EP0438942A1 - Overbased detergents for lubricating oils containing a phosphorus organic derivative and lubricating compositions containing the same - Google Patents

Overbased detergents for lubricating oils containing a phosphorus organic derivative and lubricating compositions containing the same Download PDF

Info

Publication number
EP0438942A1
EP0438942A1 EP90403692A EP90403692A EP0438942A1 EP 0438942 A1 EP0438942 A1 EP 0438942A1 EP 90403692 A EP90403692 A EP 90403692A EP 90403692 A EP90403692 A EP 90403692A EP 0438942 A1 EP0438942 A1 EP 0438942A1
Authority
EP
European Patent Office
Prior art keywords
acid
phosphorus
derivative
detergent
detergent according
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.)
Granted
Application number
EP90403692A
Other languages
German (de)
French (fr)
Other versions
EP0438942B1 (en
Inventor
Jean-Philippe Roman
Pierre Hoornaert
Anne-Christine Barbier
Christian Rodes
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.)
Societe National Elf Aquitaine
Original Assignee
Societe National Elf Aquitaine
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 Societe National Elf Aquitaine filed Critical Societe National Elf Aquitaine
Publication of EP0438942A1 publication Critical patent/EP0438942A1/en
Application granted granted Critical
Publication of EP0438942B1 publication Critical patent/EP0438942B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or 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
    • 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
    • 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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • 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
    • 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
    • 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
    • C10M2223/042—Metal 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
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • 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
    • C10M2223/061—Metal 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
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/063—Ammonium or amine 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
    • C10M2223/06—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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041—Hydrocarbon polymers
    • 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 detergents for lubricating oils containing an organic phosphorus derivative.
  • Overbased detergents are alkali or alkaline earth metal salts of organic acids overbased by carbonation with carbon dioxide.
  • overbased is used to denote the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the acid.
  • overbased detergents is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation. Micelles are stabilized by alkaline or alkaline earth salts of detergents.
  • overbased detergents are particularly useful in the lubricants used in internal combustion engines of the "gasoline” or “diesel” type, whether they are land or marine engines.
  • Overbased detergents also improve the resistance to oxidation of the oils in which they are incorporated. This function is particularly important for lubricant formulations subjected to severe thermal constraints, such as for example in highly supercharged diesel engines.
  • Overbased detergents are characterized by their alkaline value (VA) expressed in mg of KOH per gram of product.
  • lubricant formulations including, inter alia, overbased detergents and metal salts and more particularly the zinc salt of dialkyldithiophosphoric acid, exist. They are suitable for a large number of applications, for example relating to transmission fluids (WO 88-08874-A), lubricants for land petrol engines or for diesel engines (EP-A 225580, US 4664822, US 4525288, US 4704217), lubricants for marine engines (US 4681694) or hydraulic fluids (US 3899432).
  • the invention therefore relates to an overbased detergent for lubricating oils obtained by carbonation of a mixture containing a detergent chosen from alkali or alkaline earth sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates, a derivative of an alkali or alkaline earth metal chosen from oxides , hydroxides or alcoholates, a nitrogenous and / or oxygenated promoter, a hydrocarbon solvent and optionally a diluent oil and water, characterized in that the mixture contains at least 3% by weight of phosphorus in the form of a non-metallic organic derivative.
  • a detergent chosen from alkali or alkaline earth sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates
  • a derivative of an alkali or alkaline earth metal chosen from oxides , hydroxides or alcoholates
  • a nitrogenous and / or oxygenated promoter a hydrocarbon solvent and optionally a
  • the overbased detergents according to the invention contain 0.5 to 10% and preferably 1 to 5% by weight of phosphorus. They have greatly improved antiwear and antioxidant properties, while retaining detergency, dispersion and neutralization properties of acidic, unaltered compounds.
  • the antiwear and antioxidant power can be further improved by the addition of zinc dithiophosphate (DTPZ).
  • DTPZ zinc dithiophosphate
  • DTPZ is effective at very low concentrations, which results in a notable reduction in the corrosive nature of the formulations.
  • the non-metallic organic derivatives of phosphorus are chosen from phosphites, phosphoramides, derivatives of phosphoric, thiophosphoric, dithiophosphoric, trithiophosphoric, tetrathiophos-phoric acids and their organic salts.
  • Use is more particularly made of phosphosulphurous derivatives such as thiophosphoric or dithiophosphoric acids and their organic salts and preferably derivatives of dithiophosphoric acids and their organic salts.
  • dihydrocarbyldithio-phosphoric acids of general formula are generally used where R and R ′, identical or different, represent linear or branched C Problems to C20 alkyl chains, aliphatic or aromatic rings.
  • diethyldithiophosphoric acid diisopropyldithiophosphoric acid, dicyclohexyldithiophosphhoric acid or dicrésyldithiophosphoric acid.
  • the methods of the prior art made it possible to incorporate into the overbased detergents only the oil-soluble phosphorus derivatives.
  • the process of the invention allows the incorporation of both oil-soluble derivatives and of derivatives insoluble in oils. It is particularly advantageous not to be limited in the choice of the phosphorus derivative.
  • the dihydrocarbyldithiophosphoric acids of general formula (I) can be prepared by the action of phosphorus pentasulfide on an alcohol or phenol of general formula R-OH or a mixture of alcohols or phenols of formula R-OH and R′-OH.
  • the molar ratio of phosphorus pentasulfide to alcohol or phenol must be at least 1 to 4.
  • the reaction can be carried out at a temperature between 40 and 200 ° C, this depending on the type of alcohol or phenol selected.
  • dialkyldithiophosphoric acids The methods of preparation of dialkyldithiophosphoric acids are described in American patents 3089850, 3101096, 3293181 and 3489682.
  • the detergents are chosen from sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates of alkali or alkaline-earth metal.
  • the reaction medium can contain the precursors. In this case, neutralization is carried out in the reaction medium before carbonation.
  • Sulfonates are obtained from sulfonic acids of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum.
  • 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 structure of 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 an oxide or hydroxide, in a hydrocarbon solvent, optionally in the presence of an alcohol.
  • 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 and 2500.
  • alkali or alkaline earth metal derivatives oxides, hydroxides or alcoholates are used.
  • the preferred derivatives are oxides and hydroxides.
  • the reaction medium is added to stoichiometric excess relative to the phenolic compound.
  • the stoichiometric excess can vary between 5: 1 and 30: 1.
  • the oxygenated promoter is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
  • C al to C20 aliphatic alcohols or their mixtures are preferably used.
  • the aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
  • the molar ratio of the oxygenated promoter to the phenolic compound is generally between 1 and 30.
  • the use of a nitrogenous promoter is optional.
  • the nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary C2 to C10 amines and their salts, polyamines or alkanolamines as well as nitro mineral compounds.
  • ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine, as well as calcium nitrate are preferred.
  • the molar ratio of the nitrogenous promoter to the phenolic compound is generally between 0.05 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 generally represents 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 compounds and water.
  • the handling of overbased detergents is facilitated by the addition of a diluting 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 solvents.
  • the diluting 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.
  • a detergent precursor and a salt of an organic phosphorus compound are used, it is preferable to successively introduce the precursor, the salt and finally the excess of alkali or alkaline earth metal derivative.
  • the phosphorus concentration of the reaction medium must be greater than or equal to 3% by weight.
  • the stoichiometric excess of alkali or alkaline earth metal is then carbonated at a temperature between room temperature and the reflux temperature of the mixture and more particularly at a temperature between room temperature and 50 ° C. and preferably at a temperature between 30 ° C and 45 ° C.
  • the molar ratio of carbon dioxide 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 the carbonation reaction. Solid residues are removed, generally by centrifugation and / or filtration using diatomaceous earth.
  • the diluent oil has not been added before carbonation, it is then added before the elimination of the hydrocarbon solvent and possibly the alcohol. The latter are removed 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 overbased detergents according to the invention are clear and stable.
  • the color is variable depending on the detergent used.
  • the overbased sulfonates are, for example, brown-green in color, the salicylates are dark brown in color.
  • the overbased detergents according to the invention are fully compatible with hydrocarbons.
  • lubricating oils of natural or synthetic origin are incorporated into lubricating oils of natural or synthetic origin at a concentration of between approximately 0.5 and 40% by weight and preferably between 1 and 30% by weight.
  • the lubricant compositions thus obtained may contain other additives, with antiwear, dispersant, antioxidant effect and polymers improving the viscosity index.
  • the basicity of overbased detergents is characterized by their alkaline value (VA) expressed in mg KOH / g of product.
  • VA alkaline value
  • the solution is cooled and filtered on a 0.22 ⁇ m Millipore filter, then the solvent evaporated.
  • Example A The procedure is as in Example A, except that 220.8 g of anhydrous ethanol are used in place of methanol. 211 g of diethyldithiophosphoric acid at 95% purity are recovered.
  • Example A The procedure is as in Example A except that 288 g of isopropyl alcohol are used.
  • Example A The procedure is as in Example A except that 400 ml of toluene is used in place of carbon tetrachloride, 66.7 g of P2S5 and 259.2 g of para-cresol.
  • the methanol and the water produced by the reaction are removed by heating the mixture under partial vacuum.
  • the medium is clarified using 2% by weight of Diatomées Clarcel DICS from CECA SA.
  • the product is brown, clear 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 108g.
  • Example 1 The procedure is as in Example 1 except that 40 ml of methanol are introduced instead of 80 ml, and that 24 g of the product of Example A are introduced after neutralization of the sulfonic acid.
  • Example 2 The procedure is as in Example 2, but 48 g of the product of Example A are introduced after neutralization of the sulfonic acid.
  • Example 2 The procedure is as in Example 1 except that 120 ml of methanol are introduced instead of 80 ml, and that 67.5 g of the product of Example B are introduced after neutralization of the sulfonic acid.
  • Example 1 The procedure is as in Example 1 except that 29.3 g of ammonium diethyldithiophosphate at 95% purity (JANSSEN CHIMICA) are introduced just after the sulfonic acid. The rest of the procedure is identical to that of Example 1.
  • a product of VA 330, stable in dilution in oil, is collected, the calcium and phosphorus contents of which are 13% and 1.2% respectively.
  • Example 2 The procedure is as in Example 2, but 67.5 g of the product of Example B are introduced after neutralization of the sulfonic acid.
  • Example 2 The procedure is as in Example 2, but 197.3 g of sulfonic acid are introduced instead of 219.2 g. On the other hand, 44g of 95% purity ammonium diethyldithiophosphate (JANSSEN CHIMICA) are added immediately after the sulfonic acid. The rest of the procedure in Example 2 is not changed.
  • JANSSEN CHIMICA 95% purity ammonium diethyldithiophosphate
  • Example 2 The procedure is as in Example 1, but 48 g of the product of Example C are introduced after neutralization of the sulfonic acid.
  • a product of VA 326, stable on dilution in oil, is collected, the calcium and phosphorus contents of which are 12.6 % and 1.5 % respectively.
  • Example 2 The procedure is as in Example 2, but 48 g of the product of Example C are introduced after neutralization of the sulfonic acid.
  • a product of VA 302, stable on dilution in oil, is recovered, the calcium and phosphorus contents of which are 11.8% and 1.6% respectively.
  • Example 1 The procedure is as in Example 1, but 76 g of the product of Example D are introduced after neutralization of the sulfonic acid.
  • a product of VA 303, stable when diluted in oil, whose calcium and phosphorus contents are 11.7% and 1.5% respectively, is collected.
  • Example 2 The procedure is as in Example 2, but 76 g of the product of Example D are introduced after neutralization of the sulfonic acid.
  • a product of VA 295, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 11.5% and 1.5% respectively.
  • Example 1 The procedure is as in Example 1, but 80 g of the product of Example E are introduced after neutralization of the sulfonic acid.
  • a product of VA 303, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 11.8% and 0.9% respectively.
  • Example 2 The procedure is as in Example 2, but 80 g of the product of Example E are introduced after neutralization of the sulfonic acid, except that 113.2 g of slaked lime are used instead of 108.4 g.
  • a product of VA 280, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 10.9% and 0.8% respectively.
  • Example 2 The procedure is as in Example 1, but is introduced into the reactor 312g of (C14-C18 alkyl) salicylic acid, 37.5g of slaked lime, 150ml of methanol and 100g of diluent oil.
  • test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other.
  • the products are first of all tested in a lubricant formulation of API-SG type for gasoline engine.
  • compositions of the same level of VA are established by substitution of the overbased detergent, and of the same phosphorus content, by subtracting from the initial quantity of zinc dithiophosphate (DTPZ) from the formulation, the amount of DTPZ, the phosphorus content of which corresponds to the phosphorus content provided by the organic phosphorus compound contained in the overbased detergent.
  • DTPZ zinc dithiophosphate
  • the formulations contain 1.4% of overbased detergent and their phosphorus content, supplied on the one hand by DTPZ and on the other hand by the organic compound of phosphorus in the overbased detergent, is 1.3%.
  • Table I gives some results showing that an overbased detergent containing an organic phosphorus compound has equivalent or improved antiwear power compared to the reference overbased detergent described in Example 1, or compared to a commercial overbased sulfonate.
  • the rating is obtained by determining the diameter of the imprint. This imprint diameter is all the smaller the greater the anti-wear power of the formulation.
  • Table II gives some results showing the beneficial effect of the use of overbased detergents containing an organic phosphorus compound on the anti-wear performance of the lubricant.
  • an oxidation test is carried out at 165 ° C under an air flow of 1.7 liters / minute for a period of 64 h and in the presence of an oxidation catalyst (iron acetylacetonate ). This test partially simulates the conditions to which oil can be subjected in a gasoline engine.
  • Table III gives the values of the variation in viscosity of the samples at the end of the 64 h of the test (increase in dynamic viscosity in%). The higher the viscosity, the lower the resistance of the lubricant to oxidation.
  • Overbased detergents containing an organic phosphorus compound have a significantly higher resistance to oxidation than the reference overbased detergents described in Examples 1 and 2.
  • ZF corrosion tests are carried out on the same lubricant formulations. According to the procedure, an iron plate and a copper plate are immersed for 24 hours in a sample containing 1% of water and maintained at 95 ° C.
  • Table IV gives the visual rating results and shows the beneficial effect of the overbased detergent containing an organic phosphorus compound. Lubricant formulations are less aggressive towards copper, because the DTPZ content is lower.
  • overbased detergents containing an organic phosphorus compound are then tested in a lubricant formulation for a marine engine (cylinder oil).
  • the basicity of the oil is 70mg KOH / g of which only 20gK0H / g provided by the overbased detergent.
  • Table V shows that the cylinder oil for marine engines formulated with the detergents according to the invention makes it possible to significantly reduce wear.

Landscapes

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

Abstract

Overbased detergent for lubricating oils, obtained by carbonation of a mixture containing a detergent chosen from alkali or alkaline-earth metal sulphonates, naphthenates, salicylates, phosphonates and thiophosphonates, an alkali or alkaline-earth metal oxide, hydroxide or alcoholate, a nitrogenous and/or oxygen-containing promoter, at least 3 % by weight of phosphorus in the form of a nonmetallic organic derivative, a hydrocarbon solvent and optionally a diluent oil and water. These detergents contain 0.5 to 10 % and preferably 1 to 5 % by weight of phosphorus. They have greatly improved antiwear and antioxidant properties.

Description

Cette invention concerne des détergents surbasés pour huiles lubrifiantes renfermant un dérivé organique du phosphore.This invention relates to overbased detergents for lubricating oils containing an organic phosphorus derivative.

Les détergents surbasés sont des sels de métaux alcalins ou alcalinoterreux d'acides organiques surbasés par carbonatation avec l'anhydride carbonique. Le terme surbasé est utilisé pour désigner l'excès de métal alcalin ou alcalinoterreux par rapport à la quantité stoechiométrique nécessaire pour neutraliser l'acide.Overbased detergents are alkali or alkaline earth metal salts of organic acids overbased by carbonation with carbon dioxide. The term overbased is used to denote the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the acid.

La structure des détergents surbasés est celle d'une dispersion colloïdale dont les micelles renferment le carbonate de métal alcalin ou alcalinoterreux formé lors de la carbonatation. Les micelles sont stabilisées par les sels alcalins ou alcalinoterreux des détergents.The structure of overbased detergents is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation. Micelles are stabilized by alkaline or alkaline earth salts of detergents.

Ces détergents surbasés sont particulièrement utiles dans les lubrifiants utilisés dans les moteurs à combustion interne du type "essence" ou "diesel" qu'il s'agisse de moteurs terrestres ou marins.These overbased detergents are particularly useful in the lubricants used in internal combustion engines of the "gasoline" or "diesel" type, whether they are land or marine engines.

Grâce à leur effet détergent et dispersant ils empêchent la formation de laques et de vernis sur les pistons, et maintiennent en dispersion les suies issues de la combustion incomplète du carburant.Thanks to their detergent and dispersant effect, they prevent the formation of lacquers and varnishes on the pistons, and keep the soot from the incomplete combustion of the fuel in dispersion.

Une autre fonction importante de ces additifs est la neutralisation des composés acides issus de l'oxydation de l'huile ou de la combustion des produits soufrés apportés par le combustible. Cette fonction est particulièrement appréciée lors de l'utilisation de combustibles riches en soufre comme par exemple les fuels lourds utilisés dans les moteurs marins.Another important function of these additives is the neutralization of the acidic compounds resulting from the oxidation of the oil or from the combustion of the sulfur products supplied by the fuel. This function is particularly appreciated when using fuels rich in sulfur such as for example heavy fuels used in marine engines.

Les détergents surbasés améliorent en outre la résistance à l'oxydation des huiles auxquelles ils sont incorporés. Cette fonction est particulièrement importante pour les formulations lubrifiantes soumises à des contraintes thermiques sévères, comme par exemple dans les moteurs diesels fortement suralimentés.Overbased detergents also improve the resistance to oxidation of the oils in which they are incorporated. This function is particularly important for lubricant formulations subjected to severe thermal constraints, such as for example in highly supercharged diesel engines.

Les détergents surbasés sont caractérisés par leur valeur alcaline (VA) exprimée en mg de KOH par gramme de produit.Overbased detergents are characterized by their alkaline value (VA) expressed in mg of KOH per gram of product.

Elle est déterminée par titration à l'aide d'un acide fort selon la norme ASTM D-2896. Une réserve d'alcalinité importante se traduit par une VA élevée.It is determined by titration using a strong acid according to standard ASTM D-2896. A high alkalinity reserve results in a high VA.

Il est connu par ailleurs d'utiliser dans les lubrifiants des mélanges de détergents surbasés et d'additifs phosphorés ou phosphosoufrés. Ces derniers apportent des propriétés antiusure et antioxydantes. Les plus couramment utilisés sont les sels métalliques de l'acide dithiophosphorique et plus particulièrement le sel de zinc de l'acide dialkyldithiophosphorique.It is also known to use in lubricants mixtures of overbased detergents and phosphorus or phosphosulfur additives. These provide antiwear and antioxidant properties. The most commonly used are the metal salts of dithiophosphoric acid and more particularly the zinc salt of dialkyldithiophosphoric acid.

De nombreuses formulations lubrifiantes comprenant entre autres, des détergents surbasés et les sels métalliques et plus particulièrement le sel de zinc de l'acide dialkyldithiophosphorique, existent. Elles conviennent pour un grand nombre d'applications, concernant par exemple les fluides de transmission (WO 88-08874-A), les lubrifiants pour moteurs terrestres à essence ou pour les moteurs diesel (EP-A 225580, US 4664822, US 4525288, US 4704217), les lubrifiants pour moteurs marins (US 4681694) ou les fluides hydrauliques (US 3899432).Numerous lubricant formulations including, inter alia, overbased detergents and metal salts and more particularly the zinc salt of dialkyldithiophosphoric acid, exist. They are suitable for a large number of applications, for example relating to transmission fluids (WO 88-08874-A), lubricants for land petrol engines or for diesel engines (EP-A 225580, US 4664822, US 4525288, US 4704217), lubricants for marine engines (US 4681694) or hydraulic fluids (US 3899432).

Néanmoins, il s'avère que des interactions négatives peuvent exister entre les détergents surbasés et les dérivés organiques du phosphore, et notamment le sel de zinc de l'acide dialkyldithiophosphorique. La compétition, lors de l'adsorption sur les surfaces métalliques à lubrifier, entre les détergents surbasés et les sels de zinc ou des réactions entre ces deux additifs dans le volume du lubrifiant peuvent entraîner une diminution importante des propriétés antioxydantes et antiusure.Nevertheless, it turns out that negative interactions can exist between overbased detergents and organic phosphorus derivatives, and in particular the zinc salt of dialkyldithiophosphoric acid. Competition, during adsorption on metallic surfaces to be lubricated, between overbased detergents and zinc salts or reactions between these two additives in the volume of the lubricant can lead to a significant decrease in antioxidant and antiwear properties.

Nous avons trouvé maintenant qu'en effectuant le surbasage des détergents en présence d'un composé organique non-métallique du phosphore, il y a incorporation du phosphore dans la micelle, renfermant par ailleurs le carbonate de métal alcalin ou alcalinoterreux. Ainsi les interactions négatives entre les phénates surbasés et les dérivés organiques du phosphore sont évitées.We have now found that by overbasing detergents in the presence of a non-metallic organic phosphorus compound, phosphorus is incorporated into the micelle, which also contains the alkali metal or alkaline earth carbonate. Thus negative interactions between overbased phenates and organic phosphorus derivatives are avoided.

L'invention concerne donc un détergent surbasé pour huiles lubrifiantes obtenu par carbonatation d'un mélange renfermant un détergent choisi parmi les sulfonates, naphténates, salicylates, phosphonates et thiophosphonates alcalins ou alcalinoterreux, un dérivé d'un métal alcalin ou alcalinoterreux choisi parmi les oxydes, les hydroxydes ou alcoolates, un promoteur azoté et/ou oxygéné, un solvant hydrocarboné et éventuellement une huile diluante et de l'eau, caractérisé en ce que le mélange renferme au moins 3% poids de phosphore sous forme de dérivé organique non métallique.The invention therefore relates to an overbased detergent for lubricating oils obtained by carbonation of a mixture containing a detergent chosen from alkali or alkaline earth sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates, a derivative of an alkali or alkaline earth metal chosen from oxides , hydroxides or alcoholates, a nitrogenous and / or oxygenated promoter, a hydrocarbon solvent and optionally a diluent oil and water, characterized in that the mixture contains at least 3% by weight of phosphorus in the form of a non-metallic organic derivative.

Les détergents surbasés selon l'invention renferment 0,5 à 10% et de préférence 1 à 5% poids de phosphore. Ils ont des propriétés antiusure et antioxydantes grandement améliorées, tout en conservant des propriétés de détergence, de dispersion et de neutralisation des composés acides, inaltérées.The overbased detergents according to the invention contain 0.5 to 10% and preferably 1 to 5% by weight of phosphorus. They have greatly improved antiwear and antioxidant properties, while retaining detergency, dispersion and neutralization properties of acidic, unaltered compounds.

Le pouvoir antiusure et antioxydant peut être encore amélioré par l'addition de dithiophosphate de zinc (DTPZ). Dans ce cas, le DTPZ est efficace à de très faibles concentrations, ce qui résulte dans une diminution notable du caractère corrosif des formulations.The antiwear and antioxidant power can be further improved by the addition of zinc dithiophosphate (DTPZ). In this case, DTPZ is effective at very low concentrations, which results in a notable reduction in the corrosive nature of the formulations.

Les dérivés organiques non-métalliques du phosphore sont choisis parmi les phosphites, phosphoramides, les dérivés des acides phosphoriques, thiophosphoriques, dithiophosphoriques, trithiophosphoriques,tetrathiophos-phoriques et leurs sels organiques.The non-metallic organic derivatives of phosphorus are chosen from phosphites, phosphoramides, derivatives of phosphoric, thiophosphoric, dithiophosphoric, trithiophosphoric, tetrathiophos-phoric acids and their organic salts.

On utilise plus particulièrement les dérivés phosphosoufrés comme les acides thiophosphoriques ou dithiophosphoriques et leurs sels organiques et de préférence les dérivés d'acides dithiophosphoriques et leurs sels organiques.Use is more particularly made of phosphosulphurous derivatives such as thiophosphoric or dithiophosphoric acids and their organic salts and preferably derivatives of dithiophosphoric acids and their organic salts.

Parmi les dérivés d'acides dithiophosphoriques on utilise en général les acides dihydrocarbyldithio-phosphoriques, de formule générale

Figure imgb0001

où R et R′ identiques ou différents représentent des chaînes alkyles linéaires ou ramifiées en C₁ à C₂₀, les cycles aliphatiques ou aromatiques.Among the derivatives of dithiophosphoric acids, dihydrocarbyldithio-phosphoric acids of general formula are generally used
Figure imgb0001
where R and R ′, identical or different, represent linear or branched C chaînes to C₂₀ alkyl chains, aliphatic or aromatic rings.

Parmi ces dérivés nous pouvons mentionner l'acide diéthyldithiophosphorique, l'acide diisopropyldithiophosphorique, l'acide dicyclohexyldithiophosphhorique ou l'acide dicrésyldithiophosphorique.Among these derivatives we can mention diethyldithiophosphoric acid, diisopropyldithiophosphoric acid, dicyclohexyldithiophosphhoric acid or dicrésyldithiophosphoric acid.

Il est particulièrement avantageux d'utiliser les composés de formule générale (I) insolubles dans les huiles. Ces composés présentent en plus du pouvoir antioxydant et antiusure, un effet tensioactif. Ainsi ils participent comme cotensioactifs à la stabilisation des micelles.It is particularly advantageous to use the compounds of general formula (I) insoluble in oils. These compounds have, in addition to the antioxidant and anti-wear power, a surfactant effect. Thus they participate as co-surfactants in the stabilization of the micelles.

Les procédés de l'art antérieur ne permettaient d'incorporer dans les détergents surbasés que les dérivés oléosolubles du phosphore. Le procédé de l'invention permet l'incorporation aussi bien de dérivés oléosolubles que de dérivés insolubles dans les huiles. Il est particulièrement intéressant de ne pas être limité dans le choix du dérivé du phosphore.The methods of the prior art made it possible to incorporate into the overbased detergents only the oil-soluble phosphorus derivatives. The process of the invention allows the incorporation of both oil-soluble derivatives and of derivatives insoluble in oils. It is particularly advantageous not to be limited in the choice of the phosphorus derivative.

Les acides dihydrocarbyldithiophosphoriques de formule générale (I) peuvent être préparés par l'action du pentasulfure de phosphore sur un alcool ou phénol de formule générale R-OH ou un mélange d'alcools ou phénols de formule R-OH et R′-OH.The dihydrocarbyldithiophosphoric acids of general formula (I) can be prepared by the action of phosphorus pentasulfide on an alcohol or phenol of general formula R-OH or a mixture of alcohols or phenols of formula R-OH and R′-OH.

Le rapport molaire du pentasulfure de phosphore à l'alcool ou phénol doit être au moins de 1 pour 4. La réaction peut être réalisée à une température comprise entre 40 et 200°C, celle-ci dépendant du type d'alcool ou de phénol choisi.The molar ratio of phosphorus pentasulfide to alcohol or phenol must be at least 1 to 4. The reaction can be carried out at a temperature between 40 and 200 ° C, this depending on the type of alcohol or phenol selected.

Les méthodes de préparation des acides dialkyldithiophosphoriques sont décrites dans les brevets américains 3089850, 3101096, 3293181 et 3489682.The methods of preparation of dialkyldithiophosphoric acids are described in American patents 3089850, 3101096, 3293181 and 3489682.

Les détergents sont choisis parmi les sulfonates, naphténates, salicylates, phosphonates et thiophosphonates de métal alcalin ou alcalinoterreux. A la place des détergents, le milieu réactionnel peut renfermer les précurseurs. Dans ce cas la neutralisation est réalisée dans le milieu réactionnel avant carbonatation.The detergents are chosen from sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates of alkali or alkaline-earth metal. Instead of detergents, the reaction medium can contain the precursors. In this case, neutralization is carried out in the reaction medium before carbonation.

Les sulfonates sont obtenus à partir d'acides sulfoniques d'origine pétrolière ou synthétique. Les acides sulfoniques pétroliers sont préparés par sulfonation d'huiles issues de la distillation du pétrole.Sulfonates are obtained from sulfonic acids of petroleum or synthetic origin. Petroleum sulfonic acids are prepared by sulfonation of oils from the distillation of petroleum.

Leur structure ne correspond pas à une formule bien définie, mais leur poids moléculaire moyen doit être au moins égal à 300.Their structure does not correspond to a well defined formula, but their average molecular weight must be at least equal to 300.

Les acides sulfoniques synthétiques sont préparés par alkylation de composés aromatiques comme le benzène, toluène, xylène ou naphtalène avec des coupes oléfiniques puis par sulfonation de l'alkylat obtenu. La structure des chaînes alkyles fixées sur le noyau est linéaire ou ramifiée, selon la structure des oléfines utilisées pour l'alkylation. Le nombre d'atomes de carbone par chaîne alkyle est supérieur ou égal à 8.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. The structure of the alkyl chains attached to the nucleus is linear or branched, depending on the structure of the olefins used for the alkylation. The number of carbon atoms per alkyl chain is greater than or equal to 8.

La préparation du sulfonate de métal alcalin ou alcalinoterreux est réalisée par mise en contact de l'acide sulfonique avec un dérivé de métal alcalin ou alcalinoterreux, de préférence un oxyde ou hydroxyde, dans un solvant hydrocarboné, éventuellement en présence d'un alcool.
Les acides alkylsalicyliques sont préparés par alkylation de l'acide salicylique ou par carboxylation sous pression des alkylphénols. La chaîne alkyle contient un minimum de 12 atomes de carbone.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 an oxide or hydroxide, in a hydrocarbon solvent, optionally in the presence of an alcohol.
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.

Les phosphonates et thiophosphonates sont préparés par action de P₂O₅ ou P₂S₅ sur un polyisobutène, puis neutralisation par un oxyde ou hydroxyde alcalin ou alcalinoterreux. Le poids moléculaire du polyisobutène est compris entre 300 et 2000.
Tous ces détergents peuvent être utilisés en mélange avec des dispersants solubles en milieu hydrocarboné, par exemple du type alkylsuccinimide ou esters d'acides alkylsucciniques de poids moléculaire de 300 et 2500.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 and 2500.

Parmi les dérivés de métal alcalin ou alcalinoterreux on utilise les oxydes, hydroxydes ou alcoolates. Les dérivés préférés sont les oxydes et hydroxydes.Among the alkali or alkaline earth metal derivatives, oxides, hydroxides or alcoholates are used. The preferred derivatives are oxides and hydroxides.

Ceux-ci sont ajoutés au milieu réactionnel en excès stoechiométrique par rapport au composé phénolique. L'excès stoechiométrique peut varier entre 5: 1 et 30: 1.These are added to the reaction medium in stoichiometric excess relative to the phenolic compound. The stoichiometric excess can vary between 5: 1 and 30: 1.

Le promoteur oxygéné est généralement un alcool aliphatique ou aromatique, un alkoxyalcanol, un glycol ou encore une alcanolamine. On utilise de préférence les alcools aliphatiques en C₁ à C₂₀ ou leurs mélanges. Les alcools aliphatiques peuvent être utilisés en mélange avec des glycols, des alkoxyalcanols ou des alcanolamines.The oxygenated promoter is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine. C al to C₂₀ aliphatic alcohols or their mixtures are preferably used. The aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.

Le rapport molaire du promoteur oxygéné au composé phénolique est généralement compris entre 1 et 30.The molar ratio of the oxygenated promoter to the phenolic compound is generally between 1 and 30.

L'utilisation d'un promoteur azoté est facultative. Le promoteur azoté est généralement choisi parmi l'ammoniaque, les sels d'ammonium, les amines primaires, secondaires ou tertiaires en C₂ à C₁₀ et leurs sels, les polyamines ou alcanolamines ainsi que les composés minéraux nitrés.The use of a nitrogenous promoter is optional. The nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary C₂ to C₁₀ amines and their salts, polyamines or alkanolamines as well as nitro mineral compounds.

Parmi les promoteurs azotés on préfère l'ammoniaque, le carbonate et le chlorure d'ammonium, l'éthylènediamine, l'éthanolamine ou la diéthanolamine, ainsi que le nitrate de calcium.Among the nitrogenous promoters, ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine, as well as calcium nitrate are preferred.

Le rapport molaire du promoteur azoté au composé phénolique est généralement compris entre 0,05 et 30.The molar ratio of the nitrogenous promoter to the phenolic compound is generally between 0.05 and 30.

Le solvant hydrocarboné permet une homogénéisation parfaite des différents réactifs ainsi qu'un abaissement de la viscosité, ce qui facilitera ultérieurement la récupération des résidus solides de carbonatation. Le solvant représente en général 10 à 70% en poids du mélange réactionnel. Les solvants utilisés sont les composés aliphatiques ou aromatiques en C₆ à C₁₂. Les solvants préférés sont les solvants aromatiques, comme le benzène, toluène, xylène, éthylbenzène et les aromatiques chlorés. Leur choix est dicté par les caractéristiques de l'additif recueilli, par leur point d'ébullition et par le point d'ébullition des azéotropes qu'ils peuvent former avec les composés oxygénés et l'eau.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 generally represents 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 compounds and water.

La manipulation des détergents surbasés est facilitée par l'addition d'une huile diluante. L'huile représente environ 20 à 50% poids de l'additif obtenu. Celle-ci peut être ajoutée au milieu réactionnel avant la carbonatation ou encore après celle-ci, c'est-à-dire juste avant l'élimination des solvants. Les huiles diluantes utilisées sont de nature paraffinique, du type 100 ou 150 Neutral Solvant on de nature majoritairement naphténique telle que la 100-150 Pale Solvant.The handling of overbased detergents is facilitated by the addition of a diluting 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 solvents. The diluting 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.

La réaction de carbonatation peut-être réalisée après addition éventuelle d'eau au milieu réactionnel. L'addition d'eau s'avère particulièrement bénéfique lorsque le dérivé de métal alcalin ou alcalinoterreux est un oxyde.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.

Généralement la quantité d'eau ajoutée est telle que le rapport molaire eau/oxyde de métal soit de l'ordre de 5. Plus en détail, le procédé d'obtention des détergents surbasés consiste à:

  • a, neutraliser le détergent par un dérivé de métal alcalin ou alcalinoterreux, en présence d'un promoteur azoté et/ou oxygéné, un solvant hydrocarboné et éventuellement une huile diluante et de l'eau,
  • b, ajouter un dérivé organique non-métallique du phosphore, et mieux un dérivé phosphosoufré, puis carbonater le mélange par l'anhydride carbonique gazeux pendant un temps suffisant pour consommer en partie ou en totalité l'excès de métal alcalin ou alcalinoterreux,
  • c, éliminer les résidus solides ainsi que les solvants. Une mise en oeuvre préférentielle du procédé consiste à introduire successivement dans un réacteur équipé d'un agitateur, d'une régulation de température, d'un système de chauffage et de mise sous vide:
    • 0 à 700 parties poids d'un solvant hydrocarboné,
    • 100 à 400 parties poids d'un détergent ou d'un précurseur de détergent,
    • un dérivé de métal alcalin ou alcalinoterreux en excès stoechiométrique par rapport au détergent ou son précurseur
Cet excès stoechiométrique est compris entre 5: 1 et 30: 1,
  • un promoteur oxygéné dont le rapport molaire au détergent est compris entre 1 et 30,
  • éventuellement un promoteur azoté dont le rapport molaire au détergent est compris entre 0,05 et 30,
  • éventuellement une quantité d'eau telle que le rapport molaire eau/oxyde de métal alcalin ou alcalinoterreux soit de l'ordre de 0,5,
  • une huile diluante en quantité telle que celle-ci représente 20 à 50% en poids de l'additif récupéré à la fin des opérations,
  • un des composés organiques du phosphore décrit précédemment.
Generally the amount of water added is such that the water / metal oxide molar ratio is of the order of 5. In more detail, the process for obtaining overbased detergents consists in:
  • a, neutralize the detergent with an alkali or alkaline earth metal derivative, in the presence of a nitrogenous and / or oxygenated promoter, a hydrocarbon solvent and optionally a diluent oil and water,
  • b, add a non-metallic organic derivative of phosphorus, and better still a phosphosulfur derivative, then carbonate the mixture with gaseous carbon dioxide for a time sufficient to consume in part or in whole the excess of alkali or alkaline-earth metal,
  • c, remove solid residues and solvents. A preferred implementation of the process consists in successively introducing into a reactor equipped with an agitator, a temperature control, a heating and vacuum system:
    • 0 to 700 parts by weight of a hydrocarbon solvent,
    • 100 to 400 parts by weight of a detergent or a detergent precursor,
    • an alkali or alkaline earth metal derivative in stoichiometric excess relative to the detergent or its precursor
This stoichiometric excess is between 5: 1 and 30: 1,
  • an oxygenated promoter whose molar ratio to detergent is between 1 and 30,
  • optionally a nitrogenous promoter whose molar ratio to detergent is between 0.05 and 30,
  • optionally an amount of water such that the water / alkali or alkaline earth metal molar ratio is of the order of 0.5,
  • a diluent oil in quantity such as this represents 20 to 50% by weight of the additive recovered at the end of the operations,
  • one of the organic phosphorus compounds described above.

Dans le cas où l'on utilise un précurseur de détergent et un composé organique phosphoré acide, il est préférable de réaliser la neutralisation du précurseur par l'excès de dérivé de métal alcalin ou alcalinoterreux avant d'introduire le composé organique phosphoré acide.In the case where a detergent precursor and an acid phosphorus organic compound are used, it is preferable to neutralize the precursor by the excess of alkali or alkaline earth metal derivative before introducing the acid phosphorus organic compound.

Dans le cas où l'on utilise un précurseur de détergent et un sel d'un composé organique du phosphore, il est préférable d'introduire successivement le précurseur, le sel et enfin l'excès de dérivé de métal alcalin ou alcalinoterreux.
La concentration en phosphore du milieu réactionnel doit être supérieure ou égale à 3% poids.In the case where a detergent precursor and a salt of an organic phosphorus compound are used, it is preferable to successively introduce the precursor, the salt and finally the excess of alkali or alkaline earth metal derivative.
The phosphorus concentration of the reaction medium must be greater than or equal to 3% by weight.

On procède alors à la carbonatation de l'excès stoechiométrique de métal alcalin ou alcalinoterreux à une température comprise entre la température ambiante et la température de reflux du mélange et plus particulièrement à une température comprise entre la température ambiante et 50°C et préférentiellement à une température comprise entre 30°C et 45°C.The stoichiometric excess of alkali or alkaline earth metal is then carbonated at a temperature between room temperature and the reflux temperature of the mixture and more particularly at a temperature between room temperature and 50 ° C. and preferably at a temperature between 30 ° C and 45 ° C.

Le rapport molaire du gaz carbonique introduit à l'excès stoechiométrique de métal alcalin ou alcalinoterreux est compris entre 0,6 et 1,2. Le mélange est éventuellement stabilisé par chauffage sous vide ou sous courant d'azote, de façon à éliminer les promoteurs oxygénés de bas point d'ébullition et l'eau ajoutée, ainsi que l'eau produite par la réaction de carbonatation. Les résidus solides sont éliminés, en général par centrifugation et/ou filtration à l'aide de terre à diatomées.The molar ratio of carbon dioxide 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 the carbonation reaction. Solid residues are removed, generally by centrifugation and / or filtration using diatomaceous earth.

Si l'huile diluante n'a pas été ajoutée avant carbonatation, elle est alors ajoutée avant l'élimination du solvant hydrocarboné et éventuellement l'alcool. Ces derniers sont éliminés par chauffage sous vide à des températures de l'ordre de 100 à 200°C.If the diluent oil has not been added before carbonation, it is then added before the elimination of the hydrocarbon solvent and possibly the alcohol. The latter are removed by heating under vacuum at temperatures of the order of 100 to 200 ° C.

Il faut remarquer que l'opération de filtration peut être réalisée après récupération du solvant.It should be noted that the filtration operation can be carried out after recovery of the solvent.

Les détergents surbasés selon l'invention sont limpides et stables. La couleur est variable en fonction du détergent utilisé. Les sulfonates surbasés sont par exemple de couleur brun-vert, les salicylates de couleur brun foncé.The overbased detergents according to the invention are clear and stable. The color is variable depending on the detergent used. The overbased sulfonates are, for example, brown-green in color, the salicylates are dark brown in color.

Les détergents surbasés selon l'invention sont entièrement compatibles avec les hydrocarbures.The overbased detergents according to the invention are fully compatible with hydrocarbons.

Ils sont incorporés aux huiles lubrifiantes d'origine naturelle ou synthétique à une concentration comprise entre environ 0,5 et 40% en poids et de préférence entre 1 et 30% en poids.They are incorporated into lubricating oils of natural or synthetic origin at a concentration of between approximately 0.5 and 40% by weight and preferably between 1 and 30% by weight.

Les compositions lubrifiantes ainsi obtenues peuvent renfermer d'autres additifs, à effet antiusure, dispersant, antioxydant et des polymères améliorant l'indice de viscosité.The lubricant compositions thus obtained may contain other additives, with antiwear, dispersant, antioxidant effect and polymers improving the viscosity index.

Les exemples ci-dessous illustrent l'invention sans toutefois la limiter.The examples below illustrate the invention without, however, limiting it.

Dans les exemples la basicité des détergents surbasés est caractérisée par leur valeur alcaline (VA) exprimée en mg KOH/g de produit. La VA est déterminée par titration à l'aide d'un acide fort selon la norme ASTM D-2896.In the examples, the basicity of overbased detergents is characterized by their alkaline value (VA) expressed in mg KOH / g of product. The VA is determined by titration using a strong acid according to standard ASTM D-2896.

Sauf indication contraire, tous les pourcentages sont en poids.Unless otherwise indicated, all percentages are by weight.

EXEMPLE AEXAMPLE A Préparation d'acide diméthyldithiophosphoriquePreparation of dimethyldithiophosphoric acid

Dans un réacteur de 1 litre muni d'un système d'agitation, d'une régulation de température, d'un réfrigérant et d'un système d'introduction des réactifs, couplé à un système de neutralisation des gaz acides, on met en suspension dans 600ml de tétrachlorure de carbone, 133,45g de pentasulfure de phosphore. La suspension est refroidie à 3°C et 153,6g de méthanol sont additionnés en 30 minutes, en maintenant la température inférieure à 5°C.In a 1 liter reactor fitted with a stirring system, a temperature control, a coolant and a system for introducing the reagents, coupled with an acid gas neutralization system, suspension in 600ml of carbon tetrachloride, 133.45g of phosphorus pentasulfide. The suspension is cooled to 3 ° C. and 153.6 g of methanol are added over 30 minutes, keeping the temperature below 5 ° C.

On additionne alors en 60 minutes et par portions, un excès d'environ 30% de méthanol par rapport à la stoechiométrie de la réaction. Le mélange est alors porté à reflux jusqu'à ce qu'il devienne parfaitement limpide.Then added in 60 minutes and in portions, an excess of about 30% methanol relative to the stoichiometry of the reaction. The mixture is then brought to reflux until it becomes perfectly clear.

La solution est refroidie et filtrée sur filtre Millipore de 0,22 µm, puis le solvant évaporé.The solution is cooled and filtered on a 0.22 μm Millipore filter, then the solvent evaporated.

On récupère 177,6g d'acide diméthyldithiophosphorique à 75,5% de pureté.177.6 g of dimethyldithiophosphoric acid at 75.5% purity are recovered.

EXEMPLE BEXAMPLE B Préparation d'acide diéthyldithiophosphoriquePreparation of diethyldithiophosphoric acid

On procède comme dans l'exemple A, à ceci près qu'on utilise 220,8g d'éthanol anhydre à la place du méthanol. On récupère 211g d'acide diéthyldithiophosphorique à 95% de pureté.The procedure is as in Example A, except that 220.8 g of anhydrous ethanol are used in place of methanol. 211 g of diethyldithiophosphoric acid at 95% purity are recovered.

EXEMPLE CEXAMPLE C Préparation d'acide diisopropyldithiophosphoriquePreparation of diisopropyldithiophosphoric acid

On procède comme dans l'exemple A à ceci près qu'on utilise 288g d'alcool isopropylique.The procedure is as in Example A except that 288 g of isopropyl alcohol are used.

On récupère 243g d'acide diisopropyldithiophosphorique à 80% de pureté.243 g of diisopropyldithiophosphoric acid at 80% purity are recovered.

EXEMPLE DEXAMPLE D Préparation d'acide dicyclohexyldithiophosphoriquePreparation of dicyclohexyldithiophosphoric acid

On procède comme dans l'exemple A à ceci près qu'on utilise 66,7g de P₂S₅ et 240g de cyclohexanol.The procedure is as in Example A except that 66.7g of P₂S₅ and 240g of cyclohexanol are used.

On récupère 209g d'acide dicyclohexyldithiophosphorique à 75% de pureté.209 g of dicyclohexyldithiophosphoric acid at 75% purity are recovered.

EXEMPLE EEXAMPLE E Préparation d'acide dicrésyldithiophosphoriquePreparation of dicresyldithiophosphoric acid

On procède comme dans l'exemple A à ceci près qu'on utilise 400ml de toluène à la place du tétrachlorure de carbone, 66,7g de P₂S₅ et 259,2g de para-crésol.The procedure is as in Example A except that 400 ml of toluene is used in place of carbon tetrachloride, 66.7 g of P₂S₅ and 259.2 g of para-cresol.

On récupère 401,2g d'acide dicrésyldithiophosphorique à 42% de pureté.401.2 g of dicrésyldithiophosphoric acid at 42% purity are recovered.

EXEMPLE 1: ComparatifEXAMPLE 1: Comparative

Dans un réacteur de 1 litre, équipé d'une régulation de température, d'un réfrigérant, d'un système d'agitation et d'un dispositif de barbotage de gaz, on introduit successivement:

  • 520 ml de toluène, 131,8g d'acide alkylxylènesulfonique à chaîne alkyle linéaire en C₁₆-C₁₈, de poids moléculaire 430 et à 96% de matière active, 168g d'huile diluante 100 Neutral solvent, 108,4g de chaux éteinte à 96% de pureté et 80ml de méthanol.
In a 1 liter reactor, equipped with a temperature control, a coolant, a stirring system and a gas bubbling device, are successively introduced:
  • 520 ml of toluene, 131.8 g of alkylxylenesulfonic acid with linear C₁₆-C₁₈ alkyl chain, of molecular weight 430 and with 96% of active ingredient, 168g of diluent oil 100 Neutral solvent, 108.4g of lime hydrated at 96 % purity and 80ml of methanol.

Après neutralisation de l'acide sulfonique par la chaux qui peut éventuellement être réalisée par chauffage à 60°C du milieu réactionnel pendant 30 minutes, on introduit 55,2g de gaz carbonique dans le mélange maintenu à une température de 42°C.After neutralization of the sulfonic acid with lime which can optionally be carried out by heating the reaction medium at 60 ° C. for 30 minutes, 55.2 g of carbon dioxide are introduced into the mixture maintained at a temperature of 42 ° C.

Après carbonatation, on élimine le méthanol et l'eau produite par la réaction en chauffant le mélange sous vide partiel. Le milieu est clarifié en utilisant 2% poids de Diatomées Clarcel DICS de CECA SA.After carbonation, the methanol and the water produced by the reaction are removed by heating the mixture under partial vacuum. The medium is clarified using 2% by weight of Diatomées Clarcel DICS from CECA SA.

Après élimination du solvant, on récupère 407g de produit contenant 12,8% de calcium, de VA = 323.After removal of the solvent, 407 g of product containing 12.8% of calcium, of VA = 323, are recovered.

Le produit est brun, limpide et stable en dilution, dans les huiles minérales ou synthétiques. On n'observe aucun trouble ou aucune décantation après plusieurs semaines à 60°C.The product is brown, clear and stable when diluted in mineral or synthetic oils. No clouding or settling is observed after several weeks at 60 ° C.

EXEMPLE 2 (comparatif)EXAMPLE 2 (comparative)

On opère comme dans l'exemple 1, mais on introduit 219,2g d'acide alkylarylsulfonique à chaîne alkyle ramifiée (de l'acide didodécylbenzènesulfonique) dont le poids moléculaire est de 520 et à 70% de matière active.The procedure is as in Example 1, but 219.2 g of alkylarylsulfonic acid with branched alkyl chain (didodecylbenzenesulfonic acid) whose molecular weight is 520 and at 70% of active material are introduced.

La quantité d'huile diluante est de 108g.The amount of diluent oil is 108g.

Le produit se présente sous la forme d'un liquide brun de VA=298. Il est stable en dilution dans les huiles lubrifiantes.The product is in the form of a brown liquid with VA = 298. It is stable when diluted in lubricating oils.

EXEMPLE 3EXAMPLE 3

On opère comme dans l'exemple 1 à ceci près qu'on introduit 40ml de méthanol au lieu de 80ml, et qu'on introduit 24g du produit de l'exemple A après neutralisation de l'acide sulfonique.The procedure is as in Example 1 except that 40 ml of methanol are introduced instead of 80 ml, and that 24 g of the product of Example A are introduced after neutralization of the sulfonic acid.

On récupère un sulfonate surbasé de VA = 320, dont la teneur en calcium est de 12,8% et dont la teneur en phosphore est de 1,05%. Le produit est stable en dilution dans l'huile.An overbased sulfonate of VA = 320 is recovered, the calcium content of which is 12.8% and the phosphorus content of 1.05%. The product is stable when diluted in oil.

EXEMPLE 4EXAMPLE 4

On opère comme dans l'exemple 3, mais on introduit 48g du produit de l'exemple A. On récupère un sulfonate surbasé de VA = 280, stable en dilution dans l'huile, dont les teneurs en calcium et en phosphore sont respectivement de 11,8% et de 2,05%.The procedure is as in Example 3, but 48 g of the product of Example A are introduced. An overbased sulfonate of VA = 280 is recovered, stable in dilution in oil, the calcium and phosphorus contents of which are respectively 11.8% and 2.05%.

EXEMPLE 5EXAMPLE 5

On opère comme dans l'exemple 2, mais on introduit 48g du produit de l'exemple A après neutralisation de l'acide sulfonique. Le produit recueilli à la fin des opérations est stable en dilution dans l'huile. Sa VA = 295 et ses teneurs en calcium et phosphore sont respectivement de 11,4% et de 1,8%.The procedure is as in Example 2, but 48 g of the product of Example A are introduced after neutralization of the sulfonic acid. The product collected at the end of the operations is stable when diluted in oil. Its VA = 295 and its calcium and phosphorus contents are respectively 11.4% and 1.8%.

EXEMPLE 6EXAMPLE 6

On opère comme dans l'exemple 1 à ceci près qu'on introduit 120ml de méthanol au lieu de 80ml, et qu'on introduit 67,5g du produit de l'exemple B après neutralisation de l'acide sulfonique.The procedure is as in Example 1 except that 120 ml of methanol are introduced instead of 80 ml, and that 67.5 g of the product of Example B are introduced after neutralization of the sulfonic acid.

On récupère un sulfonate de VA = 300, stable en dilution dans l'huile et dont les teneurs en calcium et phosphore sont de 12,3% et 2,45% respectivement.A sulfonate of VA = 300 is recovered, stable when diluted in oil and whose calcium and phosphorus contents are 12.3% and 2.45% respectively.

EXEMPLE 7EXAMPLE 7

On opère comme dans l'exemple 1 à ceci près qu'on introduit 29,3g de diéthyldithiophosphate d'ammonium à 95% de pureté (JANSSEN CHIMICA) juste après l'acide sulfonique. Le reste de la procédure est identique à celle de l'exemple 1.The procedure is as in Example 1 except that 29.3 g of ammonium diethyldithiophosphate at 95% purity (JANSSEN CHIMICA) are introduced just after the sulfonic acid. The rest of the procedure is identical to that of Example 1.

On recueille un produit de VA = 330, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 13% et 1,2% respectivement.A product of VA = 330, stable in dilution in oil, is collected, the calcium and phosphorus contents of which are 13% and 1.2% respectively.

EXEMPLE 8EXAMPLE 8

On opère comme dans l'exemple 2, mais on introduit 67,5g du produit de l'exemple B après neutralisation de l'acide sulfonique.The procedure is as in Example 2, but 67.5 g of the product of Example B are introduced after neutralization of the sulfonic acid.

A la fin des opérations, on recueille un produit de VA = 290, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 11,8% et de 2,2% respectivement.At the end of the operations, a product of VA = 290, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 11.8% and 2.2% respectively.

EXEMPLE 9EXAMPLE 9

On opère comme dans l'exemple 2, mais on introduit 197,3g d'acide sulfonique au lieu de 219,2g. D'autre part, on additionne 44g de diéthyldithiophosphate d'ammonium à 95% de pureté (JANSSEN CHIMICA) juste après l'acide sulfonique. Le reste de la procédure de l'exemple 2 n'est pas modifié.The procedure is as in Example 2, but 197.3 g of sulfonic acid are introduced instead of 219.2 g. On the other hand, 44g of 95% purity ammonium diethyldithiophosphate (JANSSEN CHIMICA) are added immediately after the sulfonic acid. The rest of the procedure in Example 2 is not changed.

On récupère un produit de VA = 330, stable en dilution dans l'huile et dont les teneurs en calcium et phosphore sont 12% et de 1,5% respectivement.A product of VA = 330 is recovered, stable when diluted in oil and whose calcium and phosphorus contents are 12% and 1.5% respectively.

EXEMPLE 10EXAMPLE 10

On opère comme dans l'exemple 1, mais on introduit 48g du produit de l'exemple C après neutralisation de l'acide sulfonique.The procedure is as in Example 1, but 48 g of the product of Example C are introduced after neutralization of the sulfonic acid.

On recueille un produit de VA = 326, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 12,6% et 1,5% respectivement.A product of VA = 326, stable on dilution in oil, is collected, the calcium and phosphorus contents of which are 12.6 % and 1.5 % respectively.

EXEMPLE 11EXAMPLE 11

On opère comme dans l'exemple 2, mais on introduit 48g du produit de l'exemple C après neutralisation de l'acide sulfonique.The procedure is as in Example 2, but 48 g of the product of Example C are introduced after neutralization of the sulfonic acid.

On récupère un produit de VA = 302, stable en dilution dans l'huile, dont les teneurs en calcium et en phosphore sont de 11,8% et 1,6% respectivement.A product of VA = 302, stable on dilution in oil, is recovered, the calcium and phosphorus contents of which are 11.8% and 1.6% respectively.

EXEMPLE 12EXAMPLE 12

On opère comme dans l'exemple 1, mais on introduit 76g du produit de l'exemple D après neutralisation de l'acide sulfonique.The procedure is as in Example 1, but 76 g of the product of Example D are introduced after neutralization of the sulfonic acid.

On recueille un produit de VA = 303, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 11,7% et 1,5% respectivement.A product of VA = 303, stable when diluted in oil, whose calcium and phosphorus contents are 11.7% and 1.5% respectively, is collected.

EXEMPLE 13EXAMPLE 13

On opère comme dans l'exemple 2, mais on introduit 76g du produit de l'exemple D après neutralisation de l'acide sulfonique.The procedure is as in Example 2, but 76 g of the product of Example D are introduced after neutralization of the sulfonic acid.

On recueille un produit de VA = 295, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 11,5% et 1,5% respectivement.A product of VA = 295, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 11.5% and 1.5% respectively.

EXEMPLE 14EXAMPLE 14

On opère comme dans l'exemple 1, mais on introduit 80g du produit de l'exemple E après neutralisation de l'acide sulfonique.The procedure is as in Example 1, but 80 g of the product of Example E are introduced after neutralization of the sulfonic acid.

On recueille un produit de VA = 303, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 11,8% et 0,9% respectivement.A product of VA = 303, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 11.8% and 0.9% respectively.

EXEMPLE 15EXAMPLE 15

On opère comme dans l'exemple 2, mais on introduit 80g du produit de l'exemple E après neutralisation de l'acide sulfonique, et à ceci près qu'on utilise 113,2g de chaux éteinte au lieu de 108,4g.The procedure is as in Example 2, but 80 g of the product of Example E are introduced after neutralization of the sulfonic acid, except that 113.2 g of slaked lime are used instead of 108.4 g.

On recueille un produit de VA = 280, stable en dilution dans l'huile, dont les teneurs en calcium et phosphore sont de 10,9% et 0,8% respectivement.A product of VA = 280, stable when diluted in oil, is collected, the calcium and phosphorus contents of which are 10.9% and 0.8% respectively.

EXEMPLE 16 comparatifEXAMPLE 16 comparison

On opère comme dans l'exemple 1, mais on introduit dans le réacteur 312g d'acide (C₁₄-C₁₈ alkyl) salicylique, 37,5g de chaux éteinte, 150ml de méthanol et 100g d'huile diluante.The procedure is as in Example 1, but is introduced into the reactor 312g of (C₁₄-C₁₈ alkyl) salicylic acid, 37.5g of slaked lime, 150ml of methanol and 100g of diluent oil.

Après neutralisation et carbonatation à 42°C par par 7,65g CO₂ on rajoute 30g de chaux que l'on carbonate par 10g CO₂.After neutralization and carbonation at 42 ° C with 7.65g CO₂, 30g of lime is added which is carbonated with 10g CO₂.

On recueille un additif de couleur brun foncé stable dans les huiles. Sa teneur en calcium est de 7,6% VA = 205.A stable dark brown additive is collected in the oils. Its calcium content is 7.6% VA = 205.

EXEMPLE 17EXAMPLE 17

On opère comme dans l'exemple 16, mais on introduit 44g de diéthyldithiophosphate d'ammonium (JANSSEN CHIMICA) après neutralisation.The procedure is as in Example 16, but 44 g of ammonium diethyldithiophosphate (JANSSEN CHIMICA) are introduced after neutralization.

La procédure est ensuite identique à celle de l'exemple 16. On recueille un additif de couleur noire, stable en dilution dans l'huile de VA = 210. Sa teneur en phosphore est de 1,5%.The procedure is then identical to that of Example 16. An additive of black color is collected, stable when diluted in oil with VA = 210. Its phosphorus content is 1.5%.

EXEMPLE 18EXAMPLE 18

Les performances des nouveaux détergents surbasés renfermant un composé organique du phosphore sont examinées sur des essais en laboratoire, d'usure, de frottement, d'oxydation et de corrosion.The performance of new overbased detergents containing an organic phosphorus compound are examined in laboratory tests, for wear, friction, oxidation and corrosion.

Les matrices d'essai correspondent à des lubrifiants pour moteurs terrestres d'une part et pour moteur marin d'autre part.The test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other.

Les produits sont tout d'abord testés dans une formulation lubrifiante de type API-SG pour moteur à essence.The products are first of all tested in a lubricant formulation of API-SG type for gasoline engine.

Afin que les performances des différentes formulations soient comparables, on établit des compositions de même niveau de VA par substitution du détergent surbasé, et de même teneur en phosphore, en soustrayant à la quantité initiale de dithiophosphate de zinc (DTPZ) de la formulation, la quantité de DTPZ dont la teneur en phosphore correspond à la teneur en phosphore apportée par le composé organique du phosphore renfermé par le détergent surbasé.In order for the performances of the various formulations to be comparable, compositions of the same level of VA are established by substitution of the overbased detergent, and of the same phosphorus content, by subtracting from the initial quantity of zinc dithiophosphate (DTPZ) from the formulation, the amount of DTPZ, the phosphorus content of which corresponds to the phosphorus content provided by the organic phosphorus compound contained in the overbased detergent.

Les formulations renferment 1,4% de détergent surbasé et leur teneur en phosphore, apporté d'une part par le DTPZ et d'autre part par le composé organique du phosphore du détergent surbasé, est de 1,3%.The formulations contain 1.4% of overbased detergent and their phosphorus content, supplied on the one hand by DTPZ and on the other hand by the organic compound of phosphorus in the overbased detergent, is 1.3%.

ESSAI D'USURE (Lubrifiant pour moteurs essence) WEAR TESTING (Lubricant for petrol engines) 1. Essai FALEX (selon la norme ASTM 2670)1. FALEX test (according to ASTM 2670)

L'essai est réalisé dans les conditions suivantes:

  • · Rodage: 5 minutes sous 200 lbs (normal load)
  • · 3 heures d'essai sous 540 lbs (normal load)
The test is carried out under the following conditions:
  • Running-in: 5 minutes under 200 lbs (normal load)
  • · 3 hours trial under 540 lbs (normal load)

A titre d'exemple, le tableau I donne quelques résultats permettant de constater qu'un détergent surbasé renfermant un composé organique du phosphore présente un pouvoir antiusure équivalent ou amélioré par rapport au détergent surbasé de référence décrit à l'exemple 1, ou par rapport à un sulfonate surbasé commercial.

Figure imgb0002
By way of example, Table I gives some results showing that an overbased detergent containing an organic phosphorus compound has equivalent or improved antiwear power compared to the reference overbased detergent described in Example 1, or compared to a commercial overbased sulfonate.
Figure imgb0002

2. Essai sur machine 4 billes (selon la norme ASTM 2783-71)2. Test on a 4-ball machine (according to ASTM 2783-71)

Les conditions d'essai sont les suivantes:

  • vitesse: 1 500 rpm
  • durée: 1 heure
  • charge: 60 Kg
The test conditions are as follows:
  • speed: 1,500 rpm
  • duration: 1 hour
  • load: 60 Kg

La cotation est obtenue par détermination du diamètre d'empreinte. Ce diamètre d'empreinte est d'autant plus faible que le pouvoir antiusure de la formulation est importante.The rating is obtained by determining the diameter of the imprint. This imprint diameter is all the smaller the greater the anti-wear power of the formulation.

Le tableau II donne quelques résultats montrant l'effet bénéfique de l'emploi des détergents surbasés renfermant un composé organique du phosphore sur les performances antiusure du lubrifiant.

Figure imgb0003
Table II gives some results showing the beneficial effect of the use of overbased detergents containing an organic phosphorus compound on the anti-wear performance of the lubricant.
Figure imgb0003

ESSAI D'OXYDATION (Lubrifiant pour moteurs essence) OXIDATION TEST (Lubricant for petrol engines)

Sur les mêmes formules lubrifiantes, un test d'oxydation est réalisé à 165°C sous un débit d'air de 1,7 litre/minute pendant une durée de 64 h et en présence d'un catalyseur d'oxydation (acétylacétonate de fer). Ce test permet de simuler en partie les conditions auxquelles l'huile peut être soumise dans un moteur à essence.On the same lubricant formulas, an oxidation test is carried out at 165 ° C under an air flow of 1.7 liters / minute for a period of 64 h and in the presence of an oxidation catalyst (iron acetylacetonate ). This test partially simulates the conditions to which oil can be subjected in a gasoline engine.

Le tableau III donne les valeurs de la variation de viscosité des échantillons à l'issue des 64 h du test (augmentation de viscosité dynamique en %). L'augmentation de la viscosité est d'autant plus faible que la résistance du lubrifiant à l'oxydation est importante.Table III gives the values of the variation in viscosity of the samples at the end of the 64 h of the test (increase in dynamic viscosity in%). The higher the viscosity, the lower the resistance of the lubricant to oxidation.

Les détergents surbasés contenant un composé organique du phosphore présentent une résistance à l'oxydation significativement supérieure à celle des détergents surbasés de référence décrits aux exemples 1 et 2.

Figure imgb0004
Overbased detergents containing an organic phosphorus compound have a significantly higher resistance to oxidation than the reference overbased detergents described in Examples 1 and 2.
Figure imgb0004

ESSAIS DE CORROSIONCORROSION TESTS

Des essais de corrosion ZF sont réalisés sur les mêmes formulations lubrifiantes. Selon la procédure, une plaque de Fer et une plaque de Cuivre sont plongées pendant 24 heures dans un échantillon renfermant 1% d'eau et maintenu à 95°C.ZF corrosion tests are carried out on the same lubricant formulations. According to the procedure, an iron plate and a copper plate are immersed for 24 hours in a sample containing 1% of water and maintained at 95 ° C.

Le tableau IV donne les résultats de cotation visuelle et montre l'effet bénéfique du détergent surbasé renfermant un composé organique du phosphore. Les formulations lubrifiantes sont moins agressives vis-à-vis du cuivre, car la teneur en DTPZ est plus faible.

Figure imgb0005
Table IV gives the visual rating results and shows the beneficial effect of the overbased detergent containing an organic phosphorus compound. Lubricant formulations are less aggressive towards copper, because the DTPZ content is lower.
Figure imgb0005

ESSAI D'USUREWEAR TEST

Les détergents surbasés contenant un composé organique du phosphore sont ensuite testés dans une formulation lubrifiante pour moteur marin (huile cylindre).The overbased detergents containing an organic phosphorus compound are then tested in a lubricant formulation for a marine engine (cylinder oil).

La basicité de l'huile est de 70mg KOH/g dont seulement 20gK0H/g apportés par le détergent surbasé.The basicity of the oil is 70mg KOH / g of which only 20gK0H / g provided by the overbased detergent.

L'essai est réalisé dans les conditions suivantes:

  • rodage: 5 minutes sous 300 lbs (Normal load)
  • 3 heures d'essai sous 900 lbs (Normal load)
The test is carried out under the following conditions:
  • running-in: 5 minutes under 300 lbs (Normal load)
  • 3 hours trial under 900 lbs (Normal load)

Ces conditions sont proches de l'extrême pression.These conditions are close to extreme pressure.

Le tableau V permet de constater que l'huile cylindre pour moteur marin formulée avec les détergents selon l'invention permet de réduire significativement l'usure.Table V shows that the cylinder oil for marine engines formulated with the detergents according to the invention makes it possible to significantly reduce wear.

En outre, on observe que ce gain de performance s'accompagne, dans certains cas, d'un gain de stabilité de la formulation.

Figure imgb0006
In addition, it is observed that this gain in performance is accompanied, in certain cases, by a gain in stability of the formulation.
Figure imgb0006

Claims (14)

1 - Détergent surbasé,pour huiles lubrifiantes, obtenu par carbonatation d'un mélange renfermant un détergent choisi parmi les sulfonates, naphténates, salicylates, phosphonates et thiophosphonates alcalins ou alcalinoterreux, un dérivé d'un métal alcalin ou alcalinoterreux, choisi parmi les oxydes, hydroxydes ou alcoolates, un promoteur azoté et/ou oxygéné, un solvant hydrocarboné et éventuellement une huile diluante et de l'eau, caractérisé en ce que le mélange renferme au moins 3% de phosphore sous forme de dérivé organique non-métallique. 1 - Overbased detergent, for lubricating oils, obtained by carbonation of a mixture containing a detergent chosen from alkali or alkaline earth sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates, a derivative of an alkali or alkaline earth metal, chosen from oxides, hydroxides or alcoholates, a nitrogenous and / or oxygenated promoter, a hydrocarbon solvent and optionally a diluent oil and water, characterized in that the mixture contains at least 3% of phosphorus in the form of non-metallic organic derivative. 2 - Détergent selon la revendication 1 caractérisé en ce qu'il renferme 0,5 à 10% et de préférence 1 à 5% poids de phosphore. 2 - Detergent according to claim 1 characterized in that it contains 0.5 to 10% and preferably 1 to 5% by weight of phosphorus. 3 - Détergent selon la revendication 1 ou 2 caractérisé en ce que le dérivé organique non-métallique du phosphore est choisi parmi les phosphites, phosphoramides, les dérivés des acides phosphoriques, thiophosphoriques, dithiophosphoriques,trithiophosphoriques,tétrathiophosphoriques et leurs sels organiques. 3 - Detergent according to claim 1 or 2 characterized in that the non-metallic organic derivative of phosphorus is chosen from phosphites, phosphoramides, derivatives of phosphoric, thiophosphoric, dithiophosphoric, trithiophosphoric, tetrathiophosphoric acids and their organic salts. 4 - Détergent selon la revendication 3 caractérisé en ce que le dérivé organique du phosphore est un dérivé phosphosoufré comme les acides thiophosphoriques ou dithiophosphoriques et leurs sels organiques et de préférence les dérivés d'acides dithiophosphoriques et leurs sels organiques. 4 - Detergent according to claim 3 characterized in that the organic phosphorus derivative is a phosphosulfur derivative such as thiophosphoric or dithiophosphoric acids and their organic salts and preferably derivatives of dithiophosphoric acids and their organic salts. 5 - Détergent selon la revendication 4 caractérisé en ce que le dérivé d'acide dithiophosphorique est un dérivé d'acide dihydrocarbyldithiophosphorique de formule générale
Figure imgb0007
 où R et R′ identiques ou différents représentent des chaînes alkyles linéaires ou ramifiées en C₁ à C₂₀, les cycles aliphatiques ou aromatiques. 5 - Detergent according to claim 4 characterized in that the dithiophosphoric acid derivative is a dihydrocarbyldithiophosphoric acid derivative of general formula
Figure imgb0007
 where R and R ′, identical or different, represent linear or branched C chaînes to C₂₀ alkyl chains, aliphatic or aromatic rings. 6 - Détergent selon la revendication 5 caractérisé en ce que l'acide dihydrocarbyldithiophosphorique est l'acide diéthyldithiophosphorique,l'acide diisopropyldithiophosphorique, l'acide dicyclohexyldithiophosphorique ou l'acide dicrésyldithiophosphorique. 6 - Detergent according to claim 5 characterized in that the dihydrocarbyldithiophosphoric acid is the acid diethyldithiophosphoric, diisopropyldithiophosphoric acid, dicyclohexyldithiophosphoric acid or dicrésyldithiophosphoric acid. 7 - Détergent selon l'une des revendications 1 à 6 caractérisé en ce que le dérivé de métal alcalin ou alcalinoterreux est un oxyde ou hydroxyde. 7 - Detergent according to one of claims 1 to 6 characterized in that the alkali or alkaline earth metal derivative is an oxide or hydroxide. 8 - Détergent selon l'une des revendications 1 à 7 caractérisé en ce que le promoteur oxygéné est choisi parmi les alcools aliphatiques ou aromatiques, les alkoxyalcanols, les glycols, les alcanolamines ou leurs mélanges. 8 - Detergent according to one of claims 1 to 7 characterized in that the oxygenated promoter is chosen from aliphatic or aromatic alcohols, alkoxyalkanols, glycols, alkanolamines or their mixtures. 9 - Détergent selon l'une des revendications 1 à 8 caractérisé en ce que le promoteur azoté est choisi parmi l'ammoniaque, les sels d'ammonium, les amines primaires, secondaires, ou tertiaires en C₂ à C₁₀ et leurs sels, les polyamines, alcanolamines ou les composés minéraux nitrés. 9 - Detergent according to one of claims 1 to 8 characterized in that the nitrogenous promoter is chosen from ammonia, ammonium salts, primary, secondary or tertiary amines C en to C₁₀ and their salts, polyamines , alkanolamines or nitrated mineral compounds. 10 - Détergent selon l'une des revendications 1 à 9 caractérisé en ce que l'huile diluante est de nature paraffinique ou naphténique. 10 - Detergent according to one of claims 1 to 9 characterized in that the diluent oil is of paraffinic or naphthenic nature. 11 - Détergent selon l'une des revendications 1 à 10 caractérisé en ce que le solvant hydrocarboné est un composé aliphatique ou aromatique en C₆ à C₁₂ et de préférence un solvant aromatique comme le benzène, toluène, xylène, éthylbenzène et les composés aromatiques chlorés. 11 - Detergent according to one of claims 1 to 10 characterized in that the hydrocarbon solvent is an aliphatic or aromatic compound C₆ to C₁₂ and preferably an aromatic solvent such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatic compounds. 12 - Composition lubrifiante caractérisée en ce qu'elle renferme une huile lubrifiante d'origine naturelle ou synthétique et 0,5 à 40% poids et de préférence 1 à 10% poids d'un détergent selon les revendications 1 à 11. 12 - Lubricating composition characterized in that it contains a lubricating oil of natural or synthetic origin and 0.5 to 40% by weight and preferably 1 to 10% by weight of a detergent according to claims 1 to 11. 13 - Composition selon la revendication 12 caractérisée en ce qu'elle renferme des additifs à effet antiusure, dispersant, antioxydant et des polymères améliorant l'indice de viscosité. 13 - Composition according to claim 12 characterized in that it contains additives with antiwear, dispersing, antioxidant effect and polymers improving the viscosity index. 14 - Composition selon la revendication 12 ou 13 caractérisée en ce qu'elle renferme du dialkyldithiophosphate de zinc. 14 - Composition according to claim 12 or 13 characterized in that it contains zinc dialkyldithiophosphate.
EP90403692A 1989-12-28 1990-12-20 Overbased detergents for lubricating oils containing a phosphorus organic derivative and lubricating compositions containing the same. Expired - Lifetime EP0438942B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8917349A FR2656623A1 (en) 1989-12-28 1989-12-28 LUBRICATING OIL BASED DETERGENTS CONTAINING AN ORGANIC PHOSPHORIC DERIVATIVE AND LUBRICATING COMPOSITIONS COMPRISING SAID DETERGENTS.
FR8917349 1989-12-28

Publications (2)

Publication Number Publication Date
EP0438942A1 true EP0438942A1 (en) 1991-07-31
EP0438942B1 EP0438942B1 (en) 1993-10-20

Family

ID=9389087

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90403692A Expired - Lifetime EP0438942B1 (en) 1989-12-28 1990-12-20 Overbased detergents for lubricating oils containing a phosphorus organic derivative and lubricating compositions containing the same.

Country Status (3)

Country Link
EP (1) EP0438942B1 (en)
JP (1) JPH04130192A (en)
FR (1) FR2656623A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2681872A1 (en) * 1991-09-30 1993-04-02 Inst Francais Du Petrole COLLOUIDAL PRODUCTS COMPRISING BORON AND PHOSPHORUS, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR LUBRICANTS.
EP0803565A1 (en) * 1996-04-25 1997-10-29 Institut Francais Du Petrole New colloidal products, their preparation and their uses
WO2003059920A1 (en) * 2001-12-28 2003-07-24 Kaibaldin Konstantin Arturovic Additive to lubrication oils
CN103725372A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Internal combustion engine lubricating oil composition

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2616925A (en) * 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of thiophosphoric promoters
FR1083354A (en) * 1952-11-03 1955-01-07 Lubrizol Corp Improvements to lubricants containing carbonate complexes
US2723235A (en) * 1952-11-03 1955-11-08 Lubrizol Corp Lubricants
FR1142932A (en) * 1966-07-15 1957-09-24 Lubrizol Corp Organic metallic compositions and their manufacturing process
US4328111A (en) * 1978-11-20 1982-05-04 Standard Oil Company (Indiana) Modified overbased sulfonates and phenates
FR2616441A1 (en) * 1987-06-11 1988-12-16 Elf France Process for the preparation of superbase additives and compositions containing the said additives

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2616925A (en) * 1951-03-16 1952-11-04 Lubrizol Corp Organic alkaline earth metal complexes formed by use of thiophosphoric promoters
FR1083354A (en) * 1952-11-03 1955-01-07 Lubrizol Corp Improvements to lubricants containing carbonate complexes
US2723235A (en) * 1952-11-03 1955-11-08 Lubrizol Corp Lubricants
FR1142932A (en) * 1966-07-15 1957-09-24 Lubrizol Corp Organic metallic compositions and their manufacturing process
US4328111A (en) * 1978-11-20 1982-05-04 Standard Oil Company (Indiana) Modified overbased sulfonates and phenates
FR2616441A1 (en) * 1987-06-11 1988-12-16 Elf France Process for the preparation of superbase additives and compositions containing the said additives

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2681872A1 (en) * 1991-09-30 1993-04-02 Inst Francais Du Petrole COLLOUIDAL PRODUCTS COMPRISING BORON AND PHOSPHORUS, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR LUBRICANTS.
EP0536020A1 (en) * 1991-09-30 1993-04-07 Institut Francais Du Petrole Colloidal products containing boron, sulphur and phosphorus, their preparation and their use as additives for lubricants
EP0803565A1 (en) * 1996-04-25 1997-10-29 Institut Francais Du Petrole New colloidal products, their preparation and their uses
FR2748030A1 (en) * 1996-04-25 1997-10-31 Inst Francais Du Petrole NEW COLLOIDAL PRODUCTS, THEIR PREPARATION AND USES THEREOF
US5854184A (en) * 1996-04-25 1998-12-29 Institut Francais Du Petrole Colloidal products, their preparation and their uses
WO2003059920A1 (en) * 2001-12-28 2003-07-24 Kaibaldin Konstantin Arturovic Additive to lubrication oils
CN103725372A (en) * 2012-10-15 2014-04-16 中国石油化工股份有限公司 Internal combustion engine lubricating oil composition

Also Published As

Publication number Publication date
EP0438942B1 (en) 1993-10-20
JPH04130192A (en) 1992-05-01
FR2656623A1 (en) 1991-07-05

Similar Documents

Publication Publication Date Title
EP0404650B1 (en) Overbased lubricating oil additives containing a molybdenun complex, process of preparation and compositions containing the same
EP0164286B1 (en) A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals
EP1236791A1 (en) Overbased detergent additives
EP0308445B1 (en) Process for the preparation of a superalkalinized additive containing an inorganic boron derivative, additive produced by said process and lubricating compositions containing said additive
EP0536020B1 (en) Colloidal products containing boron, sulphur and phosphorus, their preparation and their use as additives for lubricants
EP0438942A1 (en) Overbased detergents for lubricating oils containing a phosphorus organic derivative and lubricating compositions containing the same
EP0425367B1 (en) Overbased lubricating oil additive containing a copper derivate or a copper and boron derivate, method of preparation and compositions containing said additive
FR2645168A1 (en) NOVEL THIOPHOSPHORUS COMPOUNDS, THEIR PREPARATION AND THEIR USE AS LUBRICANT ADDITIVES
JPH0292993A (en) Perbasic alkali metal sulfonate
FR2588269A1 (en) PROCESS FOR THE PREPARATION OF HIGH FLUID AND HIGH BASIC ADHESIVE ADDITIVES AND COMPOSITION CONTAINING SAID ADDITIVES
FR2715401A1 (en) New sulfonated compounds of bismuth, their preparation and their use especially for the preparation of overbased colloidal products, themselves usable as additives for lubricants.
EP0562912A1 (en) Overbased colloidal products containing an organic sulphurised compound and their use as detergent additives with anti-wear and extreme-pressure activity in lubricating oils
CA2044036A1 (en) Detergents for lubricating oils containing a phosphor organic derivative and lubricating compositions containing such detergents
EP0006796B1 (en) Process for the preparation of overbased metalliferous detergent-dispersant agents for lubricating oils and product obtained
NL8602502A (en) PROCESS FOR PREPARING AN ADDITIVE FOR LUBRICATING OILS, SO ADDED ADDITIVE AND LUBRICANT COMPOSITION CONTAINING THIS ADDITIVE.
EP0436422A1 (en) Overbased alcaline or alcalin earth metal phenate containing phosphorus and lubricating compositions containing the same
EP0639634A1 (en) Colloidal products containing calcium and/or magnesium as well as sulfur and nitrogen, their preparation and their use, especially as additives for lubricants
FR2616441A1 (en) Process for the preparation of superbase additives and compositions containing the said additives
FR2470155A1 (en) COMPOSITIONS CONTAINING SALTS AND COMPLEXES OF ALKYLATED AMINOPHENOLS METALS OR METALLOIDS AND LUBRICANT CONTAINING THEM
FR2484442A1 (en) PROCESS FOR THE PREPARATION OF MOLYBDENE CONTAINING COMPOSITIONS USEFUL FOR BETTER ECONOMY OF THE FUEL OF INTERNAL COMBUSTION ENGINES
CA2044035A1 (en) Phosphorus-containing alcaline or alcaline-earth phenate with excess base, and lubricant compositions holding said phenate
EP0598645A1 (en) Colloidal products containing calcium, and/or magnesium as also boron and/or phosphorus, and/or sulphur, their preparation and their application as additives for lubricants
EP0803565B1 (en) New colloidal products, their preparation and their uses
CA1113680A (en) Basic magnesium complexes and their use in the manufacture of detergent-dispersant additives for lubricating oils
EP0383359A2 (en) Process for preparing an overbased additive containing a boron derivative, additive produced by said process and lubricating compositions containing said additive

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

17P Request for examination filed

Effective date: 19910109

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES GB IT NL

17Q First examination report despatched

Effective date: 19920217

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

PUAB Information related to the publication of an a document modified or deleted

Free format text: ORIGINAL CODE: 0009199EPPU

PUAC Information related to the publication of a b1 document modified or deleted

Free format text: ORIGINAL CODE: 0009299EPPU

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES GB IT NL

DB1 Publication of patent cancelled
RA1 Application published (corrected)

Date of ref document: 19910731

Kind code of ref document: A1

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

NLXE Nl: other communications concerning ep-patents (part 3 heading xe)

Free format text: PAT.BUL.23/93 SHOULD BE DELETED

18W Application withdrawn

Withdrawal date: 19930921