EP0164286A1 - A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals - Google Patents

A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals Download PDF

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Publication number
EP0164286A1
EP0164286A1 EP85400957A EP85400957A EP0164286A1 EP 0164286 A1 EP0164286 A1 EP 0164286A1 EP 85400957 A EP85400957 A EP 85400957A EP 85400957 A EP85400957 A EP 85400957A EP 0164286 A1 EP0164286 A1 EP 0164286A1
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acid
alkaline earth
alcohol
additives according
additives
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German (de)
French (fr)
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EP0164286B1 (en
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B1/00—Engines characterised by fuel-air mixture compression
    • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
    • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder

Definitions

  • the present invention relates to detergent-dispersant additives for lubricating oils based on alkylarylsulfonates of alkaline earth metals which do not exhibit a foaming tendency and this regardless of the nature of the starting alkylarylsulfonic acid.
  • the Applicant has found additives based on alkylarylsulfonates which do not exhibit a foaming tendency, whether during their preparation or during their use and this whatever the nature of the alkyl radical (s), namely linear, branched or partially branched.
  • alkylarylsulfonic acids will be understood below as the acids obtained by sulfonation of at least one alkylbenzene, alkylorthoxylene or alkyltoluene in which the alkyl radical (s) (that or those attached to the benzene, orthoxylene or toluene group) contain from 15 to 40 carbon atoms and are derived from linear olefins, branched olefins and / or olefin oligomers, as well as those obtained by sulfonation of petroleum fractions or mixtures of said acids.
  • alkyl radical that or those attached to the benzene, orthoxylene or toluene group
  • the molecular mass of said acids expressed as the sodium salt generally corresponds to a value of 400 to 600; they are generally used in solution at least around 40% in dilution or non-diluted Itnile.
  • basic alkaline earth base is understood to mean the theoretical part of an alkaline earth base to be dispersed in the medium, that is to say that which is not attached to the alkylaryl sulfonic acid.
  • a variant of the said process consists in introducing in the 1st stage all or part of the reagents present in the 2nd stage.
  • Another variant of the process consists in carrying out a carbonation stage using carbon dioxide from the medium obtained in the second stage, prior to stage 3) of elimination of water and alcohol, and this when the alkaline earth base / alkylarylsulfonic acid molar ratio is at least 1.2, preferably at least 1.3.
  • alkaline-earth bases which can be used, mention may be made of calcium oxides, hydroxides or carbonates, barium, magnesium, and more particularly lime and "active" magnesium oxide.
  • those with a boiling point higher than 100 ° C. are preferably chosen such as linear or branched aliphatic monoalcohols containing from 4 to 10 carbon atoms such as isobutanol, alfol 6, 2-ethylhexanol, C 8 -C 10 OXO alcohols. It is advantageous industrially to use those immiscible with water (that is to say those whose solubility in water is less than 10% by weight at ordinary temperature) because they can be recycled at will by simple decantation of the aqueous phase.
  • the amount of alcohol to be used depends on the linearity rate of the "alkyl” radical (s); the higher this rate, the greater the quantity of alcohol.
  • the chloride ions can be used via ammonium chloride, calcium chloride, zinc chloride, etc.
  • paraffinic oils such as 100 Neutral oil, as well as naphthenic or mixed oils.
  • the amount of oil favorably used is such that the amount of oil contained in the final product (including that optionally coming from the starting alkylaryl sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 to 55% and very particularly from 30 to 40% by weight of the said product.
  • the detergent-dispersant additives for lubricating oil obtained by the process described above have a TBN (Total Basic Number - Standard ASTM D 2896) which can range up to around 40, an alkaline-earth / alkylarylsulfonic acid molar ratio of between 0.51 and 1.3 (preferably between 0.55 and 1.2) being then sufficient.
  • TBN Total Basic Number - Standard ASTM D 2896
  • alkaline-earth / alkylarylsulfonic acid molar ratio between 0.51 and 1.3 (preferably between 0.55 and 1.2) being then sufficient.
  • Higher TBN products of up to about 100 can be obtained by using in the 1st step an alkaline earth / alkaryl sulfonic acid molar ratio of up to 1.8 (preferably up to 1.6 ) and by carrying out an additional carbonation step prior to step 3) of elimination of water and alcohol.
  • This carbonation step is favorably carried out at a temperature between 90 and 180 ° C, preferably between 110 and 170 ° C, using an amount of C0 2 between that which can be completely absorbed by the reaction medium and 30% excess of this amount. If necessary, a mixture of water and alcohol can be introduced at the end of carbonation to reduce the viscosity of the medium to a value of the order of 100 to 600 cst at the temperature of the reaction.
  • Said detergent-dispersant additives can be added to the lubricating oils in an amount which can range up to 1.7% by weight (which corresponds to approximately 0.04% of calcium) for a petrol engine oil; up to 3.5% (which corresponds to approximately 0.08% of calcium) for a diesel or marine engine oil; up to 11.5% (which corresponds to approximately 0.25% calcium) for a protective oil.
  • 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.
  • hard coal and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers of silicon.
  • Additional additives may also be present in said lubricating oils alongside detergent-dispersants obtained according to the process of the invention: there may be mentioned, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
  • the medium is brought to 60 ° C. and a sulfonic acid solution sold by ESSO under the name AS 107 is introduced over 30 minutes; it is a solution of approximately 70% in an oil of an alkylaryl sulphonic acid having a branching rate of approximately 75%, consisting mainly of alkyl benzenesulphonic and whose molecular mass of the sodium salt is close to 490, which corresponds to an apparent molecular mass of the acid solution of approximately 650.
  • the medium is brought to and maintained at 100 ° C.
  • Example 8 prepared without formic acid is slightly viscous; the reaction is less complete but is however feasible industrially.
  • the measurement methods are as follows:
  • the viscosity is measured after diluting the product in 100 N oil until a solution with a total calcium level of 2.9% is obtained. When said product has a total calcium level of less than 2.9%, the viscosity is then measured on the product as it is.
  • An additive is prepared based on monosuccinimide, zinc dithiophosphate and comprising approximately 75% of product to be tested, additive which is dissolved in 10% in a base oil 350 N CFR.
  • the additive prepared for the compatibility test is subjected to the sequence 1 at 24 ° C. of the ASTM D 892 test carried out in a viscous oil SAE 50.
  • Example 4 The operation described in Example 4 is carried out at a temperature of 110 ° C. instead of 100 ° C.
  • Example 4 The operation described in Example 4 is carried out at a temperature of 85 ° C instead of 100 ° C.
  • This example describes the preparation of an alkylbenzene sulfonate of low TBN (equal to 8).
  • Example 4 The operation described in Example 4 is carried out by adding 2-ethylhexanol before water in the 2nd step. The results obtained are equivalent.
  • a test is carried out according to the same general operating method, starting from a 40/60 mixture by weight of AS 107 and a solution of approximately 50% in an oil of a fully branched alkylbenzene sulfonic acid (consisting of 72% about acid monoalkylbenzene sulfonic and approximately 28% dialkylbenzene sulfonic acid), the molecular weight of the sodium salt of which is approximately 420, which corresponds to an apparent molecular weight of the acid solution of approximately 800 and obtained by sulfonation of heavy from the alkylation of benzene by the propylene tetramer.
  • the ramification rate of the mixture is approximately 90%.
  • Example 28 The operation described in Example 28 is carried out using a 70/30 mixture by weight of AS 107 and the 50% solution of fully branched alkylbenzene sulfonic acid used in the previous example.
  • the branching rate is approximately 82.5%.
  • Ethylhexanol is separated by decantation from the distillate obtained in Example 29, then it is recycled in a reaction medium identical to that of the 1st step of Example 29 and a new operation is carried out similar to that of Example 29 .
  • Example 4 The operation described in Example 4 is carried out from an alkylorthoxylene sulfonic acid derived from a linear poly a olefin containing 18 carbon atoms (approximately 95% solution in an oil).
  • the molecular weight of the acid is approximately 460.
  • Example 4 The operation described in Example 4 is carried out by introducing the CaCl 2 solution and 2-ethylhexanol in the first step of the process instead of the second step.
  • Example 21 The operation described in Example 21 is carried out by replacing acetic acid with the same weight of glycolic acid.
  • a test is carried out according to the same general operating procedure, starting from a mixture of the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28 and an 85% solution of a totally branched alkylbenzene sulfonic acid.
  • linear obtained from a mixture of 90% linear C 20 -C 24 olefin and 10 X linear C 24 -C 28 olefin
  • the molecular weight of the sodium salt of which is approximately 490, which corresponds to an apparent molecular mass of the acid solution of approximately 550.
  • Example 28 A test is carried out according to the same general operating procedure from the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28.
  • An alkalinized alkylbenzene sulfonate is prepared from the 70/30 mixture by weight of sulfonic acids used in Example 29.
  • the first two steps are carried out according to the general procedure using the quantities of products indicated in Table VII.
  • the product obtained is then carbonated for 60 min at 100 ° C using 42 g of C0 2 , then a mixture of 52 g of water and 178 g of 2-ethylhexanol is added; the medium is left at 100 ° C for 45 min.

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

Abstract

Additifs détergents-dispersants pour huiles lubrifiantes à base d'alkylarylsulfonates de métaux alcalino-terreux obtenus à partir d'un acide alkylarylsulfonique et d'une base alcalino-terreuse en présence d'un alcool de point d'ébullition supérieur à 80°C, d'eau, d'ions chlorures et de préférence d'un acide carboxylique en C1-C4. Ils peuvent éventuellement être suralcalinisés par carbonatation. Lesdits additifs détergents-dispersants pour huiles lubrifiantes présentent un TBN pouvant aller jusqu'à 40 environ et jusqu'à 100 environ lorsqu'ils sont carbonatés.Detergent-dispersant additives for lubricating oils based on alkaline earth metal alkylarylsulfonates obtained from an alkylarylsulfonic acid and an alkaline earth base in the presence of an alcohol with a boiling point above 80 ° C., water, chloride ions and preferably a C1-C4 carboxylic acid. They can possibly be overbased by carbonation. Said detergent-dispersant additives for lubricating oils have a TBN which can range up to approximately 40 and up to approximately 100 when they are carbonated.

Description

La présente invention a pour objet des additifs détergents-dispersants pour huiles lubrifiantes à base d'alkylarylsulfonates de métaux alcalino-terreux ne présentant pas de tendance au moussage et ce quelle que soit la nature de l'acide alkylarylsulfonique de départ.The present invention relates to detergent-dispersant additives for lubricating oils based on alkylarylsulfonates of alkaline earth metals which do not exhibit a foaming tendency and this regardless of the nature of the starting alkylarylsulfonic acid.

Le brevet américain n° 4.235.810 et la demande européenne n° 1.318 décrivent des additifs détergents-dispersants à base d'alkylarylsulfonates ne tendant pas à faire mousser le lubrifiant pendant le fonctionnement du moteur. Ces additifs sont obtenus par coalkylation d'un hydrocarbure aromatique, benzène, toluène, orthoxylène avec un mélange de 5-95 % (de préférence 95-70 %) en poids d'une oléfine ramifiée en C15-C40 et 95-5 % (de préférence 30-5 %) en poids d'une oléfine linéaire en C16-C30, Puis sulfonation du coalkylat et neutralisation par une base alcalino-terreuse de l'acide sulfonique obtenu.US Patent No. 4,235,810 and European Application No. 1,318 describe detergent-dispersant additives based on alkylarylsulfonates which do not tend to foam the lubricant during engine operation. These additives are obtained by coalkylation of an aromatic hydrocarbon, benzene, toluene, orthoxylene with a mixture of 5-95% (preferably 95-70%) by weight of a branched C 15 -C 40 and 95-5 olefin. % (preferably 30-5%) by weight of a linear C 16 -C 30 olefin, then sulfonation of the coalkylate and neutralization with an alkaline earth base of the sulfonic acid obtained.

La demanderesse a trouvé des additifs à base d'alkylarylsulfonates ne présentant pas de tendance au moussage, que ce soit au cours de leur préparation ou lors de leur utilisation et ce quelle que soit la nature du ou des radicaux alkyles, à savoir linéaires, ramifiés ou partiellement ramifiés.The Applicant has found additives based on alkylarylsulfonates which do not exhibit a foaming tendency, whether during their preparation or during their use and this whatever the nature of the alkyl radical (s), namely linear, branched or partially branched.

On entendra ci-après par "acides alkylarylsulfoniques" les acides obtenus par sulfonation d'au moins un alkylbenzène, alkylorthoxylène ou alkyltoluène dont le ou les radicaux alkyles (celui ou ceux fixés sur le groupe benzénique, orthoxylénique ou toluénique) contiennent de 15 à 40 atomes de carbone et dérivent d'oléfines linéaires, d'oléfines ramifiées et/ou d'oligomères d'oléfines, ainsi que ceux obtenus par sulfonation de coupes pétrolières ou des mélanges desdits acides.The term “alkylarylsulfonic acids” will be understood below as the acids obtained by sulfonation of at least one alkylbenzene, alkylorthoxylene or alkyltoluene in which the alkyl radical (s) (that or those attached to the benzene, orthoxylene or toluene group) contain from 15 to 40 carbon atoms and are derived from linear olefins, branched olefins and / or olefin oligomers, as well as those obtained by sulfonation of petroleum fractions or mixtures of said acids.

Il s'agit donc :

  • - aussi bien des acides alkylaryl sulfoniques présentant un taux de linéarité de 100 % environ obtenus par sulfonation d'un alkylbenzène, d'un alkylorthoxylène ou d'un alkyltoluène dont le ou les radicaux "alkyles" sont linéaires ou d'un mélange d'alkybeazènes, d'alkylorthoxylènes ou d'alkyltoluènes dont le ou les radicaux "alkyles" sont linéaires
  • - des acides alkylarylsulfoniques présentant un taux de ramification de 100 % environ obtenus par sulfonation d'un alkylbenzène, d'un alkylorthoxylène ou d'un alkyltoluène dont le ou les radicaux alkyles sont ramifiés ou d'un mélange d'alkylbenzènes, d'alkylorthoxylènes ou d'alkyltoluènes dont le ou les radicaux "alkyles" sont ramifiés
  • - des mélanges d'acides alkylaryl sulfoniques à 100 % environ de linéarité et d'acides alkylaryl sulfoniques présentant des chaines "alkyles" ramifiées, l'ensemble des chaînes "alkyles" desdits mélanges présentant un taux de ramification pouvant aller par exemple de 5 à 95 %
  • - que des acides alkylaryl sulfoniques obtenus par sulfonation de coalkylats obtenus par coalkylation du benzène, du toluène ou de l'orthoxylène par une oléfine linéaire et une oléfine ramifiée selem la méthode décrite dans l'art antérieur ci-dessus cité.
It is therefore :
  • - both alkylaryl sulfonic acids having a linearity rate of approximately 100% obtained by sulfonation of an alkylbenzene, an alkylorthoxylene or an alkyltoluene in which the "alkyl" radical (s) are linear or a mixture alkylbeazenes, alkylorthoxylenes or alkyltoluenes in which the "alkyl" radical (s) are linear
  • - alkylarylsulfonic acids having a branching rate of approximately 100% obtained by sulfonation of an alkylbenzene, an alkylorthoxylene or an alkyltoluene in which the alkyl radical (s) are branched or of a mixture of alkylbenzenes, of alkylorthoxylenes or of alkyltoluenes in which the "alkyl" radical (s) are branched
  • - mixtures of alkylaryl sulfonic acids with approximately 100% linearity and of alkylaryl sulfonic acids having "branched" alkyl chains, all of the "alkyl" chains of said mixtures having a branching rate which may range, for example, from 5 to 95%
  • - that alkylaryl sulfonic acids obtained by sulfonation of coalkylates obtained by coalkylation of benzene, toluene or orthoxylene by a linear olefin and a branched olefin according to the method described in the prior art cited above.

La masse moléculaire desdits acides exprimée en sel de sodium correspond généralement à une valeur de 400 à 600 ; ils sont généralement utilisés en solution à au moins 40 % environ dans de l'Itnile de dilution ou bien non dilués.The molecular mass of said acids expressed as the sodium salt generally corresponds to a value of 400 to 600; they are generally used in solution at least around 40% in dilution or non-diluted Itnile.

Les additifs faisant l'objet de l'invention sont caractérisés en ce qa'ils sont obtenus selon un procédé comprenant les étapes suivautes

  • 1) on fait réagir au sein d'une huile de dilution un acide alkylaryl sulfonique avec une base alcalino-terreuse, les quantités de réactifs mises en oeuvre correspondant à un rapport molaire base alealino-terreuse/acide alkylaryl sulfonique compris entre 0,51 et 1,8 (de préférence entre 0,55 et 1,6).
  • 2) on fait réagir le milieu obtenu avec un alcool de point d'ébullition supérieur à 80°C, et éventuellement avec un acide carboxylique contenant de 1 à 4 atomes de carbone, en présence d'eau et d'ions chlorures, les quantités de réactifs mises en oeuvre correspondant aux rapports molaires suivants :
    • . acide carboxylique/sur base alcalino-terreuse "basique" inférieur à 2 (de préférence compris entre 0,15 et 1,5)
    • . ion chlorure/acide alkylaryl sulfonique compris entre 0,005 et 0,2 (de préférence entre 0,01 et 0,15)
    • . alcool/acide alkylaryl sulfonique supérieur ou égal à 0,1 (de préférence entre 0,15 et 2,5)
    • . eau/acide alkylarylsulfonique compris entre 0,2 et 5 (de préférence entre 0,5 et 4)
  • 3) on élimine l'eau et l'alcool
  • 4) et on filtre pour éliminer les matières solides.
The additives which are the subject of the invention are characterized in that they are obtained according to a process comprising the following stages
  • 1) an alkylaryl sulfonic acid is reacted in a dilution oil with an alkaline earth base, the amounts of reagents used corresponding to an alealino earth base / alkylaryl sulfonic acid molar ratio of between 0.51 and 1.8 (preferably between 0.55 and 1.6).
  • 2) the medium obtained is reacted with an alcohol with a boiling point above 80 ° C., and optionally with a carboxylic acid containing from 1 to 4 carbon atoms, in the presence of water and of chloride ions, the amounts of reagents used corresponding to the following molar ratios:
    • . carboxylic acid / on "basic" alkaline earth base less than 2 (preferably between 0.15 and 1.5)
    • . chloride ion / alkylaryl sulfonic acid between 0.005 and 0.2 (preferably between 0.01 and 0.15)
    • . alcohol / alkylaryl sulfonic acid greater than or equal to 0.1 (preferably between 0.15 and 2.5)
    • . water / alkylarylsulfonic acid between 0.2 and 5 (preferably between 0.5 and 4)
  • 3) water and alcohol are removed
  • 4) and filtered to remove the solids.

On entend par "base alcalino-terreuse basique" la partie théorique de base alcalino-terreuse à disperser dans le milieu, c'est-à-dire celle non fixée sur l'acide alkylaryl sulfonique.The expression “basic alkaline earth base” is understood to mean the theoretical part of an alkaline earth base to be dispersed in the medium, that is to say that which is not attached to the alkylaryl sulfonic acid.

Une variante dudit procédé consiste à introduire à la lère étape tout ou partie des réactifs présents à la 2ème étape.A variant of the said process consists in introducing in the 1st stage all or part of the reagents present in the 2nd stage.

Une autre variante du procédé consiste à réaliser une étape de carbonatation à l'aide de gaz carbonique du milieu obtenu à la deuxième étape, préalablement à l'étape 3) d'élimination de l'eau et de l'alcool, et ce lorsque le rapport molaire base alcalino-terreuse/acide alkylarylsulfonique est de 1,2 au moins, de préférence de 1,3 au moins.Another variant of the process consists in carrying out a carbonation stage using carbon dioxide from the medium obtained in the second stage, prior to stage 3) of elimination of water and alcohol, and this when the alkaline earth base / alkylarylsulfonic acid molar ratio is at least 1.2, preferably at least 1.3.

Parmi les bases alcalino-terreuses pouvant être mises en oeuvre on peut citer les oxydes, hydroxydes ou carbonates de calcium, barium, magnésium ... et tout particulièrement la chaux et l'oxyde de magnésium "actif".Among the alkaline-earth bases which can be used, mention may be made of calcium oxides, hydroxides or carbonates, barium, magnesium, and more particularly lime and "active" magnesium oxide.

Parmi les acides carboxyliques pouvant être mis en oeuvre on peut citer de préférence l'acide formique et/ou l'acide acétique, ainsi que les mélanges acide formique-acide glycolique ou acide formique-acide oxalique.Among the carboxylic acids which can be used, mention may preferably be made of formic acid and / or acetic acid, as well as mixtures of formic acid-glycolic acid or formic acid-oxalic acid.

Parmi les alcools on choisit de préférence ceux de point d'ébullition supérieur à 100°C tels que les monoalcools aliphatiques linéaires ou ramifiés contenant de 4 à 10 atomes de carbone tels que l'isobutanol, l'alfol 6, le 2-éthylhexanol, les alcools OXO en C8-C10. Il est avantageux industriellement d'utiliser ceux non miscibles à l'eau (c'est-à-dire ceux dont la solubilité dans l'eau est inférieure à 10% en poids à température ordinaire) car ils peuvent être recyclés à volonté par simple décantation de la phase aqueuse.Among the alcohols, those with a boiling point higher than 100 ° C. are preferably chosen such as linear or branched aliphatic monoalcohols containing from 4 to 10 carbon atoms such as isobutanol, alfol 6, 2-ethylhexanol, C 8 -C 10 OXO alcohols. It is advantageous industrially to use those immiscible with water (that is to say those whose solubility in water is less than 10% by weight at ordinary temperature) because they can be recycled at will by simple decantation of the aqueous phase.

La quantité d'alcool à mettre en oeuvre est fonction du taux de linéarité du ou des radicaux "alkyles" ; plus ce taux est élevé, plus la quantité d'alcool doit être importante.The amount of alcohol to be used depends on the linearity rate of the "alkyl" radical (s); the higher this rate, the greater the quantity of alcohol.

Les ions chlorures peuvent être mis en oeuvre par l'intermédiaire de chlorure d'ammonium, de chlorure de calcium, de chlorure de zinc ...The chloride ions can be used via ammonium chloride, calcium chloride, zinc chloride, etc.

Parmi les huiles de dilution pouvant être mises en oeuvre on peut citer les huiles paraffiniques telles que l'huile 100 Neutral, ainsi que les huiles naphténiques ou mixtes. La quantité d'huile favorablement mise en oeuvre est telle que la quantité d'huile contenue dans le produit final (y compris celle provenant éventuellement de l'acide alkylaryl sulfonique de départ) représente de 20 à 60 % en poids dudit produit, de préférence 25 à 55 Z et tout particulièrement de 30 à 40 % en poids dudit produit.Among the dilution oils which can be used, mention may be made of paraffinic oils such as 100 Neutral oil, as well as naphthenic or mixed oils. The amount of oil favorably used is such that the amount of oil contained in the final product (including that optionally coming from the starting alkylaryl sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 to 55% and very particularly from 30 to 40% by weight of the said product.

Pour une bonne mise en oeuvre du procédé faisant l'objet de l'invention, on réalise :

  • Ia lère étape à une température de l'ordre de 20 à 80°C (de préférence de l'ordre de 40 à 70° C) pendant environ 15 à 60 minutes (de préférence 30 minutes environ)
  • la 2ème étape à une température correspondant à une température de l'ordre de 50 à 120° C sous pression atmosphérique (de préférence 90-110° C) pendant environ 1 à 7 heures de préférence.
  • . la 3ème étape peut être favorablement réalisée par exemple :
    • - par distillation sous vide, en serrant le vide progressivement jusqu'à atteindre 4000 Pascals et en chauffant progressivement jusqu'à 195° C (pour empêcher les entrainements) et en restant une heure environ dans ces conditions
    • - ou en chauffant à pression atmosphérique jusqu'à 160° C, pois en distillant sous vide (4000 Pa) sur un évaporateur à couche mince dont la température de paroi est de 210-220° C.
For a good implementation of the process which is the subject of the invention, we carry out:
  • Ia 1st stage at a temperature of the order of 20 to 80 ° C (preferably of the order of 40 to 70 ° C) for about 15 to 60 minutes (preferably about 30 minutes)
  • the 2nd stage at a temperature corresponding to a temperature of the order of 50 to 120 ° C under atmospheric pressure (preferably 90-110 ° C) for approximately 1 to 7 hours preferably.
  • . the 3rd step can be favorably carried out for example:
    • - by vacuum distillation, gradually tightening the vacuum until 4000 Pascals and gradually heating up to 195 ° C (to prevent entrainments) and remaining about an hour under these conditions
    • - or by heating at atmospheric pressure up to 160 ° C, peas by vacuum distillation (4000 Pa) on a thin-layer evaporator whose wall temperature is 210-220 ° C.

Les additifs détergents-dispersants pour huile lubrifiante obtenus par le procédé ci-dessus décrit, présentent un TBN (Total Basic Number - Norme ASTM D 2896) pouvant aller jusqu'à 40 environ, un rapport molaire base alcalino-terreuse/acide alkylarylsulfonique compris entre 0,51 et 1,3 (de préférence entre 0,55 et 1,2) étant alors suffisant. Des produits de TBN plus élevé, pouvant aller jusqu'à 100 environ, peuvent être obtenus en utilisant à la lère étape un rapport molaire base alcalino-terreuse/acide alkylarylsulfonique pouvant aller jusqu' 1,8 (de préférence jusqu'à 1,6) et en réalisant une étape complémentaire de carbonatation préalablement à l'étape 3) d'élimination de l'eau et de l'alcool.The detergent-dispersant additives for lubricating oil obtained by the process described above have a TBN (Total Basic Number - Standard ASTM D 2896) which can range up to around 40, an alkaline-earth / alkylarylsulfonic acid molar ratio of between 0.51 and 1.3 (preferably between 0.55 and 1.2) being then sufficient. Higher TBN products of up to about 100 can be obtained by using in the 1st step an alkaline earth / alkaryl sulfonic acid molar ratio of up to 1.8 (preferably up to 1.6 ) and by carrying out an additional carbonation step prior to step 3) of elimination of water and alcohol.

Cette étape de carbonatation est favorablement réalisée à une température comprise entre 90 et 180°C, de préférence entre 110 et 170°C, à l'aide d'une quantité de C02 comprise entre celle pouvant être complètement absorbée par le milieu réactionnel et un excès de 30 % de cette quantité. Si nécessaire un mélange d'eau et d'alcool peut être introduit à la fin de la carbonatation pour diminuer la viscosité du milieu jusqu'à une valeur de l'ordre de 100 à 600 cst à la.température de la réaction.This carbonation step is favorably carried out at a temperature between 90 and 180 ° C, preferably between 110 and 170 ° C, using an amount of C0 2 between that which can be completely absorbed by the reaction medium and 30% excess of this amount. If necessary, a mixture of water and alcohol can be introduced at the end of carbonation to reduce the viscosity of the medium to a value of the order of 100 to 600 cst at the temperature of the reaction.

Lesdits additifs détergents-dispersants peuvent être ajoutés aux huiles lubrifiantes en quantité pouvant aller jusqu'à 1,7% en poids (ce qui correspond à environ 0,04% de calcium) pour une huile pour moteur à essence ; jusqu'à 3,5% (ce qui correspond à environ 0,08% de calcium) pour une huile pour moteur diesel ou marin ; jusqu'à 11,5% (ce qui correspond à environ 0,25% de calcium) pour une huile de protection.Said detergent-dispersant additives can be added to the lubricating oils in an amount which can range up to 1.7% by weight (which corresponds to approximately 0.04% of calcium) for a petrol engine oil; up to 3.5% (which corresponds to approximately 0.08% of calcium) for a diesel or marine engine oil; up to 11.5% (which corresponds to approximately 0.25% calcium) for a protective oil.

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 alkyl biphényléthers, 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. hard coal and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl 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 detergent-dispersants obtained according to the process of the invention: there may be mentioned, 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 15Examples 1 to 15

On réalise les étapes suivantes :

  • 1) On charge dans un réacteur tétracol de 4 litres de l'huile 100 Nemtral, de la chaux et une solution à 10 % en poids dans du dodécylbenzène d'anti-mousse SI 200 commercialisé par RHONE-POULENC.
The following steps are carried out:
  • 1) 100 Nemtral oil, lime and a solution at 10% by weight in dodecylbenzene of antifoam SI 200 sold by RHONE-POULENC are charged to a 4 liter tetracol reactor.

Le milieu est porté à 60° C et on introduit en 30 minutes une solution d'acide sulfonique commercialisée par ESSO sous l'appellation AS 107 ; il s'agit d'une solution à 70 % environ dans une huile d'un acide alkylaryl sulfonique présentant un taux de ramification de 75 % environ, constitué en majeure partie d'alkyl- benzènesulfonique et dont la masse moléculaire du sel de sodium est voisine de 490, ce qui correspond à une masse moléculaire apparente de la solution d'acide de 650 environ.The medium is brought to 60 ° C. and a sulfonic acid solution sold by ESSO under the name AS 107 is introduced over 30 minutes; it is a solution of approximately 70% in an oil of an alkylaryl sulphonic acid having a branching rate of approximately 75%, consisting mainly of alkyl benzenesulphonic and whose molecular mass of the sodium salt is close to 490, which corresponds to an apparent molecular mass of the acid solution of approximately 650.

2) On introduit ensuite de l'eau, une solution aqueuse à 36 % en poids environ de CaCl2, puis de l'acide formique et enfin du 2-éthylhexanol.2) Water is then introduced, an aqueous solution at 36% by weight approximately of CaCl 2 , then formic acid and finally 2-ethylhexanol.

Le milieu est porté et maintenu à 100° C.The medium is brought to and maintained at 100 ° C.

3) On distille sous vide (4000 Pa) pendant 1 heure à 195° C.3) It is distilled under vacuum (4000 Pa) for 1 hour at 195 ° C.

4) On filtre.4) We filter.

Les quantités de réactifs mises en oeuvre figurent aux tableaux I à IV.The quantities of reagents used are shown in Tables I to IV.

Les poids d'"AS 107" et de "CaCl2" figurant dans ce tableau correspondent aux poids des solutions respectives. Il en est de même pour les autres acides sulfoniques figurant aux tableaux VI et VII.The weights of "AS 107" and "CaCl 2 " appearing in this table correspond to the weights of the respective solutions. The same is true for the other sulfonic acids listed in Tables VI and VII.

Le produit de l'exemple 8 préparé sans acide formique est légèrement visqueux ; la réaction est moins complète mais est toutefois réalisable industriellement.The product of Example 8 prepared without formic acid is slightly viscous; the reaction is less complete but is however feasible industrially.

Sont donnés à titre comparatif les exemples :

  • - 1 et 2 réalisés sans 2-éthylhexanol ; on a constaté que la 3ème étape (distillation) n'est réalisable qu'en présence d'une très forte quantité d'anti-mousse pour éviter la formation de mousses en quantité trop importante provoquant des entraînements lors de la mise sous vide ; l'extrapolation industrielle en est de ce fait aléatoire.
  • - 13 réalisé sans chlorure de calcium ; on constate que le produit formé est distillable mais difficilement filtrable à cause de sa viscosité trop élevée.
Examples are given for comparison:
  • - 1 and 2 produced without 2-ethylhexanol; it was found that the 3rd step (distillation) is only possible in the presence of a very large amount of anti-foam to avoid the formation of foam in too large a quantity causing entrainments during the placing under vacuum; industrial extrapolation is therefore random.
  • - 13 produced without calcium chloride; it is found that the product formed is distillable but difficult to filter because of its too high viscosity.

Les méthodes de mesure sont les suivantes :The measurement methods are as follows: Viscosité à 100° C en cstViscosity at 100 ° C in cst

La viscosité est mesurée après dilution du produit dans de l'huile 100 N jusqu'à obtenir une solution présentant un taux de calcium total de 2,9 %. Lorsque ledit produit présente un taux de calcium total inférieur à 2,9 % la viscosité est alors mesurée sur le produit en l'état.The viscosity is measured after diluting the product in 100 N oil until a solution with a total calcium level of 2.9% is obtained. When said product has a total calcium level of less than 2.9%, the viscosity is then measured on the product as it is.

CompatibilitéCompatibility

On prépare un additif à base de monosuccinimide, dithio- phosphate de zinc et comprenant environ 75 % de produit à tester, additif que l'on met en solution à 10 % dans une huile de base 350 N CFR.An additive is prepared based on monosuccinimide, zinc dithiophosphate and comprising approximately 75% of product to be tested, additive which is dissolved in 10% in a base oil 350 N CFR.

L'aspect de la solution obtenue est examiné au bout de 30 jours.The appearance of the solution obtained is examined after 30 days.

MoussageFoaming

On soumet à la séquence 1 à 24° C du test ASTM D 892 réalisé dans une huile visqueuse SAE 50, l'additif préparé pour le test de compatibilité.The additive prepared for the compatibility test is subjected to the sequence 1 at 24 ° C. of the ASTM D 892 test carried out in a viscous oil SAE 50.

Exemple 16Example 16

On réalise l'opération décrite à l'exemple 4 à une température de 110° C au lieu de 100° C.The operation described in Example 4 is carried out at a temperature of 110 ° C. instead of 100 ° C.

Les résultats obtenus sont équivalents.The results obtained are equivalent.

Exemple 17Example 17

On réalise l'opération décrite à l'exemple 4 à une température de 85° C au lieu de 100° C.The operation described in Example 4 is carried out at a temperature of 85 ° C instead of 100 ° C.

Les résultats obtenus figurent au tableau IV.The results obtained are shown in Table IV.

Exemple 18Example 18

Cet exemple décrit la préparation d'un alkylbenzène sulfonate de TBN faible (égal à 8).This example describes the preparation of an alkylbenzene sulfonate of low TBN (equal to 8).

Les quantités de réactifs mises en oeuvre et les résultats obtenus figurent au tableau IV.The quantities of reagents used and the results obtained are shown in Table IV.

Exemple 19Example 19

On réalise l'opération décrite à l'exemple 4 en ajoutant le 2-éthylhexànol avant l'eau à la 2ème étape. Les résultats obtenus sont équivalents.The operation described in Example 4 is carried out by adding 2-ethylhexanol before water in the 2nd step. The results obtained are equivalent.

Exemples 20 - 21Examples 20-21

On réalise une opération selon le mode opératoire décrit dans les exemples 3-15 en remplacant l'acide formique par de l'acide acétique d'une part et par un mélange acide formique - acide acétique d'autre part.An operation is carried out according to the procedure described in Examples 3-15, replacing the formic acid with acetic acid on the one hand and a mixture of formic acid - acetic acid on the other hand.

Les quantités de réactifs mises en oeuvre et les résultats obtenus figurent au tableau IV.The quantities of reagents used and the results obtained are shown in Table IV.

Exemples 22 - 25Examples 22 - 25

On réalise les opérations décrites aux exemples 3 et 4 en reaplacant le 2-éthylhexanol par 200 g des alcools suivants :

  • - mélange 60/40 en poids d'isobutanol et d'Alfol 6
  • - isobntanol
  • - Alfol 6
  • - OXO C8
The operations described in Examples 3 and 4 are carried out by replacing the 2-ethylhexanol with 200 g of the following alcohols:
  • - 60/40 mixture by weight of isobutanol and Alfol 6
  • - isobntanol
  • - Alfol 6
  • - OXO C8

Les résultats obtenus figurent au tableau V.The results obtained are shown in Table V.

EXemples 26 et 27EXAMPLES 26 and 27

On réalise l'opération décrite à l'exemple 4 en remplaçant les 22 g de solution à 36 % de CaCl2 par :

  • - 3,4 g de ClNH4 et 54 g d'eau d'une part ; les résultats obtenus figurent au tableau V
  • - 10 g de ZnCl2 et 58 g d'eau d'autre part ; les résultats obtenus sont équivalents à ceux de l'exemple 4.
The operation described in Example 4 is carried out by replacing the 22 g of 36% CaCl 2 solution with:
  • - 3.4 g of ClNH 4 and 54 g of water on the one hand; the results obtained appear in table V
  • - 10 g of ZnCl 2 and 58 g of water on the other hand; the results obtained are equivalent to those of Example 4.

Exemple 28Example 28

On réalise selon le même mode opératoire général un essai à partir d'un mélange 40/60 en poids d'AS 107 et d'une solution à 50 % environ dans une huile d'un acide alkylbenzène sulfonique totalement ramifié (constitué de 72 % environ d'acide monoalkylbenzène sulfonique et de 28 % environ d'acide dialkylbenzène sulfonique), dont la masse moléculaire du sel de sodium est de 420 environ, ce qui correspond à une masse moléculaire apparente de la solution d'acide de 800 environ et obtenu par sulfonation des lourds provenant de l'alkylation du benzène par le tétramère du propylène.Le taux de ramification du mélange est de 90 % environ.A test is carried out according to the same general operating method, starting from a 40/60 mixture by weight of AS 107 and a solution of approximately 50% in an oil of a fully branched alkylbenzene sulfonic acid (consisting of 72% about acid monoalkylbenzene sulfonic and approximately 28% dialkylbenzene sulfonic acid), the molecular weight of the sodium salt of which is approximately 420, which corresponds to an apparent molecular weight of the acid solution of approximately 800 and obtained by sulfonation of heavy from the alkylation of benzene by the propylene tetramer. The ramification rate of the mixture is approximately 90%.

Les quantités de réactifs et les résultats obtenus figurent au tableau VI.The amounts of reagents and the results obtained are shown in Table VI.

Exemple 29Example 29

On réalise l'opération décrite à l'exemple 28 à partir d'un mélange 70/30 en poids d'AS 107 et de la solution à 50 % d'acide alkylbenzène sulfonique totalement ramifié, utilisé à l'exemple précédent. Le taux de ramification est de 82,5 % environ.The operation described in Example 28 is carried out using a 70/30 mixture by weight of AS 107 and the 50% solution of fully branched alkylbenzene sulfonic acid used in the previous example. The branching rate is approximately 82.5%.

Les quantités de réactifs et les résultats obtenus figurent au tableau VI.The amounts of reagents and the results obtained are shown in Table VI.

Exemple 30Example 30

On sépare par décantation l'éthylhexanol du distillat obtenu à l'exemple 29, puis on le recycle dans un milieu réactionnel identique à celui de la lère étape de l'exemple 29 et on réalise une nouvelle opération semblable à celle de l'exemple 29.Ethylhexanol is separated by decantation from the distillate obtained in Example 29, then it is recycled in a reaction medium identical to that of the 1st step of Example 29 and a new operation is carried out similar to that of Example 29 .

Les résultats obtenus figurent au tableau VI.The results obtained are shown in Table VI.

Exemple 31Example 31

On réalise l'opération décrite à l'exemple 4 à partir d'un acide alkylorthoxylène sulfonique dérivé d'une poly a oléfine linéaire contenant 18 atomes de carbone (solution à 95 % environ dans une huile).The operation described in Example 4 is carried out from an alkylorthoxylene sulfonic acid derived from a linear poly a olefin containing 18 carbon atoms (approximately 95% solution in an oil).

La masse moléculaire de l'acide correspond à 460 environ.The molecular weight of the acid is approximately 460.

Les quantités de réactifs et les résultats obtenus figurent au tableau VI.The amounts of reagents and the results obtained are shown in Table VI.

Exemple 32Example 32

On réalise l'opération décrite à l'exemple 4 en introduisant la solution de CaCl2 et le 2-éthylhexanol à la première étape du procédé au lieu de la deuxième étape.The operation described in Example 4 is carried out by introducing the CaCl 2 solution and 2-ethylhexanol in the first step of the process instead of the second step.

Les résultats obtenus figurent au tableau VI.The results obtained are shown in Table VI.

Exemple 33Example 33

On réalise l'opération décrite à l'exemple 21 en remplaçant l'acide acétique par le même poids d'acide glycolique.The operation described in Example 21 is carried out by replacing acetic acid with the same weight of glycolic acid.

On obtient des résultats équivalents.Equivalent results are obtained.

Exemple 34Example 34

On réalise selon le même mode opératoire général un essai à partir d'un mélange de la solution à 50 % d'acide alkylbenzène sulfonique totalement ramifié utilisé à l'exemple 28 et d'une solution à 85 % d'un acide alkylbenzène sulfonique totalement linéaire (obtenu à partir d'un mélange de 90 % d'oléfine linéaire en C20-C24 et 10 X d'oléfine linéaire en C24-C28), dont la masse moléculaire du sel de sodium est de 490 environ, ce qui correspond à une masse moléculaire apparente de la solution d'acide de 550 environ.A test is carried out according to the same general operating procedure, starting from a mixture of the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28 and an 85% solution of a totally branched alkylbenzene sulfonic acid. linear (obtained from a mixture of 90% linear C 20 -C 24 olefin and 10 X linear C 24 -C 28 olefin), the molecular weight of the sodium salt of which is approximately 490, which corresponds to an apparent molecular mass of the acid solution of approximately 550.

Les quantités de réactifs et les résultats obtenus figurent au tableau VII.The amounts of reagents and the results obtained are shown in Table VII.

Exemples 35-36Examples 35-36

On réalise selon le même mode opératoire général un essai à partir d'un mélange de la solution à 50 % d'acide alkylbenzène sulfonique totalement ramifié utilisé à l'exemple 28 et d'une solution à 85 % d'un acide alkylbenzène sulfonique fortement linéaire (obtenu à partir d'un mélange d'oléfines en C18-C24) dont la masse moléculaire du sel de sodium est de 480 environ, ce qui correspond à une masse moléculaire apparente de la solution d'acide de 540 environ.A similar test is carried out according to the same general procedure, starting from a mixture of the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28 and an 85% solution of a strongly alkylbenzene sulfonic acid. linear (obtained from a mixture of C 18 -C 24 olefins) whose molecular mass of the sodium salt is approximately 480, which corresponds to an apparent molecular mass of the acid solution of approximately 540.

Les quantités de réactifs et les résultats obtenus figurent au tableau VII.The amounts of reagents and the results obtained are shown in Table VII.

Exemple 37Example 37

On réalise selon le même mode opératoire général un essai à partir de la solution à 50 % d'acide alkylbenzène sulfonique totalement ramifié utilisée à l'exemple 28.A test is carried out according to the same general operating procedure from the 50% solution of fully branched alkylbenzene sulfonic acid used in Example 28.

Les quantités de réactifs et les résultats obtenus figurent au tableau VII.The amounts of reagents and the results obtained are shown in Table VII.

Exemple 38Example 38

On prépare un alkylbenzène sulfonate suralcalinisé à partir du mélange 70/30 en poids d'acides sulfoniques utilisé à l'exemple 29.An alkalinized alkylbenzene sulfonate is prepared from the 70/30 mixture by weight of sulfonic acids used in Example 29.

Les deux premières étapes sont réalisées selon le mode opératoire général à l'aide des quantités de produits indiquées au tableau VII.The first two steps are carried out according to the general procedure using the quantities of products indicated in Table VII.

Le produit obtenu est alors carbonaté pendant 60 mn à 100°C à l'aide de 42 g de C02, puis on ajoute un mélange de 52 g d'eau et de 178 g d'éthyl-2 hexanol ; le milieu est laissé à 100°C pendant 45 mn.The product obtained is then carbonated for 60 min at 100 ° C using 42 g of C0 2 , then a mixture of 52 g of water and 178 g of 2-ethylhexanol is added; the medium is left at 100 ° C for 45 min.

On distille sous vide (4000 Pa) pendant 1 h à 195°C et on filtre.It is distilled under vacuum (4000 Pa) for 1 h at 195 ° C and filtered.

Les résultats obtenus figurent au tableau VII.The results obtained are shown in Table VII.

Exemple 39Example 39

On réalise selon le mode opératoire général un essai à partir du mélange 70/30 en poids d'acides sulfoniques utilisé à l'exemple 29 en remplaçant la chaux par de la MAGLITE DE (oxyde de magnésium "actif").A general test is carried out according to the 70/30 mixture by weight of sulfonic acids used in Example 29, replacing the lime with MAGLITE DE ("active" magnesium oxide).

Les quantités de réactifs et les résultats obtenus figurent au tableau VIII.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
 The amounts of reagents and the results obtained are shown in Table VIII.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008

Claims (13)

1) Additifs détergents-dispersants pour huiles lubrifiantes à base d'alkylarylsulfonates de métaux alcalino-terreux caractérisés en ce qu'ils sont obtenus selon un procédé comprenant les étapes suivantes : a) on fait réagir au sein d'une huile de dilution un acide alkylaryl sulfonique avec une base alcalino-terreuse, les quantités de réactifs mises en oeuvre correspondant à un rapport molaire base alcalino-terreuse/acide alkylaryl sulfonique compris entre 0,51 et 1,8. b) on fait réagir le milieu obtenu avec un alcool de point d'ébullition supérieur à 80°C, et éventuellement avec un acide carboxylique contenant de 1 à 4 atomes de carbone, en présence d'eau et d'ions chlorures, les quantités de réactifs mises en oeuvre correspondant aux rapports molaires suivants : . acide carboxylique/sur base alcalino-terreuse "basique" inférieur à 2 . ion chlorure/acide alkylaryl sulfonique compris entre 0,005 et 0,2 . alcool/acide alkylaryl sulfonique supérieur ou égal à 0,1 . eau/acide alkylarylsulfonique compris entre 0,2 et 5 c) on élimine l'eau et l'alcool d) et on filtre pour éliminer les matières solides. 1) Detergent-dispersant additives for lubricating oils based on alkaline earth metal alkylarylsulfonates, characterized in that they are obtained according to a process comprising the following stages: a) an alkylaryl sulfonic acid is reacted in a dilution oil with an alkaline earth base, the amounts of reagents used corresponding to an alkaline earth base / alkylaryl sulfonic acid molar ratio of between 0.51 and 1.8. b) the medium obtained is reacted with an alcohol with a boiling point above 80 ° C., and optionally with a carboxylic acid containing from 1 to 4 carbon atoms, in the presence of water and of chloride ions, the amounts of reagents used corresponding to the following molar ratios: . carboxylic acid / on "basic" alkaline earth base less than 2 . chloride ion / alkylaryl sulfonic acid between 0.005 and 0.2 . alcohol / alkylaryl sulfonic acid greater than or equal to 0.1 . water / alkylarylsulfonic acid between 0.2 and 5 c) eliminating water and alcohol d) and filtered to remove the solids. 2) Additifs selon la revendication 1 caractérisés en ce que les quantités de réactifs mises en oeuvre aux deux premières étapes correspondent aux rapports molaires suivants : - base alcalino-terreuse/acide alkylarylsulfonique compris entre 0,55 et 1,6 - acide carboxylique/base alcalino-terreuse "basique" compris entre 0,15 et 1,5 - ion chlorure/acide alkylarylsulfonique compris entre 0,01 et 0,15 - alcool/acide alkylarylsulfonique compris entre 0,15 et 2,5 - eau/acide alkylarylsulfonique compris entre 0,5 et 4 2) Additives according to claim 1, characterized in that the quantities of reagents used in the first two stages correspond to the following molar ratios: - alkaline earth base / alkylarylsulfonic acid between 0.55 and 1.6 - "basic" carboxylic acid / alkaline earth base between 0.15 and 1.5 - chloride ion / alkylarylsulfonic acid between 0.01 and 0.15 - alcohol / alkylarylsulfonic acid between 0.15 and 2.5 - water / alkylarylsulfonic acid between 0.5 and 4 3) Additifs selon la revendication 1 ou 2 caractérisés en ce que la base alcalino-terreuse est de la chaux ou de l'oxyde de magnésium "actif".3) Additives according to claim 1 or 2 characterized in that the alkaline earth base is lime or "active" magnesium oxide. 4) Additifs selon l'une quelconque des revendications précédentes caractérisés en ce que l'alcool a un point d'ébullition supérieur à 100°C.4) Additives according to any one of the preceding claims, characterized in that the alcohol has a boiling point greater than 100 ° C. 5) Additifs selon la revendication 4 caractérisés en ce que l'alcool est un monoalcool aliphatique linéaire ou ramifié contenant de 4 à 10 atomes de carbone.5) Additives according to claim 4 characterized in that the alcohol is a linear or branched aliphatic monoalcohol containing from 4 to 10 carbon atoms. 6) Additifs selon la revendication 5 caractérisés en ce que l'alcool est du 2-éthylhéxanol.6) Additives according to claim 5 characterized in that the alcohol is 2-ethylhexanol. 7) Additifs selon l'une quelconque des revendications précédentes caractérisés en ce que l'acide carboxylique est de l'acide formique et/ou de l'acide acétique, ou un mélange acide formique-acide glycolique ou acide formique-acide oxalique.7) Additives according to any one of the preceding claims, characterized in that the carboxylic acid is formic acid and / or acetic acid, or a mixture of formic acid-glycolic acid or formic acid-oxalic acid. 8) Additifs selon l'une quelconque des revendications précédentes caractérisés en ce que les ions chlorures sont introduits par l'intermédiaire du chlorure de calcium, du chlorure d'ammonium ou du chlorure de zinc.8) Additives according to any one of the preceding claims, characterized in that the chloride ions are introduced via calcium chloride, ammonium chloride or zinc chloride. 9) Additifs selon l'une quelconque des revendications précédentes caractérisés en ce que la première étape est réalisée à une température de 20 à 80°C et la deuxième étape à une température de 50 à 120°C.9) Additives according to any one of the preceding claims, characterized in that the first step is carried out at a temperature of 20 to 80 ° C and the second step at a temperature of 50 to 120 ° C. 10) Additifs selon l'une quelconque des revendications précédentes caractérisés en ce que le produit obtenu à l'étape b) est carbonaté à l'aide de C02 avant élimination de l'eau et de l'alcool et filtration aux étapes c) et d), le rapport molaire base alcalino-terreuse/acide alkylarylsulfonique étant compris entre 1,2 et 1,8.10) Additives according to any one of the preceding claims, characterized in that the product obtained in step b) is carbonated using C0 2 before elimination of the water and alcohol and filtration in steps c) and d), the alkaline earth base / alkylarylsulfonic acid molar ratio being between 1.2 and 1.8. 11) Additifs selon la revendication 10 caractérisés en ce que le rapport molaire base alcalino-terreuse/acide alkylarylsulfonique est compris entre 1,3 et 1,6.11) Additives according to claim 10 characterized in that the alkaline earth base / alkylarylsulfonic acid molar ratio is between 1.3 and 1.6. 12) Additifs selon la revendication 10 ou 11 caractérisés en ce que l'opération de carbonatation est réalisée à une température de 90-180°C à l'aide d'une quantité de C02 comprise entre celle pouvant être complètement absorbée par le milieu réactionnel et un excès de 30 % de cette quantité.12) Additives according to claim 10 or 11 characterized in that the carbonation operation is carried out at a temperature of 90-180 ° C using an amount of C0 2 between that which can be completely absorbed by the medium reaction and an excess of 30% of this amount. 13) Huile lubrifiante améliorée contenant une quantité efficace d'un additif détergent-dispersant faisant l'objet de l'une quelconque des revendications précédentes.13) Improved lubricating oil containing an effective amount of a detergent-dispersant additive which is the subject of any one of the preceding claims.
EP85400957A 1984-05-25 1985-05-15 A process for the production of additives for lubricants with detergent and dispersant properties based on non-foaming alkylarylsulfonates of alkaline-earth metals Expired EP0164286B1 (en)

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Application Number Priority Date Filing Date Title
FR8408208A FR2564830B1 (en) 1984-05-25 1984-05-25 PROCESS FOR THE PREPARATION OF ALKALYLARYL SULFONATES OF ALKALINO-EARTH METALS FROM LINEAR ALKYLARYL SULFONIC ACIDS AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICANT OILS OBTAINED
FR8408208 1984-05-25

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EP0164286A1 true EP0164286A1 (en) 1985-12-11
EP0164286B1 EP0164286B1 (en) 1989-08-02

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EP (1) EP0164286B1 (en)
JP (1) JPS6112793A (en)
BR (1) BR8502363A (en)
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DE (1) DE3572007D1 (en)
FR (1) FR2564830B1 (en)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1344812A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Overbased metallic salt diesel fuel additive compositions for improvement of particulate traps

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8814012D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
GB8814010D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Addivites Ltd Lubricating oil additives
GB2232665A (en) * 1989-05-31 1990-12-19 Exxon Chemical Patents Inc Sulphonic acid derivatives and their use as emulsifiers
GB9504034D0 (en) * 1995-02-28 1995-04-19 Exxon Chemical Patents Inc Low base number sulphonates
GB9504033D0 (en) * 1995-02-28 1995-04-19 Exxon Chemical Patents Inc Magnesium low base number sulphonates
FR2731427B1 (en) 1995-03-08 1997-05-30 Chevron Chem Sa ISOMERIZED LINEAR ALKYLARYL-SULFONATES USEFUL AS ADDITIVES FOR LUBRICATING OILS AND CORRESPONDING ALKYLARYL HYDOCARBONS
EP0976810A1 (en) * 1998-07-31 2000-02-02 Chevron Chemical S.A. Mixture of alkyl-phenyl-sulfonates of alkaline earth metals, its application as an additive for lubricating oil, and methods of preparation
FR2783824B1 (en) * 1998-09-25 2001-01-05 Chevron Chem Sa LOW-BASED ALKYLARYL SULFONATES AND LUBRICATING OIL CONTAINING THEM
US6159912A (en) * 1998-11-05 2000-12-12 Chevron Chemical Company Llc Low viscosity, chloride-free, low overbased alkyl-aryl-sulfonate, its application as an additive for lubricating oil, and methods of preparation
US6204226B1 (en) 1999-06-03 2001-03-20 Chevron Oronite S.A. Mixture of alkyl-phenyl-sulfonates of alkaline earth metals, its application as an additive for lubricating oil, and methods of preparation
EP1059301B1 (en) * 1999-06-10 2003-05-21 Chevron Chemical S.A. Alkaline earth alkylaryl sulfonates, their application as an additive for lubricating oil, and methods of preparation
US6337310B1 (en) 2000-06-02 2002-01-08 Chevron Oronite Company Llc Alkylbenzene from preisomerized NAO usable in LOB and HOB sulfonate
US6756348B2 (en) 2001-11-29 2004-06-29 Chevron Oronite Company Llc Lubricating oil having enhanced resistance to oxidation, nitration and viscosity increase
US6642191B2 (en) 2001-11-29 2003-11-04 Chevron Oronite Company Llc Lubricating oil additive system particularly useful for natural gas fueled engines
EP1344811A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Iron salt diesel fuel additive composition for improvement of particulate traps
US20050059560A1 (en) * 2003-09-12 2005-03-17 Chevron Oronite Company Llc Process for the preparation of stabilized polyalkenyl sulfonic acids
US6977319B2 (en) * 2004-03-12 2005-12-20 Chevron Oronite Company Llc Alkylated aromatic compositions, zeolite catalyst compositions and processes for making the same
US6964935B2 (en) * 2004-03-12 2005-11-15 Chevron Oronite Company Llc. Mordenite zeolite alkylation catalysts
US6974788B2 (en) 2004-03-12 2005-12-13 Chevron Oronite Company Llc. Zeolite Y alkylation catalysts
US8293698B2 (en) 2005-07-20 2012-10-23 Chevron Oronite S.A. Alkylaryl sulfonate detergent mixture derived from linear olefins
US8362153B2 (en) * 2006-12-15 2013-01-29 Chevron Oronite Company Llc Polyisobutenyl sulfonates having low polydispersity
BR112013015860A2 (en) * 2010-12-21 2016-09-13 Lubrizol Corp lubricant composition containing a detergent
CN113943595B (en) * 2020-07-16 2022-07-05 中国石油天然气股份有限公司 Synthetic sulfonate additive and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1498638A (en) * 1966-09-08 1967-10-20 Exxon Standard Sa Process for preparing alkaline earth sulfonates from sulfonic acids with poorly branched paliphatic chains
FR2349573A1 (en) * 1976-04-27 1977-11-25 Witco Chemical Corp PROCESS FOR THE PREPARATION OF COMPOUNDS BASED ON SYNTHETIC CALCIUM SULPHONATES, NEUTRAL AND SLIGHTLY BASIC
DE2848672A1 (en) * 1978-11-09 1980-05-22 Bayer Ag Calcium alkylbenzene sulphonate prodn. - by reacting anhydrous alcoholic calcium oxide slurry with corresp. acid in presence of halide catalyst

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446736A (en) * 1968-02-08 1969-05-27 Mobil Oil Corp Mixed carboxylate derivatives of basic alkaline earth metal sulfonates
US3865737A (en) * 1973-07-02 1975-02-11 Continental Oil Co Process for preparing highly-basic, magnesium-containing dispersion
JPS5040525A (en) * 1973-08-15 1975-04-14
US4086170A (en) * 1976-10-08 1978-04-25 Labofina S. A. Process for preparing overbased calcium sulfonates
EP0001318B1 (en) * 1977-08-04 1981-12-02 Exxon Research And Engineering Company Overbased monoalkyl orthoxylene and monoalkyl toluene sulfonates and use as lubricant additives
US4137186A (en) * 1977-11-22 1979-01-30 Standard Oil Company (Indiana) Process for the manufacture of overbased magnesium sulfonates
US4192758A (en) * 1978-05-01 1980-03-11 Bray Oil Company, Inc. Overbased magnesium sulfonate process
US4235810A (en) * 1978-08-03 1980-11-25 Exxon Research & Engineering Co. Alkylates and sulphonic acids and sulphonates produced therefrom
JPS5573653A (en) * 1978-11-30 1980-06-03 Saapasu Chem Ltd Basified magnesium sulfonate
GB2037310A (en) * 1978-12-13 1980-07-09 Exxon Research Engineering Co Preparation of basic magnesium sulphonates
US4306983A (en) * 1979-03-26 1981-12-22 Nalco Chemical Company Process for preparing overbased magnesium sulfonates
US4252659A (en) * 1979-10-12 1981-02-24 Tenneco Chemicals, Inc. Process for the production of overbased manganese salts of organic acids
FR2529224B1 (en) * 1982-06-24 1986-02-07 Orogil NEW SURALKALINIZED 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1498638A (en) * 1966-09-08 1967-10-20 Exxon Standard Sa Process for preparing alkaline earth sulfonates from sulfonic acids with poorly branched paliphatic chains
FR2349573A1 (en) * 1976-04-27 1977-11-25 Witco Chemical Corp PROCESS FOR THE PREPARATION OF COMPOUNDS BASED ON SYNTHETIC CALCIUM SULPHONATES, NEUTRAL AND SLIGHTLY BASIC
DE2848672A1 (en) * 1978-11-09 1980-05-22 Bayer Ag Calcium alkylbenzene sulphonate prodn. - by reacting anhydrous alcoholic calcium oxide slurry with corresp. acid in presence of halide catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1344812A1 (en) * 2002-03-13 2003-09-17 Infineum International Limited Overbased metallic salt diesel fuel additive compositions for improvement of particulate traps

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US4764295A (en) 1988-08-16
JPH0457717B2 (en) 1992-09-14
CA1224804A (en) 1987-07-28
DE3572007D1 (en) 1989-09-07
JPS6112793A (en) 1986-01-21
EP0164286B1 (en) 1989-08-02
FR2564830B1 (en) 1986-09-19
MX172213B (en) 1993-12-06
FR2564830A1 (en) 1985-11-29

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