EP0308445B1 - Verfahren zur herstellung eines ein anorganisches borderivat enthaltenden überbasischen additivs, danach erhaltene additive und diese enthaltende schmiermittel - Google Patents

Verfahren zur herstellung eines ein anorganisches borderivat enthaltenden überbasischen additivs, danach erhaltene additive und diese enthaltende schmiermittel Download PDF

Info

Publication number
EP0308445B1
EP0308445B1 EP88902504A EP88902504A EP0308445B1 EP 0308445 B1 EP0308445 B1 EP 0308445B1 EP 88902504 A EP88902504 A EP 88902504A EP 88902504 A EP88902504 A EP 88902504A EP 0308445 B1 EP0308445 B1 EP 0308445B1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
reaction mixture
additive
process 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.)
Expired - Lifetime
Application number
EP88902504A
Other languages
English (en)
French (fr)
Other versions
EP0308445A1 (de
Inventor
Pierre Hoornaert
Claude Rey
Roger Gallo
Catherine Belle
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.)
Elf Antar France
Original Assignee
Elf France SA
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 Elf France SA filed Critical Elf France SA
Publication of EP0308445A1 publication Critical patent/EP0308445A1/de
Application granted granted Critical
Publication of EP0308445B1 publication Critical patent/EP0308445B1/de
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
    • 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
    • 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
    • C10M2207/02—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 overbased 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 dispersant 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 cold parts by its dispersing effect. The fixing of these particles in the form of varnish or lacquers is thus avoided.
  • the role of additives with a basicity reserve consists in combating the acidity caused in the 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-A-3907691 and 4100081) while the organic compounds provide antiwear and anti-friction properties (US-A-4549975 and 4599183).
  • US-A-3907691 provides for the formation of a complex by heating the intermediate product formed by reaction of boric acid with the overbased surfonate.
  • US-A-4539126 claims the preparation of complexes by reaction of boric acid with an overbased alkylsalicylate.
  • US-A-3928216 reports the use of catalytic amounts of boron salts of an amine during the overbasing reaction.
  • US-A-3679584 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 powder form or in aqueous solution is introduced into the reaction mixture during the carbonation reaction before the fifteenth minute of said carbonation.
  • the oxides and anhydrides of boron there may be mentioned the oxides and anhydrides of boron as well as boric acid and its salts.
  • Boric acid and its ammonium salt diammonium tetraborate ((NH4) 2B4O7 ⁇ 4H2O) its sodium salt, sodium tetraborate (Na2B4O7 ⁇ nH2O) its potassium salt, potassium tetraborate (K2B4O7 ⁇ nH2O ) and its lithium salt, lithium tetraborate (Li2 B4 O7 ⁇ 5H2O) are particularly suitable.
  • the detergents commonly used in overbased additives are salts of sulfonic acids, salicylic acids or phenols.
  • alkyl succinimides of general formula: hydrocarbon 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 alpha-olefins, 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 containing 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.
  • 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 naphthenic 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 boron derivatives are used in the form of a dispersion in oil, this dispersion is added to the reaction mixture before the introduction of carbon dioxide.
  • the boron derivatives used in dispersion are boric acid and its salts.
  • the boron derivatives used in powder form or in the form of an aqueous solution, if their solubility is sufficient, are boron oxide, boric acid and its salts.
  • the pulverulent compounds or the aqueous solutions are introduced during carbonation a few minutes after the start of the reaction.
  • 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.
  • 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 mechanical tests commonly used, 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. Solid residues are removed by centrifugation then filtration. The elimination of xylene makes it possible to recover a fluid product of basicity (VA) equal to 420 mg KOH / g containing 18% of calcium and which proves to be stable in dilution in mineral oils (absence of cloudiness after 1 month).
  • VA fluid product of basicity
  • Example 1 The procedure of Example 1 is repeated except that 5 g of sodium metaborate tetrahydrate are added to the reaction medium before the 10th minute of carbonation. A much more fluid product than VA 425 is collected, stable in oil and whose boron content is of the order of 0.37% by weight.
  • Example 2 The experiment described in Example 1 is repeated with the difference that 2 g of powdered sodium tetraborate are added to the reaction medium before the 10th minute of carbonation. A product of VA 403 mg KOH / g is collected, the boron content of which is 0.45% by weight.
  • 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 3.
  • a product of VA 350 is obtained, containing 0.36% by weight of boron, at cloudy appearance.
  • Example 3 The procedure of Example 3 is repeated with the difference that 30 grams of calcium oxide, 10.2 ml of water are introduced and the product is carbonated for 75 minutes at a flow rate of 103 ml / minute . Before the 15th minute of carbonation, 9.52 g of potassium tetraborate powder are added. A clear product of VA 310 mg KOH / g and containing 0.86% by weight of boron is collected.
  • Example 5 The procedure of Example 5 is repeated, but the boron compound is boric acid. 8.98 g of powdered boric acid are added at the 10th minute of carbonation. A product of VA 411 mg KOH / g and of very viscous consistency is then obtained. It contains 1.23% by weight of boron.
  • Example 5 The procedure of Example 5 is repeated after adding only 4.5 ml of methanol to the reaction medium. A clear, very fluid product of VA 298 mg KOH / g is obtained, containing 1.3% by weight of boron.
  • Example 6 The procedure of Example 6 is repeated, but 11.2 g of powdered boron trioxide are added.
  • Example 5 The procedure of Example 5 is repeated, but 12.3 g of trimethylborate are added at the 10th minute of carbonation. A viscous product of VA 437 mg KOH / g and at 1.2% by weight of boron is then obtained.
  • Example 2 The procedure of Example 1 is repeated except that 9.53 g of powdered diammonium tetraborate are added after 10 minutes of carbonation. A clear, relatively fluid product of VA 438 mg KOH / g and containing 1.15% by weight of boron is obtained.
  • Example 1 The procedure of Example 1 is repeated except that, instead of C d'un-benzene sulfonic acid, 23 g of an 80/20 molar mixture of C24-benzene sulfonic acid of molar weight are used. 520 to 70% of active material and C9 carboxylic acid obtained by hydroformylation of olefins (CK9 acid distributed by the company NORSOLOR). 30.7 g of slaked lime at 97% purity are added.
  • Carbonation is carried out for 25 minutes at a flow rate of 210 ml / minute.
  • the product collected is clear and stable in dilution. Its VA is 307 mg KOH / g and its boron content is 1.55% by weight.

Landscapes

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

Claims (11)

1. Verfahren zur Herstellung eines überalkalisierten Additivs mit verschleißhemmender Wirkung durch Carbonatieren eines Reaktionsgemischs, das aus mindestens einem Detergens, einem Derivat eines Alkali- oder Erdalkalimetalls und mindestens einem stickstoffhaltigen und/oder sauerstoffhaltigen Promotor in einem Öl als Verdünnungsmittel und einem Kohlenwasserstoff-Lösungsmittel besteht, dadurch gekennzeichnet, daß ein anorganisches Borderivat, das in Pulverform oder in wäßriger Lösung eingesetzt wird, während der Carbonatierungsreaktion vor dem Ablauf von 15 min in das Reaktionsgemisch eingeführt wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Reaktionsgemisch mindestens ein Detergens enthält, das unter den Sulfonsäuren auf Erdölbasis oder auf synthetischer Basis, den Salicylsäuren, den Phenolen und ihren Alkali- oder Erdalkalisalzen ausgewählt ist.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Detergens im Gemisch mit einem Alkylsuccinimid der allgemeinen Formel
Figure imgb0004
 eingesetzt wird, in der
R₄ eine C₁₂₋₁₀₀-Kohlenwasserstoffgruppe,
n eine Zahl von 1 bis 6 und
m eine Zahl von 1 bis 5
bedeuten.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Reaktionsgemisch ein Derivat eines Alkalimetalls oder Erdalkalimetalls enthält, das unter den Oxiden, Hydroxiden oder Alkoholaten dieser Metalle ausgewählt ist.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Reahtionsgemisch mindestens einen sauerstoffhaltigen Promoter enthält, der unter den aliphatischen C₁₋₅-Alkoholen, den Glycolen oder den Ethern ausgewählt ist.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Reaktionsgemisch Wasser enthält.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Reaktionsgemisch ein paraffinisches oder naphthenisches Öl als Verdünnungsmittel enthält.
8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Reaktionsgemisch ein aliphatisches oder aromatisches Kohlenwasserstoff-Lösungsmittel enthält.
9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß 50 bis 350 Gew.-Teile Kohlendioxid bei einer Temperatur von 20 bis 80°C und vorzugsweise von 35 bis 70°C während einer Dauer von 20 min bis 4 h in das Reaktionsgemisch eingeleitet werden, das 100 bis 500 Gew.-Teile mindestens eines Detergens, 100 bis 300 Gew.-Teile eines Derivats eines Alkalimetalls oder Erdalkalimetalls, 0 bis 100 Gew.-Teile eines stickstoffhaltigen Promotors, 30 bis 300 Gew.-Teile eines sauerstoffhaltigen Promotors, 0 bis 100 Gew-.-Teile Wasser, 100 bis 500 Gew.-Teile eines Öls als Verdünnungsmittel, 200 bis 800 Gew. Teile eines Kohlenwasserstoff-Lösungsmittels und 15 bis 400 Gew.-Teile eines anorganischen Borderivats enthält.
10. Überalkalisiertes Additiv mit verschleißhemmender Wirkung, dadurch gekennzeichnet, daß es nach dem in den Ansprüchen 1 bis 9 beschriebenen Verfahren hergestellt ist und 0,1 bis 10 Gew.-% und vorzugsweise 0,25 bis 5 Gew.-% eines anorganischen Borderivats enthält.
11. Schmiermittelzusammensetzung, dadurch gekennzeichnet, daß sie ein natürliches oder synthetisches Öl als Verdünnungsmittel und 0,5 bis 40 Gew.-% und vorzugsweise 1 bis 30 Gew.-% eines Additivs nach Anspruch 10 enthält.
EP88902504A 1987-03-17 1988-03-16 Verfahren zur herstellung eines ein anorganisches borderivat enthaltenden überbasischen additivs, danach erhaltene additive und diese enthaltende schmiermittel Expired - Lifetime EP0308445B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8703646 1987-03-17
FR8703646A FR2612526B1 (fr) 1987-03-17 1987-03-17 Procede de preparation d'un additif suralcanise renfermant un derive du bore, l'additif ainsi obtenue et compositions lubrifiantes renfermant ledit additif

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP90104404A Division EP0383359B1 (de) 1987-03-17 1988-03-16 Verfahren zur Herstellung eines, ein anorganisches Borderivat enthaltenden, }berbasischen Additivs, so erhaltenes Additiv und Schmiermittel, die dieses Additiv enthalten.
EP90104404.0 Division-Into 1990-03-08

Publications (2)

Publication Number Publication Date
EP0308445A1 EP0308445A1 (de) 1989-03-29
EP0308445B1 true EP0308445B1 (de) 1991-08-28

Family

ID=9349073

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88902504A Expired - Lifetime EP0308445B1 (de) 1987-03-17 1988-03-16 Verfahren zur herstellung eines ein anorganisches borderivat enthaltenden überbasischen additivs, danach erhaltene additive und diese enthaltende schmiermittel

Country Status (6)

Country Link
US (1) US5098587A (de)
EP (1) EP0308445B1 (de)
JP (1) JPH01502759A (de)
DE (1) DE3864483D1 (de)
FR (1) FR2612526B1 (de)
WO (1) WO1988007073A1 (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2653780A1 (fr) * 1989-10-26 1991-05-03 Elf Aquitaine Additif surbase pour huiles lubrifiantes renfermant un derive du cuivre ou un derive du cuivre et du bore, son procede de preparation et compositions renfermant ledit additif .
JP2814131B2 (ja) * 1990-03-14 1998-10-22 日本石油株式会社 アルコール系燃料用エンジン油組成物
JP2617807B2 (ja) * 1990-03-16 1997-06-04 日本石油株式会社 エンジン油組成物
FR2698019B1 (fr) * 1992-11-18 1995-02-24 Inst Francais Du Petrole Produits colloïdaux contenant du calcium et/ou du magnésium, ainsi que du bore et/ou du phosphore et/ou du soufre, leur préparation et leur utilisation comme additifs pour lubrifiants.
US6451745B1 (en) 1999-05-19 2002-09-17 The Lubrizol Corporation High boron formulations for fluids continuously variable transmissions
US6368969B1 (en) 2000-06-30 2002-04-09 International Business Machines Corporation Chemical-mechanical polishing methods
US7981846B2 (en) * 2005-11-30 2011-07-19 Chevron Oronite Company Llc Lubricating oil composition with improved emission compatibility
US7479568B2 (en) * 2005-11-30 2009-01-20 Chevron Oronite Company Llc Process for making alkaline earth metal borated sulfonates
US20080300154A1 (en) * 2007-05-30 2008-12-04 Chevron Oronite Company Llc Lubricating oil with enhanced protection against wear and corrosion
US7868209B2 (en) * 2007-05-30 2011-01-11 Chevron Oronite Sa Process for making borated alkaline earth metal toluene sulfonates

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB789820A (en) * 1955-03-25 1958-01-29 Continental Oil Co Improvements in or relating to dispersions of inorganic metal compounds in lubricating oil and methods of making the same
US3480548A (en) * 1967-06-21 1969-11-25 Texaco Inc Alkaline earth metal polyborate carbonate overbased alkaline earth metal sulfonate lube oil composition
US3829381A (en) * 1970-02-02 1974-08-13 Lubrizol Corp Boron-and calcium-containing compositions and process
US3679584A (en) * 1970-06-01 1972-07-25 Texaco Inc Overbased alkaline earth metal sulfonate lube oil composition manufacture
CA966148A (en) * 1971-05-07 1975-04-15 Mack W. Hunt Preparation of oil-soluble metal sulfonates
US3929650A (en) * 1974-03-22 1975-12-30 Chevron Res Extreme pressure agent and its preparation
FR2271281B2 (de) * 1974-03-29 1977-01-21 Inst Francais Du Petrole
US3907691A (en) * 1974-07-15 1975-09-23 Chevron Res Extreme-pressure mixed metal borate lubricant
US4560489A (en) * 1983-09-14 1985-12-24 Witco Chemical Corporation High performance calcium borate modified overbased calcium sulfonate complex greases
GB2149810B (en) * 1983-11-15 1987-04-08 Shell Int Research Borated basic metal salt and oil composition containing it
JPS61204298A (ja) * 1985-03-08 1986-09-10 Nippon Oil Co Ltd アルカリ土類金属ホウ酸塩分散体の製造方法
US4601837A (en) * 1985-09-06 1986-07-22 Amoco Corporation Process for the preparation of overbased, molybdenum-alkaline earth metal sulfonate dispersions
US4659488A (en) * 1985-09-18 1987-04-21 The Lubrizol Corporation Metal working using lubricants containing basic alkaline earth metal salts
FR2588268B1 (fr) * 1985-10-03 1988-02-05 Elf France Procede de synthese d'additifs surbases par carbonatation sous pression constante d'anhydride carbonique
US4744920A (en) * 1986-12-22 1988-05-17 The Lubrizol Corporation Borated overbased material
US4965003A (en) * 1989-04-21 1990-10-23 Texaco Inc. Borated detergent additive by an improved process
US4965004A (en) * 1989-04-21 1990-10-23 Texaco Inc. Process for a borated detergent additive

Also Published As

Publication number Publication date
FR2612526A1 (fr) 1988-09-23
DE3864483D1 (de) 1991-10-02
FR2612526B1 (fr) 1990-02-02
WO1988007073A1 (fr) 1988-09-22
EP0308445A1 (de) 1989-03-29
US5098587A (en) 1992-03-24
JPH01502759A (ja) 1989-09-21

Similar Documents

Publication Publication Date Title
EP0404650B1 (de) Überbasischen Molybdänkomplex enthaltende Schmieröladditive, Verfahren zu ihrer Herstellung und Zusammensetzung, die sie enthalten
BE1001979A3 (fr) Concentres et compositions d'huiles lubrifiantes.
EP0133088B1 (de) Verfahren zur Herstellung von auf Calcium basierten Detergenz-Dispergierzusätzen mit sehr hoher Alkalität und die erhaltenen Produkte
EP0007257B1 (de) Verfahren zur Herstellung von Reinigungsmittellösungen hoher Alkalität für Schmieröle und daraus hergestelltes Produkt
EP0308445B1 (de) Verfahren zur herstellung eines ein anorganisches borderivat enthaltenden überbasischen additivs, danach erhaltene additive und diese enthaltende schmiermittel
EP0003694A1 (de) Verfahren zur Bereitung von hochbasischen Mitteln mit detergierender, dispergierender Wirkung für Schmieröle, und so erhaltenes Produkt
EP0007260B1 (de) Verfahren zur Herstellung von Metall enthaltenden reinigenden dispergierenden Zusatzstoffen hoher Alkalität, besonders für Schmieröl, und daraus hergestelltes Produkt
FR2460322A1 (fr) Additif pour huile lubrifiante, a base d'un produit de reaction alkylphenol-olefine sulfure
FR2529224A1 (fr) Nouvel additif detergent-dispersant suralcalinise pour huiles lubrifiantes
EP0536020A1 (de) Bor, Schwefel und Phosphor enthaltende kolloidale Produkte, ihre Herstellung und ihre Verwendung als Schmieröladditive
FR2762848A1 (fr) Utilisation de composes borates pour ameliorer la compatibilite d'huiles lubrifiantes avec des elastomeres fluorocarbones
EP0665217B1 (de) Sulfonierte Wismutverbindungen, ihre Herstellung und ihre Verwendung zur Herstellung von überbasischen kolloidalen Produkten, verwendbar als Zusätze für Schmiermittel
EP0101334B1 (de) Metallenthaltender Detergens-Dispergierzusatz von hoher Alkalität für Schmieröle
EP0425367B1 (de) Kupferderivat oder Kupfer- und Borderivat enthaltendes Schmieröladditiv, Verfahren zu seiner Herstellung und dieses Additiv enthaltende Zusammensetzungen
US4608184A (en) Phenate process and composition improvement
FR2588267A1 (fr) Additifs aux huiles lubrifiantes comportant un sel metallique d'un acide amine, leur procede de preparation et compositions lubrifiantes renfermant lesdits additifs
FR2588269A1 (fr) Procede de preparation d'additifs surbases tres fluides et a basicite elevee et composition contenant lesdits additifs
CA1124227A (fr) Procede de preparation de detergents-dispersants metalliques suralcalinises pour huiles lubrifiantes et produits obtenus
EP0383359A2 (de) Verfahren zur Herstellung eines, ein anorganisches Borderivat enthaltenden, überbasischen Additivs, so erhaltenes Additiv und Schmiermittel, die dieses Additiv enthalten
EP0562912A1 (de) Geschaufelte organische Verbindung enthaltende überbasische kolloidale Produkte und ihre Verwendung als Reinigungsmittelzusätze mit Verschleissvermindernder und Extremdruck-Wirkung in Schmieröle
FR2588270A1 (fr) Procede de preparation d'un additif pour les huiles lubrifiantes, l'additif ainsi obtenu et une composition lubrifiante renfermant ledit additif
EP0438942A1 (de) Überbasische Detergensmittel für Schmieröle, die ein organisches Derivat von Phosphor enthalten und diese enthaltende Schmierölzusammensetzungen
FR2551765A1 (fr) Procede en une seule operation pour la preparation de graisses et de compositions epaisses a base de sulfonate de calcium a exces basique
FR2541685A1 (fr) Composition d'huile lubrifiante contenant un complexe de succinimide d'ester d'acide gras borate du glycerol
EP0639634A1 (de) Kalzium und/oder Magnesium auch Schwefel und Stickstoff enthaltende Kolloidale Produkte, ihre Herstellung und ihre Verwendung, insbesondere als Schmieröladditive

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: 19881123

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19890914

18W Application withdrawn

Withdrawal date: 19910118

D18W Application withdrawn (deleted)
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

REG Reference to a national code

Ref country code: DE

Ref legal event code: 8580

Free format text: IN HEFT 17/91, SEITE 4700, SP.3: DIE VEROEFFENTLICHUNG IST ZU STREICHEN

AK Designated contracting states

Kind code of ref document: B1

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

XX Miscellaneous (additional remarks)

Free format text: TEILANMELDUNG 90104404.0 EINGEREICHT AM 16/03/88.

REF Corresponds to:

Ref document number: 3864483

Country of ref document: DE

Date of ref document: 19911002

ITF It: translation for a ep patent filed

Owner name: DOTT. ING. FRANCO RASTELLI

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: FR

Payment date: 19930126

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930305

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19930331

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19930409

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930527

Year of fee payment: 6

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

Ref country code: GB

Effective date: 19940316

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

Ref country code: BE

Effective date: 19940331

BERE Be: lapsed

Owner name: ELF FRANCE

Effective date: 19940331

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

Ref country code: NL

Effective date: 19941001

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940316

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

Ref country code: FR

Effective date: 19941130

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

Ref country code: DE

Effective date: 19941201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: IT

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

Effective date: 20050316