EP0101334A2 - High alkalinity metallic detergent-dispersant additive for lubricating oils - Google Patents

High alkalinity metallic detergent-dispersant additive for lubricating oils Download PDF

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Publication number
EP0101334A2
EP0101334A2 EP83401255A EP83401255A EP0101334A2 EP 0101334 A2 EP0101334 A2 EP 0101334A2 EP 83401255 A EP83401255 A EP 83401255A EP 83401255 A EP83401255 A EP 83401255A EP 0101334 A2 EP0101334 A2 EP 0101334A2
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EP
European Patent Office
Prior art keywords
glycol
new additive
additive according
molar ratio
amine
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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
EP83401255A
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German (de)
French (fr)
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EP0101334B1 (en
EP0101334A3 (en
Inventor
Jean-Louis Le Coent
Bernard Demoures
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Orogil SA
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Orogil SA
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Priority to AT83401255T priority Critical patent/ATE30716T1/en
Publication of EP0101334A2 publication Critical patent/EP0101334A2/en
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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
    • 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
    • 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
    • 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
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic 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

  • the subject of the present invention is a new high alkalinity metal detergent-dispersant additive for lubricating oils.
  • the Applicant has in fact found a detergent-dispersant additive having a TBN of at least 225, containing more than 3.8% by weight of magnesium and, generally, of the order of 2 to 3 X by weight of calcium, this which gives said additive, in addition to the detergency and dispersion characteristics, a good activity as anti-wear.
  • magnesium alkylbenzenesulfonate denotes any solution containing from 25 to 80% by weight, preferably from 30 to 70%. by weight of a magnesium alkylbenzenesulfonate in a dilution oil which may or may not be the same as that used to prepare the new additive.
  • magnesium alkylbenzenesulfonates which can be used, mention may be made of the magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from C 15 -C 30 olefin polymers.
  • the amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting magnesium alkylbenzenesulfonate) represents from 20 to 60 by weight of said product, preferably from 25 to 55% and very particularly from 30 to 45% by weight of said product.
  • sulfurized calcium alkylphenate denotes any solution containing from 25 to 70% by weight, preferably from 30 to 55% by weight of a sulfurized calcium alkylphenate in a dilution oil which may or may not be the same than that used to prepare the new additive.
  • sulfurized calcium alkylphenates which can be used, there may be mentioned: those obtained by the action of lime on a sulfurized alkylphenol preferably carrying one or more C 9 -C 30 alk y substituents, (and preferably C 9 -C 22 ), such as nonyl, decyl, dodecyl or sulfurized tetradecylphenols followed optionally by carbonation; those obtained by sulfurization with sulfur of an alkylphenol preferably having one or more C 9 -C 30 alkyl substituents (preferably C 9 -C 22 ) in the presence of lime and glycol, optionally followed by carbonation .
  • a sulfurized calcium alkylphenate characterized by a lime / alkylphenol molar ratio of between 0.2 and 2.5 and preferably between 0.4 and 2, and by a sulfur / alkylphenol molar ratio of between 1.1 and 2.2 and preferably between 1.3 and 1.8.
  • active magnesium oxide denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g.
  • magnesium oxide MgO with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g.
  • Maglite DE with a specific surface area close to 140 m2 / g marketed by Merck
  • the "Ferumag” with a specific surface area close to 160 m2 / g and marketed by Rhône-Poulenc.
  • polyalkyleneamines such as polyethyleneamines and very particularly ethylenediamine
  • etheramines and most particularly tris (3-oxa-6-amino hexyl) amine.
  • the amine used may be present in the "milk of magnesia" at the start of the carbonation operation or during it.
  • the carbonation operation is favorably carried out at a temperature which can range from 90 to 140 ° C. and preferably from 110 to 140 ° C., in one or more stages with the introduction of "milk of magnesia” into the medium containing the alkylbenzenesulfonate of magnesium, the sulfurized calcium alkylphenate and the dilution oil in one or more stages, each stage of introduction of "milk of magnesia” being followed by a stage of carbonation. Said carbonation operation is carried out until the sediment level stabilizes; this lasts a maximum of 6 hours.
  • a variant of the process making it possible to prepare the new additive consists in preceding the carbonation operation with a step of precarbonation of the reaction medium consisting of magnesium alkylbenzene sulfonate, sulfurized calcium alkylphenate and oil dilution, in the presence of glycol and possibly sulfur.
  • the new additive which is the subject of the invention has the advantage of being perfectly compatible with viscous oils, of containing a low level of sediment and of being slightly viscous.
  • the present invention also relates to the use of the new additive to improve the detergent, dispersing and anti-wear properties of lubricating oils.
  • the amount of additive to be used depends on the future use of said oils.
  • the amount of additive to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5 X; for a marine engine oil, it can go up to 25%.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products.
  • coal, and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon.
  • Additional additives may also be present in said lubricating oils alongside the new additive of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives //
  • the reaction medium is heated for 30 minutes at 110 ° C at atmospheric pressure, then 30 minutes in vacuo so as to distill the reaction water.
  • the mixture is heated to 120 ° C. for 2 hours (1 hour 30 minutes at atmospheric pressure and 30 minutes under a vacuum of 120 10 2 Pa), then the vacuum is broken.
  • Milk of magnesia is prepared in a beaker by mixing, with stirring, active magnesium oxide, glycol and an amine.
  • This milk is divided into three relatively equal fractions.
  • the carbonation operation is continued for 2 hours.
  • the flask is gradually placed under vacuum (40 10 2 Pa) and then heated for 2 hours at 200 ° C.
  • This test is carried out by adding 10% by weight of product to be tested to a SAE 30 mineral oil, storing the solution obtained for 1 month at 20 ° C. and studying the appearance of the solution as a function of time.
  • the finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 milliliters of calcium + magnesium.
  • the solution is stored for 24 hours and then centrifuged under the following conditions:
  • Example 1 The operations described in Example 1 are repeated, carrying out the start of the carbonation step at 130 ° C. instead of 110 ° C.
  • the mixture is heated to 110 ° C. and 112 g of glycol are charged in 1 hour. 0n continues to heat up to 160 ° C.
  • the reactor is placed under vacuum.
  • the vacuum is broken, the heating is stopped and carbonated for 1 hour at a rate of 0.5 g / min.
  • a mixture of 129 g of Mg0 and 349 g of glycol is prepared in a beaker, which mixture is introduced into the reactor over 5 minutes.
  • CO 2 is introduced into the medium. Two hours later, 16.5 g of ethylenediamine are introduced, then two hours more after 85 g of water, then carbonation is continued for a further 2 hours.
  • Example 12 The operations described in Example 12 are repeated in the absence of ethylene diamine.

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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)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Additif détergent-dispersant contenant du calcium et du magnésium, obtenu en carbonatant un alkylbenzène sulfonate de magnésium, un alkylphénate sulfurisé de calcium en présence d'huile, d'oxyde de magnésium, de glycol et d'une amine, en éliminant l'eau et le glycol et en filtrant.Detergent-dispersant additive containing calcium and magnesium, obtained by carbonating a magnesium alkylbenzene sulfonate, a sulfurized calcium alkylphenate in the presence of oil, magnesium oxide, glycol and an amine, by removing water and glycol and filtering.

L'additif est utilisé pour améliorer les propriétés détergentes, dispersantes et anti-usure des huiles lubrifiantes.The additive is used to improve the detergent, dispersant and anti-wear properties of lubricating oils.

Description

La présente invention a pour objet un nouvel additif détergent-dispersant mÉtallique de haute alcalinité pour huiles lubrifiantes.The subject of the present invention is a new high alkalinity metal detergent-dispersant additive for lubricating oils.

La demanderesse a en effet trouvé un additif détergent-dispersant présentant un TBN d'au moins 225, contenant plus de 3,8 % en poids de magnésium et, généralement, de l'ordre de 2 à 3 X en poids de calcium, ce qui confère audit additif, outre des caractéristiques de détergence et de dispersion une bonne activité comme anti-usure.The Applicant has in fact found a detergent-dispersant additive having a TBN of at least 225, containing more than 3.8% by weight of magnesium and, generally, of the order of 2 to 3 X by weight of calcium, this which gives said additive, in addition to the detergency and dispersion characteristics, a good activity as anti-wear.

Le nouvel additif faisant l'objet de l'invention est caractérisé en ce qu'il est obtenu selon un procédé qui consiste :

  • 1) - à carbonater un milieu réactionnnel constitué :
    • . d'un alkylbenzènesulfonate de magnésium de TBN inférieur ou égal à 20
    • . d'un alkylphénate sulfurisé de calcium de TBN pouvant aller jusqu'à 200
    • . et d'une huile de dilution.

    en présence d'un "lait de magnésie" constitué d'un mélange d'oxyde de magnésium actif, de glycol et d'une amine.
  • 2) - à éliminer l'eau et le glycol
  • 3) - et à filtrer pour éliminer les sédiments.
The new additive which is the subject of the invention is characterized in that it is obtained according to a process which consists:
  • 1) - to carbonate a reaction medium consisting of:
    • . a magnesium alkylbenzene sulfonate with TBN less than or equal to 20
    • . a sulfurized calcium alkylphenate of TBN up to 200
    • . and a dilution oil.

    in the presence of a "milk of magnesia" consisting of a mixture of active magnesium oxide, glycol and an amine.
  • 2) - to remove water and glycol
  • 3) - and filter to remove sediment.

On désigne par "alkylbenzènesulfonate de magnésium" toute solution contenant de 25 à 80 X en poids, de préférence de 30 à 70%. en poids d'un alkylbenzènesulfonate de magnésium dans une huile de dilution qui peut être ou peut ne pas être la même que celle mise en oeuvre pour préparer le nouvel additif.The term “magnesium alkylbenzenesulfonate” denotes any solution containing from 25 to 80% by weight, preferably from 30 to 70%. by weight of a magnesium alkylbenzenesulfonate in a dilution oil which may or may not be the same as that used to prepare the new additive.

Parmi les alkylbenzènesulfonates de magnésium pouvant être mis en oeuvre, on peut citer les sels de magnésium d'acides sulfoniques obtenus par sulfonation d'alkylbenzènes dérivant d'oléfines ou de polymères d'oléfines en C15-C30.Among the magnesium alkylbenzenesulfonates which can be used, mention may be made of the magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from C 15 -C 30 olefin polymers.

Parmi les huiles de dilution pouvant être mises en oeuvre, on peut citer de préférence les huiles paraffiniques telles que l'huile 100 Neutral ; les huiles naphténiques ou mixtes peuvent également convenir. La quantité d'huile de dilution pouvant être mise en oeuvre est telle que la quantité d'huile contenue dans le produit final (y compris celle provenant de l'alkylbenzènesulfonate de magnésium de départ) représente de 20 à 60 en poids dudit produit, de préférence de 25 à 55 X et tout particulièrement de 30 à 45 % en poids dudit produit.Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil; naphthenic or mixed oils may also be suitable. The amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting magnesium alkylbenzenesulfonate) represents from 20 to 60 by weight of said product, preferably from 25 to 55% and very particularly from 30 to 45% by weight of said product.

On désigne par "alkylphénate sulfurisé de calcium" toute solution contenant de 25 à 70 Z en poids, de préférence de 30 à 55X en poids d'un alkylphénate sulfurisé de calcium dans une huile de dilution qui peut être ou peut ne pas être la même que celle mise en oeuvre pour préparer le nouvel additif.The term “sulfurized calcium alkylphenate” denotes any solution containing from 25 to 70% by weight, preferably from 30 to 55% by weight of a sulfurized calcium alkylphenate in a dilution oil which may or may not be the same than that used to prepare the new additive.

Parmi les alkylphénates sulfurisés de calcium pouvant être mis en oeuvre, on peut citer : ceux obtenus par action de la chaux sur un alkylphénol sulfurisé portant de préférence un ou plusieurs substituants alkyles en C9-C30, (et de préférence en C9-C22), tels que les nonyl, décyl, dodécyl ou tétradécylphénols sulfurisés suivie éventuellement d'une carbonatation ; ceux obtenus par sulfu- risation au soufre d'un alkylphénol présentant de préférence un ou plusieurs substituants alkylés en C9-C30 ( de préférence en C 9-C 22) en présence de chaux et de glycol, suivie éventuellement d'une carbonatation.Among the sulfurized calcium alkylphenates which can be used, there may be mentioned: those obtained by the action of lime on a sulfurized alkylphenol preferably carrying one or more C 9 -C 30 alk y substituents, (and preferably C 9 -C 22 ), such as nonyl, decyl, dodecyl or sulfurized tetradecylphenols followed optionally by carbonation; those obtained by sulfurization with sulfur of an alkylphenol preferably having one or more C 9 -C 30 alkyl substituents (preferably C 9 -C 22 ) in the presence of lime and glycol, optionally followed by carbonation .

Pour une bonne réalisation du procédé mis en oeuvre pour préparer le nouvel additif, on peut utiliser un alkylphénate sulfurisé de calcium caractérisé par un rapport molaire chaux/alkylphénol compris entre 0,2 et 2,5 et de préférence entre 0,4 et 2, et par un rapport molaire soufre/alkylphénol compris entre 1,1 et 2,2 et de préférence entre 1,3 et 1,8.For a good implementation of the process used to prepare the new additive, it is possible to use a sulfurized calcium alkylphenate characterized by a lime / alkylphenol molar ratio of between 0.2 and 2.5 and preferably between 0.4 and 2, and by a sulfur / alkylphenol molar ratio of between 1.1 and 2.2 and preferably between 1.3 and 1.8.

On désigne par oxyde de magnésium "actif" de l'oxyde de magnésium MgO de surface spécifique supérieure ou égale à 80 m2/g, par exemple comprise entre 100 et 170 m2/g. A titre d'exemple, on peut citer la "Maglite DE" de surface spécifique voisine de 140 m2/g commercialisée par Merck et le "Ferumag" de surface spécifique voisine de 160 m2/g et commercialisée par Rhône-Poulenc.The term "active" magnesium oxide denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g. By way of example, there may be mentioned the "Maglite DE" with a specific surface area close to 140 m2 / g marketed by Merck and the "Ferumag" with a specific surface area close to 160 m2 / g and marketed by Rhône-Poulenc.

Parmi les amines pouvant être utilisées, on peut citer : les polyalkylèneamines, telles que les polyéthylèneamines et tout particulièrement l'éthylènediamine ; les étheramines et tout particulièrement la tris(oxa-3 amino-6 hexyl)amine.Among the amines which can be used, mention may be made of: polyalkyleneamines, such as polyethyleneamines and very particularly ethylenediamine; etheramines and most particularly tris (3-oxa-6-amino hexyl) amine.

L'amine mise en oeuvre peut être présente dans le "lait de magnésie" dès le début de l'opération de carbonatation ou au cours de celle-ci.The amine used may be present in the "milk of magnesia" at the start of the carbonation operation or during it.

  • . Une bonne réalisation du procédé permettant de préparer le nouvel additif peut être obtenue en mettant en oeuvre des quantités de réactifs telles que :. A good implementation of the process making it possible to prepare the new additive can be obtained by using quantities of reagents such as:
  • - le rapport de la quantité d'alkylbenzènesulfonate de magnésium exprimée en moles d'acide alkylbenzène sulfonique à la quantité d'alkylphénate sulfurisé de calcium, exprimée en moles d'alkylphénol soit compris entre 0,15 et 5,5, et de préférence entre 0,25 et 2 ;the ratio of the amount of magnesium alkylbenzene sulfonate expressed in moles of alkylbenzene sulfonic acid to the amount of sulfurized calcium alkylphenate, expressed in moles of alkylphenol is between 0.15 and 5.5, and preferably between 0.25 and 2;
  • - la quantité de MgO actif corresponde à un "base ratio" c'est à dire à un rapport moles de magnésium basique non fixé sur l'acide alkylbenzènesulfonique/moles de magnésium non basique fixé à l'acide alkylbenzènesulfonique, compris entre 5 et 14, et de préférence entre 7 et 11 ;the amount of active MgO corresponds to a "base ratio", that is to say a ratio of moles of basic magnesium not fixed on alkylbenzenesulfonic acid / moles of non-basic magnesium fixed in alkylbenzenesulfonic acid, of between 5 and 14 , and preferably between 7 and 11;
  • - la quantité de glycol corresponde à un rapport molaire MgO/glycol compris entre 0,1 et 0,7, et de préférence entre 0,3 et 0,65 ;the amount of glycol corresponds to a MgO / glycol molar ratio of between 0.1 and 0.7, and preferably between 0.3 and 0.65;
  • - la quantité d'amine corresponde à un rapport moles d'amine/ moles de magnésium basique compris entre 0,01 et 0,4, et de préférence entre 0,04 et 0,25 ;the amount of amine corresponds to a mole of amine / moles of basic magnesium ratio of between 0.01 and 0.4, and preferably between 0.04 and 0.25;

L'opération de carbonatation est favorablement réalisée à une température pouvant aller de 90 à 140°C et de préférence de 110 à 140°C, en un ou plusieurs stades avec introduction du "lait de magnésie" dans le milieu contenant l'alkylbenzènesulfonate de magnésium, l'alkylphénate sulfurisé de calcium et l'huile de dilution en un ou plusieurs stades, chaque stade d'introduction de "lait de magnésie" étant suivi d'un stade de carbonatation. Ladite opération de carbonatation est réalisée jusqu'à stabilisation du taux de sédiments ; celle-ci dure au maximum 6 heures.The carbonation operation is favorably carried out at a temperature which can range from 90 to 140 ° C. and preferably from 110 to 140 ° C., in one or more stages with the introduction of "milk of magnesia" into the medium containing the alkylbenzenesulfonate of magnesium, the sulfurized calcium alkylphenate and the dilution oil in one or more stages, each stage of introduction of "milk of magnesia" being followed by a stage of carbonation. Said carbonation operation is carried out until the sediment level stabilizes; this lasts a maximum of 6 hours.

Il a été constaté que l'addition d'une quantité d'eau correspondant à un rapport pondéral H20/-MgO compris entre 0,1 et 0,9 vers la fin de la carbonatation est favorable au bon déroulement du procédé.It has been found that the addition of a quantity of water corresponding to a H 2 O / -MgO weight ratio of between 0.1 and 0.9 towards the end of the carbonation is favorable for the smooth running of the process.

Une variante du procédé permettant de préparer le nouvel additif, consiste à faire précéder l'opération de carbonatation d'une étape de précarbonatation du milieu réactionnel constitué de l'alkylbenzène sulfonate de magnésium, de l'alkylphénate sulfurisé de calcium et de l'huile de dilution, en présence de glycol et éventuellement de soufre.A variant of the process making it possible to prepare the new additive, consists in preceding the carbonation operation with a step of precarbonation of the reaction medium consisting of magnesium alkylbenzene sulfonate, sulfurized calcium alkylphenate and oil dilution, in the presence of glycol and possibly sulfur.

Cette opération de précarbonatation est favorablement réalisée à une température comprise entre 150 et 180°C, et de préférence entre 160 et 175°C, en présence d'une quantité :

  • . de glycol correspondant a un rapport molaire calcium/glycol compris entre 0,15 et 0,77 et de préférence entre 0,2 et 0,6 ;
  • . de soufre correspondant à un rapport molaire soufre/calcium compris entre 0 et 1,5 et de préférence entre 0 et 1 ;
  • . de C02 correspondant à un rapport molaire C02/calcium compris entre 0,2 et 0,8 et de préférence entre 0,4 et 0,65.
This precarbonation operation is favorably carried out at a temperature between 150 and 180 ° C, and preferably between 160 and 175 ° C, in the presence of a quantity:
  • . glycol corresponding to a calcium / glycol molar ratio of between 0.15 and 0.77 and preferably between 0.2 and 0.6;
  • . sulfur corresponding to a sulfur / calcium molar ratio of between 0 and 1.5 and preferably between 0 and 1;
  • . of CO 2 corresponding to a CO 2 / calcium molar ratio of between 0.2 and 0.8 and preferably between 0.4 and 0.65.

Le nouvel additif faisant l'objet de l'invention présente l'avantage d'être parfaitement compatible avec les huiles visqueuses, de contenir un faible taux de sédiments et d'être faiblement visqueux.The new additive which is the subject of the invention has the advantage of being perfectly compatible with viscous oils, of containing a low level of sediment and of being slightly viscous.

La présente invention a également pour objet l'utilisation du nouvel additif pour améliorer les propriétés détergentes, dispersantes et anti-usure des huiles lubrifiantes.The present invention also relates to the use of the new additive to improve the detergent, dispersing and anti-wear properties of lubricating oils.

La quantité d'additif à utiliser est fonction de l'utilisation future desdites huiles.The amount of additive to be used depends on the future use of said oils.

Ainsi pour une huile pour moteur à essence, la quantité d'additif à ajouter est généralement comprise entre 1 et 3,5 % ; pour une huile pour moteur diesel elle est généralement comprise entre 1,8 et 5 X ; pour une huile pour moteur marin, elle peut aller jusqu'à 25 %.Thus for a gasoline engine oil, the amount of additive to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5 X; for a marine engine oil, it can go up to 25%.

Les huiles lubrifiantes que l'on peut ainsi améliorer peuvent être choisies parmi des huiles lubrifiantes très variées, comme les huiles lubrifiantes de base naphténique, de base paraffinique et de base mixte, d'autres lubrifiants hydrocarbonés, par exemple des huiles lubrifiantes dérivées de produits de la houille, et des huiles synthétiques, par exemple des polymères d'alkylène, des polymères du type oxyde d'alkylène et leurs dérivés, y compris les polymères d'oxyde d'alkylène préparés en polymérisant de l'oxyde d'alkylène en présence d'eau ou d'alcools, par exemple d'alcool éthylique, les esters d'acides dicarboxyliques, des esters liquides d'acides du phosphore, des alkylbenzènes et des dialkylbenzènes, des polyphényles, des alkylbiphényléthers, des polymères du silicium.The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon.

Des additifs supplémentaires peuvent également être présents dans lesdites huiles lubrifiantes à côté du nouvel additif de l'invention ; on peut citer par exemple des additifs anti-oxydants, anti-corrosion, des additifs dispersants sans cendres.....Additional additives may also be present in said lubricating oils alongside the new additive of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives .....

Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.

Exemples 1 à 9Examples 1 to 9

A) Préparation d'un alkylbenzène sulfonate de magnésiumA) Preparation of a magnesium alkylbenzene sulfonate

de TBN = 3of TBN = 3

On charge dans un ballon de 3 litres :

  • - une solution à environ 70 % dans de l'huile de dilution 100 N d'acide sulfonique de masse moléculaire 470 environ (masse du sel de sodium)
  • - de l'huile 100 Neutral
We load into a 3 liter flask:
  • - a solution of approximately 70% in 100 N dilution oil of sulphonic acid with a molecular mass of approximately 470 (mass of the sodium salt)
  • - 100 Neutral oil

On chauffe à 80°C et on introduit :

  • - de la "Maglite DE" de façon à obtenir un alkylbenzène sulfonate de magnésium de TBN voisin de 3
  • - puis du glycol en cinq minutes.
The mixture is heated to 80 ° C. and the following are introduced:
  • - "Maglite DE" so as to obtain a magnesium alkylbenzene sulfonate of TBN close to 3
  • - then glycol in five minutes.

On chauffe le milieu réactionnel pendant 30 minutes à 110°C à pression atmosphérique, puis 30 minutes sous vide de façon à distiller l'eau de réaction.The reaction medium is heated for 30 minutes at 110 ° C at atmospheric pressure, then 30 minutes in vacuo so as to distill the reaction water.

On prend un échantillon pour mesurer le taux de sédiments.We take a sample to measure the sediment level.

B) Préparation de l'alkylphénate sulfurisé de calciumB) Preparation of the sulfurized calcium alkylphenate

On charge à 110°C sur le produit préparé ci-dessus :

  • - du dodécylphénol (DDP) sulfurisé contenant environ 11 % en poids de soufre
  • - de la chaux éteinte
  • - du glycol en cinq minutes
The product prepared above is charged at 110 ° C:
  • - sulfurized dodecylphenol (DDP) containing about 11% by weight of sulfur
  • - slaked lime
  • - glycol in five minutes

On chauffe à 120°C pendant 2 heures (1 h 30 à pression atmosphérique et 30 minutes sous un vide de 120 102Pa), puis on casse le vide.The mixture is heated to 120 ° C. for 2 hours (1 hour 30 minutes at atmospheric pressure and 30 minutes under a vacuum of 120 10 2 Pa), then the vacuum is broken.

C) CarbonatationC) Carbonation

On prépare dans un bécher un lait de magnésie par mélange sous agitation d'oxyde de magnésium actif, de glycol et d'une amine.Milk of magnesia is prepared in a beaker by mixing, with stirring, active magnesium oxide, glycol and an amine.

On divise ce lait en trois fractions relativement égales.This milk is divided into three relatively equal fractions.

On introduit :

  • - la première fraction de lait dans le ballon, puis du C02 à 110°C,
  • - 2 heures après, la 2ème fraction de lait et du CO2
  • - 2 heures après l'introduction de la 2ème fraction, la 3ème fraction de lait ainsi que de l'eau.
We introduce:
  • - the first fraction of milk in the flask, then C0 2 at 110 ° C,
  • - 2 hours later, the second fraction of milk and CO 2
  • - 2 hours after the introduction of the 2nd fraction, the 3rd fraction of milk and water.

On poursuit l'opération de carbonatation pendant 2 heures.The carbonation operation is continued for 2 hours.

D) Elimination du glycolD) Elimination of glycol

Après l'arrêt de la carbonatation, le ballon est mis progressivement sous vide (40 102Pa) puis est chauffé pendant 2 heures à 200°C.After the carbonation has stopped, the flask is gradually placed under vacuum (40 10 2 Pa) and then heated for 2 hours at 200 ° C.

E) FiltrationE) Filtration Caractéristiques du produitProduct Features Mesure du taux de sédimentsSediment measurement

Les % de sédiments sont mesurés selon la norme ASTMD 2273-67, en apportant toutefois les modifications suivantes :

  • - vitesse de rotation de la centrifugeuse 6000 t/mn
  • - force centrifuge relative 10000
  • - le produit à analyser est dilué au quart dans l'essence
The% of sediments are measured according to standard ASTMD 2273-67, with the following modifications, however:
  • - speed of rotation of the centrifuge 6000 rpm
  • - relative centrifugal force 10,000
  • - the product to be analyzed is diluted a quarter in gasoline

E (25 cm3 de produit à analyser + 75 cm3 d'essence E).E (25 cm3 of product to be analyzed + 75 cm3 of gasoline E).

- durée de la centrifugation 10 minutes.- duration of centrifugation 10 minutes.

Tests de compatibilitéCompatibility testing N°1# 1

Ce test est réalisé par addition de 10 % en poids de produit à tester à une huile minérale SAE 30, stockage de la solution obtenue pendant 1 mois à 20°C et étude de l'aspect de la solution en fonction du temps.

Figure imgb0001
This test is carried out by adding 10% by weight of product to be tested to a SAE 30 mineral oil, storing the solution obtained for 1 month at 20 ° C. and studying the appearance of the solution as a function of time.
Figure imgb0001

N°2# 2

Le produit fini est ajouté à une huile SAE 50 à tendance paraffinique de façon à obtenir une solution contenant 125 milli- moles de calcium + magnésium.The finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 milliliters of calcium + magnesium.

La solution est stockée pendant 24 heures puis centrifugée dans les conditions suivantes :

Figure imgb0002
The solution is stored for 24 hours and then centrifuged under the following conditions:
Figure imgb0002

Les quantités de réactifs mises en oeuvre aux différentes étapes sont indiquées aux tableaux I et II ; les résultats obtenus figurent au tableau II.The amounts of reagents used in the various stages are indicated in Tables I and II; the results obtained are shown in Table II.

Exemple 10Example 10

On répète les opérations décrites à l'exemple 1 en remplaçant les 16,5 g d'éthylènediamine par 8 g de cris(oxa-3 amino-6 hexyl) amine dénommée "TOA".The operations described in example 1 are repeated, replacing the 16.5 g of ethylenediamine with 8 g of cries (3-oxa-6-amino-hexyl) amine called "TOA".

Les résultats sont identiques à ceux de l'exemple 1.The results are identical to those of Example 1.

Exemple 11Example 11

On répète les opérations décrites à l'exemple 1 en réalisant le début de l'étape de carbonatation à 130°C au lieu de 110°C.The operations described in Example 1 are repeated, carrying out the start of the carbonation step at 130 ° C. instead of 110 ° C.

Les résultats sont identiques à ceux de l'exemple 1.The results are identical to those of Example 1.

Exemple 12Example 12 A) Préparation de l'alkylbenzène sulfonate de magnésium de TBN = 18 dans un ballon de 3 litres :A) Preparation of magnesium alkylbenzene sulfonate of TBN = 18 in a 3-liter flask:

  • - 500 g de solution à environ 70X dans de l'huile 100 Neutral d'acide sulfonique de masse moléculaire 470- 500 g of solution at approximately 70X in 100 Neutral oil of sulfonic acid of molecular weight 470
  • - 615 g d'huile 100 Neutral- 615 g of 100 Neutral oil
  • - 25 g d'oxide.de magnesium actif- 25 g of active magnesium oxide
  • - 7 g d'une solution aqueuse à environ 50 % en poids de chlorure de calcium.- 7 g of an aqueous solution at about 50% by weight of calcium chloride.

On chauffe à 110°C et on charge 112 g de glycol en 1 heure. 0n continue à chauffer jusqu'à 160°C.The mixture is heated to 110 ° C. and 112 g of glycol are charged in 1 hour. 0n continues to heat up to 160 ° C.

B) Préparation de l'alkylphénate sulfurisé de calciumB) Preparation of the sulfurized calcium alkylphenate

On charge 411 g de dodécylphénol sulfurisé contenant environ 10 % de soufre, 100 g de chaux et 45 g de soufre.411 g of sulfurized dodecylphenol containing approximately 10% sulfur, 100 g of lime and 45 g of sulfur are loaded.

On met le réacteur sous vide.The reactor is placed under vacuum.

On introduit 100 g de glycol en 1 heure tout en continuant à chauffer.100 g of glycol are introduced over 1 hour while continuing to heat.

On reste 1 heure à 165°C sous 345 102Pa.We stay 1 hour at 165 ° C under 345 102Pa.

C) PrécarbonatationC) Precarbonation

On casse le vide, on arrête le chauffage et on carbonate pendant 1 heure à un débit de 0,5 g/mn.The vacuum is broken, the heating is stopped and carbonated for 1 hour at a rate of 0.5 g / min.

D) CarbonatationD) Carbonation

On prépare dans un bécher un mélange de 129 g de Mg0 et de 349 g de glycol, mélange que l'on introduit en 5 minutes dans le réac- t.eur.A mixture of 129 g of Mg0 and 349 g of glycol is prepared in a beaker, which mixture is introduced into the reactor over 5 minutes.

On introduit du CO2 dans le milieu. Deux heures après on introduit 16,5 g d'éthylènediamine, puis deux heures encore après 85 g d'eau, puis on poursuit la carbonatation pendant encore 2 heures.CO 2 is introduced into the medium. Two hours later, 16.5 g of ethylenediamine are introduced, then two hours more after 85 g of water, then carbonation is continued for a further 2 hours.

Pendant les 6 heures de carbonatation, le débit de C02 est régulé de façon à obtenir un léger rejet de CO2.

Figure imgb0003
During the 6 hours of carbonation, the flow of C0 2 is regulated so as to obtain a slight release of CO 2 .
Figure imgb0003

Exemple 12 bisExample 12a

Les opérations décrites à l'exemple 12 sont répétées en l'absence d'éthylène diamine.The operations described in Example 12 are repeated in the absence of ethylene diamine.

Les résultats obtenus sont les suivants :

Figure imgb0004
Figure imgb0005
Figure imgb0006
 The results obtained are as follows:
Figure imgb0004
Figure imgb0005
Figure imgb0006

Claims (17)

1) Nouvel additif caractérisé en ce qu'il est obtenu selon un procédé qui consiste : a) à carbonater un milieu réactionnel constitué : - d'un alkylbenzènesulfonate de magnésium de TBN inférieur ou égal à 20; - d'un alkylphénate sulfurisé de calcium de TBN pouvant aller jusqu'à 200 ; - et d'une huile de dilution, en présence d'un "lait de magnésie" constitué d'un mélange d'oxyde de magnésium actif, de glycol et d'une amine. b) à éliminer l'eau et le glycol ; c) et à filtrer pour éliminer les sédiments. 1) New additive characterized in that it is obtained according to a process which consists: a) carbonating a reaction medium consisting of: - a magnesium alkylbenzene sulfonate with TBN less than or equal to 20; - a sulfurized calcium alkylphenate of TBN up to 200; - And a dilution oil, in the presence of a "milk of magnesia" consisting of a mixture of active magnesium oxide, glycol and an amine. b) removing water and glycol; c) and filter to remove sediment. 2) Nouvel additif selon la revendication 1, caractérisé en ce que l'alkylphénate sulfurisé de calcium présente un rapport molaire chaux/alkylphénol compris entre 0,2 et 2,5 et un rapport molaire soufre/alkylphénol compris entre 1,1 et 2,2.2) New additive according to claim 1, characterized in that the sulfurized calcium alkylphenate has a lime / alkylphenol molar ratio of between 0.2 and 2.5 and a sulfur / alkylphenol molar ratio of between 1.1 and 2, 2. 3) Nouvel additif selon la revendication 2, caractérisé en ce que l'alkylphénate sulfurisé de calcium présente un rapport molaire chaux/alkylphênol compris entre 0,4 et 2 et un rapport molaire soufre/ alkylphénol compris entre 1,3 et 1,8.3) New additive according to claim 2, characterized in that the sulfurized calcium alkylphenate has a lime / alkylphenol molar ratio of between 0.4 and 2 and a sulfur / alkylphenol molar ratio of between 1.3 and 1.8. 4) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce que l'amine mise en oeuvre est une polyéthylèneamine.4) New additive according to any one of the preceding claims, characterized in that the amine used is a polyethyleneamine. 5) Nouvel additif selon la revendication 4, caractérisé en ce que l'amine est l'éthylènediamine.5) New additive according to claim 4, characterized in that the amine is ethylenediamine. 6) Nouvel additif selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'amine est une étheramine.6) New additive according to any one of claims 1 to 3, characterized in that the amine is an etheramine. 7) Nouvel additif selon la revendication 6, caractérisé en ce que l'étheramine est la tris(oxa-3 amino-6 hexyl)amine.7) New additive according to claim 6, characterized in that the etheramine is tris (3-oxa-6-amino-6 hexyl) amine. 8) Nouvel additif selon l'une quelconque des revendications précédentes caractérisé en ce que les quantités de réactifs mises en oeuvre sont telles que : - le rapport de la quantité d'alkylbenzènesulfonate de magnésium exprimée en moles d'acide alkylbenzène sulfonique à la quantité d'alkylphénate sulfurisé de calcium, exprimée en moles d'alkylphénol soit compris entre 0,15 et 5,5 ; - la quantité de Mg0 actif corresponde à un "base ratio" compris entre 5 et 14 ; - la quantité de glycol corresponde à un rapport molaire Mg0/glycol compris entre 0,1 et 0,7 ; - la quantité d'amine corresponde à un rapport moles d'amine/ moles de magnésium basique compris entre 0,01 et 0,4 ; 8) New additive according to any one of the preceding claims, characterized in that the quantities of reagents used are such that: - The ratio of the amount of magnesium alkylbenzene sulfonate expressed in moles of alkylbenzene sulfonic acid to the amount of sulfurized calcium alkylphenate, expressed in moles of alkylphenol is between 0.15 and 5.5; - the amount of active Mg0 corresponds to a "base ratio" between 5 and 14; - The amount of glycol corresponds to a Mg0 / glycol molar ratio of between 0.1 and 0.7; the amount of amine corresponds to a mole of amine / moles of basic magnesium ratio of between 0.01 and 0.4; 9) Nouvel additif selon la revendication 8, caractérisé en ce que les quantités de réactifs sont telles que : - le rapport de la quantité d'alkylbenzènesulfonate de magnésium exprimée en moles d'acide alkylbenzène sulfonique à la quantité d'alkylphénate sulfurisé de calcium, exprimée en moles d'alkylphénol soit compris entre 0,25 et 2 ; - la quantité de Mg0 actif corresponde à un "base ratio" compris entre 7 et 11 ; - la quantité de glycol corresponde à un rapport molaire Mg0/glycol compris entre 0,3 et 0,65 ; - la quantité d'amine corresponde à un rapport moles d'amine/ moles de magnésium basique compris entre 0,04 et 0,25 ; 9) New additive according to claim 8, characterized in that the quantities of reactants are such that: - The ratio of the amount of magnesium alkylbenzene sulfonate expressed in moles of alkylbenzene sulfonic acid to the amount of sulfurized calcium alkylphenate, expressed in moles of alkylphenol is between 0.25 and 2; - the amount of active Mg0 corresponds to a "base ratio" of between 7 and 11; - The amount of glycol corresponds to a Mg0 / glycol molar ratio of between 0.3 and 0.65; - The amount of amine corresponds to a mole of amine / moles of basic magnesium ratio of between 0.04 and 0.25; 10) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce que l'opération de carbonatation est réalisée à une température allant de 90 à 140°C, en un ou plusieurs stades avec introduction du "lait de magnésie" dans le milieu contenant l'alkylbenzènesulfonate de magnésium, l'alkylphénate sulfurisé de calcium et l'huile de dilution en un ou plusieurs stades, chaque stade d'introduction de "lait de magnésie" étant suivi d'un stade de carbonatation.10) New additive according to any one of the preceding claims, characterized in that the carbonation operation is carried out at a temperature ranging from 90 to 140 ° C, in one or more stages with the introduction of "milk of magnesia" into the medium containing the magnesium alkylbenzenesulfonate, the sulfurized calcium alkylphenate and the dilution oil in one or more stages, each stage of introduction of "milk of magnesia" being followed by a stage of carbonation. 11) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce que l'amine est présente dans le "lait de magnésie" dès le début de l'opération de carbonatation ou au cours de celle-ci.11) New additive according to any one of the preceding claims, characterized in that the amine is present in the "milk of magnesia" from the start of the carbonation operation or during it. 12) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce que une quantité d'eau correspondant à un rapport pondéral H20/Mg0 compris entre 0,1 et 0,9 est introduite vers la fin de la carbonatation.12) New additive according to any one of the preceding claims, characterized in that an amount of water corresponding to a H20 / Mg0 weight ratio of between 0.1 and 0.9 is introduced towards the end of the carbonation. 13) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on fait précéder l'opération de carbonatation d'une étape de précarbonatation du milieu réactionnel constitué de l'alkylbenzène sulfonate de magnésium, de l'alkylphénate sulfurisé de calcium et de l'huile de dilution, en présence de glycol et éventuellement de soufre.13) New additive according to any one of the preceding claims, characterized in that the operation precedes carbonation of a precarbonation step of the reaction medium consisting of magnesium alkylbenzene sulfonate, sulfurized calcium alkylphenate and dilution oil, in the presence of glycol and optionally sulfur. 14) Nouvel additif selon la revendication 13, caractérisé en ce que l'opération de précarbonatation est réalisée à une température comprise entre 150 et 180°C.14) New additive according to claim 13, characterized in that the precarbonation operation is carried out at a temperature between 150 and 180 ° C. 15) Nouvel additif selon l'une quelconque des revendications précédentes, caractérisé en ce que l'étape de précarbonatation est réalisée en présence d'une quantité : . de glycol correspondant à un rapport molaire calcium/glycol compris entre 0,15 et 0,77 ; . de soufre correspondant à un rapport molaire soufre/calcium compris entre 0 et 1,5 ; . de C02 correspondant à un rapport molaire C02/calcium compris entre 0,2 et 0,8. 15) New additive according to any one of the preceding claims, characterized in that the precarbonation step is carried out in the presence of a quantity: . glycol corresponding to a calcium / glycol molar ratio of between 0.15 and 0.77; . sulfur corresponding to a sulfur / calcium molar ratio of between 0 and 1.5; . of C0 2 corresponding to a C0 2 / calcium molar ratio of between 0.2 and 0.8. 16) Nouvel additif selon la revendication 15, caractérisé en ce que l'étape de précarbonatation est réalisée en présence d'une quantité : . de glycol correspondant à un rapport molaire calcium/glycol compris entre 0,2 et 0,6 . de soufre correspondant à un rapport molaire soufre/calcium compris entre 0 et 1 ; . de CO2 correspondant à un rapport molaire CO2/calcium compris entre 0,4 et 0,65. 16) New additive according to claim 15, characterized in that the precarbonation step is carried out in the presence of a quantity: . of glycol corresponding to a calcium / glycol molar ratio of between 0.2 and 0.6 . sulfur corresponding to a sulfur / calcium molar ratio of between 0 and 1; . of CO 2 corresponding to a CO 2 / calcium molar ratio of between 0.4 and 0.65. 17) Application du nouvel additif faisant l'objet de l'une quelconque des revendications précédentes pour améliorer les propriétés détergentes, dispersantes et anti-usure des huiles lubrifiantes.17) Application of the new additive which is the subject of any one of the preceding claims to improve the detergent, dispersant and anti-wear properties of lubricating oils.
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FR2429832A1 (en) * 1978-06-26 1980-01-25 Orogil IMPROVED PROCESS FOR THE PREPARATION OF HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVES, PARTICULARLY FOR LUBRICATING OILS
FR2429833A1 (en) * 1978-06-26 1980-01-25 Orogil PROCESS FOR THE PREPARATION OF SURALKALINATED METAL DETERGENTS-DISPERSANTS FOR LUBRICATING OILS
FR2450868A1 (en) * 1979-03-09 1980-10-03 Orogil PROCESS FOR THE PREPARATION OF MAGNESIUM ALKYLPHENATES AND APPLICATION OF THE PRODUCTS OBTAINED AS DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS

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ES523539A0 (en) 1984-04-01
DE3374403D1 (en) 1987-12-17
DK289983A (en) 1983-12-25
ZA834558B (en) 1984-03-28
ES8403963A1 (en) 1984-04-01
GB2123023A (en) 1984-01-25
BR8303369A (en) 1984-02-07
DK289983D0 (en) 1983-06-23
JPS6025079B2 (en) 1985-06-15
GR78595B (en) 1984-09-27
EP0101334B1 (en) 1987-11-11
PT76929A (en) 1983-07-01
JPS5947299A (en) 1984-03-16
FR2529225B1 (en) 1986-04-25
FR2529225A1 (en) 1983-12-30
PT76929B (en) 1986-01-27
SG54685G (en) 1986-05-02
EP0101334A3 (en) 1985-10-09
CA1182627A (en) 1985-02-19
AU1612483A (en) 1984-01-05
US4470916A (en) 1984-09-11
GB2123023B (en) 1985-06-05
AU559589B2 (en) 1987-03-12
ATE30716T1 (en) 1987-11-15
PH19405A (en) 1986-04-10
GB8317024D0 (en) 1983-07-27

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