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EP0235929B1 - Additifs surbasiques - Google Patents

Additifs surbasiques Download PDF

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Publication number
EP0235929B1
EP0235929B1 EP19870300761 EP87300761A EP0235929B1 EP 0235929 B1 EP0235929 B1 EP 0235929B1 EP 19870300761 EP19870300761 EP 19870300761 EP 87300761 A EP87300761 A EP 87300761A EP 0235929 B1 EP0235929 B1 EP 0235929B1
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EP
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Prior art keywords
water
sodium hydroxide
moles
sodium
alkoxyalkanol
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Application number
EP19870300761
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German (de)
English (en)
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EP0235929A1 (fr
Inventor
John Arthur Cleverley
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • This invention relates to overbased additives containing sodium sulphonate.
  • Lubricants often need the presence of detergents and there is an increasing need for detergent additives which have high basicity, especially automotive lubricants where their high basicity neutralises acids formed during operation of the engine.
  • This invention relates to such high basicity or "overbased" additives which contain colloidally dispersed carbonates and include the presence of sodium sulphonate.
  • an oil solution of a highly basic sodium sulphonate is prepared by a process which comprises:
  • step (a) in the case when the alkoxyalkanol and sulphonic acid are the only species present capable of reacting with sodium hydroxide to form water in steps (a) and (b) the azeotrope is removed in step (a) until the sum of number of moles of sodium hydroxide in excess of that reacted in step (a) plus the number of moles of organic sulphonic acid to be added to step (b) is not more than the number of moles of sodium hydroxide reacted in step (a).
  • a + C ⁇ B (wherein A is the number of moles of sodium hydroxide in excess of that reacted with alkoxyalkanol in step (a), B is the number of moles of sodium hydroxide reacted with alkoxyalkanol in step (a) and C is the number of moles of sulphonic acid added in step (b)).
  • a + C ⁇ B and sufficient water is not formed to hydrolyse the formed sodium alkoxyalkoxide, then more water, preferably as an alkoxyalkanol/water mixture, is added after step (c) and before step (d) to hydrolyse any remaining alkoxyalkoxide.
  • additional reactants such as further surfactants may be added to the process, and in the event that these additional reactants are capable of reacting with sodium hydroxide to form water the azeotrope may be carried further to form more alkoxide provided that : where D n is the number of moles of additional reactant of which 1 mole is capable of reacting with sodium hydroxide to form n moles of water in excess of the amount of water produced if that sodium hydroxide were carbonated.
  • n y-x/2 where x moles of sodium hydroxide react with one mole of the additional reactant to produce y moles of water.
  • TBN total base numbers
  • One of the starting materials is sodium hydroxide and the normal commercial grade can be used.
  • the solvent can be, for example, any aliphatic, naphthenic or aromatic solvent provided it forms an azeotrope with water; in particular, n-hexane, n-heptane, n-octane, n-dodecane, benzene, xylene, toluene, white spirit, naphtha or isoparaffins.
  • hydrocarbon solvent usually, it is a hydrocarbon solvent but it could be a halogenated hydrocarbon, e.g. chlorobenzene.
  • halogenated hydrocarbon e.g. chlorobenzene.
  • the most preferred solvents are toluene and xylene.
  • aromatic substituted alkoxyalkanols could be used, it is preferable to use an aliphatic alkoxyalkanol, expecially those containing 2 to 10 carbon atoms per molecule.
  • Suitable examples of aliphatic alkoxyalkanols are methoxy methanol, methoxy ethanol, methoxy isopropanol, ethoxy methanol, 2-ethoxy ethanol, 2-butoxy-ethanol or propylene glycol ethers, e.g. methoxy propanols, butoxy propanols or phenoxy propanols.
  • the amount of alkoxyalkanol employed in the process per mole of sodium hydroxide will usually be in the range of 0.5 to 50, preferably 0.75 to 2.
  • the organic sulphonic acids are usually obtained from the sulphonation of natural hydrocarbons or synthetic hydrocarbons; e.g. a mahogany or petroleum alkyl sulphonic acid; an alkyl sulphonic acid or an alkaryl sulphonic acid.
  • Such sulphonic acids are obtained by treating lubricating oil basestocks with concentrated or fuming sulphuric acid to produce oil-soluble "mahogany" acids or by sulphonating alkylated aromatic hydrocarbons.
  • Sulphonates derived from synthetic hydrocarbons include those prepared by the alkylation of aromatic hydrocarbons with olefins or olefin polymers; e.g. C15-C30 polypropenes or polybutenes.
  • sulphonic acids of alkyl benzenes, alkyl toluenes or alkyl xylenes which may have one or more alkyl groups wherein each group, which may be straight or branched, preferably contains at least 12 carbon atoms.
  • the preferred sulphonic acids have molecular weights of from 300 to 1000, for example, between 400 and 800, e.g. about 500. Mixture of these sulphonic acids may also be used.
  • the mole ratio of sulphonic acid to sodium hyroxide is usually between 1:5 and 1:36, preferably 1:10 to 1:25.
  • a sulphonic acid e.g. an alkyl benzene sulphonic acid
  • an alkyl benzene sulphonic acid may be sufficient to act as the surfactant for the overbased material of the invention, especially when it has a relatively high molecular weight aliphatic chain e.g. of molecular weight more than about 400, very often it is desirable to include another surfactant having a long aliphatic chain usually with a molecular weight of 700 or greater, for example about 900, in the reaction mixture.
  • This additional surfactant is a dicarboxylic acid or anhydride, or an ester, amide imide, amine salt or ammonium salt of a dicarboxylic acid and as such include those represented by the formulae: where R1 and R2 are hydrogen or optionally-substituted hydrocarbyl groups of at least 30 carbon atoms provided they are not both hydrogen, m and n are zero or integers, R3 and R4 are hydrogen or hydrocarbyl groups and R5 and R6 are hydrocarbyl groups.
  • R2 be hydrogen and that m and n be zero or a small integer, e.g. 1 or 2.
  • acids or anhydrides are the preferred surfactant.
  • R3, R4, R5 and R6 are alkyl groups, especially a C1 to C5 alkyl group, for example, methyl, ethyl or propyl.
  • the ester could be derived from a glycol, in which case R3 and R4 would not be separate hydrocarbyl groups, but instead, the residue of a glycol, for example, ethylene glycol or propylene glycol.
  • the most preferred compounds are those where R1 contains 40 to 200 carbon atoms and where R1 has no atoms other than carbon, hydrogen and halogen, and especially when it only contains carbon and hydrogen atoms, i.e., it is a hydrocarbyl group.
  • R1 contains 40 to 200 carbon atoms and where R1 has no atoms other than carbon, hydrogen and halogen, and especially when it only contains carbon and hydrogen atoms, i.e., it is a hydrocarbyl group.
  • Preferred hydrocarbyl groups are aliphatic groups.
  • the acid, anhydride, ester, amide, imide, amine salt or ammonium salt is preferably substantially saturated, but the substituent group, for example, the group R1, may be unsaturated.
  • the substituent group be a polymer of a monolefin, for example, a C2 to C5 monolefin, such as polyethylene, polypropylene or polyisobutene. Such polymers will usually have only one double bond so that they could be regarded as predominantly saturated, especially since they must have at least 30 carbon atoms.
  • the most preferred acid or anhydride is one of the formula: especially where R1 is polyisobutenyl, i.e. a polyisobutenyl succinic acid or anhydride, preferably where R1 has 30 to 200 carbon atoms, especially 45 to 60 carbon atoms.
  • Such anhydrides are frequently known as PIBSA.
  • the molar ratio of organic sulphonic acid to the acid, amide, imide, amine salt, ammonium salt, anhydride or ester can vary but is usually between 20:1 and 2:1, e.g. between 15:1 and 4:1.
  • the first step of the process is the addition of sodium hydroxide to the mixture of alkoxyalkanol and solvent and reaction of a part of the sodium hydroxide to form the sodium alkoxyalkoxide.
  • the reaction mixture is heated so that the temperature is slowly increased and the water formed by the reaction to form sodium alkoxyalkoxide is removed as an azeotrope with the solvent and the alkoxyalkanol. Little solvent is normally removed in the azeotrope, and the reaction vessel may be equipped with a condenser so that substantially all solvent is returned to the reaction vessel.
  • the recovered azeotrope then comprises water and alkoxyalkanol with substantially no solvent.
  • This heating which in effect is azeotropic distillation effectively controls the amount of sodium hydroxide converted to alkoxyalkoxide since the removal of water drives the alkoxyalkoxide-forming reaction.
  • the extent to which this reaction is driven and formed water is removed is critical since surprisingly it has been found that excess water in the system tends to result in a hazy and unsatisfactory product.
  • a surprising and effective means of preventing this haze formation is by using the alkoxyalkoxide formation and subsequent hydrolysis as a control of the water in the system. By forming alkoxyalkoxide in such an amount that the water required to hydrolyse it is at least equal to the water generated in the remaining steps of the process, effective control over haze may be obtained.
  • azeotropic distillation takes at least an hour, and times of from 1.5 to 2 hours are typical for small scale operations.
  • the organic sulphonic acid and optionally the dicarboxylic acid, anhydride or ester, amide, imide, amine salt or ammonium salt are added preferably at 50°C to 70°C to the reaction mixture which may then be heat-soaked, e.g. at a temperature of about 80°C to 100°C.
  • the sulphonic acid and dicarboxylic acid, anhydride, ester, amide, imine, amine salt or ammonium salt are usually introduced as solutions in diluent oil, e.g. an aliphatic or aromatic hydrocarbon.
  • the purpose of this heat soaking is to effect neutralisation of the organic sulphonic acid, and if used, the dicarboxylic acid, anhydride, monoamine salt or monoammonium salt by the sodium hydroxide.
  • the time taken for this heat soaking is usually from 10 to 30 minutes, e.g. about 20 minutes.
  • the amount of sodium hydroxide and organic sulphonic acid are related and dependent on the degree of reaction with alkoxyalkanol in step (a) as discussed above.
  • a part of the sodium hydroxide reacts with the alkoxyalkanol according to the equation NaOH + ROH ----> NaOR + H2O (where R is an alkoxyalkyl group).
  • B moles of sodium hydroxide react with alkoxyalkanol in step (a) in this and B moles of water are formed and removed as azeotrope, while there is an excess of A moles of sodium hydroxide unreacted in step (a).
  • step (b) If C moles of organic sulphonic acid are introduced in step (b) to react with a further part of the sodium hydroxide then C moles of water are formed and A + C ⁇ B to ensure that excess water is not formed which would give rise to haze.
  • the reaction of sulphonic acids with sodium hydroxide may be represented: R ⁇ SO2OH + NaOH ----> R ⁇ SO2ONa + H2O (where R ⁇ is the organic group of the sulphonic acid). If a further surfactant is used, such as dicarboxylic acid or anhydride which also reacts with sodium hydroxide to form water than an appropriate adjustment must be made such that:
  • n 1 and A + C + 2D2 ⁇ B where D2 is the number of moles of dicarboxylic acid, mono-amine or salt.
  • n 0 and A + C ⁇ B, that is independent of the number of moles (D0) of the anhydride present.
  • carbon dioxide is introduced to react with the basic sodium compounds in the reaction mixture which is preferably maintained at a temperature from ambient to the reflux temperature of the mixture, typically 120°C, more preferably between 80°C and 100°C, for example, about 90°C.
  • the preferred amount of carbon dioxide which is blown into or injected into the reaction mixture is 90% to 115%, e.g. about 105% of the theoretical amount required to react with available basic sodium compounds.
  • carbon dioxide is blown in until no more carbon dioxide is absorbed, e.g. when the gas inlet and exit rates, as measured on gas rotameters are the same. Rates are usually chosen to introduce the carbon dioxide over 2 to 4 hours, e.g. about 3 hours.
  • the basic sodium compounds which will react with the carbon dioxide include the previously unreacted sodium hydroxide which will react: 2 NaOH + CO2 ----> Na2CO3 + H2O to form the desired overbased product.
  • sodium alkoxyalkoxide formed in step (a) will be hydrolysed and carbonated to form additional sodium carbonate in the product according to the overall reaction: 2 NaOR + H2O + CO2 ----> Na2CO3 + 2 ROH in which the water for the hydrolysis (on the left hand side of the reaction) is obtained from the reaction of sulphonic acid with sodium hydroxide, the reaction of carbon dioxide with sodium hydroxide and, if present, the reaction of additional materials such as further surfactants with sodium hydroxide.
  • This overall carbonation and hydrolysis may taken place in stages.
  • Either the alkoxyalkoxide may be first hydrolysed: RONa + H2O ----> ROH + Na OH for example in step (b) and then the formed sodium hydroxide subsequently carbonated, or the alkoxyalkoxide may be carbonated in step (c) according to the reaction: RONa + CO2 ----> RO-COONa and the carbonated alkoxyalkoxide subsequently hydrolysed: 2 RO-COONa + H2O ----> 2 ROH + CO2 + Na2CO3 or a combination of these steps may take place giving the overall reaction set out above.
  • water may be added, preferably as a mixture of water and alkoxyalkanol, to convert the residual carbonated sodium alkoxyalkoxide to sodium carbonate.
  • Water or any mixture of water and alkoxyalkanol can be used preferably between 1:6 and 1:2 water:alkoxyalkanol (by weight).
  • the water/alkoxyalkanol mixture is usually slowly added to the reaction mixture to convert the residual carbonated sodium alkoxyalkoxide to sodium carbonate, alkoxyalkanol and carbon dioxide and this addition continues until the evolution of carbon dioxide ceases.
  • the next step in the process is to remove the alkoyalkanol and solvent by distillation. Usually, this takes place by atmospheric distillation typically at a temperature of about 180°C, optionally followed by distillation under reduced pressure whence the residual solvent and alkoxyalkanol will be removed.
  • solid contaminants may be removed from the product preferably by filtration or centrifuging.
  • the desired product is the filtrate or centrifugate.
  • the desired product is a solution in oil and therefore base oil is added to the process in step (b), (c) or (d). Most preferably the oil is added with the sulphonic acid in step (b).
  • Base oils used in the process are preferably lubricating oils as described hereinafter.
  • the process of the invention enables a high quality, high TBN sodium sulphonate product to be obtained in good yields (e.g. 95% + of theoretical) with reduced amounts of material losses in sludge and/or sediment and reduced problems in waste disposal which can arise when large amounts of sludge or flocculent material are produced.
  • the process of the invention in particular provides a means of preparing a preferred product with a TBN of at least 250, preferably 250 to 600 mg (KOH)/g, more preferably 350 to 500, specifically in the region of 400 mg (KOH)/g.
  • the overbased additive of this invention is suitable for use in oleaginous compositions such as fuels or lubricating oils for gasoline or diesel engines, both mineral and synthetic.
  • the lubricating oil may be an animal, vegetable or mineral oil, for example, petroleum oil fractions ranging from naphthas or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oils or oxidised mineral oil.
  • Suitable synthetic ester lubricating oils include diesters such as dioctyl adipate, dioctyl sebacate, didecyl azelate, tridecyl adipate, didecyl succinate, didecyl glutarate and mixtures thereof.
  • the synthetic ester can be a polyester such as that prepared by reacting polyhydric alcohols such as trimethylolpropane and pentaerythritol with monocarboxylic acids such as butyric acid, caproic acid, caprylic acid and pelargonic acid to give the corresponding tri- and tetra-ester.
  • complex esters may be used as base oils such as those formed by esterification reactions between a dicarboxylic acid, a glycol and an alcohol and/or a monocarboxylic acid.
  • Blends of diesters with minor proportions of one or more thickening agents may also be used as lubricants.
  • the amount of overbased detergent added to the lubricating oil should be a minor proporton, e.g. between 0.01% and 10% by weight, preferably between 0.1% and 5% by weight.
  • the final lubricating oil may contain other additives according to the particular use for the oil.
  • viscosity index improvers such as ethylene-propylene copolymers may be present as may ashless dispersants such as substituted succinic acid based dispersants, other metal containing dispersant additives, well known zinc dialkyldithio-phosphate antiwear additives, antioxidants, demulsifiers, corrosion inhibitors, extreme pressure additives and friction modifiers.
  • the oils of the invention may contain ashless dispersant, a zinc dialkyl dithiophosphate and copper in an oil soluble form (preferably in an amount of 5 to 500 ppm copper) as antioxidant.
  • the invention also includes an additive concentrate comprising an oil solution of an overbased sodium sulphonate of the invention comprising 10 to 90 wt %, preferably 40 to 60 wt % overbased sodium sulphonate (active matter) based on the weight of oil.
  • the overbased material When used in fuels as a detergent or combustion improver the overbased material is used in minor proportions, e.g. between 0.01 and 10% by weight of the fuel.
  • Example H This is a repeat of Example H except that only 20 grams of hydrolysis water is used and thus all the carbonated alkoxide was not converted to the carbonate. The product was very viscous and skinned on exposure to air, but Example H shows that by addition of the appropriate amount of water an excellent product may be prepared.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)

Claims (12)

1. Procédé de production d'une solution dans l'huile d'un sulfonate de sodium rendu surbasique ayant un indice de basicité totale d'au moins 250 mg de KOH/g, procédé qui consiste :
(a) à chauffer de l'hydroxyde de sodium avec un alkoxyalcanol et un solvant pour éliminer sous forme d'azéotrope avec ledit alkoxyalcanol et ledit solvant une quantité réglée d'eau formée dans la réaction d'une partie de l'hydroxyde de sodium avec l'alkoxyalcanol ;
(b) à ajouter au mélange un acide sulfonique organique de manière qu'il réagisse avec une partie de l'hydroxyde de sodium et qu'il forme le sel de sodium de l'acide sulfonique et de l'eau ;
(c) à introduire ensuite de l'anhydride carbonique dans le mélange réactionnel de manière qu'il réagisse avec les composés de sodium basiques qui s'y trouvent ;
(d) à chasser le solvant par distillation ; et
(e) à ajouter une huile de base dans le procédé au cours de l'une des étapes (b), (c) ou (d) de manière à obtenir le produit désiré,
la quantité d'alcoolate produite dans l'étape (a) étant réglée par l'élimination azéotropique d'eau dans cette étape de manière que la quantité d'eau produite dans l'étape (b) et dans l'étape (c) ne soit pas supérieure à la quantité stoechiométriquement nécessaire pour hydrolyser l'alcoolate.
2. Procédé suivant la revendication 1, dans l'étape (b) duquel on ajoute également un acide dicarboxylique ou un anhydride, un ester, un amide, un imide, un sel d'amine ou un sel d'ammonium de cet acide, afin qu'il réagisse avec une autre partie des composés de sodium basiques qui s'y trouvent.
3. Procédé suivant la revendication 1, dans lequel l'alkoxyalcanol et l'acide sulfonique sont les seuls corps réactionnels ajoutés dans les étapes (a) et (b) qui soient capables de réagir avec l'hydroxyde de sodium pour former de l'eau, et dans lequel l'élimination azéotropique de l'eau dans l'étape (b) est conduite de manière à vérifier la relation : A + C ≦ B
Figure imgb0025
 dans laquelle B représente le nombre de moles d'hydroxyde de sodium qui réagissent avec l'alkoxyalcanol dans l'étape (a), A est le nombre de moles d'hydroxyde de sodium en plus de B, et C est le nombre de moles d'acide sulfonique ajoutées dans l'étape (b).
4. Procédé suivant la revendication 2, dans lequel sont présents d'autres corps réactionnels qui sont capables de réagir avec l'hydroxyde de sodium pour former de l'eau, et dans lequel l'élimination azéotropique d'eau dans l'étape (a) est conduite de manière que soit vérifiée la relation :
Figure imgb0026
 dans laquelle Dn représente le nombre de moles de corps réactionnel ajouté dont une mole est capable de réagir avec l'hydroxyde de sodium pour former n moles d'eau en plus de la quantité d'eau produite si cet hydroxyde de sodium est carbonaté.
5. Procédé suivant la revendication 4, dans lequel un acide dicarboxylique et/ou un sel de mono-amine ou un sel de mono-ammonium de cet acide est ajouté dans l'étape (b), et dans lequel l'élimination azéotropique d'eau dans l'étape (a) est conduite de manière que soit vérifiée la relation : A + C + 2D₂ ≦ B
Figure imgb0027
 dans laquelle D₂ représente le nombre de moles d'acide dicarboxylique, de sel de mono-amine ou de sel de monoammonium d'acide dicarboxylique.
6. Procédé suivant l'une quelconque des revendications précédentes, dans lequel le solvant est le toluène ou le xylène.
7. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'alkoxyalcanol contient 2 à 10 atomes de carbone par molécule.
8. Procédé suivant l'une quelconque des revendications précédentes, dans lequel l'acide sulfonique a un poids moléculaire compris entre 400 et 800.
9. Procédé suivant la revendication 2, dans lequel l'acide ou l'anhydride d'acide ajouté dans l'étape (b) est un acide ou anhydride d'acide polyisobuténylsuccinique.
10. Composition lubrifiante, comprenant une huile lubrifiante et 0,01 à 10 % en poids du sulfonate de sodium préparé par le procédé suivant l'une quelconque des revendications 1 à 9.
11. Composition lubrifiante suivant la revendication 10, qui contient également un dispersant sans cendres, un dialkyldithiophosphate de zinc et 5 à 500 ppm en poids de cuivre sous une forme soluble dans l'huile.
12. Composition de carburant, comprenant un carburant et un sulfonate de sodium fortement basique préparés par le procédé suivant l'une quelconque des revendications 1 à 9.
EP19870300761 1986-01-28 1987-01-28 Additifs surbasiques Expired EP0235929B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB868601990A GB8601990D0 (en) 1986-01-28 1986-01-28 Overbased additives
GB8601990 1986-01-28

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Publication Number Publication Date
EP0235929A1 EP0235929A1 (fr) 1987-09-09
EP0235929B1 true EP0235929B1 (fr) 1991-10-16

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EP (1) EP0235929B1 (fr)
JP (1) JP2512457B2 (fr)
CA (1) CA1289547C (fr)
DE (1) DE3773698D1 (fr)
GB (1) GB8601990D0 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8621343D0 (en) * 1986-09-04 1986-10-15 Exxon Chemical Patents Inc Overbased alkali metal additives
ATE142249T1 (de) * 1991-04-19 1996-09-15 Lubrizol Corp Verfahren zur herstellung von überbasischen alkalimetallsalzen
US5449470A (en) * 1991-04-19 1995-09-12 The Lubrizol Corporation Overbased alkali salts and methods for making same
US20080274921A1 (en) 2007-05-04 2008-11-06 Ian Macpherson Environmentally-Friendly Lubricant Compositions
EP2025737A1 (fr) 2007-08-01 2009-02-18 Afton Chemical Corporation Compositions de combustibles sans danger pour l'environnement

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2920105A (en) * 1957-12-13 1960-01-05 Texaco Inc Preparation of hyperbasic sulfonates
ZA738848B (en) * 1973-10-05 1975-06-25 Lubrizol Corp Basic alkali sulfonate dispersions and processes
GB1551820A (en) * 1975-05-23 1979-09-05 Exxon Research Engineering Co Production of basic magnesium sulphonates
GB2056482A (en) * 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions

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JPS62190296A (ja) 1987-08-20
DE3773698D1 (de) 1991-11-21
CA1289547C (fr) 1991-09-24
GB8601990D0 (en) 1986-03-05
JP2512457B2 (ja) 1996-07-03
EP0235929A1 (fr) 1987-09-09

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