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EP0133088A1 - Process for preparing calcium-based detergent-dispersant additives having a very high alkalinity, and products obtained by this process - Google Patents

Process for preparing calcium-based detergent-dispersant additives having a very high alkalinity, and products obtained by this process Download PDF

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Publication number
EP0133088A1
EP0133088A1 EP84401440A EP84401440A EP0133088A1 EP 0133088 A1 EP0133088 A1 EP 0133088A1 EP 84401440 A EP84401440 A EP 84401440A EP 84401440 A EP84401440 A EP 84401440A EP 0133088 A1 EP0133088 A1 EP 0133088A1
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Prior art keywords
ranging
lime
glycol
alkylphenol
carried out
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German (de)
French (fr)
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EP0133088B1 (en
Inventor
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 a process for the preparation of detergent-dispersant additives of very high alkalinity for lubricating oils as well as the products obtained.
  • the Applicant has now found a process making it possible to prepare calcium alkylphenates-alkylbenzenesulfonates of TBN at least equal to 300.
  • An improved variant of said process consists in carrying out the first step in the presence of a C 1 -C 4 carboxylic acid. optionally hydroxylated such as formic acid, acetic acid, glycolic acid or oxalic acid.
  • alkylbenzene sulfonic acids means the acids obtained by sulfonation of alkylbenzenes in which the alkyl radical (s) contain from 15 to 30 carbon atoms and are derived from linear olefins or olefin oligomers, as well as those obtained by sulfonation oil cuts; their molecular mass, expressed in sodium salt, generally corresponds to a value of 430 to 560. They are generally used in solution at approximately 70 X in dilution oil.
  • alkylphenols means alkylphenols carrying one or more C 9 -C 15 alkyl substituents and preferably nonyl, decyl, dodecyl or tetradecylphenols.
  • 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 coming from the starting alkylbenzene sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 at 55% and very particularly from 30 to 40% by weight of said product.
  • halide ions mention may preferably be made of Cl - ; they are used via ammonium or metal salts such as ammonium chloride, calcium chloride, zinc chloride ...
  • This first stage can last from a few minutes to 1 hour and generally around half an hour.
  • the step of removing the water formed is generally carried out at a temperature of 110-150 ° C and preferably 130-140 ° C.
  • C 6 -C 14 alkanols or cycloalkanols such as ethylhexanol , oxo alcohols, decyl alcohol, tridecyl alcohol, trimethylcyclohexanol ...
  • ethers of alkylene glycols such as butoxy-2 ethanol, butoxy-2 propanol, hexyloxy-2 ethanol, methyl ethers of dipropylene glycol
  • alkylene glycols such as propylene glycol, hexylene glycol; butanediols.
  • the glycol and the heavy alcohol can be introduced in full at the start of the third stage or preferably by fraction during the third stage.
  • the sulfur necessary for sulfurization can be introduced at the start of the third stage or else it can already be present at the first stage.
  • the sulfurization operation is carried out at a temperature ranging from 160 ° C. to a temperature below the boiling point of heavy alcohol at normal pressure or under slight depression; it usually lasts 1 to 2 hours.
  • the carbonation operation is favorably carried out at a temperature ranging from 160 ° C. to a temperature lower than that of boiling of the heavy alcohol, for a period which can range from 1 to 4 hours and generally about 2 hours; the amount of C0 2 introduced is between that which can be completely absorbed by the reaction medium and an excess of 30% of this amount.
  • this carbonation operation can be carried out in the presence of an additional quantity of fresh glycol to compensate for the glycol which may be vaporized.
  • the fifth step is preferably carried out under vacuum at a temperature of 180-220 ° C in about one hour.
  • the present invention also relates to detergents-dispersants of high alkalinity based on calcium obtained by the process described above.
  • the amount of TBN 350 detergent-dispersant that can be added to lubricating oils is generally between 1.5 and 2 X for a gasoline engine oil, between 3 and 4 X for a diesel engine oil and between 7 and 20% for a marine engine 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 liquid acids of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers silicon.
  • 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.
  • glycol and a fraction of butylglycol are added over ten minutes, then the remainder of butylglycol over fifty minutes. 0n heating to 160 ° C under slight vacuum for 1 hour.
  • the vacuum is gradually tightened to 66.5 X 10 2 Pa and then heated to 200 ° C for 1 hour.
  • the finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 25% of additive.
  • the amounts of reagents used are those used in Example 1.
  • glycol and a fraction of butylglycol are heated in twenty minutes and then the rest of the butylglycol in 1 hour.
  • the mixture is heated to 165 ° C. and then carbonated for 2 hours at atmospheric pressure.
  • Example 21 The operation described in Example 21 is carried out by replacing the 18 g of acetic acid with 13.8 g of formic acid.
  • Example 1 The operation described in Example 1 is carried out by replacing the (100 + 560 g) of butylglycol with a mixture of (100 + 193 g) of 1,4-butanediol and of (100 + 400 g) of 2-ethylhexanol and decreasing the amount of glycol.

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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)
  • Detergent Compositions (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Disclosed is a process for preparing very highly alkaline, calcium-based, detergent-dispersant additives for lubricating oils and products produced by such a process. The process includes the steps of reacting an alkylbenzenesulfonic acid, an alkylphenol, diluent oil, halogen ions and lime, removing water formed during the reaction, sulfurizing the resultant product in the presence of glycol and at least one additional alcohol having a boiling point in excess of about 155 DEG C., carbonating the sulfurized product, removing the glycol and heavy alcohol from the sulfurized, carbonated reaction product, and filtering to remove sediment and to obtain a reaction product comprising a highly-alkaline, calcium-based detergent-dispersant additive for lubricating oils.

Description

La présente invention a pour objet un procédé de préparation d'additifs détergents-dispersants de très haute alcalinité pour huiles lubrifiantes ainsi que les produit obtenus.The present invention relates to a process for the preparation of detergent-dispersant additives of very high alkalinity for lubricating oils as well as the products obtained.

Il a déjà été proposé dans les brevets européens n°3694, 6796, 7260 et 7257 accordés au nom de la demanderesse, de préparer des additifs du type alkylphénates-alkylbenzènesulfonates de métaux alcalino-terreux de TBN (Total Basic Number - Norme ASTM D 2896) supérieur à 200 ou 250.It has already been proposed in European patents No. 3694, 6796, 7260 and 7257 granted in the name of the applicant, to prepare additives of the alkaline earth metal alkylphenate-alkylbenzene sulfonate type from TBN (Total Basic Number - Standard ASTM D 2896 ) greater than 200 or 250.

L'expérience montre que les procédés qui y sont décrits ne permettent pas d'obtenir des additifs pouvant atteindre un TBN de 300.Experience has shown that the methods described there do not make it possible to obtain additives which can reach a TBN of 300.

La demanderesse a maintenant trouvé un procédé permettant de préparer des alkylphénates-alkylbenzènesulfonates de calcium de TBN au moins égal à 300.The Applicant has now found a process making it possible to prepare calcium alkylphenates-alkylbenzenesulfonates of TBN at least equal to 300.

Le procédé faisant l'objet de l'invention est caractérisé par les étapes suivantes :

  • 1) On met en présence :
    • . un acide alkylbenzène sulfonique
    • . un alkylphénol
    • . de l'huile de dilution
    • . des ions halogénures
    • . de la chaux
  • 2) On élimine l'eau formée
  • 3) On sulfurisé par du soufre le produit formé, en présence de glycol et d'au moins un alcool de point d'ébullition supérieur à 155°C.
  • 4) 0n carbonate le produit sulfurisé formé
  • 5) On élimine le glycol et l'alcool de haut point d'ébullition.
  • 6) On filtre pour récupérer l'additif formé.
The process which is the subject of the invention is characterized by the following stages:
  • 1) We bring together:
    • . an alkylbenzene sulfonic acid
    • . an alkylphenol
    • . dilution oil
    • . halide ions
    • . lime
  • 2) The water formed is eliminated
  • 3) The product formed is sulfurized with sulfur, in the presence of glycol and at least one alcohol with a boiling point above 155 ° C.
  • 4) 0n carbonate the sulfurized product formed
  • 5) The glycol and the alcohol of high boiling point are eliminated.
  • 6) Filter to recover the additive formed.

Une variante perfectionnée dudit procédé consiste à réaliser la première étape en présence d'un acide carboxylique en C1-C4 éventuellement hydroxylé tel que l'acide formique, l'acide acétique, l'acide glycolique ou l'acide oxalique.An improved variant of said process consists in carrying out the first step in the presence of a C 1 -C 4 carboxylic acid. optionally hydroxylated such as formic acid, acetic acid, glycolic acid or oxalic acid.

On entend par "acides alkylbenzène sulfoniques" les acides obtenus par sulfonation d'alkylbenzènes dont le ou les radicaux alkyles contiennent de 15 à 30 atomes de carbone et dérivent d'oléfines linéaires ou d'oligomères d'oléfines, ainsi que ceux obtenus par sulfonation de coupes pétrolières ; leur masse moléculaire exprimée en sel de sodium correspond généralement à une valeur de 430 à 560. Ils sont généralement utilisés en solution à 70 X environ dans de l'huile de dilution.The term "alkylbenzene sulfonic acids" means the acids obtained by sulfonation of alkylbenzenes in which the alkyl radical (s) contain from 15 to 30 carbon atoms and are derived from linear olefins or olefin oligomers, as well as those obtained by sulfonation oil cuts; their molecular mass, expressed in sodium salt, generally corresponds to a value of 430 to 560. They are generally used in solution at approximately 70 X in dilution oil.

On entend par "alkylphénols" les alkylphénols portant un ou plusieurs substituants alkyles en C9-C15 et de préférence les nonyl, décyl, dodécyl ou tétradécylphénols.The term "alkylphenols" means alkylphenols carrying one or more C 9 -C 15 alkyl substituents and preferably nonyl, decyl, dodecyl or tetradecylphenols.

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 de l'acide alkylbenzène sulfonique de départ) représente de 20 à 60 X en poids dudit produit, de préférence 25 à 55 X 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 coming from the starting alkylbenzene sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 at 55% and very particularly from 30 to 40% by weight of said product.

Parmi les ions halogénures on peut citer de préférence Cl- ; ils sont mis en oeuvre par l'intermédiaire de sels d'ammonium ou métalliques tels que le chlorure d'ammonium, le chlorure de calcium, le chlorure de zinc...Among the halide ions, mention may preferably be made of Cl - ; they are used via ammonium or metal salts such as ammonium chloride, calcium chloride, zinc chloride ...

La première étape est favorablement réalisée à une température supérieure à 70°C et inférieure à 130°C en présence de quantités de réactifs correspondant aux rapports molaires suivants :

  • . alkylphénol/acide alkylbenzène sulfonique allant de 0,4 à 10 et de préférence de 0,8 à 5.
  • . chaux/(alkylphénol + acide alkylbenzène sulfonique) allant de 2,6 à 8 et de préférence de 2,8 à 6.
  • . ion halogénure/chaux allant de 0,005 à 0,15 et de préférence de 0,015 à 0,09.
  • . acide/chaux allant de 0 à 0,2 et de préférence de 0,01 à 0,2.
The first step is favorably carried out at a temperature above 70 ° C and below 130 ° C in the presence of amounts of reagents corresponding to the following molar ratios:
  • . alkylphenol / alkylbenzene sulfonic acid ranging from 0.4 to 10 and preferably from 0.8 to 5.
  • . lime / (alkylphenol + alkylbenzene sulfonic acid) ranging from 2.6 to 8 and preferably from 2.8 to 6.
  • . halide / lime ion ranging from 0.005 to 0.15 and preferably from 0.015 to 0.09.
  • . acid / lime ranging from 0 to 0.2 and preferably from 0.01 to 0.2.

Cette première étape peut durer de quelques minutes à 1 heure et généralement de l'ordre d'une demi-heure.This first stage can last from a few minutes to 1 hour and generally around half an hour.

L'étape d'élimination de l'eau formée est réalisée généralement à une température de 110-150°C et de préférence de 130-140°C.The step of removing the water formed is generally carried out at a temperature of 110-150 ° C and preferably 130-140 ° C.

Parmi les alcools de point d'ébullition supérieur à 155°C (dénommés ci-après "alcools lourds") mis en oeuvre à la troisième étape, on peut citer : les alcanols ou cycloalcanols en C6-C14 tels que l'éthylhexanol, les alcools oxo, l'alcool décylique, l'alcool tridécylique, le triméthylcyclohexanol...; les éthers des alkylèneglycols tels que le butoxy-2 éthanol, le butoxy-2 propanol, l'hexyloxy-2 éthanol, les éthers méthyliques du dipropylèneglycol ; les alkylèneglycols tels que le propylèneglycol, l'hexylèneglycol ; les butanediols.Among the alcohols with a boiling point above 155 ° C. (hereinafter called "heavy alcohols") used in the third step, there may be mentioned: C 6 -C 14 alkanols or cycloalkanols such as ethylhexanol , oxo alcohols, decyl alcohol, tridecyl alcohol, trimethylcyclohexanol ...; ethers of alkylene glycols such as butoxy-2 ethanol, butoxy-2 propanol, hexyloxy-2 ethanol, methyl ethers of dipropylene glycol; alkylene glycols such as propylene glycol, hexylene glycol; butanediols.

Le glycol et l'alcool lourd peuvent être introduits en totalité au début de la troisième étape ou de préférence par fraction au cours de la troisième étape.The glycol and the heavy alcohol can be introduced in full at the start of the third stage or preferably by fraction during the third stage.

Le soufre nécessaire à.la sulfurisation peut être introduit au début de la troisième étape ou bien peut déjà être présent à la première étape.The sulfur necessary for sulfurization can be introduced at the start of the third stage or else it can already be present at the first stage.

L'opération de sulfurisation est réalisée à une température allant de 160°C à une température inférieure au pont d'ébullition de l'alcool lourd à pression normale ou sous légère dépression ; elle dure généralement de 1 à 2 heures.The sulfurization operation is carried out at a temperature ranging from 160 ° C. to a temperature below the boiling point of heavy alcohol at normal pressure or under slight depression; it usually lasts 1 to 2 hours.

La quantité de réactifs pouvant être mise en oeuvre pour réaliser l'opération de sulfurisation correspond aux rapports molaires suivants :

  • . soufre/alkylphénol allant de 0,6 à 2 et de préférence de 0,8 à 1,5 (correspondant à un rapport molaire soufre/chaux allant de 0,04 à 0,8 et de préférence de 0,06 à 0,5) ;
  • . glycol/chaux allant de 0,03 à 0,6 et de préférence de 0,05 à 0,4 ;
  • . alcool lourd/glycol allant de 0,1 à 30 et de préférence de 0,5 à 25.
The amount of reagents that can be used to carry out the sulfurization operation corresponds to the following molar ratios:
  • . sulfur / alkylphenol ranging from 0.6 to 2 and preferably from 0.8 to 1.5 (corresponding to a sulfur / lime molar ratio ranging from 0.04 to 0.8 and preferably from 0.06 to 0.5 );
  • . glycol / lime ranging from 0.03 to 0.6 and preferably from 0.05 to 0.4;
  • . heavy alcohol / glycol ranging from 0.1 to 30 and preferably from 0.5 to 25.

L'opération de carbonatation est favorablement réalisée à une température allant de 160°C à une température inférieure à celle d'ébullition de l'alcool lourd, pendant une durée pouvant aller de 1 à 4 heures et généralement de 2 heures environ ; la quantité de C02 introduite est comprise entre celle pouvant être complètement absorbée par le milieu réactionnel et un excès de 30 % de cette quantité.The carbonation operation is favorably carried out at a temperature ranging from 160 ° C. to a temperature lower than that of boiling of the heavy alcohol, for a period which can range from 1 to 4 hours and generally about 2 hours; the amount of C0 2 introduced is between that which can be completely absorbed by the reaction medium and an excess of 30% of this amount.

Etant exothermique cette opération de carbonatation peut se faire en présence d'une quantité supplémentaire de glycol frais pour compenser le glycol éventuellement vaporisé.Being exothermic, this carbonation operation can be carried out in the presence of an additional quantity of fresh glycol to compensate for the glycol which may be vaporized.

La cinquième étape est réalisée de préférence sous vide à une température de 180-220°C en une heure environ.The fifth step is preferably carried out under vacuum at a temperature of 180-220 ° C in about one hour.

La présente invention a également pour objet les détergents-dispersants de haute alcalinité à base de calcium obtenus par le procédé ci-dessus décrit. Ainsi la quantité de détergent-dispersant de TBN 350 pouvant être ajoutée à des huiles lubrifiantes est généralement comprise entre 1,5 et 2 X pour une huile pour moteur à essence, entre 3 et 4 X pour une huile pour moteur diesel et entre 7 et 20 % pour une huile pour moteur marin.The present invention also relates to detergents-dispersants of high alkalinity based on calcium obtained by the process described above. Thus, the amount of TBN 350 detergent-dispersant that can be added to lubricating oils is generally between 1.5 and 2 X for a gasoline engine oil, between 3 and 4 X for a diesel engine oil and between 7 and 20% for a marine engine 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 liquides d'acides du phosphore, des alkylbenzènes et des dialkylbenzènes, des polyphényles, des alkyl biphênyléthers, 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 liquid acids of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers 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 16Examples 1 to 16 A) Etape AA) Step A

On charge sous agitation :

  • . de l'acide alkylbenzène sulfonique (acide sulfonique) dont la masse molaire du sel de sodium est de 480, en solution à 70X dans de l'huile 100 Neutral ;
  • . du dodécylphénol (DDP)
  • . de l'huile 100 Neutral
  • . de l'acide acétique
  • . du chlorure d'ammonium ou de calcium.
  • . de la chaux
Charging is carried out with stirring:
  • . alkylbenzene sulfonic acid (sulfonic acid) whose molar mass of sodium salt is 480, in solution at 70X in 100 Neutral oil;
  • . dodecylphenol (DDP)
  • . 100 Neutral oil
  • . acetic acid
  • . ammonium or calcium chloride.
  • . lime

0n chauffe à 90°C pendant 30 minutes.We heat at 90 ° C for 30 minutes.

On ajoute du soufre et on chauffe à 155°C sous légère dépression (930 102 Pa).Add sulfur and heat to 155 ° C under slight vacuum (930 10 2 Pa).

On ajoute le glycol et une fraction de butylglycol en dix minutes, puis le reste de butylglycol en cinquante minutes. 0n chauffe à 160°C sous légère dépression pendant 1 heure.The glycol and a fraction of butylglycol are added over ten minutes, then the remainder of butylglycol over fifty minutes. 0n heating to 160 ° C under slight vacuum for 1 hour.

B) CarbonatationB) Carbonation

On chauffe à 165°C et carbonate pendant 2 heures à pression atmosphérique.Heated to 165 ° C and carbonate for 2 hours at atmospheric pressure.

C) Elimination du glycol et du butylglycolC) Elimination of glycol and butylglycol

Le vide est serré progressivement jusqu'à 66,5 X 102Pa puis on chauffe à 200°C pendant 1 heure.The vacuum is gradually tightened to 66.5 X 10 2 Pa and then heated to 200 ° C for 1 hour.

D) FiltrationD) Filtration

Les quantités de réactifs mises en oeuvre aux différentes étapes figurent aux tableaux I à IV ; les caractéristiques des produits obtenus figurent aux tableaux I à IV.The quantities of reagents used in the various stages are shown in Tables I to IV; the characteristics of the products obtained appear in Tables I to IV.

Caractéristiques du produitProduct Features . Mesure du taux de sédiments. Sediment measurement

Les % de sédiments sont 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 10.000
  • . le produit à analyser est dilué au quart dans l'essence E (25 cm3 de produit à analyser + 75 cm3 d'essence E)
  • . durée de la centrifugation : 10 minutes.
The% of sediments are measured according to standard ASTM D 2273-67, with the following modifications, however:
  • . speed of rotation of the centrifuge 6000 rpm
  • . relative centrifugal force 10,000
  • . the product to be analyzed is diluted to a quarter in gasoline E (25 cm3 of product to be analyzed + 75 cm3 of gasoline E)
  • . duration of centrifugation: 10 minutes.

. Test de compatibilité. Compatibility test

Le produit fini est ajouté à une huile SAE 50 à tendance paraffinique de façon à obtenir une solution contenant 25 % d'additif.The finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 25% of additive.

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

  • . vitesse de rotation : 6000 t/mn
  • . force centrifuge relative : 10.000
  • . durée de centrifugation : 1 heure
The solution is stored for 24 hours and then centrifuged under the following conditions:
  • . rotation speed: 6000 rpm
  • . relative centrifugal force: 10,000
  • . centrifugation time: 1 hour

On mesure ensuite le taux de sédimentsThen measure the sediment rate

Exemple 17Example 17

Les quantités de réactifs mises en oeuvre sont celles utilisées à l'exemple 1.The amounts of reagents used are those used in Example 1.

A) Etape AA) Step A

On charge sous agitation :

  • . de l'acide sulfonique
  • . du DDP
  • . de l'huile 100 Neutral
  • . de l'acide acétique
  • . de la chaux
Charging is carried out with stirring:
  • . sulfonic acid
  • . of the DDP
  • . 100 Neutral oil
  • . acetic acid
  • . lime

0n chauffe jusqu'à 90°C puis on ajoute du soufre et du chlorure d'ammonium.0n heated to 90 ° C and then added sulfur and ammonium chloride.

On chauffe à 155°C sous légère dépression (930 102 Pa).Heated to 155 ° C under slight vacuum (930 10 2 Pa).

On chauffe le glycol et une fraction de butylglycol en vingt minutes puis le reste du butylglycol en 1 heure.The glycol and a fraction of butylglycol are heated in twenty minutes and then the rest of the butylglycol in 1 hour.

On reste deux heures à 160°C sous la même légère dépression.We stay two hours at 160 ° C under the same slight vacuum.

B) Etape de carbonatationB) Carbonation stage

On chauffe à 165°C puis on carbonate pendant 2 heures à pression atmosphérique.The mixture is heated to 165 ° C. and then carbonated for 2 hours at atmospheric pressure.

C) et D) Etapes identiques à celles de l'exemple 1C) and D) Steps identical to those of Example 1

Les caractéristiques du produit obtenu sont semblables à celles du produit de l'exemple 1.The characteristics of the product obtained are similar to those of the product of Example 1.

Exemple 18Example 18

Les opérations décrites dans les exemples 1-16 sont réalisées en remplaçant le butylglycol par du 1,3-butane diol.The operations described in Examples 1-16 are carried out by replacing the butylglycol with 1,3-butane diol.

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

Exemple 19Example 19

Les opérations décrites dans les exemples 1-16 sont réalisées en remplaçant le butylglycol par de l'hexylglycol.The operations described in Examples 1-16 are carried out by replacing the butylglycol with hexylglycol.

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

Exemple 20Example 20

Les opérations décrites dans les exemples 1-16 sont réalisées en remplaçant le butylglycol par de l'bexylèneglycol.The operations described in Examples 1-16 are carried out by replacing the butylglycol with bexylene glycol.

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

Exemples 21-24Examples 21-24

Les opérations décrites dans les exemples 1-16 sont réalisées en remplaçant le butylglycol par le 2-éthy1hexanol. Les quantités de réactifs mises en oeuvre et les caractéristiques du produit obtenu figurent au tableau VI.The operations described in Examples 1-16 are carried out by replacing the butylglycol with 2-ethylhexanol. The quantities of reagents used and the characteristics of the product obtained are shown in Table VI.

Exemple 25Example 25

L'opération décrite à l'exemple 21 est réalisée en remplaçant les 18 g d'acide acétique par 13,8 g d'acide formique.The operation described in Example 21 is carried out by replacing the 18 g of acetic acid with 13.8 g of formic acid.

Les résultats obtenus sont identiques.The results obtained are identical.

Exemple 26Example 26

L'opération décrite à l'exemple 1 est réalisée en remplaçant les (100 + 560 g) de butylglycol par un mélange de (100 + 193 g) de butanediol-1,4 et de (100 + 400 g) de 2-éthylhexanol et en diminuant la quantité de glycol.The operation described in Example 1 is carried out by replacing the (100 + 560 g) of butylglycol with a mixture of (100 + 193 g) of 1,4-butanediol and of (100 + 400 g) of 2-ethylhexanol and decreasing the amount of glycol.

Les résultats obtenus figurent au tableau VI.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
 The results obtained are shown in Table VI.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006

Claims (18)

1) Procédé de préparation de détergents-dispersants caractérisé en ce que : a) on met en présence : . un acide alkylbenzène sulfonique . un alkylphénol . de l'huile de dilution . des ions halogénures . de la chaux b) on élimine l'eau formée c) on sulfurisé par du soufre le produit formé, en présence de glycol et d'au moins un alcool lourd de point d'ébullition supérieur à 155°C d) on carbonate le produit sulfurisé formé e) on élimine le glycol et l'alcool lourd de haut point d'ébullition f) on filtre pour récupérer l'additif formé. 1) Process for the preparation of detergent-dispersants characterized in that: a) we bring together: . an alkylbenzene sulfonic acid . an alkylphenol . dilution oil . halide ions . lime b) the water formed is eliminated c) the product formed is sulfurized with sulfur, in the presence of glycol and at least one heavy alcohol with a boiling point above 155 ° C. d) the sulfurized product formed is carbonated e) removing the glycol and heavy alcohol of high boiling point f) is filtered to recover the additive formed. 2) Procédé selon la revendication 1 caractérisé en ce que l'étape a) est réalisée en présence d'un acide carboxylique en C1-C4 éventuellement hydroxylé. 2) Method according to claim 1 characterized in that step a) is carried out in the presence of a C 1 -C 4 carboxylic acid optionally hydroxylated . 3) Procédé selon la revendication 2 caractérisé en ce que l'acide carboxylique est de l'acide formique, acétique, glycolique ou oxalique.3) Method according to claim 2 characterized in that the carboxylic acid is formic, acetic, glycolic or oxalic acid. 4) Procédé selon la revendication 1, 2 ou 3 caractérisé en ce que les ions halogénures sont des ions chlorures.4) Method according to claim 1, 2 or 3 characterized in that the halide ions are chloride ions. 5) procédé selon la revendication 4 caractérisé en ce que l'ion chlorure est mis en oeuvre sous forme de chlorure d'ammonium ou d'un chlorure métallique.5) A method according to claim 4 characterized in that the chloride ion is used in the form of ammonium chloride or a metal chloride. 6) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'alcool lourd est choisi parmi les alcanols ou cycloalcanols en C6-C14, les éthers d'alkylèneglycols, les alkylèneglycols, les butanediols.6) Process according to any one of the preceding claims, characterized in that the heavy alcohol is chosen from C 6 -C 14 alkanols or cycloalkanols, alkylene glycol ethers, alkylene glycols, butanediols. 7) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape a) est réalisée à une température supérieure à 70°C et inférieure à 130°C.7) Method according to any one of the preceding claims, characterized in that step a) is carried out at a temperature above 70 ° C and below 130 ° C. 8) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape a) est réalisée en présence de quantités de réactifs correspondant aux rapports molaires suivants . alkylphénol/acide alkylbenzène sulfonique allant de 0,4 à 10 . chaux/(alkylphénol + acide alkylbenzène sulfonique) allant de 2,6 à 8 . ion halogénure/chaux allant de 0,005 à 0,15 . acide/chaux allant de 0 à 0,2. 8) Process according to any one of the preceding claims, characterized in that step a) is carried out in the presence of quantities of reagents corresponding to the following molar ratios . alkylphenol / alkylbenzene sulfonic acid ranging from 0.4 to 10 . lime / (alkylphenol + alkylbenzene sulfonic acid) ranging from 2.6 to 8 . halide / lime ion ranging from 0.005 to 0.15 . acid / lime ranging from 0 to 0.2. 9) Procédé selon la revendication 8 caractérisé en ce que l'étape a) est réalisée en présence de quantités de réactifs correspondant aux rapports molaires suivants : . alkylphénol/acide alkylbenzène sulfonique allant de 0,8 à 5 . chaux/(alkylphénol + acide alkylbenzène sulfonique) allant de 2,8 à 6 . ion halogénure/chaux.allant de 0,015 à 0,09 . acide/chaux allant de 0,01 à 0,2. 9) Method according to claim 8 characterized in that step a) is carried out in the presence of quantities of reagents corresponding to the following molar ratios: . alkylphenol / alkylbenzene sulfonic acid ranging from 0.8 to 5 . lime / (alkylphenol + alkylbenzene sulfonic acid) ranging from 2.8 to 6 . halide / lime ion ranging from 0.015 to 0.09 . acid / lime ranging from 0.01 to 0.2. 10) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape c) de sulfurisation est réalisée à une température allant de 160°C à une température inférieure au point d'ébullition de l'alcool lourd.10) Method according to any one of the preceding claims, characterized in that step c) of sulfurization is carried out at a temperature ranging from 160 ° C to a temperature below the boiling point of heavy alcohol. 11) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le soufre est introduit à l'étape c).11) Method according to any one of the preceding claims, characterized in that the sulfur is introduced in step c). 12) procédé selon l'une quelconque des revendications 1 à 9 caractérisé en ce que le soufre est présent à l'étape a)12) Process according to any one of claims 1 to 9 characterized in that the sulfur is present in step a) 13) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la quantité de réactifs mise en oeuvre pour réaliser l'étape c) de sulfurisation correspond aux rapports molaires suivants : . soufre/alkylphénol allant de 0,6 à 2 . glycol/chaux allant de 0,03 à 0,6 . alcool lourd/glycol allant de 0,1 à 30. 13) Method according to any one of the preceding claims, characterized in that the quantity of reagents used to carry out step c) of sulfurization corresponds to the following molar ratios: . sulfur / alkylphenol ranging from 0.6 to 2 . glycol / lime ranging from 0.03 to 0.6 . heavy alcohol / glycol ranging from 0.1 to 30. 14) Procédé selon la revendication 13, caractérisé en ce que la quantité de réactifs mise en oeuvre pour réaliser l'étape c) de sulfurisation correspond aux rapports molaires suivants . soufre/alkylphénol allant de 0,8 à 1,5 . glycol/chaux allant de 0,05 à 0,4 ; . alcool lourd/glycol allant de 0,5 à 25. 14) Process according to claim 13, characterized in that the quantity of reagents used to carry out step c) of sulfurization corresponds to the following molar ratios . sulfur / alkylphenol ranging from 0.8 to 1.5 . glycol / lime ranging from 0.05 to 0.4; . heavy alcohol / glycol ranging from 0.5 to 25. 15) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que l'étape d) de carbonatation est réalisée à une température allant de 160°C à une température inférieure à celle du point d'ébullition de l'alcool lourd.15) Method according to any one of the preceding claims, characterized in that step d) of carbonation is carried out at a temperature ranging from 160 ° C to a temperature below that of the boiling point of heavy alcohol. 16) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que la quantité de C02 mise en oeuvre pour réaliser l'étape d) est comprise entre celle pouvant être complètement absorbée par le milieu réactionnel et un excès de 30 X de cette quantité.16) Method according to any one of the preceding claims, characterized in that the amount of C0 2 used to carry out step d) is between that which can be completely absorbed by the reaction medium and an excess of 30 X of this quantity. 17) Détergents-dispersants obtenus selon le procédé faisant l'objet de l'une quelconque des revendications précédentes.17) Detergent-dispersants obtained according to the process forming the subject of any one of the preceding claims. 18) Compositions lubrifiantes contenant une majeure partie d'huile lubrifiante et de 1,5 à 20 % en poids d'un détergent-dispersant faisant l'objet de la revendication 17.18) Lubricating compositions containing a major part of lubricating oil and from 1.5 to 20% by weight of a detergent-dispersant which is the subject of claim 17.
EP84401440A 1983-07-11 1984-07-06 Process for preparing calcium-based detergent-dispersant additives having a very high alkalinity, and products obtained by this process Expired EP0133088B1 (en)

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AT84401440T ATE27298T1 (en) 1983-07-11 1984-07-06 PROCESS FOR THE PREPARATION OF CALCIUM-BASED DETERGENTS-DISPERSING ADDITIVES WITH VERY HIGH ALKALINESS AND THE OBTAINED PRODUCTS.

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FR8311494A FR2549080B1 (en) 1983-07-11 1983-07-11 PROCESS FOR THE PREPARATION OF VERY HIGH ALKALINITY DETERGENT-DISPERSANT ADDITIVES BASED ON CALCIUM AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS THUS OBTAINED
FR8311494 1983-07-11

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FR2584414A1 (en) * 1985-07-08 1987-01-09 Orogil NEW SULFONES AND SULFURIZED DETERGENT-DISPERSING ADDITIVES FOR LUBRICATING OILS
EP0259974A3 (en) * 1986-08-08 1988-08-10 Chevron Research Company Overbased sulfurized alkyl-phenols as lubricating oil additives
EP0347103A1 (en) * 1988-06-14 1989-12-20 Bp Chemicals (Additives) Limited A process for the production of a lubricating oil additive concentrate
EP0347104A3 (en) * 1988-06-14 1990-01-10 Bp Chemicals (Additives) Limited A process for the production of a lubricating oil additive concentrate
EP0662508A3 (en) * 1994-01-11 1997-01-02 Bp Chemicals Additives Lubricating oil compositions comprising overbased phenate detergent.
WO1997046647A1 (en) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Overbased metal-containing detergents
US12478624B2 (en) 2019-10-02 2025-11-25 Tolremo Therapeutics Ag Heterocyclic derivatives, pharmaceutical compositions and their use in the treatment or amelioration of cancer

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US5716914A (en) * 1986-11-29 1998-02-10 Bp International Limited Alkaline earth metal hydrocarbyl phenates, their sulphurized derivatives, their production and use thereof
US4780224A (en) * 1987-12-07 1988-10-25 Texaco Inc. Method of preparing overbased calcium sulfonates
US4810396A (en) * 1988-04-29 1989-03-07 Texaco Inc. Process for preparing overbased calcium sulfonates
GB8814012D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
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US4879053A (en) * 1988-07-11 1989-11-07 Texaco Inc. Process for preparing overbased calcium sulfonates
AU638705B2 (en) * 1989-04-20 1993-07-08 Lubrizol Corporation, The Methods for reducing friction between relatively slideable components using metal overbased colloidal disperse systems
GB2232665A (en) * 1989-05-31 1990-12-19 Exxon Chemical Patents Inc Sulphonic acid derivatives and their use as emulsifiers
GB8917094D0 (en) * 1989-07-26 1989-09-13 Bp Chemicals Additives Chemical process
US4929373A (en) * 1989-10-10 1990-05-29 Texaco Inc. Process for preparing overbased calcium sulfonates
US5259966A (en) * 1992-11-10 1993-11-09 The Lubrizol Corporation Low chlorine overbased calcium salts
US5401424A (en) * 1993-10-04 1995-03-28 The Lubrizol Corporation Mixed carboxylate overbased gels
GB9611428D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611424D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
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GB9611318D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US6043209A (en) * 1998-01-06 2000-03-28 Playtex Products, Inc. Stable compositions for removing stains from fabrics and carpets and inhibiting the resoiling of same
US7238651B2 (en) * 2003-10-30 2007-07-03 The Lubrizol Corporation Process for preparing an overbased detergent
US9193933B2 (en) * 2010-12-21 2015-11-24 The Lubrizol Corporation Lubricating composition containing a detergent

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FR2584414A1 (en) * 1985-07-08 1987-01-09 Orogil NEW SULFONES AND SULFURIZED DETERGENT-DISPERSING ADDITIVES FOR LUBRICATING OILS
EP0211722A1 (en) * 1985-07-08 1987-02-25 Orogil Sulfonated and sulfurized detergent dispersant additives for lubricant oils
EP0259974A3 (en) * 1986-08-08 1988-08-10 Chevron Research Company Overbased sulfurized alkyl-phenols as lubricating oil additives
AU602343B2 (en) * 1986-08-08 1990-10-11 Chevron Research And Technology Company High TBN, low viscosity, group II metal overbased sulfurized alkylphenols
EP0347103A1 (en) * 1988-06-14 1989-12-20 Bp Chemicals (Additives) Limited A process for the production of a lubricating oil additive concentrate
EP0347104A3 (en) * 1988-06-14 1990-01-10 Bp Chemicals (Additives) Limited A process for the production of a lubricating oil additive concentrate
EP0662508A3 (en) * 1994-01-11 1997-01-02 Bp Chemicals Additives Lubricating oil compositions comprising overbased phenate detergent.
WO1997046647A1 (en) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Overbased metal-containing detergents
US6417148B1 (en) 1996-05-31 2002-07-09 Infineum Usa L.P. Overbased metal-containing detergents
US12478624B2 (en) 2019-10-02 2025-11-25 Tolremo Therapeutics Ag Heterocyclic derivatives, pharmaceutical compositions and their use in the treatment or amelioration of cancer

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GR81650B (en) 1984-12-11
ATE27298T1 (en) 1987-06-15
CA1217480A (en) 1987-02-03
US4698170A (en) 1987-10-06
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