EP0016676B1 - Verfahren zur Herstellung von Magnesium-Alkylphenaten - Google Patents

Verfahren zur Herstellung von Magnesium-Alkylphenaten Download PDF

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Publication number
EP0016676B1
EP0016676B1 EP80400270A EP80400270A EP0016676B1 EP 0016676 B1 EP0016676 B1 EP 0016676B1 EP 80400270 A EP80400270 A EP 80400270A EP 80400270 A EP80400270 A EP 80400270A EP 0016676 B1 EP0016676 B1 EP 0016676B1
Authority
EP
European Patent Office
Prior art keywords
active
magnesium oxide
weight
phenolic
magnesium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80400270A
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English (en)
French (fr)
Other versions
EP0016676A1 (de
Inventor
Jean-Pierre Tassara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orogil SA
Original Assignee
Orogil SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Orogil SA filed Critical Orogil SA
Priority to AT80400270T priority Critical patent/ATE1647T1/de
Publication of EP0016676A1 publication Critical patent/EP0016676A1/de
Application granted granted Critical
Publication of EP0016676B1 publication Critical patent/EP0016676B1/de
Expired legal-status Critical Current

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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
    • 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 process for the preparation of magnesium alkylphenates, the products obtained according to the process and the application of said products as detergent-dispersant additives for lubricating oils.
  • Such a process uses not an alkylphenol alone but an alkylphenol-sulfonic acid mixture which is easier to neutralize and requires the presence of a promoter.
  • the Applicant has found a process making it possible to prepare magnesium alkylphenates using an alkylphenol alone (that is to say not mixed with a sulfonic acid), active magnesia and which does not require the use of a promoter.
  • active magnesium oxide denotes magnesium oxide which 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 m 2 / g and generally greater than 100 m 2 / g.
  • alkylphenol denotes both non-sulfurized alkylphenols and sulfurized alkylphenols.
  • alkylphenols which can be used, mention may be made of those bearing one or more C 9 -C 15 substituents, in particular nonyl, decyl, dodecyl and tetradecylphenols, optionally sulfurized.
  • paraffin spikes such as 100 Neutral oil
  • naphthenic or mixed oils may also be suitable.
  • heavy alcohols that can be used, mention may preferably be made of isobutanol, hexanol or 2-ethylhexanol.
  • the operation of suspending the “active” magnesium oxide in methanol takes place favorably at ordinary temperature.
  • the contacting and carbonation operations can be carried out at a temperature between 0 and 40 ° C. preferably between 15 and 30 ° C.
  • the operations described above may optionally be followed by a water treatment operation, in particular when a ratio of the number of moles of “active” magnesium oxide / number of phenolic OH units greater than 1 has been set. in use and if one seeks to reduce the viscosity of the product obtained.
  • This water treatment can be carried out in a conventional manner using 1 to 2 moles of water per mole of “active active” magnesium oxide.
  • Another subject of the present invention is the magnesium alkylphenates obtained according to the process described above, as well as the application of said alkylphenates as detergent additives.
  • dispersants for lubricating oils The amount of alkylphenates to be added to petrol engine oils is generally in the range of 1 to 4% by weight; that to be added in the oils for diesel engine is generally of the order of 1 to 8% by weight.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as the naphthenic base, paraffinic base and mixed base lubricant oils, other hydrocarbon lubricants, for example lubricant oils.
  • lubricating oils such as the naphthenic base, paraffinic base and mixed base lubricant oils, other hydrocarbon lubricants, for example lubricant oils.
  • derived from coal products, and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of liquid acids of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylbiphenyl ethers, polymers of silicon.
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
  • the alkylphenol used is presulfurized paradodecyl phenol (A) containing 11.5% of sulfur (obtained by sulfurization with sulfur).
  • the “active” magnesium oxide (B) used has a specific surface of 145 m 2 / g and a purity of MgO of 90%.
  • the phenolic MgO / OH molar ratio used is 0.5.
  • the amount of active MgO is 9% relative to methanol.
  • the amount of dilution oil is 68.3% relative to the alkylphenol.
  • a suspension of 11 g of the active magnesium oxide (B) (ie 0.25 mol) in 120 g of methanol is prepared separately and this suspension is added to the preceding mixture.
  • the mixture thus obtained is then carbonated at 20 ° C with stirring by introducing into the reactor carbon dioxide under a pressure of 10 kg / cm 2 for 8 hours.
  • the apparatus is brought back to atmospheric pressure and the methanol is removed by distillation while gradually raising the temperature to 180 ° C.
  • Example 1 We repeat Example 1 but without first preparing the suspension of magnesium oxide in methanol and by loading all the constituents of the mixture without special precautions.
  • Example 1 The operation described in Example 1 is carried out in the presence of an amount of MgO "active corresponding to 5% by weight of methanol.
  • the suspension of “active MgO” thus consists of 11 g of active MgO (ie 0.25 mole) in 220 g of methanol.
  • a suspension of 22 g of active magnesium oxide (B) (i.e. 0.5 mol) in 250 g of methanol is prepared and this suspension is added to the preceding mixture.
  • the mixture is carbonated for 10 hours at room temperature under a pressure of 10 kg / cm 2 of carbon dioxide.
  • the mixture is brought back to atmospheric pressure and the alcohols are removed by distillation by heating the product to 180 ° C. under vacuum to properly remove the hexanol.
  • 270 g of finished product are thus recovered having a TBN of 170 mg and containing: 3.7% of magnesium and 3.5% of CO 2 while 20 g of crude product remain absorbed on the cake. filtration.
  • a suspension of 19 g of active magnesium oxide (B) (i.e. 0.425 mole) in 220 g of methanol is prepared and we add this suspension to the preceding mixture.
  • the mixture is carbonated for 10 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.
  • a suspension of 13 g of active magnesium oxide B (ie 0.3 mole) in 150 g of methanol is prepared and this suspension is added to the preceding mixture.
  • the resulting mixture is carbonated for 8 hours at room temperature under a pressure of 12 kg / cm 2 of carbon dioxide.

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)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Claims (7)

1. Verfahren zur Herstellung von Magnesiumalkylphenolaten ausgehend von einer Suspension aus « aktivem » Magnesiumoxid in Methanol, die bis zu 10 Gew.-% « aktives Magnesiumoxid, bezogen auf das Gewicht des Methanols enthält, dadurch gekennzeichnet, daß man
a) diese Suspension mit einem Gemisch in Berührung bringt, das
- ein Alkylphenol, welches ein oder mehrere C6-C6o-Alkylsubstituenten trägt ;
― ein Verdünnungsöl und
- gegebenenfalls einen schweren Alkohol mit Siedepunkt zwischen 100 und 200°C enthält, wobei das Verhältnis von Anzahl Mole « aktives » Magnesiumoxid zu Anzahl der phenolischen OH-Gruppen 0,25 bis 2 beträgt, die Menge an Verdünnungsöl bis zu 140 Gew.-%, bezogen auf das Gewicht des Alkylphenols ausmachen kann und das Molverhältnis von schwerem Alkohol zu « aktivem » Magnesiumoxid 0 bis 4 ausmacht, wobei dieses Molverhältnis mindestens 1,2 beträgt, wenn das Verhältnis von Anzahl Mole « aktives » Magnesiumoxid zu Anzahl der phenolischen ÖH-Gruppen über 0,75 liegt,
b) unter Druck das erhaltene Medium mit C02 sättigt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man
― 5 bis 10 Gew.-% « aktives » Magnesiumoxid, bezogen auf das Gewicht des Methanols, einsetzt ;
― ein Verhältnis von Anzahl Mole « aktives » Magnesiumoxid zu Anzahl phenolischer OH-Gruppen von 0,5 bis 1 einhält ;
- 20 bis 75 Gew.-% Verdünnungsöl, bezogen auf das Gewicht des Alkylphenols einsetzt ;
- ein Molverhältnis von schwerem Alkohol zu « aktivem » Magnesiumoxid von mindestens 1,5 einhält, wenn das Verhältnis von Anzahl Mole « aktives » Magnesiumoxid zu Anzahl phenolischer OH-Gruppen über 0,75 liegt, und daß man die Sättigung mit CO2 mit einer Menge CO2 vornimmt, die derjenigen entspricht, die von dem Medium vollständig absorbiert werden kann.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Sättigung mit CO2 während mindestens 4 Stunden bei einem Druck zwischen 3 und 30 kg/cm2 und bei einer Temperatur zwischen 0 und 40 °C ausgeführt wird.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Sättigung mit CO2 bei einem Druck von 5 bis 15 kg/cm2, bei einer Temperatur zwischen 15 und 30 °C und mit einer C02 Menge entsprechend im wesentlichen derjenigen, die vollständig absorbiert werden kann, ausgeführt wird.
5. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß die eingesetzten Alkylphenole ein oder mehrere C9-C15-Alkylsubstituenten tragen und gegebenenfalls mit Schwefel behandelt worden sind.
6. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der eingesetzte schwere Alkohol lsobutanol, Hexanol oder 2-Ethylhexanol ist.
7. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß die Sättigung mit C02 gefolgt wird von einer Behandlung mit 1 bis 2 Mol Wasser je Mol eingesetztes « aktives » Magnesiumoxid, wenn das Verhältnis von Anzahl Mole « aktives » Magnesiumoxid zu Anzal phenolischer OH-Gruppen > 1 ist.
EP80400270A 1979-03-09 1980-02-27 Verfahren zur Herstellung von Magnesium-Alkylphenaten Expired EP0016676B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80400270T ATE1647T1 (de) 1979-03-09 1980-02-27 Verfahren zur herstellung von magnesiumalkylphenaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7906060A FR2450868A1 (fr) 1979-03-09 1979-03-09 Procede de preparation d'alkylphenates de magnesium et application des produits obtenus comme additifs detergents-dispersants pour huiles lubrifiantes
FR7906060 1979-03-09

Publications (2)

Publication Number Publication Date
EP0016676A1 EP0016676A1 (de) 1980-10-01
EP0016676B1 true EP0016676B1 (de) 1982-10-13

Family

ID=9222946

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80400270A Expired EP0016676B1 (de) 1979-03-09 1980-02-27 Verfahren zur Herstellung von Magnesium-Alkylphenaten

Country Status (11)

Country Link
US (1) US4382004A (de)
EP (1) EP0016676B1 (de)
JP (1) JPS6011894B2 (de)
AT (1) ATE1647T1 (de)
BR (1) BR8001372A (de)
CA (1) CA1123015A (de)
DE (1) DE3060929D1 (de)
ES (1) ES489289A1 (de)
FR (1) FR2450868A1 (de)
MX (1) MX7049E (de)
ZA (1) ZA801364B (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529224B1 (fr) * 1982-06-24 1986-02-07 Orogil Nouvel additif detergent-dispersant suralcalinise pour huiles lubrifiantes
FR2529226B1 (fr) * 1982-06-24 1987-01-16 Orogil Procede de preparation d'alkylphenates sulfurises de metaux alcalino-terreux utilisables comme additifs pour huiles lubrifiantes
FR2529225B1 (fr) * 1982-06-24 1986-04-25 Orogil Nouvel additif detergent-dispersant metallique de haute alcalinite pour huiles lubrifiantes
JPS60127396A (ja) * 1983-12-12 1985-07-08 Cosmo Co Ltd 塩基性アルカリ土類金属サリチレ−ト型清浄剤の製造法
JPS62127886U (de) * 1986-02-06 1987-08-13
JPS62178288U (de) * 1986-05-06 1987-11-12
US4971710A (en) * 1986-10-21 1990-11-20 Chevron Research Company Methods for preparing, Group II metal overbased sulfurized alkylphenols
US4744921A (en) * 1986-10-21 1988-05-17 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
US5024773A (en) * 1986-10-21 1991-06-18 Chevron Research Company Methods for preparing, group II metal overbased sulfurized alkylphenols
GB8730220D0 (en) * 1987-12-29 1988-02-03 Exxon Chemical Patents Inc Detergents
US5292443A (en) * 1992-08-21 1994-03-08 Texaco Inc. Process for producing neutralized sulfurized alkylphenate lubricant detergent additive
US6310009B1 (en) * 2000-04-03 2001-10-30 The Lubrizol Corporation Lubricating oil compositions containing saligenin derivatives

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL107072C (de) * 1960-03-09 1964-01-15
US3350310A (en) * 1965-02-08 1967-10-31 Mobil Oil Corp Preparation of overbased calcium alkylphenate sulfides
US4065396A (en) * 1970-02-09 1977-12-27 Bray Oil Co. Magnesium oxide process
US3878116A (en) * 1970-09-09 1975-04-15 Bray Oil Co Overbased sulfonates
US3932289A (en) * 1973-11-09 1976-01-13 Chevron Research Company Preparation of overbased carbonated sulfurized magnesium alkylphenates
GB1470338A (en) * 1974-05-17 1977-04-14 Exxon Research Engineering Co Lubricating oil compositions
GB1469289A (en) * 1974-07-05 1977-04-06 Exxon Research Engineering Co Detergent additives
SU644811A1 (ru) * 1975-07-14 1980-02-05 Всесоюзный научно-исследовательский институт по переработке нефти Способ получени сульфидалкилфенол тной присадки к смазочных маслам
US4010106A (en) * 1976-02-02 1977-03-01 Chevron Research Company Corrosion-retarding functional fluid
US4016093A (en) * 1976-03-19 1977-04-05 Mobil Oil Corporation Metal alkylphenate sulfides of reduced corrosiveness and method of preparing same
FR2412607A1 (fr) * 1977-12-20 1979-07-20 Orogil Nouveaux complexes basiques de magnesium et leur application pour la fabrication d'additifs detergents-dispersants pour huiles lubrifiantes

Also Published As

Publication number Publication date
DE3060929D1 (en) 1982-11-18
ZA801364B (en) 1981-03-25
FR2450868B1 (de) 1983-05-20
ES489289A1 (es) 1980-08-16
ATE1647T1 (de) 1982-10-15
JPS55143923A (en) 1980-11-10
US4382004A (en) 1983-05-03
MX7049E (es) 1987-04-07
EP0016676A1 (de) 1980-10-01
FR2450868A1 (fr) 1980-10-03
CA1123015A (fr) 1982-05-04
BR8001372A (pt) 1980-11-11
JPS6011894B2 (ja) 1985-03-28

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