EP0002644B1 - Basische Magnesiumkomplexe und ihre Anwendung für die Bereitung von Detergentien und/oder Dispergiermittel als Zusatz für Schmieröle - Google Patents

Basische Magnesiumkomplexe und ihre Anwendung für die Bereitung von Detergentien und/oder Dispergiermittel als Zusatz für Schmieröle 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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EP
European Patent Office
Prior art keywords
magnesium
magnesium oxide
active
methanol
preparation
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Expired
Application number
EP78400238A
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English (en)
French (fr)
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EP0002644A1 (de
Inventor
Jean-Pierre Tassara
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DROGIL
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DROGIL
Orogil SA
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Classifications

    • 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

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.

Landscapes

  • 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)

Claims (8)

1. Neue basische Magnesiumkomplexe, dadurch gekennzeichnet, daß sie erhalten wurden indem eine Verbindung auf Basis von "aktivem" Magnesiumoxid in einer Menge, welche 10 Gew.% "aktives" Magnesiumoxid, bezogen auf das Methanol, nicht übersteigt, in Methanolsuspendiert wurde und diese Suspension einer Carbonierung mit Hilfe von Kohlendioxidgas bei einer Temperatur unterhalb von 50°C bis zum Ende der Absorption des Kohlendioxidgases unterworfen wurde.
2. Neue Komplexe nach Anspruch 1, dadurch gekennzeichnet, daß diese eingesetzte Verbindung auf Basis von "aktivem" Magnesiumoxid ein Magnesiumoxid mit einer spezifischen Oberfläche über 80 m2/g. ist.
3. Neue Komplexe nach Anspruch 2, dadurch gekennzeichnet, daß diese eingesetzte Verbindung auf Basis von "aktiven" Magnesiumoxid ein Magnesiumoxid mit einer spezifischen Oberfläche über 100 m2/g ist.
4. Neue Komplexe nach Anspruch 1, dadurch gekennzeichnet, daß diese Verbindung auf Basis von "aktivem" Magnesiumoxid mehr als 50 Gew.% "actives" Magnesiumoxid enthält.
5. Neue Komplexe nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die eingesetzte Menge des "aktiven" Magnesiumoxids 8 Gew.%, bezogen auf das Methanol, nicht übersteigt.
6. Neue Komplexe nach Anspruch 5, dadurch gekennzeichnet, daß die eingesetzte Menge an "aktivem" Magnesiumoxid zwischen 3 und 7 Gew.%, bezogen auf Methanol, beträgt.
7. Neue Komplexe nach Anspruch 1, dadurch gekennzeichnet, daß die Carbonierung unter einem Kohlendioxidgasdruck zwischen 5 und 50 kg/cm2 durchgeführt wurde.
8. Verwendung der neuen Komplexe nach einem der Ansprüche 1 bis 7 zur Herstellung von Detergenz-Dispergier-Zusatzstoffen für Schmieröle.
EP78400238A 1977-12-20 1978-12-13 Basische Magnesiumkomplexe und ihre Anwendung für die Bereitung von Detergentien und/oder Dispergiermittel als Zusatz für Schmieröle Expired EP0002644B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7738367 1977-12-20
FR7738367A FR2412607A1 (fr) 1977-12-20 1977-12-20 Nouveaux complexes basiques de magnesium et leur application pour la fabrication d'additifs detergents-dispersants pour huiles lubrifiantes

Publications (2)

Publication Number Publication Date
EP0002644A1 EP0002644A1 (de) 1979-06-27
EP0002644B1 true EP0002644B1 (de) 1980-08-20

Family

ID=9199050

Family Applications (1)

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EP78400238A Expired EP0002644B1 (de) 1977-12-20 1978-12-13 Basische Magnesiumkomplexe und ihre Anwendung für die Bereitung von Detergentien und/oder Dispergiermittel als Zusatz für Schmieröle

Country Status (11)

Country Link
EP (1) EP0002644B1 (de)
JP (1) JPS54154705A (de)
AT (1) AT366087B (de)
BR (1) BR7808331A (de)
CA (1) CA1113680A (de)
DE (1) DE2860245D1 (de)
ES (1) ES476112A1 (de)
FR (1) FR2412607A1 (de)
IT (1) IT1111377B (de)
MX (1) MX5158E (de)
ZA (1) ZA787091B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2450868A1 (fr) * 1979-03-09 1980-10-03 Orogil Procede de preparation d'alkylphenates de magnesium et application des produits obtenus comme additifs detergents-dispersants pour huiles lubrifiantes
JP2019161278A (ja) 2018-03-07 2019-09-19 株式会社リコー 校正基準点取得システム、及び校正基準点取得方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CA1113680A (fr) 1981-12-08
BR7808331A (pt) 1979-08-07
FR2412607B1 (de) 1981-03-06
ES476112A1 (es) 1979-04-16
FR2412607A1 (fr) 1979-07-20
IT7852354A0 (it) 1978-12-19
IT1111377B (it) 1986-01-13
ZA787091B (en) 1979-12-27
ATA909878A (de) 1981-07-15
MX5158E (es) 1983-04-07
JPS5654298B2 (de) 1981-12-24
EP0002644A1 (de) 1979-06-27
AT366087B (de) 1982-03-10
JPS54154705A (en) 1979-12-06
DE2860245D1 (en) 1980-12-04

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