EP0002644B1 - Basic complex magnesium compounds and their application to the preparation of detergent dispersant additives for lubricating oils - Google Patents

Basic complex magnesium compounds and their application to the preparation of detergent dispersant additives for lubricating oils Download PDF

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Publication number
EP0002644B1
EP0002644B1 EP78400238A EP78400238A EP0002644B1 EP 0002644 B1 EP0002644 B1 EP 0002644B1 EP 78400238 A EP78400238 A EP 78400238A EP 78400238 A EP78400238 A EP 78400238A EP 0002644 B1 EP0002644 B1 EP 0002644B1
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Prior art keywords
magnesium
magnesium oxide
active
methanol
preparation
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German (de)
French (fr)
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EP0002644A1 (en
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Jean-Pierre Tassara
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DROGIL
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DROGIL
Orogil SA
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products

Definitions

  • the present invention relates to new basic magnesium complexes and their application as intermediates for the manufacture of detergent-dispersant additives for lubricating oils.
  • such complexes can be prepared by reacting magnesium with anhydrous methanol in the presence of a volatile aromatic solvent then carbonation of the solution with carbon dioxide.
  • the disadvantage of such a process is that magnesium is an expensive product and difficult to handle; in addition, magnesium reacts on! methanol releasing hydrogen, which makes the process dangerous.
  • alkaline earth metal sulfonates from basic alkaline earth metal complexes, according to a process consisting in preparing a complex by reaction of a alkaline earth metal, methanol and CO 2 oxide, to emulsify said complex in the presence of a volatile solvent with an oil-soluble sulfonate, to remove methanol by distillation, to hydrolyze the medium to transform the complex into carbonate and then to dehydrate ; this sequence of operations is carried out a sufficient number of times to obtain a sulfonate of desired basicity.
  • Such a process is well suited to the preparation of barium or calcium sulfonates, since the barium and calcium oxides are products having a high basicity and good solubility in alcohols.
  • this process cannot make it possible to prepare magnesium sulfonates industrially even if active magnesium oxide is used; in fact, the processes of alkalinization with barium or calcium compounds used to prepare basic or superalkalinized detergent-dispersants cannot be modified simply for the preparation of detergents-dispersants containing magnesium, and this because of the low basicity and the low solubility of magnesium compounds.
  • the Applicant has found new magnesium complexes obtained from magnesium oxide, soluble in methanol, which can be isolated, optionally stored and used to prepare, in a particularly simple manner, oil-soluble detergent-dispersant compounds.
  • the new basic magnesium complexes object of the invention, are characterized in that they are obtained by suspending in methanol, a compound based on "active" magnesium oxide, the amount of magnesium oxide "active” up to 10% of the weight of methanol, and subjecting said suspension to a carbonation operation using carbon dioxide at a temperature below 50 ° C, until the end of absorption of carbon dioxide .
  • the term “active” magnesium oxide will be used to mean magnesium oxide capable of reacting with methanol and carbon dioxide and which, after carbonation, is completely dissolved in methanol; this type of oxide can be obtained by gentle calcination of the basic magnesium carbonate, for example at a temperature of the order of 500 to 700 ° C for at least 3 hours; the specific surface of this type of oxide is greater than 80 m2 / g, and generally greater than 100 m2 / g.
  • This type of oxide prepared by gentle calcination, will preferably be used to prepare the new complexes which are the subject of the invention.
  • partially active magnesium oxides generally containing more than 50% of magnesium oxide soluble in methanol after carbonation; such oxides can be obtained by calcination of basic magnesium carbonate at a temperature above 700 ° C., and have a specific surface area less than that of the "active" oxides. Since such oxides are only partially soluble in methanol after carbonation, it will be necessary to remove the insoluble part before storage or use of the complexes which are the subject of the invention.
  • the new magnesium complexes which are the subject of the invention are difficult to describe precisely; they could correspond to a solution in methanol of a mixture of the following compounds:
  • the new complexes which are the subject of the invention are preferably stored at atmospheric pressure under an atmosphere of carbon dioxide; for stability problems, it is preferable to prepare them from suspensions containing not more than 8% of "active" magnesium oxide in methanol and more particularly from suspensions containing 3 to 7% of "active" magnesium oxide.
  • the carbonation operation can be carried out at atmospheric pressure or under carbon dioxide pressure; for a preferred embodiment of the invention, said operation is carried out under a carbon dioxide pressure of between 5 and 50 kg / cm2, and generally greater than 8 kg / cm2.
  • the present invention also relates to the application of said basic magnesium complexes for the manufacture of neutral or overbased detergent-dispersant additives for lubricating oils.
  • Neutral detergent-dispersants can be prepared by simple addition of the said complexes to optionally sulfurized alkylphenols, alkylbenzenesulfonic, alkylsalicylic, alkylphosphonic, alkylthio-phosphonic acids, etc., followed by thermal decomposition of the said complexes, stripping with an inert gas. , hydrolysis ....
  • overbased detergent-dispersants can be obtained by simple addition to neutral alkylphenates, alkylbenzene sulfonates, alkylsalicylates, alkylphosphonates, alkylthiophosphonates ... or to alkenyl succinimides, followed by decomposition of said complexes by thermal means, stripping with a gas. inert, hydrolysis ....
  • Said complexes forming the subject of the invention are very particularly suitable for the preparation of optionally sulfurized alkylphenates carrying one or more C 6 ⁇ C 60 , preferably C 9 C, S alkyl substituents, of mass alkylbenzenesulfonates molecular greater than 300, neutral or overbased and overbased alkenylsuccinimides, the alkenyl radical of which contains at least 50 carbon atoms.
  • Neutral magnesium alkylphenates can be prepared in a particularly satisfactory manner by adding said basic magnesium complexes to a solution of optionally sulfurized alkylphenol in dilution oil, distilling methanol and heating the reaction medium to 150 ° -220 °. C to remove all traces of volatile products; the quantity of magnesium complex to be used corresponds to approximately 1 gram atom of magnesium for 2 phenolic OH groups.
  • the neutral alkylphenates thus obtained can be overbased by addition of basic magnesium complex at a temperature at least equal to that of methanol distillation, then heating of the reaction medium to 150-220 ° C to remove all traces of volatile products; this operation can optionally be carried out in the presence of alcohols with a boiling point of between 100 and 200 ° C. such as isobutanol, hexanol, 2-ethylhexanol; the amount of complex to be used is such that the ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of magnesium of the neutral phenate is less than or equal to 4 and preferably between 2 and 3.
  • the neutral magnesium alkylbenzene sulfonates can be prepared in a manner analogous to that described above for the neutral alkylphenates from alkylbenzene sulfonic acid; the quantity of magnesium complex to be used corresponds to 1 gram atom of magnesium for 2 sulfonic acid groups; according to a variant of said process, the complex can be introduced into the sulfonic acid solution at the methanol distillation temperature.
  • the overbased magnesium alkylbenzene sulfonates can be prepared in a similar manner to that described for the overbased alkylphenates from neutral magnesium alkylbenzene sulfonates; the quantity of magnesium complex to be used is such that the ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of magnesium of the neutral sulfonate is less than or equal to 8, preferably between 2 and 7.
  • alkalinized alkylbenzenesulfonates can be prepared by replacing all or part of the neutral magnesium sulfonates with neutral alkylbenzenesulfonates of calcium or barium.
  • the overbased alkenylsuccinimides can be prepared by adding said basic magnesium complexes to a solution of alkenylsuccinimide in dilution oil in the presence of an alcohol with a boiling point of between 100 and 200 ° C., optionally adding water. to disperse any gel particles that may form and heating the reaction medium to 180-220 ° C. under 20 mm of mercury to remove the volatile products; the quantity of magnesium complex to be used corresponds to a ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of alkenylsuccinimide nitrogen less than or equal to 3 and preferably between 1 and 2 .
  • the mixture is brought back by relaxation to atmospheric pressure and can then be kept in an airtight container indefinitely.
  • the prepared mixture contains 2% by weight of magnesium.
  • the complex obtained contains 1.85% magnesium.
  • thermometric sheath In a 1 liter flask, fitted with a stirring system, a distillation head, a pouring bulb and a thermometric sheath,
  • the apparatus is optionally placed under a CO 2 sweep, then 300 g of magnesium complex prepared in Example 1 b) are poured in for 1 hour with stirring.
  • the methanol is distilled at the end of the addition of the complex, then the mixture is heated to 180 ° C. to remove all traces of volatile products.
  • Example 6 The neutral product obtained in Example 6 is maintained between 70 and 80 ° C, then 300 g of magnesium complex prepared in Example 1 b) are introduced over 2 hours.
  • the product is heated for 1 hour at 180 ° C to remove all traces of volatile products.
  • Example 1 b The temperature is maintained between 70 and 80 ° C. and then 900 g of complex prepared in Example 1 b) are introduced over 4 hours.
  • Distillation is carried out under vacuum (20 mmHg) for 1 hour at 180 ° C. to remove the volatile products.
  • Example 5 125 g of magnesium complex prepared in Example 5 and containing 4% magnesium are added over 30 minutes, the temperature of the medium going from 20 to 45 ° C.
  • the mixture is heated to 140 ° C. to remove the methanol and the water coming from the neutralization of the sulfonic acid.
  • the mixture is heated to 180 ° C. under 20 min of mercury to remove the alcohols present in the medium.
  • the mixture is maintained at 70-80 ° C. and 300 g of magnesium complex prepared in Example 5 are introduced over 2 hours.
  • the mixture is heated to 180 ° C under a pressure of 20 mm of mercury to remove the alcohols present in the medium.
  • the temperature is maintained between 70 and 80 ° C. and 190 g of magnesium complex prepared in Example 1 b) are introduced over one hour, then 30 g of water are added in 10 minutes after the end of the addition of the complex.
  • the mixture is then brought to 180 ° C. under 20 mm of mercury to remove the remaining methanol, water and n-hexanol.

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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)

Description

La présente invention a pour objet de nouveaux complexes basiques de magnésium et leur application comme intermédiaires pour la fabrication d'additifs détergents-dispersants pour huiles lubrifiantes.The present invention relates to new basic magnesium complexes and their application as intermediates for the manufacture of detergent-dispersant additives for lubricating oils.

Il est connu d'utiliser des complexes basiques de magnésium pour préparer des additifs dispersants pour huiles lubrifiantes.It is known to use basic magnesium complexes to prepare dispersant additives for lubricating oils.

D'après le brevel américain n° 3.761.411, de tels complexes peuvent être préparés par réaction du magnésium avec du méthanol anhydre en présence d'un solvant aromatique volatil puis carbonation de la solution par du gaz carbonique. L'inconvénient d'un tel procédé consiste en ce que le magnésium est un produit cher et difficile à manipuler; de plus, le magnésium réagit sur !e méthanol en libérant de l'hydrogène, ce qui rend le procédé dangereux.According to the American brevel no. 3,761,411, such complexes can be prepared by reacting magnesium with anhydrous methanol in the presence of a volatile aromatic solvent then carbonation of the solution with carbon dioxide. The disadvantage of such a process is that magnesium is an expensive product and difficult to handle; in addition, magnesium reacts on! methanol releasing hydrogen, which makes the process dangerous.

D'après le brevet américain n° 3.878.116, il est également connu d'obtenir des sulfonates de métaux alcalino-terreux à partir de complexes basiques de métaux alcalino-terreux, selon un procédé consistant à préparer un complexe par réaction d'un oxyde de métal alcalino-terreux, de méthanol et de CO2, à émulsifier ledit complexe en présence d'un solvant volatil avec un sulfonate oléosoluble, à éliminer le méthanol par distillation, à hydrolyser le milieu pour transformer le complexe en carbonate puis à déshydrater; cette suite d'opérations est réalisée un nombre de fois suffisant pour obtenir un sulfonate de basicité désirée.According to American Patent No. 3,878,116, it is also known to obtain alkaline earth metal sulfonates from basic alkaline earth metal complexes, according to a process consisting in preparing a complex by reaction of a alkaline earth metal, methanol and CO 2 oxide, to emulsify said complex in the presence of a volatile solvent with an oil-soluble sulfonate, to remove methanol by distillation, to hydrolyze the medium to transform the complex into carbonate and then to dehydrate ; this sequence of operations is carried out a sufficient number of times to obtain a sulfonate of desired basicity.

Un tel procédé est bien adapté à la préparation de sulfonates de baryum ou de calcium, car les oxydes de baryum et de calcium sont des produits présentant une forte basicité et une bonne solubilité dans les alcools. Par contre, tel que décrit, ce procédé ne peut permettre de préparer industriellement des sulfonates de magnésium même si l'on met en oeuvre de l'oxyde de magnésium actif; en effet, les procédés d'alca- linisation par des composés du baryum ou du calcium utilisés pour préparer des détergents-dispersants basiques ou suralcalinisés, ne peuvent être modifiés simplement en vue de la préparation de détergents-dispersants contenant du magnésium, et ce en raison de la faible basicité et de la faible solubilité des composés du magnésium.Such a process is well suited to the preparation of barium or calcium sulfonates, since the barium and calcium oxides are products having a high basicity and good solubility in alcohols. On the other hand, as described, this process cannot make it possible to prepare magnesium sulfonates industrially even if active magnesium oxide is used; in fact, the processes of alkalinization with barium or calcium compounds used to prepare basic or superalkalinized detergent-dispersants cannot be modified simply for the preparation of detergents-dispersants containing magnesium, and this because of the low basicity and the low solubility of magnesium compounds.

La demanderesse a trouvé de nouveaux complexes de magnésium obtenus à partir d'oxyde de magnésium, solubles dans le méthanol, pouvant être isolés, stockés éventuellement et utilisés pour préparer, d'une manière particulièrement simple, des composés détergents-dispersants oléosolubles.The Applicant has found new magnesium complexes obtained from magnesium oxide, soluble in methanol, which can be isolated, optionally stored and used to prepare, in a particularly simple manner, oil-soluble detergent-dispersant compounds.

Les nouveaux complexes basiques de magnésium, objet de l'invention, sont caractérisés en ce qu'ils sont obtenus en mettant en suspension dans du méthanol, un composé à base d'oxyde de magnésium "actif", la quantité d'oxyde de magnésium "actif" pouvant atteindre 10% du poids de méthanol, et en soumettant ladite suspension à une opération de carbonatation à l'aide de gaz carbonique à une température inférieure à 50°C, jusqu'à la fin de l'absorption de gaz carbonique.The new basic magnesium complexes, object of the invention, are characterized in that they are obtained by suspending in methanol, a compound based on "active" magnesium oxide, the amount of magnesium oxide "active" up to 10% of the weight of methanol, and subjecting said suspension to a carbonation operation using carbon dioxide at a temperature below 50 ° C, until the end of absorption of carbon dioxide .

Dans la présente invention, on appellera oxyde de magnésium "actif", de l'oxyde de magnésium capable de réagir avec le méthanol et le gaz carbonique et qui, après carbonatation, se trouve complètement dissout dans le méthanol; ce type d'oxyde peut être obtenu par calcination douce du carbonate basique de magésium, par exemple à une température de l'ordre de 500 à 700°C pendant au moins 3 heures; la surface spécifique de ce type d'oxyde est supérieure à 80 m2/g, et généralement supérieure à 100 m2/g.In the present invention, the term “active” magnesium oxide will be used to mean magnesium oxide capable of reacting with methanol and carbon dioxide and which, after carbonation, is completely dissolved in methanol; this type of oxide can be obtained by gentle calcination of the basic magnesium carbonate, for example at a temperature of the order of 500 to 700 ° C for at least 3 hours; the specific surface of this type of oxide is greater than 80 m2 / g, and generally greater than 100 m2 / g.

Ce type d'oxyde, préparé par calcination douce, sera de préférence utilisé pour préparer les nouveaux complexes faisant l'objet de l'invention.This type of oxide, prepared by gentle calcination, will preferably be used to prepare the new complexes which are the subject of the invention.

Il est toutefois possible d'utiliser des oxydes de magnésium partiellement actifs contenant généralement plus de 50% d'oxyde de magnésium soluble dans le méthanol après carbonatation; de tels oxydes peuvent être obtenus par calcination du carbonate basique de magnésium à une température supérieure à 700°C, et présentent une surface spécifique inférieure à celle des oxydes "actifs". De tels oxydes n'étant que partiellement solubles dans le méthanol après carbonatation, il sera nécessaire d'éliminer la partie insoluble préalablement au stockage ou à l'emploi des complexes faisant l'objet de l'invention.It is however possible to use partially active magnesium oxides generally containing more than 50% of magnesium oxide soluble in methanol after carbonation; such oxides can be obtained by calcination of basic magnesium carbonate at a temperature above 700 ° C., and have a specific surface area less than that of the "active" oxides. Since such oxides are only partially soluble in methanol after carbonation, it will be necessary to remove the insoluble part before storage or use of the complexes which are the subject of the invention.

Les nouveaux complexes de magnésium objet de l'invention sont difficiles à décrire précisément; ils pourraient correspondre à une solution dans le méthanol d'un mélange des composés suivants:

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
The new magnesium complexes which are the subject of the invention are difficult to describe precisely; they could correspond to a solution in methanol of a mixture of the following compounds:
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004

Les nouveaux complexes objet de l'invention, sont de préférence conservés à pression atmosphérique sous atmosphère de gaz carbonique; pour des problèmes de stabilité, il est préférable de les préparer à partir de suspensions ne contenant pas plus de 8% d'oxyde de magnésium "actif" dans le méthanol et plus particulièrement à partir de suspensions contenant de 3 à 7% d'oxyde de magnésium "actif".The new complexes which are the subject of the invention are preferably stored at atmospheric pressure under an atmosphere of carbon dioxide; for stability problems, it is preferable to prepare them from suspensions containing not more than 8% of "active" magnesium oxide in methanol and more particularly from suspensions containing 3 to 7% of "active" magnesium oxide.

L'opération de carbonatation peut être réalisée à pression atmosphérique ou sous pression de gaz carbonique; pour une réalisation préférentielle de l'invention, ladite opération est réalisée sous une pression de gaz carbonique comprise entre 5 et 50 kg/cm2, et généralement supérieure à 8 kg/cm2.The carbonation operation can be carried out at atmospheric pressure or under carbon dioxide pressure; for a preferred embodiment of the invention, said operation is carried out under a carbon dioxide pressure of between 5 and 50 kg / cm2, and generally greater than 8 kg / cm2.

La présente invention a également pour objet l'application desdits complexes basiques de magnésium pour la fabrication d'additifs détergents-dispersants neutres ou suralcalinisés pour huiles lubrifiantes.The present invention also relates to the application of said basic magnesium complexes for the manufacture of neutral or overbased detergent-dispersant additives for lubricating oils.

A titre d'exemple, on peut citer l'application desdits complexes pour la fabrication d'alkylphénates éventuellement sulfurisés, d'alkylbenzènesulfonates, d'alkylsalicylates, d'alkylphosphonates, d'alkylthiophosphonates.... neutres ou suralcalinisés ou d'alcénylsuccinimides suralcalinisés contenant plus de 50 atomes de carbone dans leur chaîne alcényle.By way of example, mention may be made of the application of said complexes for the production of optionally sulfurized alkylphenates, alkylbenzenesulfonates, alkylsalicylates, alkylphosphonates, alkylthiophosphonates .... neutral or overalkalinated or overalkalinated alkenylsuccinimides containing more than 50 carbon atoms in their alkenyl chain.

Des détergents-dispersants neutres pourront être préparés par simple addition desdits complexes à des alkylphénols éventuellement sulfurisés, des acides alkylbenzénesulfoniques, alkylsalicyliques, alkylphosphoniques, alkylthio- phosphoniques.... suivie d'une décomposition desdits complexes par voie thermique, stripping par un gaz inerte, hydrolyse....Neutral detergent-dispersants can be prepared by simple addition of the said complexes to optionally sulfurized alkylphenols, alkylbenzenesulfonic, alkylsalicylic, alkylphosphonic, alkylthio-phosphonic acids, etc., followed by thermal decomposition of the said complexes, stripping with an inert gas. , hydrolysis ....

De même des détergents-dispersants suralcalinisés pourront être obtenus par simple addition à des alkylphénates, alkylbenzéne- sulfonates, alkylsalicylates, alkylphosphonates, alkylthiophosphonates... neutres ou à des alcénylsuccinimides, suivie d'une décomposition desdits complexes par voie thermique, stripping par un gaz inerte, hydrolyse....Similarly, overbased detergent-dispersants can be obtained by simple addition to neutral alkylphenates, alkylbenzene sulfonates, alkylsalicylates, alkylphosphonates, alkylthiophosphonates ... or to alkenyl succinimides, followed by decomposition of said complexes by thermal means, stripping with a gas. inert, hydrolysis ....

Lesdits complexes faisant l'objet de l'invention sont tout particulièrement adaptés à la pré paration d'alkylphénates éventuellement sulfurisés portant un ou plusieurs substituants alkyle en C6―C60, de préférence en C9 C,S, d'alkylbenzènesulfonates de masse moléculaire supérieure à 300, neutres ou suralcalinisés et d'alcénylsuccinimides suralcalinisés, dont le radical alcényl contient au moins 50 atomes de carbone.Said complexes forming the subject of the invention are very particularly suitable for the preparation of optionally sulfurized alkylphenates carrying one or more C 6 ―C 60 , preferably C 9 C, S alkyl substituents, of mass alkylbenzenesulfonates molecular greater than 300, neutral or overbased and overbased alkenylsuccinimides, the alkenyl radical of which contains at least 50 carbon atoms.

Les alkylphénates de magnésium neutres peuvent être préparés d'une manière particulièrement satisfaisante par addition desdits complexes basiques de magnésium à une solution d'alkylphénol éventuellement sulfurisé dans de l'huile de dilution, distillation du méthanol et chauffage du milieu réactionnel vers 150―220°C pour éliminer toute trace de produits volatils; la quantité de complexe de magnésium à mettre en oeuvre correspond à environ 1 atome-gramme de magnésium pour 2 groupes OH phénoliques.Neutral magnesium alkylphenates can be prepared in a particularly satisfactory manner by adding said basic magnesium complexes to a solution of optionally sulfurized alkylphenol in dilution oil, distilling methanol and heating the reaction medium to 150 ° -220 °. C to remove all traces of volatile products; the quantity of magnesium complex to be used corresponds to approximately 1 gram atom of magnesium for 2 phenolic OH groups.

Les alkylphénates neutres ainsi obtenus peuvent être suralcalinisés par addition de complexe basique de magnésium à une température au moins égale à celle de distillation du méthanol, puis chauffage du milieu réactionnel vers 150-220°C pour éliminer toutes traces de produits volatils; cette opération peut éventuellement être réalisée en présence d'alcools de point d'ébullition compris entre 100 et 200°C tels que l'isobutanol, l'hexanol, l'éthyl-2 hexanol; la quantité de complexe à mettre en oeuvre est telle que le rapport nombre d'atomes-grammes de magnésium à disperser/nombre d'atomes-grammes de magnésium du phénate neutre soit inférieur ou égal à 4 et de préférence compris entre 2 et 3.The neutral alkylphenates thus obtained can be overbased by addition of basic magnesium complex at a temperature at least equal to that of methanol distillation, then heating of the reaction medium to 150-220 ° C to remove all traces of volatile products; this operation can optionally be carried out in the presence of alcohols with a boiling point of between 100 and 200 ° C. such as isobutanol, hexanol, 2-ethylhexanol; the amount of complex to be used is such that the ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of magnesium of the neutral phenate is less than or equal to 4 and preferably between 2 and 3.

Les alkylbenzènes sulfonates de magnésium neutres peuvent être préparés d'une manière analogue à celle décrite ci-dessus pour les alkylphénates neutres à partir d'acide alkylbenzène sulfonique; la quantité de complexe de magnésium à mettre en oeuvre correspond à 1 atome-gramme de magnésium pour 2 groupes acides sulfoniques; selon une variante dudit procédé, on peut introduire le complexe dans la solution d'acide sulfonique à la température de distillation du méthanol.The neutral magnesium alkylbenzene sulfonates can be prepared in a manner analogous to that described above for the neutral alkylphenates from alkylbenzene sulfonic acid; the quantity of magnesium complex to be used corresponds to 1 gram atom of magnesium for 2 sulfonic acid groups; according to a variant of said process, the complex can be introduced into the sulfonic acid solution at the methanol distillation temperature.

Les alkylbenzènesulfonates de magnésium suralcalinisés peuvent être préparés d'une manière analogue à celle décrite pour les alkylphénates suralcalinisés, à partir des alkylbenzène sulfonates de magnésium neutres; la quantité de complexe de magnésium à mettre en oeuvre est telle que le rapport nombre d'atomes-grammes de magnésium à disperser/nombre d'atomes-grammes de magnésium du sulfonate neutre soit inférieur ou égal à 8, de préférence compris entre 2 et 7. Selon une variante de ce procédé des alkylbenzènesulfonates suralcalinisés peuvent être préparés en remplaçant tout ou partie des sulfonates de magnésium neutres par des alkylbenzènesulfonates neutres de calcium ou de baryum.The overbased magnesium alkylbenzene sulfonates can be prepared in a similar manner to that described for the overbased alkylphenates from neutral magnesium alkylbenzene sulfonates; the quantity of magnesium complex to be used is such that the ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of magnesium of the neutral sulfonate is less than or equal to 8, preferably between 2 and 7. According to a variant of this process, alkalinized alkylbenzenesulfonates can be prepared by replacing all or part of the neutral magnesium sulfonates with neutral alkylbenzenesulfonates of calcium or barium.

Les alcénylsuccinimides suralcalinisés peuvent être préparés par addition desdits complexes basiques de magnésium à une solution d'alcénylsuccinimide dans de l'huile de dilution en présence d'un alcool de point d'ébullition compris entre 100 et 200°C, éventuellement addition d'eau pour disperser les éventuelles particules de gel pouvant se former et chauffage du milieu réactionnel à 180-2200C sous 20 mm de mercure pour éliminer les produits volatils; la quantité de complexe de magnésium à mettre en oeuvre correspond à un rapport nombre d'atomes-grammes de magnésium à disperser/nombre d'atomes grammes d'azote de l'alcénylsuccinimide inférieur ou égal à 3 et de préférence compris entre 1 et 2.The overbased alkenylsuccinimides can be prepared by adding said basic magnesium complexes to a solution of alkenylsuccinimide in dilution oil in the presence of an alcohol with a boiling point of between 100 and 200 ° C., optionally adding water. to disperse any gel particles that may form and heating the reaction medium to 180-220 ° C. under 20 mm of mercury to remove the volatile products; the quantity of magnesium complex to be used corresponds to a ratio number of gram atoms of magnesium to be dispersed / number of gram atoms of alkenylsuccinimide nitrogen less than or equal to 3 and preferably between 1 and 2 .

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.

Exemple 1Example 1

Préparation de complexe à partir d'oxyde de magnésium actif

  • préparation de l'oxyde de magnésium actif A On calcine pendant 7 heures à 500°C, 496 g de carbonate de magnésium basique correspondant à la formule approximative (Mg CO3)4, Mg (OH)2, 5 H2O, on obtient 215 g d'un oxyde de magnésium A dont la surface spécifique est de 125 m2/g.
  • - carbonation
    • a) 2 g de l'oxyde de magnésium A sont mis en suspension dans 60 g de méthanol et car- onatés à 25°C. L'absorption de gaz carbonique cesse au bout de 100 heures; la solution obtenue est parfaitement limpide.
    • b) 18 g de l'oxyde de magnésium A sont mis en suspension dans 470 g de méthanol et sont carbonatés sous une pression de gaz carbonique maintenue entre 10 et 11 kg/cm2; l'exothermie de la réaction fait passer la température du mélange de 22°C à 36°C. Au bout de 4 h de réaction, l'absorption de C02 cesse et le mélange est parfaitement limpide.
Complex preparation from active magnesium oxide
  • preparation of active magnesium oxide A 496 g are calcined for 7 hours at 500 ° C. basic magnesium carbonate corresponding to the approximate formula (Mg CO 3 ) 4 , Mg (OH) 2 , 5 H 2 O, 215 g of a magnesium oxide A are obtained whose specific surface is 125 m2 / g.
  • - carbonation
    • a) 2 g of magnesium oxide A are suspended in 60 g of methanol and carbonated at 25 ° C. The absorption of carbon dioxide ceases after 100 hours; the solution obtained is perfectly clear.
    • b) 18 g of magnesium oxide A are suspended in 470 g of methanol and are carbonated under a carbon dioxide pressure maintained between 10 and 11 kg / cm 2; the exothermic reaction increases the temperature of the mixture from 22 ° C to 36 ° C. After 4 hours of reaction, the absorption of C0 2 ceases and the mixture is perfectly clear.

Le mélange est ramené par détente à pression atmosphérique et peut ensuite être conservé en récipient hermétique indéfiniment.The mixture is brought back by relaxation to atmospheric pressure and can then be kept in an airtight container indefinitely.

Le mélange préparé contient 2% en poids de magnésium.The prepared mixture contains 2% by weight of magnesium.

Exemple 2Example 2

Préparation de complexe à partir d'oxyde de magnésium actif du commerce.Preparation of complex from commercial active magnesium oxide.

On met en suspension 18 g de Maglite DE commercialisé par Merk dont la surface spécifique est de 140 m2/g, dans 470 g de méthanol, puis on carbonate à température ambiante sous une pression de C02 maintenue entre 10 et 11 kg/cm2. On obtient une solution limpide au bout de trois heures. Le complexe obtenu contient 2% de magnésium.18 g of Maglite DE sold by Merk, the specific surface area of which is 140 m2 / g, are suspended in 470 g of methanol, then carbonated at room temperature under a CO 2 pressure maintained between 10 and 11 kg / cm 2. A clear solution is obtained after three hours. The complex obtained contains 2% magnesium.

Exemple 3Example 3

Préparation de complexe à partir d'oxyde de magnésium actif du commerce.Preparation of complex from commercial active magnesium oxide.

On met en suspension 18 g de Ferrumag 170 commercialisé par Rhône-Poulenc dont la surface spécifique est de 170 m2/g et contenant plus de 5% de Mg (OH)2, dans 470 g de méthanol, puis on carbonate à température ambiante sous une pression de CO2maintenue entre 10 et 11 kg/cm2. Au bout de 6 heures on obtient une solution contenant 2,6 g de solides constitués notamment par de l'hydroxyde de magnésium, qui sont éliminés par filtration ou centrifugation.18 g of Ferrumag 170 marketed by Rhône-Poulenc, the specific surface of which is 170 m2 / g and containing more than 5% Mg (OH) 2 , are suspended in 470 g of methanol, then carbonated at room temperature under a CO 2 pressure maintained between 10 and 11 kg / cm2. After 6 hours, a solution is obtained containing 2.6 g of solids, in particular consisting of magnesium hydroxide, which are removed by filtration or centrifugation.

Le complexe obtenu contient 1,85% de magnésium.The complex obtained contains 1.85% magnesium.

Exemple 4Example 4

Préparation de complexe à partir d'oxyde de magnésium partiellement actif.Preparation of complex from partially active magnesium oxide.

On met en suspension 18 g d'oxyde de magnésium de surface spécifique de 25 m2/g, obtenu par calcination à 10000C de carbonate de magnésium basique, dans 470 g de méthanol.18 g of magnesium oxide with a specific surface of 25 m2 / g, obtained by calcination at 1000 ° C. of basic magnesium carbonate, are suspended in 470 g of methanol.

On carbonate à température ambiante sous une pression de gaz carbonique maintenue entre 10 et 11 kg/cm2 pendant 7 heures; on obtient une solution contenant 7,5 de solides qui peuvent être éliminés par filtration ou centrifugation. Le complexe obtenu contient 1% de magnésium.Carbonate at room temperature under a carbon dioxide pressure maintained between 10 and 11 kg / cm2 for 7 hours; a solution is obtained containing 7.5 solids which can be removed by filtration or centrifugation. The complex obtained contains 1% magnesium.

Exemple 5Example 5

Préparation de complexe à partir d'oxyde de magnésium actif du commerce.Preparation of complex from commercial active magnesium oxide.

On met en suspension 37 g de Maglite DE dans 470 g de méthanol, puis on carbonate à température ambiante sous une pression de C02 maintenue entre 10 et 11 kg/cm2.37 g of Maglite DE are suspended in 470 g of methanol, then carbonization is carried out at ambient temperature under a CO 2 pressure maintained between 10 and 11 kg / cm 2.

On obtient une solution limpide au bout de 4 heures de réaction. Le complexe obtenu contient 4% en poids de magnésium.A clear solution is obtained after 4 hours of reaction. The complex obtained contains 4% by weight of magnesium.

Exemple 6Example 6

Préparation d'un alkylphénate neutre de magnésium sulfurisé.Preparation of a neutralized sulfurized magnesium alkylphenate.

Dans un ballon de 1 litre, muni d'un système d'agitation, d'une tête de distillation, d'une ampoule de coulée et d'une gaine thermométrique,In a 1 liter flask, fitted with a stirring system, a distillation head, a pouring bulb and a thermometric sheath,

On charge:

  • - 144 g de p-dodécylphénol sulfurisé (soit environ 0,5 groupe OH phénolique) contenant 5,7% de soufre
  • - 100g d'huile 100 N comme huile de dilution.
We charge:
  • - 144 g of sulfurized p-dodecylphenol (about 0.5 phenolic OH group) containing 5.7% sulfur
  • - 100g of 100 N oil as dilution oil.

L'appareillage est mis éventuellement sous balayage de C02 puis on coule en 1 heure sous agitation et à température ambiante 300 g de complexe de magnésium préparé à l'exemple 1 b).The apparatus is optionally placed under a CO 2 sweep, then 300 g of magnesium complex prepared in Example 1 b) are poured in for 1 hour with stirring.

Le méthanol est distillé à la fin de l'addition du complexe puis le mélange est chauffé jusqu'à 180°C pour éliminer toutes traces de produits volatils.The methanol is distilled at the end of the addition of the complex, then the mixture is heated to 180 ° C. to remove all traces of volatile products.

On obtient ainsi 250 g d'alkylphénate de magnésium neutre contenant 2,4% de magnésium.250 g of neutral magnesium alkylphenate containing 2.4% magnesium are thus obtained.

Exemple 7Example 7

Préparation d'un alkylphénate de magnésium suralcalinisé.Preparation of an overbased magnesium alkylphenate.

Le produit neutre obtenu à l'exemple 6 est maintenu entre 70 et 80°C, puis on introduit en 2 heures 300 g de complexe de magnésium préparé à l'exemple 1 b).The neutral product obtained in Example 6 is maintained between 70 and 80 ° C, then 300 g of magnesium complex prepared in Example 1 b) are introduced over 2 hours.

Le méthanol distille au fur et à mesure de l'addition du réactif.Methanol distills as the reagent is added.

Une fois l'addition terminée, le produit est chauffé pendant 1 heure à 180°C pour éliminer toutes traces de produits volatils.Once the addition is complete, the product is heated for 1 hour at 180 ° C to remove all traces of volatile products.

On obtient ainsi 260 g d'un produit brut brillant et fluide pouvant être facilement filtré à l'aide de 18 g d'huile et d'une terre de filtration.260 g of a bright and fluid crude product are thus obtained which can be easily filtered using 18 g of oil and filter earth.

On obtient alors 257 g de produit fini contenant 4,2% de magnésium et 3,3% de CO2.257 g of finished product are then obtained containing 4.2% of magnesium and 3.3% of CO 2 .

Compte-tenu des 18 g d'huile de filtration et des 18 g de produit fini qui restent absorbés sur le gâteau de filtration, on constate que 96% du magnésium engagé se retrouve dans le produit fini.Taking into account the 18 g of filtration oil and the 18 g of finished product which remain absorbed on the filter cake, it is found that 96% of the magnesium used is found in the finished product.

Exemple 8Example 8

Préparation d'un alkylphénate de magnésium sulfurisé et suralcalinisé.Preparation of a sulfurized and overbased magnesium alkylphenate.

On préparé comme à l'exemple 6 un alkylphénate neutre à partir de:

  • - 144 g de p-dodécylphénol sulfurisé
  • -200 g d'huile 100 N (au lieu de 100 g)
  • - et 300 g de complexe préparé à l'exemple 1 b).
A neutral alkylphenate is prepared as in Example 6 from:
  • - 144 g of sulfurized p-dodecylphenol
  • -200 g of 100 N oil (instead of 100 g)
  • - And 300 g of complex prepared in Example 1 b).

On obtient 350 g de phénate neutre, auxquels on ajoute 150 g de n-hexanol.350 g of neutral phenate are obtained, to which 150 g of n-hexanol are added.

On maintient la température comprise entre 70 et 80°C puis on introduit en 4 h 900 g de complexe préparé à l'exemple 1 b).The temperature is maintained between 70 and 80 ° C. and then 900 g of complex prepared in Example 1 b) are introduced over 4 hours.

On distille sous vide (20 mmHg) pendant 1 heure à 180°C pour éliminer les produits volatils.Distillation is carried out under vacuum (20 mmHg) for 1 hour at 180 ° C. to remove the volatile products.

On obtient 421 g d'un produit brillant et fluide que l'on filtre à l'aide de 30 g d'huile et d'une terre de filtration.421 g of a bright and fluid product are obtained, which are filtered using 30 g of oil and filter earth.

On récupère alors 430 g de produit fini contenant 5% de magnésium, 4% de C02 et présentant un TBN de 230 mg. Compte-tenu des 30 g d'huile de filtration et des 20 g de produit fini restant sur le gâteau de filtration, on constate que 94% du magnésium se retrouve dans le produit fini.430 g of finished product are then recovered containing 5% magnesium, 4% CO 2 and having a TBN of 230 mg. Taking into account the 30 g of filtration oil and the 20 g of finished product remaining on the filter cake, it is found that 94% of the magnesium is found in the finished product.

Exemple 9Example 9

Préparation d'un alkylbenzène sulfonate de magnésium neutre.Preparation of a neutral magnesium alkylbenzene sulfonate.

Dans un ballon de 1 litre, muni d'un système d'agitation, d'une ampoule de coulée, d'une tête de distillation et d'une gaine thermométrique, on charge:

  • -260 g d'acide alkylbenzène sulfonique AS 157 commercialisé par ESSO, de masse moléculaire moyenne de 465 g (ASTM D 855) et ayant un indice d'acide de 85 mg de KOH/g.
  • - 140 g d'huile 100 N
In a 1 liter flask, fitted with a stirring system, a pouring funnel, a distillation head and a thermometric sheath, we load:
  • -260 g of alkylbenzene sulfonic acid AS 157 marketed by ESSO, with an average molecular mass of 465 g (ASTM D 855) and having an acid number of 85 mg of KOH / g.
  • - 140 g of 100 N oil

On ajoute en 30 minutes 125 g de complexe de magnésium préparé à l'exemple 5 et contenant 4% de magnésium la température du milieu passe de 20 à 45°C.125 g of magnesium complex prepared in Example 5 and containing 4% magnesium are added over 30 minutes, the temperature of the medium going from 20 to 45 ° C.

Une fois l'addition du complexe terminée, on chauffe le mélange jusqu'à 1400C pour éliminer le méthanol et l'eau provenant de la neutralisation de l'acide sulfonique.Once the addition of the complex is complete, the mixture is heated to 140 ° C. to remove the methanol and the water coming from the neutralization of the sulfonic acid.

On obtient ainsi 405 g d'alkylbenzène sulfonate neutre de magnésium contenant 1,2% de magnésium.405 g of neutral magnesium alkylbenzene sulfonate containing 1.2% magnesium are thus obtained.

Exemple 10Example 10

Préparation d'un alkylbenzène sulfonate de magnésium suralcalinisé.Preparation of an overbased magnesium alkylbenzene sulfonate.

On ajoute au mélange préparé à l'exemple 9, 200 g d'éthyl-2 hexanol et on ajuste la température du milieu à 70-80°C.200 g of 2-ethylhexanol are added to the mixture prepared in Example 9 and the temperature of the medium is adjusted to 70-80 ° C.

On introduit alors en 3 heures 500 g de complexe de magnésium préparé à l'exemple 5.500 g of magnesium complex prepared in Example 5 are then introduced over 3 hours.

Lorsque l'addition de complexe est terminée, on chauffe le mélange jusqu'à 180°C sous 20 mn de mercure pour éliminer les alcools présents dans le milieu.When the addition of complex is complete, the mixture is heated to 180 ° C. under 20 min of mercury to remove the alcohols present in the medium.

On obtient ainsi 450 g de produit brut que l'on filtre à l'aide de 20 g d'huile et de 20 g de terre de filtration; on récupère ainsi 450 g de produit fini brun clair et brillant, contenant 5,2% de magnésium et 5,5% de CO2 450 g of crude product are thus obtained which are filtered using 20 g of oil and 20 g of filter earth; thus recovering 450 g of light and shiny brown finished product, containing 5.2% magnesium and 5.5% CO 2

Exemple 11Example 11

Préparation d'un alkylbenzène sulfonate de magnésium suralcalinisé.Preparation of an overbased magnesium alkylbenzene sulfonate.

On ajoute à 204 g d'une solution dans de l'huile de dilution à environ 50% d'alkylbenzène sulfonate de calcium neutre contenant 2,3% de calcium, 201 g de n-hexanol.To 204 g of a solution in dilution oil containing approximately 50% of neutral calcium alkylbenzene sulfonate containing 2.3% of calcium, 201 g of n-hexanol are added.

Le mélange est maintenu à 70-800C et l'on introduit en 2 h 300 g de complexe de magnésium préparé à l'exemple 5.The mixture is maintained at 70-80 ° C. and 300 g of magnesium complex prepared in Example 5 are introduced over 2 hours.

Lorsque l'addition de complexe est terminée, on chauffe le mélange à 180°C sous une pression de 20 mm de mercure pour éliminer les alcools présents dans le milieu.When the addition of complex is complete, the mixture is heated to 180 ° C under a pressure of 20 mm of mercury to remove the alcohols present in the medium.

On obtient ainsi 230 g de produit brut que l'on filtre sur une terre de filtration à l'aide de 40 g d'huileThis gives 230 g of crude product which is filtered on filter earth using 40 g of oil

On obtient 250 g de produit contenant 1,93% de calcium, 4,35% de magnésium et 6% de C02.250 g of product are obtained containing 1.93% of calcium, 4.35% of magnesium and 6% of CO 2 .

Compte-tenu que 40 g d'huile ont été introduits pour la filtration et que 20 g de produit restant absorbés sur le gâteau de filtration, on constate que 98% du magnésium ont été dispersés dans le produit.Given that 40 g of oil were introduced for filtration and that 20 g of product remaining absorbed on the filter cake, it is found that 98% of the magnesium has been dispersed in the product.

Exemple 12Example 12

Préparation d'un alcénylsuccinimide suralcalinisé.Preparation of an overbased alkenylsuccinimide.

Dans un ballon de 1 litre, muni d'un système d'agitation, d'une ampoule de coulée, d'une tête de distillation et d'une gaine thermométrique, on charge:

  • -200 g d'une solution à 1,5% d'azote d'un bis (polyisobutényl succinimide) dans 50% d'huile de dilution, succinimide dérivé de la tri- éthylènetétramine, et d'un anhydride polyisobutényl succinique d'indice d'acide de 74, obtenu par condensation de l'anhydride malé- ique et d'un polyisobutène de masse moléculaire voisine de 1000,
  • - 100 g dè n-hexanol
In a 1 liter flask, fitted with a stirring system, a pouring funnel, a distillation head and a thermometric sheath, we load:
  • -200 g of a 1.5% nitrogen solution of a bis (polyisobutenyl succinimide) in 50% dilution oil, succinimide derived from triethylenetetramine, and of an index polyisobutenyl succinic anhydride 74 acid, obtained by condensation of maleic anhydride and a polyisobutene with a molecular weight close to 1000,
  • - 100 g of n-hexanol

On maintient la température entre 70 et 80°C et l'on introduit en une heure 190 g de complexe de magnésium préparé à l'exemple 1 b), puis on ajoute 30 g d'eau en 10 minutes après la fin de l'addition du complexe.The temperature is maintained between 70 and 80 ° C. and 190 g of magnesium complex prepared in Example 1 b) are introduced over one hour, then 30 g of water are added in 10 minutes after the end of the addition of the complex.

On porte ensuite le mélange à 180°C sous 20 mm de mercure pour éliminer le méthanol restant, l'eau et le n-hexanol.The mixture is then brought to 180 ° C. under 20 mm of mercury to remove the remaining methanol, water and n-hexanol.

On obtient ainsi 210 g d'un produit brillant exempt de gels ou de sédiments, contenant 1,8% de magnésium et présentant une alcal- inite de 105 mg de KOH/g.210 g of a brilliant product, free from gels or sediments, containing 1.8% of magnesium and having an alkalinity of 105 mg of KOH / g are thus obtained.

Claims (8)

1. New basic complexes of magnesium characterised in that they are obtained by putting into suspension into methanol, a compound based on "active" magnesium oxide in a quantity not exceeding 10% by weight of "active" magnesium oxide in relation to the methanol, and subjecting the said suspension to a carbonation operation by means of carbonic gas at a temperature lower than 50°C until no more carbonic gas is absorbed.
2. New complexes according to claim 1, characterised in that the said compound, based on "active" magnesium oxide, that is used, is a magnesium oxide with specific surface higher than 80 m2/g.
3. New complexes according to claim 2, characterised in that the said compound, based on "active" magnesium oxide, that is used, is a magnesium oxide with specific surface higher than 100 m2/g.
4. New complexes according to claim 1, characterised in that the said compound based on "active" magnesium oxide contains more than 50% by weight of "active" magnesium oxide.
5. New complexes according to any one of claims 1 to 4 characterised in that the quantity of "active" magnesium oxide used does not exceed 8% by weight of methanol.
6. New complexes according to claim 5, characterised in that the quantity of "active" magnesium oxide used is between 3 and 7% of the weight of methanol.
7. New complexes according to claim 1, characterised in the carbonation operation is carried out under a pressure of carbonic gas of between 5 and 50 kg/cm2.
8. Application of the new complexes object of any one of claims 1 to 7 for the manufacture of detergent-dispersant additives for lubricating oils.
EP78400238A 1977-12-20 1978-12-13 Basic complex magnesium compounds and their application to the preparation of detergent dispersant additives for lubricating oils Expired EP0002644B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7738367 1977-12-20
FR7738367A FR2412607A1 (en) 1977-12-20 1977-12-20 NEW BASIC MAGNESIUM COMPLEXES AND THEIR APPLICATION FOR THE MANUFACTURE OF DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS

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EP0002644A1 EP0002644A1 (en) 1979-06-27
EP0002644B1 true EP0002644B1 (en) 1980-08-20

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FR2450868A1 (en) * 1979-03-09 1980-10-03 Orogil PROCESS FOR THE PREPARATION OF MAGNESIUM ALKYLPHENATES AND APPLICATION OF THE PRODUCTS OBTAINED AS DETERGENT-DISPERSANT ADDITIVES FOR LUBRICATING OILS
JP2019161278A (en) 2018-03-07 2019-09-19 株式会社リコー Calibration reference point acquisition system and calibration reference point acquisition method

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US3629109A (en) * 1968-12-19 1971-12-21 Lubrizol Corp Basic magnesium salts processes and lubricants and fuels containing the same
US3878116A (en) * 1970-09-09 1975-04-15 Bray Oil Co Overbased sulfonates
GB1399092A (en) * 1971-05-27 1975-06-25 Cooper & Co Ltd Edwin Lubricant additives
US3761411A (en) * 1971-06-21 1973-09-25 C Dickey Non aqueous solutions of magnesium salts
US3865737A (en) * 1973-07-02 1975-02-11 Continental Oil Co Process for preparing highly-basic, magnesium-containing dispersion

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FR2412607A1 (en) 1979-07-20
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