EP0168110B1 - Verfahren zur Herstellung von geschwefelten, überbasischen Salicylaten - Google Patents

Verfahren zur Herstellung von geschwefelten, überbasischen Salicylaten Download PDF

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Publication number
EP0168110B1
EP0168110B1 EP85201082A EP85201082A EP0168110B1 EP 0168110 B1 EP0168110 B1 EP 0168110B1 EP 85201082 A EP85201082 A EP 85201082A EP 85201082 A EP85201082 A EP 85201082A EP 0168110 B1 EP0168110 B1 EP 0168110B1
Authority
EP
European Patent Office
Prior art keywords
metal
reaction
aliphatic hydrocarbon
meq
substituted
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
EP85201082A
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English (en)
French (fr)
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EP0168110A1 (de
Inventor
Rudolf Frank Heldeweg
Martin Booth
Eugène Marie Godfried Andre van Kruchten
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.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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

  • This invention relates to a process for the preparation of sulphurized overbased metal aliphatic hydrocarbon-substituted salicylates by sulphurization of an aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof, to products thus prepared and to oil compositions containing them.
  • UK Patent Specification 825315, and USP. 2,335,017 and USP 2311931 disclose the reaction of sulphur chlorides with phenols-and with unsubstituted salicylate esters.
  • those phenols and esters are significantly more reactive than the hydrocarbon-substituted salicylic acids (or their metal salts) which form the starting materials for the production of overbased hydrocarbon-substituted salicylates used as luboil additives.
  • hydrocarbon-substituted salicylic acids or their metal salts
  • sulphur halides can, indeed, be used in the sulphurization of hydrocarbon-substituted salicylic acids, and that the use of this reagent in place of the elemental sulphur hitherto employed results in a much lower degree of decarboxylation.
  • This invention therefore relates to a process for the preparation of sulphurized overbased, metal aliphatic hydrocarbon-substituted salicylates by sulphurization of an aliphatic hydrocarbon-substituted salicylic acid or a metal salt thereof with a sulphur halide, and subsequently by transforming the reaction product into an overbased metal salicylate.
  • the invention furthermore relates to the products thus prepared and to oil compositions containing them.
  • Suitable metals of the overbased metal salicylates are e.g. alkali metals, such as Li, Cs, Na and K, alkaline earth metals, such as Ca, Ba, Sr and Mg, and polyvalent metals, such as Zn and Cr.
  • Suitable aliphatic hydrocarbon-substituted salicylic acids are described in the above-mentioned British patent specifications. Preferred are C 8 - 30 -alkyl salicylic acids.
  • an alkali metal salt in particular the sodium salt, is preferred.
  • the sulphurization with sulphur halide is preferably carried out in a solvent such as aliphatic hydrocarbons, e.g. n-hexane.
  • a solvent such as aliphatic hydrocarbons, e.g. n-hexane.
  • aromatic solvents such as xylene
  • Preferred sulphur halides are sulphur chlorides, such as SC1 2 and S 2 C1 2 .
  • the reaction can be carried out at ambient temperature, although some heating may be applied, e.g. up to 60°C.
  • the molar ratio of S: substituted salicylic acid or salicylate is e.g. 0.25 to 3 preferably 0.5 to 2.
  • reaction mixture may then be acidified, if necessary, to obtain the free sulphurized acid and filtered if desirable.
  • the product is used for the preparation of the corresponding overbased salicylates which combine good detergency with reduced wear in lubricating oil compositions.
  • the overbasing step can be carried out by reacting the resulting product in a solvent, such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene, with a basic metal compound, preferably a hydroxide, and carbon dioxide, as described in e.g. British patent specification 786167.
  • a solvent such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene
  • a basic metal compound preferably a hydroxide, and carbon dioxide, as described in e.g. British patent specification 786167.
  • the degree of overbasing is expressed as the basicity index (B.I.), defined as the equivalent ratio of metal:salicylic acid.
  • a light mineral oil may be added and then the hydrocarbon solvent, and anywaterformed may be removed by distillation.
  • the resulting oil solution of the sulphurized. product may be filtered, if desired, and then be added to an oil, such as a lubricating oil or a fuel oil, including gasoline.
  • an oil such as a lubricating oil or a fuel oil, including gasoline.
  • the product Before or after sulphurization the product may be reacted with a boron compound, such as boric acid, as described in the copending British Patent Application 8330441.
  • a boron compound such as boric acid
  • reaction products of this invention including mixtures thereof can be incorporated in oil compositions, in particular lubricating oil compositions or concentrates or fuels, e.g., automotive crankcase oils, in concentrations within the range of 0.001 to 65, in particular 0.1 to 15 %w based on the weight of the total compositions.
  • the lubricating oils to which the additives of the invention can be added include not only mineral lubricating oils, but synthetic oils also. Synthetic hydrocarbon-lubricating oils may also be employed, as well as non-hydrocarbon synthetic oils including dibasic acids esters such as di-2-ethyl hexyl sebacate, carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters such as C, 3 oxo acid diesters of tetraethylene glycol, etc. Mixtures of these oils in particular of mineral lubricating oils, including hydrogenated oils, and synthetic lubricating oils, can also be used.
  • additives may also be present, including dyes, pour point depressants, anti-wear, e.g., tricresyl phosphate, zinc dithiophosphates, antioxidants such as phenyl- alpha-naphthyl-amine, bis-phenols such as 4,4'-methylene bis (3,6-di-tert-butyiphenoi), viscosity index improvers, such as hydrogenated (co)polymers of conjugated dienes and optionally styrene, ethylene-higher olefin copolymers, polymethylac- rylates, polyisobutylene, and the like as well as ashless dispersants, such as reaction products of polyisobutylene, maleic anhydride and amines and/or polyols, or other metal-containing detergents, such as overbased metal salicylates.
  • dyes e.g., tricresyl phosphate, zinc dithiophosphates
  • antioxidants such
  • Reaction products of amines, formaldehyde and alkyl phenols can also be present.

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)
  • Liquid Carbonaceous Fuels (AREA)

Claims (7)

1. Verfahren zur Herstellung von sulfurierten überbasischen mit aliphatischen Kohlenwasserstoffgruppe(n) substituierten Metallsalicylaten durch Sulfurierung einer mit aliphatischen Kohlenwasserstoffgruppe(n) substituierten Salicylsäure oder eines Metallsalzes derselben und anschließendem Überbasisch-Machen des Produkts durch Umsetzung mit einer basischen Metallverbindung und Kohlendioxid, dadurch gekennzeichnet, daß die Sulfurierung durch Umsetzung mit einem Schwefelhalogenid erfolgt.
2. Verfahren wie in Anspruch 1 beansprucht, in welchem das Schwefelhalogenid SCI2 oder S2C12 ist.
3. Verfahren nach Anspruch 1 oder 2, in welchem das molare Verhältnis von S: substituierter Salicylsäure oder Salicylat 0,25:1 bis 3:1 ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, in welchem das Metall des überbasischen Metallsalicylats ein Erdalkalimetall ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, in welchem die mit aliphatischen Kohlenwasserstoffgruppe(n) substituierte Salicylsäure eine C8-30-Alkylsalicylsäure ist.
6. Verfahren nach einem der Ansprüche 1 bis 5, in welchem das Produkt vor oder nach der Sulfurierung mit einer Borverbindung umgesetzt wird.
7. Ölzusammensetzung, insbesondere eine Schmierölzusammensetzung oder ein Konzentrat oder Brennstoff, enthaltend 0,001 bis 65 Gewichtsprozent eines sulfurierten überbasischen mit aliphatischen Kohlenwasserstoffgruppe(n) substituierten Metallsalicylats, wie durch das Verfahren nach Anspruch 1 hergestellt.
EP85201082A 1984-07-06 1985-07-04 Verfahren zur Herstellung von geschwefelten, überbasischen Salicylaten Expired EP0168110B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8417298 1984-07-06
GB848417298A GB8417298D0 (en) 1984-07-06 1984-07-06 Preparation of sulphurized overbased salicylates

Publications (2)

Publication Number Publication Date
EP0168110A1 EP0168110A1 (de) 1986-01-15
EP0168110B1 true EP0168110B1 (de) 1988-09-28

Family

ID=10563524

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85201082A Expired EP0168110B1 (de) 1984-07-06 1985-07-04 Verfahren zur Herstellung von geschwefelten, überbasischen Salicylaten

Country Status (8)

Country Link
EP (1) EP0168110B1 (de)
JP (1) JPS6124561A (de)
BR (1) BR8503202A (de)
CA (1) CA1255691A (de)
DE (1) DE3565258D1 (de)
GB (1) GB8417298D0 (de)
SG (1) SG6790G (de)
ZA (1) ZA855047B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2149810B (en) * 1983-11-15 1987-04-08 Shell Int Research Borated basic metal salt and oil composition containing it
JPH059522Y2 (de) * 1986-10-16 1993-03-09
GB8714922D0 (en) * 1987-06-25 1987-07-29 Shell Int Research Lubricating oil composition
US6828415B2 (en) 1993-02-19 2004-12-07 Zentaris Gmbh Oligopeptide lyophilisate, their preparation and use
US7956022B2 (en) * 2005-07-29 2011-06-07 Chevron Oronite Company Llc Low sulfur metal detergent-dispersants
GB201501991D0 (en) * 2015-02-06 2015-03-25 Castrol Ltd Uses and compositions

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2256441A (en) * 1940-03-08 1941-09-16 Socony Vacuum Oil Co Inc Mineral oil composition and improving agent therefor
US2319662A (en) * 1941-10-31 1943-05-18 American Cyanamid Co Lubricating oils
US2311931A (en) * 1941-12-27 1943-02-23 American Cyanamid Co Lubricant
USRE22910E (en) * 1941-12-31 1947-09-02 E-oxcxs-m
US2336074A (en) * 1942-05-16 1943-12-07 American Cyanamid Co Lubricating oil
GB786167A (en) * 1954-09-27 1957-11-13 Shell Res Ltd Improvements in or relating to the preparation of basic oil-soluble polyvalent metalsalts of organic acids and solutions of said basic salts in oils, and the resultingsalts
GB825315A (en) * 1957-02-18 1959-12-16 Socony Mobil Oil Co Inc Complex carbonated metal salts of alkyl phenol sulphides
GB1094609A (en) * 1965-08-23 1967-12-13 Lubrizol Corp Oil soluble basic alkaline earth metal salts of phenol sulfides
US3595791A (en) * 1969-03-11 1971-07-27 Lubrizol Corp Basic,sulfurized salicylates and method for their preparation
US3595790A (en) * 1969-10-22 1971-07-27 Lubrizol Corp Oil soluble highly basic metal salts of organic acids
GB1597482A (en) * 1977-01-28 1981-09-09 Exxon Research Engineering Co Metal phenates
US4320016A (en) * 1979-09-24 1982-03-16 Texaco Inc. Carbon dioxide-blown overbased calcium alkylphenolate lubricating compositions
JPS60147497A (ja) * 1984-01-09 1985-08-03 Cosmo Co Ltd サリチレ−トを含有する塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造方法
JPS60168793A (ja) * 1984-02-13 1985-09-02 Cosmo Co Ltd 塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造法

Also Published As

Publication number Publication date
GB8417298D0 (en) 1984-08-08
ZA855047B (en) 1986-02-26
SG6790G (en) 1990-07-13
EP0168110A1 (de) 1986-01-15
DE3565258D1 (en) 1988-11-03
BR8503202A (pt) 1986-03-25
JPS6124561A (ja) 1986-02-03
JPH0580518B2 (de) 1993-11-09
CA1255691A (en) 1989-06-13

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