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 C8-30-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 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
• 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 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 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 550 mm Hg. Then the temperature was raised to 195 °C and the pressure lowered to 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.

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Liquid Carbonaceous Fuels (AREA)

Applications Claiming Priority (2)

Publications (2)

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Cited By (7)

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Citations (12)

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• 1984
  • 1984-07-06 GB GB848417297A patent/GB8417297D0/en active Pending
• 1985
  • 1985-06-17 CA CA000484253A patent/CA1253873A/fr not_active Expired
  • 1985-07-04 ZA ZA855048A patent/ZA855048B/xx unknown
  • 1985-07-04 BR BR8503201A patent/BR8503201A/pt not_active IP Right Cessation
  • 1985-07-04 DE DE8585201083T patent/DE3564570D1/de not_active Expired
  • 1985-07-04 JP JP14760585A patent/JPS6124560A/ja active Granted
  • 1985-07-04 EP EP85201083A patent/EP0168880B1/fr not_active Expired
• 1990
  • 1990-02-05 SG SG70/90A patent/SG7090G/en unknown

Patent Citations (12)

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