EP0102255B1 - Process for the preparation of sulphurized alkylphenates for use as lubricating oil addtives - Google Patents

Process for the preparation of sulphurized alkylphenates for use as lubricating oil addtives Download PDF

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Publication number
EP0102255B1
EP0102255B1 EP83401269A EP83401269A EP0102255B1 EP 0102255 B1 EP0102255 B1 EP 0102255B1 EP 83401269 A EP83401269 A EP 83401269A EP 83401269 A EP83401269 A EP 83401269A EP 0102255 B1 EP0102255 B1 EP 0102255B1
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Prior art keywords
alkaline
glycol
process according
molar ratio
alcohol
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German (de)
French (fr)
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EP0102255A1 (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
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Definitions

  • the present invention relates to a new process for the preparation of sulfurized alkylphenates of alkaline earth metals, especially calcium, of high alkalinity and the application of said sulfurized alkylphenates as detergent-dispersant additives for lubricating oils.
  • the process for the preparation of sulfurized alkylphenate of alkaline earth metals of high alkalinity comprises the following steps:
  • a simplified representation of the said mixture constituting the “sulfurized alkylphenol may be the following average formula: where X 'varies from 1 to 3 and generally from 1.4 to 2.5
  • alkaline-earth bases mention may be made of calcium, barium or strontium oxides or hydroxides, and very particularly lime.
  • the amount of dilution oil that can be used is such that the amount of oil contained in the final product represents from 25 to 65% by weight of said product and preferably from 30 to 50% by weight of said product.
  • alkanols such as ethylhexanol, oxo alcohol, decyl alcohol, tridecyl alcohol
  • alkoxyalkanols such as. 2-butoxyethanol, 2-butoxypropanol, dipropylene glycol methyl ether.
  • halide ions are preferably CI- ions; these can be implemented via ammonium chloride or metal chlorides such as calcium chloride, zinc ...
  • the neutralization operation is favorably carried out at a temperature between 120 and 180 ° C and preferably between 130 and 170 ° C at a pressure slightly lower than atmospheric pressure (930 10 2 Pa-96010 2 Pa).
  • Said neutralization operation can also be carried out in the presence of an amine, according to a molar ratio of amine / alkaline earth base, which can range up to 0.2.
  • an amine according to a molar ratio of amine / alkaline earth base, which can range up to 0.2.
  • amines that can be used, there may be mentioned: polyalkyleneamines, such as polyethyleneamines and very particularly ethylenediamine and tris (3-oxa-6-amino-6 hexyl) amine.
  • Said operation is also favorably carried out in the presence of acetic acid in an amount corresponding to a molar ratio of acetic acid / alkaline earth base which can range up to 0.2 and preferably up to 0.1.
  • distillation operations succeeding the neutralization operation and the possible carbonation operation are carried out so as to remove water, glycol and alkanol.
  • the carbonation operation is carried out at a temperature between 145 and 180 ° C at a pressure less than or equal to atmospheric pressure (93010 2 to 1010 10 2 Pa).
  • the present invention also relates to a variant of the process described above, variant consisting in preparing "in situ in the neutralization medium the alkylphenolsulfurized from alkylphenol and sulfur.
  • the quantity of sulfur used corresponds to a sulfur / alkylphenol molar ratio of between 0.8 and 2.
  • the sulfurization-neutralization operation is favorably carried out at a temperature between 145 and 175 ° C and preferably between 155 and 170 ° C, optionally in the presence of an amine as above indicated for the general neutralization step.
  • the carbonation operation is then carried out at a temperature between 155 and 180 ° C and preferably between 165 and 175 ° C, optionally in the presence of halide ions as above indicated.
  • the present invention also relates to the product obtained according to the process described above as well as its application as an additive to improve the detergent and dispersing properties of lubricating oils.
  • the amount of additive to be used depends on the future use of said oils. Thus for a petrol engine oil, the amount of additive to be added is generally between 1 and 2.5%; for a diesel engine oil it is generally between 1.8 and 4%, for a marine engine oil, this can go up to 30%.
  • 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, oxide type polymers of alkylene and their derivatives, including polymers of alkylene oxide prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids , liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenylethers, polymers of silicon.
  • 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, oxide type polymers of alky
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; mention may, for example, be made of antioxidant, anti-corrosion additives, ashless dispersant additives.
  • the product to be analyzed is diluted to a quarter in gasoline E (25 cm 3 of product to be analyzed + 75 cm 3 of gasoline E)
  • the finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 25% of additive.
  • glycol is added as a mixture with ethylhexanol or 2-butoxyethanol.
  • the mixture is heated to 145 ° C., then it remains under a vacuum of 345 ⁇ 10 2 Pa for 30 minutes.
  • a distillate D 1 is collected.
  • the vacuum is gradually tightened to 66.5 10 2 Pa while heating up to 190 ° C. It remains for one hour at 190 ° C., then stripping is carried out with nitrogen for 1 hour at 190 ° C.
  • the mixture is heated to 155 ° C. under slight depression (930 10 2 Pa), a first charge of alcohol consisting of a mixture of glycol and butoxyethanol or butoxypropanol is slowly added over 30 minutes, then a second charge of butoxyethanol or butoxypropanol alone in 40 minutes.
  • a D1 distillate is collected.
  • the vacuum is gradually tightened to 66.5 ⁇ 10 2 Pa.
  • the mixture is heated to 190 ° C. for 1 hour, then a nitrogen stripping is carried out for 1 hour at 190 ° C.
  • a D2 distillate is collected.
  • Example 13 The operation described in Example 13 is carried out by introducing the mixture of 10 g of glycol and 10 g of butoxyethanol (1st charge) from the start (and not when the temperature reaches 155 ° C).
  • Example 12 The operation described in Example 12 is carried out by introducing the 10 g of glycol at the start and then the 10 g of butoxyethanol at 155 ° C.
  • Example 26 The operation described in Example 26 is carried out using a dodecylphenol containing 7% sulfur and an additional quantity of sulfur.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

High alkalinity sulfurized alkylphenates of alkaline earth metals useful as lubricating oil additives and methods of making them are disclosed. A sulfurized alkylphenol is neutralized with an alkaline-earth base in the presence of an oil, a glycol, and halide ions, the glycol being present in the form of a mixture with an alcohol having a boiling point above 150 DEG C. Alcohol, glycol, water, and sediment are removed from the resultant medium and the medium is then carbonated. After carbonation, alcohol, glycol, water, and sediment are removed.

Description

La présente invention a pour objet un nouveau procédé de préparation d'alkylphénates sulfurisés de métaux alcalino-terreux, notamment de calcium, de haute alcalinité et l'application desdits alkylphénates sulfurisés comme additifs détergents-dispersants pour huiles lubrifiantes.The present invention relates to a new process for the preparation of sulfurized alkylphenates of alkaline earth metals, especially calcium, of high alkalinity and the application of said sulfurized alkylphenates as detergent-dispersant additives for lubricating oils.

Il est connu (brevet français 2.271.280) de préparer des alkylphénates sulfurisés de calcium de haute alcalinité :

  • en sulfurisant-neutralisant du dodécylphénol par du soufre et de la chaux en présence d'huile, de glycol et d'un alcool de point d'ébullition supérieur à 150 °C (ou en neutralisant un alkylphénol sulfurisé par de la chaux en présence d'huile et de glycol et d'un alcool de point d'ébullition supérieur à 150 °C)
  • en carbonatant
It is known (French patent 2,271,280) to prepare sulfurized calcium alkylphenates of high alkalinity:
  • by sulfurizing-neutralizing dodecylphenol with sulfur and lime in the presence of oil, glycol and an alcohol with a boiling point above 150 ° C (or by neutralizing a sulfurized alkylphenol with lime in the presence of oil and glycol and an alcohol with a boiling point above 150 ° C)
  • carbonating

puis en filtrant la solution huileuse d'alkylphénate sulfurisé de calcium après distillation du glycol.then by filtering the oily solution of sulfurized calcium alkylphenate after distillation of the glycol.

Il est nécessaire pour réaliser ce procédé de mettre en œuvre une grande quantité de glycol, car celui-ci joue à la fois le rôle de solvant diluant et celui de dispersant du carbonate de calcium dans le milieu.To carry out this process, it is necessary to use a large amount of glycol, since it plays both the role of diluent solvent and that of dispersant of calcium carbonate in the medium.

On a constaté :

  • - qu'environ 50 % du glycol mis en oeuvre reste dans le produit fini, ce qui est néfaste pour les moteurs ;
  • - que la viscosité du milieu, notamment en fin de sulfurisation-neutralisation est élevée ;
  • - qu'il se produit des réactions d'oxydo-réduction entre le soufre et le glycol, ce qui est néfaste pour les performances du produit fini (en particulier pour ses propriétés antioxydantes) ;
  • - qu'un grand excès de soufre est nécessaire pour sulfuriser l'alkylphénol, ce qui crée un fort dégagement d'H2S et un phénomène important d'oxydo-réduction avec le glycol.
We observed :
  • - that approximately 50% of the glycol used remains in the finished product, which is harmful for the engines;
  • - that the viscosity of the medium, especially at the end of sulfurization-neutralization is high;
  • - there are oxidation-reduction reactions between sulfur and glycol, which is harmful for the performance of the finished product (in particular for its antioxidant properties);
  • - A large excess of sulfur is necessary to sulfurize the alkylphenol, which creates a strong release of H 2 S and a significant phenomenon of redox with glycol.

Il est également connu (brevet français n° 2.026.567) de préparer des sels basiques dispersants par carbonatation d'un acide organique oléosoluble en présence d'un alcool, d'un diluant, d'un oxyde métallique et d'un halogénure, cela en l'absence d'eau.It is also known (French Patent No. 2,026,567) to prepare basic dispersing salts by carbonation of an oil-soluble organic acid in the presence of an alcohol, a diluent, a metal oxide and a halide, this in the absence of water.

La demanderesse a trouvé un procédé permettant de diminuer la quantité de glycol à mettre en œuvre, ce qui présente l'avantage:

  • - de diminuer la viscosité du milieu notamment après sulfurisation-neutralisation et de ce fait de diminuer la quantité d'huile de dilution ;
  • - de diminuer la quantité de glycol résiduaire ;
  • - de diminuer le dégagement d'H2S ;
  • - de diminuer l'importance de la réaction d'oxydo-réduction

entre le soufre et le glycol.The Applicant has found a method for reducing the amount of glycol to be used, which has the advantage:
  • - Reduce the viscosity of the medium, especially after sulfurization-neutralization and thereby reduce the amount of dilution oil;
  • - reduce the amount of residual glycol;
  • - reduce the release of H 2 S;
  • - to reduce the importance of the redox reaction

between sulfur and glycol.

Selon l'invention, le procédé de préparation d'alkylphénate sulfurisé de métaux alcalino-terreux de haute alcalinité comprend les étapes suivantes :According to the invention, the process for the preparation of sulfurized alkylphenate of alkaline earth metals of high alkalinity comprises the following steps:

- neutralisation d'un alkylphénol sulfurisé par une base alcalino-terreuse en présence d'huile de dilution, de glycol et d'un alcool de point d'ébullition supérieur à 150 °C ;

  • - filtration après distillation de l'eau et du glycol ;
  • - carbonatation du filtrat suivie d'une distillation de l'eau et du glycol puis d'une filtration pour éliminer les sédiments, ledit procédé étant caractérisé en ce que :
  • la quantité d'alcool mise en œuvre correspond à un rapport molaire alcool/glycol supérieur ou égal à 0,4, généralement de l'ordre de 0,4 à 10 ;
  • le rapport de la quantité de base alcalino-terreuse mise en œuvre exprimée en mole à la quantité d'alkylphénol sulfurisé exprimée en moles d'alkylphénol est compris entre 0,4 et 3 et de préférence entre 0,6 et 2,5 ;
  • la quantité de glycol mise en œuvre correspond à un rapport molaire base alcalino-terreux/glycol compris entre 2,6 et 8, et de préférence entre 2,7 et 6 ;-
  • les opérations de neutralisation et de carbonatation sont réalisées en présence d'ions halogénures en quantité correspondant à un rapport atome-gramme d'halogénure/mole de base alcalino-terreuse compris entre 0,01 et 0,15 et de préférence entre 0,015 et 0,09 ;
  • la quantité de CO2 mise en œuvre corespond à un rapport molaire CO2/métal alcalino-terreux compris entre 0,25 et 0,75.
- neutralization of a sulfurized alkylphenol with an alkaline earth base in the presence of dilution oil, glycol and an alcohol with a boiling point above 150 ° C;
  • - filtration after distillation of water and glycol;
  • carbonation of the filtrate followed by distillation of the water and glycol and then filtration to remove the sediments, said process being characterized in that:
  • the amount of alcohol used corresponds to an alcohol / glycol molar ratio greater than or equal to 0.4, generally of the order of 0.4 to 10;
  • the ratio of the quantity of alkaline earth base used, expressed in moles to the quantity of sulfurized alkylphenol expressed in moles of alkylphenol, is between 0.4 and 3 and preferably between 0.6 and 2.5;
  • the amount of glycol used corresponds to an alkaline earth / glycol base molar ratio of between 2.6 and 8, and preferably between 2.7 and 6;
  • the neutralization and carbonation operations are carried out in the presence of halide ions in an amount corresponding to an atom-gram ratio of halide / mole of alkaline earth base between 0.01 and 0.15 and preferably between 0.015 and 0 , 09;
  • the amount of CO 2 used corresponds to a CO 2 / alkaline earth metal molar ratio of between 0.25 and 0.75.

On entend par « alkylphénol sulfurisé le mélange obtenu par sulfurisation de l'alkylphénol à l'aide de soufre ou de chlorure de soufre, ledit mélange étant constitué principalement d'alkylphénol non sulfurisé et d'alkylphénol sulfurisé pouvant être représenté par la formule suivante :

Figure imgb0001
où

  • R représente un radical alkyl en C9-C30 (de préférence en C9-C22)
  • x varie de 1 à 3
  • y varie de 0 à 6.
The term "sulfurized alkylphenol" means the mixture obtained by sulfurization of the alkylphenol with sulfur or sulfur chloride, the said mixture consisting mainly of non-sulfurized alkylphenol and sulfurized alkylphenol which may be represented by the following formula:
Figure imgb0001
 or
  • R represents a C 9 -C 30 (preferably C 9 -C 22 ) alkyl radical
  • x varies from 1 to 3
  • y varies from 0 to 6.

Une représentation simplifiée dudit mélange constituant l'«alkylphénol sulfurisé peut être la formule moyenne suivante :

Figure imgb0002
où X' varie de 1 à 3 et généralement de 1,4 à 2,5A simplified representation of the said mixture constituting the “sulfurized alkylphenol may be the following average formula:
Figure imgb0002
 where X 'varies from 1 to 3 and generally from 1.4 to 2.5

Parmi les bases alcalino-terreuses, on peut citer les oxydes ou hydroxydes de calcium, baryum ou strontium, et tout particulièrement la chaux.Among the alkaline-earth bases, mention may be made of calcium, barium or strontium oxides or hydroxides, and very particularly lime.

Parmi les huiles de dilution pouvant être mises en oeuvre, on peut citer de préférence les huiles paraffiniques telles que l'huile 100 Neutral, les huiles naphténiques ou mixtes peuvent également convenir. La quantité d'huile de dilution pouvant être mise en oeuvre est telle que la quantité d'huile contenue dans le produit final représente de 25 à 65 % en poids dudit produit et de préférence de 30 à 50 % en poids dudit produit.Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil, naphthenic or mixed oils may also be suitable. The amount of dilution oil that can be used is such that the amount of oil contained in the final product represents from 25 to 65% by weight of said product and preferably from 30 to 50% by weight of said product.

Parmi les alcools de point d'ébullition supérieur à 150 °C, on peut citer les alcanols en C6-C14 tels que l'éthylhexanol, les alcool oxo, l'alcool décylique, l'alcool tridécylique ; des alcoxyalcanols tels que le. butoxy-2 éthanol, le butoxy-2 propanol, l'éther méthylique du dipropylène glycol.Among the alcohols with a boiling point greater than 150 ° C., mention may be made of C 6 -C 14 alkanols such as ethylhexanol, oxo alcohol, decyl alcohol, tridecyl alcohol; alkoxyalkanols such as. 2-butoxyethanol, 2-butoxypropanol, dipropylene glycol methyl ether.

Les ions halogénures sont de préférence des ions CI-; ceux-ci peuvent être mis en oeuvre par l'intermédiaire du chlorure d'ammonium ou de chlorures métalliques tels que chlorure de calcium, de zinc...The halide ions are preferably CI- ions; these can be implemented via ammonium chloride or metal chlorides such as calcium chloride, zinc ...

L'opération de neutralisation est favorablement réalisée à une température comprise entre 120 et 180 °C et de préférence entre 130 et 170 °C à une pression légèrement inférieure à la pression atmosphérique (930 102 Pa-960102 Pa).The neutralization operation is favorably carried out at a temperature between 120 and 180 ° C and preferably between 130 and 170 ° C at a pressure slightly lower than atmospheric pressure (930 10 2 Pa-96010 2 Pa).

Ladite opération de neutralisation peut également être réalisée en présence d'une amine, selon un rapport molaire amine/base alcalino-terreuse, pouvant aller jusqu'à 0,2. Parmi les amines pouvant être utilisées, on peut citer : les polyalkylèneamines, telles que les polyéthylèneamines et tout particulièrement l'éthylènediamine et la tris(oxa-3 amino-6 hexyl)amine. Ladite opération est également favorablement réalisée en présence d'acide acétique en quantité correspondant à un rapport molaire acide acétique/base alcalino-terreuse pouvant aller jusqu'à 0,2 et de préférence jusqu'à 0,1.Said neutralization operation can also be carried out in the presence of an amine, according to a molar ratio of amine / alkaline earth base, which can range up to 0.2. Among the amines that can be used, there may be mentioned: polyalkyleneamines, such as polyethyleneamines and very particularly ethylenediamine and tris (3-oxa-6-amino-6 hexyl) amine. Said operation is also favorably carried out in the presence of acetic acid in an amount corresponding to a molar ratio of acetic acid / alkaline earth base which can range up to 0.2 and preferably up to 0.1.

Les opérations de distillation succédant à l'opération de neutralisation et à l'éventuelle opération de carbonatation sont réalisées de manière à éliminer de l'eau, du glycol et de l'alcanol.The distillation operations succeeding the neutralization operation and the possible carbonation operation are carried out so as to remove water, glycol and alkanol.

L'opération de carbonatation est réalisée à une température comprise entre 145 et 180 °C à une pression inférieure ou égale à la pression atmosphérique (930102 à 1 010 102 Pa).The carbonation operation is carried out at a temperature between 145 and 180 ° C at a pressure less than or equal to atmospheric pressure (93010 2 to 1010 10 2 Pa).

La présente invention a également pour objet une variante du procédé ci-dessus décrit, variante consistant à préparer « in situ dans le milieu de neutralisation l'alkylphénolsulfurisé à partir d'alkylphénol et de soufre.The present invention also relates to a variant of the process described above, variant consisting in preparing "in situ in the neutralization medium the alkylphenolsulfurized from alkylphenol and sulfur.

La quantité de soufre mise en oeuvre correspond à un rapport molaire soufre/alkylphénol compris entre 0,8 et 2.The quantity of sulfur used corresponds to a sulfur / alkylphenol molar ratio of between 0.8 and 2.

L'opération de sulfurisation-neutralisation est favorablement réalisée à une température comprise entre 145 et 175 °C et de préférence entre 155 et 170 °C, éventuellement en présence d'une amine comme ci-dessus indiqué pour l'étape générale de neutralisation.The sulfurization-neutralization operation is favorably carried out at a temperature between 145 and 175 ° C and preferably between 155 and 170 ° C, optionally in the presence of an amine as above indicated for the general neutralization step.

L'opération de carbonatation est alors réalisée à une température comprise entre 155 et 180 °C et de préférence entre 165 et 175 °C, éventuellement en présence d'ions halogénures comme ci-dessus indiqué.The carbonation operation is then carried out at a temperature between 155 and 180 ° C and preferably between 165 and 175 ° C, optionally in the presence of halide ions as above indicated.

La présente invention a également pour objet le produit obtenu selon le procédé ci-dessus décrit ainsi que son application comme additif pour améliorer les propriétés détergentes et dispersantes des huiles lubrifiantes.The present invention also relates to the product obtained according to the process described above as well as its application as an additive to improve the detergent and dispersing properties of lubricating oils.

La quantité d'additif à utiliser est fonction de l'utilisation future desdites huiles. Ainsi pour une huile pour moteur à essence, la quantité d'additif à ajouter est généralement comprise entre 1 et 2,5 % ; pour une huile pour moteur diesel elle est généralement comprise entre 1,8 et 4 %, pour une huile pour moteur marin, celle-ci peut aller jusqu'à 30 %.The amount of additive to be used depends on the future use of said oils. Thus for a petrol engine oil, the amount of additive to be added is generally between 1 and 2.5%; for a diesel engine oil it is generally between 1.8 and 4%, for a marine engine oil, this can go up to 30%.

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

Des additifs supplémentaires peuvent également être présents dans lesdites huiles lubrifiantes à côté des détergents-dispersants obtenus selon le procédé de l'invention ; on peut citer par exemple des additifs anti-oxydants, anti-corrosion, des additifs dispersants sans cendres.Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; mention may, for example, be made of antioxidant, anti-corrosion additives, ashless dispersant additives.

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

Exemples 1 à 8Examples 1 to 8 A) Sulfurisation, déshydratation, neutralisationA) Sulfurization, dehydration, neutralization

On charge sous agitation :

  • du dodécylphénol (DDP)
  • du soufre
  • de la chaux
  • du chlorure de calcium, de zinc ou d'ammonium
  • de l'huile
Charging is carried out with stirring:
  • dodecylphenol (DDP)
  • sulfur
  • lime
  • calcium, zinc or ammonium chloride
  • oil

On chauffe jusqu'à 160 °C puis on ajoute lentement un mélange de glycol et d'éthylhexanol en 80 minutes, sous légère dépression.

  • On reste 1 heure à 165 OC sous legère dépression (930 102 Pa)
  • On recueille un distillat D1.
The mixture is heated to 160 ° C. and then a mixture of glycol and ethylhexanol is slowly added over 80 minutes, under slight depression.
  • We stay 1 hour at 165 O C under slight depression (930 10 2 Pa)
  • A distillate D 1 is collected.

B) CarbonatationB) Carbonation

On carbonate pendant 100 minutes à 165-175 °C à pression atmosphérique puis on ajoute le restant d'huile de dilution.Carbonated for 100 minutes at 165-175 ° C at atmospheric pressure and then the remaining dilution oil is added.

C) Elimination du glycolC) Elimination of glycol

On serre le vide progressivement jusqu'à 66,5 102 Pa. On chauffe à 190 OC pendant 1 heure, puis on effectue un stripping à l'azote pendant 1 heure à 190 °C.Is tightened gradually to 66.5 × 10 2 Pa vacuum. 190 O is heated for 1 hour, followed by stripping with nitrogen for 1 hour at 190 ° C.

On recueille un distillat D2.A D 2 distillate is collected.

D) FiltrationD) Filtration Caractéristiques du produitProduct Features

Mesure du taux de sédimentsSediment 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 6 000 t/mn
  • force centrifuge relative 10000
The% of sediments are measured according to standard ASTM D 2273-67, with the following modifications, however:
  • spin speed of the centrifuge 6,000 rpm
  • relative centrifugal force 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)the product to be analyzed is diluted to a quarter in gasoline E (25 cm 3 of product to be analyzed + 75 cm 3 of gasoline E)

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

Test de compatibilitéCompatibility 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 pendant 24 heures puis centrifugée dans les conditions suivantes :

  • vitesse de rotation 6 000 t/mn
  • force centrifuge relative 10 000
  • durée de centrifugation 1 heure.
  • puis on mesure le taux de sédiments.
The solution is stored for 24 hours and then centrifuged under the following conditions:
  • rotation speed 6,000 rpm
  • relative centrifugal force 10,000
  • centrifugation time 1 hour.
  • then measure the sediment rate.

Les quantités de réactifs mises en œuvre aux différentes étapes sont indiquées aux tableaux 1 à IV ; les résultats obtenus figurent aux tableaux III et IV.The quantities of reagents used in the various stages are indicated in Tables 1 to IV; the results obtained appear in Tables III and IV.

Exemples 9 à 11Examples 9 to 11 A) NeutralisationA) Neutralization

On charge :

  • - du dodécylphénol sulfurisé contenant environ 11 % de soufre
  • - de la chaux
  • - de l'huile de dilution.
We charge:
  • - sulfurized dodecylphenol containing about 11% sulfur
  • - lime
  • - dilution oil.

On chauffe jusqu'à 130 °C, puis on ajoute du glycol en mélange avec de l'éthylhexanol ou du butoxy-2 éthanol.The mixture is heated to 130 ° C., then glycol is added as a mixture with ethylhexanol or 2-butoxyethanol.

On chauffe jusqu'à 145°C, puis on reste sous vide de 345 102 Pa pendant 30 minutes.The mixture is heated to 145 ° C., then it remains under a vacuum of 345 × 10 2 Pa for 30 minutes.

On recueille un distillat D1.A distillate D 1 is collected.

On casse le vide.We break the vacuum.

B) CarbonatationB) Carbonation

On carbonate pendant 100 minutes à pression atmosphérique ; la température de début de carbonatation est de 145 °C, puis on chauffe pour atteindre 170 °C en fin de carbonatation.Carbonate for 100 minutes at atmospheric pressure; the temperature at the start of carbonation is 145 ° C., then it is heated to reach 170 ° C. at the end of carbonation.

On ajoute le restant d'huile de dilution.The remaining dilution oil is added.

C) Elimination du glycolC) Elimination of glycol

On serre progressivement le vide jusqu'à 66,5 102 Pa tout en chauffant jusqu'à 190 °C. On reste une heure à 190 °C, puis on effectue un stripping à l'azote pendant 1 heure à 190 °C.The vacuum is gradually tightened to 66.5 10 2 Pa while heating up to 190 ° C. It remains for one hour at 190 ° C., then stripping is carried out with nitrogen for 1 hour at 190 ° C.

On recueille un distillat D2-D) On filtreCollect a distillate D 2 -D) Filter

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

Exemples 12 à 23 et 28Examples 12 to 23 and 28 A) Sulfurisation, déshydratation, neutralisationA) Sulfurization, dehydration, neutralization

On charge sous agitation :

  • - du dodécylphénol
  • - du soufre
  • - de la chaux
  • - du chlorure de calcium ou d'ammonium
  • - de l'huile
Charging is carried out with stirring:
  • - dodecylphenol
  • - sulfur
  • - lime
  • - calcium or ammonium chloride
  • - oil

On chauffe jusqu'à 155 °C sous légère dépression (930 102 Pa), on ajoute lentement une première charge d'alcool constituée d'un mélange de glycol et de butoxyéthanol ou butoxypropanol en 30 minutes, puis une deuxième charge de butoxyéthanol ou butoxypropanol seul en 40 minutes.The mixture is heated to 155 ° C. under slight depression (930 10 2 Pa), a first charge of alcohol consisting of a mixture of glycol and butoxyethanol or butoxypropanol is slowly added over 30 minutes, then a second charge of butoxyethanol or butoxypropanol alone in 40 minutes.

On reste 1 heure à 165 °C sous légère dépression (930 102 Pa).We stay 1 hour at 165 ° C under slight vacuum (930 10 2 Pa).

On recueille un distillat D1.A D1 distillate is collected.

B) CarbonatationB) Carbonation

On carbonate pendant 120 minutes à 165 °C à pression atmosphérique puis on ajoute lentement l'huile de dilution.It is carbonated for 120 minutes at 165 ° C. at atmospheric pressure and then the dilution oil is added slowly.

C) Elimination du glycolC) Elimination of glycol

On serre le vide progressivement jusqu'à 66,5 102 Pa. On chauffe à 190 °C pendant 1 heure, puis on effectue un stripping à l'azote pendant 1 heure à 190 °C.The vacuum is gradually tightened to 66.5 × 10 2 Pa. The mixture is heated to 190 ° C. for 1 hour, then a nitrogen stripping is carried out for 1 hour at 190 ° C.

On recueille un distillat D2.A D2 distillate is collected.

D) FiltrationD) Filtration

Les quantités de réactifs mises en œuvre aux différentes étapes sont indiquées aux tableaux V à VIII ; les résultats obtenus figurent aux tableaux VI et VIII.The quantities of reagents used in the various stages are indicated in Tables V to VIII; the results obtained appear in Tables VI and VIII.

Exemple 24Example 24

On réalise l'opération décrite à l'exemple 13 en introduisant le mélange de 10 g de glycol et de 10 g de butoxyéthanol (1ère charge) dès le départ (et non lorsque la température atteint 155 °C).The operation described in Example 13 is carried out by introducing the mixture of 10 g of glycol and 10 g of butoxyethanol (1st charge) from the start (and not when the temperature reaches 155 ° C).

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

Exemple 25Example 25

On réalise l'opération décrite à l'exemple 12 en introduisant les 10 g de glycol au départ puis les 10 g de butoxyéthanol à 155 °C.The operation described in Example 12 is carried out by introducing the 10 g of glycol at the start and then the 10 g of butoxyethanol at 155 ° C.

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

Exemple 26Example 26

On réalise les opérations décrites aux exemples 9 à 11 à partir d'un dodécylphénol sulfurisé contenant environ 8 % de soufre.The operations described in Examples 9 to 11 are carried out from a sulfurized dodecylphenol containing approximately 8% of sulfur.

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

Exemple 27Example 27

On réalise l'opération décrite à l'exemple 26 en mettant en œuvre un dodécylphénol contenant 7 % de soufre et une quantité supplémentaire de soufre.The operation described in Example 26 is carried out using a dodecylphenol containing 7% sulfur and an additional quantity of sulfur.

Les quantités de réactifs mises en œuvre figurent aux tableaux VII et VIII ; les résultats obtenus figurent au tableau VIII.
(Voir tableaux pages suivantes)The quantities of reagents used are shown in Tables VII and VIII; the results obtained are shown in Table VIII.
(See tables on the following pages)

Figure imgb0003
Figure imgb0003
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Figure imgb0004
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Figure imgb0007
Figure imgb0007
Figure imgb0008
Figure imgb0008
Figure imgb0009
Figure imgb0009
Figure imgb0010
Figure imgb0010

Claims (13)

1. A process for the preparation of sulphurised alkylphenates of alkaline-earth metals with a high degree of alkalinity, comprising the following steps :
- neutralisation of a sulphurised alkylphenol by an alkaline-earth base in the presence of dilution oil, glycol and an alcohol with a boiling point of higher than 150 °C,
- filtration after distillation of the water and the glycol,
- carbonation of the filtrate followed by distillation of the water and the glycol and then filtration to eliminate sediments, said process being characterised in that;
- the neutralisation and carbonation operations are carried out in the presence of halide ions, and
- that the following amounts of reactants are used :
the amount of alcohol corresponds to an alcohol/glycol molar ratio of higher than or equal to 0.4,
the amount of alkaline-earth base coresponds to an alkaline-earth base/alkylphenol molar ratio of between 0.4 and 3,
the amount of glycol corresponds to an alkaline-earth base/glycol molar ratio of between 2.6 and 8, the amount of halide ions corresponds to a ratio of gram-atom of halide/mole of alkaline-earth base of between 0.01 and 0.15, and
the amount of CO2 corresponds to a CO2/alkaline-earth metal molar ratio of between 0.25 and 0.75.
2. A process according to claim 1 characterised in that:
- the alcohol/glycol molar ratio is from 0.4 to 10,
- the alkaline-earth baselalkylphenol molar ratio is from 0.6 to 2.5
- the alkaline-earth base/glycol molar ratio is from 2.7 to 6,
- the ratio of gram-atom of halide/mole of alkaline-earth base is from 0.015 to 0.09.
3. A process according to either one of the preceding claims characterized in that the alkaline-earth base is calcium hydroxide.
4. A process according to any one of the preceding claims characterised in that the alcohol with a boiling point of higher than 150 °C is a C6-C14 alkanol or an alkoxyalkanol.
5. A process according to claim 4 characterised in that the alcohol is ethylhexanol or 2-butoxyethanol..
6. A process according to claim 2 characterised in that the ratio of gram-atom of halide/mole of alkaline-earth base is from 0.015 to 0.09.
7. A process according to any one of the preceding claims characterised in that the halide ions are chloride ions.
8. A process according to claim 7 characterised in that the chloride ions are introduced by way of CaCl2, ZnCl2 or NH4Cl.
9. A process according to any one of the preceding claims characterised in that the neutralisation operation is carried out in the presence of an amine, in an amount corresponding to an amine/alkaline- earth base molar ratio which can be up to 0.2.
10. A process according to claim 9 characterised in that the amine is ethylene diamine or tris(3-oxa-6-aminohexyl) amine.
11. A process according to any one of the preceding claims characterised in that the neutralisation operation is carried out in the presence of acetic acid, in an amount corresponding to an acetic acid/alkaline-earth base molar into ratio which can be up to 0.2.
12. A process according to claim 11 characterised in that the acetic acid/alkaline-earthlbase molar ratio can be up to 0.1.
13. Use of the product obtained by the process as set forth in any one of the preceding claims as an additive for improving the detergent and dispersant properties of lubricating oils.
EP83401269A 1982-06-24 1983-06-20 Process for the preparation of sulphurized alkylphenates for use as lubricating oil addtives Expired EP0102255B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83401269T ATE22112T1 (en) 1982-06-24 1983-06-20 PROCESS FOR PRODUCTION OF SULFURATED ALKALINE-EARTH METAL ALKYLPHENATES USABLE AS LUBRICATION OIL ADDITIVE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211060A FR2529226B1 (en) 1982-06-24 1982-06-24 PROCESS FOR THE PREPARATION OF SULFURIZED ALKYLPHENATES OF ALKALINE EARTH METALS FOR USE AS ADDITIVES FOR LUBRICATING OILS
FR8211060 1982-06-24

Publications (2)

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EP0102255B1 true EP0102255B1 (en) 1986-09-10

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AT (1) ATE22112T1 (en)
AU (1) AU557851B2 (en)
BR (1) BR8303347A (en)
CA (1) CA1182628A (en)
DE (1) DE3366063D1 (en)
DK (1) DK162398C (en)
ES (1) ES8403964A1 (en)
FR (1) FR2529226B1 (en)
GB (1) GB2123022B (en)
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FR2564830B1 (en) * 1984-05-25 1986-09-19 Orogil PROCESS FOR THE PREPARATION OF ALKALYLARYL SULFONATES OF ALKALINO-EARTH METALS FROM LINEAR ALKYLARYL SULFONIC ACIDS AND DETERGENT-DISPERSANT ADDITIVES FOR LUBRICANT OILS OBTAINED
EP0212922B1 (en) * 1985-08-13 1991-01-02 Exxon Chemical Patents Inc. Overbased additives
FR2587353B1 (en) * 1985-09-17 1987-11-20 Orogil NOVEL HYDROLYSIS-STABLE SURALKALINIZED DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS AND PROCESS FOR PREPARING THE SAME
US4776969A (en) * 1986-03-31 1988-10-11 Exxon Chemical Patents Inc. Cyclic phosphate additives and their use in oleaginous compositions
NZ221128A (en) * 1986-08-08 1989-09-27 Chevron Res Overbased sulphurised alkylphenols as lube oil additives
GB8621343D0 (en) * 1986-09-04 1986-10-15 Exxon Chemical Patents Inc Overbased alkali metal additives
JPH04183792A (en) * 1990-11-19 1992-06-30 Idemitsu Kosan Co Ltd Perbasic sulfurized alkaline earth metal phenate and use thereof
GB9213723D0 (en) * 1992-06-27 1992-08-12 Bp Chemicals Additives Process for the production of lubricating oil additives
US5292443A (en) * 1992-08-21 1994-03-08 Texaco Inc. Process for producing neutralized sulfurized alkylphenate lubricant detergent additive
US5529705A (en) * 1995-03-17 1996-06-25 Chevron Chemical Company Methods for preparing normal and overbased phenates
US5759966A (en) * 1996-10-01 1998-06-02 Chevron Chemical Company High overbased metal sulfurized alkyphenates
US20030195126A1 (en) * 2002-04-12 2003-10-16 Boons Cornelis Hendrikus Maria Carboxylated detergent-dispersant-containing compositions having improved properties in lubricating oils
US7163911B2 (en) * 2003-05-22 2007-01-16 Chevron Oronite Company Llc Carboxylated detergent-dispersant additive for lubricating oils
US20040235682A1 (en) * 2003-05-22 2004-11-25 Chevron Oronite Company Llc Low emission diesel lubricant with improved corrosion protection
US7435709B2 (en) * 2005-09-01 2008-10-14 Chevron Oronite Company Llc Linear alkylphenol derived detergent substantially free of endocrine disruptive chemicals
US8399388B2 (en) 2009-07-01 2013-03-19 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same

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DE3366063D1 (en) 1986-10-16
PH19427A (en) 1986-04-15
DK162398C (en) 1992-03-23
JPS5946262A (en) 1984-03-15
EP0102255A1 (en) 1984-03-07
GB2123022A (en) 1984-01-25
JPS6242957B2 (en) 1987-09-10
US4514313A (en) 1985-04-30
AU1612583A (en) 1984-01-05
BR8303347A (en) 1984-02-07
AU557851B2 (en) 1987-01-08
PT76930A (en) 1983-07-01
MX26983A (en) 1994-03-31
ES523542A0 (en) 1984-04-01
GB8317023D0 (en) 1983-07-27
GR78596B (en) 1985-09-27
CA1182628A (en) 1985-02-19
GB2123022B (en) 1985-11-13
FR2529226B1 (en) 1987-01-16
ES8403964A1 (en) 1984-04-01
PT76930B (en) 1986-03-11
ZA834555B (en) 1984-03-28
DK162398B (en) 1991-10-21

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