EP0308445A1 - Process for the preparation of a superalkalinized additive containing an inorganic boron derivative, additive produced by said process and lubricating compositions containing said additive. - Google Patents

Process for the preparation of a superalkalinized additive containing an inorganic boron derivative, additive produced by said process and lubricating compositions containing said additive.

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Publication number
EP0308445A1
EP0308445A1 EP88902504A EP88902504A EP0308445A1 EP 0308445 A1 EP0308445 A1 EP 0308445A1 EP 88902504 A EP88902504 A EP 88902504A EP 88902504 A EP88902504 A EP 88902504A EP 0308445 A1 EP0308445 A1 EP 0308445A1
Authority
EP
European Patent Office
Prior art keywords
weight
boron
reaction mixture
additive
esters
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
EP88902504A
Other languages
German (de)
French (fr)
Other versions
EP0308445B1 (en
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
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Application filed by Elf France SA filed Critical Elf France SA
Publication of EP0308445A1 publication Critical patent/EP0308445A1/en
Application granted granted Critical
Publication of EP0308445B1 publication Critical patent/EP0308445B1/en
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Expired - Lifetime legal-status Critical Current

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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 over-alkalized additive for lubricating oils containing a boron derivative, the additive thus obtained and a lubricant composition containing said additive.
  • additives improving their properties.
  • these additives are detergents, dispersants, anti-wear and extreme pressure additives and additives providing a basic reserve.
  • the detergent and dispersing properties of a lubricant correspond to its ability to maintain impurities and burnt i 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.
  • Anti-wear additives act by forming a solid or plastic thin 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 metal carbonates in a detergent solution of the al yl sulfonate, phenate or salicylate type.
  • Antiwear additives are generally sulfur and / or phosphorus compounds, the most commonly used being the 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 the 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 format of a complex by heating the intermediate product fo by reaction of boric acid with the overbased sulfonate.
  • US Patent 4,539,126 claims the preparation of complexes by reaction of boric acid with overbased alkylsalicylate.
  • the alkaline value (VA) is fictitiously equivalent to the number of milligrams of KOH per gram of additive surba titrated by a strong acid. It is determined by direct potentiometric dosa according to standard ASTM D-2896.
  • the process for the preparation of overbased additi with antiwear effect consists in carbonating a reaction mixture composed of at least detergent, of a metal, alkali or alkaline earth derivative of at least one nitrogenous and / or oxygenated promoter in a diluting oil and a hydrocarbon solvent characterized in that it operates in the presence of at least one boron derivative.
  • Inorganic or bi organic derivatives of boron can be used.
  • the oxides and anhydrides of boron as well as boric ac and its salts.
  • esters boric acid and the liberated or esterified alkyl and arylboronic acids are particularly useful.
  • Esters are formed with aliphatic, cyclic or phenol alcohols.
  • the aliphatic alcohols are generally linear or branched in C. to C__ and preferably in C.
  • glycols having the two hydroxyl groups in positions 1-2, 1-3, or 1-4, such as glycol, propylene glycol or neopentyl glycol as well as polyglycols such as diethylene glycol, dipropyl glycol or tripropylene glycol.
  • Polyols such as glycerol, trimethylolpropane or pentaerythritol are also suitable.
  • alkoxyalkanols and preferably the alkoxyalkanols corresponds to the general formula RO (CHR .. (CH_) JOL H or R is C 1 to C alkyl group, R. hydrogen or an alk group C- to C. ,, a is between 1 and 3 and b corresponds or 2.
  • alkoxyalkanols examples include methoxyethanol, 1 • ethoxyethanol or ETHYL-CELLOSOLVE and BUTYL-CELLOSOLVE.
  • Alcohols the molecule of which contains several amino functions, are also suitable.
  • alkanolamines such as diethanolamine or triethanola ine and oxyalkylated alkylmono polyamines.
  • the oxyalkylated alkyl monoamines preferably correspond to the formula R_NH Z, or R is hydrogen or alkyl, C. to C__ preferably C.
  • Q to C-, g corresponds to the group -CHR, -CH? -OH, R., being a C 1 to C 4 alkyl group or an aromatic ring, c may be 0 or and c + d is equal to 2.
  • the oxyalkylated alkyl polyamines preferably correspond to the formula R_NZ n - (CH_) -NZ_Z, or Z., Z_ and identical or different correspond to hydrogen and at least one of the three corresponds to Z defined above, R_ has the same meaning as above .
  • cyclic alcohols cyclopentanol, cyclohexanol and their mono polyalkylated derivatives can be mentioned on the ring.
  • phenols phenol itself and its substituted derivatives, such as cresols, are most commonly used.
  • the boric acid esters can be prepared by any known method, in particular by reacting boron trichloride with alcohols and phenols. In the event of the esterification of boric acid by the polyols, the water formed must be removed by azeotropic entrainment.
  • boron derivatives are used alone or as a mixture.
  • the boron derivatives can be added to the reaction mixture in pulverulent form, optionally previously dispersed in an oil, in the form of an aqueous solution or in liquid form.
  • the detergents commonly used in overbased additives are salts of sulfonic acids, salicyclic acids or phenols
  • R 4 is a radical hydrocarbon from 12 to 100 carbon atoms, n is between i and 6 and m is between 1 and 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.
  • Oil-soluble salicylic acids substituted on the aromatic ring by a chain have at least 10 and in general 16 to 18 carbon atoms.
  • the phenols soluble in organic medium which are particularly advantageous in the context of the invention are phenols substituted by one or more linear or branched alkyl chai comprising at least 8 carbon atoms.
  • the most common commercial products are for example nonylphenol, dinonylphenol, dodecylphenol and their mixtures.
  • Phenols are used in the form of alkali or alkaline earth metal salts. They are particularly appreciated after having undergone sulfurization by reaction with the flower of sulfur or enc with sulfur chloride.
  • Sulfonic salicylic acids or phenols can be used in mela with dispersants derived from alkenylsuccinic acids chain greater than or equal to 12 carbon atoms or b 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 C 1 to C 2, most often methanol, ethanol, butanol or glycols. Ethers such as dioxolane or dialkoxymethanes are also used.
  • the alcohols can be used alone when mixed with water.
  • the nitrogen promoters are among others 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 7,100 or 150 Neutral or naphtenic oils, type 100 Pa 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. o a slight overpressure, a gas diffuser and a solvent recovery system.
  • the boron derivatives are used in the form of an oil dispersion, 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 boron derivatives used in liquid form are certain boric esters and alkyl or ary boronic acids.
  • the pulverulent, liquid compounds or the aqueous solutions are introduced before carbonation o during carbonation a few minutes after starting the starting of the reaction.
  • the reaction mixture is subjected to vigorous stirring until the introduction of 50 to 350 parts by inch of carbon dioxide by bubbling into the reaction millet.
  • the duration of carbonation generally varies from 20 minutes to 4 hours at constant flow.
  • 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 just one step, but generally there are two steps.
  • the solvents, apart from the hydrocarbon diluent, are removed by heating and then the solid residues by centrifugation or filtrate 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 KOH / g. VAs greater than 300 and even 500 can be obtained.
  • VA alkaline values
  • reaction mixture free of bo 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 d alkaline values (VA) generally greater than 150 KOH / g. VAs greater than 250 even 320 can be obtained.
  • the amount of boron incorporated can vary between 0 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 by mechanical tests commonly used, such as the method of the 4 wear balls (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 limpid aspect and keep a homogeneous consistency over time. They have viscosities sufficiently low to allow easy handling and are compatible with the other additives usually 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.
  • Example 3 The procedure of Example 1 is repeated except that 1 'adds 5 g of sodium metaborate tetrahydrate to the reaction medium before the 10th minute of carbonation. collects a product much more fluid than the previous VA 425, stable in oil and whose boron content is about 0.37% by weight EXAMPLE 3
  • Example 4 The experiment described in Example 1 is repeated, except that 2g of powdered sodium tetraborate are added to the reaction medium before the 10th minute of carbonation. A product of VA 403 mg KOH / g whose boron content is 0.45% by weight is collected. EXAMPLE 4
  • Example 6 A simple mixture of 13 g of overbased sulfonate in Example 1 is prepared with 3 g of the dispersion of sodium tetraborate in Example 4. A product of VA 35 containing 0.36% by weight of boron, with a cloudy appearance, is obtained. Examination with an electron microscope of the product shows the presence of calcium carbonate globules of 60 A diameter and sodium borate particles of 0.6 ⁇ m diameter. EXAMPLE 6
  • Example 3 The procedure described in Example 3 is repeated, with the difference that 4 g of 200N diluent oil are introduced instead of 22.5 g. 20.5 g of the sodium tetraborate dispersion of Example 4 are added before the carbonation begins. A product with a clear appearance, of 369 mg KOH / g at 0.46% by weight of boron, is then collected. IL "examination with an electron microscope reveals the presence of globules of approximately 60 A in diameter only. The analysis of globules in loss of energy gives a spectrum where 1'O notices a peak characteristic of the presence of boron.
  • Example 6 according to the invention allows effective incorporation of boron into the globules of the colloidal dispersion.
  • Example 3 The procedure of Example 3 is repeated, except that 30 grams of calcium oxide, 10.2 ml of water are introduced and the product is carbonated for 75 minutes at a rate of 103 ml / minute. Before the 15th minute of carbonation o add 9.52g of potassium tetraborate powder. O collects a clear product of VA 310 mg KOH / g and contains 0.86% by weight of boron.
  • Example 9 The procedure of Example 7 is repeated, but the boron compound is boric acid. 8.98 g of boric acid and powder are added to the 10th minute of carbonation. We then obtain a product of VA 411 mg KOH / g and of very viscous consistency. It contains 1.23% by weight of boron. EXAMPLE 9
  • Example 10 The procedure of Example 7 is repeated after adding only 4.5 ml of methanol to the reaction medium. O obtains a clear, very fluid product of VA 298 mg KOH / and containing 1.3% by weight of boron.
  • EXAMPLE 10 The procedure of Example 7 is repeated after adding only 4.5 ml of methanol to the reaction medium. O obtains a clear, very fluid product of VA 298 mg KOH / and containing 1.3% by weight of boron.
  • Example 8 The procedure of Example 8 is repeated, but the diluent oil is replaced with 28.5 g of a dispersion of boric acid in the oil at around 5% by weight of boron. This dispersion is introduced into the mixture before the start of carbonation. A clear product of VA 303 KOH / g and 1.2% by weight of boron is obtained.
  • Example 8 The procedure of Example 8 is repeated, but 11.2 of powdered boron trioxide are added.
  • Example 7 The procedure of Example 7 is repeated but 1 of trimethylborate is added to the 10th minute of carbonation. then obtains a viscous product of VA 437 mg KOH / g e 1.2% by weight of boron.
  • Example 14 The procedure of Example 1 is repeated except that 9.53 g of powdered diammonium tetraborate are added after minutes of carbonation. A relatively fluid limp product of VA 438 mg KOH / g and containing 1, weight of boron is obtained.
  • EXAMPLE 14 The procedure of Example 1 is repeated except that 9.53 g of powdered diammonium tetraborate are added after minutes of carbonation. A relatively fluid limp product of VA 438 mg KOH / g and containing 1, weight of boron is obtained.
  • Example 10 The procedure of Example 10 is repeated but the same conditions are added 19.06 g of diammonium tetraborate.
  • a product of VA 437 mg KOH / g is collected which contains 1, weight of boron.
  • Example 10 The procedure of Example 10 is repeated, but the carbonate additive for 23 minutes at 148 ml / minute.
  • reaction mixture is carbonated as soon as the temperature has dropped to 49 ° C.
  • Example 1 The procedure of Example 1 is repeated except that the o uses instead of the C_ 4 -benzene sulfonic acid, 23 of an 80/20 mixture by mole of C_ 4 acid ⁇ benzene sulfonic acid by weight. molar 520 to 70% of active material and C_ carboxylic acid obtained by hydroformylation of olefin (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 210ml / minute.
  • a solution of propylene glycol borate in xylene is prepared by heating to 50 ° C. with stirring of a mixture of 46.4 g of propylene glycol, 41 g of boric acid and 300 m of xylene. The water formed is removed by azeotropic distillatio. 314 g of a 2.6% boron solution are obtained Into the reactor described above, from Example 1, 34.6 g of the propylene glycol borate solution, 16.61 g of C., ⁇ -alkylbenzenesulfonic acid 96% of active material and of molecular weight 430, 24, d are introduced. diluent oil, 112ml of xylene, 7ml of methanol and 23ml of slaked lime at 99% purity.
  • the mixture is carbonated for 26 minutes at 42 at a flow rate of 230ml / minute.
  • the mixture is carbonate at a flow rate of 156 ml / minute for 26 minutes at a temperature of 42 ° C.
  • the limpi product collected has a VA of 351 and contains 0.36% of boron.
  • the mixture is brought to reflux for 3 hours then it is carbonated for 50 minutes a flow rate of approximately 90 ml / minute at a temperature of 53 ° C.
  • the solvents and the hydrocarbon diluent are removed by heating to 100 ° under reduced pressure.
  • Example 19 The procedure of Example 19 is repeated, except that 6.75 g of powdered diammoni tetraborate are added to the reaction medium after 10 minutes of carbonation. A relatively fluid product is obtained, of VA 267 mg KOH and containing 1.43% of boron.
  • the procedure is as in the previous example but by introducing 40.6 g of tributylborate and 28 ml of methanol before carbonation.
  • the product has a VA of 265 and contains 1.8% boron.

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

Abstract

Cette invention concerne un procédé de préparation d'un additif suralcanisé à effet anti-usure pour huiles lubrifiantes par carbonation d'un mélange réactionnel composé d'au moins un détergent, d'un dérivé d'un métal alcalin ou alcalinoterreux, d'au moins un promoteur azoté et/ou oxygéné et d'un dérivé du bore, dans une huile diluante et un solvant hydrocarboné.This invention relates to a process for the preparation of an overbased additive with an anti-wear effect for lubricating oils by carbonation of a reaction mixture composed of at least one detergent, a derivative of an alkali metal or alkaline earth metal, least one nitrogenous and/or oxygenated promoter and of a boron derivative, in a diluent oil and a hydrocarbon solvent.

Description

PROCEDE DE PREPARATION D'UN ADDITIF SURALCANISE RENFERMANT UN DERIVE DU BORE, L'ADDITIF AINSI OBTENU ET COMPOSITIONS LUBRIFIANTES RENFERMANT LEDIT ADDITIF PROCESS FOR THE PREPARATION OF AN OVERALCANIZED ADDITIVE CONTAINING A BORON DERIVATIVE, THE ADDITIVE THUS OBTAINED AND LUBRICANT COMPOSITIONS CONTAINING THE ADDITIVE
Cette invention concerne un procédé de préparation d'un additif suralcanisé pour huiles lubrifiantes renfermant un dérivé du bore, l'additif ainsi obtenu et une composition lubrifiante renfermant ledit additif.This invention relates to a process for preparing an over-alkalized additive for lubricating oils containing a boron derivative, the additive thus obtained and a lubricant composition containing said additive.
Les combustibles, en particulier ceux utilisés dans les moteurs à fuel ou à fuel lourd contiennent des quantités de plus en plus importantes de soufre. En même temps, les conditions de fonctionnement deviennent plus sévères.Fuels, in particular those used in fuel or heavy fuel engines, contain increasing amounts of sulfur. At the same time, the operating conditions become more severe.
Il est devenu nécessaire d'ajouter aux huiles lubrifiantes divers additifs améliorant leurs propriétés. Parmi ces additifs on trouve des détergents, des dis¬ persants, des additifs- antiusure et extrême pression et des additifs apportant une réserve de basicité.It has become necessary to add to the lubricating oils various additives improving their properties. Among these additives are detergents, dispersants, anti-wear and extreme pressure additives and additives providing a basic reserve.
Les propriétés détergentes et dispersantes d'un lubrifiant correspondent à son aptitude à maintenir en suspension les impuretés et les i brulés dans les parties chaudes du moteur par son effet de détergence mais également dans les parties froides par son effet dispersant. La fixation de ces particules sous forme de vernis ou de laques est ainsi évitée.The detergent and dispersing properties of a lubricant correspond to its ability to maintain impurities and burnt i 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.
Le rôle des additifs à réserve de basicité consiste à combattre l'acidité provoquée dans les moteurs par la combustion des dérivés organiques soufrés contenus dans les carburants et par l'oxydation des composants des huiles lubrifiantes.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.
Les additifs antiusure agissent par formation d'un film mince solide ou plastique qui sépare les surfaces frottantes et évitent l'usure des différentes parties du moteur. Les propriétés détergentes et dispersantes ains que la réserve de basicité sont apportées en général par de additifs suralcalinisés. Il s'agit de carbonates de métau alcalins ou alcalinoterreux dans une solution de détergen du type al yl sulfonate, phénate ou salicylate.Anti-wear additives act by forming a solid or plastic thin 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 metal carbonates in a detergent solution of the al yl sulfonate, phenate or salicylate type.
Les additifs antiusure sont en général de composés soufrés et/ou phosphor s, les plus courammen utilisés étant les dialkyldithiophosphates de Zn.Antiwear additives are generally sulfur and / or phosphorus compounds, the most commonly used being the Zn dialkyldithiophosphates.
Les dérivés du bore forment une autre class d'additifs antiusure. Les composés minéraux du bor apportent une fonction antiusure et extrême pressio (brevets américains 3 907691 et 4 100081) tandis que le composés organiques apportent plutôt des propriété antiusure et antifriction (brevets américains 4 549975 e 4 599 183).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 the organic compounds provide antiwear and antifriction properties rather (American patents 4,549,775 and 4,599,183).
L'incorporation d'un composé du bore dans u additif suralcalinisé permettrait de disposer d'un additi ultifonctionnel présentant une réserve de basicité, de propriétés de détergent, de dispersant et d'antiusure Différentes méthodes d'incorporation du bore dans un additi surbasé ont été envisagées.The incorporation of a boron compound into an overbased additive would make it possible to have a multifunctional additive having a reserve of basicity, detergent, dispersant and anti-wear properties. Various methods of incorporating boron into an overbased additi have been considered.
La méthode la plus évidente serait le remplacemen pur et simple de l'anhydride carbonique par l'acide borique Ce procédé est envisagé dans les brevets américains 3 85377 et 4 601837. Cependant pour des raisons liées à l différence de réactivité entre l'anhydride carbonique e l'acide ou l'anhydride borique, signalées dans le breve américain 3 785976, cette substitution se révèle difficile.The most obvious method would be the pure and simple replacement of carbon dioxide by boric acid. This process is envisaged in American patents 3 85377 and 4 601837. However for reasons related to the difference in reactivity between carbon dioxide e boric acid or anhydride, reported in the US patent 3 785976, this substitution proves difficult.
L'art antérieur s'est orienté vers des composés d bore tels que l'acide borique et ses esters organiques o bien l'oxyde de bore qui sont alors ajoutés à des additif préalablement suralcalinisés classiques renfermant d carbonate de calcium. De tels mélanges décrits dans le brevets américains 3 480548, 4 089790, 3 829381 et 4 56048 présentent des inconvénients du point de vue de leu stabilité et de leur compatibilité avec les autres additif de la formulation lubrifiante. Afin d'améliorer leur stabilité, le bre américain 3 929650 revendique la possibilité d'utiliser produit dispersant du type alkénylsuccinimide.The prior art has focused on boron compounds such as boric acid and its organic esters or boron oxide, which are then added to conventional over-alkalinized additives containing calcium carbonate. Such mixtures described in US Patents 3,480,548, 4,089,790, 3,829,381 and 4,56048 have drawbacks from the point of view of their stability and their compatibility with the other additives of the lubricant formulation. In order to improve their stability, US Patent 3,929,650 claims the possibility of using a dispersant of the alkenyl succinimide type.
Le brevet américain 3 907691 prévoit la format d'un complexe par chauffage du produit intermédiaire fo par réaction de l'acide borique avec le sulfonate surbas Le brevet américain 4 539126 revendique la préparation complexes par réaction d'acide borique avec alkylsalicylate surbasé.US Patent 3,907,691 provides for the format of a complex by heating the intermediate product fo by reaction of boric acid with the overbased sulfonate. US Patent 4,539,126 claims the preparation of complexes by reaction of boric acid with overbased alkylsalicylate.
Le brevet américain 3 928216 signale l'utilisati de quantités catalytiques de sels de bore d'une a i pendant la réaction de surbasage.US Patent 3,928,216 reports the use of catalytic amounts of boron salts from one to one during the overbasing reaction.
Le brevet américain 3 679584 suggère un mo opératoire en deux étapes. A un additif suralcalini classique préparé dans une première étape, on ajoute da une deuxième étape 1*acide borique et 1'anhydri carbonique. Cependant la valeur alcaline du mélan suralcalinisé chute très fortement pendant cette secon étape, passant par exemple de 295 à 177.American patent 3 679584 suggests a two-step procedure. To a conventional surcalcalini additive prepared in a first step, is added in a second step 1 * boric acid and carbon dioxide. However, the alkaline value of the overbased melan drops very sharply during this second stage, passing for example from 295 to 177.
La valeur alcaline (VA) équivaut fictivement nombre de milligrammes de KOH par gramme d'additif surba titré par un acide fort. Elle est déterminée par dosa potentiométrique direct suivant la norme ASTM D-2896.The alkaline value (VA) is fictitiously equivalent to the number of milligrams of KOH per gram of additive surba titrated by a strong acid. It is determined by direct potentiometric dosa according to standard ASTM D-2896.
Tous les procédés basés sur le mélange d'un déri du bore avec un additif déjà suralcalinisé donnent d produits peu stables dont la teneur en bore et la vale alcaline sont également faibles.All the processes based on the mixture of a boron derivative with an already overbased additive give unstable products whose boron and alkaline value are also low.
Ces mélanges se présentent en général sous for de liquide d'aspect trouble. Contrairement aux carbonat alcalinoterreux qui forment des dispersions colloïdales, l dérivés du bore restent sous forme de particules solid grossières responsables de l'aspect trouble du liquid Ces particules solides en suspension pourraient aller 1 'encontre de l'effet recherché avec des additifs antiusu en provoquant par exemple l'abrasion des moteurs. précipitant ils conduisent à des sédiments gênants et à u hétérogénité dans la concentration en métal. La présente invention permet de palier c inconvénients et de préparer des additifs suralcalinisés teneur significative en bore et à valeur alcaline élevé Les dérivés du bore étant incorporés dans les globules de dispersion colloïdale, ces additifs sont homogènes stables et présentent de très bonnes propriétés antiusure.These mixtures are generally in the form of a liquid with a cloudy appearance. Unlike the alkaline earth carbonates which form colloidal dispersions, the boron derivatives remain in the form of coarse solid particles responsible for the cloudy appearance of the liquid. These solid particles in suspension could go against the desired effect with antiusu additives by causing for example the abrasion of engines. precipitating they lead to troublesome sediments and to heterogeneity in the metal concentration. The present invention makes it possible to overcome these drawbacks and to prepare overbased additives with a significant boron content and a high alkaline value. The boron derivatives being incorporated in the globules of colloidal dispersion, these additives are homogeneous stable and have very good antiwear properties.
Le procédé de préparation d'additi suralcalinisés à effet antiusure selon l'invention consis à carbonater un mélange réactionnel composé d'au moins détergent, d'un dérivé de métal, alcalin ou alcalinoterreu d'au moins un promoteur azoté et/ou oxygéné dans une hui diluante et un solvant hydrocarboné caractérisé en ce qu' opère en présence d'au moins un dérivé du bore.The process for the preparation of overbased additi with antiwear effect according to the invention consists in carbonating a reaction mixture composed of at least detergent, of a metal, alkali or alkaline earth derivative of at least one nitrogenous and / or oxygenated promoter in a diluting oil and a hydrocarbon solvent characterized in that it operates in the presence of at least one boron derivative.
On peut utiliser les dérivés inorganiques ou bi organiques du bore.Inorganic or bi organic derivatives of boron can be used.
Parmi les dérivés inorganiques du bore on pe mentionner les oxydes et anhydrides du bore ainsi que l'ac borique et ses sels. L'acide borique et son sel d'ammoniu le tétraborate de diammonium ( (NH.) _ B.07.4H_0) son sel sodium, le tétraborate de sodium (Na_B407.nH_0) son sel potassium, le tétraborate de potassium (K_B.0_.nH_0) et s sel de lithium, le tétraborate de lithium (Li_B.0_.5H_ conviennent particulièrement.Among the inorganic boron derivatives, for example, the oxides and anhydrides of boron as well as boric ac and its salts. Boric acid and its ammonium salt diammonium tetraborate ((NH.) _ B.0 7 .4H_0) its sodium salt, sodium tetraborate (Na_B 4 0 7 .nH_0) its potassium salt, tetraborate potassium (K_B.0_.nH_0) and s lithium salt, lithium tetraborate (Li_B.0_.5H_ are particularly suitable.
Nous pouvons mentionner également le métaborate baryum (Ba0.B_0_.nH_0) , le borate de manganèse (MnB.07)et borate de plomb (Pb(B0_)_) .We can also mention barium metaborate (Ba0.B_0_.nH_0), manganese borate (MnB.0 7 ) and lead borate (Pb (B0 _) _).
Parmi le dérivés organiques du bore les esters 1'acide borique et les acides alkyl et arylboroniques libr ou estérifiés sont particulièrement utiles.Among the organic boron derivatives, the esters boric acid and the liberated or esterified alkyl and arylboronic acids are particularly useful.
Les esters sont formés avec des alcoo aliphatiques, cycliques ou avec des phénols.Esters are formed with aliphatic, cyclic or phenol alcohols.
Les alcools aliphatiques sont en général à chai linéaire ou ramifiée en C. à C__ et de préférence en C.The aliphatic alcohols are generally linear or branched in C. to C__ and preferably in C.
C4. A la place des monoalcools on peut avantageusem utiliser les glycols, ayant les deux groupes hydroxyl position 1-2, 1-3, ou 1-4, comme le glycol, propylène-glycol ou le neopentylglycol ainsi que polyglycols tels que le diethylèneglycol, le dipropyl glycol ou le tripropylèneglycol. C 4. Instead of monoalcohols, it is advantageous to use glycols, having the two hydroxyl groups in positions 1-2, 1-3, or 1-4, such as glycol, propylene glycol or neopentyl glycol as well as polyglycols such as diethylene glycol, dipropyl glycol or tripropylene glycol.
Les polyols comme le glycerol, triméthylolpropane ou le pentaerythritol convienn également.Polyols such as glycerol, trimethylolpropane or pentaerythritol are also suitable.
Il est également possible d'utilier alkoxyalcanols et de préférence les alkoxyalcanols répond à la formule générale RO(CHR.. (CH_) J-O-L H ou R est groupe alkyle en C. à C . , R. l'hydrogène ou un groupe alk en C- à C.,, a est compris entre 1 et 3 et b correspond ou 2.It is also possible to use alkoxyalkanols and preferably the alkoxyalkanols corresponds to the general formula RO (CHR .. (CH_) JOL H or R is C 1 to C alkyl group, R. hydrogen or an alk group C- to C. ,, a is between 1 and 3 and b corresponds or 2.
Comme exemples d'alkoxyalcanols on peut mention le methoxyethanol, 1•éthoxyethanol ou ETHYL-CELLOSOLVE et BUTYL-CELLOSOLVE.As examples of alkoxyalkanols one can mention methoxyethanol, 1 • ethoxyethanol or ETHYL-CELLOSOLVE and BUTYL-CELLOSOLVE.
Les alcools dont la molécule renferme un plusieurs fonctions aminés conviennent également. Ainsi peut utiliser les alkanolamines, telles que diethanolamine ou la triethanola ine et les alkylmono polyamines oxyalkylées.Alcohols, the molecule of which contains several amino functions, are also suitable. Thus can use alkanolamines, such as diethanolamine or triethanola ine and oxyalkylated alkylmono polyamines.
Les alkylmonoamines oxyalkylées répondent préférence à la formule R_NH Z, ou R_ est l'hydrogène ou groupe alkyle en C. à C__ de préférence en C.Q à C-,g, correspond au groupement -CHR,-CH?-OH, R., étant un grou alkyle en C.. à C4 ou un noyau aromatique, c peut être 0 ou et c+d est égal à 2.The oxyalkylated alkyl monoamines preferably correspond to the formula R_NH Z, or R is hydrogen or alkyl, C. to C__ preferably C. Q to C-, g, corresponds to the group -CHR, -CH? -OH, R., being a C 1 to C 4 alkyl group or an aromatic ring, c may be 0 or and c + d is equal to 2.
Les alkylpolyamines oxyalkylées répondent préférence à la formule R_NZn- (CH_) -NZ_Z, ou Z. ,Z_ et identiques ou différents correspondent à l'hydrogène et moins un des trois correspond à Z défini ci-dessus, R_ a même signification que précédemment.The oxyalkylated alkyl polyamines preferably correspond to the formula R_NZ n - (CH_) -NZ_Z, or Z., Z_ and identical or different correspond to hydrogen and at least one of the three corresponds to Z defined above, R_ has the same meaning as above .
Parmis les alcools cycliques on peut mentionner cyclopentanol, le cyclohexanol et leurs dérivés mono polyalkylés sur le cycle. Parmi les phénols on utilise le plus couramment le phénol lui même et ses dérivés substitués comme les crésols.Among the cyclic alcohols, cyclopentanol, cyclohexanol and their mono polyalkylated derivatives can be mentioned on the ring. Among the phenols, phenol itself and its substituted derivatives, such as cresols, are most commonly used.
Les esters de 1'acide borique peuvent être préparés par toute méthode connue, notamment par réaction du trichlorure de bore sur les alcools et phénols. En cas de l'estérification de l'acide borique par les polyols, l'eau formée doit être éliminée par entraînement azeotropique.The boric acid esters can be prepared by any known method, in particular by reacting boron trichloride with alcohols and phenols. In the event of the esterification of boric acid by the polyols, the water formed must be removed by azeotropic entrainment.
Ces dérivés du bore sont utilisés seuls ou e mélange. Selon leur nature,les dérivés du bore peuvent êtr ajoutés au mélange réactionnel sous forme pulvérulente, éventuellement préalablement dispersé dans une huile, sous forme de solution aqueuse ou sous forme liquide.These boron derivatives are used alone or as a mixture. Depending on their nature, the boron derivatives can be added to the reaction mixture in pulverulent form, optionally previously dispersed in an oil, in the form of an aqueous solution or in liquid form.
Les détergents couramment utilisés dans les additifs suralcalinisés sont des sels d'acides sulfoniques, d'acides salicycliques ou de phénolsThe detergents commonly used in overbased additives are salts of sulfonic acids, salicyclic acids or phenols
Ces détergents peuvent être avantageusemen utilisés en mélange avec des alkyl-succinamides de formul générale :These detergents can be advantageously used in admixture with alkyl succinamides of general formula:
- •*-£+-(CH2 ) ou R 4. est un radical hydrocarboné de- 12 à 100 atomes de carbone, n est compri entre i et 6 et m est compris entre 1 à 5.- • * - £ + - ( CH 2 ) or R 4. is a radical hydrocarbon from 12 to 100 carbon atoms, n is between i and 6 and m is between 1 and 5.
Les acides sulfoniques sont d'origine pétrolière ou synthétiques. Le poids moléculaire moyen des sulfonate pétroliers est en général supérieur à 320. Ils sont obtenu par sulfonation de distillats de pétrole. Les acide sulfoniques de synthèse sont particulièrement utiles dans l cadre de l'invention. Il peut s'agir de produits obtenus pa sulfonation 'oléfines de nombre de carbones supérieur o égal à 12 ou encore d'acides alkylarylsulfoniques.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.
Les acides alkylarylsulfoniques comportent une o plusieurs chaînes alkyles sur un noyau aromatique, e général un noyau benzenique. Les chaînes alkyles doiven comporter un minimum de 8 atomes de carbone. Leur structur est linéaire ou ramifiée. On utilise couramment le benzène toluène, xylène ou napthalène alkyles avec des alpha oléfines en C._ à C.,, avec des paraffines en C_0^___ ou ave les tetramέres de propylène (acide C_4-benzenesulfonique) . Les acides salicyliques solubles dans l'huile s substitués sur le noyau aromatique par une chaine comport au moins 10 et en général 16 à 18 atomes de carbone.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. Are commonly used toluene, benzene, xylene or naphthalene alkylated with alpha olefins to C._ C. ,, with paraffins C_ 0 ^ ___ ave or propylene tetramέres (C_ 4- -benzenesulfonique). Oil-soluble salicylic acids substituted on the aromatic ring by a chain have at least 10 and in general 16 to 18 carbon atoms.
Les phénols solubles en milieu organique particulièrement intéressants dans le cadre de l'invent sont des phénols subsitués par une ou plusieurs chai alkyles linéaires ou ramifiées comportant au moins 8 ato de carbone. Les produits commerciaux les plus courants s par exemple le nonylphenol, le dinonylphenol, dodecylphenol et leurs mélanges.The phenols soluble in organic medium which are particularly advantageous in the context of the invention are phenols substituted by one or more linear or branched alkyl chai comprising at least 8 carbon atoms. The most common commercial products are for example nonylphenol, dinonylphenol, dodecylphenol and their mixtures.
Les phénols sont utilisés sous forme de sels métaux alcalins ou alcalinoterreux. Ils s particulièrement appréciés après avoir subi sulfurisation par réaction avec la fleur de soufre ou enc avec le chlorure de soufre.Phenols are used in the form of alkali or alkaline earth metal salts. They are particularly appreciated after having undergone sulfurization by reaction with the flower of sulfur or enc with sulfur chloride.
Les additifs suralcalinisés renferment un plusieurs de ces détergents. Les acides sulfoniqu salicyliques ou les phénols peuvent être utilisés en méla avec des dispersants dérivés des acides alkenylsuccinique chaine supérieure ou égale à 12 atomes de carbone ou b avec des acides carboxyliques ayant au moins 8 atomes carbone.Overbased additives contain several of these detergents. Sulfonic salicylic acids or phenols can be used in mela with dispersants derived from alkenylsuccinic acids chain greater than or equal to 12 carbon atoms or b with carboxylic acids having at least 8 carbon atoms.
Le dérivé de métal alcalin ou alcalinoterreux es en général un oxyde, hydroxyde ou alcoolate d'un tel métalThe alkali or alkaline earth metal derivative is generally an oxide, hydroxide or alcoholate of such a metal
Les promoteurs oxygénés sont surtout des alcoo aliphatiques, en général en C. à C_ , le plus souvent methanol, l'ethanol, le butanol ou les glycols. On utili également des ethers comme le dioxolanne ou l dialkoxymethanes. Les alcools peuvent être utilisés seuls en mélange avec de l'eau.The oxygenated promoters are mainly aliphatic alcohols, generally C 1 to C 2, most often methanol, ethanol, butanol or glycols. Ethers such as dioxolane or dialkoxymethanes are also used. The alcohols can be used alone when mixed with water.
Les promoteurs azotés sont entre autr l'ammoniaque, 1 'ethylènediamine, les ethanolamines, chlorure d'ammonium ou le carbonate d'ammonium.The nitrogen promoters are among others ammonia, ethylenediamine, ethanolamines, ammonium chloride or ammonium carbonate.
Le rôle de l'huile diluante est de permettre u manipulation aisée à la température ambiante. Parmi c huiles on peut citer les huiles paraffiniques comme les 7 100 ou 150 Neutral ou les huiles naphteniques, type 100 Pa solvant. Les solvants hydrocarbonés ont une structur aliphatique, comme l'heptane, l'isooctane, le nonane ou un structure aromatique, comme le toluène ou le xylène. Ce solvants peuvent être utilisés en mélange. Il es particulièrement avantageux d'utiliser des solvants qu donnent des azeotropes avec de l'eau, comme les alcools, le glycols ou les alkoxyalcanolsThe role of the diluent oil is to allow easy handling at room temperature. Among these oils, mention may be made of paraffinic oils such as 7,100 or 150 Neutral or naphtenic oils, type 100 Pa 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
Pour la mise en oeuvre de l'invention on utilis en général un réacteur à double enveloppe, muni d'un systèm d'agitation vigoureux, d'un régulateur de température, d'u condenseur, d'un système permettant de réaliser un vide o une légère surpression, d'un diffuseur de gaz et d'u système de récupération des solvants.For the implementation of the invention, 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. o a slight overpressure, a gas diffuser and a solvent recovery system.
Selon une mise en oeuvre préférée de l'inventio on. introduit dans le réacteur :According to a preferred implementation of the invention. introduced into the reactor:
- 100 à 500 parties en poids de détergents- 100 to 500 parts by weight of detergents
- 100 à 300 parties en poids d'un dérivé de métal alcalin o alcalinoterreux- 100 to 300 parts by weight of an alkali or alkaline earth metal derivative
- 0 à 100 parties poids d'un promoteur azoté- 0 to 100 parts by weight of a nitrogenous promoter
- 30 à 300 parties poids d'un promoteur oxygéné- 30 to 300 parts by weight of an oxygenated promoter
- 0 à 100 parties poids d'eau- 0 to 100 parts by weight of water
- 100 à 500 parties poids d'une huile diluante- 100 to 500 parts by weight of a diluent oil
- 200 à 800 parties poids d'un solvant hydrocarboné- 200 to 800 parts by weight of a hydrocarbon solvent
- 15 à 400 parties en poids d'un dérivé du bore.- 15 to 400 parts by weight of a boron derivative.
Si les dérivés du bore sont utilisés sous forme d dispersion dans l'huile, cette dispersion est ajoutée a mélange réactionnel avant l'introduction de l'anhydrid carbonique. Les dérivés du bore utilisés en dispersion son l'acide borique et ses sels. Les dérivés du bore utilisé sous forme pulvérulente ou sous forme de solution aqueuse si leur solubilité est suffisante, sont l'oxyde du bore l'acide borique et ses sels.If the boron derivatives are used in the form of an oil dispersion, 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.
Les dérivés du bore utilisés sous forme liquid sont certains esters boriques et acides alkyl ou ary boroniques. Les composés pulvérulents, liquides ou le solutions aqueuses sont introduits avant la carbonatation o pendant la carbonatation quelques minutes après le démarrag le démarrage de la réaction. En utilisant des détergents du type sulfonate mélange réactionnel est soumis à une forte agitation pend que commence l'introduction de 50 à 350 parties en po d'anhydride carbonique par barbotage dans le mil réactionnel. La durée de la carbonatation varie en géné de 20 minutes à 4 heures à débit constant. La réaction exothermique. Le mélange est maintenu à une températ variant de 20 à 80°C et de préférence de 35 à 70°C.The boron derivatives used in liquid form are certain boric esters and alkyl or ary boronic acids. The pulverulent, liquid compounds or the aqueous solutions are introduced before carbonation o during carbonation a few minutes after starting the starting of the reaction. Using detergents of the sulfonate type, the reaction mixture is subjected to vigorous stirring until the introduction of 50 to 350 parts by inch of carbon dioxide by bubbling into the reaction millet. The duration of carbonation generally varies from 20 minutes to 4 hours at constant flow. The exothermic reaction. The mixture is maintained at a temperature varying from 20 to 80 ° C and preferably from 35 to 70 ° C.
Il peut être avantageux de porter à reflux mélange réactionnel renfermant le dérivé du bore, penda une durée de 30 minutes à 2 heures avant la carbonatation.It 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.
Les solvants peuvent être éliminés en une seu étape, mais en général on procède en deux étapes. On élimi les solvants, hormis le diluant hydrocarboné, par chauffag puis les résidus solides par centrifugation ou filtrati avant l'élimination du solvant hydrocarboné.Solvents can be removed in just one step, but generally there are two steps. The solvents, apart from the hydrocarbon diluent, are removed by heating and then the solid residues by centrifugation or filtrate before the removal of the hydrocarbon solvent.
Les additifs suralcalinisés obtenus par le procé selon l'invention ont des valeurs alcalines (VA), mesuré selon la norme ASTM D-2896, généralement supérieures à 200 KOH/g. Des VA supérieures à 300 et même 500 peuvent êt obtenues.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 KOH / g. VAs greater than 300 and even 500 can be obtained.
Dans le cas de l'utilisation de détergents du ty phénolique, le mélange réactionnel exempt de dérivé du bo est porté à reflux pendant au moins une demi heure. Apr refroidissement on ajoute le dérivé du bore. L'introducti de l'anhydride carbonique et le traitement subséquent déroulent comme précédemment.In the case of the use of phenolic ty detergents, the reaction mixture free of bo 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.
Les phénates suralcalinisés obtenus ont d valeurs alcalines (VA) généralement supérieures à 150 KOH/g. Des VA supérieures à 250 même à 320 peuvent êt obtenues.The overbased phenates obtained have d alkaline values (VA) generally greater than 150 KOH / g. VAs greater than 250 even 320 can be obtained.
La quantité de bore incorporé peut varier entre 0 et 10% poids et de préférence 0,25 à 5%. Cette quantité e suffisante pour apporter des propriétés antiusure aux huil lubrifiantes. Les propriétés antiusure sont mesurées av des essais mécaniques couramment utilisés, comme la métho des 4 billes usure (NF-E 48-617) et 4 billes extrê pression (ASTM D 2783-69T ou NF E 48-617) et les essa FALEX (ASTM D 32-33) . Les additifs selon l'invention ont un aspe limpide et gardent une consistance homogène dans le temp Ils ont des viscosités suffisamment faibles pour permett une manipulation aisée et sont compatibles avec les autr additifs utilisés habituellement dans les huil lubrifiantes.The amount of boron incorporated can vary between 0 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 by mechanical tests commonly used, such as the method of the 4 wear balls (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 limpid aspect and keep a homogeneous consistency over time. They have viscosities sufficiently low to allow easy handling and are compatible with the other additives usually used in lubricating oils.
Les additifs suralcalinisés sont ajoutés a huiles lubrifiantes d'origine naturelle ou synthétique à u concentration comprise entre 0,5 et 40% poids et préférence entre 1 et 30 % poids.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.
Les exemples suivants illustrent l'invention sa toutefois la limiter. EXEMPLE 1 : (Comparatif)The following examples illustrate the invention, however, limit it. EXAMPLE 1: (Comparative)
Dans un réacteur de 250ml, équipé d'un agitateur, d'u arrivée de gaz carbonique et d'un réfrigérant, on introdu 27g d'acide C_ .-alkylbenzenesulfonique à 70% de matiè active, 35g d'hydroxyde de calcium à 97% de pureté, 13,3 de methanol, 22,5g d'huile 100 N, 1,1ml d'ammoniaque à 20 150ml de xylène.27g of C_. -Alkylbenzenesulfonic acid containing 70% active material, 35g of 97% calcium hydroxide are introduced into a 250 ml reactor, equipped with an agitator, with a carbon dioxide inlet and with a condenser. % purity, 13.3 methanol, 22.5 g of 100 N oil, 1.1 ml of ammonia to 150 ml of xylene.
Le mélange est agité à 700 tours/minute et température est régulée à 49°C. L'anhydride carbonique e introduit à un débit de 230 ml/minute pendant 30 minutes. la fin de la réaction, le mélange est chauffé à 100°C po éliminer le methanol et l'eau produite par la carbonatatio Les résidus solides sont éliminés par centrifugatio pu filtration. L'élimination du xylène permet de récupérer produit fluide de basicité (VA) égale à 420mg KOH contenant 18% de calcium et qui se révèle stable en diluti dans les huiles minérales (absence de trouble après 1 mois) EXEMPLE 2 :The mixture is stirred at 700 rpm and the 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. In order to remove the methanol and the water produced by carbonation. The solid residues are removed by centrifugation or filtration. The elimination of xylene makes it possible to recover fluid product of basicity (VA) equal to 420 mg KOH containing 18% of calcium and which proves to be stable in diluti in mineral oils (absence of cloudiness after 1 month) EXAMPLE 2:
On répète la procédure de 1*exemple 1 à ceci près que 1' ajoute 5g de métaborate de sodium tetrahydrate au mili réactionnel avant la lOème minute de carbonatation. recueille un produit beaucoup plus fluide que précédemme de VA 425, stable dans l'huile et dont la teneur en bore e de l'ordre de 0,37% en poids EXEMPLE 3The procedure of Example 1 is repeated except that 1 'adds 5 g of sodium metaborate tetrahydrate to the reaction medium before the 10th minute of carbonation. collects a product much more fluid than the previous VA 425, stable in oil and whose boron content is about 0.37% by weight EXAMPLE 3
On répète l'expérience décrite dans l'exemple 1 à différence que l'on ajoute 2g de tétraborate de sod pulvérulent au milieu réactionnel avant la lOème minute carbonatation. On recueille un produit de VA 403mg KOH/g dont la teneur en bore est de 0,45% en poids. EXEMPLE 4The experiment described in Example 1 is repeated, except that 2g of powdered sodium tetraborate are added to the reaction medium before the 10th minute of carbonation. A product of VA 403 mg KOH / g whose boron content is 0.45% by weight is collected. EXAMPLE 4
Dans un réacteur d'un litre thermostaté à 60°C contena 114g d'huile 200 Neutral additivée de 12,8% de dispersant introduit, sous forte agitation 500ml d'une solution aqueu à 80°C contenant 50g/l de tétraborate de sodium. L'additi de la solution aqueuse se fait au goutte à goutte en heures.In a one liter reactor thermostatically controlled at 60 ° C contained 114 g of 200 Neutral oil with 12.8% dispersant added, with vigorous stirring 500 ml of an aqueous solution at 80 ° C containing 50 g / l of sodium tetraborate . Addition of the aqueous solution is done dropwise over hours.
L'émulsion homogène ainsi obtenue est deshydratée le pl rapidement possible. On obtient ainsi une dispersion flui de tétraborate de sodium à 17% poids dans l'huile. EXEMPLE 5 (Comparatif)The homogeneous emulsion thus obtained is dehydrated as quickly as possible. A fluid dispersion of sodium tetraborate at 17% by weight in oil is thus obtained. EXAMPLE 5 (Comparative)
On prépare un simple mélange de 13g de sulfonate surbasé 1'exemple 1 avec 3g de la dispersion de tétraborate sodium de l'exemple 4. On obtient un produit de VA 35 contenant 0,36% poids de bore, à l'aspect trouble. L'examen au microscope électronique du produit montre présence de globules de carbonate de calcium de 60 A diamètre et de particules de borate de sodium de 0,6μm diamètre. EXEMPLE 6A simple mixture of 13 g of overbased sulfonate in Example 1 is prepared with 3 g of the dispersion of sodium tetraborate in Example 4. A product of VA 35 containing 0.36% by weight of boron, with a cloudy appearance, is obtained. Examination with an electron microscope of the product shows the presence of calcium carbonate globules of 60 A diameter and sodium borate particles of 0.6 μm diameter. EXAMPLE 6
On répète la procédure décrite dans l'exemple 3 à différence qu'on introduit que 4g d'huile diluante 200N lieu de 22,5g. On ajoute avant le début de la carbonatati 20,5g de la dispersion de tétraborate de sodium de l'exemp 4. On recueille alors un produit à l'aspect limpide, de 369mg KOH/g à 0,46% poids de bore. IL"examen au microscope électronique révèle la présence d globules d'environ 60 A de diamètre uniquement. L'analys des globules en perte d'énergie donne un spectre où 1'o remarque un pic caractéristique de la présence de bore. La procédure de l'exemple 6 selon l'invention, perme d'incorporer effectivement le bore dans les globules de l dispersion colloïdale. EXEMPLE 7The procedure described in Example 3 is repeated, with the difference that 4 g of 200N diluent oil are introduced instead of 22.5 g. 20.5 g of the sodium tetraborate dispersion of Example 4 are added before the carbonation begins. A product with a clear appearance, of 369 mg KOH / g at 0.46% by weight of boron, is then collected. IL "examination with an electron microscope reveals the presence of globules of approximately 60 A in diameter only. The analysis of globules in loss of energy gives a spectrum where 1'O notices a peak characteristic of the presence of boron. Example 6 according to the invention allows effective incorporation of boron into the globules of the colloidal dispersion.
On répète la procédure de l'exemple 3 à la différence qu'o introduit 30 grammes d'oxyde de calcium, 10,2ml d'eau et qu l'on carbonate le produit pendant 75 minutes à un débit d 103ml/minute. Avant la 15ème minute de carbonatation o ajoute 9,52g de tétraborate de potassium en poudre. O recueille un produit limpide de VA 310mg KOH/g et contenan 0,86% poids de bore. EXEMPLE 8The procedure of Example 3 is repeated, except that 30 grams of calcium oxide, 10.2 ml of water are introduced and the product is carbonated for 75 minutes at a rate of 103 ml / minute. Before the 15th minute of carbonation o add 9.52g of potassium tetraborate powder. O collects a clear product of VA 310 mg KOH / g and contains 0.86% by weight of boron. EXAMPLE 8
On répète la procédure de 1'exemple 7 mais le composé d bore est l'acide borique. On ajoute 8,98g d'acide borique e poudre à la lOème minute de carbonatation. On obtient alor un produit de VA 411mg KOH/g et de consistence trè visqueuse. Il contient 1,23% poids de bore. EXEMPLE 9The procedure of Example 7 is repeated, but the boron compound is boric acid. 8.98 g of boric acid and powder are added to the 10th minute of carbonation. We then obtain a product of VA 411 mg KOH / g and of very viscous consistency. It contains 1.23% by weight of boron. EXAMPLE 9
On répète la procédure de l'exemple 7 après avoir ajout seulement 4,5ml de methanol au milieu réactionnel. O obtient un produit limpide, très fluide, de VA 298mg KOH/ et contenant 1,3% poids de bore. EXEMPLE 10The procedure of Example 7 is repeated after adding only 4.5 ml of methanol to the reaction medium. O obtains a clear, very fluid product of VA 298 mg KOH / and containing 1.3% by weight of boron. EXAMPLE 10
On répète la procédure de l'exemple 8 mais on remplac l'huile diluante par 28,5g d'une dispersion d'acide boriqu dans l'huile à environ 5% poids de bore. Cette dispersio est introduite dans le mélange avant le début de l carbonatation. On obtient un produit limpide de VA 303 KOH/g et à 1,2% poids de bore. EXEMPLE 11The procedure of Example 8 is repeated, but the diluent oil is replaced with 28.5 g of a dispersion of boric acid in the oil at around 5% by weight of boron. This dispersion is introduced into the mixture before the start of carbonation. A clear product of VA 303 KOH / g and 1.2% by weight of boron is obtained. EXAMPLE 11
On répète la procédure de l'exemple 8 mais on ajoute 11,2 de trioxyde de bore en poudre.The procedure of Example 8 is repeated, but 11.2 of powdered boron trioxide are added.
On recueille un produit limpide de VA 229mg KOH/g e contenant 2,4% poids de bore. EXEMPLE 12A clear product of VA 229 mg KOH / ge containing 2.4% by weight of boron is collected. EXAMPLE 12
On répète la procédure de l'exemple 7 mais on ajoute 1 de triméthylborate à la lOème minute de carbonatation. obtient alors un produit visqueux de VA 437mg KOH/g e 1,2% poids de bore. EXEMPLE 13The procedure of Example 7 is repeated but 1 of trimethylborate is added to the 10th minute of carbonation. then obtains a viscous product of VA 437 mg KOH / g e 1.2% by weight of boron. EXAMPLE 13
On répète la procédure de l'exemple 1 à ceci près que ajoute 9,53g de diammonium tétraborate en poudre après minutes de carbonatation. On obtient un produit limp relativement fluide de VA 438mg KOH/g et contenant 1, poids de bore. EXEMPLE 14The procedure of Example 1 is repeated except that 9.53 g of powdered diammonium tetraborate are added after minutes of carbonation. A relatively fluid limp product of VA 438 mg KOH / g and containing 1, weight of boron is obtained. EXAMPLE 14
On répète la procédure de l'exemple 10 mais on ajoute les mêmes conditions 19,06g de diammonium tétraborate.The procedure of Example 10 is repeated but the same conditions are added 19.06 g of diammonium tetraborate.
On recueille un produit de VA 437mg KOH/g qui contient 1, poids de bore.A product of VA 437 mg KOH / g is collected which contains 1, weight of boron.
EXEMPLE 15EXAMPLE 15
On répète la procédure de l'exemple 10 mais l'additif carbonate pendant 23 minutes à 148ml/minute.The procedure of Example 10 is repeated, but the carbonate additive for 23 minutes at 148 ml / minute.
On recueille alors un produit de VA 281mg KOH/g et conteWe then collect a product of VA 281 mg KOH / g and tale
2% poids de bore.2% by weight of boron.
EXEMPLE 16EXAMPLE 16
On introduit dans le réacteur les mêmes quantités produits que dans la procédure -décrite à l'exemple 14. contre, on chauffe à reflux le mélange réactionnel pendThe same quantities produced as in the procedure described in Example 14 are introduced into the reactor. However, the reaction mixture is heated under reflux.
30 minutes, avant carbonatation. • On procède à carbonatation du mélange réactionnel dès lors que température est redescendue à 49°C.30 minutes before carbonation. • The reaction mixture is carbonated as soon as the temperature has dropped to 49 ° C.
Le traitement ultérieur est conforme à la procédure l'exemple 1. On recueille un produit de VA 398mg KOH/g contenant 1,7% en poids de bore. EXEMPLE 17The subsequent treatment is in accordance with the procedure of Example 1. A product of VA 398 mg KOH / g containing 1.7% by weight of boron is collected. EXAMPLE 17
Dans un réacteur de 250ml équipé d'un agitateur, d'un arrivée de gaz carbonique et d'un réfrigérant on introdui 30g d'acide C_4~benzène sulfonique à 70% de matière active 23,4g d'oxyde de magnésium "léger", 12ml de methanol, 30,6 d'huile diluante 100 Neutral, 2,3 ml d'ammoniaque à 20% 120ml d'un mélange 50/50 en volume d'heptane et de xylène La carbonatation est réalisée pendant une- durée de 3h30 à u débit de 45ml/minute et à une température de 53°C. On ajoute après 35 minutes de carbonatation 8,7g d diammonium tétraborate tétrahydrate.30g of C_ 4 ~ benzene sulfonic acid containing 70% active material 23.4g of "light" magnesium oxide are introduced into a 250ml reactor equipped with an agitator, a carbon dioxide inlet and a condenser. ", 12ml of methanol, 30.6 of 100 Neutral diluent oil, 2.3ml of 20% ammonia 120ml of a 50/50 mixture by volume of heptane and xylene Carbonation is carried out for a period of time from 3:30 at a flow rate of 45ml / minute and at a temperature of 53 ° C. 8.7 g of diammonium tetraborate tetrahydrate are added after 35 minutes of carbonation.
On récupère un produit limpide contenant 11% poids d magnésium, 1,15% poids de bore et dont le VA est de 523m KOH/g. EXEMPLE 18A clear product is recovered containing 11% by weight of magnesium, 1.15% by weight of boron and whose VA is 523m KOH / g. EXAMPLE 18
On répète la procédure de l'exemple 1 à ceci près que l'o utilise à la place de l'acide C_4-benzène sulfonique, 23 d'un mélange 80/20 en mole d'acide C_4~benzène sulfonique d poids molaire 520 à 70% de matière active et d'acid carboxylique en C_ obtenu par hydroformylation d'oléfine (Acide CK9 distribué par la Société NORSOLOR) . On ajout 30,7g de chaux éteinte à 97% de pureté.The procedure of Example 1 is repeated except that the o uses instead of the C_ 4 -benzene sulfonic acid, 23 of an 80/20 mixture by mole of C_ 4 acid ~ benzene sulfonic acid by weight. molar 520 to 70% of active material and C_ carboxylic acid obtained by hydroformylation of olefin (CK9 acid distributed by the company NORSOLOR). 30.7 g of slaked lime at 97% purity are added.
La carbonatation est réalisée pendant 25 minutes à un débi de 210ml/minute.-Carbonation is carried out for 25 minutes at a flow rate of 210ml / minute.
On ajoute 9,53g de diammonium tétraborate tétrahydrate aprè dix minutes de carbonatation.9.53 g of diammonium tetraborate tetrahydrate are added after ten minutes of carbonation.
Le produit recueilli est limpide et stable en dilution. So VA est de 307mg KOH/g et sa teneur en bore de 1,55% poids. EXEMPLE 19The product collected is clear and stable in dilution. So VA is 307 mg KOH / g and its boron content is 1.55% by weight. EXAMPLE 19
On prépare une solution de borate de propylèneglycol dans l xylène par chauffage à 50°C sous agitation d'un mélange d 46,4g de propylèneglycol, de 41g d'acide borique et de 300m de xylène. L'eau formée est éliminée par distillatio azeotropique. On obtient 314g d'une solution à 2,6% de bore Dans le réacteur décrit précédemment, da l'exemple 1, on introduit 34,6g de la solution de borate propylèneglycol, 16,61g d'acide C., β-alkylbenzènesulfonique 96% de matière active et de poids moléculaire 430, 24, d'huile diluante, 112ml de xylène, 7ml de methanol et 23, de chaux éteinte à 99% de pureté.A solution of propylene glycol borate in xylene is prepared by heating to 50 ° C. with stirring of a mixture of 46.4 g of propylene glycol, 41 g of boric acid and 300 m of xylene. The water formed is removed by azeotropic distillatio. 314 g of a 2.6% boron solution are obtained Into the reactor described above, from Example 1, 34.6 g of the propylene glycol borate solution, 16.61 g of C., β -alkylbenzenesulfonic acid 96% of active material and of molecular weight 430, 24, d are introduced. diluent oil, 112ml of xylene, 7ml of methanol and 23ml of slaked lime at 99% purity.
Le mélange est carbonate pendant 26 minutes à 42 à un débit de 230ml/minute.The mixture is carbonated for 26 minutes at 42 at a flow rate of 230ml / minute.
Après élimination de l'eau produite par réaction, du m thanol, du propylène glycol excédentaire, d résidus solides et du solvant (par chauffage sous pressi réduite) on recueille un produit limpide, marron claire, très faible viscosité, de VA 302 et contenant 0,87% de bor EXEMPLE 20After elimination of the water produced by reaction, of m thanol, of excess propylene glycol, of solid residues and of the solvent (by heating under reduced pressure) a clear, light brown product, very low viscosity, of VA 302 and containing is collected. 0.87% bor EXAMPLE 20
On introduit dans le réacteur décrit précédemment 8,3 d'acide C. fi-alkylbenzènesulfonique, 24,4g d'huile diluant 137ml de xylène, 7ml de methanol et 16,24g de chaux étein à 96,5% de pureté. On ajoute avant la carbonatation 19,8 d'une solution dans le xylène de l'ester borique N-oelyldihydroxyethylamine (NORAMOX 02 de CECA S.A. contenant 1,03% de bore.Is introduced into the reactor described above 8.3 C. fi -alkylbenzènesulfonique acid, 24.4 g of diluent oil 137ml of xylene, 7ml methanol and lime 16,24g étein 96.5% purity. 19.8 of a solution in xylene of the boric ester N-oelyldihydroxyethylamine (NORAMOX 0 2 from CECA SA containing 1.03% of boron) is added before carbonation.
Le mélange est carbonate à un débit de 156ml/minute penda 26 minutes à une température de 42°C. Le produit limpi recueilli a une VA de 351 et contient 0,36% de bore. EXEMPLE 21The mixture is carbonate at a flow rate of 156 ml / minute for 26 minutes at a temperature of 42 ° C. The limpi product collected has a VA of 351 and contains 0.36% of boron. EXAMPLE 21
On introduit dans le réacteur décrit précédemment 19,8 d'acide C.g-alkyl-benzène-sulfonique, 1,1ml d'ammoniaque 20%, 13ml de methanol, 30,8g d'huile diluante et 116ml xylène. On ajoute avant carbonatation 31,4g d'une soluti de borate de propylèneglycol dans le xylène contenant 2,6 de bore. Le milieu est carbonate à 42°C pendant 26 minutes un débit de 254ml/minute.19.8 C.g-alkyl-benzene-sulfonic acid, 1.1 ml of 20% ammonia, 13 ml of methanol, 30.8 g of diluent oil and 116 ml of xylene are introduced into the reactor described above. 31.4 g of a propylene glycol borate solution in xylene containing 2.6 boron are added before carbonation. The medium is carbonate at 42 ° C for 26 minutes, a flow rate of 254 ml / minute.
Le produit limpide, de couleur marron a une VA 360 e contient 0,82% de bore. EXEMPLE 22The clear, brown product with a VA 360 e contains 0.82% boron. EXAMPLE 22
On introduit dans le réacteur déjà décrit 17,86g d'acide C, -alkylbenzènesulfonique, 10,66g de succinimide à 50% poid dans l'huile, 1,1ml d'ammoniaque à 20%, 13ml de methanol 30,8g d'huile diluante et 116ml de xylène. On ajoute avan la carbonatation 31,4g d'une solution de borate de propylèn glycol dans le xylène contenant 2,6% de bore. La carbonatation dans les conditions de l'exemple 21 donn un produit de VA 374 et contenant 0,8% poids de bore. EXEMPLE 23 (Comparatif)17.86 g of C, -alkylbenzenesulfonic acid, 10.66 g of succinimide at 50% weight in oil, 1.1 ml of 20% ammonia, 13 ml of methanol 30.8 g of are introduced into the reactor already described. diluent oil and 116ml of xylene. 31.4 g of a propylene glycol borate solution in xylene containing 2.6% boron are added before carbonation. The carbonation under the conditions of Example 21 gives a product of VA 374 and containing 0.8% by weight of boron. EXAMPLE 23 (Comparative)
Dans un réacteur de 250ml muni d'un condenseur on introdui 77,8g de dodécyl-phénol et 20,04g de chlorure de soufre. O chauffe ensuite le mélange sous agitation et.sous barbota d'azote pendant une heure à 150°C puis 1 heure 30 à 170°C On recueille un produit noirâtre, visqueux, constitué d dodécyl-phénol sulfurisé.77.8 g of dodecylphenol and 20.04 g of sulfur chloride are introduced into a 250 ml reactor fitted with a condenser. O then heats the mixture with stirring and under nitrogen bubbled for one hour at 150 ° C and then 1 hour 30 to 170 ° C. A blackish, viscous product is collected, consisting of sulfurized dodecylphenol.
Dans un second réacteur de 250ml équipé d'un agitateur d' réfrigérant et d'une arrivée de gaz carbonique, on introdui successivement 32g de dodécyl-phénol sulfurisé, 24,5 d'huile diluante du type 100N, 16,8g d'hydroxyde de calci à 97% de pureté, 25ml d'un mélange butanol/methanol 75/25 lg de CaCl_ et enfin 100ml de xylène.In a second 250ml reactor equipped with a refrigerant stirrer and a carbon dioxide inlet, 32g of sulfurized dodecylphenol, 24.5 of diluent oil of the 100N type, 16.8g of hydroxide are successively introduced. calci at 97% purity, 25 ml of a butanol / methanol mixture 75/25 lg of CaCl 2 and finally 100 ml of xylene.
Le mélange est porté au reflux pendant 3 heures puis il es carbonate pendant 50 minutes un débit d'envir 90ml/minute à une température de 53°C. Les solvants et l diluant hydrocarboné sont éliminés par chauffage à 100° sous pression réduite.The mixture is brought to reflux for 3 hours then it is carbonated for 50 minutes a flow rate of approximately 90 ml / minute at a temperature of 53 ° C. The solvents and the hydrocarbon diluent are removed by heating to 100 ° under reduced pressure.
Le produit après filtration à chaud se caractérise par un de 283mg KOH/g, une teneur eh calcium de 11,2% poids et u stabilité acceptable en dilution dans les huiles. EXEMPLE 24The product after hot filtration is characterized by a 283 mg KOH / g, a calcium content of 11.2% by weight and an acceptable stability when diluted in oils. EXAMPLE 24
On répète la procédure de l'exemple 19 à la différence q l'on ajoute au milieu réactionnel 6,75g de diammoni tétraborate en poudre après 10 minutes de carbonatation. On obtient un produit relativement fluide, de VA 267mg KOH et contenant 1,43% de bore. EXEMPLE 25The procedure of Example 19 is repeated, except that 6.75 g of powdered diammoni tetraborate are added to the reaction medium after 10 minutes of carbonation. A relatively fluid product is obtained, of VA 267 mg KOH and containing 1.43% of boron. EXAMPLE 25
Dans un réacteur de 250ml équipé d'une agitation, d' arrivée de gaz carbonique et d'un réfrigérant, on ontrod 20,4g d'acide C_4-benzène sulfonique à 70% de mati active, 30g d'oxyde de calcium en poudre, 5ml de methan 225g d'huile 100N, 3,53g d'acide phényl boronique, 1,16g carbonate d'ammonium dissout dans 10,5ml d'eau et 150ml xylène. La carbonatation est réalisée sous forte agitati à une température de 52°C et à un débit de 103ml/ in pendant 75 minutes.20.4 g of C_ 4 -benzene sulfonic acid containing 70% active material, 30 g of calcium oxide are introduced into a 250 ml reactor equipped with stirring, carbon dioxide inlet and a condenser. powder, 5ml of methan 225g of 100N oil, 3.53g of phenyl boronic acid, 1.16g of ammonium carbonate dissolved in 10.5ml of water and 150ml of xylene. The carbonation is carried out under strong agitation at a temperature of 52 ° C. and at a flow rate of 103 ml / in for 75 minutes.
L'élimination des résidus solides et des solvants condui un produit de VA 303mg KOH/g et contenant 0,43% en poids bore.The elimination of solid residues and solvents leads to a product of VA 303 mg KOH / g and containing 0.43% by weight boron.
EXEMPLE 26EXAMPLE 26
On introduit dans le réacteur décrit précédemment 43g dodecylphénol sulfurisé préparé selon l'exemple 23, 19,5g chaux éteinte, 30g d'huile 100N, 90ml de toluène et 49ml m thanol. Le mélange est porté à reflux pendant au mo trente minutes.Is introduced into the reactor described above 43g dodecylphenol sulfurized prepared according to Example 23, 19.5 g slaked lime, 30g of 100N oil, 90ml of toluene and 49ml m thanol. The mixture is brought to reflux for at least thirty minutes.
Après élimination de l'eau et du methanol on ajoute 36, d'une solution dans le toluène de borate de propylène glyc à 2,6% de bore et 49ml de methanol. Le mélange est carbona à 85% à une température de 50°C.After removing the water and methanol, 36 of a toluene solution of propylene glycate borate containing 2.6% boron and 49 ml of methanol are added. The mixture is carbona at 85% at a temperature of 50 ° C.
Le produit limpide et verdatre obtenu a une VA de 260 contient 0,82% de bore. EXEMPLE 27The clear and greenish product obtained at a VA of 260 contains 0.82% boron. EXAMPLE 27
On opère comme dans 1'exemple précédent mais on introdu 70ml de toluène et 18,3g de solution de borate propylèneglycol à 2,6% de bore avant la carbonatation. Le produit limpide de couleur vert claire obtenu a une VA 281 et une teneur en bore de 0,42%. EXEMPLE 28The procedure is as in the previous example, but 70 ml of toluene and 18.3 g of propylene glycol borate solution containing 2.6% boron are introduced before carbonation. The clear, light green product obtained has a VA 281 and a boron content of 0.42%. EXAMPLE 28
On opère comme dans l'exemple précédent mais introduitsant 40ml de methanol et 36,5g de la solution borate de propylène glycol à 2,6% de bore. Le produit a une VA de 267 et une teneur en bore de 0,91%. EXEMPLE 29The procedure is as in the previous example but introducing 40 ml of methanol and 36.5 g of the propylene glycol borate solution containing 2.6% boron. The product has a VA of 267 and a boron content of 0.91%. EXAMPLE 29
On opère comme dans 1'exemple précédent mais en introduisan avant carbonatation 38ml de methanol et 20,6g d tributylborate.The procedure is as in the previous example but by introducing 38 ml of methanol and 20.6 g of tributylborate before carbonation.
Le produit a une VA de 273 et une teneur en bore de 0,9%. EXEMPLE 30The product has a VA of 273 and a boron content of 0.9%. EXAMPLE 30
On opère comme dans l'exemple précédent mais en introduisan avant carbonatation 40,6g de tributylborate et 28ml d methanol. Le produit a une VA de 265 et contient 1,8% de bore.The procedure is as in the previous example but by introducing 40.6 g of tributylborate and 28 ml of methanol before carbonation. The product has a VA of 265 and contains 1.8% boron.
EXEMPLE 31EXAMPLE 31
Les additifs suralcalinisés ont été soumis aux essai mécaniques suivants :The overbased additives were subjected to the following mechanical tests:
4 billes usures NF-E 48-617 usure FALEX D 32-33 4 billes EP D 2783-69T E 48-617 Les produits sont testés après dilution dans le mélang d'huile suivant Ï 600N/BSS (Bright Stock Solvent) = 80/2 jusqu'à une VA de 70mg KOH/g ou encore 10 mg KOH/g. A titre d'exemple le tableau suivant présente quelque résultats obtenus, on constate ainsi que les produit obtenus selon 1'invention présentent un pouvoir antiusure e extrême pression - -amélioré par rapport au produi suralcalinisé de référence décrit à l'exemple 1. 4 balls NF-E 48-617 wear FALEX D 32-33 4 balls EP D 2783-69T E 48-617 The products are tested after dilution in the oil mixture according to Ï 600N / BSS (Bright Stock Solvent) = 80 / 2 up to a VA of 70mg KOH / g or even 10 mg KOH / g. By way of example, the following table presents some results obtained, it can thus be seen that the products obtained according to the invention have anti-wear power at extreme pressure - -improved compared to the reference over-alkalized product described in Example 1.
ESSAIS MECANIQUESMECHANICAL TESTS
Ex. 1Ex. 1
ESSAI Dilution Compa¬ Ex. 2 Ex. 9 Ex.10 Ex. ratifTEST Dilution Compa¬ Ex. 2 Ex. 9 Ex. 10 Rat.
nb de dentsnb of teeth
FALEX VA 70 perte poids 6,2 4,0 4,0 en mgFALEX VA 70 weight loss 6.2 4.0 4.0 mg
VA 10 diam. 2,26 2,28 0,57 0,7 0,VA 10 diam. 2.26 2.28 0.57 0.7 0,
4 billes d'empreinte lusure mm4 mm wear balls
VA 70 0,58 0,36 0,42 0,64 0VA 70 0.58 0.36 0.42 0.64 0
grippage(kgf 100 126 126 126 1seizure (kgf 100 126 126 126 1
4 billes VA 70 Soudure (kgf 250 250 200 200 24 balls VA 70 Soldering (kgf 250 250 200 200 2
EP ICU* 46,3 53,3 50,4 50,2 61EP ICU * 46.3 53.3 50.4 50.2 61
*I.CU : Indice charge-usure * I.CU: Load-wear index

Claims

REVENDICATIONS - Procédé de préparation d'un additif suralcalinisé effet antiusure par carbonatation d'un mélang réactionnel composé d'au moins un détergent, d'u dérivé d'un métal alcalin ou alcalinoterreux, d'a moins un promoteur azoté et/ou oxygéné dans une huil diluante et un solvant hydrocarboné caractérisé en c qu'on opère en présence d'au moins un dérivé du bore. - Procédé selon la revendication 1 caractérisé en ce qu le dérivé du bore est un composé inorganique du bor comme les oxydes et anhydrides du bore et l'acid borique et ses sels. - Procédé selon les revendications 1 ou 2 caractérisé e ce que le dérivé du bore est 1'acide borique ou se d'ammonium, de sodium, de potassium, ou de lithium. - Procédé selon la revendication 1 caractérisé en ce qu le dérivé du bore est un composé organique comme le esters de l'acide borique et les acides alkyls e arylboroniques libres et estérifiés. - Procédé selon la revendication 4 caractérisé en ce qu les esters sont formés avec les alcools aliphatiques chaine linéaire ou ramifié en C. à C__ et de préférenc - Procédé selon la revendication 4 caractérisé en ce qu les esters sont formés avec les glycols 1-2, 1-3 ou 1- comme le glycol, le propylèneglycol, le néopentylglyco ou les polyglycols comme le diéthylèneglycol, l dipropylèneglycol ou le tripropylèneglycol. - Procédé selon la revendication 4 caractérisé en ce qu les esters sont formés avec les polyols, comme l glycérol,le triméthylolpropane ou le pentaerythritol. - Procédé selon la revendication 4 caractérisé en ce les esters sont formés avec des alkoxyalcanols et préférence les alkoxyalkanols répondant à la form générale R0* CHR. (CH_) -O , H où R est un groupe alk en C. à C4, R. est l'hydrogène ou un groupe alkyle C1 à C,, a est compris entre 1 et 3 et b correspond ou 2, comme le méthoxyethanol, 1'ethoxyethanol ou buthoxy ethanol. - Procédé selon la revendication 4 caractérisé en ce les esters sont formés avec des alcools dont molécule renferme au moins une fonction aminé. - Procédé selon la revendication 9 caractérisé en ceCLAIMS - Process for the preparation of an overbased additive with antiwear effect by carbonation of a reaction mixture composed of at least one detergent, of an derivative of an alkali or alkaline earth metal, of at least one nitrogenous and / or oxygenated promoter in a diluting oil and a hydrocarbon solvent characterized in c which is operated in the presence of at least one boron derivative. - Method according to claim 1 characterized in that the boron derivative is an inorganic boron compound such as oxides and anhydrides of boron and boric acid and its salts. - A method according to claims 1 or 2 characterized e that the boron derivative is boric acid or se ammonium, sodium, potassium, or lithium. - Method according to claim 1 characterized in that the boron derivative is an organic compound such as esters of boric acid and free and esterified alkyl and arylboronic acids. - Method according to claim 4 characterized in that the esters are formed with aliphatic alcohols linear or branched in C. to C__ and preferably - Method according to claim 4 characterized in that the esters are formed with glycols 1-2, 1-3 or 1- such as glycol, propylene glycol, neopentylglyco or polyglycols such as diethylene glycol, dipropylene glycol or tripropylene glycol. - Method according to claim 4 characterized in that the esters are formed with polyols, such as glycerol, trimethylolpropane or pentaerythritol. - Process according to claim 4 characterized in that the esters are formed with alkoxyalkanols and preferably the alkoxyalkanols corresponding to the general form R0 * CHR. (CH_) -O, H where R is a C 1 to C 4 alk group, R. is hydrogen or a C 1 to C 4 alkyl group, a is between 1 and 3 and b corresponds or 2, as methoxyethanol, ethoxyethanol or buthoxy ethanol. - Method according to claim 4 characterized in that the esters are formed with alcohols whose molecule contains at least one amino function. - Method according to claim 9 characterized in that
1'alcool renfermant au moins une fonction aminé est alkanolamine telle que la diéthanolamine ou tri.ethanolamine. - Procédé selon la revendication 9 caractérisé en ceThe alcohol containing at least one amino function is alkanolamine such as diethanolamine or tri.ethanolamine. - Method according to claim 9 characterized in that
1'alcool renfermant au moins une fonction aminé est alkylmonoamine oxyalkylée répondant de préférence à formule R_NH Z, ou R_ est l'hydrogène ou un grou alkyle ou C. à C__, de préférence- en C-_ à C._, correspond au groupement -CHR- - CH_OH, R- étant groupe alkyle en C. à C4 ou un noyau aromatique, £ pe être 0 ou 1 et c + d est égal à 2. - Procédé selon la revendication 9 caractérisé en ce q l'alcool renfermant au moins une fonction aminé est u alkylpolyamine oxyalkylée, répondant de préférence à formule R2_NZ_1, - (CH2_)e-NZ2_Z3, ou R2_ a la mê signification que précédemment et Z.. , Z_ et identiques ou différents correspondent à l'hydrogène au moins un des trois correspond à Z défi précédemmen . - Procédé selon la revendication 4 caractactérisé en que les esters sont formés avec les alcools cycliqu comme le cyclopentanol,1e cyclohexanol ou leurs dériv mono et polyalkylés sur le cycle. - Procédé selon la revendication 4 caractérisé en ce qu les esters sont formés avec les phénols, comme l phénol lui même ou les crésols. - Procédé selon l'une des revendications précédente caractérisé en ce que le dérivé du bore utilisé sou forme de dispersion dans l'huile est ajouté au mélang réactionnel avant l'introduction de l'anhydrid carbonique. - Procédé selon l'une des revendications précédente caractérisé en ce que le dérivé du bore utilisé sou forme pulvérulent, liquide ou en solution aqueuse es' introduit dans le mélange réactionnel pendant l réaction de carbonatation. - Procédé selon l'une des revendications précédente caractérisé en ce que le mélange réactionnel renferm au moins un détergent choisi parmi les acide sulfoniques d'origine pétrolière ou synthétique, le acides salicyliques, les phénols et leurs sels alcalin ou alcalinoterreux. - Procédé selon l'une des revendications précédente caractérisé en ce que le détergent est utilisé e méla e de formule généraleThe alcohol containing at least one amino function is an oxyalkylated alkylmonoamine preferably corresponding to formula R_NH Z, or R_ is hydrogen or an alkyl or C.sub.1 to C.sub.4, preferably C.sub.1 to C.sub.3, corresponds to the group -CHR- - CH_OH, R- being a C 4 -C 4 alkyl group or an aromatic nucleus, £ pe being 0 or 1 and c + d is equal to 2. - Method according to claim 9 characterized in that q l alcohol containing at least one amino function is u oxyalkylated alkylpolyamine, preferably corresponding to formula R2_NZ_1, - (CH2_) e-NZ2_Z3, or R2_ has the same meaning as above and Z .., Z_ and identical or different correspond to hydrogen at least one of the three corresponds to Z previous challenge. - Method according to claim 4 characterized in that the esters are formed with cyclic alcohols such as cyclopentanol, 1e cyclohexanol or their mono and polyalkylated derivatives on the cycle. - Method according to claim 4 characterized in that the esters are formed with phenols, such as phenol itself or cresols. - Method according to one of the preceding claims, characterized in that the boron derivative used in the form of a dispersion in oil is added to the reaction mixture before the introduction of carbon dioxide. - Method according to one of the preceding claims, characterized in that the boron derivative used in its pulverulent, liquid or aqueous solution form is introduced into the reaction mixture during the carbonation reaction. - Method according to one of the preceding claims, characterized in that the reaction mixture contains at least one detergent chosen from sulphonic acids of petroleum or synthetic origin, salicylic acids, phenols and their alkali or alkaline-earth salts. - Method according to one of the preceding claims characterized in that the detergent is used e mela e of general formula
ou R4 est un radical hydrocarboné en C._ à 10n, n est compris entre 1 et et m est compris entre 1 à 5. - Procédé selon l'une des revendications précédente caractérisé en ce que le mélange réactionnel renferm un dérivé d'un métal alcalin ou alcalinoterreux chois parmi les oxydes, hydroxydes ou alcoolates d'un te métal. - Procédé selon l'une des revendications précédente caractérisé en ce que le mélange réactionnel renferm au moins un promoteur oxygéné choisi parmi les alcool aliphatiques en C.. à Cς, les glycols ou les ethers. - Procédé selon l'une des revendications précéden caractérisé caractérisé en ce que le méla réactionnel renferme de l'eau. - Procédé selon l'une des revendications précédentes caractérisé en ce que le mélange réactionnel renferm une huile diluante paraffinique ou naphténique. - Procédé selon l'une des revendications précéden caractérisé en ce que le mélange réactionnel renfe un solvant hydrocarboné aliphatique ou aromatique. - Procédé selon l'une des revendications précéden caractérisé en ce que dans le mélange réaction renfermant 100 à 500 parties poids d'au moins détergent, 100 à 300 parties poids d'un dérivé d' métal alcalin, ou alcalinoterreux, 0 à 100 parti poids d'un promoteur azoté, 30 à 300 parties poids d' promoteur oxygéné, 0 à 100 parties poids d'eau, 100 500 parties poids d'une huile diluante, 200 à 8 parties poids d'un solvant hydrocarboné et 15 à 4 parties poids d'un dérivé du bore on introduit à u température de 20 à 80°C et de préférence de 35 à 70 pendant 20 minutes à 4 heures, 50 à 350 parties poi d'anhydride carbonique. - Procédé selon l'une des revendications précédent caractérisé en ce que le mélange réactionnel e chauffé à reflux pendant 30 minutes à 2 heures avant carbonatation. - Additif suralcalinisé à effet antiusure caractérisé ce qu'il est préparé selon le procédé décrit dans l revendications 1. à 25 et en ce qu'il renferme 0,1 à 1 poids et de préférence 0,25 à 5% poids d'un dérivé bore. - Composition lubrifiante caractérisée en ce qu'el renferme une huile lubrifiante naturelle ou synthétiq et 0,5 à 40% poids et de préférence 1 à 30% poids d' additif selon la revendication 26. where R 4 is a radical hydrocarbon in C._ at 10n , n is between 1 and and m is between 1 and 5. - Method according to one of the preceding claims, characterized in that the reaction mixture contains a derivative of an alkali or alkaline earth metal chosen among the oxides, hydroxides or alcoholates of a metal. - Method according to one of the preceding claims characterized in that the reaction mixture renferm at least one oxygen-containing promoter selected from aliphatic alcohol C .. for C ς, glycols or ethers. - Method according to one of the preceding claims characterized in that the reaction mela contains water. - Method according to one of the preceding claims, characterized in that the reaction mixture contains a diluting paraffinic or naphthenic oil. - Method according to one of the preceding claims characterized in that the reaction mixture contains an aliphatic or aromatic hydrocarbon solvent. - Method according to one of the preceding claims characterized in that in the reaction mixture containing 100 to 500 parts by weight of at least detergent, 100 to 300 parts by weight of an alkali metal or alkaline earth metal derivative, 0 to 100 parts weight of a nitrogenous promoter, 30 to 300 parts weight of oxygenated promoter, 0 to 100 parts weight of water, 100 500 parts weight of a diluent oil, 200 to 8 parts weight of a hydrocarbon solvent and 15 to 4 weight parts of a boron derivative are introduced at a temperature of 20 to 80 ° C and preferably from 35 to 70 for 20 minutes to 4 hours, 50 to 350 parts poi of carbon dioxide. - Method according to one of the preceding claims characterized in that the reaction mixture is heated at reflux for 30 minutes to 2 hours before carbonation. - Overbased additive with antiwear effect, characterized in that it is prepared according to the process described in claims 1 to 25 and in that it contains 0.1 to 1 weight and preferably 0.25 to 5% by weight of a boron derivative. - Lubricating composition characterized in that it contains a natural or synthetic lubricating oil and 0.5 to 40% by weight and preferably 1 to 30% by weight of additive according to claim 26.
EP88902504A 1987-03-17 1988-03-16 Process for the preparation of a superalkalinized additive containing an inorganic boron derivative, additive produced by said process and lubricating compositions containing said additive Expired - Lifetime EP0308445B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8703646 1987-03-17
FR8703646A FR2612526B1 (en) 1987-03-17 1987-03-17 PROCESS FOR THE PREPARATION OF AN OVERALCANIZED ADDITIVE CONTAINING A BORON DERIVATIVE, THE ADDITIVE THUS OBTAINED AND LUBRICANT COMPOSITIONS CONTAINING THE ADDITIVE

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP90104404A Division EP0383359B1 (en) 1987-03-17 1988-03-16 Process for preparing an overbased additive containing a boron derivative, additive produced by said process and lubricating compositions containing said additive.
EP90104404.0 Division-Into 1990-03-08

Publications (2)

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EP0308445A1 true EP0308445A1 (en) 1989-03-29
EP0308445B1 EP0308445B1 (en) 1991-08-28

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EP (1) EP0308445B1 (en)
JP (1) JPH01502759A (en)
DE (1) DE3864483D1 (en)
FR (1) FR2612526B1 (en)
WO (1) WO1988007073A1 (en)

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JP2814131B2 (en) * 1990-03-14 1998-10-22 日本石油株式会社 Engine oil composition for alcohol fuel
JP2617807B2 (en) * 1990-03-16 1997-06-04 日本石油株式会社 Engine oil composition
FR2698019B1 (en) * 1992-11-18 1995-02-24 Inst Francais Du Petrole Colloidal products containing calcium and / or magnesium, as well as boron and / or phosphorus and / or sulfur, their preparation and their use as additives for lubricants.
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WO1988007073A1 (en) 1988-09-22
US5098587A (en) 1992-03-24
FR2612526A1 (en) 1988-09-23
EP0308445B1 (en) 1991-08-28
JPH01502759A (en) 1989-09-21
FR2612526B1 (en) 1990-02-02

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