chains attached to the nucleus is linear or branched depending on the olefins used for the alkylation.
  • the number of carbon atoms per alkyl chain is greater than or equal to 8.
  • the preparation of the alkali or alkaline earth metal sulfonate is carried out by bringing the sulfonic acid into contact with an alkali or alkaline earth metal derivative (preferably oxide or hydroxide) in a hydrocarbon solvent optionally in the presence of an alcohol.
  • an alkali or alkaline earth metal derivative preferably oxide or hydroxide
  • the alkali or alkaline earth metal phenates are prepared under analogous conditions from sulfurized alkylphenol or alkylphenol.
  • the phenol ring can carry one or two straight or branched alkyl chains, having at least eight carbon atoms.
  • the most common compound is dodecylphenol.
  • the optional sulfurization of phenol is carried out by the action of sulfur monochloride S2Cl2 or by the action of elemental sulfur at temperatures ranging from 150 to 200 ° C.
  • the sulfurized product contains approximately 0.6 to 2 sulfur atoms per phenolic nucleus.
  • the alkylsalicylic acids are prepared by alkylation of salicylic acid or by carboxylation under pressure of alkylphenols.
  • the alkyl chain contains a minimum of 12 carbon atoms.
  • the phosphonates and thiophosphonates are prepared by the action of P2O5 or P2S5 on a polyisobutene then neutralization with an alkali or alkaline earth oxide or hydroxide.
  • the molecular weight of polyisobutene is between 300 and 2000.
  • All of these detergents can be used in admixture with dispersants which are soluble in a hydrocarbon medium, for example of the alkylsuccinimide type or esters of alkylsuccinic acids with a molecular weight of 300 to 2500.
  • the reaction medium can contain the precursors.
  • neutralization is carried out in the reaction medium just before carbonation.
  • the alkali or alkaline earth metal carbonate used in the composition of the additive according to the invention is generally calcium carbonate or magnesium carbonate.
  • the multifunctional additive according to the invention is prepared by carbonation of a reaction medium containing a mixture of detergents, a derivative of an alkali or alkaline earth metal, a nitrogenous and / or oxygenated promoter and optionally a hydrocarbon solvent in a diluent oil, characterized in that the detergent mixture contains at least one copper carboxylate derived from aliphatic acids with a straight or branched chain C7 to C10 or a combination of this carboxylate with an inorganic boron derivative.
  • the detergent mixture contains in addition to copper carboxylate, a usual detergent for overbased additives, such as naphthenates, sulfonates, phenates, salicylates, phosphonates and thiophosphonates, alkali or alkaline earth.
  • a usual detergent for overbased additives such as naphthenates, sulfonates, phenates, salicylates, phosphonates and thiophosphonates, alkali or alkaline earth.
  • the alkali or alkaline earth metal derivatives can be oxides, hydroxides or alcoholates.
  • the preferred derivatives are the oxides and hydroxides and particularly the oxide or hydroxide of calcium or magnesium.
  • the reaction medium is added to stoichiometric excess relative to the detergent or its precursor.
  • the stoichiometric excess can vary between 5: 1 and 30: 1.
  • an oxygenated promoter is introduced into the reaction medium before carbonation, which is generally an aliphatic alcohol or aromatic, an alkoxyalkanol, a glycol or even an alkanolamine.
  • reaction medium which is generally an aliphatic alcohol or aromatic, an alkoxyalkanol, a glycol or even an alkanolamine.
  • aliphatic alcohols C1 to C20 or mixtures thereof.
  • the aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
  • the molar ratio of the oxygenated promoter to the detergent is generally between 1 and 30.
  • nitrogenous promoter is optional.
  • This nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary amines in C2 to C10 and their salts with carboxylic acids or boric acid, polyamines or even alkanolamines.
  • ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine are preferred.
  • the promoter to detergent molar ratio is generally between 1 and 30.
  • the hydrocarbon solvent allows perfect homogenization of the various reactants as well as a lowering of the viscosity which will subsequently facilitate the recovery of solid carbonation residues.
  • the solvent represents from 10 to 70% by weight of the reaction mixture.
  • the solvents used are the Chat to C ar aliphatic or aromatic compounds.
  • the preferred solvents are aromatic solvents such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatics. Their choice is dictated by the characteristics of the additive collected, by their boiling point and by the boiling point of the azeotropes which they can form with oxygenated promoters and water.
  • the handling of the overbased additive obtained according to the invention is facilitated by the addition of oil.
  • the oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or even after this, that is to say just before the removal of the solvent.
  • the diluent oils used are of a paraffinic nature of the 100 or 150 Neutral solvent type or of a predominantly naphthenic nature such as 100 - 150 pale solvent.
  • the carbonation reaction can be carried out after optional addition of water to the reaction medium.
  • the addition of water is particularly beneficial when the alkali or alkaline earth metal derivative is an oxide.
  • the amount of water added is such that the water / metal oxide molar ratio is of the order of 0.5.
  • a detergent precursor it is preferable to successively introduce the precursor, the excess of the alkali or alkaline earth metal derivative and the oxygenated promoter. Neutralization of the precursor is then carried out before adding the other constituents of the mixture with a view to carbonation.
  • the stoichiometric excess of the alkali metal derivative is carbonated or alkaline earth at a temperature between room temperature and the reflux temperature of the mixture.
  • the molar ratio of CO2 introduced to the stoichiometric excess of alkali or alkaline earth metal is between 0.6 and 1.2.
  • the mixture is optionally stabilized by heating under vacuum or under a stream of nitrogen so as to eliminate the oxygenated promoters of low boiling point and the water added as well as the water produced by carbonation. Solid residues are removed by centrifugation and / or filtration using diatomaceous earth. If the diluent oil has not been added before carbonation, it is then added before possible elimination of the hydrocarbon solvent and heavy alcohols, by heating under vacuum at temperatures of the order of 100 to 200 ° C.
  • the filtration operation can be carried out after recovery of the solvent.
  • the incorporation rate of copper and possibly boron is close to 100%.
  • the overbased additives according to the invention are clear and stable liquids. Their coloring is generally blue. Phenates and salicylates are much darker than sulfonates.
  • additives have a copper content of between 0.2 and 5% by weight, preferably 0.8 to 3%, and a boron content of between 0 and 1%, preferably 0.2 to 0.8%.
  • VA alkaline value
  • additives are incorporated into lubricating oils of natural origin in the synthetic at a concentration between 0.5 and 40% by weight and preferably 1 to 30% by weight, which corresponds to a concentration of 0.004 to 1.2%. weight of copper and 0 to 0.32% weight of boron in the final lubricant formula.
  • the lubricant compositions thus obtained can contain other additives with antiwear, dispersant, detergent, antioxidant, friction modifier effect, as well as polymers improving the viscosity index.
  • Example B 770 g of a solution of carboxylate obtained in Example B are used. This is maintained at 130 ° C. 32 g of boric anhydride B2O3 are dissolved in 288 g of methyl ether of propylene glycol (PE: 120 ° C.) at a temperature of 100 ° C. The boron solution is introduced in 20 minutes into the carboxylate solution. After one hour of reflux, a total clarification of the reaction medium is observed; then distilling all of the ether and part of the solvent so as to obtain a copper content of the order of 11.2%. We then add 30g of butylglycol to perfectly stabilize the mixture: the product obtained contains 10.7% copper and 1.38% boron.
  • PE methyl ether of propylene glycol
  • the product is limpid brown and stable when diluted in mineral or synthetic oils. No clouding or settling is observed after several weeks at 60 ° C.
  • the amount of diluent oil is 22.5 g.
  • the product is in the form of a brown liquid, its alkaline value is 378mg KOH / g. It is stable when diluted in lubricating oils and its viscosity is 18,250 mPa.s at 20 ° C;
  • Example 2 The procedure is as in Example 1, but 10 g of a solution prepared in Example C are introduced into the reaction medium, before carbonating with 12 g of carbon dioxide. 112 g of overbased sulfonate containing 0.96% copper and 0.117% boron are recovered. Its alkaline value is 314 mg KOH / g and its viscosity is 3500 mPa.s at 20 ° C. It is blue in color and perfectly stable when diluted in oils.
  • Example 2 The procedure is as in Example 1, but 15g of solution described in Example C are introduced before carbonating with 12g of CO2. 111 g of overbased sulfonate containing 1.41% copper and 0.15% boron are then collected. The alkaline value is 309 mg KOH / g and the viscosity at 20 ° C is 4950 mPa.s. The dilution stability in oils is remarkable.
  • Example 2 The procedure is as in Example 1, but 20g of solution prepared in Example C are added before carbonating with 11g of carbon dioxide. 115.5 g of an overbased sulfonate containing 1.88% copper and 0.224% boron are collected. The alkaline value is 297 mg KOH / g and the viscosity at 20 ° C is 11,650 mPa.s. It is perfectly stable in mineral and synthetic oils.
  • Example 2 The procedure is as in Example 2, but 4 g of copper carboxylate described in Example A are added to the reaction medium before carbonating with 8.3 g of carbon dioxide. 75 g of overbased sulfonate containing 0.85% copper are recovered and the dilution stability in oils is correct. The color is dark green, the viscosity at 20 ° C is 260,000 mPa.s and the alkaline value is 334 mg KOH / g.
  • Example 2 The procedure is as in Example 2, but 1.5 g of the copper carboxylate described in Example A are introduced before carbonating with 8.3 g of carbon dioxide.
  • Example 2 The procedure is as in Example 1, but 20 g of the cupric solution prepared in Example B are introduced before carbonating with 12 g of carbon dioxide. After a treatment similar to that of Example 1, 113 g of an overbased sulfonate containing 1.77% of copper and whose alkaline value is 321 mg KOH / g are recovered. Its color is blue-green and its stability in oils is remarkable.
  • 77.8 g of dodecylphenol and 20 g of sulfur chloride are introduced into a 250 ml reactor equipped with a condenser, a temperature control and a gas bubbling device at a temperature of 20 to 30 ° C.
  • the mixture is heated under nitrogen sweep and with stirring for one hour at 150 ° C then 1 hour at 180 ° C and finally 1 hour at 200 ° C.
  • the sulfurized dodecylphenol is collected, the respective chlorine and sulfur contents of which are 2200 ppm and 11.4%.
  • Example 9 The procedure is as in Example 9, but 10 g of a cupric solution such as that prepared in Example B are introduced into the reaction medium just after the removal of the neutralized water from the sulfurized dodecylphenol. The rest of the procedure is identical to that of Example 9. 91 g of overbased sulfurized calcium dodecylphenate containing 1.1% copper and an alkaline value of 251 mg KOH / g are then recovered. The color of the product is blackish green and it is stable when diluted in base oils.
  • Example 2 The procedure is as in Example 1, but 78g (C14, C18-alkyl) salicylic acid, 9.49g of slaked lime, 37ml of methanol and 25g of diluent oil are introduced into the reactor. After neutralization and carbonation at 42 ° C with 1.9g of CO2, 7.5g of lime is added which is carbonated with 2.5g of CO2. A dark brown additive is collected which is stable in oils. Its calcium content is 7.6%, and its alkaline value 205mgKOH / g.
  • Example 11 The procedure is as in Example 11 but 10 g of the cupric solution of Example B are introduced after neutralization of the salicylic acid. The rest of the operations are identical to those of Example 11. 120 g of an overbased calcium alkylsalicylate containing 0.85% copper are then recovered. Its alkaline value is 201 mg KOH / g and it is stable when diluted in base oils.
  • Example 2 The procedure is as in Example 2, but 4 g of copper carboxylate are added to the reaction medium after carbonation. described in Example B. A slightly cloudy blue color mixture is obtained. Its alkaline value is 300mgKOH / g.
  • the performance of the additives is evaluated using an oxidation test.
  • the 30g samples of lubricant, containing variable amounts of additives, are heated at 165 ° C for 64 hours.
  • the oxidation is catalyzed by 40 ppm of iron in the form of acetylacetonate.
  • the temperature is brought back to 40 ° C., and the viscosity is compared to 40 ° C. before and after oxidation.
  • the increase in viscosity ( ⁇ V) is expressed as a percentage of the initial viscosity. The lower this percentage, the more effective the additive.
  • Tables 1 and 2 summarize the viscosity measurement results with two lubricant formulas A and B.
  • A mineral oil with 0.6% sulfur
  • B mineral oil with 0.6% sulfur 1% primary Zn dithiophosphate 3.3% dispersant.
  • the two tables show the pro-oxidant effect of overbased sulfonates.
  • the overbased sulfonates prepared according to Comparative Examples 1 and 2 lead to solidification, and the viscosity can no longer be measured.
  • the overbased phenates (comparative example 9) also increase the viscosity compared to the sample without additive, but their pro-oxidant effect is weaker.
  • Table 1 shows that the addition of additives according to the invention makes it possible to reduce or even eliminate the pro-oxidant effect of the overbased additives (Examples 5, 7 and 10). Additive 5 also containing boron is more effective than additive 7 containing only copper.
  • the additives according to the invention can be used in admixture with conventional overbased additives, provided that the copper content is at least 160 ppm: in fact the presence of 40 ppm of copper does not prevent solidification.
  • Table 2 shows that the pro-oxidant effect of the overbased additive is attenuated by the addition of an additive to copper (Example 7), on the other hand the addition of a conventional amino antioxidant does not prevent solidification of the sample.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
EP90402981A 1989-10-26 1990-10-23 Additif surbasé pour huiles lubrifiantes renfermant un dérivé du cuivre ou un dérivé du cuivre et du bore, son procédé de préparation et compositions renfermant ledit additif Expired - Lifetime EP0425367B1 (fr)

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FR8914053A FR2653780A1 (fr) 1989-10-26 1989-10-26 Additif surbase pour huiles lubrifiantes renfermant un derive du cuivre ou un derive du cuivre et du bore, son procede de preparation et compositions renfermant ledit additif .
FR8914053 1989-10-26

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EP0425367B1 true EP0425367B1 (fr) 1992-12-30

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JP (1) JPH03153794A (es)
DE (1) DE69000705T2 (es)
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FR (1) FR2653780A1 (es)

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AT400242B (de) * 1992-02-18 1995-11-27 Oemv Ag Additiv für unverbleite ottokraftstoffe, dessen herstellung und verwendung
GB9409756D0 (en) * 1994-05-16 1994-07-06 Exxon Chemical Patents Inc Lubricating compositions
JP3454593B2 (ja) * 1994-12-27 2003-10-06 旭電化工業株式会社 潤滑油組成物
US9487971B2 (en) 2013-03-15 2016-11-08 Spectrum Brands, Inc. Electro-mechanical locks with bezel turning function
EP3115443A1 (en) * 2015-07-07 2017-01-11 Ab Nanol Technologies Oy Organometallic salt composition, a method for its preparation and a lubricant additive composition
WO2019086178A1 (en) 2017-11-03 2019-05-09 Telefonaktiebolaget Lm Ericsson (Publ) Receiver, communication apparatus, method and computer program for receiving binary information

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FR1538885A (fr) * 1966-09-29 1968-09-06 Chevron Res Procédé perfectionné de préparation de dispersions de carbonates de métaux alcalinoterreux
US4659488A (en) * 1985-09-18 1987-04-21 The Lubrizol Corporation Metal working using lubricants containing basic alkaline earth metal salts
US4767551A (en) * 1985-12-02 1988-08-30 Amoco Corporation Metal-containing lubricant compositions
CA1290314C (en) * 1986-01-21 1991-10-08 David E. Ripple Lubricant composition containing transition metals for viscosity control
FR2612526B1 (fr) * 1987-03-17 1990-02-02 Elf France Procede de preparation d'un additif suralcanise renfermant un derive du bore, l'additif ainsi obtenue et compositions lubrifiantes renfermant ledit additif

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FR2653780A1 (fr) 1991-05-03
JPH03153794A (ja) 1991-07-01
DE69000705D1 (de) 1993-02-11
DE69000705T2 (de) 1993-06-24
ES2045856T3 (es) 1994-01-16

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