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.

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• 1989
  • 1989-12-28 FR FR8917349A patent/FR2656623A1/fr not_active Withdrawn
• 1990
  • 1990-12-20 EP EP90403692A patent/EP0438942B1/de not_active Expired - Lifetime
  • 1990-12-27 JP JP2414791A patent/JPH04130192A/ja active Pending

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