EP0007257B1 - Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained - Google Patents

Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained Download PDF

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Publication number
EP0007257B1
EP0007257B1 EP79400376A EP79400376A EP0007257B1 EP 0007257 B1 EP0007257 B1 EP 0007257B1 EP 79400376 A EP79400376 A EP 79400376A EP 79400376 A EP79400376 A EP 79400376A EP 0007257 B1 EP0007257 B1 EP 0007257B1
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weight
parts
alkylbenzenesulphonate
magnesium
alkylphenol
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German (de)
French (fr)
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EP0007257A1 (en
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Bernard Demoures
Jean-Louis Le Coent
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Orogil SA
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Orogil SA
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    • 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

Definitions

  • the present invention relates to new detergent-dispersants of high alkalinity for lubricating oils.
  • D 2896 can only be obtained by using an alcohol of the methanol type and this preferably with an organic solvent of the toluene type.
  • Such a process has the drawback of using toxic methanol or a toxic mixture containing methanol which, in addition, forms with water an azeotrope which is difficult to remove.
  • the Applicant has found how to adapt this type of process using an alkylene glycol, to the preparation of TBN products greater than 200 containing at least 2% magnesium and possibly at least 0.5% calcium, said products also having good properties anti-wear.
  • the quantity of CO 2 used to carry out the step of over-alkalinization-carbonation can vary between the quantity which can be completely absorbed and an excess of 40% by weight of this quantity; preferably, the amount of CO 2 will correspond substantially to that which can be completely absorbed.
  • calcium and / or magnesium alkylbenzene sulfonate denotes any solution containing from 40 to 95% by weight, preferably from 55 to 85% by weight of a calcium and / or magnesium alkylbenzene sulfonate in an oil of dilution which may or may not be the same as that used to carry out the process which is the subject of the invention.
  • calcium and / or magnesium alkylbenzenesulfonates which can be used, mention may be made of the calcium and / or magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or polymers of C 15 ⁇ C 30 olefins.
  • alkylphenols which can be used to carry out the process which is the subject of the invention, mention may preferably be made of those carrying one or more C 9 ⁇ C 15 alkyl substituents, and very particularly nonyl, decyl, dodecyl or tetradecylphenols.
  • 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.
  • MgO 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 and marketed by Merck, as well as “Ferumag”, with a specific surface area close to 160 m2 / g and marketed by RHONE-POULENC INDUSTRIES.
  • alkali metal hydroxides mention may be made of sodium hydroxide, lithium hydroxide, potassium hydroxide.
  • 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 alkylbenzenesulfonate) represents from 20 to 60% by weight of said product and preferably 25 to 55% of said product.
  • alkylene glycols which can be used, mention may very particularly be made of glycol; these can optionally be present in mixture with up to 200% of their weight of a monoalcohol such as ethylhexanol, tridecyl alcohol, oxo alcohols in C $ -C, 4 and in general the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.
  • a monoalcohol such as ethylhexanol, tridecyl alcohol, oxo alcohols in C $ -C, 4 and in general the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.
  • a variant of the process which is the subject of the invention consists in carrying out a precarbonation operation after the suifurization step and before the over-alkalinization-carbonation step.
  • This operation can be carried out at a temperature between 100 and 250 ° C and preferably between 100 and 185 ° C, using carbon dioxide.
  • the quantity of CO 2 that can be used corresponds, to more or less 30%, by weight, to that which can be completely absorbed by the sulfurized medium; preferably this quantity of CO 2 will correspond substantially to that which can be completely absorbed.
  • a treatment with water may be carried out in addition to or in place of that provided for in the step of over-alkalinization-carbonation; this treatment can be carried out under the same conditions as those indicated above.
  • the present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above.
  • 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 type polymers prepared by polymerizing alkylene oxide in the 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.
  • 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 poly
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
  • the medium is brought to 145 ° C. under 260 mm of mercury, then glycol is added over 1 hour; it is heated to 165 ° C. and this temperature is maintained for 1 hour under 260 mm of mercury.
  • the superalkalinized and carbonated medium is brought to a temperature of 184 ° C. under 30 mm of mercury; glycol distills; it is filtered to remove the sediment and a solution in 100 N oil of overbased detergent-dispersant is recovered, the characteristics of which appear in Tables 1 to III '.
  • Example 3 The operation described in Example 3 is carried out by carrying out the precarbonation step at 140 ° C. at atmospheric pressure.
  • Example 3 The operation described in Example 3 is carried out from an 80% solution in 100 N oil of a magnesium alkylbenzenesulfonate of molecular weight approximately 470, solution containing 2.25% of magnesium and having a TBN of 32.
  • Example 3 The operation described in Example 3 is carried out, carried out from a 60% solution in 100 N oil of a magnesium aikylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 2.2% magnesium and having a TBN of 45.
  • Example 3 The operation described in Example 3 is carried out from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate of molecular weight approximately 470, solution containing 2.7% of calcium and having a TBN of 25, and without adding water during the precarbonation and carbonation operations.
  • Example 3 The operation described in Example 3 is carried out without adding water during the precarbonation and carbonation operations.
  • the product obtained has characteristics equivalent to those of Example 3.
  • Example 17 The operation described in Example 17 is carried out from a 60% solution in 100 N oil of a calcium alkylbenzenesulfonate of molecular weight approximately 470, solution containing 2.7% of calcium and having a TBN of 25 and performing a carbonation step.
  • Example 17 The operation described in Example 17 is carried out using the same quantities of reagents, but. by carrying out the sulfurization operation first at 165 ° C for 1 hour under 260 mm of mercury and then for 2 hours at 185 ° C under 700 mm of mercury.
  • the product obtained has characteristics equivalent to those of Example 17.
  • Example 7 The product of Example 7 is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium. The solution is stored for 15 days at 20 ° C; we see that the solution remains clear.
  • mixture (A) is brought for 25 days to 80 ° C. and is then added to an SAE 30 oil so as to have a concentration of 6.6% by weight of mixture (A).
  • the solution is stored for 5 days at 80 ° C.

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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)

Abstract

A process is provided for preparing detergent-dispersant compositions of a TBN of at least about 200, containing at least about 2 percent magnesium, by: (1) sulfurization by sulfur of an alkylphenol in the presence of a magnesium and/or calcium alkylbenzene-sulfonate of a TBN less than or equal to about 150, an alkaline-earth component selected from among lime, mixtures of magnesium oxide and lime, or a magnesium oxide and alkali hydroxide, and an alkylene glycol; (2) optionally precarbonation of the resultant mixture by means of CO2; (3) super-alkalinization and carbonation of the resultant mixture by means of magnesium oxide and possibly lime, CO2 and alkylene glycol; and (4) removal of the excess alkylene glycol. The detergent-dispersant compositions obtained are useful in the improvement of the detergent-dispersant properties of lubricating oils.

Description

La présente invention a pour objet de nouveaux détergents-dispersants de haute alcalinité pour huiles lubrifiantes.The present invention relates to new detergent-dispersants of high alkalinity for lubricating oils.

II est connu (brevet américain n° 4.049.560) de préparer des détergents-dispersants à base d'alkylphénates et d'alkyibenzène sulfonates de magnésium en opérant à une température inférieure à 100°C à partir d'un milieu réactionnel contenant notamment un alkylphénol sulfurisé, un acide alkylbenzène sulfonique ou un de ses sels alcalino-terreux, un alcool, de l'oxyde de magnésium, un promoteur (formiate d'ammonium par exemple), une huile de dilution et éventuellement un solvant organique. Il a été constaté que des produits de TBN élevé (Total Basic Number - Norme A.S.T.M. D 2896) ne peuvent être obtenus qu'en utilisant un alcool du type méthanol et ce de préférence avec un solvant organique du type toluène. Un tel procédé présente l'inconvénient d'utiliser du méthanol toxique ou un mélange toxique contenant du méthanol formant en outre avec l'eau un azéotrope difficile à éliminer.It is known (US Pat. No. 4,049,560) to prepare detergent-dispersants based on magnesium alkylphenates and alkylibenzene sulfonates by operating at a temperature below 100 ° C. from a reaction medium containing in particular a sulfurized alkylphenol, an alkylbenzene sulfonic acid or one of its alkaline-earth salts, an alcohol, magnesium oxide, a promoter (ammonium formate for example), a dilution oil and optionally an organic solvent. It has been observed that high TBN products (Total Basic Number - Standard A.S.T.M. D 2896) can only be obtained by using an alcohol of the methanol type and this preferably with an organic solvent of the toluene type. Such a process has the drawback of using toxic methanol or a toxic mixture containing methanol which, in addition, forms with water an azeotrope which is difficult to remove.

Il est également connu (brevets français n° 2.335.588 et n° 1.080.531, anglais n° 1.015.769 et américain n° 3.923.670) de préparer des détergents-dispersants à base d'alkylphénates et d'alkylbenzène sulfonates de métaux alcalino-terreux, à partir d'un milieu réactionnel contenant du soufre, un alkylphénol, un alkyl-benzène sulfonate de métaux. alcalino-terreux, une base alcalino-terreuse, un alkylèneglycol, une huile de dilution et éventuellement un alcool lourd. Ce type procédé utilisant un alkylène-glycol non toxique et ne formant pas d'azéotrope avec l'eau, est tout particulièrement intéressant pour préparer des produits contenant du calcium mais n'est toutefois pas satisfaisant pour préparer des produits contenant un fort pourcentage de magnésium.It is also known (French patents No. 2,335,588 and No. 1,080,531, English No. 1,015,769 and American No. 3,923,670) to prepare detergent-dispersants based on alkylphenates and alkylbenzene sulfonates of alkaline earth metals, from a reaction medium containing sulfur, an alkylphenol, an alkyl benzene sulfonate of metals. alkaline earth, an alkaline earth base, an alkylene glycol, a dilution oil and optionally a heavy alcohol. This type of process using a non-toxic alkylene glycol which does not form an azeotrope with water is very particularly advantageous for preparing products containing calcium but is however not satisfactory for preparing products containing a high percentage of magnesium .

La demanderesse a trouvé comment adapter ce type de procédé utilisant un alkylèneglycol, à la préparation de produits de TBN supérieur à 200 contenant au moins 2% de magnésium et éventuellement au moins 0,5% de calcium, lesdits produits présentant en outre de bonnes propriétés antl-usure.The Applicant has found how to adapt this type of process using an alkylene glycol, to the preparation of TBN products greater than 200 containing at least 2% magnesium and possibly at least 0.5% calcium, said products also having good properties anti-wear.

Le procédé faisant l'objet de la présente invention vise la préparation de détergents-dispersants par action du soufre à une température comprise entre 100 et 190°C sur un alkylphénol. portant un ou plusieurs radicaux alkyles en C5―C50, en présence d'une huile de dilution, d'un alkylbenzène sulfonate de métal alcalino-terreux de masse moléculaire supérieure à 300 et de TBN inférieur à 150, d'une base alcalino-terreuse et d'un alkylèneglycol, suralcalinisation-carbonatation du milieu sulfurisé au moins en une fois à l'aide d'une base alcalino-terreuse et de C02 à une température comprise entre 100 et 250°C, élimination de l'alkylèneglycol et récupération du détergent-dispersant obtenu, ledit procédé étant caractérisé en ce que:

  • - la base alcalino-terreuse est choisie parmi la chaux, l'oxyde de magnésium, ou les mélanges chaux-oxyde de magnésium;
    • a) A l'étape de sulfurisation, on introduit:
      • de 27 à 53% de la quantité molaire totale de base alcalino-terreuse;
      • de 0 à 50% de la quantité totale d'oxyde de magnésium;
      • de 18 à 45% de la quantité totale d'alkylène glycol;
      • de 0,1 à 2,8 moles, de préférence de 0,16 à 1,77 moles d'alkylbenzènesulfonate de calcium et/ou de magnésium par mole d'alkylphénol;
      • une quantité de soufre correspondant à un rapport molaire soufre/quantité totale de base alcalino-terreuse compris entre 0,42 et 0,8;
      • de 0,69 à 1,69 mole de base alcalino-terreuse par mole d'alkylphénol;
      • une quantité d'alkylèneglycol correspondant à un rapport molaire base alcalino-terreuse- alkylèneglycol comprise entre 0,28 et 1,4 et entre 0,81 et 1,4 lorsque ladite base alcalino-terreuse est constituée essentiellement de chaux à l'étape de suifurisation;
      • en outre de 0,02 à 0,75 mole, de préférence de 0,02 à 0,33 mole d'un hydroxyde alcalin par mole d'alkylphénol lorsque la base alcalino-terreuse est constituée essentiellement d'oxyde de magnésium à l'étape de sulfurisation.
    • b) A l'étape de suralcalinisation-carbonatation:
      • les quantités restantes de base alcalinc- terreuse et d'alkylène glycol sont introduites selon un rapport molaire base alcalino- terreuse/gtycol compris entre 0,14 et 0,82
      • le milieu est traité à un stade quelconque de ladite étape par 0 à 10% en poids, de préférence 0 à 5% en poids d'eau par rapport au poids dudit milieu, à une température comprise entre 100 et 150°C.
The process which is the subject of the present invention relates to the preparation of detergent-dispersants by the action of sulfur at a temperature between 100 and 190 ° C. on an alkylphenol. bearing one or more C 5 ―C 50 alkyl radicals, in the presence of a dilution oil, an alkaline earth metal alkylbenzene sulfonate of molecular mass greater than 300 and TBN less than 150, of an alkaline base -terreuse and an alkylene glycol, over-alkalinization-carbonation of the sulfurized medium at least once using an alkaline earth base and C0 2 at a temperature between 100 and 250 ° C, elimination of the alkylene glycol and recovering the detergent-dispersant obtained, said process being characterized in that:
  • the alkaline earth base is chosen from lime, magnesium oxide, or lime-magnesium oxide mixtures;
    • a) At the sulfurization stage, the following are introduced:
      • from 27 to 53% of the total molar amount of alkaline earth base;
      • from 0 to 50% of the total amount of magnesium oxide;
      • from 18 to 45% of the total amount of alkylene glycol;
      • from 0.1 to 2.8 moles, preferably from 0.16 to 1.77 moles of calcium and / or magnesium alkylbenzenesulfonate per mole of alkylphenol;
      • an amount of sulfur corresponding to a sulfur / total amount of alkaline earth base molar ratio of between 0.42 and 0.8;
      • from 0.69 to 1.69 moles of alkaline earth base per mole of alkylphenol;
      • an amount of alkylene glycol corresponding to an alkaline earth base-alkylene glycol molar ratio of between 0.28 and 1.4 and between 0.81 and 1.4 when said alkaline earth base consists essentially of lime in the step of tallow;
      • additionally from 0.02 to 0.75 mole, preferably from 0.02 to 0.33 mole of an alkali hydroxide per mole of alkylphenol when the alkaline earth base consists essentially of magnesium oxide with sulfurization stage.
    • b) At the over-alkalization-carbonation stage:
      • the remaining amounts of alkaline earth base and alkylene glycol are introduced according to an alkaline earth base / gtycol molar ratio of between 0.14 and 0.82
      • the medium is treated at any stage of the said stage with 0 to 10% by weight, preferably 0 to 5% by weight of water relative to the weight of the said medium, at a temperature between 100 and 150 ° C.

La quantité de CO2 mise en oeuvre pour réaliser l'étape de suralcalinisation-carbonatation peut varier entre la quantité pouvant être complètement absorbée et un excès de 40% en poids de cette quantité; de préférence, la quantité de CO2 correspondra sensiblement à celle pouvant être absorbée complètement.The quantity of CO 2 used to carry out the step of over-alkalinization-carbonation can vary between the quantity which can be completely absorbed and an excess of 40% by weight of this quantity; preferably, the amount of CO 2 will correspond substantially to that which can be completely absorbed.

On désigne par "alkylbenzènesulfonate de calcium et/ou de magnésium" toute solution contenant de 40 à 95% en poids, de préférence de 55 à 85% en poids d'un alkylbenzène- sulfonate de calcium et/ou de magnésium dans une huile de dilution qui peut être ou peut ne pas être la même que celle mise en oeuvre pour réaliser le procédé objet de l'invention. Parmi les alkylbenzènesulfonates de calcium et/ou de magnésium pouvant être mis en oeuvre, on peut citer les sels de calcium et/ou de magnésium d'acides sulfoniques obtenus par sulfonation d'alkylbenzénes dérivant d'oléfines ou de polymères d'oléfines en C15―C30.The term “calcium and / or magnesium alkylbenzene sulfonate” denotes any solution containing from 40 to 95% by weight, preferably from 55 to 85% by weight of a calcium and / or magnesium alkylbenzene sulfonate in an oil of dilution which may or may not be the same as that used to carry out the process which is the subject of the invention. Among the calcium and / or magnesium alkylbenzenesulfonates which can be used, mention may be made of the calcium and / or magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or polymers of C 15 ―C 30 olefins.

Parmi les alkylphénols pouvant être mis en oeuvre pour réaliser le procédé objet de l'invention, on peut citer de préférence ceux portant un ou plusiers substituants alkyles en C9―C15, et tout particulièrement les nonyl, décyl, dodécyl ou tétradécylphénols.Among the alkylphenols which can be used to carry out the process which is the subject of the invention, mention may preferably be made of those carrying one or more C 9 ―C 15 alkyl substituents, and very particularly nonyl, decyl, dodecyl or tetradecylphenols.

Bien que n'importe quel type d'oxyde de magnésium puisse être utilisé, on préfère toutefois utiliser de l'oxyde de magnésium "actif". 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 et commercialisée par Merck, ainsi que le "Ferumag", de surface spécifique voisine de 160 m2/g et commercialisé par RHONE-POULENC INDUSTRIES.Although any type of magnesium oxide can be used, it is preferred however to use "active" magnesium oxide. 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, mention may be made of "Maglite DE" with a specific surface area close to 140 m2 / g and marketed by Merck, as well as "Ferumag", with a specific surface area close to 160 m2 / g and marketed by RHONE-POULENC INDUSTRIES.

Comme exemple d'hydroxydes de métaux alcalins on peut citer l'hydroxyde de sodium, l'hydroxyde de lithium, l'hydroxyde de potassium.As an example of alkali metal hydroxides, mention may be made of sodium hydroxide, lithium hydroxide, potassium hydroxide.

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 départ) représente de 20 à 60% en poids dudit produit et de préférence de 25 à 55% dudit produit.Among the dilution oils which can be used, mention may preferably be made of them. 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 alkylbenzenesulfonate) represents from 20 to 60% by weight of said product and preferably 25 to 55% of said product.

Parmi les alkylèneglycols pouvant être mis en oeuvre, on peut citer tout particulièrement le glycol; ceux-ci peuvent éventuellement être présents en mélange avec jusqu'à 200% de leur poids d'un monoalcool tel que l'éthylhexanol, l'alcool tridécylique, les alcools oxo en C$-C,4 et d'une manière générale les alcools ayant un point d'ébullition supérieur à 120°C et de préférence supérieur à 150°C.Among the alkylene glycols which can be used, mention may very particularly be made of glycol; these can optionally be present in mixture with up to 200% of their weight of a monoalcohol such as ethylhexanol, tridecyl alcohol, oxo alcohols in C $ -C, 4 and in general the alcohols having a boiling point higher than 120 ° C and preferably higher than 150 ° C.

D'une manière préférentielle, on réalisera:

  • - l'étape de suifurisation en présence d'un alkylbenzène sulfonate de magnésium et/ou de calcium, de TBN inférieur ou égal à 50 à une température comprise entre 120 et 190°C, à une pression inférieure ou égale à la pression atmosphérique; cette étape peut éventuellement être suivie d'une étape supplémentaire réalisée à une température supérieure comprise entre 130 et 185°C, à une pression inférieure ou égale à la pression atmosphérique, afin de terminer l'étape de sulfurisation,
  • - l'étape de suralcalinisation-carbonatation au moins en une fois (généralement en une ou deux fois) à une température comprise entre 100 et 185°C,
  • - le traitement à l'eau à une température comprise entre 100 et 145°C.
Preferably, we will realize:
  • - The sufurization step in the presence of a magnesium and / or calcium alkylbenzene sulfonate, of TBN less than or equal to 50 at a temperature between 120 and 190 ° C, at a pressure less than or equal to atmospheric pressure; this step may possibly be followed by an additional step carried out at a higher temperature of between 130 and 185 ° C., at a pressure less than or equal to atmospheric pressure, in order to complete the sulfurization step,
  • - the over-alkalinization-carbonation stage at least once (generally once or twice) at a temperature between 100 and 185 ° C,
  • - water treatment at a temperature between 100 and 145 ° C.

Une variante du procédé faisant l'objet de l'invention consiste à réaliser une opération de précarbonatation après l'étape de suifurisation et avant l'étape de suralcalinisation-carbonatation. Cette opération peut être réalisée à une température comprise entre 100 et 250°C et de préférence entre 100 et 185°C, à l'aide de gaz carbonique. La quantité de CO2 pouvant être utilisée correspond, à plus ou moins 30%, en poids près, à celle qui peut être complètement absorbée par le milieu sulfurisé; de préférence cette quantité de CO2 correspondra sensiblement à celle pouvant être complètement absorbée.A variant of the process which is the subject of the invention consists in carrying out a precarbonation operation after the suifurization step and before the over-alkalinization-carbonation step. This operation can be carried out at a temperature between 100 and 250 ° C and preferably between 100 and 185 ° C, using carbon dioxide. The quantity of CO 2 that can be used corresponds, to more or less 30%, by weight, to that which can be completely absorbed by the sulfurized medium; preferably this quantity of CO 2 will correspond substantially to that which can be completely absorbed.

A un stade quelconque de cette opération peut être effectué un traitement à l'eau en supplément ou à la place de celui prévu à l'étape de suralcalinisation-carbonatation; ce traitement peut être effectué dans les mêmes conditions que celles indiquées ci-dessus.At any stage of this operation, a treatment with water may be carried out in addition to or in place of that provided for in the step of over-alkalinization-carbonation; this treatment can be carried out under the same conditions as those indicated above.

Le procédé faisant l'objet de l'invention peut être en particulier réalisé en mettant en oeuvre:

  • a) A l'étape de sulfurisation:
    • du dodécylphénol comme alkylphénol;
    • une solution à 60-80% dans l'huile d'un alkylbenzène sulfonate de Ca et/ou Mg dérivé d'un acide sulfonique de masse moléculaire 470 environ;
    • de 10 à 70 parties en poids, de préférence de 15 à 60 parties en poids d'alkylphénol pour 100 parties en poids de mélange alkylphénol-alkylbenzènesulfonate de magnésium et/ou de calcium;
    • de 30 à 90 parties en poids, de préférence 40 à 85 parties en poids d'alkylbenzène- sulfonate de magnésium et/ou de calcium pour 100 parties en poids de mélange alkylphénol alkylbenzènesulfonate de magnésium et/ou de calcium;
    • de 1,5 à 12 parties en poids, de préférence de 2,5 à 11 parties en poids de soufre pour 100 parties en poids de mélange alkylphénol-alkylbenzènesulfonate de magnésium et/ou de calcium, avec un rapport molaire soufre/quantité totale de base alcalino-terreuse compris entre 0,42 et 0',8;
    • de 2 à 30 parties en poids, de préférence de 4 à 20 parties en poids de base alcalino- terreuse pour 100 parties en poids de mélange alkylphénol-alkylbenzènesulfonate de magnésium et/ou de calcium, avec un rapport moles de base alcalino-terreuse introduites à l'étape de sulfurisation/moles totales de base alcalino-terreuse mises en oeuvre, compris entre 0,27 et 0,53;
    • jusqu'à 20 parties en poids, de préférence jusqu'à 15 parties en poids d'hydroxyde de calcium pour 100 parties en poids de mélange alkylphénol-alkylbenzène-sulfonate de magnésium et/ou de calcium;
    • jusqu'à 20 parties en poids, de prétérence jusqu'à 15 parties en poids d'oxyde ou de magnésium pour 100 parties en poids de mélange alkylphénoi-alkylbenzène sulfonate de magnésium et/ou de calcium, avec un rapport poids d'oxyde de magnésium introduit à l'étape de sulfurisation/poids total d'oxyde de magnésium mis en oeuvre, compris et 0,5;
    • jusqu'à 8 parties en poids, de conférence 0,05 à 3 parties en poids
      Figure imgb0001
      de de métal alcalin pour 100 parties en
      Figure imgb0002
      de mélange alkylphénoi-alkylbenzène-suifonate de magnésium et/ou de calcium, lorsque la base alcatino- terreuse est constituée essentiellement d'oxyde de magnésium, avec un rapport molaire hydroxyde alcalin/alkylphénoi compris entre 0,02 et 0,33;
    • de 5 à 50 parties en poids, de préférence de 5 à 30 parties en poids de glycol pour 100 parties en poids de mélange alkylphénol-alkyl- benzène sulfonate de magnésium et/ou de calcium, avec un rapport poids de glycol introduit à l'étape de sulfurisation/poids total de glycol mis en oeuvre compris entre 0,18 et 0,45.
  • b) A l'étape de suralcalinisation-carbonatation:
    • de 2 à 15 parties en poids, de préférence de 3 à 15 parties en poids d'oxyde de magnésium pour 100 parties en poids de mélange sulfurisé;
    • jusqu'à 15 parties en poids, de préférence jusqu'à 10 parties en poids d'hydroxyde de calcium pour 100 parties en poids de mélange sulfurisé;
    • de 4 à 100 parties en poids, de préférence de 6,5 à 70 parties en poids de glycol pour 100 parties en poids de mélange sulfurisé, avec un rapport molaire base alcalino-terreuse/glycot compris entre 0,14 et 0,82.
The process which is the subject of the invention can in particular be carried out by implementing:
  • a) At the sulfurization stage:
    • dodecylphenol as alkylphenol;
    • a 60-80% solution in oil of an alkylbenzene sulfonate of Ca and / or Mg derived from a sulfonic acid of molecular weight 470 approximately;
    • from 10 to 70 parts by weight, preferably from 15 to 60 parts by weight of alkylphenol per 100 parts by weight of magnesium and / or calcium alkylphenol-alkylbenzenesulfonate mixture;
    • from 30 to 90 parts by weight, preferably 40 to 85 parts by weight of magnesium and / or calcium alkylbenzene sulfonate per 100 parts by weight of mixture of magnesium and / or calcium alkylphenol alkylbenzene sulfonate;
    • 1.5 to 12 parts by weight, preferably 2.5 to 11 parts by weight of sulfur per 100 parts by weight of magnesium and / or calcium alkylphenol-alkylbenzenesulfonate mixture, with a sulfur / total quantity molar ratio alkaline earth base between 0.42 and 0 ', 8;
    • 2 to 30 parts by weight, preferably 4 to 20 parts by weight of base alkaline - earth metal per 100 parts by weight of magnesium alkylphenol alkylbenzenesulfonate mixing and / or calcium, with a mole ratio of alkaline earth base introduced at the sulfurization stage / total moles of alkaline earth base used, between 0.27 and 0.53;
    • up to 20 parts by weight, preferably up to 15 parts by weight of calcium hydroxide per 100 parts by weight of alkylphenol-alkylbenzene-magnesium and / or calcium mixture;
    • up to 20 parts by weight, preferably up to 15 parts by weight of oxide or magnesium per 100 parts by weight of alkylphenoi-alkylbenzene sulfonate mixture of magnesium and / or calcium, with a weight ratio of oxide of magnesium introduced in the sulfurization stage / total weight of magnesium oxide sium used, understood and 0.5;
    • up to 8 parts by weight, conference 0.05 to 3 parts by weight
      Figure imgb0001
      of alkali metal per 100 parts in
      Figure imgb0002
      of an alkylphenoi-alkylbenzene-magnesium and / or calcium sulfonate mixture, when the alkaline earth base consists essentially of magnesium oxide, with an alkali hydroxide / alkylphenoi molar ratio of between 0.02 and 0.33;
    • from 5 to 50 parts by weight, preferably from 5 to 30 parts by weight of glycol per 100 parts by weight of alkylphenol-alkyl-benzene sulfonate mixture of magnesium and / or calcium, with a weight ratio of glycol introduced to the sulfurization step / total weight of glycol used between 0.18 and 0.45.
  • b) At the over-alkalization-carbonation stage:
    • from 2 to 15 parts by weight, preferably from 3 to 15 parts by weight of magnesium oxide per 100 parts by weight of sulfurized mixture;
    • up to 15 parts by weight, preferably up to 10 parts by weight of calcium hydroxide per 100 parts by weight of sulfurized mixture;
    • from 4 to 100 parts by weight, preferably from 6.5 to 70 parts by weight of glycol per 100 parts by weight of sulfurized mixture, with a molar ratio of alkaline earth base / glycot of between 0.14 and 0.82.

La présente invention a également pour objet les détergents-dispersants de haute alcalinité obtenus par le procédé décrit ci-dessus.The present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above.

Ceux-ci présentent l'avantage d'une très bonne compatibilité avec les huiles visqueuses ainsi qu'un très faible taux de sédiments Ils peuvent être ajoutés à des huiles lubrifiantes selon des quantités fonction du TBN desdits détergents-dispersants et fonction de l'utilisation future desdites huiles; ainsi pour une huile moteur à essence, la quantité de détergent-dispersant de TBN compris entre 200 et 300 par exemple 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%; pour une huile pour moteur marin, celle-ci peut aller jusqu'à 25%.These have the advantage of very good compatibility with viscous oils as well as a very low rate of sediments. They can be added to lubricating oils according to quantities depending on the TBN of said detergent-dispersants and depending on the use. future of said oils; thus for a petrol engine oil, the quantity of TBN detergent-dispersant between 200 and 300 for example to be added is generally between 1 and 3.5%; pour.une diesel engine oil it is generally between 1.8 and 5%; for a marine engine oil, this can be 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'alkyiène, des polymères du type oxyde d'alkylène et leurs dérivés, y compris les polymères du type 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 type polymers prepared by polymerizing alkylene oxide in the 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 des détergents-dispersants obtenus selon le procédé 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 detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.

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 11Examples 1 to 11

On donne ci-après le mode général de préparation (cinq phases) des détergents-dispersants suralcalinisés faisant l'objet des exemples 1 à 11, et dans les tableaux 1 à III les quantités de réactifs nécessaires à leur préparation.The general mode of preparation (five phases) of the overbased detergent-dispersants given in Examples 1 to 11 is given below, and the quantities of reagents necessary for their preparation are given in Tables 1 to III.

― 1 ére phase (sulfurisation)- 1 st phase (sulfurization)

On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage:

  • - du dodécylphénol (DDP)
  • - de l'huile 100 N
  • - une solution à environ 60% dans de l'huile de dilution 100 N d'un alkylbenzènesulfonate de magnésium (sulfonate Mg en abréviation) de masse moléculaire 470 environ (masse du sel de sodium), solution contenant 1,8% de magnésium et présentant un TBN de 25 environ,
  • - un antimousse commercialisé par RHONE-POULENC sous la dénomination SI 200.
The following are introduced into a 4-liter tetracol reactor equipped with a stirring system and a heating device:
  • - dodecylphenol (DDP)
  • - 100 N oil
  • a solution of approximately 60% in 100 N dilution oil of a magnesium alkylbenzenesulfonate (sulfonate Mg for short) with a molecular mass of approximately 470 (mass of the sodium salt), solution containing 1.8% of magnesium and with a TBN of around 25,
  • - an antifoam sold by RHONE-POULENC under the name SI 200.

On introduit alors sous agitation le constituant alcalino-terreux choisi parmi la chaux, les mélanges "Maglite DE"-chaux ou "Maglite DE"-soude et du soufre.Then introduced with stirring the alkaline earth constituent selected from lime, mixtures "Maglite DE" -lime or "Maglite DE" -solder and sulfur.

On porte le milieu à 145°C sous 260 mm de mercure, puis on ajoute du glycol en 1 heure; on chauffe à 165°C et on maintient cette température pendant 1 heure sous 260 mm de mercure.The medium is brought to 145 ° C. under 260 mm of mercury, then glycol is added over 1 hour; it is heated to 165 ° C. and this temperature is maintained for 1 hour under 260 mm of mercury.

2ème phase (précarbonatation)2nd phase (precarbonation)

Après avoir cassé le vide et chauffé à 170°C, on réalise un opération de précarbonatation à 170°C à l'aide de gaz carbonique jusqu'à la fin de l'absorption de C02 (cette phase dure environ 1 h).After breaking the vacuum and heating to 170 ° C, a precarbonation operation is carried out at 170 ° C using carbon dioxide until the absorption of C0 2 is complete (this phase lasts approximately 1 h).

On refroidit à 110°C et on ajoute de l'eau.Cool to 110 ° C and add water.

3ème phase (suralcalinisation-carbonatation)3rd phase (over-alkalinization-carbonation)

On introduit à 110°C un mélange de "Maglite DE" et de glycol. On carbonate pendant 4 heures à 110°C.A mixture of "Maglite DE" and glycol is introduced at 110 ° C. Carbonate for 4 hours at 110 ° C.

4ème phase (suralcalinisation-carbonatation)4th phase (over-alkalinization-carbonation)

On ajoute de l'eau. On réalise l'opération. décrite à la 3ème phase une seconde foise pendant 3 heures.Water is added. We carry out the operation. described in the 3rd phase a second time for 3 hours.

5ème phase (séparation)5th phase (separation)

On porte le milieu suralcalinisé et carbonaté à une température de 184°C sous 30 mm de mercure; le glycol distille; on filtre pour éliminer les sédiments et on récupère une solution dans de l'huile 100 N de détergent-dispersant suralcalinisé dont les caractéristiques figurent aux tableaux l' à III'.The superalkalinized and carbonated medium is brought to a temperature of 184 ° C. under 30 mm of mercury; glycol distills; it is filtered to remove the sediment and a solution in 100 N oil of overbased detergent-dispersant is recovered, the characteristics of which appear in Tables 1 to III '.

. Exemple 12. Example 12

On réalise l'opération décrite à l'exemple 3 en effectuant l'étape de précarbonatation à 140°C à pression atmosphérique.The operation described in Example 3 is carried out by carrying out the precarbonation step at 140 ° C. at atmospheric pressure.

Les caractéristiques du produit obtenu sont semblables à celles de celui obtenu.à l'exemple 3.The characteristics of the product obtained are similar to those of that obtained. In Example 3.

Exemple 13Example 13

On réalise l'opération décrite a l'exemple 3 à partir d'une solution à 80% dans de l'huile 100 N d'un alkylbenzènesulfonate de magnésium de masse moléculaire 470 environ, solution contenant 2,25% de magnésium et présentant un TBN de 32.The operation described in Example 3 is carried out from an 80% solution in 100 N oil of a magnesium alkylbenzenesulfonate of molecular weight approximately 470, solution containing 2.25% of magnesium and having a TBN of 32.

Les quantités de réactifs mises en oeuvre figurent au tableau IV, les caractéristiques du produit obtenu figurent au tableau IV'.The quantities of reagents used appear in Table IV, the characteristics of the product obtained appear in Table IV '.

Exemple 14Example 14

On réalise l'opération décrite à l'exemple 3, effectuée à partir d'une solution à 60% dans de l'huile 100 N d'un aikylbenzène sulfonate de magnésium, de masse moléculaire de 470 environ, solution contenant 2,2% de magnésium et présentant un TBN de 45.The operation described in Example 3 is carried out, carried out from a 60% solution in 100 N oil of a magnesium aikylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 2.2% magnesium and having a TBN of 45.

Les quantités de réactifs mises en oeuvre figurent au tableau IV, les caractéristiques du produit obtenu figurent au tableau IV'.The quantities of reagents used appear in Table IV, the characteristics of the product obtained appear in Table IV '.

Exemple 15Example 15

On réalise l'opération décrite à l'exemple 3 à partir d'une solution à 60% dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium de masse moléculaire 470 environ, solution contenant 2,7% de calcium et présentant un TBN de 25, et sans ajouter d'eau au cours des opérations de précarbonatation et de carbonatation.The operation described in Example 3 is carried out from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate of molecular weight approximately 470, solution containing 2.7% of calcium and having a TBN of 25, and without adding water during the precarbonation and carbonation operations.

Les quantités de réactifs mises en oeuvre figurent au tableau IV; les caractéristiques du produit obtenu figurent au tableau IV'.The quantities of reagents used are shown in Table IV; the characteristics of the product obtained are shown in Table IV '.

Exemple 16Example 16

On réalise l'opération décrite à l'exemple 3 sans ajouter d'eau au cours des opérations de précarbonatation et de carbonatation.The operation described in Example 3 is carried out without adding water during the precarbonation and carbonation operations.

Le produit obtenu présente des caractéristiques équivalentes à celles de celui de l'exemple 3.The product obtained has characteristics equivalent to those of Example 3.

Exemples 17 à 24Examples 17 to 24

Les opérations décrites aux exemples 1 à 1 1 sont réalisées dans les mêmes conditions, en supprimant l'étape de précarbonatation et avec les quantités de réactifs figurant au tableau V et V', VI et VI.The operations described in examples 1 to 1 1 are carried out under the same conditions, by eliminating the precarbonation step and with the quantities of reagents appearing in tables V and V ′, VI and VI.

Les caractéristiques des produits obtenus figurent aux tableaux V' et VI'.The characteristics of the products obtained are shown in Tables V 'and VI'.

Exemples 25 et 26Examples 25 and 26

On réalise l'opération décrite à l'exemple 17 à partir d'une solution à 60% dans de l'huile 100 N d'un alkylbenzènesulfonate de calcium de masse moléculaire 470 environ, solution contenant 2,7% de calcium et présentant un TBN de 25 et en effectuant une étape de carbonatation.The operation described in Example 17 is carried out from a 60% solution in 100 N oil of a calcium alkylbenzenesulfonate of molecular weight approximately 470, solution containing 2.7% of calcium and having a TBN of 25 and performing a carbonation step.

Les quantités de réactifs ainsi que les caractéristiques des produits obtenus figurent aux tableaux VII et VII'.The quantities of reagents as well as the characteristics of the products obtained are shown in Tables VII and VII '.

Exemple 27Example 27

On réalise l'opération décrite à l'exemple 17 à partir des mêmes quantités de réactifs, mais. en réalisant l'opération de sulfurisation d'abord à 165°C pendant 1 heure sous 260 mm de mercure puis pendant 2 heures à 185°C sous 700 mm de mercure.The operation described in Example 17 is carried out using the same quantities of reagents, but. by carrying out the sulfurization operation first at 165 ° C for 1 hour under 260 mm of mercury and then for 2 hours at 185 ° C under 700 mm of mercury.

Le produit obtenu présente des caractéristiques équivalentes à celles de celui de l'exemple 17.The product obtained has characteristics equivalent to those of Example 17.

Taux de sédimentsSediment rate

Les % de sédiments figurant dans les tableaux ci-dessous ont été mesurés selon la norme ASTM D 2273-67, en apportant toutefois les modifications suivantes:

  • -vitesse de rotation de la centrifugeuse 6000 t/mn
  • -force centrifuge relative 10.00
  • -le produit à analyser est dilué au quart dans de l'essence E (25 cm3 de produit à analyser + 75 cm3 d'essence E)
  • ― durée de la centrifugation: 10 minutes.
The% of sediments appearing in the tables below were measured according to standard ASTM D 2273-67, with the following modifications, however:
  • -speed of rotation of the centrifuge 6000 rpm
  • - relative centrifugal force 10.00
  • -the product to be analyzed is diluted to a quarter in gasoline E (25 cm 3 of product to be analyzed + 75 cm3 of gasoline E)
  • - duration of centrifugation: 10 minutes.

CompatabilitéCompatibility

Les tests de compatibilité figurant dans les tableaux ci-dessous ont été réalisés 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.The compatibility tests appearing in the tables below were carried out by adding 10% by weight of product to be tested to a SAE 30 mineral oil, storage of the solution obtained for 1 month at 20 ° C. and study of the appearance. of the solution as a function of time.

Comparaison avec les produits du commerceComparison with commercial products - test avec l'additif seul- test with the additive alone

Le produit de l'exemple 7 est ajouté à une huile SAE 50 à tendance paraffinique de façon à obtenir une solution contenant 125 millimoles de calcium + magnésium. La solution est stockée pendant 15 jours à 20°C; on constate que la solution reste limpide.The product of Example 7 is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium. The solution is stored for 15 days at 20 ° C; we see that the solution remains clear.

Le même test est réalisé avec un mélange:

  • ― d'alkylbenzènesulfonate de magnésium de TBN 400
  • -d'alkylbenzènesulfonate de calcium de TBN 25
  • -d'alkylphénate de calcium de TBN 150 en quantité telle que la solution obtenue contienne 125 millimoles de calcium + magnesium.
The same test is carried out with a mixture:
  • - magnesium alkylbenzene sulfonate from TBN 400
  • - TBN 25 calcium alkylbenzenesulfonate
  • of calcium alkylphenate of TBN 150 in an amount such that the solution obtained contains 125 millimoles of calcium + magnesium.

Après 15 jours de stockage à 20°C, la solution est trouble et floculeuse.After 15 days of storage at 20 ° C, the solution is cloudy and flocculent.

― test avec l'additif en formulation- test with the additive in formulation

On prépare un mélange (A) d'additifs contenant:

  • ―2% d'un dispersant à base de polyiso- butényl succinimide
  • - 1,6 millimole d'un dithiophosphate de zinc
  • -et 2,3% de produit de l'exemple 7
A mixture (A) of additives is prepared containing:
  • ―2% of a dispersant based on polyisobutenyl succinimide
  • - 1.6 millimole of a zinc dithiophosphate
  • -and 2.3% of product from Example 7

Ce mélange est porté pendant 25 jours à 80°C puis est ajouté à une huile SAE 30 de manière à avoir une concentration de 6,6% en poids de mélange (A).This mixture is brought for 25 days to 80 ° C. and is then added to an SAE 30 oil so as to have a concentration of 6.6% by weight of mixture (A).

La solution est stockée pendant 5 jours à 80°C.The solution is stored for 5 days at 80 ° C.

Le même test est réalisée avec un mélange (B) constitué de

  • -2% du dispersant à base de poly- isobutényl-succinimide
  • -1,6 millimole du dithiophosphate de zinc
  • - et 2,3% d'un mélange constitué:
    • d'aikylbenzènesulfonate de magnésium de TBN 400
    • d'alkylbenzènesulfonate de calcium de TBN 25
    • d'alkylphénate de calcium de TBN 150 présentant un nombre de millimoles de calcium + magnésium équivalent à celui du produit de l'exemple 7.
The same test is carried out with a mixture (B) consisting of
  • -2% of the dispersant based on polyisobutenyl succinimide
  • -1.6 millimole of zinc dithiophosphate
  • - and 2.3% of a mixture consisting of:
    • TBN 400 magnesium aikylbenzenesulfonate
    • of TBN 25 calcium alkylbenzenesulfonate
    • of calcium alkylphenate of TBN 150 having a number of millimoles of calcium + magnesium equivalent to that of the product of Example 7.

On constate que la solution contenant le mélange (A) est plus claire et plus brillante que celle contenant le mélange (B).

Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
 It is found that the solution containing the mixture (A) is lighter and brighter than that containing the mixture (B).
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
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Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016

Claims (9)

1. Process for the preparation of detergents- dispersants by the reaction of sulphur, at a temperature between 100 and 190°C, with an alkylphenol carrying one or more C6-C60 alkyl radicals, In the presence of a diluting oil, an alkaline earth metal alkylbenzenesulphonate having a molecular weight of more than 300 and a TBN of less than 150, an alkaline earth metal base and an alkylene glycol, superalkalisation-carbonation of the sulphurised medium, in at least one step, with the aid of an alkaline earth metal base and CO2, at a temperature between 100 and 250°C, removal of the alkylene glycol and recovery of the detergent-dispersed obtained, the said process being characterised in that:
the alkaline earth metal base is chosen from amongst lime, magnesium oxide or lime/mag- nesium oxide mixtures;
a) in the suiphurisation step, the following are introduced:
from 27 to 53% of the total molar amount of alkaline earth metal base;
from 0 to 50% of the total amount of magnesium oxide;
from 18 to 45% of the total amount of alkylene glycol;
from 0.1 to 2.8 mols of calcium alkylbenzenesulphonate and/or magnesium alkyl- . benzenesulphonate per mol of alkylphenol;
an amount of sulphur corresponding to a molar ratio sulphur/total amount of alkaline earth metal.base of between 0.42 and 0.8;
from 0.69 to 1.69 mols of alkaline earth metal base per mol of alkylphenol;
an amount of alkylene glycol corresponding to a molar ratio alkaline earth metal/alkylene glycol of between 0.28 and 1.4, and of between 0.81 and 1.4 if the said alkaline earth metal base consists essentially of lime in the- sulphurisation step; and also
from 0.02 to 0.33 mol of an alkali metal hydroxide per mol of alkylphenol if the alkaline earth metal base consists essentially of magnesium oxide in the sulphurisation step; and
b) in the superalkalisation-carbonation step:
the remaining amounts of alkaline earth metal base and alkylene glycol are introduced in a molar ratio alkaline earth metal base/glycol of between 0.14 and 0.82; and
the medium is treated at any stage of the said step with 0 to 10% by weight of water, relative to the weight of the said medium, at a temperature between 100 and 150°C.
2. Process according to Claim 1, characterised in that the sulphurisation step is carried out in the presence of 0.16 to 1.77 mols of Ca alkylbenzenesulphonate and/or Mg alkylbenzenesulphonate per mol of alkylphenol.
3. Process according to Claim 1, characterised in that, at any stage of the superalkalisation-carbonation step, the medium is treated with 0 to 5% by weight of water, relative to the weight of the said medium.
4. Process according to Claim 1, characterised in that:
a) in the sulphurisation step, the following are used:
dodecylphenol as the alkylphenol;
a 60-80% strength solution, in oil, of a Ca alkylbenzenesulphonate and/or Mg alkylbenzenesulphonate derived from a sulphonic acid having a molecular weight of about 470;
from 10 to 70 parts by weight of alkylphenol per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
from 30 to 90 parts by weight of magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
from 1.5 to 12 parts by weight of sulphur per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a molar ratio sulphur/total amount of alkaline earth metal base of between 0.42 and 0.8;
from 2 to 30 parts by weight of alkaline earth metal base per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a ratio mols of alkaline earth metal base introduced in the sulphurisation step/total mols of alkaline earth metal base used of between 0.27 and 0.53.
up to 20 parts by weight of calcium hydroxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
up to 20 parts by weight of magnesium oxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a ratio weight of magnesium oxide introduced into the sulphurisation step/total weight of magnesium oxide used of between 0 and 0.5;
up to 8 parts by weight of alkali metal hydroxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate if the alkaline earth metal base consists essentially of magnesium oxide, with a molar ratio alkali metal hydroxide/alkyl- phenol of between 0.2 and 0.33; and
from 5 to 50 parts by weight of glycol per TOO parts by weight of the mixture of alkylphenol and magnesium alkylbenzene; sulphonate and/or calcium alkylbenzenesulphonate, with a ratio weight of glycol introduced in the sulphurisation step/total weight of glycol used of between 0.18 and 0.45; and
b) in the superalkalisation-carbonation step, the following are used:
from 2 to 25 parts by weight of magnesium oxide per 100 parts by weight of sulphurised mixture;
up to 15 parts by weight of calcium hydroxide per 100 parts by weight of sulphurised mixture; and
from 4 to 100 parts by weight of glycol per 100 parts by weight of sulphurised mixture, with a molar ratio alkaline earth metal base/glycol of between 0.14 and 0.82.
5. Process according to Claim 4, characterised in that:
a) the sulphurisation step is carried out in the presence of:
15 to 60 parts by weight of alkylphenol per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
from 40 to 85 parts by weight of magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
from 2.5 to 11 parts by weight of sulphur per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a molar ratio sulphur/total amount of alkaline earth metal base of between 0.42 and 0.8;
from 4 to 20.parts by weight of alkaline earth metal base per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a ratio mols of alkaline earth metal base introduced in the sulphurisation step/total mols of alkaline earth metal base used of between 0.27 and 0.53;
from 0 to 15 parts by weight of calcium hydroxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate;
from 0 to 15 parts by weight of magnesium oxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a ratio weight of magnesium oxide introduced in the sulphurisation step/total weight of magnesium oxide used of between 0 and 0.5;
from 0.05 to 3 parts by weight of alkali metal hydroxide per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate if the alkaline earth metal base consists essentially of magnesium oxide, with a molar ratio alkali metal hydroxide/alkyl- phenol of between 0.02 and 0.33; and
from 5 to 30 parts by weight of glycol per 100 parts by weight of the mixture of alkylphenol and magnesium alkylbenzenesulphonate and/or calcium alkylbenzenesulphonate, with a ratio weight of glycol introduced in the sulphurisation step/total weight of glycol used of between 0.18 and 0.45; and
b) the superalkalisation-carbonation step is carried out in the presence of:
3 to 15 parts by weight of magnesium oxide per 100 parts by weight of sulphurised mixture;
from 0 to 10 parts by weight of calcium hydroxide per 100 parts by weight of sulphurised mixture; and
from 6.5 to 70 parts by weight of glycol per 100 parts by weight of sulphurised mixture, with a molar ratio alkaline earth metal base/glycol of between 0.14 and 0.82.
6. Process according to any one of Claims 1, 4 or 5, characterised in that a precarbonation step is carried out after the sulphurisation step and before the superalkalisation-carbonation step.
7. Process according to Claim 6, characterised in that the reaction medium is subjected to a treatment with 0 to 10% by weight of water at any stage of the precarbonation step, at a temperature between 100 and 150° C, in addition to or in place of the treatment with water envisaged in the superalkalisation-carbonation step.
8. Application of the products obtained by the process described in any one of the preceding claims as detergent-dispersant additives for lubricating oils.
EP79400376A 1978-06-26 1979-06-11 Process for the preparation of detergent-dispersant agents of high alkali content for lubricating oils and product obtained Expired EP0007257B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79400376T ATE1342T1 (en) 1978-06-26 1979-06-11 PROCESS FOR THE MANUFACTURE OF HIGH ALKALINE DETERGENT SOLUTIONS FOR LUBRICATION OILS AND PRODUCT MADE THEREOF.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7818945 1978-06-26
FR7818945A FR2429831A2 (en) 1978-06-26 1978-06-26 NOVEL PROCESS FOR THE PREPARATION OF HIGH ALKALINITY DETERGENT DISPERSANTS FOR LUBRICATING OILS

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EP0007257A1 EP0007257A1 (en) 1980-01-23
EP0007257B1 true EP0007257B1 (en) 1982-07-14

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US (1) US4302342A (en)
EP (1) EP0007257B1 (en)
JP (1) JPS555991A (en)
AT (1) ATE1342T1 (en)
BR (1) BR7904003A (en)
CA (1) CA1122963A (en)
DE (1) DE2963335D1 (en)
ES (1) ES481863A1 (en)
FR (1) FR2429831A2 (en)
MX (1) MX5733E (en)
ZA (1) ZA793194B (en)

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US4710308A (en) * 1982-04-08 1987-12-01 Amoco Corporation Process for preparing overbased sulfurized phenates
FR2529225B1 (en) * 1982-06-24 1986-04-25 Orogil NEW HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
FR2529226B1 (en) * 1982-06-24 1987-01-16 Orogil PROCESS FOR THE PREPARATION OF SULFURIZED ALKYLPHENATES OF ALKALINE EARTH METALS FOR USE AS ADDITIVES FOR LUBRICATING OILS
FR2529224B1 (en) * 1982-06-24 1986-02-07 Orogil NEW SURALKALINIZED DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS
JPS5931724A (en) * 1982-08-16 1984-02-20 Cosmo Co Ltd Preparation of basic alkaline earth metal phenate
JPS59232190A (en) * 1983-06-15 1984-12-26 Taiyo Kako Kk Preparation of oil solution containing alkaline earth metal salt of alkylphenol sulfide with high basicity
FR2584414B1 (en) * 1985-07-08 1987-10-30 Orogil NEW SULFONATED AND SULFURIZED DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS
FR2588269B1 (en) * 1985-10-03 1988-02-05 Elf France PROCESS FOR THE PREPARATION OF HIGHLY BASIC, HIGHLY FLUID BASED ADDITIVES AND COMPOSITION CONTAINING SAID ADDITIVES
DE69009236T2 (en) * 1989-02-25 1994-09-08 Bp Chemicals Additives Process for the preparation of an additional concentrate for lubricating oils.
US4973411A (en) * 1989-09-15 1990-11-27 Texaco Inc. Process for the preparation of sulfurized overbased phenate detergents
US5332514A (en) * 1990-08-06 1994-07-26 Texaco Inc. Continuous process for preparing overbased salts
US5330664A (en) * 1992-09-02 1994-07-19 Chevron Research And Technology Company Neutral and low overbased alkylphenoxy sulfonate additive compositions derived from alkylphenols prepared by reacting an olefin or an alcohol with phenol in the presence of an acidic alkylation catalyst
US5330663A (en) * 1992-09-02 1994-07-19 Chevron Research And Technology Company Neutral and low overbased alkylphenoxy sulfonate additive compositions
TW278098B (en) * 1992-09-18 1996-06-11 Cosmo Sogo Kenkyusho Kk
US5320762A (en) * 1993-03-12 1994-06-14 Chevron Research And Technology Company Low viscosity Group II metal overbased sulfurized C12 to C22 alkylphenate compositions
US5318710A (en) * 1993-03-12 1994-06-07 Chevron Research And Technology Company Low viscosity Group II metal overbased sulfurized C16 to C22 alkylphenate compositions
US5320763A (en) * 1993-03-12 1994-06-14 Chevron Research And Technology Company Low viscosity group II metal overbased sulfurized C10 to C16 alkylphenate compositions
US6235688B1 (en) 1996-05-14 2001-05-22 Chevron Chemical Company Llc Detergent containing lithium metal having improved dispersancy and deposit control
US7405185B2 (en) * 2003-09-26 2008-07-29 Chevron Oronite Company Llc Process for making Group II metal overbased sulfurized alkylphenols
EP3508533B1 (en) 2016-09-01 2024-07-17 Dow Toray Co., Ltd. Curable organopolysiloxane composition, and protection agent or adhesive composition for electrical/electronic components

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JPS555991A (en) 1980-01-17
ZA793194B (en) 1980-06-25
EP0007257A1 (en) 1980-01-23
US4302342A (en) 1981-11-24
ATE1342T1 (en) 1982-07-15
BR7904003A (en) 1980-03-25
FR2429831B2 (en) 1982-06-11
JPH0142998B2 (en) 1989-09-18
ES481863A1 (en) 1980-02-16
DE2963335D1 (en) 1982-09-02
CA1122963A (en) 1982-05-04
MX5733E (en) 1984-01-25
FR2429831A2 (en) 1980-01-25

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