EP0211722B1 - Sulfonierte und sulfurisierte Detergens Dispergierzusätze für Schmieröle - Google Patents

Sulfonierte und sulfurisierte Detergens Dispergierzusätze für Schmieröle Download PDF

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Publication number
EP0211722B1
EP0211722B1 EP86401497A EP86401497A EP0211722B1 EP 0211722 B1 EP0211722 B1 EP 0211722B1 EP 86401497 A EP86401497 A EP 86401497A EP 86401497 A EP86401497 A EP 86401497A EP 0211722 B1 EP0211722 B1 EP 0211722B1
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Prior art keywords
additives
alkaline
earth base
alcohol
range
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EP86401497A
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English (en)
French (fr)
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EP0211722A1 (de
Inventor
Savino Leone
Henri Gaessler
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Orogil SA
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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
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals

Definitions

  • the subject of the present invention is new detergent-dispersant additives stable to hydrolysis for lubricating oils, based on sulfurized and over-alkalized alkylphenatesulfonates derived from alkylphenolsulfonic acids.
  • the additives which are the subject of the invention are sulfurized alkaline earth metal salts derived from alkylphenolsulfonic acids containing a lower rate of sulfonic functions (they contain at most about three times less); they are stable to hydrolysis and have antioxidant characteristics.
  • alkylphenolsulfonic acid is understood to mean the mixture obtained by sulfonation of an alkylphenol in which the alkyl radical or radicals may have from 8 to 30 carbon atoms and preferably from 12 to 30 carbon atoms, according to known methods, for example at using sulfuric or chlorosulfonic acid or sulfuric anhydride; said mixture consists mainly of alkylphenolsulfonic acid and alkylphenol, the levels of SO 3 H functions corresponding to 6 to 35 SO 3 H functions per 100 OH functions of said mixture.
  • alkaline earth bases which can be used to carry out the various stages of preparation of the additives, mention may be made of the oxides or hydroxides of calcium, barium or strontium and preferably those of calcium.
  • alkaline earth base is extended to the amount of alkaline earth base necessary for the neutralization of the alkylphenolsulfonic acid in the 1st stage and for the over-alkalinization of the alkylphenolsulfonate in the 2nd stage.
  • vector alcohols that can be used in the 2nd step, or may include alkylene glycols such as glycol, diethylene glycol, propylene glycol alkoxyalkanols such as butoxy-2 ethanol, butoxy-2 propanol, propylene glycol methyl ether and generally those having the formula R (OR ') x OH where R represents a methyl, ethyl or butyl radical, R' an ethyl or propyl radical and x is equal to 1 or 2.
  • alkylene glycols such as glycol, diethylene glycol, propylene glycol alkoxyalkanols such as butoxy-2 ethanol, butoxy-2 propanol, propylene glycol methyl ether
  • R represents a methyl, ethyl or butyl radical
  • R' an ethyl or propyl radical
  • x is equal to 1 or 2.
  • the first step that is to say neutralization of the alkylphenolsulfonic acid, is favorably carried out at a pressure close to atmospheric pressure; it can be catalyzed using COOH ions originating from carboxylic acids such as formic, acetic, glycolic acid, halide ions, in particular chlorides introduced via ammonium chloride, calcium, zinc or NH 2 functions originating from amines such as polyethylene polyamines, tris (3-oxa-6-amino-6 hexyl) amine, the amounts of catalyst used being able to range up to 0.1 mole of COOH ion, halide or NH 2 function per mole of starting alkylphenolsufonic acid.
  • carboxylic acids such as formic, acetic, glycolic acid, halide ions, in particular chlorides introduced via ammonium chloride, calcium, zinc or NH 2 functions originating from amines such as polyethylene polyamines, tris (3-oxa-6-amino-6 hexyl)
  • This first step is carried out in the presence of a solvent capable of forming an azeotrope with water; the operation is carried out at a temperature at least equal to that of formation of the water-solvent azeotrope.
  • the amount of solvent used in this 1st stage corresponds to that necessary to obtain a fluid medium, that is to say of viscosity less than 50 10-6 m2 / s (50 cSt) approximately under the reaction conditions.
  • the 2nd stage that of sulfurization-over-alkalization is carried out at a temperature of the order of 140 to 195 ° C for 3 to approximately hours; it can be achieved if necessary in the presence of a diluent oil to reduce the viscosity of the medium to a value of less than 50 10 -6 m 2 / s (50 cSt) about.
  • the actual descaling process is preferably carried out at a temperature of the order of 140 to 170 ° C for approximately 1 to 3 hours; it can be catalyzed as the neutralization step by halide ions, COOH or by NH 2 functions, the amounts of catalyst used being able to range up to 0.1 mole of halide ion, COOH or of NH 2 function per mole of starting alkylphenolsulfonic acid.
  • total alkaline earth base means the total amount of alkaline earth base (s) used to carry out all of the steps; "alkaline earth base of sulfurization-over-alkalization” is understood to mean that intervening in the 2nd stage, that is to say of sulfurization-over-alkalization.
  • the amount of third solvent used in this 2nd step corresponds to that necessary to obtain a fluid medium, that is to say of viscosity less than 50 10- 6 m 2 / s (50 cSt) approximately under the reaction conditions .
  • the third stage that of carbonation, is favorably carried out at a temperature of 145-180 ° C. under a pressure of 930 10 Z to 1010 10 2 Pa approximately.
  • dilution oil is introduced in an amount 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.
  • paraffinic oils such as 100 Neutral oil
  • naphthenic or mixed oils may also be suitable.
  • the additives which are the subject of the invention have a high basicity; the TBN (Total Basic Number-Norm A.S.T.M. D 2896) of additives based on calcium salts, for example, easily reaches 250.
  • TBN Total Basic Number-Norm A.S.T.M. D 2896
  • the amount of additive to be used to improve the detergent-dispersant properties of lubricating oils is a function of the future use of said oils.
  • the amount of additive to be added is generally between 1 and 3% by weight; for a diesel engine oil, it is generally between 1.5 and 5% by weight, for a marine engine oil, it is generally between 10 and 30%.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as lubricating oils of naphthenic base, of paraffinic base and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from products.
  • coal, and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkybiphenyl 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; there may be mentioned, for example, antioxidant, anti-corrosion additives, dispersant and ash additives.
  • a dodecylphenol sulfonic acid containing 20 SO 3 H functions per 100 OH functions is prepared, by the action of 100 g of concentrated sulfuric acid (96% by weight) on 1048 g of p-dodecylphenol in the presence of 270 g of hexane; the reaction water and the hexane are removed from the medium by azeotropic distillation.
  • the medium is heated with stirring until the water-2-ethylhexanol azeotrope is distilled.
  • the medium is heated to 150 ° C. with stirring and slight depression (980 10 2 Pa).
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for about 1 hour.
  • Sediment is removed by centrifugation.
  • the additive obtained has a TBN of 256 (standard ASTM D 2896).
  • a 1% by weight solution of calcium of the additive obtained is prepared in 350 Neutral CFR oil, to which 2% by weight of water is added.
  • the solution obtained is brought to 93 ° C for 73 hours, then is filtered.
  • the TBN of the filtrate is measured.
  • the ratio TBN of the filtrate / TBN of the initial additive in% indicates the basicity retained by the treated additive.
  • the medium is heated with stirring until distillation of the water-hexane azetrope.
  • the medium is heated to 150 ° C. with stirring and slight depression (980 10 2 Pa).
  • the water is removed by distillation of the azeotrope water-2-ethyl hexanol.
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for about 1 hour.
  • Sediment is removed by centrifugation.
  • the additive obtained has a TBN of 250.
  • the medium is heated with stirring until the water-xylene azeotrope is distilled.
  • the medium is heated to 140 ° C. with stirring and slight depression (980 10 2 Pa).
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for about 1 hour.
  • the additive obtained has a TBN of 284.
  • alkylphenol sulfonic acid containing 21 SO 3 H functions per 100 OH functions is prepared by the action of sulfur trioxide diluted with nitrogen (2% by volume) on a mixture of 1860 g of p.dodecylphenol and 800 g of tetracosylphenol in presence of 670 g of hexane, at a temperature between 5 and 10 ° C.
  • the hexane is evaporated under reduced pressure (60 10 2 Pa) by heating to 30 ° C.
  • the medium is heated with stirring until the water-2-ethylhexanol azeotrope is distilled.
  • the medium is heated to 155 ° C with gentle vacuum stirring (980 10 z Pa).
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for approximately 1 hour.
  • the additive obtained has a TBN of 250.
  • a dodecylphenol sulfonic acid containing 35 sulfonic functions per 100 OH functions is prepared by the action of sulfur trioxide diluted with nitrogen (2% by volume) on 1048 g of p.dodecylphenol in the presence of 300 g of hexane, at a temperature between 5 and 10 ° C.
  • the hexane is evaporated under reduced pressure (60 10 2 Pa) by heating to 30 ° C.
  • the medium is heated with stirring until the water-2-ethylhexanol azeotrope is distilled. Thirty minutes later, the reaction is complete and the medium is cooled.
  • the medium is heated to 150 ° C. with stirring and slight depression (980 10 2 Pa).
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for approximately 1 hour.
  • the medium is heated with stirring until the water-2-ethylhexanol azeotrope is distilled. Thirty minutes later, the reaction is complete.
  • the medium is heated to 150 ° C. with stirring and slight depression (980 10 2 Pa).
  • a mixture of 170 g of ethylene glycol and 350 g of ethylene glycol and 350 g of 2-ethylhexanol is then added over 1 hour.
  • the water is removed by distillation of the azeotrope water-2-ethyl hexanol.
  • the pressure is brought to 965 10 2 Pa and the temperature fixed at 165 ° C for 1 hour.
  • the product obtained is carbonated by bubbling C0 2 introduced at the flow rate of 2 g / min for approximately 1 hour.
  • the additive obtained has a TBN of 280

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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)

Claims (12)

1. Sulfonierte und sulfurierte, als Detergentien und Dispergiermittel wirkende Additive für Schmieröle, dadurch gekennzeichnet, daß sie erhalten werden durch:
a) Neutralisation einer Alkylphenolsulfonsäure mit einem Ausmaß an Sulfonfunktionen von 6 bis 35 S03H-Funktionen pro 100 OH-Funktionen mit einer Erdalkilibase in einem Molverhältnis Erdal- kibase/S03H-Funktion von wenigstens 1, gegebenenfalls in Gegenwart eines Neutralisationskatalysators,
(b) zusätzliche Zugabe eines Verdünnungsöls, anschließende Sulfurierung und Überalkalisierung des erhaltenen Salzes durch Schwefel in Gegenwart einer Erdalkalibase, eins Alkoholvektors, ausgewählt aus Ethylenglykolen und Alkoxyalkanolen, eines dritten Lösungsmittels mit einem Siedepunkt von mehr als 120°C, ausgewählt aus aliphatischen Kohlenwasserstoffen, aromatischen Kohlenwasserstoffen und Alkoholen, wobei die Mengen der eingesetzten Reagentien den folgenden Molverhältnissen entsprechen:
Schwefel/Ausgangsalkylphenolsulfonsäure im Bereich von 0,4 bis 1,3
Gesamterdalkalibase/Ausgangsalkylphenolsulfonsäure in einem Bereich von 1,5 bis 2,2 und
Erdalkalibase für die Sulfurierung und ÜberalkalisierungNektoralkohol im Bereich von 1,4 bis 2,5,
(c) Carbonisierung des auf diese Weise erhaltenen sulfurierten Alkylphenatsulfonats mit Kohlendioxid bei einer Temperatur von 100 bis 185°C unter einem Druck, der nahe Atmosphärendruck ist, wobei die eingesetzte C02-Menge zwischen der Menge liegt, die vollständig durch das Reaktionsmedium absorbiert werden kann, und einem Überschuß von 30% dieser Menge,
(d) Entfernung des Vektoralkohols, des Wassers und des dritten Lösungsmittels nach der Zugabe von Verdünnungsöl durch Destillation und
(e) Entfernung der Sedimente durch Filtrieren oder durch zentrifugieren.
2. Additive nach Anspruch 1, dadurch gekennzeichnet, daß die Mengen der bei der Neutralisations-, Sulfurierungs- und Überalkalisierungsstufe eingesetzten Reagentien den folgenden Molverhältnissen entsprechen:
Erdalkalibase/S03H-Funktion im Bereich von 1 bis 1,2,
Schwefel/Ausgangsalkylphenolsulfonsäure im Bereich von 0,6 bis 1,1,
Gesamteralkalibase/Ausgangsalkylphenolsulfonsäure in einem Bereich von 1,7 bis 2 und
Erdalkalibase für die Sulfurierung und ÜberalkalisierungNektoralkohol im Bereich von 1,6 bis 2,3.
3. Additive nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Erdalkalibase ein Oxid oder Hydroxid von Kalzium, Barium oder Strontium ist.
4. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Alkylenglykole aus Glykol, Diethylenglykol oder Propylenglykol bestehen.
5. Additive nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Alkoxyalkanole der Formel R(OR')x0H entsprechen, wobei R ein Methyl-, Ethyl- oder Butylrest ist, R' ein Ethyl oder Propylrest ist und x 1 oder 2 ist.
6. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das dritte Lösungsmittel aus Xylol, 2-Ethylhexanol, Decylalkohol oder Tridecylalkohol besteht.
7. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Neutralisationsstufe und/oder die Überalkalisierungsstufe in Gegenwart von 0 bis 0,1 Mol COOHlonen, Halogendionen oder NH2-Funktion pro Mol der Ausgangsalkylphenolsulfonsäure durchgeführt wird (werden).
8. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Neutralisation in Gegenwart eines Lösungsmittels durchgeführt wird, das mit Wasser einen Azeotrop bei einer Temperatur bildet, die wenigstens gleich derjenigen der Bildung des Wasser/ Lösungsmittel-Azeotrops ist.
9. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die zweite Stufe bei einer Temperatur in der Größenordnung von 140 bis 195°C während ungefähr 3 bis 6 Stunden durchgeführt wird und die. Überalkalisierung bei einer Temperatur in der Größenordnung von 140 bis 170°C ausgeführt wird.
10. Additive nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Carbonisierungsstufe bei einer Temperatur von 145 bis 180°C unter einem Druck von ungefähr 930 102 bis 1010 102 Pa ausgeführt wird.
11. Schmiermittelzubereitungen, enthaltend ein Schmieröl mit einer geeigneten Viskosität und 1 bis 30% eines der sulfonierten oder sulfurierten, als Deteregentien und Dispergiermittel wirkenden Additive, welche Gegenstand eines der vorstehenden Ansprüche sind.
EP86401497A 1985-07-08 1986-07-04 Sulfonierte und sulfurisierte Detergens Dispergierzusätze für Schmieröle Expired - Lifetime EP0211722B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8510399A FR2584414B1 (fr) 1985-07-08 1985-07-08 Nouveaux additifs detergents-dispersants sulfones et sulfurises pour huiles lubrifiantes
FR8510399 1985-07-08

Publications (2)

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EP0211722A1 EP0211722A1 (de) 1987-02-25
EP0211722B1 true EP0211722B1 (de) 1990-05-23

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EP86401497A Expired - Lifetime EP0211722B1 (de) 1985-07-08 1986-07-04 Sulfonierte und sulfurisierte Detergens Dispergierzusätze für Schmieröle

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US (1) US4751010A (de)
EP (1) EP0211722B1 (de)
JP (1) JPH07116460B2 (de)
BR (1) BR8603151A (de)
CA (1) CA1269973A (de)
DE (1) DE3671469D1 (de)
FR (1) FR2584414B1 (de)
MX (1) MX26908A (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2625220B1 (fr) * 1987-12-23 1990-12-21 Orogil Procede de preparation d'additifs detergents-dispersants suralcalinises pour huiles lubrifiantes
FR2625219B1 (fr) * 1987-12-23 1990-12-21 Orogil Additifs detergents-dispersants a base de sels de metaux alcalino-terreux et alcalins pour huiles lubrifiantes
US5330664A (en) * 1992-09-02 1994-07-19 Chevron Research And Technology Company Neutral and low overbased alkylphenoxy sulfonate additive compositions derived from alkylphenols prepared by reacting an olefin or an alcohol with phenol in the presence of an acidic alkylation catalyst
US5330663A (en) * 1992-09-02 1994-07-19 Chevron Research And Technology Company Neutral and low overbased alkylphenoxy sulfonate additive compositions
MX9305120A (es) * 1992-09-04 1994-03-31 Lubrizol Corp Composiciones sobrebasificadas sulfuradas.
DE69531043T2 (de) * 1994-12-28 2003-12-04 Chevron Oronite Co. Llc, San Ramon Überbasische alkyloxybenzolsulfonate als detergentien
US5556569A (en) * 1995-04-06 1996-09-17 The Lubrizol Corporation Non-conventional overbased materials
US5780398A (en) * 1996-12-27 1998-07-14 Chevron Chemical Company High overbased alkyloxy aromatic sulfonate-carboxylates as lube oil additives

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1352898A (en) * 1919-07-08 1920-09-14 Houck George Henry Wrecking-trailer for automobiles
US3523898A (en) * 1966-04-05 1970-08-11 Phillips Petroleum Co Increased base number metal petroleum sulfonate and process for its preparation
US3429811A (en) * 1966-08-17 1969-02-25 Exxon Research Engineering Co Preparation of overbased sulfonates
JPS5017953B1 (de) * 1969-09-26 1975-06-25
FR2416942A1 (fr) * 1978-02-08 1979-09-07 Orogil Procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes
US4192758A (en) * 1978-05-01 1980-03-11 Bray Oil Company, Inc. Overbased magnesium sulfonate process
FR2429831A2 (fr) * 1978-06-26 1980-01-25 Orogil Nouveau procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes
FR2549080B1 (fr) * 1983-07-11 1986-04-04 Orogil Procede de preparation d'additifs detergents-dispersants de tres haute alcalinite a base de calcium et additifs detergents-dispersants pour huiles lubrifiantes ainsi obtenus
US4615841A (en) * 1983-09-22 1986-10-07 Dresser Industries, Inc. Process for making alkaline-earth metal salts of alkaryl sulfonic acids

Also Published As

Publication number Publication date
BR8603151A (pt) 1987-02-24
EP0211722A1 (de) 1987-02-25
JPH07116460B2 (ja) 1995-12-13
JPS6284191A (ja) 1987-04-17
FR2584414B1 (fr) 1987-10-30
DE3671469D1 (de) 1990-06-28
FR2584414A1 (fr) 1987-01-09
CA1269973A (fr) 1990-06-05
US4751010A (en) 1988-06-14
MX26908A (es) 1994-01-31

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