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
  • 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
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
  • C10M133/56—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol 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
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts

Definitions

• This invention relates to a process for preparing an over-alkalized additive for lubricating oils containing an inorganic boron derivative, the additive thus obtained and a lubricating composition containing said additive.
• additives improving their properties.
• these additives are detergents, dispersants, antiwear and extreme pressure additives and additives providing a basic reserve.
• the detergent and dispersing properties of a lubricant correspond to its ability to keep impurities and unburned particles in suspension in the hot parts of the engine by its detergency effect but also in the cold parts by its dispersing effect. The fixing of these particles in the form of varnish or lacquers is thus avoided.
• the role of basic reserve additives consists in combating the acidity caused in engines by the combustion of organic sulfur derivatives contained in fuels and by the oxidation of the components of lubricating oils.
• the antiwear additives act by forming a thin solid or plastic film which separates the friction surfaces and prevents wear of the different parts of the engine.
• the detergent and dispersant properties as well as the basicity reserve are generally provided by overbased additives. These are alkali or alkaline earth carbonates in a detergent solution of the alkyl sulfonate, phenate or salicylate type.
• Antiwear additives are generally sulfur and / or phosphorus compounds, the most commonly used being Zn dialkyldithiophosphates.
• Boron derivatives form another class of antiwear additives.
• the boron mineral compounds provide an antiwear and extreme pressure function (US patents 3,907,691 and 4,10081) while organic compounds provide antiwear and antifriction properties rather (American patents 4,549,775 and 4,599,183).
• US Patent 3,907,691 provides for the formation of a complex by heating the intermediate product formed by the reaction of boric acid with the overbased sulfonate.
• US Patent 4,539,126 claims the preparation of complexes by reacting boric acid with an overbased alkylsalicylate.
• US Patent 3,679,584 suggests a two-step procedure.
• boric acid and carbon dioxide are added in a second step.
• the alkaline value of the over-alkalized mixture drops very sharply during this second stage, passing for example from 295 to 177.
• the alkaline value (VA) is fictitiously equivalent to the number of milligrams of KOH per gram of overbased additive titrated by a strong acid. It is determined by direct potentiometric assay according to standard ASTM D-2896.
• the present invention overcomes these drawbacks and prepares overbased additives with significant boron content and high alkaline value.
• these additives are homogeneous and stable and have very good antiwear properties.
• the process for the preparation of overbased additives with antiwear effect consists in carbonating a reaction mixture composed of at least one detergent, of an alkali or alkaline earth metal derivative, of at least one nitrogenous and / or oxygenated promoter in a diluent oil and a hydrocarbon solvent, characterized in that an inorganic boron derivative used in the form of a dispersion in oil is added to the reaction mixture before the introduction of carbon dioxide.
• the oxides and anhydrides of boron as well as boric steel and its salts.
• Boric acid and its ammonium salt diammonium tetraborate ((NH4) 2 B4O7.4H2O) its sodium salt, sodium tetraborate (Na2B4O7.nH2O) its potassium salt, potassium tetraborate (K2B4O7. nH2O) and its lithium salt, lithium tetraborate (Li2B4O7.5H2O) are particularly suitable.
• the detergents commonly used in overbased additives are salts of sulfonic acids, salicyclic acids or phenols
• detergents can advantageously be used in admixture with alkyl succinamides of general formula: or R4 is a hydrocarbon radical of 12 to 100 carbon atoms, n is between 1 and 6 and m is between 1 to 5.
• the sulfonic acids are of petroleum or synthetic origin.
• the average molecular weight of petroleum sulfonates is generally greater than 320. They are obtained by sulfonation of petroleum distillates. Synthetic sulfonic acids are particularly useful in the context of the invention. They may be products obtained by sulfonation of olefins with a carbon number greater than or equal to 12 or alternatively alkylarylsulfonic acids.
• Alkylarylsulfonic acids have one or more alkyl chains on an aromatic ring, generally a benzenic ring.
• the alkyl chains must contain a minimum of 8 carbon atoms. Their structure is linear or branched. Benzene, toluene, xylene or napthalene alkylated with C13 to C16 alphaolefins, with C20 ⁇ 22 paraffins or with propylene tetramers (C24-benzenesulfonic acid) are commonly used.
• oil-soluble salicylic acids are substituted on the aromatic ring by a chain comprising at least 10 and in general 16 to 18 carbon atoms.
• the phenols which are soluble in organic medium and which are particularly advantageous in the context of the invention are phenols substituted by one or more linear or branched alkyl chains containing at least 8 carbon atoms.
• the most common commercial products are, for example, nonylphenol, dinonylphenol, dodecylphenol and mixtures thereof.
• Phenols are used in the form of alkali or alkaline earth metal salts. They are particularly appreciated after having undergone a sulfurization by reaction with the flower of sulfur or with sulfur chloride.
• the overbased additives contain one or more of these detergents.
• the sulfonic or salicylic acids or the phenols can be used in admixture with dispersants derived from alkenylsuccinic acids with a chain greater than or equal to 12 carbon atoms or with carboxylic acids having at least 8 carbon atoms.
• the alkali or alkaline earth metal derivative is generally an oxide, hydroxide or alcoholate of such a metal.
• the oxygenated promoters are mainly aliphatic alcohols, generally C1 to C5, most often methanol, ethanol, butanol or glycols. Ethers such as dioxolane or dialkoxymethanes are also used.
• the alcohols can be used alone or in admixture with water.
• the nitrogenous promoters are inter alia ammonia, ethylenediamine, ethanolamines, ammonium chloride or ammonium carbonate.
• the role of the diluent oil is to allow easy handling at room temperature.
• paraffinic oils such as 75, 100 or 150 Neutral or naphtenic oils, type 100 Pale solvent.
• Hydrocarbon solvents have an aliphatic structure, such as heptane, isooctane, nonane or an aromatic structure, such as toluene or xylene. These solvents can be used as a mixture. It is particularly advantageous to use solvents which give azeotropes with water, such as alcohols, glycols or alkoxyalkanols
• a double jacket reactor is generally used, provided with a vigorous stirring system, a temperature regulator, a condenser, a system allowing a vacuum to be produced. or a slight overpressure, a gas diffuser and a solvent recovery system.
• the following are introduced into the reactor: - 100 to 500 parts by weight of detergents - 100 to 300 parts by weight of an alkali or alkaline earth metal derivative - 0 to 100 parts by weight of a nitrogenous promoter - 30 to 300 parts by weight of an oxygenated promoter - 0 to 100 parts by weight of water - 100 to 500 parts by weight of a diluent oil - 200 to 800 parts by weight of a hydrocarbon solvent - 15 to 400 parts by weight of an inorganic boron derivative.
• the reaction mixture is subjected to strong stirring while the introduction of 50 to 350 parts by weight of carbon dioxide begins by bubbling into the reaction medium.
• the duration of carbonation generally varies from 20 minutes to 4 hours at constant flow.
• the reaction is exothermic.
• the mixture is maintained at a temperature varying from 20 to 80 ° C and preferably from 35 to 70 ° C.
• reaction mixture containing the boron derivative may be advantageous to bring the reaction mixture containing the boron derivative to reflux for a period of 30 minutes to 2 hours before carbonation.
• Solvents can be removed in one step, but generally there are two steps.
• the solvents, except the hydrocarbon diluent, are removed by heating, then the solid residues by centrifugation or filtration before the removal of the hydrocarbon solvent.
• the overbased additives obtained by the process according to the invention have alkaline values (VA), measured according to standard ASTM D-2896, generally greater than 200 mg KOH / g. VAs greater than 300 and even 500 can be obtained.
• VA alkaline values
• reaction mixture free of boron derivative is brought to reflux for at least half an hour. After cooling, the boron derivative is added. The introduction of carbon dioxide and the subsequent treatment proceed as before.
• the overbased phenates obtained have alkaline values (VA) generally greater than 150 mg KOH / g. VAs greater than 250 even 320 can be obtained.
• the amount of boron incorporated can vary between 0.1 and 10% by weight and preferably 0.25 to 5%. This amount is sufficient to provide antiwear properties to lubricating oils.
• the antiwear properties are measured with commonly used mechanical tests, such as the 4 wear balls method (NF-E 48-617) and 4 extreme pressure balls (ASTM D 2783-69T or NF E 48-617) and the FALEX tests ( ASTM D 32-33).
• the additives according to the invention have a clear appearance and keep a homogeneous consistency over time. They have viscosities low enough to allow easy handling and are compatible with the other additives commonly used in lubricating oils.
• the overbased additives are added to lubricating oils of natural or synthetic origin at a concentration of between 0.5 and 40% by weight and preferably between 1 and 30% by weight.
• the mixture is stirred at 700 revolutions / minute and its temperature is regulated at 49 ° C. Carbon dioxide is introduced at a flow rate of 230 ml / minute for 30 minutes. At the end of the reaction, the mixture is heated to 100 ° C to remove the methanol and the water produced by carbonation. The solid residues are removed by centrifugation then filtration.
• VA fluid product of basicity
• a simple mixture of 13 g of overbased sulfonate from Example 1 is prepared with 3 g of the dispersion of sodium tetraborate from Example 2.
• a product of VA 350 is obtained, containing 0.36% by weight of boron, with cloudy appearance. Examination of the product under an electron microscope shows the presence of 6nm diameter calcium carbonate globules and 0.6 ⁇ m diameter sodium borate particles.
• Example 2 The experiment described in Example 1 is repeated, with the difference that only 4g of 200N diluent oil is introduced instead of 22.5g. 20.5 g of the sodium tetraborate dispersion of Example 2 are added before the start of carbonation. A product with a clear appearance is then collected, with VA 369 mg KOH / g at 0.46% by weight of boron.
• Example 4 makes it possible to effectively incorporate boron into the globules of the colloidal dispersion.

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• 1988
  • 1988-03-16 EP EP90104404A patent/EP0383359B1/de not_active Expired - Lifetime

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