EP0168880B1 - Procédé de préparation de salicylates surbasiques sulfurés - Google Patents

Procédé de préparation de salicylates surbasiques sulfurés Download PDF

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Publication number
EP0168880B1
EP0168880B1 EP85201083A EP85201083A EP0168880B1 EP 0168880 B1 EP0168880 B1 EP 0168880B1 EP 85201083 A EP85201083 A EP 85201083A EP 85201083 A EP85201083 A EP 85201083A EP 0168880 B1 EP0168880 B1 EP 0168880B1
Authority
EP
European Patent Office
Prior art keywords
process according
meq
overbased
metal
salicylic acid
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
EP85201083A
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German (de)
English (en)
Other versions
EP0168880A1 (fr
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
Original Assignee
Shell Internationale Research Maatschappij BV
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Publication date
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Publication of EP0168880A1 publication Critical patent/EP0168880A1/fr
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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, to products thus prepared and to oil compositions containing them.
  • This invention therefore relates to a process for the preparation of sulphurized overbased metal aliphatic hydrocarbon-substituted salicylates, characterized in that an aliphatic hydrocarbon-substituted salicylic acid is transformed into an overbased metal salicylate having a basicity index of at least 1.5 by means of a basic metal compound and with carbon dioxide, and subsequently the overbased metal salicylate is sulphurized by heating with elemental sulphur.
  • the invention furthermore relates to the products thus prepared and to oil compositions containing them.
  • Suitable metals 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.
  • alkali metals such as Li, Cs, Na and K
  • alkaline earth metals such as Ca, Ba, Sr and Mg
  • polyvalent metals such as Zn and Cr.
  • Alkaline earth metals such as calcium, barium and magnesium are preferred.
  • Suitable aliphatic hydrocarbon-substituted salicylic acids are described in the above-mentioned British patent specifications. Preferred are C 8 - 30 - alkyl salicylic acids.
  • the overbasing step can be carried out by reacting the hydrocarbon substituted salicylic acid 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 786 167.
  • 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 786 167.
  • a light mineral oil may be added and then the hydrocarbon solvent, and any water formed may be removed by distillation.
  • the basicity index (BI) of the overbased salicylate defined as the equivalent ratio of metal: salicylic acid, is at least 1.5, preferably at least 3. It has been found that this is of importance in order to avoid any substantial amount of decarboxylation in the sulphurization step.
  • the sulphurization step can be carried out by contacting the resulting oil solution of the overbased salt with elemental sulphur, preferably in the presence of a solvent, at a temperature in the range of 100-250 °C, preferably 150-225 °C, whereby the final temperature should be at least 175 °C and preferably at least 195 °C.
  • 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 above-mentioned solvent of the sulphurization step preferably is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British patent specifications 1 287 812 and 1 194 503.
  • a promotor such as a carboxylic acid or a metal salt thereof, as described in British patent specification 1 194 503, may also be present in the sulphurization step.
  • the molar ratio of S: substituted salicylic acid is e.g. 0.25 to 3, preferably 0.5 to 2.
  • 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 83 30 441.
  • 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 acid esters such as di-2-ethyl hexyl sebacate, carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters such as C 13 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-butylphenol), viscosity index improvers, such as hydrogenated (co)polymers of conjugated dienes and optionally styrene, ethylene-higher olefin copolymers, polymethylacrylates, 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 as phenyl-
  • Reaction products of amines, formaldehyde and alkyl phenols can also be present.
  • Overbased calcium C 14-18 -alkyl salicylate having a BI of 3 (Product A) was prepared from C 14 - 18 -alkyl salicylic acid by means of calcium hydroxide and carbon dioxide, and was taken up in a mineral lubricating oil.
  • a reaction vessel (5 litre) was charged with 2500 g (2530 meq acid) of a concentrate of 67%w of the overbased calcium C 14 - 18 -alkyl salicylate in 33%w of the mineral lubricating oil, 80 g (2500 meq) elemental sulphur and 20 g ethylene glycol. Under stirring this mixture was heated to 125 °C and kept at that temperature for one hour. The temperature was then raised to 150 °C and kept at that temperature for one hour at a pressure of about 0.73 Bar (550 mm Hg). Then the temperature was raised to 195 °C and the pressure lowered to 0.067-0.08 Bar 50-60 mm Hg), these conditions were maintained for two hours.
  • reaction product was then allowed to cool to about 100 °C before filtering through filter aid, to give a dark viscous product (yield: 2500 g, S: 1.6%w (Product B). It appeared that sulphurization at a lower temperature (175 °C) resulted in some dissolved unreacted sulphur, which is inclined to precipitate on standing.
  • Formulation I contained Product A in an amount of 0.14%w as Ca in lubricating oil 1.
  • Formulation II contained lubricating oil 1 and 0.14%w (as Ca) of Product B.
  • Formulations III and IV comprised lubricating oil 2 with 0.19%w as Ca of Product A and B, respectively.
  • Formulations III and IV were tested in the MS Sequence IIID engine test in which the cam and lifter wear and cleanliness performance were determined.

Claims (8)

1. Procédé pour la préparation de sels métalliques surbasiques sulfurés d'acides salicyliques substitués par des hydrocarbures aliphatiques, caractérisé en ce qu'un acide salicylique substitué par des hydrocarbures aliphatiques est transformé en un salicylate métallique surbasique ayant un indice de basicité d'au moins 1,5 au moyen d'un composé basique de métal et d'anhydride carbonique et ensuite le salicylate métallique surbasique est sulfuré par chauffage avec du soufre élémentaire.
2. Procédé selon la revendication 1, dans lequel le métal est un métal alcalino-terreux.
3. Procédé selon la revendication 1 ou 2, dans lequel l'acide salicylique substitué par des hydrocarbures aliphatiques est un acide C8-30-alcoyl- salicylique.
4. Procédé selon l'une quelconque des revendications 1-3, dans lequel l'indice de basicité du salicylate surbasique est d'au moins 3.
5. Procédé selon l'une quelconque des revendications 1-4, dans lequel la sulfuration est effectuée à au moins 175 °C.
6. Procédé selon l'une quelconque des revendications 1-5, dans lequel le rapport molaire du soufre à l'acide salicylique substitué est de 0,25 à 3.
7. Procédé selon l'une quelconque des revendications 1-6, dans lequel le produit avant ou après la sulfuration est mis à réagir avec un composé du bore.
8. Composition d'huile, en particulier composition d'huile lubrifiante ou concentré ou combustible, comprenant une huile et 0,001-65% en poids d'un produit obtenu selon le procédé de la revendication 1.
EP85201083A 1984-07-06 1985-07-04 Procédé de préparation de salicylates surbasiques sulfurés Expired EP0168880B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8417297 1984-07-06
GB848417297A GB8417297D0 (en) 1984-07-06 1984-07-06 Preparation of sulphurized overbased salicylates

Publications (2)

Publication Number Publication Date
EP0168880A1 EP0168880A1 (fr) 1986-01-22
EP0168880B1 true EP0168880B1 (fr) 1988-08-24

Family

ID=10563523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85201083A Expired EP0168880B1 (fr) 1984-07-06 1985-07-04 Procédé de préparation de salicylates surbasiques sulfurés

Country Status (8)

Country Link
EP (1) EP0168880B1 (fr)
JP (1) JPS6124560A (fr)
BR (1) BR8503201A (fr)
CA (1) CA1253873A (fr)
DE (1) DE3564570D1 (fr)
GB (1) GB8417297D0 (fr)
SG (1) SG7090G (fr)
ZA (1) ZA855048B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004133932A (ja) * 2002-10-09 2004-04-30 Xerox Corp 動画ソース画像を形成するためのソース画像のスペクトル多重化及びレンダリング、及びスペクトル逆多重化のためのシステム

Families Citing this family (10)

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JPS63266424A (ja) * 1987-04-24 1988-11-02 Alps Electric Co Ltd 液晶表示素子
GB8714922D0 (en) * 1987-06-25 1987-07-29 Shell Int Research Lubricating oil composition
JPH0676589B2 (ja) * 1987-07-24 1994-09-28 コスモ石油株式会社 ヒドロキシアルキル安息香酸およびアルキルフェノ−ルのアルカリ土類金属塩硫化混合物の製造法
JPH083767Y2 (ja) * 1992-07-09 1996-01-31 日本ピラー工業株式会社 軸封装置
MX9305120A (es) * 1992-09-04 1994-03-31 Lubrizol Corp Composiciones sobrebasificadas sulfuradas.
TW278098B (fr) * 1992-09-18 1996-06-11 Cosmo Sogo Kenkyusho Kk
US6828415B2 (en) 1993-02-19 2004-12-07 Zentaris Gmbh Oligopeptide lyophilisate, their preparation and use
JPH1161165A (ja) * 1997-06-12 1999-03-05 Tonen Corp サリチル酸金属塩からなる摩擦低減剤およびそれを含有する潤滑油組成物
JP2005220197A (ja) * 2004-02-04 2005-08-18 Nippon Oil Corp 鉛含有金属材料と接触する潤滑油組成物
US7956022B2 (en) 2005-07-29 2011-06-07 Chevron Oronite Company Llc Low sulfur metal detergent-dispersants

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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
IT1044574B (it) * 1975-07-14 1980-03-31 Liquichimica Robassomero Spa Additivo detergentfe per la sua preparazione
GB1597482A (en) * 1977-01-28 1981-09-09 Exxon Research Engineering Co Metal phenates
US4228022A (en) * 1979-06-28 1980-10-14 Chevron Research Company Sulfurized alkylphenol-olefin reaction product lubricating oil additive
US4320016A (en) * 1979-09-24 1982-03-16 Texaco Inc. Carbon dioxide-blown overbased calcium alkylphenolate lubricating compositions
IN155264B (fr) * 1979-11-07 1985-01-12 Lubrizol Corp
JPH07103390B2 (ja) * 1982-05-14 1995-11-08 エクソン リサーチ アンド エンヂニアリング コムパニー 潤滑油添加剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004133932A (ja) * 2002-10-09 2004-04-30 Xerox Corp 動画ソース画像を形成するためのソース画像のスペクトル多重化及びレンダリング、及びスペクトル逆多重化のためのシステム

Also Published As

Publication number Publication date
EP0168880A1 (fr) 1986-01-22
GB8417297D0 (en) 1984-08-08
BR8503201A (pt) 1986-03-25
CA1253873A (fr) 1989-05-09
JPS6124560A (ja) 1986-02-03
ZA855048B (en) 1986-02-26
JPH0580517B2 (fr) 1993-11-09
DE3564570D1 (en) 1988-09-29
SG7090G (en) 1990-07-13

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